CN106032487B

CN106032487B - Lubricant composition and preparation method thereof

Info

Publication number: CN106032487B
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: 2019-01-08
Anticipated expiration: 2035-03-11
Also published as: CN106032487A

Abstract

The present invention relates to lubricating grease fields, disclose a kind of lubricant composition, lubricant composition contains base oil and thickening agent, thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium and higher fatty acids zirconates, thickening agent also optionally contains non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, one of zirconates of small molecule inorganic acid and/or lower fatty acid is a variety of, on the basis of the weight of the lubricant composition, the content of base oil is 10-80 weight %, non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content is 10-70 weight %, the content of the zirconates of higher fatty acids is 1-10 weight %, the content of remaining optional components is respectively 0-70 weight %, 0-70 weight %, 0-70 weight %, 0-15 weight % , 0-15 weight %.Also disclose preparation method.Lubricant composition of the invention has excellent performance.

Description

Lubricant composition and preparation method thereof

Technical field

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

Background technique

SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusion Property, it is used as the detersive of lubricating oil, is widely used in modulation medium and high classes I. C. engine oil, is particularly suitable for supercharged diesel engine For oil to reduce the carbon deposit of top land and the additive of marine cylinder oil, technology development mainly makes its height alkalization, be exactly Calcium carbonate, which is distributed in flux oil with the sulfurized alkylphenol calcium with surface-active, becomes a kind of colloidal dispersion system.High base number Sulfurized alkylphenol calcium is that alkyl phenol is reacted with CaO, vulcanized, carbonated contour alkalization technology and obtain, and the correlation in relation to preparation is specially Benefit has CN101423483 etc..

It is that raw material produces lubricating grease using calcium sulfonate with high base number, because it is with excellent antirust and anticorrosive property, from investment Since market, the extensive concern of domestic and international lubricating grease industry is caused, however, although high base number composite calcium sulfonate base grease has Very excellent antirust and anticorrosive property, but hardening is easy in storage process, and its raw materials for production calcium sulfonate with high base number is high Price and complicated preparation process itself cause it not promoted rapidly, meanwhile, the requirement with people to environmental protection is got over Come higher, necessary sulfonation process is also increasingly subject to the concern of people to the pollution of environment in calcium sulfonate with high base number production process. It finds a kind of antirust and anticorrosive property is similar with high base number composite calcium sulfonate base grease but can reduce the lubrication of the above problem Rouge becomes the big problem that people face at present.

Zirconium belongs to Group IVB as a kind of transition metal element, is located at for the 5th period.Zirconium-containing compound has excellent lubrication Effect, is often used as lubricating additive, as CN101113382 and JP1973038444 is added the oxide of zirconium as lubricant Agent improves abrasiveness；WO2007143414 and US20060063682, which describes zirconium tetrafluoride and can be used as wear reducing additive, to be become One of component of lubricant；Lubricant of the US20060254823 discovery containing 2-thylhexoic acid zirconates shows resistance to heavy well Load and abrasion resistance；US20050043189 discovery fluozirconate such as fluorine zirconic acid aluminium can be used as oxidation retarder used in lubricant In；The inorganic salts such as zirconium carbonate, sulfonic acid zirconium or basic zirconium phosphate are added to inside lubricating grease and can be improved by DE102004021812 discovery Abrasion resistance.

Summary of the invention

The object of the present invention is to provide one kind to have good antirust and anticorrosive property, storage good security and its raw material system Standby simple process, lubricating grease of environmental protection and preparation method thereof.

The present inventor has found that sulfurized alkylphenol calcium may hold at high temperature due to containing active sulfur under study for action Elemental sulfur easily is precipitated and generates corrosion, therefore, when as detersive, the antirust and anticorrosive property of sulfurized alkylphenol calcium are far below Sulfoacid calcium, but when sulfurized alkylphenol calcium is prepared lubricating grease as thickening agent, but it can get and high base number composite calcium sulfonate Ji Run Consistent lubricant quite even preferably antirust and anticorrosive property, and storage good security.

Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of lubricant composition, the lubricating grease Composition contains base oil and thickening agent, and the thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium and higher aliphatic The zirconates of acid, the thickening agent also optionally contain non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid oleic acid Calcium, the zirconates of aromatic acid, small molecule inorganic acid and/or lower fatty acid one of zirconates or a variety of, with the lubricating grease group On the basis of the weight for closing object, the content of base oil is 10-80 weight %, non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content For 10-70 weight %, the content of the zirconates of higher fatty acids is 1-10 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 Weight %, the content of non-newtonian fluid calcium salicylate are 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 %, and the content of the zirconates of small molecule inorganic acid and/or lower fatty acid is 0-15 weight Measure %, wherein the zirconates of the higher fatty acids is to be reacted by higher fatty acids with component A, and the zirconates of the aromatic acid is It is reacted by aromatic acid with component A, the zirconates of the small molecule inorganic acid and/or lower fatty acid is by small molecule inorganic acid And/or lower fatty acid is reacted with component A, the component A is in the hydroxide and zirconium alkoxide of the oxide of zirconium, zirconium At least one.

Preferably, on the basis of lubricant composition weight, the content of base oil is 20-70 weight %, non-newtonian fluid sulphur Change alkyl phenol calcium-sulfoacid calcium content is 20-60 weight %, and the content of the zirconates of higher fatty acids is 2-6 weight %, non-ox The content of body calcium naphthenate is 0-50 weight %, and the content of non-newtonian fluid calcium salicylate is 0-50 weight %, non-newtonian fluid oil The content of sour calcium is 0-50 weight %, and the content of the zirconates of aromatic acid is 2-10 weight %, small molecule inorganic acid and/or lower aliphatic The content of the zirconates of acid is 2-10 weight %.

Preferably, the component A contains the oxide and/or hydroxide of zirconium, in terms of zirconium, the oxide and/or hydrogen of zirconium The molar ratio of oxide and zirconium alkoxide is 1:0-10, more preferably 1:0.5-5.

Second aspect, the present invention provides the preparation methods of lubricant composition as described above, this method comprises: by thick Agent and part basis oil are uniformly mixed, and refine in 180-230 DEG C of constant temperature, surplus base oil is added, necessary additive is added, Finished product is obtained, the thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium and higher fatty acids zirconates, described thick Agent also optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, aromatic acid zirconates, One of zirconates of small molecule inorganic acid and/or lower fatty acid is a variety of.

The third aspect, the present invention provides a kind of preparation methods of lubricant composition, this method comprises:

(1) will contain newton body sulfurized alkylphenol calcium, newton body and/or non-newtonian fluid sulfoacid calcium, or containing newton body and/ Or non-newtonian fluid sulfurized alkylphenol calcium, the high base number material of newton body sulfoacid calcium and the mixing of part basis oil, mixture is obtained, The high base number material also optionally contains newton body and/or non-newtonian fluid calcium naphthenate, newton body and/or non-newtonian fluid bigcatkin willow Sour calcium and one of newton body and/or non-newtonian fluid calcium oleate or a variety of；

(2) it optionally carries out the reaction of at least partly compound zirconium: component A is added, higher fatty acids, optional virtue is added Sour, optional small molecule inorganic acid and/or lower fatty acid, are reacted, and the component A is the hydrogen-oxygen of the oxide of zirconium, zirconium At least one of compound and zirconium alkoxide；

(3) transforming agent is added, heats up to material retrogradation；

(4) reaction of remaining compound zirconium is carried out；

(5) heating dehydration；

(6) 180-230 DEG C of constant temperature refinings are warming up to, surplus base oil is added, necessary additive is added, obtains finished product.

Preferably, in step (2), the reaction of at least partly compound zirconium is carried out.

Fourth aspect, the present invention provides the lubricant compositions as made from method as described above.

Lubricant composition of the invention with the antirust quite even more excellent with complex calcium sulfonate grease and is prevented Corrosivity, and there is excellent storage stability, also there is mechanical stability, water resistant better than complex calcium sulfonate grease Property, colloid stability, abrasion resistance and extreme pressure anti-wear, and also there are the performances such as excellent heat-resisting quantity.Lubrication of the invention The feed preparation process of rouge is simple and environmentally-friendly, stable product quality.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

The present invention provides a kind of lubricant composition, this lubricant composition uses calcium mahogany sulfonate and/or conjunction At sulfoacid calcium, synthesis sulfurized alkylphenol calcium, optional petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, optional synthesis bigcatkin willow Sour calcium, optional natural calcium oleate and/or synthesis calcium oleate are raw material, contain compound zirconium thickening agent simultaneously.

The present invention also provides the preparation methods of foregoing grease composition.

On the one hand, the present invention provides a kind of lubricant composition, lubricant composition contains base oil and thickening agent, thick Agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium and higher fatty acids zirconates, and thickening agent also optionally contains non-ox Body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, small molecule inorganic acid and/or rudimentary One of zirconates of fatty acid is a variety of, and on the basis of the weight of lubricant composition, the content of base oil is 10-80 weights % is measured, non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content 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 are 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 weight % is measured, 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 %, and small molecule is inorganic The content of the zirconates of acid and/or lower fatty acid is 0-15 weight %, wherein the zirconates of higher fatty acids is by higher fatty acids It is reacted with component A, the zirconates of aromatic acid is to be reacted by aromatic acid with component A, small molecule inorganic acid and/or lower fatty acid Zirconates be to be reacted by small molecule inorganic acid and/or lower fatty acid with component A, component A is the hydrogen of the oxide of zirconium, zirconium At least one of oxide and zirconium alkoxide.

Preferably, on the basis of the weight of lubricant composition, the content of base oil is 20-70 weight %, non-newtonian fluid Sulfurized alkylphenol calcium-sulfoacid calcium content is 20-60 weight %, and the content of the zirconates of higher fatty acids is 2-6 weight %, non- The content of newton body calcium naphthenate is 0-50 weight %, and 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 %, small molecule inorganic acid and/or rudimentary rouge The content of the zirconates of fat acid is 2-10 weight %.

In the present invention, " optionally containing " refers to can be containing the component or without containing the component, that is, non-newtonian fluid Calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, small molecule inorganic acid and/or lower aliphatic One of zirconates of acid or it is a variety of be optional component, may include the component in lubricant composition of the invention, can also be with It does not include the component.

Non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non newtonian Body calcium oleate or combinations thereof object is in infrared spectrum 873cm^–1–886cm^–1There is crystal form calcium carbonate characteristic absorption peak in place.Non-newtonian fluid Sulfurized alkylphenol calcium-sulfoacid calcium is to convert to obtain by transforming agent by newton body sulfoacid calcium and newton body sulfurized alkylphenol calcium, non- Newton body sulfurized alkylphenol calcium-sulfoacid calcium total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non- ox The body calcium naphthenate that pauses is converted by newton body calcium naphthenate, and the total base number of non-newtonian fluid calcium naphthenate is 250- 450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid calcium salicylate is converted by newton body calcium salicylate, The total base number of non-newtonian fluid calcium salicylate is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid calcium oleate It is to be converted by newton body calcium oleate, 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 sulfurized alkylphenol calcium, newton body calcium naphthenate, newton body calcium salicylate, ox Contain unformed calcium carbonate in body calcium oleate, in infrared spectrum 860cm^–1–865cm^–1There is unformed calcium carbonate feature and inhales in place Receive peak.Newton body sulfurized alkylphenol calcium is synthesis sulfurized alkylphenol calcium, total base number 250-450mgKOH/g, preferably 300- 400mgKOH/g；Newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, total base number 250-450mgKOH/g, Preferably 300-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, total base number are 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body calcium salicylate is salicylate calcium, and total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body calcium oleate be natural calcium oleate and/or synthesis calcium oleate, Its total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g.It is non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, non- The base number of newton body calcium naphthenate, non-newtonian fluid calcium salicylate and the mixing of non-newtonian fluid calcium oleate is the weight of the base number of each component Weighted average.

In the present invention, higher fatty acids can be that carbon number is 8-20, preferably 10-18 fatty acid or hydroxy fatty acid, Such as at least one of lauric acid, palmitinic acid, stearic acid, 12-hydroxy stearic acids, eicosyl carboxylic acid, preferably 12-hydroxyls Stearic acid.

In the present invention, aromatic acid is the carboxylic acid that at least 1 carboxyl and aromatic ring are connected directly, and aromatic acid can be substituted or not Substituted aromatic acid, substituent group can be in alkyl, alkenyl, alkynyl, aryl, halogenated or perhalogeno alkyl or aryl etc. extremely The molecular weight of few one kind, aromatic acid is preferably smaller than equal to 550.Aromatic acid is preferably binary aromatic acid, for example, can selected from unsubstituted or The alkyl-substituted phthalic acid of C1-C5, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, in multi-joint phthalic acid extremely Few one kind.Preferably phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid and methyl substituted biphenyl two At least one of formic acid, multi-joint phthalic acid etc..

In the present invention, the molecular weight of small molecule inorganic acid and lower fatty acid is less than or equal to 250.Wherein, small molecule is inorganic Acid can be selected from least one of boric acid, phosphoric acid, sulfuric acid etc., preferably boric acid and/or phosphoric acid；Lower fatty acid can be selected from At least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid etc., preferably acetic acid.

The present inventor has been surprisingly found that under study for action, when component A contains the oxide and/or hydroxide of zirconium, That is when the raw material of zirconium contains the oxide and/or hydroxide of zirconium, it can further improve grease thickening, machinery is stabilized Property, water-resistance, colloid stability and abrasion resistance, therefore, component A preferably comprises the oxide and/or hydroxide of zirconium, In, in terms of zirconium, the oxide and/or hydroxide of zirconium and the molar ratio of zirconium alkoxide are preferably 1:0-10, more preferably 1: 0.2-8, it is still more preferably 1:0.5-5, in the preferred molar ratio of the oxide and/or hydroxide and zirconium alkoxide of zirconium In the case of, grease thickening, mechanical stability, water-resistance, colloid stability and abrasion resistance can be further increased.

In the present invention, the oxide and/or hydroxide of zirconium are preferably selected from ZrO₂、ZrO(OH)₂、Zr(OH)₄And they At least one of hydrate.ZrO(OH)₂Hydrate can be brand-new wet hydrogen zirconium oxide, ZrOX can be passed through₂· 8H₂O (X F, Cl, Br or I) or ZrO (NO₃)₂·2H₂O etc. reacts acquisition with alkali, wherein alkali can be NaOH, KOH, dense ammonia Water etc., preferably ZrOCl₂·8H₂O is reacted with NaOH.

In the present invention, the general formula of zirconium alkoxide can be Zr (OR₁)₄, R₁It can be the alkyl of C1-C10, preferably C2-C6 Alkyl；It is highly preferred that zirconium alkoxide in ethyl alcohol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and n-amyl alcohol zirconium extremely Few one kind.

In the present invention, base oil can be mineral oil, synthetic oil, vegetable oil or their mixture, 100 DEG C of dynamic viscosities For 4-60mm²/ s, preferably 10-30mm²/s.Synthetic oil can be poly- α-alkene oily (PAO), Esters oil, alkyl-silicone oil, Fischer-Tropsch and close At oil etc..

Various additives can also be contained in lubricant composition of the invention, such as antioxidant, extreme pressure anti-wear additives, antirust agent Etc..Wherein, the preferred arylamine kind antioxidant of antioxidant, accounts for the 0.01-5% of lubricating grease total weight, preferably 0.1-2.5%, can be with It is diphenylamines, phenyl-α-at least one of naphthylamines and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme-pressure anti-wear Agent accounts for the 0.5-12% of lubricating grease total weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl group Carbamic acid molybdenum, two thio dialkyl amido lead formates, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, two sulphur Change molybdenum, polytetrafluoroethylene (PTFE), thiophosphoric acid molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, At least one of fluorographite, calcium carbonate and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease total weight, preferably 0.1- 2%, it can be in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid It is at least one.

Second aspect, the present invention provides the preparation methods of lubricant composition as described above, this method comprises: by thick Agent and part basis oil are uniformly mixed, and refine in 180-230 DEG C of constant temperature, surplus base oil is added, necessary additive is added, Finished product is obtained, thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium and higher fatty acids zirconates, and thickening agent is also appointed Selection of land contain non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, small molecule without One of zirconates of machine acid and/or lower fatty acid is a variety of.

In the present invention, " optionally containing " is as previously mentioned, details are not described herein.

In the present invention, non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, the zirconates of higher fatty acids, non-newtonian fluid aphthenic acids Calcium, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, small molecule inorganic acid and/or lower fatty acid zirconium Salt, base oil and additive are as previously mentioned, details are not described herein.

It will be understood by those skilled in the art that the sum of the amount of part basis oil and the amount of surplus base oil are used Base oil total amount, in the present invention, the weight ratio of part basis oil and surplus base oil is preferably 1:0.1-5.

For non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non- Newton body calcium oleate or combinations thereof object, can by newton body sulfurized alkylphenol calcium, newton body sulfoacid calcium, newton body calcium naphthenate, Newton body calcium salicylate, newton body calcium oleate or combinations thereof object pass through transforming agent respectively and convert to obtain, for example, newton body is vulcanized Alkyl phenol calcium, newton body sulfoacid calcium, optional newton body calcium naphthenate, optional newton body calcium salicylate, optional newton body Calcium oleate and base oil Hybrid Heating are added required transforming agent and are reacted to 50-80 DEG C, after all transforming agents add, 80-100 DEG C constant temperature 60-90 minutes, then heat to 110-130 DEG C of dehydration.

In the present invention, " optional " refer to can there is the raw material or no raw material, for example, " optional newton body Calcium naphthenate ", which refers to, can this raw material of newton body calcium naphthenate, can also not have this raw material of newton body calcium naphthenate.

(3) transforming agent is added, heats up to material retrogradation；

(4) reaction of remaining compound zirconium is carried out；

(5) heating dehydration；

" optionally containing " is as previously mentioned, details are not described herein.

In the present invention, newton body sulfurized alkylphenol calcium, non-newtonian fluid sulfurized alkylphenol calcium, newton body sulfoacid calcium, non newtonian Body sulfoacid calcium, newton body calcium naphthenate, non-newtonian fluid calcium naphthenate, newton body calcium salicylate, non-newtonian fluid calcium salicylate, newton Body calcium oleate, non-newtonian fluid calcium oleate, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid, the oxide of zirconium, zirconium Hydroxide, zirconium alkoxide and base oil as previously mentioned, details are not described herein.

In step (1) of the present invention, " containing newton body sulfurized alkylphenol calcium, newton body and/or non-newtonian fluid sulfoacid calcium, or High base number material containing newton body and/or non-newtonian fluid sulfurized alkylphenol calcium, newton body sulfoacid calcium " refers to high base number material In sulfurized alkylphenol calcium and at least one of sulfoacid calcium be newton figure.

In step (1) of the present invention, for sulfoacid calcium and sulfurized alkylphenol calcium weight ratio without particular/special requirement, preferably 1: 0.25–4.For other optional high base number materials amount without particular/special requirement, can be according to actual needs using commonly used in the art Amount, the weight ratio of high base number material total weight and part basis oil is preferably 1:0.1-3.

In step (2) of the present invention, " optionally carrying out the reaction of at least partly compound zirconium " i.e. include three kinds of situations: (i) not Carry out the reaction of compound zirconium, that is, do not have step (2), the reaction of whole compound zirconiums is only carried out in step (4), that is, The method of the present invention is first added transforming agent and is converted, and carries out the reaction of compound zirconium after conversion again；(ii) the compound zirconium in part is carried out Reaction carries out the reaction of the compound zirconium in part in step (2), carry out the reaction of remaining compound zirconium, i.e. phase again in step (4) When the reaction for carrying out the compound zirconium in part before conversion in the method for the present invention, the reaction of the compound zirconium in part is carried out again in post-conversion； (iii) reaction for carrying out all compound zirconiums, i.e., carry out the reaction of whole compound zirconiums in step (2), without step (4), That is, the method for the present invention first carries out the reaction of compound zirconium, then converted.

This field is generally transforming agent to be first added to be converted, then carry out the reaction of compound zirconium when preparing lubricating grease, When such as preparing complex calcium sulfonate zirconium base lubricating grease.But the present inventor has found under study for action, according to above situation (ii) or (iii) method of the invention is carried out, than carrying out method of the invention according to situation (i), i.e., is first carried out all or part of compound Zirconium reaction, then converted, it can further improve the performance of lubricating grease obtained.This may be due to first carrying out compound zirconium Reaction, can preferably convert the newton body sulfurized alkylphenol calcium of oily to the non-newtonian fluid sulfurized alkylphenol calcium of smectic. It is therefore preferred that carrying out the reaction of at least partly compound zirconium in step (2).

As previously mentioned, the present inventor has been surprisingly found that under study for action, when component A contains the oxide and/or hydrogen of zirconium When oxide, i.e. when the raw material of zirconium contains the oxide and/or hydroxide of zirconium, it can further improve the machine of lubricating grease obtained Tool stability, water-resistance and adhesiveness, colloid stability.It is therefore preferred that when carrying out step (2) and step (4), 85- At 100 DEG C, component A is added, higher fatty acids is added, stirs 5-30 minutes, it is inorganic that optional aromatic acid, optional small molecule is added Acid and/or lower fatty acid stir 5-30 minutes, and the component A contains the oxide and/or hydroxide of zirconium, in terms of zirconium, zirconium Oxide and/or the molar ratio of hydroxide and zirconium alkoxide be preferably 1:0-10, more preferably 1:0.2-8, further Preferably 1:0.5-5.Wherein, the addition of component A, higher fatty acids, aromatic acid, small molecule inorganic acid and/or lower fatty acid is suitable Sequence can exchange.

In the present invention, higher fatty acids and optional aromatic acid and optional small molecule inorganic acid and/or lower fatty acid H⁺H needed for the amount of total material is equal to all oxide of neutralization zirconium, the hydroxide and zirconium alkoxide of zirconium⁺Molal quantity, but The oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide are inorganic relative to the small molecule of higher fatty acids, aromatic acid and selectivity Acid and/or lower fatty acid can excessive 1-10%.

In the present invention, the additional amount of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide is preferably that high base number material is total The 1-15% of weight；With H⁺Substance meter, higher fatty acids and optional aromatic acid and optional small molecule inorganic acid and/or The molar ratio of lower fatty acid is preferably 1:1-10.

In step (3) of the present invention, it is preferable that at 50-80 DEG C, required transforming agent is added in preferred constant temperature 10-30 minutes It is reacted, is stirred 8-12 minutes after preferably adding every kind of transforming agent, after all transforming agents add, in 80-100 DEG C of constant temperature 60- 90 minutes.

The transforming agent be preferably selected from fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, In phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonate, C16-C24 alkyl phenol and water At least one；Be more preferably selected from the fatty alcohol of C1-C5, the fatty acid of C1-C5, the aliphatic ketone of C1-C5, C1-C5 fatty aldehyde, The fatty amine of C1-C5, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, C6-C20 aryl Phosphonic acids, the diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate, cycloalkanes At least one of acid, C16-C22 alkyl phenol and water；Still more preferably it is selected from dodecyl benzene sulfonic acid, aphthenic acids, octadecane At least one of base phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water.The additional amount of transforming agent is preferably high base number object Expect the 2-30% of total weight, more preferably the 6-22% of high base number material total weight.

In the present invention, fatty alcohol includes straight chain, branch and cricoid fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fat Amine is similarly.

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

In step (6) of the present invention, it is preferable that be warming up to 180-230 DEG C of constant temperature 5-30 minutes；Surplus base oil is added, to Temperature is cooled to 100-120 DEG C, and necessary additive is added, stirring, circulating filtration, homogenizing, degassing.

In the present invention, the weight ratio of surplus base oil is preferably 1 in part basis oil used and step (6) in step (1): 0.1–5。

Fourth aspect, the present invention also provides grease compositions made from the preparation method provided as third aspect present invention Object.

Compared with the lubricant composition made from the preparation method provided as second aspect, preparation side that the third aspect provides Lubricant composition made from method has better viscous resistance, mechanical stability, water-resistance, colloid stability and abrasion resistance.

Embodiment

The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.

In the following Examples and Comparative Examples:

Non-newtonian fluid sulfenyl phenolate-sulfoacid calcium in lubricant composition obtained, non-newtonian fluid calcium naphthenate, non-ox The total content of body calcium salicylate and non-newtonian fluid calcium oleate uses non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium % to indicate, That is,

Non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium %=(overbased or calcium sulfonate with high base number raw material weight+superelevation Base number 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 total weight)/lubricating grease is total Weight × 100%.Transforming agent is included in non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content.

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.

Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd.

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.

(NLGI Spokeman, 2009,73 (2): 1-17) prepared by method according to document for high base number calcium oleate.

Embodiment 1

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

Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 24kg)；Overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 6kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4-ten Eight alkylphenols (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil²/ s, 17kg).

It in a volume is 110L and with 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number be 400mgKOH/g overbased sulfurized alkylphenol calcium and The HVI150BS lubricating base oil of 30kg, stirring are warming up to 95 DEG C, and the Zr (OH) that solid content is 20 weight % is added₄Suspension 19.5kg is stirred 10 minutes；12-hydroxy stearic acid of 2kg is added, stirs 10 minutes；3.5kg terephthalic acid (TPA), stirring 10 is added Minute.The HVI500SN lubricating base oil of 10kg is added and material is made to be down to 50 DEG C, constant temperature 30 minutes；2.8kg 4-ten eight is added Alkylphenol, temperature are controlled at 50 DEG C, are stirred 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight %, stirring 10 is added Minute；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.It is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration.It is warming up to 200 DEG C constant temperature 10 minutes.Then, the HVI500SN lubricating base oil of 7kg is added；110 DEG C are cooled to temperature, circulating filtration, Homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 37.7 weight % of calcium-sulfoacid calcium；53.2 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.6 weight %；Terephthaldehyde Sour 6.5 weight % of oxygen zirconium.

Embodiment 2

Raw material components: overbased sulfoacid calcium (total base number 420mgKOH/g, 6kg)；Overbased sulfurized alkylphenol calcium (total base number 420mgKOH/g, 24kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4– Octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Ethyl alcohol zirconium (5.5kg)；Zr(OH)₄(0.65kg)；12-hydroxy stearic acids (2kg)；Phthalic acid (3.5kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil²/ s, 17kg).

It in a volume is 110L and with 6kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfoacid calcium of 420mgKOH/g, 24kg total base number be 420mgKOH/g overbased sulfurized alkylphenol calcium and The HVI150BS lubricating base oil of 30kg, stirring are warming up to 85 DEG C, and 0.55kg ethyl alcohol zirconium is added and solid content is 20 weight %'s Zr(OH)₄Suspension 0.325kg, in terms of zirconium, Zr (OH)₄Molar ratio with ethyl alcohol zirconium is 1:5, is stirred 10 minutes；0.2kg is added 12-hydroxy stearic acids stir 10 minutes；0.35kg phthalic acid is added, stirs 10 minutes.At 65 DEG C, constant temperature 20 minutes, 4-octadecylphenol of 2.8kg is added, temperature is controlled at 65 DEG C, stirred 10 minutes, and it is 20 weight %'s that 2.8kg concentration, which is added, Aqueous acetic acid stirs 10 minutes；It is warming up to 85 DEG C, constant temperature 80 minutes, material retrogradation.4.95kg ethyl alcohol zirconium is successively added and consolidates Content is the Zr (OH) of 20 weight %₄Suspension 2.925kg, in terms of zirconium, Zr (OH)₄Molar ratio with ethyl alcohol zirconium is 1:5, stirring 10 minutes；12-hydroxy stearic acid of 1.8kg is added, stirs 10 minutes；3.15kg phthalic acid is added, stirs 10 minutes.It stirs It mixes down and is warming up to 110 DEG C, kept for 60 minutes, dehydration.Being warming up to 230 DEG C, constant temperature for 5 minutes.Then, the HVI500SN of 17kg is added Lubricating base oil；120 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 37.7 weight % of calcium-sulfoacid calcium；53.2 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.6 weight %；O-phthalic Sour 6.5 weight % of oxygen zirconium.

Embodiment 3

Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 24kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 6kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 20kg)；4-ten Eight alkylphenols (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 viscosity are 11mm to HVI500SN lubricating base oil²/ s, 28kg).

It in a volume is 110L and with 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and 20kg HVI150BS lubricating base oil, stirring is warming up to 90 DEG C, 3.13kg zirconium-n-butylate is added and Zr that solid content is 20 weight % (OH)₄Suspension 13kg, in terms of zirconium, Zr (OH)₄Molar ratio with zirconium-n-butylate is 1:0.5, is stirred 10 minutes；It is hard that 1.9kg is added Resin acid stirs 10 minutes；3.5kg M-phthalic acid is added, stirs 10 minutes.At 80 DEG C, constant temperature 10 minutes；2.8kg is added 4-octadecylphenols, temperature are controlled at 80 DEG C, are stirred 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, Stirring 10 minutes；It is warming up to 100 DEG C, constant temperature 60 minutes, material retrogradation.It is warming up to 130 DEG C under stirring, is kept for 30 minutes, dehydration； It is warming up to 180 DEG C of constant temperature 20 minutes.Then, the HVI500SN lubricating base oil of 28kg is added；100 DEG C are cooled to temperature, is followed Ring filtering, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 37.8 weight % of calcium-sulfoacid calcium；53.2 weight % of lubricating base oil；2.5 weight % of zirconyl stearate；M-phthalic acid oxygen zirconium 6.5 weight %.

Embodiment 4

Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 33kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 6kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 20kg)；12 Alkyl benzene sulphonate (1.2kg)；4-octadecylphenols (1.6kg)；Acetic acid (0.56kg)；Zirconium-n-propylate (4.0kg)；Zr(OH)₄ (2.0kg)；12-hydroxy stearic acids (2kg)；Boric acid (2.32kg)；(100 DEG C of kinematic viscosity are HVI500SN lubricating base oil 11mm²/ s, 28kg).

Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfurized alkylphenol calcium is using total base number The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g；Transforming agent increases dodecyl benzene sulfonic acid；It is added Zr (OH)₄When be additionally added just Propyl alcohol zirconium, in terms of zirconium, Zr (OH)₄Molar ratio with zirconium-n-propylate is 1:1；Terephthalic acid (TPA) is replaced with into boric acid；Each ingredient Dosage is as above.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 44.0 weight % of calcium-sulfoacid calcium；49.8 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.4 weight %；Boric acid oxygen zirconium 3.8 weight %.

Embodiment 5

Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 23kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 6kg)；Overbased calcium salicylate (total base number 400mgKOH/g, 10kg)；HVI150BS profit (100 DEG C of kinematic viscosity are 31mm to sliding base oil²/ s, 20kg)；4-octadecylphenols (2.8kg)；Acetic acid (0.56kg)；Positive third Alcohol zirconium (4.0kg)；Zr(OH)₄(2.0kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；HVI500SN lubrication (100 DEG C of kinematic viscosity are 11mm to base oil²/ s, 28kg)；It is right, right '-di-iso-octyldiphenylamine (0.2kg).

Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfurized alkylphenol calcium is using total base number The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g increases overbased calcium salicylate；It is added Zr (OH)₄When be additionally added positive third Alcohol zirconium, in terms of zirconium, Zr (OH)₄Molar ratio with zirconium-n-propylate is 1:1；And 110 DEG C are cooled to temperature, is added 0.2kg's Right, right '-di-iso-octyldiphenylamine, after ten minutes, then circulating filtration, homogenizing, degassing obtain finished product for stirring；The use of each ingredient Amount is as above.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 43.7 weight % of calcium-sulfoacid calcium；49.5 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.2 weight %；Terephthaldehyde Sour 4.4 weight % of oxygen zirconium；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine.

Embodiment 6

Raw material components: calcium sulfonate with high base number (total base number 320mgKOH/g, 20kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is (total Base number is 320mgKOH/g, 6kg)；Overbased calcium oleate (total base number 400mgKOH/g, 4kg)；HVI150BS lubrication base (100 DEG C of kinematic viscosity are 31mm to oil²/ s, 15kg)；4-octadecylphenols (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄ (3.9kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscosity For 11mm²/ s, 7kg).

Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfoacid calcium is using total base number The calcium sulfonate with high base number of 320mgKOH/g, the high base number sulfenyl phenolate that sulfurized alkylphenol calcium is 320mgKOH/g using total base number Calcium increases overbased calcium oleate；The dosage of each ingredient is as above.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 52.6 weight % of calcium-sulfoacid calcium；34.7 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 3.7 weight %；Terephthaldehyde Sour 9.0 weight % of oxygen zirconium.

Embodiment 7

Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 6kg)；Overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 8kg)；Overbased calcium alkyl-salicylate (total base number 300mgKOH/g, 8kg)；High base number salicylic acid Calcium (total base number 300mgKOH/g, 8kg)；(100 DEG C of kinematic viscosity are 40mm to poly- α-olefin oil PAO 40²/ s, 30kg)； 4-octadecylphenols (1.8kg)；Dodecyl benzene sulfonic acid (1.0kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12-hydroxyls Base stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；(100 DEG C of kinematic viscosity are 11mm to poly- α-olefin oil PAO 10²/ s, 17kg)。

Lubricant composition is prepared according to the method for embodiment 1, unlike, increase overbased calcium alkyl-salicylate and high-alkali It is worth calcium salicylate, transforming agent increases dodecyl benzene sulfonic acid；Using poly- α-olefin oil PAO 40, (100 DEG C of kinematic viscosity are 40mm²/ s) and poly- α-olefin oil PAO 10 (100 DEG C of kinematic viscosity are 11mm²/ s) HVI150BS (100 DEG C of fortune are replaced respectively Kinetic viscosity is 31mm²/ s) and HVI500SN (100 DEG C of kinematic viscosity are 11mm²/s)；The dosage of each ingredient is as above.Inspection result is shown in Table 1.

Embodiment 8

Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 6kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is (total Base number is 320mgKOH/g, 10kg)；High base number calcium salicylate (total base number 360mgKOH/g, 7kg)；High base number calcium oleate is (total Base number is 400mgKOH/g, 7kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4-ten eight Alkylphenol (2kg)；Aphthenic acids (total acid number 180mgKOH/g, 0.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)； 12-hydroxy stearic acids (2kg)；2-- 1,4-phthalic acids of methyl (3.8kg)；(100 DEG C of movements are viscous for HVI500SN lubricating base oil Degree is 11mm²/ s, 16.7kg).

Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfurized alkylphenol calcium is using total base number The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, while increasing high base number calcium salicylate and high base number calcium oleate；Transforming agent Increase aphthenic acids；Terephthalic acid (TPA) is replaced with 2-- 1,4-phthalic acids of methyl；The dosage of each ingredient is as above.Inspection result is shown in Table 1。

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 37.7 weight % of calcium-sulfoacid calcium；52.8 weight % of lubricating base oil；12-hydroxy stearic acid 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 320mgKOH/g, 6kg)；Overbased sulfurized alkylphenol calcium is (total Base number is 400mgKOH/g, 12kg)；Overbased calcium alkyl-salicylate (total base number 360mgKOH/g, 6kg)；High base number calcium oleate is (total Base number is 320mgKOH/g, 6kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4-ten eight Alkylphenol (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12-hydroxy stearic acids (2kg)；4,4'- biphenyl diformazan Sour (5.1kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil²/ s, 20kg)；It is right, right '-diisooctyl hexichol Amine (0.2kg)；Two thio dibutylamino formic acid molybdenums (4kg)；Selenium disulfide (4kg)；Benzotriazole (0.4kg).

Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfoacid calcium is using total base number The calcium sulfonate with high base number of 320mgKOH/g increases overbased calcium alkyl-salicylate and high base number calcium oleate；With 4,4'- biphenyl dicarboxylic acid Instead of terephthalic acid (TPA)；And 110 DEG C are cooled to temperature, pair of 0.2kg, right '-di-iso-octyldiphenylamine, stirring 10 is added Minute, the two thio dibutylamino formic acid molybdenums of 4kg are added, stir 10 minutes, the selenium disulfide of 4kg is added, stir 10 minutes, The benzotriazole of 0.4kg is added, stirs 10 minutes, then circulating filtration, homogenizing, degassing obtain finished product；The dosage of each ingredient As above.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 32.9 weight % of calcium-sulfoacid calcium；49.2 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.3 weight %；4,4'- connection 7.2 weight % of phthalic acid oxygen zirconium；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine；Two thio dibutylamino formic acid molybdenums 3.9 weight %；3.9 weight % of selenium disulfide；0.4 weight % of benzotriazole.

Embodiment 10

Raw material components: calcium sulfonate with high base number (total base number 320mgKOH/g, 8kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total alkali Value is 320mgKOH/g, 10kg)；Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 5kg)；Overbased salicylic acid Calcium (total base number 400mgKOH/g, 3kg)；Overbased calcium oleate (total base number 400mgKOH/g, 4kg)；HVI150BS profit (100 DEG C of kinematic viscosity are 31mm to sliding base oil²/ s, 15kg)；4-octadecylphenols (2.8kg)；Acetic acid (0.56kg)；Zr (OH)₄(3.9kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；HVI500SN lubricating base oil (100 DEG C of fortune Kinetic viscosity is 11mm²/ s, 32kg).

Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfoacid calcium is using total base number The calcium sulfonate with high base number of 320mgKOH/g, the high base number sulfenyl phenolate that sulfurized alkylphenol calcium is 320mgKOH/g using total base number Calcium, and increase naphthenate with superhigh base number calcium, calcium salicylate and calcium oleate；The dosage of each ingredient is as above.Inspection result is shown in Table 1.

Embodiment 11

Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 9kg)；Overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 10kg)；Overbased calcium alkyl-salicylate (total base number 300mgKOH/g, 5kg)；High base number salicylic acid Calcium (total base number 300mgKOH/g, 3kg)；High base number calcium oleate (total base number 300mgKOH/g, 3kg)；HVI150BS lubrication (100 DEG C of kinematic viscosity are 31mm to base oil²/ s, 30kg)；Dodecyl benzene sulfonic acid (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄ (7.1kg)；12-hydroxy stearic acids (2kg)；Boric acid (2.32kg)；Terephthalic acid (TPA) (3.5kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscosity are 11mm²/ s, 15kg)；It is right, right '-di-iso-octyldiphenylamine (0.2kg).

Lubricant composition is prepared according to the method for embodiment 1, unlike, increase overbased calcium alkyl-salicylate, bigcatkin willow Sour calcium and calcium oleate replace 4-octadecylphenols using dodecyl benzene sulfonic acid；It is additionally added after 12-hydroxy stearic acids are added Then boric acid adds terephthalic acid (TPA)；And 110 DEG C are cooled to temperature, pair of 0.2kg, right '-diisooctyl two is added Aniline, after ten minutes, then circulating filtration, homogenizing, degassing obtain finished product for stirring；The dosage of each ingredient is as above.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 37.0 weight % of calcium-sulfoacid calcium；49.9 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.6 weight %；Boric acid oxygen zirconium 4.0 weight %；6.3 weight % of terephthalic acid (TPA) oxygen zirconium；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine.

Embodiment 12

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

The preparation of non-newtonian fluid calcium sulfonate with high base number: in a volume being 30L and with heating, stirring, circulation, cooling 100 DEG C of kinematic viscosity of calcium sulfonate with high base number and 5kg that 15kg total base number is 350mgKOH/g are added in normal-pressure reaction kettle is 31mm²The HVI150BS lubricating base oil of/s, stirring, heats to 80 DEG C, constant temperature 10 minutes；2.5kg dodecyl is added Benzene sulfonic acid, temperature are controlled at 80 DEG C or so, are stirred 10 minutes；The acetic acid and 4 times of acetic acid weight of aqueous solution of 0.5kg is added, stirs It mixes 10 minutes；85 DEG C are warming up to, constant temperature 90 minutes, it is spare to obtain non-newtonian fluid sulfoacid calcium at smectic for material retrogradation.

Lubricant composition is prepared according to the method for embodiment 1, unlike, calcium sulfonate with high base number is directly using preparing Non-newtonian fluid sulfoacid calcium, sulfurized alkylphenol calcium using total base number be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, simultaneously Increase calcium naphthenate；It is additionally added acetic acid after terephthalic acid (TPA) is added, then adds transforming agent conversion；And it is cold to temperature But to 110 DEG C, be added pair of 0.2kg, right '-di-iso-octyldiphenylamine, stirring after ten minutes, then circulating filtration, homogenizing, take off It is so incensed that finished product；The dosage of each ingredient is as above.Inspection result is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate 37.1 weight % of calcium-sulfoacid calcium；48.9 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.6 weight %；Terephthaldehyde Sour 4.8 weight % of oxygen zirconium；6.4 weight % of zirconyl acetate；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine.

Embodiment 13

It in a volume is 110L and with 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number be 400mgKOH/g overbased sulfurized alkylphenol calcium and The HVI150BS lubricating base oil of 30kg, stirring, heats to 50 DEG C, constant temperature 30 minutes；4-octadecyl of 2.8kg is added Phenol, temperature are controlled at 50 DEG C, are stirred 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 points Clock；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.

It in another volume is 50L and with 7kg is added in heating, stirring, circulation, cooling normal-pressure reaction kettle The Zr (OH) that solid content is 20 weight % is added in HVI500SN lubricating base oil at 100 DEG C₄Suspension 19.5kg, stirring 10 Minute；12-hydroxy stearic acid of 2kg is added, stirs 10 minutes；3.5kg terephthalic acid (TPA) is added, stirs 10 minutes, obtains 12- Hydroxy stearic acid oxygen zirconium and terephthalic acid (TPA) oxygen zirconium.

Gained 12-hydroxy stearic acid oxygen zirconium and terephthalic acid (TPA) oxygen zirconium are all squeezed into a upper kettle, stirs evenly, stirs It mixes down and is warming up to 120 DEG C, kept for 45 minutes, dehydration；It is warming up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN is added Lubricating base oil；110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.

Embodiment 14

It in a volume is 110L and with 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number be 400mgKOH/g overbased sulfurized alkylphenol calcium and The HVI150BS lubricating base oil of 30kg, stirring, is warming up at 50 DEG C, constant temperature 30 minutes；4-octadecyl of 2.8kg benzene is added Phenol, temperature are controlled at 50 DEG C, are stirred 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 minutes； It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.100 DEG C are warming up to, the Zr (OH) that solid content is 20 weight % is added₄It is suspended Liquid 19.5kg is stirred 10 minutes；12-hydroxy stearic acid of 2kg is added, stirs 10 minutes；3.5kg terephthalic acid (TPA), stirring is added 10 minutes.It is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration.It is warming up to 200 DEG C of constant temperature 10 minutes.Then, 17kg is added HVI500SN lubricating base oil；110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.

Embodiment 15

Lubricant composition is prepared according to the method for embodiment 1, unlike, 4-octadecylphenols are replaced with 18 Acetic acid is replaced with ethylene glycol monobutyl ether by amine.Inspection result is shown in Table 1.

Embodiment 16

Lubricant composition is prepared according to the method for embodiment 4, unlike, at Zr (OH)₄With always rubbing for zirconium-n-propylate In the case that your number is constant, adjust Zr (OH)₄Molar ratio with zirconium-n-propylate is 1:10.Each physicochemical property of gained rouge is shown in Table 1.

Embodiment 17

Lubricant composition is prepared according to the method for embodiment 4, unlike, zirconium-n-propylate is replaced with into equimolar Zr (OH)₄.Each physicochemical property of gained rouge is shown in Table 1.

Embodiment 18

Lubricant composition is prepared according to the method for embodiment 4, unlike, by Zr (OH)₄Replace with it is equimolar just Propyl alcohol zirconium.Each physicochemical property of gained rouge is shown in Table 1.

Comparative example 1

Lubricant composition is prepared according to the method for embodiment 1, unlike, overbased sulfurized alkylphenol calcium is replaced The overbased sulfoacid calcium for being 400mgKOH/g for total base number.Each physicochemical property of gained rouge is shown in Table 1.

In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, composition are as follows: 37.7 weight of non-newtonian fluid sulfoacid calcium Measure %；53.2 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.6 weight %；6.5 weight % of terephthalic acid (TPA) oxygen zirconium.

Each lubricating grease properties of sample data of table 1

Each indication test method: appearance: range estimation；Dropping point: GB/T 3498；Work cone penetration and extension work cone penetration: 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 spraying: SH/T0643；Stencil oil-dividing: SH/T 0324；Surface hardened layer value: 0370 appendix A of SH/T；Coefficient of friction: SH/T 0721；Tetra-ball machine test: SH/T 0202.

Each lubricating grease properties of sample data of 1 (Continued) of table

It will be understood by those skilled in the art that work cone penetration is smaller, grease thickening performance is better；Extend work The difference for making cone penetration and the cone penetration that works is smaller, and the mechanical stability of lubricating grease can be better；Water leaching number of dropouts is smaller, lubricating grease Water-resistance it is better；Salt spray test higher grade, and the antirust and anticorrosive property of lubricating grease are better；Water resistant is worth smaller, lubrication by spraying The adhesiveness and water-resistance of rouge are better；Stencil oil-dividing value is smaller, and the colloid stability of lubricating grease is better；Surface hardened layer value it is absolute It is worth smaller, the storage stability of lubricating grease is better；Coefficient of friction is smaller, and the abrasion resistance of lubricating grease is better；PB, PD value are bigger, The extreme pressure anti-wear of lubricating grease is better.

Embodiment 1 and comparative example 1 are compared to antirust and anticorrosion as can be seen that lubricant composition of the invention Property, storage stability be substantially better than complex calcium sulfonate zirconium base lubricating grease.Moreover, lubricant composition of the invention has better than multiple Close mechanical stability, water-resistance, colloid stability, abrasion resistance and the extreme pressure anti-wear of sulfoacid calcium zirconium base lubricating grease.Moreover, this The lubricant composition of invention also has excellent heat-resisting quantity.

Embodiment 1 and embodiment 13 are compared the lubricant composition as can be seen that being prepared in situ, had better Viscous resistance, mechanical stability, water-resistance, colloid stability and abrasion resistance；By embodiment 1 and embodiment 13, embodiment 14 into Row relatively can be seen that the reaction for first carrying out compound zirconium, then be converted, and lubricant composition obtained has preferably thickening Property, mechanical stability, water-resistance, colloid stability and abrasion resistance；Embodiment 1 is compared and can be seen with embodiment 15 Out, transforming agent is selected from dodecyl benzene sulfonic acid, aphthenic acids, octadecyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water At least one of, the lubricant composition of preparation has better viscous resistance, mechanical stability, water-resistance, colloid stability And abrasion resistance；Embodiment 4 is compared with embodiment 16, embodiment 17, embodiment 18 to the raw material as can be seen that zirconium respectively Oxide and/or hydroxide containing zirconium, and the molar ratio of the oxide of zirconium and/or hydroxide and zirconium alkoxide is 1: 0.5-5, can further increase the viscous resistance of the lubricant composition of preparation, mechanical stability, water-resistance, colloid stability and Abrasion resistance.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims

1. a kind of lubricant composition, the lubricant composition contains base oil and thickening agent, which is characterized in that the thickening Agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium and higher fatty acids zirconates, and the thickening agent is also optionally containing non- Newton body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, small molecule inorganic acid and/or low One of zirconates of grade fatty acid is a variety of, and on the basis of the weight of the lubricant composition, the content of base oil is 10- 80 weight %, non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content are 10-70 weight %, and the zirconates of higher fatty acids contains Amount is 1-10 weight %, and 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 are 0-70 weight %, and the content of the zirconates of aromatic acid is 0-15 weight %, small molecule The content of the zirconates of inorganic acid and/or lower fatty acid is 0-15 weight %, wherein the zirconates of the higher fatty acids is by height Grade fatty acid is reacted with component A, and the zirconates of the aromatic acid is to be reacted by aromatic acid with component A, and the small molecule is inorganic The zirconates of acid and/or lower fatty acid is to be reacted by small molecule inorganic acid and/or lower fatty acid with component A, described group Dividing A is at least one of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide.

2. lubricant composition according to claim 1, wherein on the basis of lubricant composition weight, base oil Content is 20-70 weight %, and non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content is 20-60 weight %, higher fatty acids The content of zirconates be 2-6 weight %, the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, non-newtonian fluid calcium salicylate Content is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, and the content of the zirconates of aromatic acid is 2-10 weight The content of the zirconates of amount %, small molecule inorganic acid and/or lower fatty acid is 2-10 weight %.

3. lubricant composition according to claim 1 or 2, wherein the non-newtonian fluid sulfurized alkylphenol calcium-sulfonic acid Calcium is converted by newton body sulfoacid calcium and newton body sulfurized alkylphenol calcium, the non-newtonian fluid sulfurized alkylphenol calcium-sulphur The total base number of sour calcium is 250-450mgKOH/g；The non-newtonian fluid calcium naphthenate is to convert to obtain by newton body calcium naphthenate , the total base number of the non-newtonian fluid calcium naphthenate is 250-450mgKOH/g；The non-newtonian fluid calcium salicylate is by newton Body calcium salicylate converts, and the total base number of the non-newtonian fluid calcium salicylate is 250-450mgKOH/g；The non newtonian Body calcium oleate is converted by newton body calcium oleate, and the total base number of the non-newtonian fluid calcium oleate is 250-450mgKOH/ g。

4. lubricant composition according to claim 1 or 2, wherein the higher fatty acids is the rouge that carbon number is 8-20 Fat acid.

5. lubricant composition according to claim 1 or 2, wherein the higher fatty acids is the hydroxyl that carbon number is 8-20 Base fatty acid.

6. lubricant composition according to claim 4, wherein the higher fatty acids is selected from lauric acid, palmitinic acid, hard At least one of resin acid, 12-hydroxy stearic acids, eicosyl carboxylic acid.

7. lubricant composition according to claim 1 or 2, wherein the aromatic acid is substituted or unsubstituted aromatic acid, Substituent group is at least one of alkyl, alkenyl, alkynyl, aryl and halogenated alkyl or aryl, and the molecular weight of the aromatic acid is small In equal to 550.

8. lubricant composition according to claim 7, wherein the halogenated alkyl or aryl is the alkyl of perhalogeno Or aryl.

9. lubricant composition according to claim 7, wherein the aromatic acid is selected from unsubstituted or C₁–C₅Alkyl replaces Phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, at least one of multi-joint phthalic acid.

10. lubricant composition according to claim 1 or 2, wherein the small molecule inorganic acid and the lower aliphatic The molecular weight of acid is less than or equal to 250.

11. lubricant composition according to claim 10, wherein the small molecule inorganic acid is selected from boric acid, phosphoric acid, sulphur At least one of acid, the lower fatty acid in acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid at least It is a kind of.

12. lubricant composition according to claim 1 or 2, wherein the component A contains the oxide and/or hydrogen of zirconium Oxide, in terms of zirconium, the oxide and/or hydroxide of zirconium and the molar ratio of zirconium alkoxide are 1:0-10.

13. lubricant composition according to claim 12, wherein in terms of zirconium, the oxide and/or hydroxide of zirconium with The molar ratio of zirconium alkoxide is 1:0.5-5.

14. lubricant composition according to claim 1 or 2, wherein the oxide and/or hydroxide of zirconium are selected from ZrO₂、ZrO(OH)₂、Zr(OH)₄And at least one of their hydrate.

15. lubricant composition according to claim 1 or 2, wherein the general formula of the zirconium alkoxide is Zr (OR₁)₄, R₁ For C₁–C₁₀Alkyl.

16. lubricant composition according to claim 15, wherein the zirconium alkoxide be selected from ethyl alcohol zirconium, zirconium-n-propylate, At least one of zirconium-n-butylate, zirconium tert-butoxide and n-amyl alcohol zirconium.

17. the preparation method of lubricant composition described in any one of claim 1-16, this method comprises: by thickening agent It is uniformly mixed with part basis oil, is refined in 180-230 DEG C of constant temperature, surplus base oil is added, necessary additive is added, obtains Finished product, which is characterized in that the thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium and higher fatty acids zirconates, The thickening agent is also optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, aromatic acid One of zirconates of zirconates, small molecule inorganic acid and/or lower fatty acid is a variety of.

18. a kind of preparation method of lubricant composition, which is characterized in that this method comprises:

(1) newton body sulfurized alkylphenol calcium, newton body and/or non-newtonian fluid sulfoacid calcium will be contained, or contain newton body and/or non- Newton body sulfurized alkylphenol calcium, the high base number material of newton body sulfoacid calcium and the mixing of part basis oil, obtain mixture, described High base number material also optionally contains newton body and/or non-newtonian fluid calcium naphthenate, newton body and/or non-newtonian fluid calcium salicylate With one of newton body and/or non-newtonian fluid calcium oleate or a variety of；

(2) it optionally carries out the reaction of at least partly compound zirconium: component A is added, higher fatty acids is added, optional aromatic acid, appoints The small molecule inorganic acid and/or lower fatty acid of choosing, are reacted, the component A be the oxide of zirconium, zirconium hydroxide and At least one of zirconium alkoxide；

(3) transforming agent is added, heats up to material retrogradation；

(4) reaction of remaining compound zirconium is carried out；

(5) heating dehydration；

(6) 180-230 DEG C of constant temperature refinings are warming up to, surplus base oil is added, necessary additive is added, obtains finished product, with institute On the basis of the weight for obtaining finished product, the content of base oil is 10-80 weight %, and non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium contains Amount is 10-70 weight %, and the content of the zirconates of higher fatty acids is 1-10 weight %, and the content of non-newtonian fluid calcium naphthenate is 0- 70 weight %, the content of non-newtonian fluid calcium salicylate are 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 %, and the content of the zirconates of small molecule inorganic acid and/or lower fatty acid is 0-15 weight Measure %.

19. according to the method for claim 18, wherein in step (2), carry out the reaction of at least partly compound zirconium.

20. method described in 8 or 19 according to claim 1, wherein in step (2) and step (4), at 85-100 DEG C, be added Higher fatty acids is added in component A, stirs 5-30 minutes, and optional aromatic acid, optional small molecule inorganic acid and/or rudimentary is added Fatty acid, stir 5-30 minutes, the component A contains the oxide and/or hydroxide of zirconium, in terms of zirconium, the oxide of zirconium and/ Or the molar ratio of hydroxide and zirconium alkoxide is 1:0-10.

21. according to the method for claim 20, wherein in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium Molar ratio be 1:0.5-5.

22. method described in 8 or 19 according to claim 1, wherein in step (3), at 50-80 DEG C, required conversion is added Agent is reacted, after all transforming agents add, 80-100 DEG C constant temperature 60-90 minutes.

23. method described in 8 or 19 according to claim 1, wherein in step (5), be warming up to 110-130 DEG C of dehydration.

24. method described in 8 or 19 according to claim 1, wherein in step (6), be warming up to 5-30 points of 180-230 DEG C of constant temperature Clock, be added surplus base oil, be cooled to 100-120 DEG C to temperature, necessary additive be added, stir, circulating filtration, homogenizing, Degassing.

25. method described in 8 or 19 according to claim 1, wherein the newton body sulfurized alkylphenol calcium is synthesis alkyl monosulfide Phenol calcium, the total base number of the newton body sulfurized alkylphenol calcium are 250-450mgKOH/g；The newton body sulfoacid calcium is petroleum sulphur Sour calcium and/or calcium alkylbenzenesulfonate, the total base number of the newton body sulfoacid calcium are 250-450mgKOH/g；The newton body aphthenic acids Calcium is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and the total base number of the newton body calcium naphthenate is 250-450mgKOH/g； The newton body calcium salicylate is salicylate calcium, and the total base number of the newton body calcium salicylate is 250-450mgKOH/g； The newton body calcium oleate is natural calcium oleate and/or synthesis calcium oleate, and the total base number of the newton body calcium oleate is 250- 450mgKOH/g。

26. method described in 8 or 19 according to claim 1, wherein the transforming agent be 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–C₂₀Alkane Base benzene sulfonic acid, C₁₆-C₂₄At least one of alkyl phenol and water, the additional amount of transforming agent are the high base number material total weight 2-30%.

27. according to the method for claim 26, wherein the transforming agent is selected from dodecyl benzene sulfonic acid, aphthenic acids, 18 At least one of alkyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water, the additional amount of transforming agent are the high base number The 6-22% of material total weight.

28. lubricant composition made from the method as described in any one of claim 18-27.