CN106032482B

CN106032482B - Lubricant composition and preparation method thereof

Info

Publication number: CN106032482B
Application number: CN201510105344.3A
Authority: CN
Inventors: 何懿峰; 孙洪伟; 段庆华; 张建荣; 刘中其; 孔锡奎; 郑会; 姜靓; 陈政
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-03-11
Filing date: 2015-03-11
Publication date: 2019-01-08
Anticipated expiration: 2035-03-11
Also published as: CN106032482A

Abstract

Lubricant composition and preparation method thereof.The present invention relates to lubricating grease fields, disclose a kind of lubricant composition, contain base oil and thickening agent, thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, the zirconates and polyurea compound of higher fatty acids, also optionally contain 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 lubricant composition, base oil is 10-80 weight %, non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium is 10-70 weight %, the zirconates of higher fatty acids is 1-10 weight %, polyurea compound is 0.5-30 weight %, 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.

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, higher aliphatic Acid zirconates and polyurea compound, the thickening agent also optionally containing 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 fatty acid one of zirconates or a variety of, with 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- The content of sulfoacid calcium is 10-70 weight %, and the content of the zirconates of higher fatty acids is 1-10 weight %, the content of polyurea compound For 0.5-30 weight %, the content of non-newtonian fluid calcium naphthenate is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0- 70 weight %, the content of non-newtonian fluid calcium oleate 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.

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 %, is gathered The content of carbamide compound is 1-20 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, non-newtonian fluid salicylic acid The content of calcium 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 The content of the zirconates of weight %, small molecule inorganic acid and/or lower fatty acid is 2-10 weight %.

The component A contains the oxide and/or hydroxide of zirconium, in terms of zirconium, the oxide and/or hydroxide of zirconium with The molar ratio of 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 the zirconates and polyureas of non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, higher fatty acids Close object, the thickening agent also optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, One of zirconates of the zirconates of aromatic acid, 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；And/or optionally carry out the reaction of at least partly polyurea compound: part base is added Plinth oil and monoamine, or it is additionally added diamines, diisocyanate is added and is reacted；

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

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

(5) heating dehydration；

(6) reaction of remaining polyurea compound is carried out；

(7) 180-230 DEG C of constant temperature refinings are warming up to, surplus base oil is added, necessary additive is added, obtains finished product.

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

Lubricant composition of the invention has and quite even more excellent anti-of complex calcium sulfonate zirconium base polyurea grease Rust and anticorrosive property, and there is excellent storage stability, also there is the thickening better than complex calcium sulfonate zirconium base polyurea grease Property, mechanical stability, water-resistance, colloid stability, abrasion resistance, extreme pressure anti-wear and lubricating life, and also have excellent The performances such as heat-resisting quantity.The feed preparation process of lubricating grease of the invention 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, isocyanates and amine simultaneously React the polyurea compound generated.

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, the lubricant composition contains base oil and thickening Agent, the thickening agent contain the zirconates and polyurea compound of non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, higher fatty acids, institute State thickening agent also optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, aromatic acid zirconium One of zirconates of salt, small molecule inorganic acid and/or lower fatty acid is a variety of, on the basis of the weight of the lubricating grease, The content of base oil is 10-80 weight %, and non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content is 10-70 weight %, high The content of the zirconates of grade fatty acid is 1-10 weight %, and the content of polyurea compound is 0.5-30 weight %, non-newtonian fluid cycloalkanes The content of sour calcium is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 weight %, and non-newtonian fluid calcium oleate contains Amount is 0-70 weight %, and the content of the zirconates of aromatic acid is 0-15 weight %, the zirconates of small molecule inorganic acid and/or lower fatty acid Content be 0-15 weight %, wherein the zirconates of the higher fatty acids is to be reacted by higher fatty acids with component A, institute The zirconates for stating aromatic acid is to be reacted by aromatic acid with component A, the zirconates of the small molecule inorganic acid and/or lower fatty acid be by Small molecule inorganic acid and/or lower fatty acid are reacted with component A, and the component A is the hydroxide of the oxide of zirconium, zirconium At least one of with zirconium alkoxide.

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 is that carbon number is 8-20, the preferably fatty acid of 10-18 or hydroxy fatty acid, such as the moon At least one of cinnamic acid, palmitinic acid, stearic acid, 12- hydroxy stearic acid, eicosyl carboxylic acid, preferably 12- hydroxy stearate 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 or 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, polyurea compound can be polyurea compound commonly used in the art, for example, polyureas without particular/special requirement The structural formula of compound can be

Wherein, n is preferably 0-3 integer.

Wherein, R¹、R⁴It can be the same or different, can be alkyl, naphthenic base or aryl, the carbon of alkyl or cycloalkyl Number can be 8-24, preferably 10-18, and aryl can be phenyl or substituted phenyl, preferably the alkyl of phenyl or C1-C3 or The phenyl that halogen replaces.

Wherein, R²It can be alkylidene or arlydene, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can To be phenylene or biphenylene.

Wherein, R³It can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R³More preferably With-(CH₂)₆At least one of.

In the present invention, single polyureas can be used, mixing polyureas also can be used, for example, polyurea compound can be two At least one of polyurea compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds.

Above-mentioned polyurea compound can be obtained using the thinkable various methods of those skilled in the art institute, such as can be by The method preparation recorded according to CN103060069A, CN103060070A, CN103060068A, CN103060067A, US3243372 It obtains.

The lubricating base oil can be mineral oil, synthetic oil, vegetable oil or their mixture, 100 DEG C of dynamic viscosities For 4-150mm²/ s, preferably 10-60mm²/s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, Fischer-Tropsch Synthetic 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.

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

In the present invention, for non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid water Poplar acid calcium, non-newtonian fluid calcium oleate, the zirconates of higher fatty acids, the zirconates of aromatic acid, small molecule inorganic acid and/or lower fatty acid Zirconates, polyurea compound, base oil and additive as described above, 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 sulfoacid calcium, newton body sulfurized alkylphenol calcium, newton body calcium naphthenate, Non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate or combinations thereof object pass through transforming agent respectively and convert to obtain, for example, by newton body Sulfoacid calcium, newton body sulfurized alkylphenol calcium, optional newton body calcium naphthenate, optional newton body calcium salicylate, optional ox Body calcium oleate and base oil Hybrid Heating are added required transforming agent and are reacted, all transforming agents add to 50-80 DEG C Afterwards, 80-100 DEG C constant temperature 60-90 minutes, then heat to 110-130 DEG C of dehydrations.

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；

(6) reaction of remaining polyurea compound is carried out；

" 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, the reaction in step (2) without compound zirconium only carries out whole compound zirconiums in step (4) Reaction, converted that is, transforming agent is first added in the method for the present invention, carry out the reaction of compound zirconium after conversion again；(ii) into The reaction of the compound zirconium in row part carries out the reaction of the compound zirconium in part in step (2), carry out again in step (4) remaining multiple The reaction of zirconium carries out part that is, the method for the present invention carries out the reaction of the compound zirconium in part before conversion again in post-conversion The reaction of compound zirconium；(iii) reaction for carrying out all compound zirconiums, i.e., carry out the reaction of whole compound zirconiums, no in step (2) It carries out step (4), that is, the method for the present invention first carries out the reaction of compound zirconium, then is converted.

In step (2) of the present invention, " optionally carrying out the reaction of at least partly polyurea compound " includes three kinds of situations: (i) without the reaction of polyurea compound, that is, the reaction in step (2) without polyurea compound, only in step (6) into The reaction of the whole polyurea compound of row, is converted that is, transforming agent is first added in the method for the present invention, is carried out again after conversion The reaction of polyurea compound；(ii) reaction for carrying out part polyurea compound, i.e., carry out part polyurea compound in step (2) Reaction, the reaction of remaining polyurea compound is carried out again in step (6), that is, the method for the present invention carry out portion before conversion The reaction for dividing polyurea compound, carries out the reaction of part polyurea compound again in post-conversion；(iii) whole polyurea compounds are carried out Reaction, i.e., the reaction of whole polyurea compounds is carried out in the step (2), without step (6), that is, side of the present invention Method first carries out the reaction of polyurea compound, then is converted.

This field is generally transforming agent to be first added to be converted, then carry out compound zirconium and polyureas when preparing lubricating grease The reaction of compound, when such as preparing sulfoacid calcium zirconium base polyurea grease.But the present inventor has found under study for action, according to upper The case where stating the reaction of the compound zirconium of progress of step (2) (ii) or (iii), and/or the carry out polyureas according to above-mentioned steps (2) The case where closing the reaction of object (ii) or (iii), carries out method of the invention, i.e., first carries out all or part of compound zirconium reaction And/or polyurea compound reaction, then converted, it can further improve the performance of lubricating grease obtained.This may be by It, can be preferably by the newton body of oily in first carrying out all or part of compound zirconium reaction and/or the reaction of polyurea compound Sulfurized alkylphenol calcium is converted into the non-newtonian fluid sulfurized alkylphenol calcium of smectic.It is therefore preferred that carrying out at least portion in step (2) Divide the reaction of compound zirconium；And/or carry out the reaction of at least partly polyurea compound.That is, it is preferred that first carrying out all or part of multiple Zirconium reacts and/or first carries out all or part of polyurea compound reaction, then is converted.

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, colloid stability, abrasion resistance and lubricating life.It is therefore preferred that in step (2) and step (4), When carrying out the reaction of compound zirconium, at 85-100 DEG C, component A is added, higher fatty acids is added, stirs 5-30 minutes, is added and appoints The aromatic acid of choosing, optional small molecule inorganic acid and/or lower fatty acid stir 5-30 minutes, and the component A contains the oxidation of zirconium Object and/or hydroxide, 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 is still more preferably 1:0.5-5.Wherein, component A, higher fatty acids, aromatic acid, small molecule inorganic acid And/or the addition sequence of lower fatty acid 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 (2) of the present invention and step (6), when carrying out the reaction of polyurea compound, single polyureas can be prepared, it can also Polyureas is mixed with preparation.The method of polyurea compound is prepared without particular/special requirement, those skilled in the art can be used commonly each Kind of method, for example, can using CN103060069A, CN103060070A as described above, CN103060068A, The method preparation that CN103060067A, US3243372 are recorded.Preferably, part basis oil, monoamine, optional diamines, two is added After isocyanates, 100-120 DEG C constant temperature 10-30 minutes, wherein monoamine, optional diamines, diisocyanate substance amount Meet following relationship: amount × 2 of amount+diamines substance of the amount of the substance of diisocyanate × 2=monoamine substance, or, two Isocyanates is excessive, excessive amount≤10%.

The structure of the diisocyanate is OCN-R³- NCO, R³Can be carbon number is 6-30, preferably 6-20 Arlydene, alkylidene or cycloalkylidene, preferably -(CH₂)₆Etc..For example, the diisocyanate can be toluene two Isocyanates (TDI), methyl diphenylene diisocyanate (MDI), six hexylidene diisocyanates (HDI), dicyclohexyl methyl hydride At least one of diisocyanate (HMDI) and xylylene diisocyanate (XDI) etc..

The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, structural formula R¹–NH₂、R⁴–NH₂, R therein¹、R⁴It can be with It is alkyl, naphthenic base or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, and aryl can be phenyl or take The phenyl that the phenyl in generation, preferably phenyl or C1-C3 alkyl or halogen replace.Preferred monoamine can be selected from aniline, chlorobenzene The arylamine of amine, parachloroanilinum and/or para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, octadecylamine fatty amine.

The diamines can be fatty amine or arylamine, structural formula NH₂–R²–NH₂, wherein R²It can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferred diamines can Be selected from p-phenylenediamine, o-phenylenediamine, 4,4 '-benzidines aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6-oneself The straight-chain fatty amine of diamines.

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.

Transforming agent be preferably selected from fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, In carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonate, C16-C24 alkyl phenol and water at least It is a kind of；It is more preferably selected from the fatty alcohol of C1-C5, the fatty acid of C1-C5, the aliphatic ketone of C1-C5, the fatty aldehyde of C1-C5, C1-C5 Fatty amine, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, C6-C20 arylphosphonic acid, The diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate, C16-C22 alkane At least one of base phenol and water；Still more preferably selected from dodecyl benzene sulfonic acid, aphthenic acids, octadecyl phenol, methanol, different At least one of propyl alcohol, butanol, boric acid, acetic acid and water.The additional amount of transforming agent is preferably the 2-of high base number material total weight 30%, 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 (7) 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, in step (1) in the total amount of base oil used and step (2) and (6) total amount of base oil used and The weight ratio of the total amount of base oil used is preferably 1:0.1-5:0.1-5 in step (7).

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, water-resistance, colloid stability, abrasion resistance and lubricating life.

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)；Methanol (1kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12-hydroxy stearic acids (2kg)；It is right Phthalic acid (3.5kg)；Octadecylamine (1.5kg)；MDI(0.7kg)；(100 DEG C of kinematic viscosity are HVI500SN lubricating base oil 11mm²/ s, 17kg).

It in a volume is 160L 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, and 1kg methanol is added, stirs 10 minutes, and addition 2.8kg concentration is 20 weights The aqueous acetic acid of % is measured, stirs 10 minutes, is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation；120 DEG C are warming up under stirring, It is kept for 45 minutes, dehydration；The HVI500SN lubricating base oil and 1.5kg octadecylamine of 2kg is added, stirs 4 minutes, adds and be dissolved in 0.7kg MDI in the HVI500SN lubricating base oil of 2kg is stirred 4 minutes, and the molar ratio of added MDI and octadecylamine is 1: 2,120 DEG C constant temperature 20 minutes；Finally it is warming up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubrication base is added Oil；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 36.8 weight % of calcium-sulfoacid calcium；2.4 weight % of polyureas；51.9 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconiums 2.6 Weight %；6.3 weight % of terephthalic acid (TPA) oxygen zirconium.

Embodiment 2

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, 24kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 20kg)；4-ten eight Alkylphenol (2.8kg)；Acetic acid (0.56kg)；Zirconium-n-butylate (7.83k)；Zr(OH)₄(0.65kg)；Stearic acid (1.9kg)；It is adjacent Phthalic acid (3.5kg)；Lauryl amine (1.31kg)；MDI(0.89kg)；(100 DEG C of kinematic viscosity are HVI500SN lubricating base oil 11mm²/ s, 27kg).

It in a volume is 160L and with 6kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfoacid calcium of 400mgKOH/g, 24kg total base number be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and 20kg HVI150BS lubricating base oil, stirring；100 DEG C are warming up to, the HVI500SN lubricating base oil and 0.131kg of 0.2kg is added Lauryl amine stirs 8 minutes, adds the 0.089kg MDI being dissolved in the HVI500SN lubricating base oil of 0.2kg, stirs 8 points The molar ratio of clock, added MDI and lauryl amine be 1:2,100 DEG C constant temperature 10 minutes；At 85 DEG C, 0.783kg n-butanol is added The Zr (OH) that zirconium and solid content are 20 weight %₄Suspension 0.325kg, in terms of zirconium, Zr (OH)₄Molar ratio with zirconium-n-butylate is 1:5 is stirred 10 minutes, and 0.19kg stearic acid is added, and is stirred 10 minutes, and 0.35kg phthalic acid is added, and is stirred 10 minutes；? At 80 DEG C, constant temperature 10 minutes, 4-octadecylphenol of 2.8kg is added, temperature is controlled at 80 DEG C, stirred 10 minutes, is added 2.8kg concentration is the aqueous acetic acid of 20 weight %, stirs 10 minutes, is warming up to 90 DEG C, constant temperature 60 minutes, material retrogradation；? At 85 DEG C, 7.047kg zirconium-n-butylate and solid content is added successively as the Zr (OH) of 20 weight %₄Suspension 2.925kg, with zirconium Meter, Zr (OH)₄Molar ratio with zirconium-n-butylate is 1:5, is stirred 10 minutes, and 1.71kg stearic acid is added, and is stirred 10 minutes, is added 3.15kg phthalic acid stirs 10 minutes；It is warming up to 110 DEG C under stirring, is kept for 60 minutes, dehydration；It is added 1.8kg's HVI500SN lubricating base oil and 1.179kg lauryl amine stir 8 minutes, add the HVI500SN lubrication base for being dissolved in 1.8kg 0.801kg MDI in oil is stirred 8 minutes, and the molar ratio of added MDI and octadecylamine is 1:2,100 DEG C constant temperature 10 minutes；Most After be warming up to 230 DEG C constant temperature for 5 minutes, then, be cooled to 160 DEG C, remaining HVI500SN lubricating base oil be added, it is cold to temperature But to 120 DEG C, 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 36.9 weight % of calcium-sulfoacid calcium；2.4 weight % of polyureas；51.9 weight % of lubricating base oil；2.5 weight % of zirconyl stearate； 6.3 weight % of phthalic acid oxygen zirconium.

Embodiment 3

Raw material components: calcium sulfonate with high base number (total base number 320mgKOH/g, 24kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is (total Base number is 320mgKOH/g, 6kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 15kg)；4-ten eight Alkylphenol (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Zirconium-n-propylate (4.0kg)；Zr(OH)₄(2.0kg)；12-hydroxyls Stearic acid (2kg)；2-- 1,4-phthalic acids of methyl (3.8kg)；Octadecylamine (1.5kg)；MDI(0.7kg)；HVI500SN lubrication (100 DEG C of kinematic viscosity are 11mm to base oil²/ s, 7kg).

It in a volume is 160L and with 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and 15kg that calcium sulfonate with high base number, 6kg total base number for 320mgKOH/g are 320mgKOH/g HVI150BS lubricating base oil, stirring；110 DEG C are warming up to, the HVI500SN lubricating base oil and 1.5kg octadecylamine of 2kg is added, Stirring 4 minutes adds the 0.7kg MDI being dissolved in the HVI500SN lubricating base oil of 2kg, stirs 4 minutes, added MDI Be 1:2 with the molar ratio of octadecylamine, 110 DEG C constant temperature 15 minutes；At 65 DEG C, constant temperature 30 minutes, 4-octadecane of 2.8kg is added Base phenol, temperature are controlled at 65 DEG C, are stirred 10 minutes, and 1kg methanol is added, stirs 10 minutes, and addition 2.8kg concentration is 20 weights The aqueous acetic acid of % is measured, stirs 10 minutes, is warming up to 100 DEG C, constant temperature 70 minutes, material retrogradation；At 90 DEG C, it is added The Zr (OH) that 4.0kg zirconium-n-propylate and solid content are 20 weight %₄Suspension 10kg, in terms of zirconium, Zr (OH)₄With zirconium-n-propylate Molar ratio is 1:1, is stirred 10 minutes, and 12-hydroxy stearic acid of 2kg is added, and is stirred 10 minutes, and 2-methyl of 3.8kg-Isosorbide-5-Nitrae-is added Phthalic acid stirs 10 minutes；It is warming up to 130 DEG C under stirring, is kept for 30 minutes, dehydration；180 DEG C of constant temperature 20 are finally warming up to divide Clock.Then, remaining HVI500SN lubricating base oil is added；100 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 50.6 weight % of calcium-sulfoacid calcium；3.3 weight % of polyureas；33.4 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconiums 3.6 Weight %；2-methyl-1,4-phthalic acid oxygen zirconium, 9.1 weight %.

Embodiment 4

Raw material components: calcium sulfonate with high base number (total base number 320mgKOH/g, 14kg)；Overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 6kg)；Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 10kg)；HVI150BS profit (100 DEG C of kinematic viscosity are 31mm to sliding base oil²/ s, 25kg)；Dodecyl benzene sulfonic acid (1.2kg)；4-octadecylphenols (1.6kg)；Methanol (1kg)；Acetic acid (0.56kg)；Ethyl alcohol zirconium (2.21kg)；Zr(OH)₄(2.6kg)；12-hydroxy stearic acids (2kg)；M-phthalic acid (3.5kg)；Octadecylamine (1.66kg)；TDI(0.54kg)；HVI500SN lubricating base oil (100 DEG C of fortune Kinetic viscosity is 11mm²/ s, 22kg).

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, and increase the naphthenate with superhigh base number calcium that total base number is 400kgKOH/g；Transforming agent Increase dodecyl benzene sulfonic acid；Terephthalic acid (TPA) is replaced with M-phthalic acid；MDI is replaced with toluene di-isocyanate(TDI) (TDI)；Add Enter Zr (OH)₄When be additionally added ethyl alcohol zirconium, in terms of zirconium, Zr (OH)₄Molar ratio with ethyl alcohol zirconium is 1:0.5；The dosage of each ingredient is such as On.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 36.8 weight % of calcium-sulfoacid calcium；2.4 weight % of polyureas；51.9 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconiums 2.6 Weight %；6.3 weight % of M-phthalic acid oxygen zirconium.

Embodiment 5

Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 6kg)；Overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 14kg)；Overbased calcium salicylate (total base number 400mgKOH/g, 10kg)；HVI150BS (100 DEG C of kinematic viscosity are 31mm to lubricating base oil²/ s, 25kg)；4-octadecylphenols (2.8kg)；Acetic acid (0.56kg)；Zr (OH)₄(3.9kg)；12-hydroxy stearic acids (2kg)；4,4'- biphenyl dicarboxylic acid (5.1kg)；Octadecylamine (4.5kg)；MDI (2.1kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil²/ s, 18.6kg).

Lubricant composition is prepared according to the method for embodiment 1, unlike, high base number material increases overbased water 4-octadecylphenols and acetic acid is used only in poplar acid calcium, transforming agent, saves the step of methanol is added；With 4,4'- biphenyl dicarboxylic acid Instead of terephthalic acid (TPA)；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 35.8 weight % of calcium-sulfoacid calcium；7.1 weight % of polyureas；46.8 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconiums 2.5 Weight %；7.8 weight % of 4,4'- biphenyl dicarboxylic acid oxygen zirconium.

Embodiment 6

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, 20kg)；Overbased calcium oleate (total base number 400mgKOH/g, 4kg)；Poly- α-olefin oil (100 DEG C of kinematic viscosity are 40mm to PAO 40²/ s, 30kg)；4-octadecylphenols (2kg)；(total acid number is aphthenic acids 180mgKOH/g, 0.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；Octadecylamine (1.5kg)；MDI(0.7kg)；(100 DEG C of kinematic viscosity are 11mm to poly- α-olefin oil PAO 10²/ s, 9kg)；Two thio dibutylphosphoric acid zinc (2kg)；Dibutyl dithiocaarbamate molybdenum (1kg)；Tungsten disulfide (2kg)；Two selenizings Tungsten (2kg)；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, and increase the overbased calcium oleate that total base number is 400kgKOH/g；Make With 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 fortune Kinetic viscosity is 11mm²/ s) replacing HVI150BS respectively, (100 DEG C of kinematic viscosity are 31mm²/ s) and HVI500SN (100 DEG C of movements are viscous Degree is 11mm²/s)；Transforming agent replaces methanol with aphthenic acids；And 110 DEG C are cooled to temperature, two thio two fourths of 2kg are added Base trbasic zinc phosphate stirs 10 minutes, and the dibutyl dithiocaarbamate molybdenum of 1kg is added, and stirs 10 minutes, two sulphur of 2kg are added Change tungsten, stir 10 minutes, two tungsten selenides of 2kg are added, stirs 10 minutes, pair of 0.2kg, right '-diisooctyl hexichol is added Amine stirs 10 minutes, and then circulating filtration, homogenizing, degassing obtain 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 37.2 weight % of calcium-sulfoacid calcium；2.5 weight % of polyureas；43.4 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconiums 2.6 Weight %；6.4 weight % of terephthalic acid (TPA) oxygen zirconium；Two thio 2.2 weight % of dibutylphosphoric acid zinc；Dibutyl dithio amino first Sour 1.1 weight % of molybdenum；2.2 weight % of tungsten disulfide；Two tungsten selenides, 2.2 weight %；It is right, right ' 0.2 weight of-di-iso-octyldiphenylamine Measure %.

Embodiment 7

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, 10kg)；Overbased calcium alkyl-salicylate (total base number 300mgKOH/g, 8kg)；High base number calcium salicylate (total base number 300mgKOH/g, 6kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 15kg)；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)；Octadecylamine (0.94kg)；Para-totuidine (0.38kg)；MDI(0.88kg)；(100 DEG C of HVI500SN lubricating base oil Kinematic viscosity is 11mm²/ s, 33kg).

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, while increasing overbased calcium alkyl-salicylate and high base number calcium salicylate；Transforming agent only makes With 4-octadecylphenols and acetic acid, the step of methanol is added is saved；When octadecylamine is added, it is additionally added para-totuidine；Respectively at The dosage divided 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 36.4 weight % of calcium-sulfoacid calcium；2.4 weight % of polyureas；52.4 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconiums 2.6 Weight %；6.2 weight % of terephthalic acid (TPA) oxygen zirconium.

Embodiment 8

Raw material components: calcium sulfonate with high base number (total base number 320mgKOH/g, 6kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total alkali Value is 320mgKOH/g, 10kg)；High base number calcium salicylate (total base number 360mgKOH/g, 6kg)；High base number calcium oleate (total alkali Value is 400mgKOH/g, 8kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil²/ s, 20kg)；4-octadecanes Base phenol (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(11.2kg)；12-hydroxy stearic acids (2kg)；Boric acid (2.32kg)；It is right Phthalic acid (7.6kg)；Octadecylamine (0.84kg)；Lauryl amine (0.58kg)；MDI(0.78kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscosity are 11mm²/ s, 28kg)；It is right, right '-di-iso-octyldiphenylamine (0.2kg).

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, while increasing high base number calcium salicylate and high base number calcium oleate；4-octadecylphenols and acetic acid is used only in transforming agent, saves Go the step of methanol is added；After 12-hydroxy stearic acids are added, it is additionally added boric acid, then adds terephthalic acid (TPA)；It is added 18 When amine, it is additionally added lauryl amine；And 110 DEG C are cooled to temperature, pair of 0.2kg, right '-di-iso-octyldiphenylamine, stirring is added After ten minutes, then circulating filtration, homogenizing, degassing obtain 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 32.7 weight % of calcium-sulfoacid calcium；2.2 weight % of polyureas；47.0 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconiums 2.3 Weight %；3.5 weight % of boric acid oxygen zirconium；12.1 weight % of terephthalic acid (TPA) oxygen zirconium；It is right, right ' 0.2 weight of-di-iso-octyldiphenylamine Measure %.

Embodiment 9

Raw material components: non-newtonian fluid calcium sulfonate with high base number (15kg)；(total base number is for overbased sulfurized alkylphenol calcium 400mgKOH/g, 5kg)；Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 4kg)；Overbased calcium salicylate is (total Base number is 400mgKOH/g, 3kg)；Overbased calcium oleate (total base number 400mgKOH/g, 3kg)；HVI150BS lubrication base (100 DEG C of kinematic viscosity are 31mm to oil²/ s, 15kg)；Aphthenic acids (total acid number 180mgKOH/g, 2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(6.5kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；Acetic acid (2kg)；Octadecylamine (1.5kg)；MDI(0.7kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil²/ s, 33kg).

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 8kg 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；1.7kg 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 0.33kg 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, overbased sulfoacid calcium is directly using preparation Good non-newtonian fluid sulfoacid calcium, while overbased calcium alkyl-salicylate, calcium salicylate and calcium oleate are increased, cycloalkanes is used only in transforming agent Acid and acetic acid；After terephthalic acid (TPA) is added, it is additionally added acetic acid；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 35.0 weight % of calcium-sulfoacid calcium；2.3 weight % of polyureas；50.3 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconiums 2.5 Weight %；6.0 weight % of terephthalic acid (TPA) oxygen zirconium；3.9 weight % of zirconyl acetate.

Embodiment 10

It in a volume is 160L 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 heat to 100 DEG C, and the Zr (OH) that solid content is 20 weight % is added₄It is outstanding Turbid 19.5kg is stirred 10 minutes；12-hydroxy stearic acid of 2kg is added, stirs 10 minutes；3.5kg terephthalic acid (TPA) is added, stirs It mixes 10 minutes；Cool to 50 DEG C, constant temperature 30 minutes；4-octadecylphenol of 2.8kg is added, temperature is controlled at 50 DEG C or so, stirred It mixes 10 minutes；1kg methanol is added, stirs 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 is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration.

It in another volume is 30L and with being added 2kg's in heating, stirring, circulation, cooling normal-pressure reaction kettle HVI500SN lubricating base oil and 1.5kg octadecylamine are warming up to 120 DEG C, stir 4 minutes, add the HVI500SN for being dissolved in 2kg 0.7kg MDI in lubricating base oil is stirred 4 minutes, and the molar ratio of added MDI and octadecylamine is 1:2,120 DEG C of constant temperature 20 Minute, obtain polyureas.

Gained polyureas is all squeezed into a upper kettle, is stirred evenly, is finally warming up to 200 DEG C of constant temperature 10 minutes.Then, Remaining HVI500SN lubricating base oil is added；110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection It tests and the results are shown in Table 1.

The polyureas molecular structural formula contained in component are as follows:

Embodiment 11

It in a volume is 160L 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 or so, are stirred 10 minutes；1kg methanol is added, stirs 10 minutes；Addition 2.8kg concentration is 20 weights The aqueous acetic acid of % is measured, is stirred 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.

It in another volume is 50L and with being added 5kg's in heating, stirring, circulation, cooling normal-pressure reaction kettle HVI500SN lubricating base oil is warming up to 100 DEG C, and the Zr (OH) that solid content is 20 weight % is added₄Suspension 19.5kg, stirring 10 minutes；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 zirconiums and terephthalic acid (TPA) oxygen zirconium.

It in third volume is 50L and with being added 2kg's in heating, stirring, circulation, cooling normal-pressure reaction kettle HVI500SN lubricating base oil and 1.5kg octadecylamine stir 4 minutes, add and be dissolved in the HVI500SN lubricating base oil of 2kg 0.7kg MDI, stir 4 minutes, the molar ratio of added MDI and octadecylamine is 1:2,120 DEG C constant temperature 20 minutes, gathered Urea.

Resulting 12-hydroxy stearic acid oxygen zirconium and terephthalic acid (TPA) oxygen zirconium are all squeezed into first kettle, stirred evenly, It is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration all squeezes into third reaction kettle resulting polyureas in the kettle, stirs Uniformly, 200 DEG C of constant temperature are finally warming up to 10 minutes.Then, remaining HVI500SN lubricating base oil is added；It is cooled to temperature 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.

Embodiment 12

It is 160L in volume and is with 10kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle A The calcium sulfonate with high base number of 350mgKOH/g, the overbased sulfurized alkylphenol calcium and 25kg that 20kg total base number is 400mgKOH/g 100 DEG C of kinematic viscosity are 31mm²The HVI150BS lubricating base oil of/s, stirring, heats to 60 DEG C, constant temperature 10 minutes；Add Enter 4-octadecylphenol of 3kg, temperature is controlled at 60 DEG C or so, stirred 10 minutes；The 12.5kg butanol that concentration is 20% is added Aqueous solution stirs 10 minutes；87 DEG C constant temperature 70 minutes, material retrogradation.

In volume for 30L and with heating, the HVI500SN for stirring, recycling, 5kg being added in the normal-pressure reaction kettle B of cooling Lubricating base oil is warming up to 90 DEG C, and the Zr (OH) that solid content is 20 weight % is added₄Suspension 28.9kg is stirred 10 minutes, is added Enter the palmitinic acid of 2.4kg, stir 10 minutes, the ethanedioic acid of the biphenyl dicarboxylic acid of 4.2kg, the phosphoric acid of 1kg and 2kg is added, stirs 10 minutes, obtain palmitinic acid oxygen zirconium, biphenyl dicarboxylic acid oxygen zirconium, zirconium phosphate oxygen and ethanedioic acid oxygen zirconium.

It in volume is 20L and viscous with 5kg100 DEG C of movement is added in heating, stirring, circulation, cooling normal-pressure reaction kettle C Degree is 11mm²The HVI500SN lubricating base oil and 1kg MDI rapidly pre-warming of/s is quickly added with stirring 0.12kg second to 90 DEG C Diamines stirs 4 minutes, and 1.08kg octadecylamine is added and stirs 4 minutes, and the molar ratio of added MDI, ethylenediamine and octadecylamine are 2: 1:2,120 DEG C constant temperature 20 minutes, obtain polyureas I.

It in volume is 30L and with 10kg100 DEG C of movement is added in heating, stirring, circulation, cooling normal-pressure reaction kettle D Viscosity is 11mm²The HVI500SN lubricating base oil and 1.29kg MDI of/s is preheating to 90 DEG C, is quickly added with stirring 0.84kg Octadecylamine and 0.19kg ethylenediamine, stir 4 minutes, added MDI, octadecylamine, ethylenediamine molar ratio be 3.3:2:2,120 DEG C Constant temperature 20 minutes, obtain polyureas II.

Gained palmitinic acid oxygen zirconium, biphenyl dicarboxylic acid oxygen zirconium, zirconium phosphate oxygen and ethanedioic acid oxygen zirconium are all squeezed into reaction kettle A In, it stirs evenly, 120 DEG C is warming up under stirring, kept for 30 minutes, gained polyureas I and polyureas II are all squeezed into reaction by dehydration It in kettle A, stirs evenly, being finally warming up to 200 DEG C, constant temperature for 5 minutes.Then, 150 DEG C are cooled to, the HVI500SN profit of 8kg is added Sliding base oil；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 32.6 weight % of calcium-sulfoacid calcium；2.7 weight % of palmitinic acid oxygen zirconium；5.6 weight % of biphenyl dicarboxylic acid oxygen zirconium；Zirconium phosphate oxygen 2.4 Weight %；4.0 weight % of ethanedioic acid oxygen zirconium；4.0 weight % of polyureas；48.7 weight % of lubricating base oil.

Embodiment 13

It in a volume is 160L and with 20kg total alkali is added in heating, stirring, circulation, cooling normal-pressure reaction kettle A Overbased sulfurized alkylphenol calcium that overbased sulfoacid calcium that value is 400mgKOH/g, 10kg total base number are 420mgKOH/g and 100 DEG C of kinematic viscosity of 10kg are 31mm²The HVI150BS lubricating base oil of/s, stirring, heats to 50 DEG C, constant temperature 10 divides Clock；4-octadecylphenol of 2kg is added, temperature is controlled at 50 DEG C or so, stirred 10 minutes；1kg methanol is added, stirs 10 points Clock；The aqueous acetic acid that 2kg concentration is 20 weight % is added, stirs 10 minutes；83 DEG C constant temperature 80 minutes, material retrogradation.

In volume for 30L and with heating, the HVI500SN for stirring, recycling, 8kg being added in the normal-pressure reaction kettle B of cooling The Zr (OH) that solid content is 50 weight % is added in lubricating base oil at 95 DEG C₄Suspension 7.7kg is stirred 10 minutes, is added The lauric acid of 2.4kg stirs 10 minutes, is added the M-phthalic acid of 7.9kg, stirs 10 minutes, obtain lauric acid oxygen zirconium and Phthalic acid oxygen zirconium.

It in volume is 30L and with 10kg100 DEG C of movement is added in heating, stirring, circulation, cooling normal-pressure reaction kettle C Viscosity is 11mm²The HVI500SN lubricating base oil and 1.17kg MDI of/s is preheating to 80 DEG C, is quickly added with stirring 0.84kg The mixture of octadecylamine, 0.19kg ethylenediamine, added MDI, monoamine, diamines molar ratio be 3:2:2,120 DEG C of constant temperature 20 divide Clock obtains polyureas.

Gained lauric acid oxygen zirconium and M-phthalic acid oxygen zirconium are all squeezed into reaction kettle A, stirred evenly, lower heating is stirred It to 110 DEG C, is kept for 45 minutes, gained polyureas is all squeezed into reaction kettle A, stirred evenly, is finally warming up to 200 DEG C by dehydration Constant temperature for 5 minutes.Then, the HVI500SN lubricating base oil of 2kg is added；110 DEG C are cooled to temperature, circulating filtration, takes off homogenizing It is so incensed that 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 44.0 weight % of calcium-sulfoacid calcium；4.1 weight % of lauric acid oxygen zirconium；8.2 weight % of M-phthalic acid oxygen zirconium；3.0 weight of polyureas Measure %；40.7 weight % of lubricating base oil.

Embodiment 14

It in a volume is 160L 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, is warming up at 50 DEG C under stirring, and constant temperature 30 minutes, 4-octadecyl of 2.8kg benzene is added Phenol, temperature are controlled at 50 DEG C, are stirred 10 minutes, and 1kg methanol is added, stirs 10 minutes, and it is 20 weight %'s that 2.8kg concentration, which is added, Aqueous acetic acid stirs 10 minutes, is warming up to 80 DEG C, and constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, solid content, which is added, is The Zr (OH) of 20 weight %₄Suspension 19.5kg is stirred 10 minutes；12-hydroxy stearic acid of 2kg is added, stirs 10 minutes；Add Enter 3.5kg terephthalic acid (TPA), stirs 10 minutes；It is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration；It is added 2kg's HVI500SN lubricating base oil and 1.5kg octadecylamine stir 4 minutes, add and be dissolved in the HVI500SN lubricating base oil of 2kg 0.7kg MDI, stir 4 minutes, the molar ratio of added MDI and octadecylamine is 1:2,120 DEG C constant temperature 20 minutes；Finally heat up To 200 DEG C constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oil is added；110 DEG C are cooled to temperature, is circulated throughout Filter, 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 into methyl Propyl ketone, replaces with octadecylamine for methanol, and aqueous acetic acid is replaced with butyl ether.Inspection result is shown in Table 1.

Embodiment 16

Lubricant composition is prepared according to the method for embodiment 3, 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 3, 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 3, 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 total alkali Value is replaced by the overbased sulfoacid calcium of 400mgKOH/g, and obtained each performance data of lubricating grease finished product 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: 36.8 weight of non-newtonian fluid sulfoacid calcium Measure %；2.4 weight % of polyureas；51.9 weight % of lubricating base oil；12-hydroxy stearic acid oxygen zirconium, 2.6 weight %；Terephthalic acid (TPA) 6.3 weight % of oxygen zirconium.

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.

Each lubricating grease properties of sample data of table 1

Each indication test method: dropping point: GB/T 3498；Work cone penetration and extension work cone penetration: GB/T 269；It is rotten Erosion: GB/T 7326；Anticorrosive property: GB/T 5018；Water drenches number of dropouts: SH/T 0109；Salt spray test: SH/T 0081；Water resistant It 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；The bearing lubrication service life: ASTM D 3336.

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

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 polyurea grease.Moreover, lubricant composition of the invention is with excellent In the viscous resistance of complex calcium sulfonate zirconium base polyurea grease, mechanical stability, water-resistance, colloid stability, abrasion resistance, extreme pressure Wear resistence and lubricating life.Moreover, lubricant composition of the invention also has excellent heat-resisting quantity.

Embodiment 1 is compared with embodiment 10 and embodiment 11 to the lubricating grease group as can be seen that being prepared in situ respectively Object is closed, there is better viscous resistance, water-resistance, colloid stability, abrasion resistance and lubricating life；By embodiment 1 and embodiment 11, embodiment 14, which is compared, can be seen that the reaction for first carrying out compound zirconium and/or polyurea compound, then be converted, and be made Lubricant composition have better viscous resistance, water-resistance, colloid stability, abrasion resistance and lubricating life；By embodiment 1 It is compared with embodiment 15 as can be seen that transforming agent is selected from dodecyl benzene sulfonic acid, aphthenic acids, octadecyl phenol, methanol, different At least one of propyl alcohol, butanol, boric acid, acetic acid and water, the lubricant composition of preparation have better viscous resistance, water resistant Property, colloid stability, abrasion resistance and lubricating life；Embodiment 3 is compared with embodiment 16-18 respectively can be seen that The raw material of zirconium contains the oxide and/or hydroxide of zirconium, and mole of the oxide of zirconium and/or hydroxide and zirconium alkoxide Than the mechanical stability of the lubricant composition of preparation, water-resistance, colloid stability, anti-for 1:0.5-5, can be further increased Abrasiveness and lubricating life.

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 the zirconates and polyurea compound of non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, higher fatty acids, and the thickening agent is also Optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, small molecule One of zirconates of inorganic acid and/or lower fatty acid is a variety of, on the basis of the weight of the lubricant composition, basis The content of oil is 10-80 weight %, and non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content is 10-70 weight %, advanced rouge The content of the zirconates of fat acid is 1-10 weight %, and the content of polyurea compound is 0.5-30 weight %, non-newtonian fluid calcium naphthenate Content be 0-70 weight %, the content of non-newtonian fluid calcium salicylate is 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, the content of the zirconates of aromatic acid are 0-15 weight %, and the zirconates of small molecule inorganic acid and/or lower fatty acid contains Amount is 0-15 weight %, wherein the zirconates of the higher fatty acids is to be reacted by higher fatty acids with component A, the virtue The zirconates of acid is to be reacted by aromatic acid with component A, and the zirconates of the small molecule inorganic acid and/or lower fatty acid is by small point Sub- inorganic acid and/or lower fatty acid are reacted with component A, and the component A is the hydroxide and alkane of the oxide of zirconium, zirconium At least one of oxygroup zirconium.

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

Wherein, n is 0-3 integer, R¹、R⁴It is alkyl, naphthenic base or aryl, R²It is alkylidene or arlydene, R³It is arlydene, Asia Alkyl or cycloalkylidene.

18. lubricant composition according to claim 17, wherein polyurea compound is two polyurea compounds, four polyureas At least one of compound, six polyurea compounds and eight polyurea compounds.

19. lubricant composition according to claim 17, wherein R¹、R⁴It is phenyl or substituted phenyl or carbon number is 8-24 alkyl or cycloalkyl；R²It is the alkylidene that phenylene or biphenylene or carbon number are 2-12；R³Be carbon number be 6-30 Arlydene, alkylidene or cycloalkylidene.

20. lubricant composition according to claim 19, wherein R¹、R⁴It is phenyl or C₁–C₃Alkyl or halogen take The alkyl or cycloalkyl that the phenyl or carbon number in generation are 10-18；R²It is the alkylidene that phenylene or biphenylene or carbon number are 2-8； R³It is With-(CH₂)₆At least one of.

21. the preparation method of lubricant composition described in any one of claim 1-20, 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 contain non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, higher fatty acids zirconates and Polyurea compound, the thickening agent is also optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid oil Sour calcium, the zirconates of aromatic acid, small molecule inorganic acid and/or lower fatty acid one of zirconates or a variety of.

22. 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；And/or optionally carry out the reaction of at least partly polyurea compound: be added part basis oil and Monoamine, or it is additionally added diamines, diisocyanate is added and is reacted；

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

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

(5) heating dehydration；

(6) reaction of remaining polyurea compound is carried out；

(7) 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 polyurea compound is 0.5-30 weight % is measured, 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 %, non- The content of newton body calcium oleate is 0-70 weight %, and the content of the zirconates of aromatic acid is 0-15 weight %, small molecule inorganic acid and/or The content of the zirconates of lower fatty acid is 0-15 weight %.

23. according to the method for claim 22, wherein in step (2), carry out the reaction of at least partly compound zirconium；With/ Or, carrying out the reaction of at least partly polyurea compound.

24. the method according to claim 22 or 23, wherein in step (2) and step (4), carry out the reaction of compound zirconium When, at 85-100 DEG C, component A is added, higher fatty acids is added, stirs 5-30 minutes, optional aromatic acid, optional small is added Molecule inorganic 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, the oxide and/or hydroxide of zirconium and the molar ratio of zirconium alkoxide are 1:0-10.

25. according to the method for claim 24, wherein in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium Molar ratio be 1:0.5-5.

26. the method according to claim 22 or 23, wherein in step (2) and step (6), carry out polyurea compound When reaction, be added part basis oil, monoamine, optional diamines, after diisocyanate, 100-120 DEG C constant temperature 10-30 minutes, Wherein, monoamine, optional diamines, diisocyanate the amount of substance meet following relationship: amount × 2 of the substance of diisocyanate Amount × 2 of amount+diamines substance of the substance of=monoamine, or, diisocyanate is excessive, excessive amount≤10%.

27. the method according to claim 22 or 23, wherein in step (3), at 50-80 DEG C, required transforming agent is added Reacted, after all transforming agents add, 80-100 DEG C constant temperature 60-90 minutes.

28. the method according to claim 22 or 23, wherein in step (5), be warming up to 110-130 DEG C of dehydration.

29. the method according to claim 22 or 23, wherein in step (7), 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.

30. the method according to claim 22 or 23, 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。

31. the method according to claim 22 or 23, 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%.

32. according to the method for claim 31, 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.

33. the method according to claim 22 or 23, wherein the structural formula of the monoamine is R¹–NH₂、R⁴–NH₂, wherein R¹、R⁴It is phenyl or C₁–C₃The alkyl or cycloalkyl that the phenyl or carbon number that alkyl or halogen replace are 10-18.

34. according to the method for claim 33, wherein the monoamine be selected from aniline, m-chloroaniline, parachloroanilinum and/ Or para-totuidine aromatic amine and/or fatty amine selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.

35. the method according to claim 22 or 23, wherein the structural formula of the diamines is NH₂–R²–NH₂, wherein R²It is The alkylidene or phenylene or biphenylene that carbon number is 2-8.

36. according to the method for claim 35, wherein the diamines is selected from p-phenylenediamine, o-phenylenediamine, 4,4 '-connection The aromatic amine of phenylenediamine and/or selected from ethylenediamine, propane diamine, 1,6-hexamethylene diamines straight-chain fatty amine.

37. the method according to claim 22 or 23, wherein the structure of the diisocyanate is OCN-R³- NCO, R³It is Arlydene, alkylidene or the cycloalkylidene that carbon number is 6-30.

38. according to the method for claim 37, wherein the diisocyanate is selected from toluene di-isocyanate(TDI), diphenyl Methane diisocyanate, six hexylidene diisocyanates, dicyclohexyl methyl hydride diisocyanate and xyxylene diisocyanate At least one of ester.

39. lubricant composition made from the method as described in any one of claim 22-38.