CN104560317A

CN104560317A - Compound calcium sulfonate-calcium naphthenate zirconium-based polyurea lubricating grease and preparation method thereof

Info

Publication number: CN104560317A
Application number: CN201310520603.XA
Authority: CN
Inventors: 何懿峰; 孙洪伟; 段庆华; 张建荣; 刘中其; 姜靓; 陈政; 郑会
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: 2013-10-29
Filing date: 2013-10-29
Publication date: 2015-04-29
Anticipated expiration: 2033-10-29
Also published as: CN104560317B

Abstract

The invention discloses compound calcium sulfonate-calcium naphthenate zirconium-based polyurea lubricating grease. The lubricating grease comprises the following components in percentage by weight: 10-70 percent of non-newton calcium sulfonate-calcium naphthenate, 1-10 percent of zirconium salt of higher fatty acid, 1-15 percent of zirconium salt of aromatic acid, 0.5-30 percent of a polyurea compound and 10-80 percent of base oil, and optionally comprises 1-15 percent of zirconium salt of micromolecular inorganic acid and/or lower fatty acid, wherein the zirconium salts are respectively prepared by reaction of higher fatty acid, aromatic acid, and micromolecular inorganic acid and/or lower fatty acid with a component A; and the component A is at least one of oxide of zirconium, hydroxide of zirconium and zirconium alkoxide. The invention further discloses a method for preparing the lubricating grease and the lubricating grease prepared by the method. The lubricating grease has good mechanical stability, good water resistance, good adhesion, salt mist resistance, colloid stability, extreme pressure antiwear property and the like, and has a long lubricating life.

Description

A kind of complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease and preparation method thereof

Technical field

The present invention relates to lubricating grease, particularly, relate to a kind of complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease and preparation method thereof.

Background technology

Calcium sulphonate is used as the history that the purification agent of lubricating oil and rust-preventive agent have decades, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active alkyl benzene calcium sulfonate or alkyl carboxylic acid calcium.Calcium sulfonate with high base number can be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate according to mode of production difference.Calcium mahogany sulfonate is with oleum or SO ₃sulfonation mineral lubricating oils produces by product mahogany acid during white oil, warp and Ca (OH) ₂reaction, the contour alkalization technology of carbonating and obtaining; Calcium alkylbenzenesulfonate is with oleum or SO ₃the alkylbenzene of sulfonation synthesis, alkyl benzene sulphonate (ABS) warp and Ca (OH) of generation ₂reaction, the contour alkalization technology of carbonating and obtaining.

Overbased calcium alkyl-salicylate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffustivity, the purification agent of lubricating oil can be used as, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active naphthenic acid calcium.Mostly overbased calcium alkyl-salicylate is the acidic components extracted from the distillate that crude distillation obtains, warp and Ca (OH) ₂reaction, the contour alkalization technology of carbonating and obtain, about the Patents prepared has CN1465560 etc.

Utilize calcium sulfonate with high base number for raw material production lubricating grease, because it has excellent high temperature performance, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion, since putting goods on the market, cause the extensive concern of domestic and international lubricating grease industry, but, although high base number composite calcium sulfonate base grease has very excellent over-all properties, but the high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, simultaneously, along with the requirement of people to environment protection is more and more higher, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment also received day by day to the concern of people.Find a kind of performance and high base number composite calcium sulfonate base grease is similar but the lubricating grease that can alleviate the problems referred to above becomes the large problem that people face at present.

Zirconium belongs to IVB race as a kind of transition metal, is positioned at for the 5th cycle.Zirconium-containing compound has excellent lubrication, is often used as slip additive, as the oxide compound of zirconium is improved abradability as lubricant additive by CN101113382 and JP1973038444; WO2007143414 and US20060063682 describes zirconium tetrafluoride and can be used as one of wear reducing additive component becoming lubricant; US20060254823 finds that the lubricant containing 2 ethyl hexanoic acid zirconates shows good resistance to heavy loading and abrasion resistance; US20050043189 finds that fluozirconate is used in the lubricant as fluorine zirconic acid aluminium can be used as oxidation retarder; DE102004021812 finds the inorganic salt such as zirconium carbonate, sulfonic acid zirconium or zirconium phosphate to join inside lubricating grease and can improve abrasion resistance.

Summary of the invention

The object of this invention is to provide a kind of mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear all better, lubricating life is longer, and cost is low, and preparation technology is simple, the lubricating grease of environmental protection and preparation method thereof.

The present inventor finds under study for action, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The zirconates of the higher fatty acid of 1-10 % by weight; The zirconates of the aromatic acid of 1-15 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the zirconates of lower fatty acid, wherein, the zirconates of described higher fatty acid is reacted by higher fatty acid and component A to form, the zirconates of described aromatic acid is reacted by aromatic acid and component A to form, the zirconates of described small molecules mineral acid and/or lower fatty acid is reacted by small molecules mineral acid and/or lower fatty acid and component A to form, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.This lubricating grease has good mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear, have longer lubricating life, and cost is low, and preparation technology is simple, environmental protection.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The zirconates of the higher fatty acid of 1-10 % by weight; The zirconates of the aromatic acid of 1-15 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the zirconates of lower fatty acid, wherein, the zirconates of described higher fatty acid is reacted by higher fatty acid and component A to form, the zirconates of described aromatic acid is reacted by aromatic acid and component A to form, the zirconates of described small molecules mineral acid and/or lower fatty acid is reacted by small molecules mineral acid and/or lower fatty acid and component A to form, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.

Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-60 % by weight; The zirconates of the higher fatty acid of 2-6 % by weight; The zirconates of the aromatic acid of 2-10 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the zirconates of lower fatty acid.

Preferably, described component A is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, and in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10, is more preferably 1:0.5-5.

Second aspect, the invention provides the preparation method of complex calcium sulfonate as above-calcium naphthenate zirconium base polyurea grease, the method comprises: by the zirconates of the zirconates of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, aromatic acid, polyurea compound and part basis, oily and optionally small molecules mineral acid and/or lower fatty acid zirconates mixes, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.

The third aspect, the invention provides the preparation method of a kind of complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease, the method comprises:

(1) newton's body calcium sulphonate, newton's body calcium naphthenate, base oil and transforming agent are mixed, heat up and treat material retrogradation;

(2) in step (1) products therefrom, component A is added, add higher fatty acid, aromatic acid and optionally small molecules mineral acid and/or lower fatty acid react, heat up after reaction dehydration, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide;

(3) in step (2) gained mixture, add base oil and monoamine, or also add diamines, add vulcabond and react;

(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.

Fourth aspect, the invention provides the complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease obtained by method as above.

Complex calcium sulfonate of the present invention-calcium naphthenate zirconium base polyurea grease, compare Composite calcium-sulfonate-batetrapolyurea polyurea grease, there is the performance such as better mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.

Other features and advantages of the present invention are described in detail in embodiment part subsequently.

Accompanying drawing explanation

Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 5.

Embodiment

Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.

The invention provides a kind of complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease, this lubricating grease have employed calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate be raw material, simultaneously containing compound zirconium viscosifying agent, isocyanic ester and amine reaction produce polyurea compound.

Present invention also offers above-mentioned preparation of greases method.

On the one hand, the invention provides a kind of complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The zirconates of the higher fatty acid of 1-10 % by weight; The zirconates of the aromatic acid of 1-15 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the zirconates of lower fatty acid, wherein, the zirconates of higher fatty acid is reacted by higher fatty acid and component A to form, the zirconates of aromatic acid is reacted by aromatic acid and component A to form, the zirconates of small molecules mineral acid and/or lower fatty acid is reacted by small molecules mineral acid and/or lower fatty acid and component A to form, and component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.

Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-60 % by weight; The zirconates of the higher fatty acid of 2-6 % by weight; The zirconates of the aromatic acid of 2-10 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the zirconates of lower fatty acid; More preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 30-55 % by weight; 2.2-4.2 the zirconates of the higher fatty acid of % by weight; The zirconates of the aromatic acid of 3-8 % by weight; The polyurea compound of 2-10 % by weight; The base oil of 30-60 % by weight; Optionally also comprise the small molecules mineral acid of 3-8 % by weight and/or the zirconates of lower fatty acid.

In the present invention, " optionally also comprise " and refer to comprise and also can not comprise, that is, the zirconates of small molecules mineral acid and/or lower fatty acid is selectable components, this component can be comprised in composite calcium naphthenate calcium zirconium base grease of the present invention, also can not comprise this component.

Non-newtonian fluid calcium sulphonate-calcium naphthenate is at infrared spectrum 873cm ^-1-886cm ^-1there is crystal form calcium carbonate charateristic avsorption band in place, total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid calcium sulphonate-calcium naphthenate is obtained by transforming agent conversion by newton's body calcium sulphonate and newton's body calcium naphthenate.And containing unformed calcium carbonate in newton's body calcium sulphonate, newton's body calcium naphthenate, at infrared spectrum 860cm ^-1-865cm ^-1there is unformed calcium carbonate charateristic avsorption band in place.Newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.The base number of non-newtonian fluid calcium sulphonate-calcium naphthenate is the weight mean value of the base number of newton's body calcium sulphonate and the base number of newton's body calcium naphthenate.

In the present invention, higher fatty acid is carbon number is 8-20, the straight chain fatty acid of preferred 10-16 or hydroxy fatty acid, such as, at least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, is preferably 12-oxystearic acid.

In the present invention, aromatic acid is the carboxylic acid having at least 1 carboxyl to be directly connected with aromatic ring, aromatic acid can be replace or unsubstituted aromatic acid, its substituting group can be at least one in alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno etc., and the molecular weight of aromatic acid is less than or equal to 550.Aromatic acid is preferably binary aromatic acid, such as, can be selected from least one in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.Be preferably phthalic acid, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, and at least one in methyl substituted biphenyl dicarboxylic acid, santowax dioctyl phthalate etc.

In the present invention, the molecular weight of small molecules mineral acid or lower fatty acid is less than or equal to 150.Wherein, small molecules mineral acid can be selected from least one in boric acid, phosphoric acid, sulfuric acid etc., is preferably boric acid and/or phosphoric acid; Lower fatty acid can be selected from least one in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid etc., is preferably acetic acid.

The present inventor surprisingly finds under study for action, when component A is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, namely when the raw material of zirconium is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, can further improve the mechanical stability of lubricating grease, water resisting property and adhesivity, colloid stability and lubricating life, therefore, component A is preferably the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is preferably 1:0.1-10, be more preferably 1:0.2-8, further be preferably 1:0.5-5, when the preferred molar ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, the mechanical stability of lubricating grease can be improved further, water resisting property and adhesivity, colloid stability and lubricating life.

In the present invention, oxide compound and/or the oxyhydroxide of zirconium are preferably selected from ZrO ₂, ZrO (OH) ₂, Zr (OH) ₄and at least one in their hydrate.ZrO (OH) ₂hydrate can be the wet hydrogen zirconium white of brand-new, it can pass through ZrOX ₂8H ₂o(X is F, Cl, Br or I) or ZrO (NO ₃) ₂2H ₂o etc. obtain with alkali reaction, and wherein, alkali can be NaOH, KOH, strong aqua etc., preferred ZrOCl ₂8H ₂o and NaOH reacts.

In the present invention, the general formula of zirconium alkoxide can be Zr (OR ₁) ₄, R ₁can be the alkyl of C1-C10, be preferably the alkyl of C2-C6; More preferably, zirconium alkoxide is selected from least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and Pentyl alcohol zirconium.

In the present invention, described polyurea compound is without particular requirement, and the polyurea compound can commonly used for this area can be such as at least one in dimerization carbamide compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds.Wherein the weight ratio of two polyurea compounds, four polyurea compounds, six polyurea compounds, eight polyurea compounds can be arbitrary proportion.More preferably described polyurea compound is two polyurea compounds.

In the present invention, described two polyurea compounds preferably have following structure:

Wherein, R ¹, R ^{1 '}can be the same or different, can be alkyl, cycloalkyl or aryl, and the carbon number of alkyl or cycloalkyl can be 8-24, and be preferably 10-18, aryl can be the phenyl of phenyl or replacement, is preferably the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.

Wherein, R ³can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R ³be more preferably in at least one.

In the present invention, described four polyurea compounds preferably have following structure:

Wherein, R ¹can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of phenyl or replacement, is preferably the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.

Wherein, R ²can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.

In the present invention, described six polyurea compounds preferably have following structure:

Wherein, R ¹can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.

In the present invention, described eight polyurea compounds preferably have following structure:

Wherein, R ¹can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, and be preferably 10-18, aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.

Above-mentioned polyurea compound can adopt the thinkable various method of those skilled in the art institute to obtain, and the method such as can recorded according to CN103060069A, CN103060070A, CN103060068A, CN103060067A prepares.

Described lubricating base oil can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 DEG C of kinematic viscosities are 4-150mm ²/ s, is preferably 10-60mm ²/ s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.

Can also various additive be contained, as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc. in lubricating grease of the present invention.Wherein, the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.01-5% of lubricating grease gross weight, preferred 0.1-2.5%, can be at least one in pentanoic, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of lubricating grease gross weight, preferred 0.8-8% can be at least one in dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenumdisulphide, tetrafluoroethylene, thiophosphoric acid molybdenum, clorafin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, calcium carbonate and zinc oxide; Rust-preventive agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferred 0.1-2%, can be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.

In the present invention, described above for the zirconates of the zirconates of the zirconates of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, aromatic acid, small molecules mineral acid and/or lower fatty acid, polyurea compound, base oil and additive, do not repeat them here.

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

For non-newtonian fluid calcium sulphonate-calcium naphthenate, can be obtained by transforming agent conversion by newton's body calcium sulphonate, newton's body calcium naphthenate, such as, by newton's body calcium sulphonate, newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 60-90 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.

In step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, preferred constant temperature 10-30 minute, add required transforming agent to react, 8-12 minute is stirred after preferably adding often kind of transforming agent, after all transforming agents add, at 60-90 DEG C of constant temperature 60-90 minute.

In step of the present invention (1), for the weight ratio of newton's body calcium sulphonate and newton's body calcium naphthenate without particular requirement, be preferably 1:0.25-4.The gross weight of newton's body calcium sulphonate and newton's body calcium naphthenate and the weight ratio of part basis oil are preferably 1:0.1-3.

In the present invention, newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.

Described transforming agent is preferably selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water; More preferably at least one in the fatty alcohol of C1-C5, the lipid acid of C1-C5, the aliphatic ketone of C1-C5, the alkanoic of C1-C5, the aliphatic amide of C1-C5, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, the arylphosphonic acid of C6-C20, the diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate (ABS) and water is selected from; Further be preferably selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water.The add-on of transforming agent is preferably the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight, is more preferably the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.

In the present invention, fatty alcohol comprises the fatty alcohol of straight chain, side chain and ring-type, and lipid acid, aliphatic ketone, alkanoic, aliphatic amide are in like manner.

As previously mentioned, the present inventor surprisingly finds under study for action, in step (2), when component A is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, namely when the raw material of zirconium is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, can further improve the mechanical stability of obtained lubricating grease, water resisting property and adhesivity, colloid stability and lubricating life, therefore, preferably, in step (2), at 85-100 DEG C, add component A, add higher fatty acid, stir 5-20 minute, add aromatic acid, and optionally small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 100-120 DEG C, preferred maintenance 30-60 minute, dehydration, described component A is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is preferably 1:0.1-10, be more preferably 1:0.2-8, further be preferably 1:0.5-5.Wherein, the addition sequence of higher fatty acid and aromatic acid, small molecules mineral acid and/or lower fatty acid can exchange.

In the present invention, " optionally small molecules mineral acid and/or lower fatty acid " refers in step (2) can comprise small molecules mineral acid and/or lower fatty acid, also small molecules mineral acid and/or lower fatty acid can not be comprised, that is, small molecules mineral acid and/or lower fatty acid are optional raw materials.

In the present invention, higher fatty acid, aromatic acid, small molecules mineral acid, lower fatty acid, the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide as previously mentioned, do not repeat them here.

In the present invention, the H of higher fatty acid and aromatic acid and optionally small molecules mineral acid and/or lower fatty acid ⁺total amount of substance equals all and the oxide compound of zirconium, the oxyhydroxide of zirconium and the H needed for zirconium alkoxide ⁺mole number, but the oxyhydroxide of the oxide compound of zirconium, zirconium and zirconium alkoxide are relative to higher fatty acid and aromatic acid and optionally small molecules mineral acid and/or lower fatty acid can excessive 1-10%.

In the present invention, the add-on of the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide is preferably the 1-15% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight; In the amount of substance of H+, the mol ratio of higher fatty acid and aromatic acid and optionally small molecules mineral acid and/or lower fatty acid is preferably 1:1-10.

In step (3), base oil and monoamine is added in step (2) gained mixture, or also add diamines, add vulcabond to react, namely be prepare polyurea compound in step (2) gained mixture, mixing polyureas can be prepared, also can prepare two independent polyurea compounds, four polyurea compounds, six polyurea compounds or eight polyurea compounds.

The method preparing mixing polyureas, without particular requirement, can adopt the thinkable various method of those skilled in the art, such as, can adopt the method for US Patent No. 3243372.

Prepare the method for two polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, can add base oil and monoamine in step (2) gained mixture, stir 2-8 minute, then add the vulcabond be dissolved in base oil, stir 2-8 minute, the mol ratio of vulcabond and monoamine is 1:2.

Prepare the method for four polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, can add base oil and vulcabond, stir, add diamines in step (2) gained mixture, stir 2-8 minute, add monoamine, stir 2-8 minute, the mol ratio of vulcabond, diamines and monoamine is 2:1:2.

Prepare the method for six polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, base oil and vulcabond can be added in step (2) gained mixture, stir, add monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, then add vulcabond, stir 2-8 minute, the mol ratio of added successively vulcabond, monoamine, diamines and vulcabond is 2:2:2:1.

Prepare the method for eight polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, base oil and vulcabond can be added in step (2) gained mixture, stir, add diamines, stir 2-8 minute, again add diamines, stir 2-8 minute, add monoamine, stir 2-8 minute, the mol ratio of added successively vulcabond, diamines, diamines and monoamine is 4:2:1:2.

It will be understood by those skilled in the art that when preparing polyurea compound, the mol ratio of above-mentioned each raw material can fluctuate in ± 5% scope.

Described vulcabond structure is OCN-R ³-NCO, R ³can be carbon number be 6-30, the arylidene of preferred 6-20, alkylidene group or cycloalkylidene, be preferably deng.Such as, described vulcabond can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), at least one in dicyclohexyl methane diisocyanate (HMDI) and an xylylene diisocyanate (XDI) etc.

Described monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R ¹-NH ₂, R ^{1 '}-NH ₂, R wherein ¹, R ^{1 '}can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.Preferred monoamine can be the arylamine being selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.

Described diamines can be aliphatic amide or arylamine, and structural formula is NH ₂-R ²-NH ₂, R wherein ²can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, preferred 2-8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from Ursol D, O-Phenylene Diamine, 4,4-benzidines aromatic amine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.

In step (4), first at 100-120 DEG C of constant temperature 10-20 minute, be finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.

In the present invention, in step (1), in the total amount of base oil used and step (3), in the total amount of base oil used and step (4), the weight ratio of the total amount of base oil used is preferably 1:0.1-5:0.1-5.

Fourth aspect, the complex calcium sulfonate that the preparation method that present invention also offers is provided by third aspect present invention obtains-calcium naphthenate zirconium base polyurea grease.

Compared with the complex calcium sulfonate obtained with the preparation method provided by second aspect-calcium naphthenate zirconium base polyurea grease, the complex calcium sulfonate that the preparation method that the third aspect provides obtains-calcium naphthenate zirconium base polyurea grease has better water resisting property and adhesivity, colloid stability, has longer lubricating life.

Embodiment

The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.

In the following Examples and Comparative Examples:

Overbased or calcium sulfonate with high base number raw material weight+the overbased or overbased calcium alkyl-salicylate raw material weight+transforming agent gross weight of non-newtonian fluid calcium sulphonate-calcium naphthenate %=()/lubricating grease gross weight × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium sulphonate-calcium naphthenate.

The content of the zirconates of the zirconates of higher fatty acid, the zirconates of aromatic acid and small molecules mineral acid and/or lower fatty acid, the gauge generating zirconates according to added higher fatty acid, aromatic acid and the oxide compound of small molecules mineral acid and/or lower fatty acid and zirconium, the oxyhydroxide of zirconium and zirconium alkoxide complete reaction is calculated.

Overbased and overbased calcium alkyl-salicylate raw material, also can according to method preparation disclosed in CN101885677A purchased from Xinjiang Land Fine Petrochemical Co., Ltd.

Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..

Naphthenic acid is purchased from Jinzhou Tie Chen petrochemical complex limited liability company.

Embodiment 1

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease that the present embodiment is prepared for illustration of the present invention.

Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil ²/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Zr (OH) ₄(3.9kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil ²/ s, 17kg).

A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 30 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 60 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 100 DEG C, add the Zr (OH) that solid content is 20 % by weight ₄suspension liquid 19.5kg, stirs 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir 10 minutes, under stirring, be warmed up to 110 DEG C, keep 45 minutes, dehydration; Add HVI500SN lubricating base oil and the 1.5kg stearylamine of 2kg, stir 4 minutes, add the 0.7kg MDI be dissolved in the HVI500SN lubricating base oil of 2kg again, stir 4 minutes, added MDI and the mol ratio of stearylamine are 1:2,120 DEG C of constant temperature 20 minutes, is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oil is added; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 36.8 % by weight; Two polyureas 2.4 % by weight; Lubricating base oil 51.9 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.3 % by weight.

Embodiment 2

A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 30 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 60 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 100 DEG C, add the Zr (OH) that solid content is 20 % by weight ₄suspension liquid 19.5kg, stirs 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir 10 minutes, under stirring, be warmed up to 110 DEG C, keep 45 minutes, dehydration.

Another volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add HVI500SN lubricating base oil and the 1.5kg stearylamine of 2kg, be warmed up to 120 DEG C, stir 4 minutes, add the 0.7kg MDI be dissolved in the HVI500SN lubricating base oil of 2kg again, stir 4 minutes, added MDI and the mol ratio of stearylamine are 1:2, and 120 DEG C of constant temperature 20 minutes, obtains two polyureas.

Gained two polyureas is all squeezed in a upper still, stirs, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oil is added; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.

The two polyureas molecular structural formulas contained in component are:

Embodiment 3

Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil ²/ s, 20kg); Propyl carbinol (2.8kg); Acetic acid (0.56kg); Zirconium-n-butylate (7.83k); Zr (OH) ₄(0.65kg); Stearic acid (1.9kg); Phthalic acid (3.5kg); Lauryl amine (1.31kg); MDI(0.89kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil ²/ s, 27kg).

A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the overbased calcium alkyl-salicylate of 320mgKOH/g and the HVI150BS lubricating base oil of 20kg, stir, heat to 80 DEG C, constant temperature 10 minutes; Add 2.8kg propyl carbinol, temperature controls at about 80 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 90 DEG C, constant temperature 60 minutes, material retrogradation; Successively add the Zr (OH) that 7.83kg zirconium-n-butylate and solid content are 20 % by weight ₄suspension liquid 3.25kg, in zirconium, Zr (OH) ₄be 1:5 with the mol ratio of zirconium-n-butylate, stir 10 minutes; Add 1.9kg stearic acid, stir 10 minutes; Add 3.5kg phthalic acid, stir 10 minutes, under stirring, be warmed up to 120 DEG C, keep 30 minutes, dehydration; Add HVI500SN lubricating base oil and the 1.31kg lauryl amine of 2kg, stir 8 minutes, add the 0.89kg MDI be dissolved in the HVI500SN lubricating base oil of 2kg again, stir 8 minutes, added MDI and the mol ratio of stearylamine are 1:2,100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 36.9 % by weight; Two polyureas 2.4 % by weight; Lubricating base oil 51.9 % by weight; Zirconyl stearate 2.5 % by weight; Phthalic acid oxygen zirconium 6.3 % by weight.

Embodiment 4

Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil ²/ s, 25kg); Witco 1298 Soft Acid (2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Ethanol zirconium (2.21kg); Zr (OH) ₄(2.6kg); 12-oxystearic acid (2kg); M-phthalic acid (3.5kg); Stearylamine (1.66kg); TDI(0.54kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil ²/ s, 22kg).

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; Naphthenic acid is replaced with Witco 1298 Soft Acid; Terephthalic acid is replaced with m-phthalic acid; MDI is replaced with tolylene diisocyanate (TDI); Add Zr (OH) ₄time also add ethanol zirconium, in zirconium, Zr (OH) ₄be 1:0.5 with the mol ratio of ethanol zirconium; The consumption of each composition as above.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 36.8 % by weight; Two polyureas 2.4 % by weight; Lubricating base oil 51.9 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; M-phthalic acid oxygen zirconium 6.3 % by weight.

Embodiment 5

Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil ²/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Zirconium-n-propylate (4.0kg); Zr (OH) ₄(2.0kg); 12-oxystearic acid (2kg); 2-methyl isophthalic acid, 4-phthalic acid (3.8kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil ²/ s, 7kg).

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Use 2-methyl isophthalic acid, 4-phthalic acid replaces terephthalic acid; Add Zr (OH) ₄time also add zirconium-n-propylate, in zirconium, Zr (OH) ₄be 1:1 with the mol ratio of zirconium-n-propylate; The consumption of each composition as above.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 50.6 % by weight; Two polyureas 3.3 % by weight; Lubricating base oil 33.4 % by weight; 12-oxystearic acid oxygen zirconium 3.6 % by weight; 2-methyl isophthalic acid, 4-phthalic acid oxygen zirconium 9.1 % by weight.

Embodiment 6

Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil ²/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Zr (OH) ₄(3.9kg); 12-oxystearic acid (2kg); 4,4'-biphenyl dicarboxylic acid (5.1kg); Stearylamine (4.5kg); MDI(2.1kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil ²/ s, 18.6kg).

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, transforming agent only uses naphthenic acid and acetic acid, saves the step adding methyl alcohol; Terephthalic acid is replaced with 4,4'-biphenyl dicarboxylic acid; The consumption of each composition as above.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 35.8 % by weight; Two polyureas 7.1 % by weight; Lubricating base oil 46.8 % by weight; 12-oxystearic acid oxygen zirconium 2.5 % by weight; 4,4'-biphenyl dicarboxylic acid oxygen zirconium 7.8 % by weight.

Embodiment 7

Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); Poly alpha olefine synthetic oil PAO40(100 DEG C kinematic viscosity is 40mm ²/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Zr (OH) ₄(3.9kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.5kg); MDI(0.7kg); Poly alpha olefine synthetic oil PAO10(100 DEG C kinematic viscosity is 11mm ²/ s, 9kg); Dithio Acidic phosphates zinc (2kg); Molybdenum dialkyldithiocarbamacompositions (1kg); Tungsten disulfide (2kg); Two tungsten selenide (2kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Poly alpha olefine synthetic oil PAO40(100 DEG C of kinematic viscosity is used to be 40mm ²/ s) and poly alpha olefine synthetic oil PAO10(100 DEG C kinematic viscosity be 11mm ²/ s) replace HVI150BS(100 DEG C of kinematic viscosity to be 31mm respectively ²/ s) and HVI500SN(100 DEG C of kinematic viscosity be 11mm ²/ s); Transforming agent only uses naphthenic acid and acetic acid, saves the step adding methyl alcohol; And treat that temperature is cooled to 110 DEG C, add the dithio Acidic phosphates zinc of 2kg, stir 10 minutes, add the molybdenum dialkyldithiocarbamacompositions of 1kg, stir 10 minutes, add the tungsten disulfide of 2kg, stir 10 minutes, add two tungsten selenide of 2kg, stir 10 minutes, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.2 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 43.4 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.4 % by weight; Dithio Acidic phosphates zinc 2.2 % by weight; Molybdenum dialkyldithiocarbamacompositions 1.1 % by weight; Tungsten disulfide 2.2 % by weight; Two tungsten selenide 2.2 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.

Embodiment 8

Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil ²/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Zr (OH) ₄(3.9kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (0.94kg); Para-totuidine (0.38kg); MDI(0.88kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil ²/ s, 33kg).

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; Transforming agent only uses naphthenic acid and acetic acid, saves the step adding methyl alcohol; When adding stearylamine, also add para-totuidine; The consumption of each composition as above.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 36.4 % by weight; Two polyureas 2.4 % by weight; Lubricating base oil 52.4 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.2 % by weight.

Embodiment 9

Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil ²/ s, 20kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Zr (OH) ₄(11.2kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Terephthalic acid (7.6kg); Stearylamine (0.84kg); Lauryl amine (0.58kg); MDI(0.78kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil ²/ s, 28kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Transforming agent only uses naphthenic acid and acetic acid, saves the step adding methyl alcohol; After adding 12-oxystearic acid, also add boric acid, and then add terephthalic acid; When adding stearylamine, also add lauryl amine; And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir after 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 32.7 % by weight; Two polyureas 2.2 % by weight; Lubricating base oil 47.0 % by weight; 12-oxystearic acid oxygen zirconium 2.3 % by weight; Boric acid oxygen zirconium 3.5 % by weight; Terephthalic acid oxygen zirconium 12.1 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.

Embodiment 10

Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 15kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil ²/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Zr (OH) ₄(6.5kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Acetic acid (2kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil ²/ s, 33kg).

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, transforming agent only uses naphthenic acid and acetic acid, saves the step adding methyl alcohol; After adding terephthalic acid, also add acetic acid, and then the dehydration that heats up; The consumption of each composition as above.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 35.0 % by weight; Two polyureas 2.3 % by weight; Lubricating base oil 50.3 % by weight; 12-oxystearic acid oxygen zirconium 2.5 % by weight; Terephthalic acid oxygen zirconium 6.0 % by weight; Zirconyl acetate 3.9 % by weight.

Embodiment 11

A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 30 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 60 DEG C, constant temperature 90 minutes, material retrogradation.

Another volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add the HVI500SN lubricating base oil of 5kg, be warmed up to 100 DEG C, add the Zr (OH) that solid content is 20 % by weight ₄suspension liquid 19.5kg, stirs 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir 10 minutes, obtain 12-oxystearic acid oxygen zirconium and terephthalic acid oxygen zirconium.

The 3rd volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add HVI500SN lubricating base oil and the 1.5kg stearylamine of 2kg, stir 4 minutes, add the 0.7kg MDI be dissolved in the HVI500SN lubricating base oil of 2kg again, stir 4 minutes, added MDI and the mol ratio of stearylamine are 1:2,120 DEG C of constant temperature 20 minutes, obtains two polyureas.

The 12-oxystearic acid oxygen zirconium of gained and terephthalic acid oxygen zirconium are all squeezed in first still, stir, 110 DEG C are warmed up under stirring, keep 45 minutes, dehydration, two polyureas of the 3rd reactor gained are all squeezed in this still, stirs, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oil is added; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.

Embodiment 12

Volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle A in add calcium sulfonate with high base number that 10kg total basicnumber is 350mgKOH/g, naphthenate with superhigh base number calcium that 20kg total basicnumber is 400mgKOH/g and 25kg100 DEG C of kinematic viscosity is 31mm ²the HVI150BS lubricating base oil of/s, stirs, heats to 60 DEG C, constant temperature 10 minutes; Add 3kg naphthenic acid, temperature controls at about 60 DEG C, stirs 10 minutes; Add the 12.5kg butanols aqueous solution that concentration is 20%, stir 10 minutes; 87 DEG C of constant temperature 70 minutes, material retrogradation.

Volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle B in add the HVI500SN lubricating base oil of 5kg, be warming up to 90 DEG C, add the Zr (OH) that solid content is 20 % by weight ₄suspension liquid 28.9kg, stirs 10 minutes, adds the palmitinic acid of 2.4kg, stir 10 minutes, add the oxalic acid of the biphenyl dicarboxylic acid of 4.2kg, the phosphoric acid of 1kg and 2kg, stir 10 minutes, obtain palmitinic acid oxygen zirconium, biphenyl dicarboxylic acid oxygen zirconium, zirconium phosphate oxygen and oxalic acid oxygen zirconium.

Volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle C in add 5kg100 DEG C of kinematic viscosity be 11mm ²the HVI500SN lubricating base oil of/s and 1kg MDI rapidly pre-warming, to 90 DEG C, add 0.12kg quadrol under rapid stirring, stir 4 minutes, add 1.08kg stearylamine and stir 4 minutes, the mol ratio of added MDI, quadrol and stearylamine is 2:1:2, and 120 DEG C of constant temperature 20 minutes, obtains four polyureas.

Volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle D in add 10kg100 DEG C of kinematic viscosity be 11mm ²hVI500SN lubricating base oil and the 0.78kg MDI of/s are preheating to 90 DEG C, 0.84kg stearylamine is added under rapid stirring, stir 4 minutes, 0.19kg quadrol is added under rapid stirring, stir 4 minutes, add 0.39kg MDI, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.

Gained palmitinic acid oxygen zirconium, biphenyl dicarboxylic acid oxygen zirconium, zirconium phosphate oxygen and oxalic acid oxygen zirconium are all squeezed in reactor A, stir, 120 DEG C are warmed up under stirring, keep 30 minutes, dehydration, gained four polyureas and six polyureas are all squeezed in reactor A, stirs, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, be cooled to 150 DEG C, add the HVI500SN lubricating base oil of 8kg; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 32.6 % by weight; Palmitinic acid oxygen zirconium 2.7 % by weight; Biphenyl dicarboxylic acid oxygen zirconium 5.6 % by weight; Zirconium phosphate oxygen 2.4 % by weight; Oxalic acid oxygen zirconium 4.0 % by weight; Four polyureas 2.0 % by weight; Six polyureas 2.0 % by weight; Lubricating base oil 48.7 % by weight.

Embodiment 13

A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle A in add overbased calcium sulphonate that 20kg total basicnumber is 400mgKOH/g, naphthenate with superhigh base number calcium that 10kg total basicnumber is 420mgKOH/g and 10kg100 DEG C of kinematic viscosity is 31mm ²the HVI150BS lubricating base oil of/s, stirs, heats to 50 DEG C, constant temperature 10 minutes; Add 2kg Witco 1298 Soft Acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2kg concentration is 20 % by weight, stir 10 minutes; 83 DEG C of constant temperature 80 minutes, material retrogradation.

Volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle B in add the HVI500SN lubricating base oil of 8kg, at 95 DEG C, add the Zr (OH) that solid content is 50 % by weight ₄suspension liquid 7.7kg, stirs 10 minutes, adds the lauric acid of 2.4kg, stirs 10 minutes, adds the m-phthalic acid of 7.9kg, stirs 10 minutes, obtains lauric acid oxygen zirconium and m-phthalic acid oxygen zirconium.

Volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle C in add 10kg100 DEG C of kinematic viscosity be 11mm ²hVI500SN lubricating base oil and the 1.17kg MDI of/s are preheating to 80 DEG C, the mixture of 0.84kg stearylamine, 0.19kg quadrol is added under rapid stirring, the mol ratio of added MDI, monoamine, diamines is 3:2:2, and 120 DEG C of constant temperature 20 minutes, obtains mixing polyureas.

Gained lauric acid oxygen zirconium and m-phthalic acid oxygen zirconium are all squeezed in reactor A, stirs, under stirring, be warmed up to 110 DEG C, keep 45 minutes, dehydration, all squeezes in reactor A by gained mixing polyureas, stir, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, the HVI500SN lubricating base oil of 2kg is added; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.

In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 44.0 % by weight; Lauric acid oxygen zirconium 4.1 % by weight; M-phthalic acid oxygen zirconium 8.2 % by weight; Polyurea compound 3.0 % by weight; Lubricating base oil 40.7 % by weight.

Embodiment 14

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with phenol, acetic acid is replaced with butyric acid.Assay is in table 1.

Embodiment 15

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with methyl propyl ketone, aqueous acetic acid is replaced with butyl ether.Assay is in table 1.

Embodiment 16

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 5, unlike, at Zr (OH) ₄when constant with the total mole number of zirconium-n-propylate, adjustment Zr (OH) ₄be 1:0.1 with the mol ratio of zirconium-n-propylate.Each physicochemical property of gained fat is in table 1.

Embodiment 17

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 5, unlike, at Zr (OH) ₄when constant with the total mole number of zirconium-n-propylate, adjustment Zr (OH) ₄be 1:10 with the mol ratio of zirconium-n-propylate.Each physicochemical property of gained fat is in table 1.

Embodiment 18

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 5, unlike, zirconium-n-propylate is replaced with equimolar Zr (OH) ₄.Each physicochemical property of gained fat is in table 1.

Embodiment 19

Complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 5, unlike, by Zr (OH) ₄replace with equimolar zirconium-n-propylate.Each physicochemical property of gained fat is in table 1.

Comparative example 1

Composite calcium-sulfonate-batetrapolyurea polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number calcium total basicnumber is that the overbased calcium sulphonate of 400mgKOH/g replaces, Zr (OH) used ₄with Ca (OH) ₂replace, adjust consumption simultaneously and make each component content consistent with embodiment 1, each performance data of lubricating grease finished product obtained is in table 1.

In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate 36.8 % by weight; Two polyureas 2.4 % by weight; Lubricating base oil 51.9 % by weight; 12-oxystearic acid calcium 2.6 % by weight; Terephthalic acid calcium 6.3 % by weight.

Comparative example 2

Composite calcium-sulfonate-batetrapolyurea polyurea grease is prepared according to the method for embodiment 5, unlike, overbased calcium alkyl-salicylate total basicnumber is the calcium sulfonate with high base number replacement of 320mgKOH/g, zirconium-n-propylate used and Zr (OH) ₄all with Ca (OH) ₂replace, adjust consumption simultaneously and make each component content consistent with embodiment 5, each performance data of lubricating grease finished product obtained is in table 1.

In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate 50.6 % by weight; Two polyureas 3.3 % by weight; Lubricating base oil 33.4 % by weight; 12-oxystearic acid calcium 3.6 % by weight; 2-methyl isophthalic acid, 4-phthalic acid calcium 9.1 % by weight.

Embodiment 1 and comparative example 1 are compared, embodiment 5 and comparative example 2 are compared, can find out, complex calcium sulfonate of the present invention-prolongation Drawing cone the in-degree of calcium naphthenate zirconium base polyurea grease and the difference of Drawing cone in-degree are less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, water drenches number of dropouts and is less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, salt-fog test is better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, water resistant spraying value is less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, Stencil oil-dividing value is less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, tetra-ball machine test value is greater than Composite calcium-sulfonate-batetrapolyurea polyurea grease, the bearing lubrication life-span is greater than Composite calcium-sulfonate-batetrapolyurea polyurea grease, the mechanical stability of complex calcium sulfonate of the present invention-calcium naphthenate zirconium base polyurea grease is described, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear, lubricating life is all better than Composite calcium-sulfonate-batetrapolyurea polyurea grease.

Embodiment 1 is compared can find out with embodiment 2 and embodiment 11 respectively, complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease prepared by original position, there is better water resisting property and adhesivity, colloid stability, there is longer lubricating life; Embodiment 1 is compared can find out with embodiment 14 and embodiment 15 respectively, transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, butanols, Virahol, boric acid, acetic acid and water, complex calcium sulfonate-calcium naphthenate zirconium base the polyurea grease of preparation, there is better water resisting property and adhesivity, colloid stability, there is longer lubricating life; Embodiment 5 is compared can find out with embodiment 16 and embodiment 17 respectively, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5, complex calcium sulfonate-calcium naphthenate zirconium base the polyurea grease of preparation, there is better mechanical stability, water resisting property and adhesivity, colloid stability, there is longer lubricating life; Embodiment 5 is compared can find out with embodiment 18 and embodiment 19 respectively, the raw material of zirconium is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, complex calcium sulfonate-calcium naphthenate zirconium base the polyurea grease of preparation, there is better mechanical stability, water resisting property and adhesivity, colloid stability, there is longer lubricating life.

Table 1 each lubricating grease properties of sample data

Each indication test method: outward appearance: range estimation; Dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion:

GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643;

Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.

Table 1(continues) each lubricating grease properties of sample data

As can be seen from Figure 1, the lubricating grease of embodiment 5 preparation is at 873cm ^-1-886cm ^-1there is crystal form calcium carbonate charateristic avsorption band in place.Meanwhile, at 3300cm ^-1-3323cm ^-1the peak at place is the stretching vibration absorption peak of-NH-in two polyureas molecules.

Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.

It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.

In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims

1. complex calcium sulfonate-calcium naphthenate zirconium base polyurea grease, is characterized in that, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The zirconates of the higher fatty acid of 1-10 % by weight; The zirconates of the aromatic acid of 1-15 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the zirconates of lower fatty acid, wherein, the zirconates of described higher fatty acid is reacted by higher fatty acid and component A to form, the zirconates of described aromatic acid is reacted by aromatic acid and component A to form, the zirconates of described small molecules mineral acid and/or lower fatty acid is reacted by small molecules mineral acid and/or lower fatty acid and component A to form, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.

2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-60 % by weight; The zirconates of the higher fatty acid of 2-6 % by weight; The zirconates of the aromatic acid of 2-10 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the zirconates of lower fatty acid.

3. lubricating grease according to claim 1 and 2, wherein, described non-newtonian fluid calcium sulphonate-calcium naphthenate is at infrared spectrum 873cm ^-1-886cm ^-1there is crystal form calcium carbonate charateristic avsorption band in place.

4. lubricating grease according to claim 3, wherein, described non-newtonian fluid calcium sulphonate-calcium naphthenate is transformed by newton's body calcium sulphonate and newton's body calcium naphthenate and obtains, and the total basicnumber of described non-newtonian fluid calcium sulphonate-calcium naphthenate is 250-450mgKOH/g.

5. lubricating grease according to claim 1 and 2, wherein, straight chain fatty acid or the hydroxy fatty acid of described higher fatty acid to be carbon number be 8-20.

6. lubricating grease according to claim 5, wherein, described higher fatty acid is selected from least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.

7. lubricating grease according to claim 1 and 2, wherein, described aromatic acid is that replace or unsubstituted aromatic acid, and substituting group is at least one in the alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, and the molecular weight of described aromatic acid is less than or equal to 550.

8. according to lubricating grease according to claim 7, wherein, described aromatic acid is selected from least one in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.

9. lubricating grease according to claim 1 and 2, wherein, the molecular weight of small molecules mineral acid and lower fatty acid is less than or equal to 150.

10. lubricating grease according to claim 9, wherein, described small molecules mineral acid is selected from least one in boric acid, phosphoric acid, sulfuric acid, and described lower fatty acid is selected from least one in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.

11. lubricating grease according to claim 1 and 2, wherein, described component A is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, and in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10.

12. lubricating grease according to claim 11, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5.

13. lubricating grease according to claim 1 and 2, wherein, oxide compound and/or the oxyhydroxide of zirconium are selected from ZrO ₂, ZrO (OH) ₂, Zr (OH) ₄and at least one in their hydrate.

14. lubricating grease according to claim 1 and 2, wherein, the general formula of described zirconium alkoxide is Zr (OR ₁) ₄, R ₁for the alkyl of C1-C10.

15. lubricating grease according to claim 14, wherein, described zirconium alkoxide is selected from least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and Pentyl alcohol zirconium.

16. lubricating grease according to claim 1 and 2, wherein, described polyurea compound is at least one in two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.

17. lubricating grease according to claim 16, wherein, described polyurea compound is two polyurea compounds, and this compound has following structure:

Wherein, R ¹, R ^{1 '}alkyl, cycloalkyl or aryl, R ³arylidene, alkylidene group or cycloalkylidene.

18. lubricating grease according to claim 17, wherein, R ¹, R ^{1 '}be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8-24; R ³the arylidene of 6-30, alkylidene group or cycloalkylidene.

19. lubricating grease according to claim 18, wherein, R ¹, R ^{1 '}be the alkyl of phenyl or C1-C3 or the phenyl of halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18, R ³be in at least one.

The preparation method of the complex calcium sulfonate in 20. claim 1-19 described in any one-calcium naphthenate zirconium base polyurea grease, it is characterized in that, the method comprises: by the zirconates of the zirconates of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, aromatic acid, polyurea compound and part basis, oily and optionally small molecules mineral acid and/or lower fatty acid zirconates mixes, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.

The preparation method of 21. 1 kinds of complex calcium sulfonate-calcium naphthenate zirconium base polyurea greases, it is characterized in that, the method comprises:

22. methods according to claim 21, wherein, in step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 60-90 DEG C of constant temperature 60-90 minute.

23. methods according to claim 21, wherein, in step (2), at 85-100 DEG C, add component A, add higher fatty acid, stir 5-20 minute, add aromatic acid and optionally small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 100-120 DEG C of dehydration, described component A is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10.

24. methods according to claim 23, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5.

25. methods according to claim 21, wherein, in step (3), add base oil and monoamine in step (2) gained mixture, stir 2-8 minute, then add vulcabond, and stir 2-8 minute, the mol ratio of vulcabond and monoamine is 1:2.

26. methods according to claim 21, wherein, in step (4), first at 100-120 DEG C of constant temperature 10-20 minute, are finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.

27. methods according to claim 21, wherein, described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and the total basicnumber of described newton's body calcium sulphonate is 250-450mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and the total basicnumber of described newton's body calcium naphthenate is 250-450mgKOH/g.

28. methods according to claim 21, wherein, described transforming agent is selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water, and the add-on of transforming agent is the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.

29. methods according to claim 28, wherein, described transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water, and the add-on of transforming agent is the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.

30. methods according to claim 21, wherein, the structural formula of described monoamine is R ¹-NH2, R ^{1 '}-NH ₂, wherein, R ¹, R ^{1 '}be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18.

31. methods according to claim 30, wherein, described monoamine is the arylamine being selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide and/or para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.

32. methods according to claim 21, wherein, the structural formula of described diamines is NH ₂-R ²-NH ₂, wherein, R ²the alkylidene group of to be carbon number be 2-8, or phenylene or biphenylene.

33. methods according to claim 32, wherein, described diamines be selected from Ursol D, O-Phenylene Diamine, 4,4-benzidines aromatic amine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.

34. methods according to claim 21, wherein, the structure of described vulcabond is OCN-R ³-NCO, R ³the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.

35. methods according to claim 34, wherein, described vulcabond is selected from least one in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene vulcabond, dicyclohexyl methane diisocyanate and an xylylene diisocyanate.

36. complex calcium sulfonate-calcium naphthenate zirconium base the polyurea greases obtained by the method in claim 21-35 described in any one.