CN104560321B

CN104560321B - A kind of polyurea grease of sulfoacid calcium calcium naphthenate zirconium base six and preparation method thereof

Info

Publication number: CN104560321B
Application number: CN201310521458.7A
Authority: CN
Inventors: 何懿峰; 孙洪伟; 段庆华; 刘中其; 张建荣; 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: 2017-09-29
Anticipated expiration: 2033-10-29
Also published as: CN104560321A

Abstract

The invention discloses a kind of polyurea grease of sulfoacid calcium calcium naphthenate zirconium base six, including：10 70 weight % non-newtonian fluid sulfoacid calcium calcium naphthenate；The zirconates of 1 10 weight % higher fatty acids；1 15 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；0.5 30 weight % polyurea compound；10 80 weight % base oil, wherein, the zirconates of the zirconates of higher fatty acids, small molecule inorganic acid and/or lower fatty acid is formed by higher fatty acids, small molecule inorganic acid and/or lower fatty acid and component A reactions respectively, component A is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium, and polyurea compound is six polyurea compounds.Also disclose the lubricating grease of preparation of greases method and its preparation.Lubricating grease of the present invention, there is the performances such as more preferable mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, there is longer lubricating life.

Description

A kind of sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six and preparation method thereof

Technical field

The present invention relates to lubricating grease, in particular it relates to a kind of sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six and its system Preparation Method.

Background technology

Sulfoacid calcium is used as the history of detersive and the antirust agent existing decades of lubricating oil, is widely used in internal combustion engine lubrication The additive of oil, its technology development mainly makes its height alkalization, is exactly alkyl benzene sulphonate of the calcium carbonate with surface-active Calcium or alkyl carboxylic acid calcium turn into a kind of colloidal dispersion system to be distributed in flux oil.Calcium sulfonate with high base number according to the mode of production not It is same to be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate.Calcium mahogany sulfonate is to use oleum or SO₃Sulfonation mineral lubricating oil is produced Accessory substance mahogany acid during white oil, through with Ca (OH)₂React, the contour alkalization technology that is carbonated and obtain；Calcium alkylbenzenesulfonate is to use Oleum or SO₃The alkylbenzene of sulfonation synthesis, the alkyl benzene sulphonate of generation is passed through and Ca (OH)₂React, be carbonated contour alkalization skill Art and obtain.

Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusivity, can To be used as the detersive of lubricating oil, the additive of IC engine lubricating oil is widely used in, the development of its technology mainly makes its high-alkali Change, exactly calcium carbonate, which is distributed to the naphthenic acid calcium with surface-active in flux oil, turns into a kind of colloidal dispersion system.It is high Base number calcium naphthenate mostly be the acidic components extracted from the distillate that crude distillation is obtained, through with Ca (OH)₂Reaction, carbonating Contour alkalization technology and obtain, about prepare Patents have CN1465560 etc..

Using calcium sulfonate with high base number be raw material produce lubricating grease, because its have excellent high temperature performance, mechanical stability, Colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, have caused domestic and international profit The extensive concern of consistent lubricant industry, although however, high base number composite calcium sulfonate base grease has very excellent combination property, 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, together When, the requirement more and more higher with people to environmental protection, in calcium sulfonate with high base number production process must through sulfonation process to ring The pollution in border is also increasingly subject to the concern of people.Find a kind of performance it is similar with high base number composite calcium sulfonate base grease but can Mitigating the lubricating grease of above mentioned problem turns into the big problem that people face at present.

Zirconium belongs to Group IVB as a kind of transition metal, positioned at the 5th cycle.Zirconium-containing compound has excellent lubrication Effect, is often used as lubricating additive, such as CN101113382 and JP1973038444 add the oxide of zirconium as lubricant Agent improves abrasiveness；WO2007143414 and US20060063682, which describe zirconium tetrafluoride, to be turned into as wear reducing additive One of component of lubricant；It is resistance to heavy well that US20060254823 has found that the lubricant containing 2 ethyl hexanoic acid zirconates is shown Load and abrasion resistance；US20050043189 has found that fluozirconate such as fluorine zirconic acid aluminium can be used in lubricant as oxidation retarder In；DE102004021812 has found that the inorganic salts such as zirconium carbonate, sulfonic acid zirconium or basic zirconium phosphate are added to inside lubricating grease and can improved Abrasion resistance.

The content of the invention

It is an object of the invention to provide a kind of mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and Extreme pressure anti-wear is preferable, and lubricating life is longer, and cost is low, simple and environmentally-friendly lubricating grease of preparation technology and preparation method thereof.

The present inventor has found under study for action, on the basis of lubricating grease weight, including following components：10-70 weight % Non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 weight % small molecule inorganic acid And/or the zirconates of lower fatty acid；0.5-30 weight % polyurea compound；10-80 weight % base oil, wherein, the height The zirconates of level aliphatic acid is to be formed by higher fatty acids with component A reactions, the small molecule inorganic acid and/or lower fatty acid Zirconates is to be formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, and the component A is the oxide of zirconium, zirconium At least one of hydroxide and zirconium alkoxide, the polyurea compound are six polyurea compounds.The lubricating grease has preferable Mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and extreme pressure anti-wear, with the longer lubrication longevity Life, and cost is low, preparation technology is simple and environmentally-friendly.

Therefore, to achieve these goals, on the one hand, poly- the invention provides a kind of sulfoacid calcium-calcium naphthenate zirconium base six Urea grease, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate； The zirconates of 1-10 weight % higher fatty acids；1-15 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；0.5- 30 weight % polyurea compound；10-80 weight % base oil, wherein, the zirconates of the higher fatty acids is by higher aliphatic Acid reacts with component A to be formed, the zirconates of the small molecule inorganic acid and/or lower fatty acid be by small molecule inorganic acid and/or Lower fatty acid and component A reaction are formed, the component A in oxide, the hydroxide of zirconium and the zirconium alkoxide of zirconium extremely Few one kind, the polyurea compound is six polyurea compounds.

Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid sulfoacid calcium-ring Alkanoic acid calcium；The zirconates of 2-6 weight % higher fatty acids；2-10 weight % small molecule inorganic acid and/or the zirconium of lower fatty acid Salt；1-20 weight % six polyurea compounds；20-70 weight % base oil.

Second aspect, the invention provides the preparation of sulfoacid calcium as described above-polyurea grease of calcium naphthenate zirconium base six Method, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid and/or The zirconates of lower fatty acid, six polyurea compounds and part basis oil are well mixed, in 180-230 DEG C of constant temperature refining, add remaining Base oil is measured, necessary additive is added, obtains finished product.

The third aspect, should the invention provides a kind of preparation method of sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six Method includes：

（1）Newton body sulfoacid calcium, newton body calcium naphthenate, base oil and transforming agent are mixed, material retrogradation is treated in heating；

（2）In step（1）Component A is added in products therefrom, add higher fatty acids and small molecule inorganic acid and/or Lower fatty acid is reacted, and heat up dehydration after reaction, and the component A is oxide, the hydroxide and alkoxy of zirconium of zirconium At least one of zirconium；

（3）In step（2）Base oil and diisocyanate are added in gained mixture, monoamine, diamines is then sequentially added Reacted with diisocyanate；

（4）By step（3）Gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds base oil, adds necessary add Plus agent, obtain finished product.

Fourth aspect, the invention provides the sulfoacid calcium as made from method as described above-polyureas of calcium naphthenate zirconium base six Lubricating grease.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six of the present invention, compared to the polyurea grease of sulfoacid calcium base six, has The performances such as more preferable mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, with longer Lubricating life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, and product quality is stable.

Other features and advantages of the present invention will be described in detail in subsequent embodiment part.

Brief description of the drawings

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

Embodiment

The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The invention provides a kind of sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six, this lubricating grease employs oil Sulfoacid calcium and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, simultaneously containing compound zirconium Six polyurea compounds that thickening agent, isocyanates and amine reaction are produced.

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

On the one hand, the invention provides a kind of sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six, using lubricating grease weight as Benchmark, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；1-10 weight % higher fatty acids Zirconates；1-15 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；0.5-30 weight % polyurea compound；10- 80 weight % base oil, wherein, the zirconates of higher fatty acids is to be formed by higher fatty acids with component A reactions, and small molecule is inorganic The zirconates of acid and/or lower fatty acid is to be formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, and component A is At least one of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide, polyurea compound are six polyurea compounds.

Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid sulfoacid calcium-ring Alkanoic acid calcium；The zirconates of 2-6 weight % higher fatty acids；2-10 weight % small molecule inorganic acid and/or the zirconium of lower fatty acid Salt；1-20 weight % six polyurea compounds；20-70 weight % base oil；It is highly preferred that on the basis of lubricating grease weight, bag Include following components：30-55 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconium of 2.2-4.2 weight % higher fatty acids Salt；3-8 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；2-10 weight % six polyurea compounds；30-60 Weight % base oil.

Non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1There is the suction of crystal form calcium carbonate feature in place Peak is received, total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid sulfonic acid Calcium-calcium naphthenate is to be obtained by newton body sulfoacid calcium and newton body calcium naphthenate by transforming agent conversion.And newton body sulfoacid calcium, Contain unformed calcium carbonate in newton body calcium naphthenate, in infrared spectrum 860cm^-1-865cm^-1It is special that unformed calcium carbonate occurs in place Levy absworption peak.Newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g- 450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis Calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid The base number of sulfoacid calcium-calcium naphthenate is averaged for the base number of newton body sulfoacid calcium with the weight of the base number of newton body calcium naphthenate Value.

In the present invention, higher fatty acids is that carbon number is 8-20, preferably 10-16 straight chain fatty acid or hydroxy fatty acid, example Such as at least one of laurate, palmitic acid, stearic acid, 12- hydroxy stearic acids, eicosyl carboxylic acid, preferably 12- hydroxyls are hard Resin acid.

In the present invention, the molecular weight of small molecule inorganic acid or lower fatty acid is less than or equal to 150.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 the oxide and/or hydroxide and alcoxyl that component A is zirconium During the mixture of base zirconium, i.e., the raw material of zirconium for zirconium oxide and/or hydroxide and zirconium alkoxide mixture when, one can be entered Step improves mechanical stability, water-resistance and adhesiveness, colloid stability and the lubricating life of lubricating grease, and therefore, component A is preferably The oxide and/or hydroxide and the mixture of zirconium alkoxide of zirconium, wherein, in terms of zirconium, the oxide and/or hydroxide of zirconium Mol ratio with zirconium alkoxide is preferably 1：0.1-10, more preferably 1：0.2-8, is still more preferably 1：0.5-5, in zirconium In the case of the preferred molar ratio of oxide and/or hydroxide and zirconium alkoxide, the machinery of lubricating grease can be further improved Stability, water-resistance and adhesiveness, colloid stability and lubricating life.

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, it can pass through ZrOX₂· 8H₂O（X is F, Cl, Br or I）Or ZrO (NO₃)₂·2H₂O etc. reacts with alkali to be obtained, wherein, alkali can be NaOH, KOH, dense ammonia Water etc., preferably ZrOCl₂·8H₂O and NaOH reacts.

In the present invention, the formula of zirconium alkoxide can be Zr (OR₁)₄, R₁Can be C1-C10 alkyl, preferably C2-C6 Alkyl；It is highly preferred that zirconium alkoxide in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and n-amyl alcohol zirconium extremely Few one kind.

In the present invention, six polyurea compound preferably has following structure：

Wherein, R1 can be alkyl, cycloalkyl or aryl, and the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10- 18, aryl can be the phenyl of phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen substitution.

Wherein, R²Can 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, R³Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R³More preferably In It is at least one.

Above-mentioned six polyurea compound can be obtained using the thinkable various methods of those skilled in the art institute, for example can be with Prepared according to the CN103060067A methods recorded.

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

Various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the present invention.Its In, the preferred arylamine kind antioxidant of antioxidant accounts for the 0.01-5% of lubricating grease gross weight, preferably 0.1-2.5%, can be diphenylamines, At least one of phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease The 0.5-12% of gross weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethyl-ne Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid At least one of calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil At least one of barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.

In the present invention, for non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid and/ Or zirconates, six polyurea compounds, base oil and the additive of lower fatty acid are as described above, will not be repeated 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 used Base oil total amount, in the present invention, part basis oil and the weight ratio preferably 1 of surplus base oil：0.1-5.

For non-newtonian fluid sulfoacid calcium-calcium naphthenate, conversion can be passed through by newton body sulfoacid calcium, newton body calcium naphthenate Agent conversion is obtained, for example, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, adding institute The transforming agent needed is reacted, after all transforming agents are added, and in 60-90 DEG C of constant temperature 60-90 minutes, then heats to 100-120 DEG C dehydration.

Step（1）In, by newton body sulfoacid calcium, newton body calcium naphthenate, the oily Hybrid Heating of part basis to 50-80 DEG C, It is preferred that constant temperature 10-30 minutes, the transforming agent needed for adding is reacted, stirring 8-12 minutes after every kind of transforming agent are preferably added, After all transforming agents are added, in 60-90 DEG C of constant temperature 60-90 minutes.

Step of the present invention（1）In, for newton body sulfoacid calcium and newton body calcium naphthenate weight ratio without particular/special requirement, it is excellent Elect 1 as：0.25-4.The weight ratio of newton body sulfoacid calcium and the gross weight of newton body calcium naphthenate and part basis oil is preferably 1： 0.1-3。

In the present invention, newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/ G-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or conjunction Into calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.

The transforming agent be preferably selected from fatty alcohol, aliphatic acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, At least one of phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonates and water；It is more excellent Fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine selected from C1-C5, C1-C5 ether, boric acid, C1-C10 alkyl phosphonic acid, C2-C16 di alkyl phosphonic acid, C6-C20 arylphosphonic acid, C12-C24 At least one of diaryl phosphonic acids, C7-C20 aromatic alcohol, C7-C20 aromatic amine, C8-C20 alkyl benzene sulphonates and water；More At least one further preferably in DBSA, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water Kind.The addition of transforming agent is preferably the 2-30% of newton body sulfoacid calcium and newton body calcium naphthenate gross weight, more preferably newton The 6-22% of body sulfoacid calcium and newton body calcium naphthenate gross weight.

In the present invention, fatty alcohol includes the fatty alcohol of straight chain, side chain and ring-type, aliphatic acid, aliphatic ketone, fatty aldehyde, fat Amine is similarly.

As it was previously stated, the present inventor has been surprisingly found that under study for action, step（2）In, when the oxide that component A is zirconium And/or hydroxide and zirconium alkoxide mixture when, i.e., the raw material of zirconium be zirconium oxide and/or hydroxide and alkoxy During the mixture of zirconium, can further improve mechanical stability, water-resistance and the adhesiveness of obtained lubricating grease, colloid stability and Lubricating life, it is therefore preferred that step（2）In, at 85-100 DEG C, component A is added, higher fatty acids is added, 5-20 is stirred Minute, small molecule inorganic acid and/or lower fatty acid are added, is stirred 5-20 minutes, is warming up to 100-120 DEG C, preferably keeps 30- 60 minutes, dehydration, the component A was the oxide of zirconium and/or the mixture of hydroxide and zirconium alkoxide, in terms of zirconium, zirconium The mol ratio of oxide and/or hydroxide and zirconium alkoxide is preferably 1：0.1-10, more preferably 1：0.2-8, further Preferably 1：0.5-5.Wherein, higher fatty acids can be exchanged with the addition sequence of small molecule inorganic acid and/or lower fatty acid.

In the present invention, higher fatty acids, small molecule inorganic acid, lower fatty acid, the oxide of zirconium, the hydroxide of zirconium and Zirconium alkoxide is as it was previously stated, will not be repeated here.

In the present invention, higher fatty acids and small molecule inorganic acid and/or the H of lower fatty acid⁺The amount of total material is equal to complete Portion neutralizes the H needed for oxide, the hydroxide of zirconium and the zirconium alkoxide of zirconium⁺Molal quantity, but oxide, the hydrogen-oxygen of zirconium of zirconium Compound and zirconium alkoxide can excess 1-10% relative to higher fatty acids and small molecule inorganic acid and/or lower fatty acid.

In the present invention, the addition of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide is preferably newton body sulfoacid calcium With the 1-15% of newton body calcium naphthenate gross weight；With H⁺Material gauge, higher fatty acids and small molecule inorganic acid and/or The mol ratio of lower fatty acid is preferably 1：1-10.

Step（3）In, in step（2）Base oil and diisocyanate are added in gained mixture, list is then sequentially added Amine, diamines and diisocyanate are reacted, and are in step（2）Six polyurea compounds are prepared in gained mixture.

The method of six polyurea compounds is prepared without particular/special requirement, various methods commonly used in the art can be used.For example, , can be in step in the present invention（2）Base oil and diisocyanate are added in gained mixture, monoamine, 2-8 points of stirring is added Clock, adds diamines, stirs 2-8 minutes, adds the diisocyanate being dissolved in base oil, stirs 2-8 minutes, each time added Diisocyanate, monoamine, the mol ratio of diamines and diisocyanate be 2:2:2:1, those skilled in the art should understand that , the mol ratio can fluctuate in the range of ± 5%.

Step of the present invention（3）In, the diisocyanate added twice can be the same or different, in order to easy to operate, The diisocyanate that preferably twice is added is identical.

The diisocyanate structure is OCN-R³- NCO, R³Can be that carbon number is 6-30, preferably 6-20 arlydene, Asia Alkyl or cycloalkylidene, be preferably Deng. Such as described diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), 1,6- Asia Hexyl diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate（HMDI）With an xylylene diisocyanate（XDI）Deng At least one of.

The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, and structural formula is R¹-NH₂、R^1’-NH₂, R therein¹、R^1’Can To be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, aryl can be phenyl or Substituted phenyl, preferably phenyl or C1-C3 alkyl or the phenyl of halogen substitution.It is preferred that monoamine can be selected from aniline, m-chloro Aniline, parachloroanilinum, the arylamine of para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, octadecylamine fatty amine.

The diamines can be fatty amine or arylamine, and structural formula is NH₂-R²-NH₂, R therein²Can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, and preferably 2-8, arlydene can be phenylene or biphenylene.It is preferred that diamines can Be selected from p-phenylenediamine, o-phenylenediamine, the aromatic amine of 4,4 '-benzidine and/or selected from ethylenediamine, propane diamine, 1,6- oneself The straight-chain fatty amine of diamines.

Step（4）In, first in 100-120 DEG C of constant temperature 10-20 minutes, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minutes； Base oil is added, treats that temperature is cooled to 100-120 DEG C, necessary additive, stirring, circulating filtration, homogenizing, degassing is added.

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

Fourth aspect, present invention also offers sulfoacid calcium-ring made from the preparation method provided as third aspect present invention The polyurea grease of alkanoic acid calcium zirconium base six.

Compared with the sulfoacid calcium as made from the preparation method that second aspect is provided-polyurea grease of calcium naphthenate zirconium base six, Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six made from the preparation method that the third aspect is provided has preferably mechanical stable Property, water-resistance and adhesiveness, colloid stability, and with longer lubricating life.

Embodiment

The present invention is further illustrated for following embodiment, but and is not so limited the present invention.

In the following Examples and Comparative Examples：

Non-newtonian fluid sulfoacid calcium-calcium naphthenate %=（Overbased or calcium sulfonate with high base number raw material weight+overbased or height Base number calcium naphthenate raw material weight+transforming agent gross weight）/ lubricating grease gross weight × 100%.Transforming agent is included in non-newtonian fluid sulphur In the content of sour calcium-calcium naphthenate.

The content of the zirconates of higher fatty acids and the zirconates of small molecule inorganic acid and/or lower fatty acid, according to added Higher fatty acids and the oxide of small molecule inorganic acid and/or lower fatty acid and zirconium, the hydroxide of zirconium and the alcoxyl entered The amount that base zirconium reacts generation zirconates completely is calculated.

Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd, also may be used To be prepared according to method disclosed in CN101885677A.

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

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

Embodiment 1

The present embodiment is used for the sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six for illustrating prepared by the present invention.

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 30kg）；Aphthenic acids （Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；Boron Acid（2.32kg）；Octadecylamine（0.84kg）；Ethylenediamine（0.19kg）；MDI（1.17kg）；HVI500SN lubricating base oils（100℃ Kinematic viscosity is 11mm²/ s, 18kg）.

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control exists 50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；60 DEG C are warming up to, Constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, the Zr (OH) that solid content is 20 weight % is added₄Suspension 19.5kg, stirring 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, is stirred Mix and 110 DEG C are warming up under 10 minutes, stirring, kept for 45 minutes, dehydration；Add 2kg HVI500SN lubricating base oils and 0.78kg MDI, quick stirring 4 minutes, quick stirring is lower to add 0.84kg octadecylamines, stirs 4 minutes, and quick stirring is lower to be added 0.19kg ethylenediamines, are stirred 4 minutes, add the 0.39kg MDI being dissolved in 2kg HVI500SN lubricating base oils, successively institute Plus MDI, octadecylamine, the ratio between ethylenediamine and the MDI amount of material be 2:2:2:1,120 DEG C of constant temperature 20 minutes, is finally warming up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, Homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.3；The weight % of six polyureas 2.5；The weight % of lubricating base oil 53.6；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；Boron The sour weight % of oxygen zirconium 4.0.

Embodiment 2

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control exists 50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；60 DEG C are warming up to, Constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, the Zr (OH) that solid content is 20 weight % is added₄Suspension 19.5kg, stirring 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, is stirred Mix and 110 DEG C are warming up under 10 minutes, stirring, kept for 45 minutes, dehydration.

In another volume be 30L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg HVI500SN lubricating base oils and 0.78kg MDI, are warming up to 120 DEG C, quick stirring 4 minutes, and quick stirring is lower to add 0.84kg Octadecylamine, is stirred 4 minutes, and quick stirring is lower to add 0.19kg ethylenediamines, stirs 4 minutes, adds the HVI500SN for being dissolved in 2kg 0.39kgMDI in lubricating base oil, the ratio between added MDI, octadecylamine, ethylenediamine and MDI amount of material is 2 successively:2: 2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.

The polyureas of gained six is all squeezed into a upper kettle, stirred, 200 DEG C of constant temperature is finally warming up to 10 minutes.So Afterwards, remaining HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product. Assay is shown in Table 1.

The six polyureas molecular structural formulas contained in component are：

Embodiment 3

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total alkali It is worth for 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 20kg）；N-butanol （2.8kg）；Acetic acid（0.56kg）；Zirconium-n-butylate（7.83k）；Zr(OH)₄（0.65kg）；Stearic acid（1.9kg）；Boric acid （2.32kg）；Lauryl amine（0.66kg）；Ethylenediamine（0.21kg）；MDI（1.33kg）；HVI500SN lubricating base oils（100 DEG C of fortune Kinetic viscosity is 11mm²/ s, 28kg）.

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The naphthenate with superhigh base number calcium and 20kg for being 320mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers HVI150BS lubricating base oils, stirring, heat to 80 DEG C, constant temperature 10 minutes；2.8kg n-butanols are added, temperature control exists 80 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；90 DEG C are warming up to, Constant temperature 60 minutes, material retrogradation；Successively add the Zr (OH) of 7.83kg zirconium-n-butylates and solid content for 20 weight %₄Suspension 3.25kg, in terms of zirconium, Zr (OH)₄Mol ratio with zirconium-n-butylate is 1：5, stir 10 minutes；Add 1.9kg stearic acid, stirring 10 minutes；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, is stirred 10 minutes, 120 DEG C, holding are warming up under stirring 30 minutes, dehydration；Add 2kg HVI500SN lubricating base oils and 0.89kg MDI, quick stirring 8 minutes, under quick stirring 0.66kg lauryl amines are added, are stirred 8 minutes, quick stirring is lower to add 0.21kg ethylenediamines, stirs 8 minutes, addition is dissolved in 2kg HVI500SN lubricating base oils in 0.45kgMDI, successively added MDI, octadecylamine, ethylenediamine and MDI material amount The ratio between be 2:2:2:1,100 DEG C of constant temperature 10 minutes, is finally warming up to 230 DEG C of constant temperature 5 minutes.Then, 160 DEG C, addition are cooled to Remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Examine knot Fruit is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.3；The weight % of six polyureas 2.5；The weight % of lubricating base oil 53.7；The weight % of zirconyl stearate 2.5；Boric acid oxygen zirconium 4.0 weight %.

Embodiment 4

Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Total alkali It is worth for 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 25kg）；Dodecyl Benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Ethanol zirconium（2.21kg）；Zr(OH)₄（2.6kg）；12- hydroxy stearic acids（2kg）； Boric acid（2.32kg）；Octadecylamine（1kg）；Ethylenediamine（0.22kg）；TDI（0.97kg）；HVI500SN lubricating base oils（100℃ Kinematic viscosity is 11mm²/ s, 23kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, sulfoacid calcium Use the calcium sulfonate with high base number that total base number is 320mgKOH/g；Aphthenic acids is replaced with DBSA；Use toluene diisocyanate Acid esters（TDI）Instead of MDI；Add Zr (OH)₄When be additionally added ethanol zirconium, in terms of zirconium, Zr (OH)₄Mol ratio with ethanol zirconium is 1： 0.5；The consumption of each composition is as above.Assay is shown in Table 1.

Embodiment 5

Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total base number For 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 15kg）；Aphthenic acids（Total acid It is worth for 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zirconium-n-propylate（4.0kg）；Zr(OH)₄（2.0kg）；12- hydroxy stearates Acid（2kg）；Boric acid（2.32kg）；Octadecylamine（0.84kg）；Ethylenediamine（0.19kg）；MDI（1.17kg）；HVI500SN lubricates base Plinth oil（100 DEG C of kinematic viscosity are 11mm²/ s, 7kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, sulfoacid calcium Using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate uses the high base number ring that total base number is 320mgKOH/g Alkanoic acid calcium；Add Zr (OH)₄When be additionally added zirconium-n-propylate, in terms of zirconium, Zr (OH)₄Mol ratio with zirconium-n-propylate is 1：1；It is each into The consumption divided is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 52.5；The weight % of six polyureas 3.5；The weight % of lubricating base oil 34.6；The weight % of 12- hydroxy stearic acid oxygen zirconium 3.7；Boron The sour weight % of oxygen zirconium 5.7.

Embodiment 6

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total alkali It is worth for 400mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 25kg）；Aphthenic acids （Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；Boron Acid（2.32kg）；Octadecylamine（2.52kg）；Ethylenediamine（0.56kg）；MDI（3.51kg）；HVI500SN lubricating base oils（100℃ Kinematic viscosity is 11mm²/ s, 18.6kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, each composition Consumption as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.3；The weight % of six polyureas 7.4；The weight % of lubricating base oil 48.7；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；Boron The sour weight % of oxygen zirconium 4.0.

Embodiment 7

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number For 320mgKOH/g, 24kg）；Poly alpha olefine synthetic oil PAO40（100 DEG C of kinematic viscosity are 40mm²/ s, 30kg）；Aphthenic acids（Always Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；Boric acid （2.32kg）；Octadecylamine（0.84kg）；Ethylenediamine（0.19kg）；MDI（1.17kg）；Poly alpha olefine synthetic oil PAO10（100℃ Kinematic viscosity is 11mm²/ s, 9kg）；Two thio Acidic phosphates zinc（2kg）；Molybdenum dialkyldithiocarbamacompositions（1kg）；Two Tungsten sulfide（2kg）；Two tungsten selenides（2kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, aphthenic acids Calcium uses the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g；Use poly alpha olefine synthetic oil PAO40（100 DEG C of motions are viscous Spend for 40mm²/s）With poly alpha olefine synthetic oil PAO10（100 DEG C of kinematic viscosity are 11mm²/s）Respectively instead of HVI150BS（100 DEG C kinematic viscosity is 31mm²/s）And HVI500SN（100 DEG C of kinematic viscosity are 11mm²/s）；And treat that temperature is cooled to 110 DEG C, 2kg two thio Acidic phosphates zinc are added, are stirred 10 minutes, 1kg molybdenum dialkyldithiocarbamacompositions, stirring 10 are added Minute, 2kg tungsten disulfide is added, is stirred 10 minutes, 2kg two tungsten selenides are added, stirred 10 minutes, 0.2kg pair is added, Right '-di-iso-octyldiphenylamine, is stirred 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The consumption of each composition is such as On.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 38.0；The weight % of six polyureas 2.5；The weight % of lubricating base oil 44.5；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；Boron The sour weight % of oxygen zirconium 4.1；The two thio weight % of Acidic phosphates zinc 2.3；The weight % of molybdenum dialkyldithiocarbamacompositions 1.1；Two sulphur Change the weight % of tungsten 2.3；The weight % of two tungsten selenide 2.3；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 8

Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total base number For 400mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 15kg）；Aphthenic acids（Always Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；Boric acid （2.32kg）；Octadecylamine（0.84kg）；Ethylenediamine（0.19kg）；MDI（1.17kg）；HVI500SN lubricating base oils（100 DEG C of fortune Kinetic viscosity is 11mm²/ s, 33kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, sulfoacid calcium Use the calcium sulfonate with high base number that total base number is 320mgKOH/g；The consumption of each composition is as above.Assay is shown in Table 1.

Embodiment 9

Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number is 320mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 20kg）；Aphthenic acids（Total acid It is worth for 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（6.3kg）；12- hydroxy stearic acids（2kg）；Boric acid （2.32kg）；Phosphoric acid（1kg）；Octadecylamine（0.84kg）；Ethylenediamine（0.19kg）；MDI（1.17kg）；HVI500SN lubrication bases Oil（100 DEG C of kinematic viscosity are 11mm²/ s, 28kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, sulfoacid calcium Using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate uses the high base number ring that total base number is 320mgKOH/g Alkanoic acid calcium；Add after boric acid, be additionally added phosphoric acid, then heat up dehydration again；And treat that temperature is cooled to 110 DEG C, add 0.2kg's It is right, right '-di-iso-octyldiphenylamine, after stirring 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The use of each composition Amount is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 36.1；The weight % of six polyureas 2.4；The weight % of lubricating base oil 52.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；Boron The sour weight % of oxygen zirconium 3.9；The weight % of zirconium phosphate oxygen 2.8；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 10

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 15kg）；Naphthenate with superhigh base number calcium（Always Base number is 400mgKOH/g, 15kg）；Aphthenic acids（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄ （6.6kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；Acetic acid（2kg）；Octadecylamine（0.84kg）；Ethylenediamine （0.19kg）；MDI（1.17kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, add boron After acid, acetic acid is additionally added, then heat up dehydration again；The consumption of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 35.8；The weight % of six polyureas 2.4；The weight % of lubricating base oil 51.4；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.5；Boron The sour weight % of oxygen zirconium 3.9；The weight % of zirconyl acetate 4.0.

Embodiment 11

Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 15kg）；Overbased calcium alkyl-salicylate（Total base number For 320mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 30kg）；Aphthenic acids（Always Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（1.8kg）；12- hydroxy stearic acids（2kg）；Boric acid （2.32kg）；Para-totuidine（0.43kg）；Ethylenediamine（0.25kg）；MDI（1.52kg）；HVI500SN lubricating base oils（100℃ Kinematic viscosity is 11mm²/ s, 18kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, sulfoacid calcium Using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate uses the high base number ring that total base number is 320mgKOH/g Alkanoic acid calcium；Octadecylamine is replaced with para-totuidine；The consumption of each composition is as above.Assay is shown in Table 1.

Embodiment 12

Raw material components：Calcium sulfonate with high base number（Total base number is 360mgKOH/g, 15kg）；Overbased calcium alkyl-salicylate（Total base number For 360mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 15kg）；Detergent alkylate Sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（1.8kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；18 Amine（0.78kg）；1,6- hexamethylene diamines（0.34kg）；MDI（1.08kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, sulfoacid calcium Using the calcium sulfonate with high base number that total base number is 360mgKOH/g, calcium naphthenate uses the high base number ring that total base number is 360mgKOH/g Alkanoic acid calcium；Aphthenic acids is replaced with DBSA；Ethylenediamine is replaced with 1,6- hexamethylene diamines；The consumption of each composition is as above.Inspection Test and the results are shown in Table 1.

Embodiment 13

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control exists 50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；60 DEG C are warming up to, Constant temperature 90 minutes, material retrogradation.

In another volume be 50L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 5kg HVI500SN lubricating base oils, are warming up to 100 DEG C, add the Zr (OH) that solid content is 20 weight %₄Suspension 19.5kg, stirring 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, is stirred Mix 10 minutes, obtain 12- hydroxy stearic acid oxygen zirconiums and boric acid oxygen zirconium.

In the 3rd volume be 20L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg HVI500SN lubricating base oils and 0.78kg MDI, quick stirring 4 minutes, quick stirring is lower to add 0.84kg octadecylamines, stirring 4 Minute, quick stirring is lower to add 0.19kg ethylenediamines, stirs 4 minutes, addition is dissolved in 2kg HVI500SN lubricating base oils 0.39kg MDI, successively the ratio between added MDI, octadecylamine, ethylenediamine and MDI amount of material be 2:2:2:1,120 DEG C of perseverance Temperature 20 minutes, obtains six polyureas.

The 12- hydroxy stearic acid oxygen zirconiums and boric acid oxygen zirconium of gained are all squeezed into first kettle, stirred, under stirring 110 DEG C are warming up to, is kept for 45 minutes, dehydration all squeezes into six polyureas obtained by the 3rd reactor in the kettle, and stirring is equal It is even, finally it is warming up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

Embodiment 14

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, by cycloalkanes Acid replaces with phenol, and acetic acid is replaced with into butyric acid.Assay is shown in Table 1.

Embodiment 15

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 1, unlike, by cycloalkanes Acid replaces with methyl propyl ketone, and aqueous acetic acid is replaced with into butyl ether.Assay is shown in Table 1.

Embodiment 16

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 5, unlike, in Zr (OH)₄With the total mole number of zirconium-n-propylate it is constant in the case of, adjust Zr (OH)₄Mol ratio with zirconium-n-propylate is 1：0.1.Institute Each physicochemical property for obtaining fat is shown in Table 1.

Embodiment 17

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 5, unlike, in Zr (OH)₄With the total mole number of zirconium-n-propylate it is constant in the case of, adjust Zr (OH)₄Mol ratio with zirconium-n-propylate is 1：10.Gained Each physicochemical property of fat is shown in Table 1.

Embodiment 18

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six is prepared according to the method for embodiment 5, unlike, by positive third Alcohol zirconium replaces with equimolar Zr (OH)₄.Each physicochemical property of gained fat is shown in Table 1.

Embodiment 19

Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six 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 shown in Table 1.

Comparative example 1

Method according to embodiment 1 prepares the polyurea grease of sulfoacid calcium base six, unlike, naphthenate with superhigh base number calcium is used Total base number replaces for 400mgKOH/g overbased sulfoacid calcium, Zr (OH) used₄With Ca (OH)₂Instead of while adjusting consumption Make each component content consistent with embodiment 1, obtained each performance data of lubricating grease finished product is shown in Table 1.

In the lubricating grease that this comparative example is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 37.3 Measure %；The weight % of six polyureas 2.5；The weight % of lubricating base oil 53.6；The weight % of 12- hydroxy stearic acids calcium 2.6；The weight of line borate 4.0 Measure %.

Comparative example 2

Method according to embodiment 5 prepares the polyurea grease of sulfoacid calcium base six, unlike, overbased calcium alkyl-salicylate is with always Calcium sulfonate with high base number replacement, zirconium-n-propylate used and Zr (OH) that base number is 320mgKOH/g₄With Ca (OH)₂Instead of simultaneously Adjustment consumption makes each component content consistent with embodiment 5, and obtained each performance data of lubricating grease finished product is shown in Table 1.

In the lubricating grease that this comparative example is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 52.5 Measure %；The weight % of six polyureas 3.5；The weight % of lubricating base oil 34.6；The weight % of 12- hydroxy stearic acids calcium 3.7；The weight of line borate 5.7 Measure %.

Each lubricating grease properties of sample data of table 1

Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion： GB/T7326；

Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Water resistant is sprayed：SH/ T0643；Steel

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

Table 1（It is continuous）Each lubricating grease properties of sample data

Embodiment 1 is compared with comparative example 1, embodiment 5 is compared with comparative example 2, it can be seen that the present invention Sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six extension work cone penetration with work cone penetration difference be less than sulfoacid calcium The polyurea grease of base six, water drenches number of dropouts and is much smaller than the polyurea grease of sulfoacid calcium base six, and salt spray test is poly- better than sulfoacid calcium base six Urea grease, water resistant spraying value is less than the polyurea grease of sulfoacid calcium base six, and Stencil oil-dividing value lubricates less than the polyureas of sulfoacid calcium base six Fat, tetra-ball machine test value is more than the polyurea grease of sulfoacid calcium base six, and the bearing lubrication life-span is more than the polyurea grease of sulfoacid calcium base six, Illustrate sulfoacid calcium-mechanical stability, water-resistance and the adhesiveness of the polyurea grease of calcium naphthenate zirconium base six, the salt fog resistance of the present invention Property, colloid stability, extreme pressure anti-wear, lubricating life are superior to the polyurea grease of sulfoacid calcium base six.

Embodiment 1 is compared with embodiment 2 and embodiment 13 respectively as can be seen that sulfoacid calcium-the ring in situ prepared The polyurea grease of alkanoic acid calcium zirconium base six, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, and has Longer lubricating life；Embodiment 1 is compared with embodiment 14 and embodiment 15 respectively as can be seen that transforming agent is selected from ten At least one of dialkyl benzene sulfonic acids, aphthenic acids, methanol, butanol, isopropanol, boric acid, acetic acid and water, the sulfoacid calcium of preparation- The polyurea grease of calcium naphthenate zirconium base six, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, and has There is longer lubricating life；Embodiment 5 is compared to the oxide as can be seen that zirconium with embodiment 16 and embodiment 17 respectively And/or the mol ratio of hydroxide and zirconium alkoxide is 1：0.5-5, the sulfoacid calcium-polyureas of calcium naphthenate zirconium base six lubrication of preparation Fat, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, and with longer lubricating life；It will implement Example 5 is compared with embodiment 18 and embodiment 19 respectively as can be seen that the raw material of zirconium is the oxide and/or hydroxide of zirconium With the mixture of zirconium alkoxide, sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six of preparation is stabilized with more preferable machinery Property, water-resistance and adhesiveness, colloid stability, and with longer lubricating life.

It will be seen from figure 1 that lubricating grease prepared by embodiment 5 is in 873cm^-1-886cm^-1There is crystal form calcium carbonate feature in place Absworption peak.Meanwhile, in 3300cm^-1-3323cm^-1The stretching vibration absworption peak that the peak at place is-NH- in six polyureas molecules.

The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited to above-mentioned reality The detail in mode is applied, in the range of the technology design of the present invention, a variety of letters can be carried out to technical scheme Monotropic type, these simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

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 equally be considered as content disclosed in this invention.

Claims

1. a kind of sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six, it is characterised in that on the basis of lubricating grease weight, including Following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1- 15 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；0.5-30 weight % polyurea compound；10-80 weights % base oil is measured, wherein, the zirconates of the higher fatty acids is to be formed by higher fatty acids with component A reactions, described small point The zirconates of sub- inorganic acid and/or lower fatty acid is to be formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, The component A is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium, and the polyurea compound is six poly- Carbamide compound, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1There is crystal form calcium carbonate in place Characteristic absorption peak.

2. lubricating grease according to claim 1, wherein, on the basis of lubricating grease weight, including following components：20-60 weights Measure % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 2-6 weight % higher fatty acids；2-10 weight % small molecule The zirconates of inorganic acid and/or lower fatty acid；1-20 weight % six polyurea compounds；20-70 weight % base oil.

3. lubricating grease according to claim 1, wherein, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is by newton body sulphur What sour calcium and the conversion of newton body calcium naphthenate were obtained, the total base number of the non-newtonian fluid sulfoacid calcium-calcium naphthenate is 250- 450mgKOH/g。

4. lubricating grease according to claim 1 or 2, wherein, the higher fatty acids is the straight chain fatty that carbon number is 8-20 Acid or hydroxy fatty acid.

5. lubricating grease according to claim 4, wherein, the higher fatty acids be selected from laurate, palmitic acid, stearic acid, At least one of 12- hydroxy stearic acids, eicosyl carboxylic acid.

6. lubricating grease according to claim 1 or 2, wherein, the molecular weight of small molecule inorganic acid or lower fatty acid is less than Equal to 150.

7. lubricating grease according to claim 6, wherein, the small molecule inorganic acid in boric acid, phosphoric acid, sulfuric acid extremely Few one kind, the lower fatty acid is selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid.

8. lubricating grease according to claim 1 or 2, wherein, the component A for zirconium oxide and/or hydroxide with The mixture of zirconium alkoxide, in terms of zirconium, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：0.1-10.

9. lubricating grease according to claim 8, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium Mol ratio be 1：0.5-5.

10. lubricating grease according to claim 1 or 2, wherein, the oxide and/or hydroxide of zirconium are selected from ZrO₂、ZrO (OH)₂、Zr(OH)₄At least one of and their hydrate.

11. lubricating grease according to claim 1 or 2, wherein, the formula of the zirconium alkoxide is Zr (OR₁)₄, R₁For C1- C10 alkyl.

12. lubricating grease according to claim 11, wherein, the zirconium alkoxide is selected from ethanol zirconium, zirconium-n-propylate, n-butanol At least one of zirconium, zirconium tert-butoxide and n-amyl alcohol zirconium.

13. lubricating grease according to claim 1 or 2, wherein, six polyurea compound has following structure：

Wherein, R¹It is alkyl, cycloalkyl or aryl, R²It is alkylidene or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.

14. lubricating grease according to claim 13, wherein, R¹It is phenyl or substituted phenyl, or the alkyl that carbon number is 8-24 Or cycloalkyl；R²It is the alkylidene that phenylene or biphenylene or carbon number are 2-12；R³It is arlydene, alkylene that carbon number is 6-30 Base or cycloalkylidene.

15. lubricating grease according to claim 14, wherein, R¹It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or carbon Number is 10-18 alkyl or cycloalkyl, R²It is phenylene or biphenylene, or the alkylidene that carbon number is 2-8；R³It is selected from With-(CH₂)₆At least one of-.

16. the preparation method of sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six in claim 1-15 described in any one, Characterized in that, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid And/or zirconates, six polyurea compounds and the part basis oil of lower fatty acid are well mixed, in 180-230 DEG C of constant temperature refining, plus Enter surplus base oil, add necessary additive, obtain finished product.

17. the preparation method of sulfoacid calcium-polyurea grease of calcium naphthenate zirconium base six in claim 1-15 described in any one, Characterized in that, this method includes：

(1) newton body sulfoacid calcium, newton body calcium naphthenate, base oil and transforming agent are mixed, material retrogradation is treated in heating；

(2) component A is added in step (1) products therefrom, higher fatty acids and small molecule inorganic acid is added and/or rudimentary Aliphatic acid is reacted, and heat up dehydration after reaction, and the component A is the oxide of zirconium, in the hydroxide and zirconium alkoxide of zirconium At least one；

(3) base oil and diisocyanate are added in mixture obtained by step (2), monoamine, diamines and two is then sequentially added Isocyanates is reacted；

(4) mixture obtained by step (3) is warming up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary addition Agent, obtains finished product.

18. method according to claim 17, wherein, in step (1), by newton body sulfoacid calcium, newton body calcium naphthenate, Part basis oil Hybrid Heating is to 50-80 DEG C, and the transforming agent needed for adding is reacted, after all transforming agents are added, in 60-90 DEG C constant temperature 60-90 minutes.

19. method according to claim 17, wherein, in step (2), at 85-100 DEG C, component A is added, is added high Level aliphatic acid, is stirred 5-20 minutes, adds small molecule inorganic acid and/or lower fatty acid, is stirred 5-20 minutes, is warming up to 100- 120 DEG C of dehydrations, the component A is the oxide of zirconium and/or the mixture of hydroxide and zirconium alkoxide, in terms of zirconium, the oxygen of zirconium Compound and/or the mol ratio of hydroxide and zirconium alkoxide are 1：0.1-10.

20. method according to claim 19, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium Mol ratio be 1：0.5-5.

21. method according to claim 17, wherein, in step (3), basis is added in mixture obtained by step (2) Oil and diisocyanate, add monoamine, stir 2-8 minutes, add diamines, stir 2-8 minutes, add and be dissolved in base oil Diisocyanate, stir 2-8 minute, the mol ratio of diisocyanate, monoamine, diamines and diisocyanate added by each time For 2:2:2:1.

22. method according to claim 17, wherein, in step (4), first in 100-120 DEG C of constant temperature 10-20 minutes, most After be warming up to 180-230 DEG C of constant temperature 5-20 minutes；Base oil is added, treats that temperature is cooled to 100-120 DEG C, adds necessary addition Agent, stirring, circulating filtration, homogenizing, degassing.

23. method according to claim 17, wherein, the newton body sulfoacid calcium is calcium mahogany sulfonate and/or synthesis sulphur Sour calcium, the total base number of the newton body sulfoacid calcium is 250-450mgKOH/g；The newton body calcium naphthenate is petroleum naphthenic acid Calcium and/or synthesis calcium naphthenate, the total base number of the newton body calcium naphthenate is 250-450mgKOH/g.

24. method according to claim 17, wherein, the transforming agent is selected from fatty alcohol, aliphatic acid, aliphatic ketone, fat Aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkylbenzenes At least one of sulfonic acid and water, the addition of transforming agent are the 2- of newton body sulfoacid calcium and newton body calcium naphthenate gross weight 30%.

25. method according to claim 24, wherein, the transforming agent is selected from DBSA, aphthenic acids, first At least one of alcohol, isopropanol, butanol, boric acid, acetic acid and water, the addition of transforming agent is newton body sulfoacid calcium and newton body The 6-22% of calcium naphthenate gross weight.

26. method according to claim 17, wherein, the structural formula of the monoamine is R¹-NH₂, wherein, R¹Be phenyl, C1-C3 alkyl or the phenyl of halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.

27. method according to claim 26, wherein, the monoamine be selected from aniline, m-chloroaniline, parachloroanilinum and/ Or the arylamine of para-totuidine, and/or the fatty amine selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.

28. method according to claim 17, wherein, the structural formula of the diamines is NH₂-R²-NH₂, wherein, R²It is carbon number For 2-8 alkylidene, or phenylene or biphenylene.

29. method according to claim 28, wherein, the diamines is to be 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.

30. method according to claim 17, wherein, the structure of the diisocyanate is OCN-R³- NCO, R³It is carbon number For 6-30 arlydene, alkylidene or cycloalkylidene.

31. method according to claim 30, wherein, the diisocyanate is selected from toluene di-isocyanate(TDI), diphenyl Methane diisocyanate, 1,6- hexylidene diisocyanates, dicyclohexyl methyl hydride diisocyanate and the isocyanide of an xyxylene two At least one of acid esters.