CN104560274B

CN104560274B - A kind of sulfoacid calcium calcium naphthenate zirconium base polyurea grease and preparation method thereof

Info

Publication number: CN104560274B
Application number: CN201310522905.0A
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: 2017-12-22
Anticipated expiration: 2033-10-29
Also published as: CN104560274A

Abstract

The invention discloses a kind of sulfoacid calcium calcium naphthenate zirconium base polyurea grease, on the basis of lubricating grease weight, 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, and component A is at least one of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide.The invention also discloses preparation of greases method and its lubricating grease of preparation.The lubricating grease of the present invention, there is more preferable mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and extreme pressure anti-wear, there is longer lubricating life.

Description

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

Technical field

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

Background technology

Sulfoacid calcium is used as the detersive and the history of antirust agent existing decades of lubricating oil, is widely used in internal combustion engine lubrication The additive of oil, the development of its technology mainly make its height alkalization, are 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 produces 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 pass 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, calcium carbonate is exactly turned into a kind of colloidal dispersion system with the naphthenic acid calcium with surface-active to be distributed in flux oil.It is high Base number calcium naphthenate mostly be the acidic components extracted in the distillate obtained from crude distillation, 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, domestic and international profit is caused The extensive concern of consistent lubricant industry, however, although high base number composite calcium sulfonate base grease has very excellent combination property, 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, together When, with requirement more and more higher of the 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, if CN101113382 and JP1973038444 is using the oxide of zirconium as lubricant addition Agent improves abrasiveness；WO2007143414 and US20060063682, which describes 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 formed by higher fatty acids and 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 lubricating grease has preferable mechanical stability, water-resistance and adhesiveness, resisted Salt fog, colloid stability and extreme pressure anti-wear, there is longer lubricating life, and cost is low, preparation technology is simple and environmentally-friendly.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of sulfoacid calcium-calcium naphthenate zirconium base polyureas Lubricating grease, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；1- The zirconates of 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 fatty acids Formed with component A reactions, the zirconates of the small molecule inorganic acid and/or lower fatty acid is by small molecule inorganic acid and/or low Level aliphatic acid and component A reaction forms, the component A be the oxide of zirconium, zirconium hydroxide and zirconium alkoxide at least It is a kind of.

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 % polyurea compound；20-70 weight % base oil.

Second aspect, the invention provides the preparation side of sulfoacid calcium as described above-calcium naphthenate zirconium base polyurea grease Method, this method include：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid and/or low Zirconates, polyurea compound and the part basis oil of level aliphatic acid are well mixed, and are refined in 180-230 DEG C of constant temperature, are added surplus base Plinth oil, adds necessary additive, obtains finished product.

The third aspect, the invention provides a kind of preparation method of sulfoacid calcium-calcium naphthenate zirconium base polyurea grease, the party 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 monoamine are added in gained mixture, or is additionally added diamines, adds diisocyanate Reacted；

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

Fourth aspect, the invention provides the sulfoacid calcium as made from method as described above-calcium naphthenate zirconium base polyureas profit Consistent lubricant.

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease of the present invention, compared to sulfoacid calcium base polyurea grease, have more preferable Mechanical stability, water-resistance and adhesiveness, resistance to saltfog, the performance such as colloid stability and extreme pressure anti-wear, have 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 specific embodiment part.

Embodiment

The embodiment of the present invention is described in detail below.It is 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-calcium naphthenate zirconium base polyurea grease, this lubricating grease employs oil sulphur Sour calcium and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, it is simultaneously thick containing compound zirconium Agent, isocyanates and polyurea compound caused by amine reaction.

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

On the one hand, the invention provides a kind of sulfoacid calcium-calcium naphthenate zirconium base polyurea grease, using lubricating grease weight as base Standard, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconium of 1-10 weight % higher fatty acids Salt；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 formed by higher fatty acids and component A reactions, small molecule inorganic acid And/or the zirconates of lower fatty acid is to be formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, component A is zirconium Oxide, the hydroxide and at least one of zirconium alkoxide of zirconium.

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 % polyurea compound；20-70 weight % base oil；It is highly preferred that on the basis of lubricating grease weight, including Following components：30-55 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 2.2-4.2 weight % higher fatty acids； 3-8 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；2-10 weight % polyurea compound；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 Receive peak, preferably total base number 250mgKOH/g-450mgKOH/g, 300mgKOH/g-400mgKOH/g.Non-newtonian fluid sulfonic acid Calcium-calcium naphthenate is to convert to obtain by transforming agent by newton body sulfoacid calcium and newton body calcium naphthenate.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 are 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid The base number of sulfoacid calcium-calcium naphthenate is averaged for the weight of the base number and the base number of newton body calcium naphthenate of newton body sulfoacid calcium 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., when the raw material of zirconium is the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, 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 of zirconium and the mixture of zirconium alkoxide, 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, it 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, the polyurea compound can be polyurea compound commonly used in the art without particular/special requirement, such as can Think at least one of two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.Wherein dimerization Carbamide compound, four polyurea compounds, six polyurea compounds, the weight ratio of eight polyurea compounds can be arbitrary proportion.More preferably The polyurea compound is two polyurea compounds.

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

Wherein, R¹、R¹' can be the same or different, can be alkyl, cycloalkyl or aryl, the carbon of alkyl or cycloalkyl Number can be 8-24, preferably 10-18, and aryl can be phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen The phenyl of element substitution.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, arlydene, alkylidene or Asia The carbon number of cycloalkyl can be 6-30, preferably 6-20, R³More preferably WithIn At least one.

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

Wherein, R¹Can be alkyl, cycloalkyl or aryl, 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, arlydene, alkylidene or sub- cycloalkanes The carbon number of base can be 6-30, preferably 6-20, R³More preferably WithIn At least one.

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

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

Above-mentioned polyurea compound can use the thinkable various methods of those skilled in the art institute to obtain, such as can be by It is prepared according to CN103060069A, CN103060070A, CN103060068A, CN103060067A method 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, account for 0.01-5%, the preferably 0.1-2.5% of lubricating grease gross weight, 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, polyurea compound, 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 converts to obtain, for example, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, adds institute The transforming agent needed is reacted, and after all transforming agents add, in 60-90 DEG C of constant temperature 60-90 minute, then heats to 100-120 DEG C dehydration.

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

Step of the present invention（1）In, it is excellent for the weight ratio of newton body sulfoacid calcium and newton body calcium naphthenate without particular/special requirement Elect 1 as：0.25-4.Newton body sulfoacid calcium and the gross weight of newton body calcium naphthenate and the weight ratio of part basis oil are 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 Choosing selected from C1-C5 fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine, 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 during the mixture of hydroxide and zirconium alkoxide, i.e., the raw material of zirconium is the oxide and/or hydroxide and alkoxy of zirconium 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, adds higher fatty acids, stirs 5-20 Minute, small molecule inorganic acid and/or lower fatty acid are added, 5-20 minutes is stirred, is warming up to 100-120 DEG C, preferably keeps 30- 60 minutes, dehydration, the component A was the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, 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 exchange 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, zirconium hydroxide 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 the hydroxide and zirconium alkoxide of the oxide of zirconium, zirconium⁺Molal quantity, but the hydrogen-oxygen of the oxide of zirconium, zirconium Compound and zirconium alkoxide can excessive 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 monoamine are added in gained mixture, or is additionally added diamines, it is different to add two Cyanate is reacted, and is in step（2）Polyurea compound is prepared in gained mixture, mixing polyureas can be prepared, also may be used To prepare single two polyurea compound, four polyurea compounds, six polyurea compounds or eight polyurea compounds.

The method of mixing polyureas is prepared without particular/special requirement, the thinkable various sides of those skilled in the art institute can be used Method, it is for instance possible to use United States Patent (USP) US3243372 method.

The method of two 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 monoamine are added in gained mixture, 2-8 minutes is stirred, adds and be dissolved in base Diisocyanate in plinth oil, stir 2-8 minutes, the mol ratio of diisocyanate and monoamine is 1:2.

The method of four 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, is stirred, diamines is added, stirs Mix 2-8 minutes, add monoamine, stir 2-8 minutes, the mol ratio of diisocyanate, diamines and monoamine is 2:1:2.

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, is stirred, monoamine is added, stirs Mix 2-8 minutes, add diamines, stir 2-8 minutes, add diisocyanate, stir 2-8 minutes, successively two added isocyanides Acid esters, monoamine, the mol ratio of diamines and diisocyanate are 2:2:2:1.

The method of eight 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, is stirred, diamines is added, stirs Mix 2-8 minutes, add diamines again, stir 2-8 minutes, add monoamine, stir 2-8 minutes, successively added diisocyanate, The mol ratio of 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 be Fluctuated in the range of ± 5%.

The diisocyanate structure is OCN-R³- NCO, R³Can be that carbon number is 6-30, preferably 6-20 arlydene, alkylidene or cycloalkylidene, it is preferably Deng. For example, the diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), 1,6- is sub- 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, structural formula R¹-NH₂、R¹’-NH₂, R therein¹、R¹' 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.Preferable 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, structural formula NH₂-R²-NH₂, R therein²Can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferable diamines can Be selected from p-phenylenediamine, o-phenylenediamine, 4,4- benzidines aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6- oneself two The straight-chain fatty amine of amine.

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

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 Alkanoic acid calcium zirconium base polyurea grease.

Compared with the sulfoacid calcium as made from the preparation method that second aspect provides-calcium naphthenate zirconium base polyurea grease, the Three aspect provide preparation method made from sulfoacid calcium-calcium naphthenate zirconium base polyurea grease have more preferable mechanical stability, Water-resistance and adhesiveness, colloid stability, there is 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 high 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 zirconates of higher fatty acids and the content of the zirconates of small molecule inorganic acid and/or lower fatty acid, according to added Higher fatty acids and small molecule inorganic acid and/or the oxide of lower fatty acid and zirconium, the hydroxide and alcoxyl of zirconium entered The amount that base zirconium reacts generation zirconates completely calculates.

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-calcium naphthenate zirconium base polyurea grease 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（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 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, adds 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, 110 DEG C are warming up under stirring, kept for 45 minutes, dehydration；Add 2kg HVI500SN lubricating base oils and 1.5kg Octadecylamine, stir 4 minutes, add the 0.7kg MDI being dissolved in 2kg HVI500SN lubricating base oils, stir 4 minutes, institute The ratio between the MDI added and the amount of material of octadecylamine are 1:2,120 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 into Product.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.3；The weight % of two 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, adds 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, 110 DEG C are warming up under stirring, kept for 45 minutes, dehydration.

Another volume be 30L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 2kg HVI500SN lubricating base oils and 1.5kg octadecylamines, 120 DEG C are warming up to, stir 4 minutes, add the HVI500SN for being dissolved in 2kg 0.7kg MDI in lubricating base oil, stir 4 minutes, the ratio between amount of material of added MDI and octadecylamine is 1:2,120 DEG C Constant temperature 20 minutes, obtains two polyureas.

The polyureas of gained two is all squeezed into a upper kettle, stirred, is finally warming up to 200 DEG C of constant temperature 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 two 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（1.31kg）；MDI（0.89kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 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 are warming up under stirring, is kept 30 minutes, dehydration；2kg HVI500SN lubricating base oils and 1.31kg lauryl amines is added, is stirred 8 minutes, is added and be dissolved in 2kg HVI500SN lubricating base oils in 0.89kg MDI, stir 8 minutes, the ratio between amount of material of added MDI and lauryl amine For 1:2,100 DEG C of constant temperature 10 minutes, is finally warming up to 230 DEG C of constant temperature 5 minutes.Then, 160 DEG C are cooled to, is added remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1。

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.3；The weight % of two 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（1.66kg）；TDI（0.54kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 23kg）.

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes The calcium sulfonate with high base number for being 320mgKOH/g with total base number；Aphthenic acids is replaced with DBSA；Use toluene diisocynate Ester（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 dosage 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（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of motions are viscous Spend for 11mm²/ s, 7kg）.

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes The calcium sulfonate with high base number for being 320mgKOH/g with total base number, calcium naphthenate use the high base number cycloalkanes that total base number is 320mgKOH/g Sour calcium；Calcium naphthenate uses the overbased calcium alkyl-salicylate that total base number is 360mgKOH/g；Add Zr (OH)₄When be additionally added normal propyl alcohol Zirconium, in terms of zirconium, Zr (OH)₄Mol ratio with zirconium-n-propylate is 1：1；The dosage of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 52.5；The weight % of two 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（4.5kg）；MDI（2.1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ S, 18.6kg）.

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

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.3；The weight % of two 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（1.5kg）；MDI（0.7kg）；Poly alpha olefine synthetic oil PAO10（100 DEG C of kinematic viscosity are 11mm²/ s, 9kg）；Two thio Acidic phosphates zinc（2kg）；Molybdenum dialkyldithiocarbamacompositions（1kg）；Tungsten disulfide（2kg）；Two selenizings Tungsten（2kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate Use the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g；Use poly alpha olefine synthetic oil PAO40（100 DEG C of kinematic viscosity For 40mm²/s）With poly alpha olefine synthetic oil PAO10（100 DEG C of kinematic viscosity are 11mm²/s）Respectively instead of HVI150BS（100℃ 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, add Enter 2kg two thio Acidic phosphates zinc, stir 10 minutes, add 1kg molybdenum dialkyldithiocarbamacompositions, stir 10 points Clock, 2kg tungsten disulfide is added, stirred 10 minutes, add 2kg two tungsten selenides, stirred 10 minutes, add 0.2kg pair, Right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The dosage of each composition is such as On.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 38.0；The weight % of two 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, 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（0.94kg）；Para-totuidine（0.38kg）；MDI（0.88kg）；HVI500SN lubricating base oils（100℃ Kinematic viscosity is 11mm²/ s, 18kg）.

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes The calcium sulfonate with high base number for being 320mgKOH/g with total base number；When adding octadecylamine, para-totuidine is additionally added；The dosage of each composition 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 360mgKOH/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）；Lauryl amine（0.58kg）；MDI（0.78kg）；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-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes The calcium sulfonate with high base number for being 320mgKOH/g with total base number, calcium naphthenate use the high base number cycloalkanes that total base number is 360mgKOH/g Sour calcium；After adding boric acid, phosphoric acid is additionally added, then heat up dehydration again；When adding octadecylamine, lauryl amine is additionally added；And treat temperature Degree is cooled to 110 DEG C, adds 0.2kg pair, right '-di-iso-octyldiphenylamine, after stirring 10 minutes, then circulating filtration, Change, degassing obtains finished product；The dosage of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 36.1；The weight % of two 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）；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（6.6kg）；12- hydroxy stearic acids（2kg）；Boron Acid（2.32kg）；Acetic acid（2kg）；Octadecylamine（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of motions are viscous Spend for 11mm²/ s, 18kg）.

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

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 35.8；The weight % of two 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

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.

Another volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 5kg HVI500SN lubricating base oils, 100 DEG C are warming up to, 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.

The 3rd volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 2kg HVI500SN lubricating base oils and 1.5kg octadecylamines, stir 4 minutes, add and be dissolved in 2kg HVI500SN lubricating base oils 0.7kg MDI, stir 4 minutes, the ratio between amount of material of added MDI and octadecylamine is 1:2,120 DEG C of constant temperature 20 minutes, is obtained To two polyureas.

The 12- hydroxy stearic acid oxygen zirconiums of gained and boric acid oxygen zirconium are all squeezed into first kettle, stirred, under stirring 110 DEG C are warming up to, is kept for 45 minutes, dehydration, two polyureas obtained by the 3rd reactor are all squeezed into the kettle, 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 12

Volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add 10kg total base numbers be 350mgKOH/g calcium sulfonate with high base number, the naphthenate with superhigh base number calcium that 20kg total base numbers are 400mgKOH/g and 25kg100 DEG C Kinematic viscosity is 31mm²/ s HVI150BS lubricating base oils, stirring, heat to 60 DEG C, constant temperature 10 minutes；Add 3kg Aphthenic acids, temperature control stir 10 minutes at 60 DEG C or so；The 12.5kg butanol aqueous solution that concentration is 20% is added, stirs 10 points Clock；In 87 DEG C of constant temperature 70 minutes, material retrogradation.

It is 100L and with heating, stirring, the HVI500SN for circulating, 5kg being added in the normal-pressure reaction kettle B of cooling in volume Lubricating base oil, 90 DEG C are warming up to, add the Zr (OH) that solid content is 20 weight %₄Suspension 28.9kg, stir 10 minutes, add Enter 2.4kg palmitic acid, stir 10 minutes, add the ethanedioic acid of 4.78kg boric acid, 1kg phosphoric acid and 2kg, stir 10 points Clock, obtain palmitic acid oxygen zirconium, boric acid oxygen zirconium, zirconium phosphate oxygen and ethanedioic acid oxygen zirconium.

Volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle C in add 5kg100 DEG C of motion viscous Spend for 11mm²For/s HVI500SN lubricating base oils and 1kg MDI rapidly pre-warmings to 90 DEG C, quick stirring is lower to add 0.12kg second Diamines, stir 4 minutes, add 1.08kg octadecylamines and stir 4 minutes, added MDI, ethylenediamine and octadecylamine mol ratio are 2: 1:2,120 DEG C of constant temperature 20 minutes, obtains four polyureas.

Volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle D in add 10kg100 DEG C motion Viscosity is 11mm²/ s HVI500SN lubricating base oils and 0.78kg MDI is preheating to 90 DEG C, and quick stirring is lower to add 0.84kg Octadecylamine, stir 4 minutes, quick stirring is lower to add 0.19kg ethylenediamines, stirs 4 minutes, adds 0.39kg MDI, added successively MDI, octadecylamine, ethylenediamine and MDI mol ratio be 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.

Gained palmitic acid oxygen zirconium, boric acid oxygen zirconium, zirconium phosphate oxygen and ethanedioic acid oxygen zirconium are all squeezed into reactor A, stirred Uniformly, 120 DEG C are warming up under stirring, is kept for 30 minutes, dehydration, the polyureas of gained four and six polyureas are all squeezed into reactor A, Stir, be finally warming up to 200 DEG C of constant temperature 5 minutes.Then, 150 DEG C are cooled to, adds 8kg HVI500SN lubrication bases Oil；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 obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 30.7；The weight % of palmitic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 6.9；The weight % of zirconium phosphate oxygen 2.5；Ethanedioic acid oxygen zirconium 4.0 weight %；The weight % of four polyureas 2.0；The weight % of six polyureas 2.0；The weight % of lubricating base oil 49.2.

Embodiment 13

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add 20kg total alkalis Be worth the overbased sulfoacid calcium for 400mgKOH/g, the naphthenate with superhigh base number calcium that 10kg total base numbers are 420mgKOH/g and 10kg100 DEG C of kinematic viscosity is 31mm²/ s HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 divides Clock；2kg DBSAs are added, temperature control stirs 10 minutes at 50 DEG C or so；1kg methanol is added, stirs 10 points Clock；The aqueous acetic acid that 2kg concentration is 20 weight % is added, is stirred 10 minutes；In 83 DEG C of constant temperature 80 minutes, material retrogradation.

It is 50L and with heating, stirring, the HVI500SN for circulating, 8kg being added in the normal-pressure reaction kettle B of cooling in volume Lubricating base oil, the Zr (OH) that solid content is 50 weight % is added at 95 DEG C₄Suspension 12.3kg, stir 10 minutes, add 2.4kg laurate, stir 10 minutes, add 7.98kg butyric acid, stir 10 minutes, obtain laurate oxygen zirconium and butyric acid oxygen Zirconium.

Volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle C in add 10kg100 DEG C motion Viscosity is 11mm²/ s HVI500SN lubricating base oils and 1.17kg MDI is preheating to 80 DEG C, and quick stirring is lower to add 0.84kg The mixture of octadecylamine, 0.19kg ethylenediamines, added MDI, monoamine, the mol ratio of diamines are 3:2:2,120 DEG C of constant temperature 20 divide Clock, obtain mixing polyureas.

Gained laurate oxygen zirconium and butyric acid oxygen zirconium are all squeezed into reactor A, stirred, 110 are warming up under stirring DEG C, kept for 45 minutes, dehydration, gained mixing polyureas is all squeezed into reactor A, stirred, is finally warming up to 200 DEG C of perseverances Temperature 5 minutes.Then, 2kg 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 obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 40.3；The weight % of laurate oxygen zirconium 3.8；The weight % of butyric acid oxygen zirconium 15.9；The weight % of polyurea compound 2.7；Lubricate base 37.3 weight % of plinth oil.

Embodiment 14

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, by aphthenic acids Phenol is replaced with, acetic acid is replaced with into butyric acid.Assay is shown in Table 1.

Embodiment 15

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, by aphthenic acids Methyl propyl ketone is replaced with, aqueous acetic acid is replaced with into butyl ether.Assay is shown in Table 1.

Embodiment 16

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 5, unlike, at Zr (OH)₄ With 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.Gained fat Each physicochemical property be shown in Table 1.

Embodiment 17

Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease is prepared according to the method for embodiment 5, unlike, at Zr (OH)₄ With 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 fat Each physicochemical property is shown in Table 1.

Embodiment 18

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

Embodiment 19

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

Comparative example 1

Sulfoacid calcium base polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number calcium is with always The overbased sulfoacid calcium that base number is 400mgKOH/g replaces, Zr used (OH)₄With Ca (OH)₂Instead of, while adjust dosage and make Each component content is consistent with embodiment 1, and obtained each performance data of lubricating grease finished product is shown in Table 1.

In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight of non-newtonian fluid sulfoacid calcium 37.3 Measure %；The weight % of two 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

Sulfoacid calcium base polyurea grease is prepared according to the method for embodiment 5, unlike, overbased calcium alkyl-salicylate total alkali It is worth calcium sulfonate with high base number replacement, zirconium-n-propylate used and the Zr (OH) for 320mgKOH/g₄With Ca (OH)₂Instead of adjusting simultaneously Whole dosage 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 obtains, on the basis of lubricating grease weight, form and be：The weight of non-newtonian fluid sulfoacid calcium 52.5 Measure %；The weight % of two 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 %.

By embodiment 1 compared with comparative example 1, by embodiment 5 compared with comparative example 2, it can be seen that the present invention Sulfoacid calcium-calcium naphthenate zirconium base polyurea grease extension work cone penetration with work cone penetration difference be less than sulfoacid calcium base Polyurea grease, water leaching number of dropouts are much smaller than sulfoacid calcium base polyurea grease, and salt spray test is better than sulfoacid calcium base polyurea grease, Water resistant spraying value is less than sulfoacid calcium base polyurea grease, and Stencil oil-dividing value is less than sulfoacid calcium base polyurea grease, tetra-ball machine test Value is more than sulfoacid calcium base polyurea grease, and the bearing lubrication life-span is more than sulfoacid calcium base polyurea grease, illustrates the sulfonic acid of the present invention Calcium-mechanical stability, water-resistance and adhesiveness of calcium naphthenate zirconium base polyurea grease, resistance to saltfog, colloid stability, extreme pressure Wear resistence, lubricating life are superior to sulfoacid calcium base polyurea grease.

By embodiment 1 respectively compared with embodiment 2 and embodiment 11 as can be seen that sulfoacid calcium-the ring in situ prepared Alkanoic acid calcium zirconium base polyurea grease, there is more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, have longer Lubricating life；By embodiment 1 respectively compared with embodiment 14 and embodiment 15 as can be seen that transforming agent is selected from dodecane At least one of base benzene sulfonic acid, aphthenic acids, methanol, butanol, isopropanol, boric acid, acetic acid and water, sulfoacid calcium-cycloalkanes of preparation Sour calcium zirconium base polyurea grease, there is more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, have longer Lubricating life；By embodiment 5 respectively compared with embodiment 16 and embodiment 17 as can be seen that the oxide and/or hydrogen of zirconium The mol ratio of oxide and zirconium alkoxide is 1：0.5-5, sulfoacid calcium-calcium naphthenate zirconium base polyurea grease of preparation, have more Mechanical stability, water-resistance and adhesiveness well, colloid stability, have longer lubricating life；By embodiment 5 respectively with reality Apply example 18 and embodiment 19 is compared as can be seen that the raw material of zirconium is the oxide and/or hydroxide and zirconium alkoxide of zirconium Mixture, sulfoacid calcium-calcium naphthenate zirconium base polyurea grease of preparation, there is more preferable mechanical stability, water-resistance and viscous Attached property, colloid stability, there is longer lubricating life.

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；Stencil oil-dividing：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

The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little 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

A kind of 1. sulfoacid calcium-calcium naphthenate zirconium base polyurea grease, it is characterised in that on the basis of lubricating grease weight, including with Lower component：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 formed by higher fatty acids and 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 the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide, the non-newtonian fluid sulfoacid calcium- Calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1There is crystal form calcium carbonate characteristic absorption peak in place.
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 % polyurea compound；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 Sour calcium and newton body calcium naphthenate convert what is obtained, and 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 are 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 be 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)₄And at least one of 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, the polyurea compound is two polyurea compounds, four polyureas At least one of compound, six polyurea compounds and eight polyurea compounds.
14. lubricating grease according to claim 13, wherein, the polyurea compound is two polyurea compounds, the compound With following structure：

Wherein, R¹、R^1’It is alkyl, cycloalkyl or aryl, R³It is arlydene, alkylidene or cycloalkylidene.
15. lubricating grease according to claim 14, wherein, R¹、R^1’It is phenyl or substituted phenyl, or carbon number is 8-24's Alkyl or cycloalkyl；R³It is 6-30 arlydene, alkylidene or cycloalkylidene.
16. lubricating grease according to claim 15, wherein, R¹、R^1’It is phenyl, C1-C3 alkane Base or the phenyl of halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18, R³It is With- (CH₂)₆At least one of-.
17. the preparation method of sulfoacid calcium-calcium naphthenate zirconium base polyurea grease in claim 1-16 described in any one, its It is characterised by, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid And/or zirconates, polyurea compound and the part basis oil of lower fatty acid are well mixed, and are refined, are added in 180-230 DEG C of constant temperature Surplus base oil, necessary additive is added, obtains finished product.
18. the preparation method of sulfoacid calcium-calcium naphthenate zirconium base polyurea grease in claim 1-16 described in any one, its It is characterised by, 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, adds higher fatty acids and small molecule inorganic acid and/or rudimentary Aliphatic acid is reacted, and heat up dehydration after reaction, and the component A is in the hydroxide and zirconium alkoxide of the oxide of zirconium, zirconium At least one；

(3) base oil and monoamine are added in mixture obtained by step (2), or is additionally added diamines, diisocyanate is added and carries out Reaction；

(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, obtain finished product.
19. according to the method for claim 18, wherein, in step (1), by newton body sulfoacid calcium, newton body calcium naphthenate, Part basis oil Hybrid Heating adds required transforming agent and reacted, after all transforming agents add, in 60-90 to 50-80 DEG C DEG C constant temperature 60-90 minutes.
20. according to the method for claim 18, wherein, in step (2), at 85-100 DEG C, component A is added, is added high Level aliphatic acid, stirs 5-20 minutes, adds small molecule inorganic acid and/or lower fatty acid, stirs 5-20 minutes, is warming up to 100- 120 DEG C of dehydrations, the component A is the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, in terms of zirconium, the oxygen of zirconium Compound and/or the mol ratio of hydroxide and zirconium alkoxide are 1：0.1-10.
21. the method according to claim 11, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium Mol ratio be 1：0.5-5.
22. according to the method for claim 18, wherein, in step (3), basis is added in mixture obtained by step (2) Oil and monoamine, 2-8 minutes are stirred, add diisocyanate, stirred 2-8 minutes, the mol ratio of diisocyanate and monoamine is 1:2。
23. according to the method for claim 18, wherein, in step (4), first in 100-120 DEG C of constant temperature 10-20 minute, most After be warming up to 180-230 DEG C of constant temperature 5-20 minute；Base oil is added, treats that temperature is cooled to 100-120 DEG C, adds necessary addition Agent, stirring, circulating filtration, homogenizing, degassing.
24. according to the method for claim 18, 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.
25. according to the method for claim 18, 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%.
26. according to the method for claim 25, 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.
27. according to the method for claim 18, wherein, the structural formula of the monoamine is R¹-NH₂、R^1’-NH₂, wherein, R¹、 R^1’It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or carbon number is 10-18 alkyl or cycloalkyl.
28. according to the method for claim 27, 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.
29. according to the method for claim 18, wherein, the structural formula of the diamines is NH₂-R²-NH₂, wherein, R²It is carbon number For 2-8 alkylidene, or phenylene or biphenylene.
30. according to the method for claim 29, wherein, the diamines is selected from p-phenylenediamine, o-phenylenediamine, 4,4- biphenyl The aromatic amine of diamines and/or selected from ethylenediamine, propane diamine, 1,6- hexamethylene diamines straight-chain fatty amine.
31. according to the method for claim 18, wherein, the structure of the diisocyanate is OCN-R³- NCO, R³It is carbon number For 6-30 arlydene, alkylidene or cycloalkylidene.
32. according to the method for 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.