CN104560320B

CN104560320B - A kind of composite calcium naphthenate calcium zirconium base polyurea grease and preparation method thereof

Info

Publication number: CN104560320B
Application number: CN201310520957.4A
Authority: CN
Inventors: 何懿峰; 孙洪伟; 段庆华; 张建荣; 刘中其; 姜靓; 陈政; 郑会
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-10-29
Filing date: 2013-10-29
Publication date: 2018-03-20
Anticipated expiration: 2033-10-29
Also published as: CN104560320A

Abstract

The invention discloses a kind of composite calcium naphthenate calcium zirconium base polyurea grease, on the basis of lubricating grease weight, including：10 70 weight % non-newtonian fluid calcium naphthenate；The zirconates of 1 10 weight % higher fatty acids；The zirconates of 1 15 weight % aromatic acid；0.5 30 weight % polyurea compound；10 80 weight % base oil；The optionally zirconates of the small molecule inorganic acid also including 1 15 weight % and/or lower fatty acid, zirconates is formed by higher fatty acids, aromatic acid, 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 the performances such as 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 composite calcium naphthenate calcium 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 composite calcium naphthenate calcium zirconium base polyurea grease and its preparation side Method.

Background technology

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 performance to be better than sulfonate with high base number calcium-base grease, and cost is low, preparation technology letter Single, environmental protection lubricating grease 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 calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；The zirconates of 1-15 weight % aromatic acid；0.5-30 weights Measure % polyurea compound；10-80 weight % base oil；Optionally also including 1-15 weight % small molecule inorganic acid and/or The zirconates of lower fatty acid, wherein, the zirconates of the higher fatty acids is formed by higher fatty acids and component A reactions, described The zirconates of aromatic acid is formed by aromatic acid and component A reactions, and the zirconates of the small molecule inorganic acid and/or lower fatty acid is by small Molecule inorganic acid and/or lower fatty acid form with component A reactions, the component A be the oxide of zirconium, zirconium hydroxide and At least one of zirconium alkoxide.Mechanical stability, water-resistance and the adhesiveness of the lubricating grease, resistance to saltfog, colloid stability, The performances such as extreme pressure anti-wear are better than sulfonate with high base number calcium-base grease, and lubricating life is longer, and cost is low, preparation technology is simple, Environmental protection.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of composite calcium naphthenate calcium zirconium base polyureas lubrication Fat, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid calcium naphthenate；1-10 weight % height The zirconates of level aliphatic acid；The zirconates of 1-15 weight % aromatic acid；0.5-30 weight % polyurea compound；10-80 weight % basis Oil；The optionally zirconates of the small molecule inorganic acid also including 1-15 weight % and/or lower fatty acid, wherein, the advanced fat The zirconates of fat acid is formed by higher fatty acids and component A reactions, the zirconates of the aromatic acid be reacted by aromatic acid and component A and Into the zirconates of the small molecule inorganic acid and/or lower fatty acid is by small molecule inorganic acid and/or lower fatty acid and component A reactions form, and the component A is at least one of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide.

Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid calcium naphthenate； The zirconates of 2-6 weight % higher fatty acids；The zirconates of 2-10 weight % aromatic acid；1-20 weight % polyurea compound；20-70 Weight % base oil；The optionally zirconates of the small molecule inorganic acid also including 2-10 weight % and/or lower fatty acid.

Preferably, the component A is the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, in terms of zirconium, zirconium Oxide and/or the mol ratio of hydroxide and zirconium alkoxide be 1：0.1-10, more preferably 1：0.5-5.

Second aspect, the invention provides the preparation method of composite calcium naphthenate calcium zirconium base polyurea grease as described above, This method includes：By non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid, polyurea compound and part base Plinth oil and the small molecule inorganic acid of selectivity and/or the zirconates of lower fatty acid are well mixed, and are refined in 180-230 DEG C of constant temperature System, surplus base oil is added, necessary additive is added, obtains finished product.

The third aspect, the invention provides a kind of preparation method of composite calcium naphthenate calcium zirconium base polyurea grease, this method Including：

（1）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, adds the small molecule of higher fatty acids, aromatic acid and selectivity Inorganic acid and/or lower fatty acid are reacted, and heat up dehydration after reaction, and the component A is oxide, the hydroxide of zirconium of zirconium At least one of thing and zirconium alkoxide；

（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 composite calcium naphthenate calcium zirconium base polyureas as made from method as described above to lubricate Fat.

The composite calcium naphthenate calcium zirconium base polyurea grease of the present invention, compared to Composite calcium-sulfonate-batetrapolyurea polyurea grease, have more The performances such as mechanical stability, water-resistance and adhesiveness well, resistance to saltfog, colloid stability, 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.

Brief description of the drawings

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

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 composite calcium naphthenate calcium zirconium base polyurea grease, this lubricating grease employs petroleum naphthenic acid Calcium and/or synthesis calcium naphthenate are raw material, simultaneously containing polyureas chemical combination caused by the reaction of compound zirconium thickening agent, isocyanates and amine Thing.

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

On the one hand, the invention provides a kind of composite calcium naphthenate calcium zirconium base polyurea grease, on the basis of lubricating grease weight, Including following components：10-70 weight % non-newtonian fluid calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 weights Measure the zirconates of % aromatic acid；0.5-30 weight % polyurea compound；10-80 weight % base oil；Optionally also include 1-15 Weight % small molecule inorganic acid and/or the zirconates of lower fatty acid, wherein, the zirconates of higher fatty acids is by higher fatty acids Formed with component A reactions, the zirconates of aromatic acid is formed by aromatic acid and component A reactions, small molecule inorganic acid and/or lower fatty acid Zirconates be to be formed by small molecule inorganic acid and/or lower fatty acid and component A reactions, component A is oxide, the hydrogen of zirconium of zirconium At least one of oxide and zirconium alkoxide.

Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid calcium naphthenate； The zirconates of 2-6 weight % higher fatty acids；The zirconates of 2-10 weight % aromatic acid；1-20 weight % polyurea compound；20-70 Weight % base oil；The optionally zirconates of the small molecule inorganic acid also including 2-10 weight % and/or lower fatty acid；It is more excellent Selection of land, on the basis of lubricating grease weight, including following components：30-55 weight % non-newtonian fluid calcium naphthenate；2.2-4.2 weight Measure the zirconates of % higher fatty acids；The zirconates of 3-8 weight % aromatic acid；2-10 weight % polyurea compound；30-60 weight %'s Base oil；The optionally zirconates of the small molecule inorganic acid also including 3-8 weight % and/or lower fatty acid.

In the present invention, " optionally also including " refer to can include can not also include, i.e. small molecule inorganic acid and/ Or the zirconates of lower fatty acid is optional component, the component can be included in composite calcium naphthenate calcium zirconium base lubricating grease of the invention, The component can not also be included.

Non-newtonian fluid calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1There is crystal form calcium carbonate characteristic absorption peak in place, always Base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid calcium naphthenate be by Newton body calcium naphthenate converts to obtain by transforming agent.And contain unformed calcium carbonate in newton body calcium naphthenate, in INFRARED SPECTRUM Figure 86 0cm^-1-865cm^-1There is unformed calcium carbonate characteristic absorption peak in place.Newton body calcium naphthenate be petroleum naphthenic acid calcium and/ Or synthesis calcium naphthenate, its total base number are 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g, are turned After being melted into non-newtonian fluid calcium naphthenate, its base number is constant.

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, aromatic acid is the carboxylic acid that at least 1 carboxyl is joined directly together with aromatic ring, and aromatic acid can be substitution or not Substituted aromatic acid, its substituent can be in alkyl or aryl of alkyl, alkenyl, alkynyl, aryl, halo or perhalogeno etc. extremely Few one kind, the molecular weight of aromatic acid are less than or equal to 550.Aromatic acid is preferably binary aromatic acid, for example, unsubstituted or C1- can be selected from In the alkyl-substituted phthalic acids of C5, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid at least It is a kind of.Preferably phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, and methyl substituted biphenyl diformazan At least one of sour, multi-joint phthalic acid etc..

In the present invention, the molecular weight of small molecule inorganic acid or lower fatty acid is less than or equal to 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 the water-resistance and adhesiveness of lubricating grease, colloid stability and lubricating life, and therefore, component A is preferably the oxide of zirconium And/or the mixture of hydroxide and zirconium alkoxide, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium Mol ratio be preferably 1：0.1-10, more preferably 1：0.2-8, it is still more preferably 1：0.5-5, zirconium oxide and/ Or in the case of the preferred molar ratio of hydroxide and zirconium alkoxide, it can further improve water-resistance and the adhesion of lubricating grease Property, 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、R^1’It 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, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R³More preferably With-(CH₂)₆- in extremely Few one kind.

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.

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.

It is inorganic for non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid, small molecule in the present invention Zirconates, polyurea compound, base oil and the additive of acid and/or 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 calcium naphthenate, it can convert to obtain by transforming agent by newton body calcium naphthenate, for example, by ox Body calcium naphthenate, base oil Hybrid Heating pause to 50-80 DEG C, adds required transforming agent and is reacted, all transforming agents add Afterwards, in 60-90 DEG C of constant temperature 60-90 minute, 100-120 DEG C of dehydration is then heated to.

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

Step of the present invention（1）In, the weight ratio preferably 1 of newton body calcium naphthenate and base oil：0.1-3.

In the present invention, newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesizes calcium naphthenate, and 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 calcium naphthenate weight, more preferably newton body calcium naphthenate weight 6-22%。

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, water-resistance and adhesiveness, the colloid stability and lubricating life of obtained lubricating grease are can further improve, because This, it is preferable that step（2）In, at 85-100 DEG C, component A is added, adds higher fatty acids, stirs 5-20 minutes, adds virtue The small molecule inorganic acid and/or lower fatty acid of acid and selectivity, 5-20 minutes are stirred, are warming up to 100-120 DEG C, preferably Kept for 30-60 minutes, dehydration, the component A is the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, with zirconium Meter, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are preferably 1：0.1-10, more preferably 1：0.2-8, more More preferably 1：0.5-5.Wherein, the addition of higher fatty acids and aromatic acid, small molecule inorganic acid and/or lower fatty acid is suitable Sequence can exchange.

In the present invention, " selective small molecule inorganic acid and/or lower fatty acid " refers to step（2）In can include it is small Molecule inorganic acid and/or lower fatty acid, small molecule inorganic acid and/or lower fatty acid can not also be included, i.e. small molecule without Machine acid and/or lower fatty acid are an optional raw materials.

In the present invention, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid, the oxide of zirconium, the hydrogen-oxygen of zirconium Compound and zirconium alkoxide are as it was previously stated, will not be repeated here.

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

In the present invention, the addition of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide is preferably newton body aphthenic acids The 1-15% of calcium weight；With H⁺Material gauge, the small molecule inorganic acid of higher fatty acids and aromatic acid and selectivity and/or low The mol ratio of level aliphatic 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, Asia Alkyl or cycloalkylidene, it is preferably —(CH₂)₆- etc..For example, The diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), 1,6- hexylidene Diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate（HMDI）With an xylylene diisocyanate（XDI）In It is at least one.

The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, structural formula 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.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 composite calcium naphthenate made from the preparation method provided as third aspect present invention Calcium zirconium base polyurea grease.

Compared with the composite calcium naphthenate calcium zirconium base polyurea grease as made from the preparation method that second aspect provides, third party Composite calcium naphthenate calcium zirconium base polyurea grease made from the preparation method that face provides has more preferable 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 calcium naphthenate %=（Overbased or overbased calcium alkyl-salicylate raw material weight+transforming agent gross weight）/ profit Consistent lubricant gross weight × 100%.Transforming agent is included in the content of non-newtonian fluid calcium naphthenate.

The zirconates of higher fatty acids, the zirconates of aromatic acid and the zirconates of small molecule inorganic acid and/or lower fatty acid contain Amount, according to higher fatty acids, aromatic acid and small molecule inorganic acid and/or the oxide of lower fatty acid and zirconium, the zirconium added Hydroxide and zirconium alkoxide react completely generation zirconates amount calculate.

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 sulfoacid calcium 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 composite calcium naphthenate calcium zirconium base polyurea grease for illustrating prepared by the present invention.

Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；HVI150BS lubricating base oils （100 DEG C of kinematic viscosity are 31mm²/ s, 30kg）；Aphthenic acids（Total acid number is 180mgKOH/g, 2.8kg）；Methanol（1kg）；Acetic acid （0.56kg）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；Octadecylamine（1.5kg）； MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 17kg）.

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers The HVI150BS lubricating base oils of naphthenate with superhigh base number calcium and 30kg for 400mgKOH/g, stirring, heat to 50 DEG C, Constant temperature 30 minutes；2.8kg aphthenic acids is 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 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；60 DEG C are warming up to, constant temperature 90 minutes, material becomes It is thick；100 DEG C are warming up to, adds the Zr (OH) that solid content is 20 weight %₄Suspension 19.5kg, stir 10 minutes；Add 2kg12- Hydroxy stearic acid, stir 10 minutes；3.5kg terephthalic acid (TPA)s are added, are stirred 10 minutes, 110 DEG C are warming up under stirring, keep 45 Minute, dehydration；2kg HVI500SN lubricating base oils and 1.5kg octadecylamines is added, is stirred 4 minutes, is added and be dissolved in 2kg's 0.7kg MDI in HVI500SN lubricating base oils, stir 4 minutes, the mol ratio of added MDI and octadecylamine is 1:2,120 DEG C 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 temperature Degree is cooled to 110 DEG C, and 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 calcium naphthenate 36.8 Weight %；The weight % of two polyureas 2.4；The weight % of lubricating base oil 51.9；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；Terephthalic acid (TPA) The weight % of oxygen zirconium 6.3.

Embodiment 2

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers The HVI150BS lubricating base oils of naphthenate with superhigh base number calcium and 30kg for 400mgKOH/g, stirring, heat to 50 DEG C, Constant temperature 30 minutes；2.8kg aphthenic acids is 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 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；60 DEG C are warming up to, constant temperature 90 minutes, material becomes It is thick；100 DEG C are warming up to, adds the Zr (OH) that solid content is 20 weight %₄Suspension 19.5kg, stir 10 minutes；Add 2kg12- Hydroxy stearic acid, stir 10 minutes；3.5kg terephthalic acid (TPA)s are added, are stirred 10 minutes, 110 DEG C are warming up under stirring, keep 45 Minute, 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 mol ratio of added MDI and octadecylamine is 1:2,120 DEG C of constant temperature 20 Minute, obtain 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：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；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）；Phthalic acid（3.5kg）；Lauryl amine（1.31kg）；MDI（0.89kg）； HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 27kg）.

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers The HVI150BS lubricating base oils of naphthenate with superhigh base number calcium and 20kg for 400mgKOH/g, stirring, heat to 80 DEG C, Constant temperature 10 minutes；2.8kg n-butanols are added, temperature control stirs 10 minutes at 80 DEG C or so；It is 20 weights to add 2.8kg concentration % aqueous acetic acid is measured, is stirred 10 minutes；It is warming up to 90 DEG C, constant temperature 60 minutes, material retrogradation；Successively add the positive fourths of 7.83kg Alcohol zirconium and the Zr (OH) that solid content is 20 weight %₄Suspension 3.25kg, in terms of zirconium, Zr (OH)₄Mol ratio with zirconium-n-butylate is 1：5, stir 10 minutes；1.9kg stearic acid is added, is stirred 10 minutes；3.5kg phthalic acids are added, are stirred 10 minutes, stirring Under be warming up to 120 DEG C, kept for 30 minutes, dehydration；Add 2kg HVI500SN lubricating base oils and 1.31kg lauryl amines, stirring 8 Minute, the 0.89kg MDI being dissolved in 2kg HVI500SN lubricating base oils are added, are stirred 8 minutes, added MDI and ten The mol ratio of eight amine is 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, Add remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection Test and the results are 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 calcium naphthenate 36.9 Weight %；The weight % of two polyureas 2.4；The weight % of lubricating base oil 51.9；The weight % of zirconyl stearate 2.5；Phthalic acid oxygen zirconium 6.3 Weight %.

Embodiment 4

Raw material components：Overbased calcium alkyl-salicylate（Total base number is 320mgKOH/g, 30kg）；HVI150BS lubricating base oils （100 DEG C of kinematic viscosity are 31mm²/ s, 25kg）；DBSA（2.8kg）；Methanol（1kg）；Acetic acid（0.56kg）；Second Alcohol zirconium（2.21kg）；Zr(OH)₄（2.6kg）；12- hydroxy stearic acids（2kg）；M-phthalic acid（3.5kg）；Octadecylamine （1.66kg）；TDI（0.54kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 22kg）.

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses Total base number is 320mgKOH/g overbased calcium alkyl-salicylate；Aphthenic acids is replaced with DBSA；With M-phthalic acid generation For terephthalic acid (TPA)；Use toluene di-isocyanate(TDI)（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.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid calcium naphthenate 36.8 Weight %；The weight % of two polyureas 2.4；The weight % of lubricating base oil 51.9；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；M-phthalic acid The weight % of oxygen zirconium 6.3.

Embodiment 5

Raw material components：Overbased calcium alkyl-salicylate（Total base number is 360mgKOH/g, 30kg）；HVI150BS lubricating base oils （100 DEG C of kinematic viscosity are 31mm²/ s, 15kg）；Aphthenic acids（Total acid number is 180mgKOH/g, 2.8kg）；Methanol（1kg）；Acetic acid （0.56kg）；Zirconium-n-propylate（4.0kg）；Zr(OH)₄（2.0kg）；12- hydroxy stearic acids（2kg）；2- methyl isophthalic acids, 4- benzene diformazans Acid（3.8kg）；Octadecylamine（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 7kg）.

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses Total base number is 360mgKOH/g overbased calcium alkyl-salicylate；With 2- methyl isophthalic acids, 4- phthalic acids replace terephthalic acid (TPA)；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；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 calcium naphthenate 50.6 Weight %；The weight % of two polyureas 3.3；The weight % of lubricating base oil 33.4；The weight % of 12- hydroxy stearic acid oxygen zirconium 3.6；2- methyl isophthalic acids, The weight % of 4- phthalic acid oxygen zirconium 9.1.

Embodiment 6

Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；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）；4,4'- biphenyl dicarboxylic acids（5.1kg）；Octadecylamine（4.5kg）；MDI （2.1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 18.6kg）.

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, transforming agent is used only Aphthenic acids and acetic acid, save the step of adding methanol；Terephthalic acid (TPA) is replaced with 4,4'- biphenyl dicarboxylic acids；The dosage of each composition 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 calcium naphthenate 35.8 Weight %；The weight % of two polyureas 7.1；The weight % of lubricating base oil 46.8；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.5；4,4'- biphenyl The weight % of dioctyl phthalate oxygen zirconium 7.8.

Embodiment 7

Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；Poly alpha olefine synthetic oil PAO40（100 DEG C of kinematic viscosity are 40mm²/ 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）；Terephthalic acid (TPA)（3.5kg）；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 tungsten selenides（2kg）；It is right, right '-diisooctyl Diphenylamines（0.2kg）.

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, use poly alpha olefin Artificial oil PAO40（100 DEG C of kinematic viscosity are 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 of kinematic viscosity are 31mm²/s）And HVI500SN（100 DEG C of kinematic viscosity are 11mm²/s）； Aphthenic acids and acetic acid is used only in transforming agent, saves the step of adding methanol；And treat that temperature is cooled to 110 DEG C, add the two of 2kg Thio Acidic phosphates zinc, stir 10 minutes, add 1kg molybdenum dialkyldithiocarbamacompositions, stir 10 minutes, add 2kg tungsten disulfide, stir 10 minutes, add 2kg two tungsten selenides, stir 10 minutes, add 0.2kg pair, it is right '-two different Octyl diphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The dosage of each composition is as above.Examine knot Fruit 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 calcium naphthenate 37.2 Weight %；The weight % of two polyureas 2.5；The weight % of lubricating base oil 43.4；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；Terephthalic acid (TPA) The weight % of oxygen zirconium 6.4；The two thio weight % of Acidic phosphates zinc 2.2；The weight % of molybdenum dialkyldithiocarbamacompositions 1.1；Curing The weight % of tungsten 2.2；The weight % of two tungsten selenide 2.2；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 8

Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；HVI150BS lubricating base oils （100 DEG C of kinematic viscosity are 31mm²/ s, 15kg）；Aphthenic acids（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）； Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；Octadecylamine（0.94kg）；Para-totuidine （0.38kg）；MDI（0.88kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, transforming agent is used only Aphthenic acids and acetic acid, save the step of adding methanol；When adding octadecylamine, para-totuidine is additionally added；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 calcium naphthenate 36.4 Weight %；The weight % of two polyureas 2.4；The weight % of lubricating base oil 52.4；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；Terephthalic acid (TPA) The weight % of oxygen zirconium 6.2.

Embodiment 9

Raw material components：Overbased calcium alkyl-salicylate（Total base number is 360mgKOH/g, 30kg）；HVI150BS lubricating base oils （100 DEG C of kinematic viscosity are 31mm²/ s, 20kg）；Aphthenic acids（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）； Zr(OH)₄（11.2kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；Terephthalic acid (TPA)（7.6kg）；Octadecylamine （0.84kg）；Lauryl amine（0.58kg）；MDI（0.78kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ S, 28kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses Total base number is 360mgKOH/g overbased calcium alkyl-salicylate；Aphthenic acids and acetic acid is used only in transforming agent, saves the step for adding methanol Suddenly；After adding 12- hydroxy stearic acids, boric acid is additionally added, then adds terephthalic acid (TPA)；When adding octadecylamine, the moon is additionally added Osmanthus amine；And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, right '-di-iso-octyldiphenylamine, after stirring 10 minutes, then Circulating filtration, homogenizing, degassing obtain 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 calcium naphthenate 32.7 Weight %；The weight % of two polyureas 2.2；The weight % of lubricating base oil 47.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.3；Boric acid oxygen zirconium 3.5 weight %；The weight % of terephthalic acid (TPA) oxygen zirconium 12.1；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 10

Raw material components：Overbased calcium alkyl-salicylate（Total base number is 360mgKOH/g, 30kg）；HVI150BS lubricating base oils （100 DEG C of kinematic viscosity are 31mm²/ s, 15kg）；Aphthenic acids（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）； Zr(OH)₄（6.5kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；Acetic acid（2kg）；Octadecylamine（1.5kg）； MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses Total base number is 360mgKOH/g overbased calcium alkyl-salicylate；Aphthenic acids and acetic acid is used only in transforming agent, saves the step for adding methanol Suddenly；After adding terephthalic acid (TPA), 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 calcium naphthenate 35.0 Weight %；The weight % of two polyureas 2.3；The weight % of lubricating base oil 50.3；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.5；Terephthalic acid (TPA) The weight % of oxygen zirconium 6.0；The weight % of zirconyl acetate 3.9.

Embodiment 11

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers The HVI150BS lubricating base oils of naphthenate with superhigh base number calcium and 30kg for 400mgKOH/g, stirring, heat to 50 DEG C, Constant temperature 30 minutes；2.8kg aphthenic acids is 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 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；60 DEG C are warming up to, constant temperature 90 minutes, material becomes It is thick.

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；3.5kg terephthalic acid (TPA)s are added, stirs 10 minutes, obtains 12- Hydroxy stearic acid oxygen zirconium and terephthalic acid (TPA) 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 mol ratio of added MDI and octadecylamine is 1:2,120 DEG C of constant temperature 20 minutes, obtains dimerization Urea.

The 12- hydroxy stearic acid oxygen zirconiums of gained and terephthalic acid (TPA) oxygen zirconium are all squeezed into first kettle, stirred, 110 DEG C are warming up under stirring, is kept for 45 minutes, dehydration, two polyureas obtained by the 3rd reactor is all squeezed into the kettle, stirred Mix uniformly, be finally warming up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oils are added；Treat that temperature cools down 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 30kg total base numbers be 400mgKOH/g naphthenate with superhigh base number calcium and 25kg100 DEG C of kinematic viscosity are 31mm²/ s HVI150BS lubricating base oils, Stirring, heats to 60 DEG C, constant temperature 10 minutes；3kg aphthenic acids is added, temperature control stirs 10 minutes at 60 DEG C or so；Add Enter the 12.5kg butanol aqueous solution that concentration is 20%, stir 10 minutes；In 87 DEG C of constant temperature 70 minutes, material retrogradation.

It is 30L 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 50 weight %₄Suspension 19.0kg, stir 10 minutes, add Enter 2.4kg palmitic acid, stir 10 minutes, add the ethanedioic acid of 4.2kg biphenyl dicarboxylic acid, 1kg phosphoric acid and 2kg, stirring 10 minutes, obtain palmitic acid oxygen zirconium, biphenyl dicarboxylic 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 30L 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, biphenyl dicarboxylic acid oxygen zirconium, zirconium phosphate oxygen and ethanedioic acid oxygen zirconium are all squeezed into reactor A In, stir, 120 DEG C are warming up under stirring, kept for 30 minutes, dehydration, the polyureas of gained four and six polyureas are all squeezed into instead Answer in kettle 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 Lubricating base 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 calcium naphthenate 32.6 Weight %；The weight % of palmitic acid oxygen zirconium 2.7；The weight % of biphenyl dicarboxylic acid oxygen zirconium 5.6；The weight % of zirconium phosphate oxygen 2.4；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 48.7.

Embodiment 13

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add 30kg total alkalis It is 31mm to be worth for 420mgKOH/g naphthenate with superhigh base number calcium and 10kg100 DEG C of kinematic viscosity²/ s HVI150BS lubrication bases Plinth oil, stirring, heats to 50 DEG C, constant temperature 10 minutes；Add 2kg DBSAs, temperature control at 50 DEG C or so, Stirring 10 minutes；1kg methanol is added, is stirred 10 minutes；The aqueous acetic acid that 2kg concentration is 20 weight % is added, stirs 10 points Clock；In 83 DEG C of constant temperature 80 minutes, material retrogradation.

It is 30L 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 17.0kg, stir 10 minutes, add 2.4kg laurate, stir 10 minutes, add 7.9kg M-phthalic acid, stir 10 minutes, obtain laurate oxygen zirconium and Phthalic acid oxygen zirconium.

Volume be 30L 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 M-phthalic acid oxygen zirconium are all squeezed into reactor A, stirred, stirs lower heat up To 110 DEG C, kept for 45 minutes, dehydration, gained mixing polyureas is all squeezed into reactor A, stirs, is finally warming up to 200 DEG C of constant temperature 5 minutes.Then, 2kg HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, Change, degassing obtains 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 calcium naphthenate 44.0 Weight %；The weight % of laurate oxygen zirconium 4.1；The weight % of M-phthalic acid oxygen zirconium 8.2；The weight % of polyurea compound 3.0；Lubricating base oil 40.7 weight %.

Embodiment 14

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

Embodiment 15

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

Embodiment 16

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 5, unlike, at Zr (OH)₄With In the case that the total mole number of zirconium-n-propylate is constant, Zr (OH) is adjusted₄Mol ratio with zirconium-n-propylate is 1：0.1.Gained fat Each physicochemical property is shown in Table 1.

Embodiment 17

Composite calcium naphthenate calcium zirconium base polyurea grease is prepared according to the method for embodiment 5, unlike, at Zr (OH)₄With In the case that the total mole number of zirconium-n-propylate is constant, Zr (OH) is adjusted₄Mol ratio with zirconium-n-propylate is 1：10.Gained fat it is each Physicochemical property is shown in Table 1.

Embodiment 18

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

Embodiment 19

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

Comparative example 1

Composite calcium-sulfonate-batetrapolyurea polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number calcium The overbased sulfoacid calcium for being 400mgKOH/g with total base number replaces, Zr used (OH)₄With Ca (OH)₂Instead of, while adjust use Amount makes each component content 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 36.8 Measure %；The weight % of two polyureas 2.4；The weight % of lubricating base oil 51.9；The weight % of 12- hydroxy stearic acids calcium 2.6；Terephthalic acid (TPA) calcium 6.3 weight %.

Comparative example 2

Composite calcium-sulfonate-batetrapolyurea polyurea grease is prepared according to the method for embodiment 5, unlike, overbased calcium alkyl-salicylate is used Calcium sulfonate with high base number replacement, zirconium-n-propylate used and the Zr (OH) that total base number is 360mgKOH/g₄With Ca (OH)₂Instead of together When adjustment dosage make each component content and embodiment 5 consistent, 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 50.6 Measure %；The weight % of two polyureas 3.3；The weight % of lubricating base oil 33.4；The weight % of 12- hydroxy stearic acids calcium 3.6；2- methyl isophthalic acids, 4- benzene The weight % of dioctyl phthalate calcium 9.1.

Each lubricating grease properties of sample data of table 1

Each indication test method：Outward appearance：Range estimation；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；It is anti- Water spray：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

By embodiment 1 compared with comparative example 1, by embodiment 5 compared with comparative example 2, it can be seen that the present invention Composite calcium naphthenate calcium zirconium base polyurea grease extension work cone penetration with work cone penetration difference be less than complex calcium sulfonate Base polyurea grease, water leaching number of dropouts are less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and salt spray test is gathered better than Composite calcium-sulfonate-batetrapolyurea Urea grease, water resistant spraying value are less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and Stencil oil-dividing value is less than Composite calcium-sulfonate-batetrapolyurea polyureas Lubricating grease, tetra-ball machine test value are more than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and the bearing lubrication life-span gathers more than Composite calcium-sulfonate-batetrapolyurea Urea grease, illustrate mechanical stability, water-resistance and the adhesiveness of the composite calcium naphthenate calcium zirconium base polyurea grease of the present invention, resist Salt fog, colloid stability, extreme pressure anti-wear, lubricating life are superior to Composite calcium-sulfonate-batetrapolyurea polyurea grease.

By embodiment 1 respectively compared with embodiment 2 and embodiment 11 as can be seen that the composite calcium naphthenate in situ prepared Calcium zirconium base polyurea grease, there is more preferable water-resistance and adhesiveness, colloid stability, there is longer lubricating life；Will be real Example 1 is applied respectively compared with embodiment 14 and embodiment 15 as can be seen that transforming agent is selected from DBSA, cycloalkanes At least one of acid, methanol, butanol, isopropanol, boric acid, acetic acid and water, the composite calcium naphthenate calcium zirconium base polyureas lubrication of preparation Fat, there is more preferable water-resistance and adhesiveness, colloid stability, there is longer lubricating life；By embodiment 5 respectively with implementation Example 16 and embodiment 17 are compared as can be seen that the oxide and/or the mol ratio of hydroxide and zirconium alkoxide of zirconium are 1： 0.5-5, the composite calcium naphthenate calcium zirconium base polyurea grease of preparation, there is more preferable water-resistance and adhesiveness, colloid stability, have There is longer lubricating life；By embodiment 5 respectively compared with embodiment 18 and embodiment 19 as can be seen that the raw material of zirconium is The oxide and/or hydroxide of zirconium and the mixture of zirconium alkoxide, the composite calcium naphthenate calcium zirconium base polyurea grease of preparation, tool There are more preferable water-resistance and adhesiveness, colloid stability, there is 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 peak at place is the stretching vibration absworption peak of-NH- in two 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 composite calcium naphthenate calcium zirconium base polyurea grease, it is characterised in that on the basis of lubricating grease weight, including with the following group Point：10-70 weight % non-newtonian fluid calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 weight % virtue The zirconates of acid；0.5-30 weight % polyurea compound；10-80 weight % base oil；Optionally also include 1-15 weights % small molecule inorganic acid and/or the zirconates of lower fatty acid are measured, wherein, the zirconates of the higher fatty acids is by higher aliphatic Acid forms with component A reactions, and the zirconates of the aromatic acid is to be reacted to form by aromatic acid and component A, the 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, and the component A is zirconium Oxide, the hydroxide and at least one of zirconium alkoxide of zirconium, the non-newtonian fluid 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 calcium naphthenate；The zirconates of 2-6 weight % higher fatty acids；The zirconates of 2-10 weight % aromatic acid；1- 20 weight % polyurea compound；20-70 weight % base oil；Optionally also the small molecule including 2-10 weight % is inorganic The zirconates of acid and/or lower fatty acid.

3. lubricating grease according to claim 2, wherein, the non-newtonian fluid calcium naphthenate is turned by newton body calcium naphthenate Change what is obtained, the total base number of the non-newtonian fluid 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 aromatic acid is substituted or unsubstituted aromatic acid, substituent For alkyl, alkenyl, alkynyl, aryl, halo at least one of alkyl or aryl, the molecular weight of the aromatic acid is less than or equal to 550。

7. according to the lubricating grease described in claim 6, wherein, the aromatic acid is selected from the alkyl-substituted neighbours of unsubstituted or C1-C5 At least one of phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid.

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

9. lubricating grease according to claim 8, 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.

10. 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.

11. lubricating grease according to claim 10, wherein, in terms of zirconium, the oxide and/or hydroxide and alkoxy of zirconium The mol ratio of zirconium is 1：0.5-5.

12. 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.

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

14. lubricating grease according to claim 13, 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.

15. lubricating grease according to claim 1 or 2, wherein, the polyurea compound is two polyurea compounds, the chemical combination Thing has following structure：

Wherein, R¹、R¹' it is alkyl, cycloalkyl or aryl, R³It is arlydene, alkylidene or cycloalkylidene.

16. lubricating grease according to claim 15, wherein, R¹、R¹' it is phenyl or substituted phenyl, or carbon number is 8-24's Alkyl or cycloalkyl；R³It is 6-30 arlydene, alkylidene or cycloalkylidene.

17. lubricating grease according to claim 16, wherein, R¹、R¹' it is the benzene that phenyl, C1-C3 alkyl or halogen substitute Base, or the alkyl or cycloalkyl that carbon number is 10-18, R³It is With- (CH₂)₆At least one of-.

18. the preparation method of the composite calcium naphthenate calcium zirconium base polyurea grease in claim 1-17 described in any one, it is special Sign is that this method includes：By non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid, polyurea compound and Part basis oil and the small molecule inorganic acid of selectivity and/or the zirconates of lower fatty acid are well mixed, at 180-230 DEG C Constant temperature is refined, and is added surplus base oil, is added necessary additive, obtain finished product.

19. the preparation method of the composite calcium naphthenate calcium zirconium base polyurea grease in claim 1-17 described in any one, it is special Sign is that this method includes：

(1) 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, the small molecule for adding higher fatty acids, aromatic acid and selectivity is inorganic Acid and/or lower fatty acid are reacted, and heat up dehydration after reaction, the component A be the oxide of zirconium, zirconium hydroxide and At least one of zirconium alkoxide；

(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.

20. according to the method for claim 19, wherein, in step (1), newton body calcium naphthenate, part basis oil are mixed Conjunction is heated to 50-80 DEG C, adds required transforming agent and is reacted, after all transforming agents add, in 60-90 DEG C of constant temperature 60-90 Minute.

21. according to the method for claim 19, wherein, in step (2), at 85-100 DEG C, component A is added, is added high Level aliphatic acid, stirs 5-20 minutes, adds aromatic acid and the small molecule inorganic acid and/or lower fatty acid of selectivity, stirs 5- 20 minutes, it is warming up to 100-120 DEG C of dehydration.

22. according to the method for claim 19, 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 19, 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 19, wherein, the newton body calcium naphthenate is petroleum naphthenic acid calcium and/or conjunction Into calcium naphthenate, the total base number of the newton body calcium naphthenate is 250-450mgKOH/g.

25. according to the method for claim 19, 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 2-30% of newton body calcium naphthenate weight.

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 calcium naphthenate weight 6-22%.

27. according to the method for claim 19, 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 19, 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 19, 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 31, 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.