CN104560324B

CN104560324B - A kind of polyurea grease of composite calcium naphthenate calcium zirconium base four and preparation method thereof

Info

Publication number: CN104560324B
Application number: CN201310522238.6A
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: 2017-11-03
Anticipated expiration: 2033-10-29
Also published as: CN104560324A

Abstract

The invention discloses a kind of lubricating grease, 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；Small molecule inorganic acid and/or the zirconates of lower fatty acid optionally also including 1 15 weight %, the zirconates of higher fatty acids, the zirconates of aromatic acid, the zirconates of small molecule inorganic acid and/or lower fatty acid are formed by the reaction of at least one of higher fatty acids, aromatic acid, small molecule inorganic acid and/or the oxide of lower fatty acid and zirconium, the hydroxide of zirconium and zirconium alkoxide respectively, and polyurea compound is four polyurea compounds.Also disclose the lubricating grease of preparation of greases method and its preparation.The lubricating grease of the present invention, has excellent mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, there is longer lubricating life.

Description

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

Technical field

The present invention relates to lubricating grease, in particular it relates to a kind of polyurea grease of composite calcium naphthenate calcium zirconium base four and its preparation 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, exactly calcium carbonate, which is distributed to the naphthenic acid calcium with surface-active in flux oil, turns into a kind of colloidal dispersion system.It is high Base number calcium naphthenate mostly be the acidic components extracted from the distillate that crude distillation is obtained, through with Ca (OH)₂Reaction, carbonating Contour alkalization technology and obtain, about prepare Patents have CN1465560 etc..

Using calcium sulfonate with high base number be raw material produce lubricating grease, because its have excellent high temperature performance, mechanical stability, Colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, have caused domestic and international profit The extensive concern of consistent lubricant industry, although however, high base number composite calcium sulfonate base grease has very excellent combination property, The high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, together When, the requirement more and more higher with people to environmental protection, in calcium sulfonate with high base number production process must through sulfonation process to ring The pollution in border is also increasingly subject to the concern of people.Find a kind of performance it is similar with high base number composite calcium sulfonate base grease but can Mitigating the lubricating grease of above mentioned problem turns into the big problem that people face at present.

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

The content of the invention

It is better than sulfonate with high base number calcium-base grease it is an object of the invention to provide a kind of performance, 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 to be formed by higher fatty acids with component A reactions, described The zirconates of aromatic acid is to be formed by aromatic acid with 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 are formed with component A reactions, the component A is the oxide of zirconium, the hydroxide of zirconium and At least one of zirconium alkoxide, the polyurea compound is four polyurea compounds.Mechanical stability, the water-resistance of the lubricating grease Be better than sulfonate with high base number calcium-base grease with the performance such as adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, with compared with Long 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 polyureas of composite calcium naphthenate calcium zirconium base four profit Consistent lubricant, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid calcium naphthenate；1-10 weight %'s The zirconates of higher fatty acids；The zirconates of 1-15 weight % aromatic acid；0.5-30 weight % polyurea compound；10-80 weight % base Plinth oil；Small molecule inorganic acid and/or the zirconates of lower fatty acid optionally also including 1-15 weight %, wherein, it is described senior The zirconates of aliphatic acid is formed by higher fatty acids and component A reaction, 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 are formed, and the component A is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium, the polyureas Compound is four polyurea compounds.

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 % four polyurea compounds；20- 70 weight % base oil；Small molecule inorganic acid and/or the zirconates of lower fatty acid optionally also including 2-10 weight %.

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

Second aspect, the invention provides the preparation side of the polyurea grease of composite calcium naphthenate calcium zirconium base four as described above Method, this method includes：By non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid, four polyurea compounds and portion Base oil and the small molecule inorganic acid of selectivity and/or the zirconates of lower fatty acid is divided to be well mixed, in 180-230 DEG C of perseverance Temperature refining, adds surplus base oil, adds necessary additive, obtains finished product.

The third aspect, the invention provides a kind of preparation method of the polyurea grease of composite calcium naphthenate calcium zirconium base four, the party Method includes：

（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, the small molecule of higher fatty acids, aromatic acid and selectivity is added 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 diisocyanate are added in gained mixture, diamines and monoamine is then sequentially added 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 Plus agent, obtain finished product.

Fourth aspect, lubricates the invention provides the polyureas of composite calcium naphthenate calcium zirconium base four as made from method as described above Fat.

The polyurea grease of composite calcium naphthenate calcium zirconium base four of the present invention, compared to the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, tool There are the performances such as more preferable mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, with more Long lubricating life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, and product quality is stable.

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

Brief description of the drawings

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

Embodiment

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

The invention provides a kind of polyurea grease of composite calcium naphthenate calcium zirconium base four, this lubricating grease employs oil cycloalkanes Sour calcium and/or synthesis calcium naphthenate are raw material, react four polyureas produced containing compound zirconium thickening agent, isocyanates and amine simultaneously Compound.

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

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

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 % four polyurea compounds；20- 70 weight % base oil；Small molecule inorganic acid and/or the zirconates of lower fatty acid optionally also including 2-10 weight %；More Preferably, 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 % four polyurea compounds；30-60 weight % Base oil；Small molecule inorganic acid and/or the zirconates of lower fatty acid optionally also including 3-8 weight %.

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 is obtained by transforming agent conversion.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 is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g, is turned It is melted into after 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, the carboxylic acid that aromatic acid is at least 1 carboxyl to be joined directly together with aromatic ring, 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 is 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., the raw material of zirconium for zirconium oxide and/or hydroxide and zirconium alkoxide mixture when, one can be entered Step improves mechanical stability, water-resistance and adhesiveness, colloid stability and the lubricating life of lubricating grease, and therefore, component A is preferably The oxide and/or hydroxide and the mixture of zirconium alkoxide of zirconium, wherein, in terms of zirconium, the oxide and/or hydroxide of zirconium Mol ratio with zirconium alkoxide is preferably 1：0.1-10, more preferably 1：0.2-8, is still more preferably 1：0.5-5, in zirconium In the case of the preferred molar ratio of oxide and/or hydroxide and zirconium alkoxide, the machinery of lubricating grease can be further improved Stability, water-resistance and adhesiveness, colloid stability and lubricating life.

In the present invention, the oxide and/or hydroxide of zirconium are preferably selected from ZrO₂、ZrO(OH)₂、Zr(OH)₄And they At least one of hydrate.ZrO(OH)₂Hydrate can be brand-new wet hydrogen zirconium oxide, it can pass through ZrOX₂· 8H₂O（X is F, Cl, Br or I）Or ZrO (NO₃)₂·2H₂O etc. reacts with alkali to be obtained, wherein, alkali can be NaOH, KOH, dense ammonia Water etc., preferably ZrOCl₂·8H₂O and NaOH reacts.

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

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

Above-mentioned four polyurea compound can be obtained using the thinkable various methods of those skilled in the art institute, for example can be with Prepared according to the CN103060070A methods recorded.

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

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

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, four polyurea compounds, 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 be obtained by newton body calcium naphthenate by transforming agent conversion, for example, by ox Body calcium naphthenate, the base oil Hybrid Heating of pausing are to 50-80 DEG C, and the transforming agent needed for adding is reacted, and all transforming agents are added Afterwards, in 60-90 DEG C of constant temperature 60-90 minutes, 100-120 DEG C of dehydration is then heated to.

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

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 synthesis 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 Fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine selected from C1-C5, C1-C5 ether, boric acid, C1-C10 alkyl phosphonic acid, C2-C16 di alkyl phosphonic acid, C6-C20 arylphosphonic acid, C12-C24 At least one of diaryl phosphonic acids, C7-C20 aromatic alcohol, C7-C20 aromatic amine, C8-C20 alkyl benzene sulphonates and water；More At least one further preferably in DBSA, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water Kind.The addition of transforming agent is preferably the 2-30% of newton body 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 hydroxide and zirconium alkoxide mixture when, i.e., the raw material of zirconium be zirconium oxide and/or hydroxide and alkoxy During the mixture of zirconium, can further improve mechanical stability, water-resistance and the adhesiveness of obtained lubricating grease, colloid stability and Lubricating life, it is therefore preferred that step（2）In, at 85-100 DEG C, component A is added, higher fatty acids is added, 5-20 is stirred Minute, the small molecule inorganic acid and/or lower fatty acid of aromatic acid and selectivity are added, stirs 5-20 minutes, is warming up to 100- 120 DEG C, preferably kept for 30-60 minutes, dehydration, the component A is the oxide and/or hydroxide of zirconium and mixing for zirconium alkoxide Compound, in terms of zirconium, 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, is still more preferably 1：0.5-5.Wherein, higher fatty acids and aromatic acid, small molecule inorganic acid and/or lower aliphatic The addition sequence of acid can be exchanged.

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, can not also include small molecule inorganic acid and/or lower fatty acid, 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 oxide, the hydroxide of zirconium and the zirconium alkoxide that all neutralize zirconium⁺Molal quantity, but zirconium Oxide, the hydroxide of zirconium 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 excess 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 diisocyanate are added in gained mixture, two are then sequentially added Amine and monoamine are reacted, and are in step（2）Four polyurea compounds are prepared in gained mixture.

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 2-8 minutes, two are added Amine, is stirred 2-8 minutes, adds monoamine, is stirred 2-8 minutes, and the mol ratio of diisocyanate, diamines and monoamine is 2:1:2, ability Field technique personnel should be understood that the mol ratio can be fluctuated in the range of ± 5%.

The diisocyanate structure is OCN-R³- NCO, R³Can be carbon number be 6-30, preferably 6-20 arlydene, Alkylidene or cycloalkylidene, be preferably -(CH₂)₆- Deng.Such as described 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） At least one of Deng.

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

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

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

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

Fourth aspect, present invention also offers composite calcium naphthenate made from the preparation method provided as third aspect present invention The polyurea grease of calcium zirconium base four.

Compared with the polyurea grease of composite calcium naphthenate calcium zirconium base four as made from the preparation method that second aspect is provided, the 3rd The polyurea grease of composite calcium naphthenate calcium zirconium base four made from the preparation method that aspect is provided have more preferable water-resistance and adhesiveness, Colloid stability, and with longer lubricating life.

Embodiment

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

In the following Examples and Comparative Examples：

Non-newtonian fluid 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 the zirconates of higher fatty acids, the zirconates of aromatic acid and small molecule inorganic acid and/or lower fatty acid contains Amount, according to the higher fatty acids added, the oxide of aromatic acid and small molecule inorganic acid and/or lower fatty acid and zirconium, zirconium 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 polyurea grease of composite calcium naphthenate calcium zirconium base four 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（1.08kg）； Ethylenediamine（0.12kg）；MDI（1kg）；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 is stirred 10 minutes at 50 DEG C or so；1kg methanol is added, 10 points are stirred 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, the Zr (OH) that solid content is 20 weight % is added₄Suspension 19.5kg, is stirred 10 minutes；Add 2kg12- Hydroxy stearic acid, is stirred 10 minutes；3.5kg terephthalic acid (TPA)s are added, are stirred 10 minutes, 110 DEG C are warming up under stirring, 45 are kept Minute, dehydration；2kg HVI500SN lubricating base oils and 1kg MDI is added, quick stirring 4 minutes is quick to stir lower add 0.12kg ethylenediamines, are stirred 4 minutes, add 1.08kg octadecylamines, are stirred 4 minutes, added MDI, ethylenediamine and octadecylamine Mol ratio is 2:1:2,120 DEG C of constant temperature 20 minutes, is finally warming up to 200 DEG C of constant temperature 10 minutes.Then, add remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1。

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 36.8 Weight %；The weight % of four 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

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（1.08kg）；Second Diamines（0.12kg）；MDI（1kg）；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 is stirred 10 minutes at 50 DEG C or so；1kg methanol is added, 10 points are stirred 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, the Zr (OH) that solid content is 20 weight % is added₄Suspension 19.5kg, is stirred 10 minutes；Add 2kg12- Hydroxy stearic acid, is stirred 10 minutes；3.5kg terephthalic acid (TPA)s are added, are stirred 10 minutes, 110 DEG C are warming up under stirring, 45 are kept Minute, dehydration.

In another volume be 30L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg HVI500SN lubricating base oils and 1kg MDI, are warming up to 120 DEG C, quick stirring 4 minutes, and quick stirring is lower to add 0.12kg second Diamines, is stirred 4 minutes, adds 1.08kg octadecylamines, is stirred 4 minutes, and added MDI, ethylenediamine and octadecylamine mol ratio are 2:1:2,120 DEG C of constant temperature 20 minutes, obtains four polyureas.

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

The four 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（0.88kg）；Ethylenediamine（0.14kg）； MDI（1.18kg）；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 is stirred 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；Add 3.5kg phthalic acids, stirring, the lower heating of stirring To 120 DEG C, kept for 30 minutes, dehydration；Add 2kg HVI500SN lubricating base oils and 1.18kg MDI, quick 4 points of stirring Clock, quick stirring is lower to add 0.14kg ethylenediamines, stirs 4 minutes, adds 0.88kg lauryl amines, stirs 4 minutes, added MDI, The mol ratio of ethylenediamine and octadecylamine is 2:1:2,100 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, remaining HVI500SN lubricating base oils are added；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 is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 36.9 Weight %；The weight % of four 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 （1.25kg）；Ethylenediamine（0.14kg）；TDI（0.81kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ S, 22kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, calcium naphthenate makes The overbased calcium alkyl-salicylate for being 320mgKOH/g with total base number；Aphthenic acids is replaced with DBSA；Use M-phthalic acid Instead of 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 consumption of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 36.8 Weight %；The weight % of four 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（1.08kg）；Ethylenediamine（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of motions Viscosity is 11mm²/ s, 7kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, calcium naphthenate makes The overbased calcium alkyl-salicylate for being 360mgKOH/g with total base number；2- methyl isophthalic acids are used, 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 consumption of each composition is such as On.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 50.6 Weight %；The weight % of four 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（3.24kg）；Second two Amine（0.36kg）；MDI（3kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 18.6kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, transforming agent only makes With aphthenic acids and acetic acid, the step of saving addition methanol；Terephthalic acid (TPA) is replaced with 4,4'- biphenyl dicarboxylic acids；The use of each composition Amount is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 35.8 Weight %；The weight % of four 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（1.08kg）； Ethylenediamine（0.12kg）；MDI（1kg）；Poly alpha olefine synthetic oil PAO10（100 DEG C of kinematic viscosity are 11mm²/ s, 9kg）；Two sulphur For Acidic phosphates zinc（2kg）；Molybdenum dialkyldithiocarbamacompositions（1kg）；Tungsten disulfide（2kg）；Two tungsten selenides（2kg）； It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, use poly- α-alkene Hydrocarbon 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, the step of saving addition methanol；And treat that temperature is cooled to 110 DEG C, plus Enter 2kg two thio Acidic phosphates zinc, stir 10 minutes, add 1kg molybdenum dialkyldithiocarbamacompositions, stir 10 points Clock, adds 2kg tungsten disulfide, stirs 10 minutes, adds 2kg two tungsten selenides, stirs 10 minutes, adds 0.2kg pair, Right '-di-iso-octyldiphenylamine, is stirred 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The consumption of each composition is such as On.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.2 Weight %；The weight % of four 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（1.08kg）；Ethylenediamine （0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, transforming agent only makes With aphthenic acids and acetic acid, the step of saving addition methanol；The consumption of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 36.4 Weight %；The weight % of four 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 （1.08kg）；Ethylenediamine（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 28kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, calcium naphthenate makes The overbased calcium alkyl-salicylate for being 360mgKOH/g with total base number；Aphthenic acids and acetic acid is used only in transforming agent, saves and adds methanol Step；Add after 12- hydroxy stearic acids, be additionally added boric acid, then add terephthalic acid (TPA)；And treat that temperature is cooled to 110 DEG C, addition 0.2kg pair, right '-di-iso-octyldiphenylamine, after stirring 10 minutes, then circulating filtration, homogenizing, degassing is obtained into Product；The consumption of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 32.7 Weight %；The weight % of four 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（1.08kg）； Ethylenediamine（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, calcium naphthenate makes The overbased calcium alkyl-salicylate for being 360mgKOH/g with total base number；Aphthenic acids and acetic acid is used only in transforming agent, saves and adds methanol Step；Add after terephthalic acid (TPA), be additionally added acetic acid, then heat up dehydration again；The consumption of each composition is as above.Assay is shown in Table 1。

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 35.0 Weight %；The weight % of four 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

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）；Para-totuidine （0.61kg）；Ethylenediamine（0.17kg）；MDI（1.42kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ S, 17kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, use para-totuidine Instead of octadecylamine；The consumption of each composition is as above.Assay is shown in Table 1.

Embodiment 12

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）；DBSA（2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄ （3.9kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；Octadecylamine（1.03kg）；1,6- hexamethylene diamines （0.22kg）；MDI（0.95kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, use dodecyl Benzene sulfonic acid replaces aphthenic acids；DBSA and acetic acid is used only in transforming agent, the step of saving addition methanol；With 1,6- oneself Diamines replaces ethylenediamine；The consumption of each composition is as above.Assay is shown in Table 1.

Embodiment 13

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 is stirred 10 minutes at 50 DEG C or so；1kg methanol is added, 10 points are stirred 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.

In another volume be 50L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 5kg HVI500SN lubricating base oils, are warming up to 100 DEG C, add the Zr (OH) that solid content is 20 weight %₄Suspension 19.5kg, stirring 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；3.5kg terephthalic acid (TPA)s are added, stirs 10 minutes, obtains 12- Hydroxy stearic acid oxygen zirconium and terephthalic acid (TPA) oxygen zirconium.

In the 3rd volume be 20L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg HVI500SN lubricating base oils and 1kg MDI, quick stirring 4 minutes, quick stirring is lower to add 0.12kg ethylenediamines, stirs 4 points Clock, adds 1.08kg octadecylamines, stirs 4 minutes, and added MDI, ethylenediamine and octadecylamine mol ratio are 2:1:2,120 DEG C of perseverances Temperature 20 minutes, obtains four polyureas.

The 12- hydroxy stearic acid oxygen zirconiums and terephthalic acid (TPA) oxygen zirconium of gained are all squeezed into first kettle, stirred, 110 DEG C are warming up under stirring, is kept for 45 minutes, four polyureas obtained by the 3rd reactor are all squeezed into the kettle, stirred by dehydration Mix uniform, be 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 down To 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

Embodiment 14

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, aphthenic acids is replaced Phenol is changed to, acetic acid is replaced with into butyric acid.Assay is shown in Table 1.

Embodiment 15

Method according to embodiment 1 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, unlike, aphthenic acids is replaced Methyl propyl ketone is changed to, aqueous acetic acid is replaced with into butyl ether.Assay is shown in Table 1.

Embodiment 16

Method according to embodiment 5 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, 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

Method according to embodiment 5 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, 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

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

Embodiment 19

Method according to embodiment 5 prepares the polyurea grease of composite calcium naphthenate calcium zirconium base four, 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

The polyurea grease of Composite calcium-sulfonate-batetrapolyurea four is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number The overbased sulfoacid calcium that calcium is 400mgKOH/g with total base number is replaced, Zr (OH) used₄With Ca (OH)₂Instead of adjusting simultaneously Consumption 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 is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 36.8 Measure %；The weight % of four 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

The polyurea grease of Composite calcium-sulfonate-batetrapolyurea four is prepared according to the method for embodiment 5, unlike, overbased calcium alkyl-salicylate The calcium sulfonate with high base number for being 360mgKOH/g with total base number is replaced, zirconium-n-propylate used and Zr (OH)₄With Ca (OH)₂Instead of, Adjusting consumption simultaneously makes each component content consistent with embodiment 5, and obtained each performance data of lubricating grease finished product is shown in Table 1.

In the lubricating grease that this comparative example is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 50.6 Measure %；The weight % of four 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

Embodiment 1 is compared with comparative example 1, embodiment 5 is compared with comparative example 2, it can be seen that the present invention The polyurea grease of composite calcium naphthenate calcium zirconium base four extension work cone penetration with work cone penetration difference be less than composite sulfoacid The polyurea grease of calcium base four, water drenches number of dropouts and is much smaller than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, and salt spray test is better than compound sulphur The sour polyurea grease of calcium base four, water resistant spraying value is less than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, and Stencil oil-dividing value is much smaller than multiple Calcium sulfonate tetra-polyurea lubricating grease is closed, tetra-ball machine test value is more than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, bearing lubrication life-span More than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, illustrate the machinery peace of the polyurea grease of composite calcium naphthenate calcium zirconium base four of the present invention Qualitative, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, lubricating life are superior to Composite calcium-sulfonate-batetrapolyurea Four polyurea greases.

Embodiment 1 is compared with embodiment 2 and embodiment 13 respectively as can be seen that the composite calcium naphthenate in situ prepared The polyurea grease of calcium zirconium base four, with more preferable water-resistance and adhesiveness, colloid stability, and with longer lubricating life； Embodiment 1 is compared with embodiment 14 and embodiment 15 respectively as can be seen that transforming agent is selected from DBSA, ring At least one of alkanoic acid, methanol, butanol, isopropanol, boric acid, acetic acid and water, the polyureas of composite calcium naphthenate calcium zirconium base four of preparation Lubricating grease, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, and with longer lubricating life；Will Embodiment 5 is compared oxide and/or hydroxide and alcoxyl as can be seen that zirconium with embodiment 16 and embodiment 17 respectively The mol ratio of base zirconium is 1：0.5-5, the polyurea grease of composite calcium naphthenate calcium zirconium base four of preparation is stable with more preferable machinery Property, water-resistance and adhesiveness, colloid stability, and with longer lubricating life；By embodiment 5 respectively with embodiment 18 and real Example 19 is applied to be compared as can be seen that the raw material of zirconium is the oxide of zirconium and/or the mixture of hydroxide and zirconium alkoxide, system The standby polyurea grease of composite calcium naphthenate calcium zirconium base four, stabilizes with more preferable mechanical stability, water-resistance and adhesiveness, colloid Property, and with longer lubricating life.

It will be seen from figure 1 that lubricating grease prepared by embodiment 5 is in 873cm^-1-886cm^-1There is crystal form calcium carbonate feature in place Absworption peak.Meanwhile, in 3300cm^-1-3323cm^-1The stretching vibration absworption peak that the peak at place is-NH- in four 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 polyurea grease of composite calcium naphthenate calcium zirconium base four, it is characterised in that on the basis of lubricating grease weight, including it is following Component：10-70 weight % non-newtonian fluid calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 weight %'s The zirconates of aromatic 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 is formed with component A reactions, and the zirconates of the aromatic acid is to be reacted to form with component A by aromatic acid, 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 At least one of oxide, the hydroxide of zirconium and zirconium alkoxide, the polyurea compound is four polyurea compounds, described 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 % four polyurea compounds；20-70 weight % base oil；Optionally also including 2-10 weight % small molecule without The zirconates of machine acid and/or lower fatty acid.

3. lubricating grease according to claim 1, 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 at least one of alkyl, alkenyl, alkynyl, aryl, the alkyl or aryl of halo, 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 or 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 is 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 for zirconium oxide and/or hydroxide with The mixture of zirconium alkoxide, in terms of zirconium, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：0.1-10.

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)₄At least one of and 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, four polyurea compound has following structure：

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

16. lubricating grease according to claim 15, wherein, R¹It is phenyl or substituted phenyl, or the alkyl that carbon number is 8-24 Or cycloalkyl；R²It is the alkylidene that phenylene or biphenylene or carbon number are 2-12；R³It is arlydene, alkylene that carbon number is 6-30 Base or cycloalkylidene.

17. lubricating grease according to claim 16, wherein, R¹It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or carbon Number is 10-18 alkyl or cycloalkyl, R²It is phenylene or biphenylene, or the alkylidene that carbon number is 2-8；R³It is selected from With-(CH₂)₆At least one of-.

18. the preparation method of the polyurea grease of composite calcium naphthenate calcium zirconium base four in claim 1-17 described in any one, its It is characterised by, this method includes：By non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid, four polyureas chemical combination The zirconates of thing and the small molecule inorganic acid and/or lower fatty acid of part basis oil and selectivity is well mixed, in 180- 230 DEG C of constant temperature refinings, add surplus base oil, add necessary additive, obtain finished product.

19. the preparation method of the polyurea grease of composite calcium naphthenate calcium zirconium base four in claim 1-17 described in any one, its It is characterised by, 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, the hydroxide of zirconium and At least one of zirconium alkoxide；

(3) base oil and diisocyanate are added in mixture obtained by step (2), diamines is then sequentially added and monoamine is carried 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, obtains finished product.

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

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

22. method according to claim 21, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium Mol ratio be 1：0.5-5.

23. method according to claim 19, wherein, in step (3), basis is added in mixture obtained by step (2) Oil and diisocyanate, are stirred 2-8 minutes, add diamines, are stirred 2-8 minutes, add monoamine, are stirred 2-8 minutes, two isocyanic acids The mol ratio of ester, diamines and monoamine is 2:1:2.

24. method according to claim 19, wherein, in step (4), first in 100-120 DEG C of constant temperature 10-20 minutes, most After be warming up to 180-230 DEG C of constant temperature 5-20 minutes；Base oil is added, treats that temperature is cooled to 100-120 DEG C, adds necessary addition Agent, stirring, circulating filtration, homogenizing, degassing.

25. method according to 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.

26. method according to 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.

27. method according to claim 26, 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%.

28. method according to claim 19, wherein, the structural formula of the monoamine is R¹-NH₂, wherein, R¹Be phenyl, C1-C3 alkyl or the phenyl of halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.

29. method according to claim 28, 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.

30. method according to 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.

31. method according to claim 30, wherein, the diamines is to be selected from p-phenylenediamine, o-phenylenediamine, 4,4 '-connection The aromatic amine of phenylenediamine and/or selected from ethylenediamine, propane diamine, 1,6- hexamethylene diamines straight-chain fatty amine.

32. method according to claim 19, wherein, the structure of the diisocyanate is OCN-R³- NCO, R³It is carbon number For 6-30 arlydene, alkylidene or cycloalkylidene.

33. method according to claim 32, 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.