CN106032480A - Lubricating grease composition and preparation method thereof - Google Patents

Abstract

A lubricating grease composition and a preparation method thereof are disclosed. The invention relates to the field of lubricating grease, and discloses a lubricating grease composition. The lubricating grease composition comprises base oil (10-80 wt%) and a thickening agent, which comprises non-Newton fluid sulfurized calcium alkyl phenate (10-70 wt%), calcium salts of higher fatty acid (1-20 wt%), and polyurea compounds (0.5-30 wt%), and also optionally comprises one or more of non-Newton fluid calcium sulfonate (0-70 wt%), non-Newton fluid calcium naphthenate (0-70 wt%), non-Newton fluid calcium salicylate (0-70 wt%), non-Newton fluid calcium oleate (0-70 wt%), calcium salts of aromatic acid (0-15 wt%), and calcium salts of micro-molecular inorganic acid and/or lower fatty acid (0-15 wt%). The invention also discloses a preparation method of the lubricating grease composition. The provided lubricating grease composition has excellent performances.

Description

Lubricant composition and preparation method thereof

Technical field

The present invention relates to a kind of lubricant composition and preparation method thereof.

Background technology

SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER has preferable detergent-dispersant performance, good acid neutralization capacity and excellence Diffusibility, be used as the detersive of lubricating oil, be widely used in modulation medium and high classes I. C. engine oil, It is particularly suited for pressurized diesel engine oil to reduce the carbon deposit of top land and the additive of marine cylinder oil, its Technology development mainly makes its high alkalization, it is simply that the calcium carbonate calcium sulfenyl phenolate with surface activity It is distributed in flux oil become a kind of colloidal dispersion system.SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is alkyl phenol warp React with CaO, vulcanize, carbonating contour alkalization technology and obtain, the Patents about preparation has CN101423483 etc..

Utilize calcium sulfonate with high base number for raw material production grease, because of its have excellence antirust and anticorrosion Property, since putting goods on the market, cause the extensive concern of domestic and international grease industry, but, although high-alkali Value complex calcium sulfonate grease has the most excellent antirust and anticorrosive property, but easy in storage process Harden, and the high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it Do not promoted rapidly, meanwhile, along with people are more and more higher to the requirement of environmental conservation, sulfonate with high base number In calcium production process must through sulfonation process the pollution of environment is also increasingly subject to the concern of people.Find one Plant antirust and anticorrosive property is similar with high base number composite calcium sulfonate base grease but can alleviate the problems referred to above Grease become the big problem that people face at present.

Summary of the invention

It is an object of the invention to provide one have the most antirust and anticorrosive property, storage good security and Grease that its feed preparation process is simple and environmentally-friendly and preparation method thereof.

The present inventor finds under study for action, and calcium sulfenyl phenolate is due to containing active sulfur, at high temperature Under easily may separate out elemental sulfur and produce corrosion, therefore, when as detersive, calcium sulfenyl phenolate Antirust and anticorrosive property far below sulfoacid calcium, but calcium sulfenyl phenolate is prepared grease as thickening agent Time, but can obtain and anticorrosion the most antirust with high base number composite calcium sulfonate base grease Property, and storage good security.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of lubricant composition, Described lubricant composition contains base oil and thickening agent, and described thickening agent contains non-newtonian fluid alkyl monosulfide Phenol calcium, the calcium salt of higher fatty acids and polyurea compound, described thickening agent is also optionally with non-newtonian fluid Sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, aromatic acid One or more in the calcium salt of calcium salt, little molecule mineral acid and/or lower fatty acid, with described grease On the basis of the weight of compositions, the content of base oil is 10 80 weight %, non-newtonian fluid sulfenyl phenolate The content of calcium is 10 70 weight %, and the content of the calcium salt of higher fatty acids is 1 20 weight %, polyureas The content of compound is 0.5 30 weight %, and the content of non-newtonian fluid sulfoacid calcium is 0-70 weight %, non-cattle The content of body calcium naphthenate is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 weight %, the content of non-newtonian fluid calcium oleate is 0-70 weight %, and the content of the calcium salt of aromatic acid is 0-15 weight %, the content of the calcium salt of little molecule mineral acid and/or lower fatty acid is 0 15 weight %.

Preferably, on the basis of the weight of lubricant composition, the content of base oil is 20-70 weight %, The content of non-newtonian fluid calcium sulfenyl phenolate is 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, the content of polyurea compound is 1-20 weight %, and the content of non-newtonian fluid sulfoacid calcium is 0-50 weight %, the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, non-newtonian fluid calcium salicylate Content be 0-50 weight %, the content of non-newtonian fluid calcium oleate is 0-50 weight %, the calcium salt of aromatic acid Content be 2-10 weight %, the content of the calcium salt of little molecule mineral acid and/or lower fatty acid is 2-10 Weight %.

Second aspect, the invention provides the preparation method of lubricant composition as above, the method Including: by thickening agent and part basis oil mix homogeneously, refine at 180 230 DEG C of constant temperature, add surplus Base oil, adds necessary additive, obtains finished product, and described thickening agent contains non-newtonian fluid alkyl monosulfide Phenol calcium, the calcium salt of higher fatty acids and polyurea compound, described thickening agent is also optionally with non-newtonian fluid Sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, aromatic acid One or more in the calcium salt of calcium salt, little molecule mineral acid and/or lower fatty acid.

The third aspect, the invention provides the preparation method of a kind of lubricant composition, and the method includes:

(1) by containing newton body calcium sulfenyl phenolate, optional newton body and/or non-newtonian fluid sulfoacid calcium, Optional newton body and/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid salicylic acid Calcium and optional newton body and/or the high base number material of non-newtonian fluid calcium oleate and the mixing of part basis oil, To mixture；

(2) optionally carry out the reaction of at least part of composite calcium: add Calx or calcium hydroxide, add Higher fatty acids, optional aromatic acid, optional little molecule mineral acid and/or lower fatty acid, react； And/or optionally carry out the reaction of at least part of polyurea compound: add part basis oil and monoamine, or go back Add diamidogen, add diisocyanate and react；

(3) add transforming agent, heat up and treat material retrogradation；

(4) carry out remaining the reaction of composite calcium；

(5) heat up dehydration；

(6) carry out remaining the reaction of polyurea compound；

(7) it is warmed up to 180 230 DEG C of constant temperature refinings, adds surplus base oil, add necessary additive, Obtain finished product.

Fourth aspect, the invention provides the lubricant composition prepared by method as above.

The lubricant composition of the present invention, has the most excellent with Composite calcium-sulfonate-batetrapolyurea polyurea grease Good antirust and anticorrosive property, and there is excellent storage stability, also have and be better than Composite calcium-sulfonate-batetrapolyurea The viscous resistance of polyurea grease, mechanical stability, water-resistance, colloid stability, abrasion resistance, extreme pressure Wear resistence and lubricating life, and also there is the performances such as excellent heat-resisting quantity.The grease of the present invention former Preparation technology is simple and environmentally-friendly for material, constant product quality.

Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.

Detailed description of the invention

Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.

The invention provides a kind of lubricant composition, this lubricant composition have employed synthesis sulfuration alkane Base phenol calcium, and optional calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, optional petroleum naphthenic acid calcium and/ Or synthesis calcium naphthenate, optional salicylate calcium, optional natural calcium oleate and/or synthesis calcium oleate For raw material, contain the polyurea compound that composite calcium thickening agent, isocyanates and amine reaction produce simultaneously.

Present invention also offers the preparation method of foregoing grease composition.

On the one hand, the invention provides a kind of lubricant composition, lubricant composition contain base oil and Thickening agent, thickening agent contains non-newtonian fluid calcium sulfenyl phenolate, the calcium salt of higher fatty acids and polyureas chemical combination Thing, thickening agent is also optionally with non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid water Poplar acid calcium, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, little molecule mineral acid and/or the calcium of lower fatty acid One or more in salt, on the basis of the weight of lubricant composition, the content of base oil is 10 80 Weight %, the content of non-newtonian fluid calcium sulfenyl phenolate is 10 70 weight %, the calcium salt of higher fatty acids Content be 1 20 weight %, the content of polyurea compound is 0.5 30 weight %, non-newtonian fluid sulfonic acid The content of calcium is 0-70 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 weight %, non newtonian The content of body calcium salicylate is 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, The content of the calcium salt of aromatic acid is 0-15 weight %, the calcium salt of little molecule mineral acid and/or lower fatty acid Content is 0 15 weight %.

Preferably, on the basis of the weight of lubricant composition, the content of base oil is 20-70 weight %, The content of non-newtonian fluid calcium sulfenyl phenolate is 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, the content of polyurea compound is 1-20 weight %, and the content of non-newtonian fluid sulfoacid calcium is 0-50 weight %, the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, non-newtonian fluid calcium salicylate Content be 0-50 weight %, the content of non-newtonian fluid calcium oleate is 0-50 weight %, the calcium salt of aromatic acid Content be 2-10 weight %, the content of the calcium salt of little molecule mineral acid and/or lower fatty acid is 2-10 Weight %.

In the present invention, " optionally with " refer to can not contain this component containing this component, That is, non-newtonian fluid sulfoacid calcium, newton body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid oleic acid One or more in the calcium salt of calcium, the calcium salt of aromatic acid, little molecule mineral acid and/or lower fatty acid are can Select component, the lubricant composition of the present invention can include this component, it is also possible to do not include this component.

Non-newtonian fluid calcium sulfenyl phenolate, non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non newtonian Body calcium salicylate, non-newtonian fluid calcium oleate or a combination thereof thing are at infrared spectrum 873cm^-1-886cm^-1Place goes out Existing crystal form calcium carbonate characteristic absorption peak.Non-newtonian fluid calcium sulfenyl phenolate is by newton body calcium sulfenyl phenolate Conversion obtains, and the total base number of non-newtonian fluid calcium sulfenyl phenolate is 250-450mgKOH/g, is preferably 300-400mgKOH/g；Non-newtonian fluid sulfoacid calcium is converted by newton body sulfoacid calcium and obtains, non newtonian The total base number of body sulfoacid calcium is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non newtonian Body calcium naphthenate is converted by newton body calcium naphthenate and obtains, and the total base number of non-newtonian fluid calcium naphthenate is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid calcium salicylate is by newton The conversion of body calcium salicylate obtains, and the total base number of non-newtonian fluid calcium salicylate is 250-450mgKOH/g, It is preferably 300-400mgKOH/g；Non-newtonian fluid calcium oleate is converted by newton body calcium oleate and obtains, The total base number of non-newtonian fluid calcium oleate is 250-450mgKOH/g, preferably 300-400mgKOH/g. And newton body calcium sulfenyl phenolate, newton body sulfoacid calcium, newton body calcium naphthenate, newton body calcium salicylate, Containing unformed calcium carbonate in newton body calcium oleate, at infrared spectrum 860cm^-1-865cm^-1There is nothing in place Sizing calcium carbonate characteristic absorption peak.Newton body calcium sulfenyl phenolate is synthesis calcium sulfenyl phenolate, its total alkali Value is 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body sulfoacid calcium is oil sulphur Acid calcium and/or calcium alkylbenzenesulfonate, its total base number is 250-450mgKOH/g, is preferably 300-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, its Total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body calcium salicylate is Salicylate calcium, its total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g； Newton body calcium oleate is natural calcium oleate and/or synthesis calcium oleate, and its total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g.Non-newtonian fluid calcium sulfenyl phenolate, non- Newton body sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate and non-newtonian fluid calcium oleate are mixed The weight meansigma methods of the base number that base number is each component of the high base number material closed.

In the present invention, higher fatty acids can be carbon number be 8-20, preferably 10-18 fatty acid or Hydroxy fatty acid, can be such as lauric acid, Palmic acid, stearic acid, 12-hydroxy stearic acid, 20 At least one in alkyl carboxylic acid, preferably 12-hydroxy stearic 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 Substituted or unsubstituted aromatic acid, its substituent group can be alkyl, thiazolinyl, alkynyl, aryl, halo or At least one in the alkyl or aryl of perhalogeno etc., the molecular weight of aromatic acid is preferably smaller than equal to 550.Virtue Acid is preferably binary aromatic acid, for example, it is possible to selected from the unsubstituted or substituted adjacent benzene two of C1-C5 alkyl At least one in formic acid, M-phthalic acid, p-phthalic acid, biphenyl dicarboxylic acid, polyphenyls dioctyl phthalate. It is preferably phthalic acid, M-phthalic acid, p-phthalic acid, biphenyl dicarboxylic acid, and methyl replaces Biphenyl dicarboxylic acid, at least one in polyphenyls dioctyl phthalate etc..

In the present invention, the molecular weight of little molecule mineral acid or lower fatty acid is less than or equal to 250.Wherein, Little molecule mineral acid can be selected from least one in boric acid, phosphoric acid, sulphuric acid etc., preferably boric acid and/ Or phosphoric acid；Lower fatty acid can be selected from acetic acid, ethanedioic acid, propanoic acid, malonic acid, butanoic acid, succinic acid At least one in Deng, preferably acetic acid.

In the present invention, polyurea compound, without particular/special requirement, can be polyurea compound commonly used in the art, Such as, the structural formula of polyurea compound can be

Wherein, n is preferably the integer of 03.

Wherein, R¹、R⁴Can be the same or different, can be alkyl, cycloalkyl or aryl, alkyl Or the carbon number of cycloalkyl can be 8 24, preferably 10 18, aryl can be phenyl or substituted phenyl, It is preferably phenyl or the alkyl of C1 C3 or the phenyl of halogen substiuted.

Wherein, R²Can be alkylidene or arlydene, the carbon number of alkylidene can be 2 12, is preferably 28, arlydene can be phenylene or biphenylene.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, arlydene, alkylidene or sub-cycloalkanes The carbon number of base can be 6 30, preferably 6 20, R³More preferably In At least one.

In the present invention, it is possible to use single polyureas, it is possible to use mixing polyureas, such as, polyureas chemical combination Thing can be in dimerization carbamide compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds At least one.

Above-mentioned polyurea compound can use the thinkable various methods of those skilled in the art institute to obtain, example As can according to CN103060069A, CN103060070A, CN103060068A, The method that CN103060067A, US3243372 record prepares.

In the present invention, base oil can be mineral oil, artificial oil, vegetable oil or their mixture, 100 DEG C dynamic viscosity is 4 150mm²/ s, preferably 10 60mm²/s.Artificial oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, Fischer-Tropsch synthesis oil etc..

The lubricant composition of the present invention can also contain various additives, such as antioxidant, extreme-pressure anti-wear Agent, antirust agent etc..Wherein, antioxidant preferred arylamine kind antioxidant, account for grease gross weight 0.01 5%, preferably 0.1 2.5%, can be in diphenylamines, phenyl αnaphthylamine and di-iso-octyldiphenylamine At least one, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5 12% of grease gross weight, Preferably 0.8 8%, can be dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, two Sulfur for dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, two Molybdenum sulfide, politef, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, At least one in tungsten disulfide, selenium sulfide, fluorographite, calcium carbonate and zinc oxide；Antirust agent accounts for The 0.01 4.5% of grease gross weight, preferably 0.1 2%, can be barium mahogany sulfonate, petroleum sodium sulfonate, At least one in benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.

Second aspect, the invention provides the preparation method of lubricant composition as above, the method Including: by thickening agent and part basis oil mix homogeneously, refine at 180 230 DEG C of constant temperature, add surplus Base oil, adds necessary additive, obtains finished product, thickening agent contain non-newtonian fluid calcium sulfenyl phenolate, The calcium salt of higher fatty acids and polyurea compound, thickening agent is also optionally with non-newtonian fluid sulfoacid calcium, non- Newton body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, little point One or more in the calcium salt of sub-mineral acid and/or lower fatty acid.

In the present invention, " optionally with " as it was previously stated, do not repeat them here.

In the present invention, for non-newtonian fluid calcium sulfenyl phenolate, non-newtonian fluid sulfoacid calcium, non-newtonian fluid ring Alkanoic acid calcium, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of higher fatty acids, aromatic acid Calcium salt, little molecule mineral acid and/or the calcium salt of lower fatty acid, polyurea compound, base oil and additive As it has been described above, do not repeat them here.

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

For non-newtonian fluid calcium sulfenyl phenolate, non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non- Newton body calcium salicylate, non-newtonian fluid calcium oleate or a combination thereof thing, can by newton body calcium sulfenyl phenolate, Newton body sulfoacid calcium, newton body calcium naphthenate, newton body calcium salicylate, newton body calcium oleate or a combination thereof Thing is converted by transforming agent respectively and obtains, such as, by newton body calcium sulfenyl phenolate, optional newton body Sulfoacid calcium, optional newton body calcium naphthenate, optional newton body calcium salicylate, optional newton body oils Acid calcium and base oil Hybrid Heating to 50-80 DEG C, the transforming agent needed for addition reacts, all conversions After agent adds, 80-100 DEG C of constant temperature 60-90 minute, then heat to 110-130 DEG C of dehydration.

In the present invention, " optional " refer to have this raw material can also not this raw material, such as, " appoint The newton body sulfoacid calcium of choosing " i.e. refer to there is newton this raw material of body sulfoacid calcium, it is also possible to there is no newton This raw material of body sulfoacid calcium.

The third aspect, the invention provides the preparation method of a kind of lubricant composition, and the method includes:

(1) by containing newton body calcium sulfenyl phenolate, optional newton body and/or non-newtonian fluid sulfoacid calcium, Optional newton body and/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid salicylic acid Calcium and optional newton body and/or the high base number material of non-newtonian fluid calcium oleate and the mixing of part basis oil, To mixture；

(2) optionally carry out the reaction of at least part of composite calcium: add Calx or calcium hydroxide, add Higher fatty acids, optional aromatic acid, optional little molecule mineral acid and/or lower fatty acid, react； And/or optionally carry out the reaction of at least part of polyurea compound: add part basis oil and monoamine, or go back Add diamidogen, add diisocyanate and react；

(3) add transforming agent, heat up and treat material retrogradation；

(4) carry out remaining the reaction of composite calcium；

(5) heat up dehydration；

(6) carry out remaining the reaction of polyurea compound；

(7) it is warmed up to 180 230 DEG C of constant temperature refinings, adds surplus base oil, add necessary additive, Obtain finished product.

" optional " be not as it was previously stated, repeat them here.

In the present invention, newton body calcium sulfenyl phenolate, newton body sulfoacid calcium, non-newtonian fluid sulfoacid calcium, cattle Body calcium naphthenate, non-newtonian fluid calcium naphthenate, newton body calcium salicylate, non-newtonian fluid calcium salicylate, Newton body calcium oleate, non-newtonian fluid calcium oleate, higher fatty acids, aromatic acid, little molecule mineral acid, rudimentary Fatty acid and base oil be not as it was previously stated, repeat them here.

In step of the present invention (1), " optional newton body and/or non-newtonian fluid sulfoacid calcium " i.e. refers to sulphur Acid calcium is optional component, and sulfoacid calcium can be newton body sulfoacid calcium, it is also possible to for non-newtonian fluid sulfoacid calcium. Remaining is same.

In step of the present invention (1), the weight ratio of high base number material gross weight and part basis oil is preferably 1: 0.1–3。

In step of the present invention (2), " optionally carrying out the reaction of at least part of composite calcium " i.e. includes three kinds Situation: (i) does not carry out the reaction of composite calcium, i.e. do not carry out the reaction of composite calcium in step (2), only In step (4), carry out the reaction of whole composite calciums, be i.e. equivalent to the inventive method and be initially charged conversion Agent converts, and carries out the reaction of composite calcium after conversion again；(ii) reaction of part composite calcium is carried out, i.e. In step (2), carry out the reaction of part composite calcium, carry out again remaining composite calcium in step (4) Reaction, is i.e. equivalent to the inventive method and carries out the reaction of part composite calcium before conversion, enter The reaction of row part composite calcium；(iii) carry out the reaction of whole composite calcium, i.e. carry out in step (2) The reaction of whole composite calciums, does not carry out step (4), is i.e. equivalent to the inventive method and first carries out composite calcium Reaction, then convert.

In step of the present invention (2), " optionally carrying out the reaction of at least part of polyurea compound " i.e. includes Three kinds of situations: (i) does not carry out the reaction of polyurea compound, i.e. do not carry out polyureas chemical combination in step (2) The reaction of thing, only carries out the reaction of whole polyurea compounds in step (6), is i.e. equivalent to this Bright method is initially charged transforming agent and converts, and carries out the reaction of polyurea compound after conversion again；(ii) carry out The reaction of part polyurea compound, i.e. carries out the reaction of part polyurea compound in step (2), Step (6) carries out remaining the reaction of polyurea compound again, is i.e. equivalent to the inventive method before conversion Carry out the reaction of part polyurea compound, carry out the reaction of part polyurea compound the most again；(iii) Carry out the reaction of whole polyurea compound, i.e. in step (2), carry out the anti-of whole polyurea compounds Should, do not carry out step (6), be i.e. equivalent to the inventive method and first carry out the reaction of polyurea compound, then enter Row converts.

This area, when preparing grease, is generally individually to be initially charged transforming agent to convert, then is combined Calcium and the reaction of polyurea compound, during as prepared sulfonic acid calcio polyurea grease.But the present inventor Find under study for action, according to the situation (ii) of the reaction carrying out composite calcium or (iii) of above-mentioned steps (2), And/or according to the situation (ii) of the reaction carrying out polyurea compound of above-mentioned steps (2) or (iii), enter The method of the row present invention, the most first carries out all or part of composite calcium reaction and/or polyurea compound reaction, Convert again, it is possible to further improve the performance of prepared grease.This is likely due to first carry out The reaction of all or part of composite calcium and/or the reaction of polyurea compound, it is possible to preferably by the newton of oily Body calcium sulfenyl phenolate is converted into the non-newtonian fluid calcium sulfenyl phenolate of smectic.It is therefore preferred that step (2), in, the reaction of at least part of composite calcium is carried out；And/or, carry out at least part of polyurea compound Reaction.I.e., preferably first carry out all or part of composite calcium reaction and/or first carry out all or part of poly- Carbamide compound reacts, then converts.

In step of the present invention (2) and step (4), when carrying out the reaction of composite calcium, it is preferable that at 85-100 At DEG C, add Calx or the suspension of calcium hydroxide, add higher fatty acids, stir 5-20 minute, Add optional aromatic acid, optional little molecule mineral acid and/or lower fatty acid, stir 5-20 minute. Wherein, higher fatty acids can be handed over the addition sequence of aromatic acid, little molecule mineral acid and/or lower fatty acid Change.

In the present invention, higher fatty acids and optional aromatic acid and optional little molecule mineral acid and/or low The H of level fatty acid⁺The amount of total material and Calx or the OH contained by suspension of calcium hydroxide^-Total material Measure equal, OH^-Amount also can excess 1-10%.

In the present invention, in terms of calcium hydroxide, the addition of the suspension of Calx or calcium hydroxide is preferably height The 1-15% of base number material gross weight；With H⁺The gauge of material, higher fatty acids and optional aromatic acid It is preferably 1:1-10 with the mol ratio of optional little molecule mineral acid and/or lower fatty acid.

In the present invention, the suspension of Calx or calcium hydroxide i.e. refers to that Calx or calcium hydroxide are formed in water Suspension, the solid content of suspension is preferably 10-60 weight %.

In step of the present invention (2) and step (6), when carrying out the reaction of polyurea compound, can prepare Single polyureas, it is also possible to preparation mixing polyureas.Prepare the method for polyurea compound without particular/special requirement, permissible The various methods using those skilled in the art to commonly use, such as, can use as above CN103060069A、CN103060070A、CN103060068A、CN103060067A、 Prepared by the method that US3243372 records.Preferably, add part basis oil, monoamine, optional diamidogen, After diisocyanate, 100 120 DEG C of constant temperature 10 30 minutes, wherein, monoamine, optional diamidogen, The amount of the material of diisocyanate meets following relation: the thing of the amount of the material of diisocyanate × 2=monoamine Amount × 2 of the material of the amount+diamidogen of matter, or, diisocyanate excess, amount≤10% of excess.

The structure of described diisocyanate is OCN R³NCO, R³Can be carbon number be 6 30, preferably Arlydene, alkylidene or the cycloalkylidene of 6 20, is preferably Deng. Such as, described diisocyanate can be toluene di-isocyanate(TDI) (TDI), diphenylmethane diisocyanate Ester (MDI), six hexylidene diisocyanates (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI) With at least one in xylylene diisocyanate (XDI) etc..

Described monoamine can be fatty amine, aliphatic cyclic amine or arylamine, and structural formula is R¹–NH₂、R⁴–NH₂, R therein¹、R⁴Can 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 halogen Substituted phenyl.Preferably monoamine can be selected from aniline, m-chloroaniline, parachloroanilinum and/or to toluene The arylamine of amine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, the fatty amine of 18-amine..

Described diamidogen can be fatty amine or arylamine, and structural formula is NH₂–R²–NH₂, wherein, R²Permissible Being alkylidene or arlydene, the carbon number of alkylidene can be 2 12, preferably 28, and arlydene can be sub- Phenyl or biphenylene.Preferably diamidogen can be selected from p-phenylenediamine, o-phenylenediamine, 4,4 ' biphenyl two The aromatic amine of amine and/or selected from ethylenediamine, propane diamine, the straight-chain fatty amine of 1,6 hexamethylene diamines.

In step of the present invention (3), it is preferable that at 50 80 DEG C, preferably constant temperature 10 30 minutes, adds Enter required transforming agent to react, preferably add and stir 8 12 minutes after every kind of transforming agent, all turns After agent adds, 80 100 DEG C of constant temperature 60 90 minutes.

Transforming agent is preferably selected from fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, carbonic acid Calcium, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8 C20 alkane At least one in base benzenesulfonic acid, C16 C24 alkyl phenol and water；It is more preferably selected from the fat of C1 C5 Alcohol, the fatty acid of C1 C5, the aliphatic ketone of C1 C5, the fatty aldehyde of C1 C5, the fat of C1 C5 Amine, the ether of C1 C5, boric acid, the alkyl phosphonic acid of C1 C10, the di alkyl phosphonic acid of C2 C16, C6 C20 Arylphosphonic acid, the diaryl phosphonic acids of C12 C24, the aromatic alcohol of C7 C20, the aromatic amine of C7 C20, At least one in C8 C20 alkyl benzene sulphonate, C16-C22 alkyl phenol and water；The most preferably select From DBSA, aphthenic acids, octadecyl phenol, methanol, isopropanol, butanol, boric acid, vinegar At least one in acid and water.The addition of transforming agent is preferably the 2 30% of high base number material gross weight, More preferably the 6 22% of high base number material gross weight.

In the present invention, fatty alcohol includes straight chain, side chain and ring-type fatty alcohol, fatty acid, aliphatic ketone, Fatty aldehyde, fatty amine are in like manner.

In step of the present invention (5), it is preferable that be warming up to 110-130 DEG C, 30-60 is preferably kept to divide Clock is to realize dehydration.

In step of the present invention (7), it is preferable that be warmed up to 180 230 DEG C of constant temperature 5 30 minutes；Add Surplus base oil, treats that temperature is cooled to 100 120 DEG C, adds necessary additive, stirring, is circulated throughout Filter, homogenizing, degassing.

In the present invention, in step (1), the total amount of base oil used is used with step (2) and (6) In the total amount of base oil and step (7), the weight ratio of the total amount of base oil used is preferably 1:0.1 5: 0.1–5。

Fourth aspect, the profit that the preparation method that present invention also offers is provided by third aspect present invention prepares Grease composition.

Compared with the lubricant composition that the preparation method provided by second aspect prepares, the third aspect provides Preparation method prepare lubricant composition have more preferable mechanical stability, water-resistance, colloid stabilize Property, abrasion resistance and lubricating life.

Embodiment

The present invention is further illustrated for below example, but and is not so limited the present invention.

In the following Examples and Comparative Examples:

Non-newtonian fluid calcium sulfenyl phenolate in the lubricant composition prepared, non-newtonian fluid sulfoacid calcium, non- The total content of newton body calcium naphthenate, non-newtonian fluid calcium salicylate and non-newtonian fluid calcium oleate all uses non newtonian Body calcium sulfenyl phenolate % represents, i.e.

Non-newtonian fluid calcium sulfenyl phenolate %=(overbased or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER raw material weight+ Overbased or calcium sulfonate with high base number raw material weight+overbased or overbased calcium alkyl-salicylate raw material weight+ Overbased or high base number calcium salicylate raw material weight+overbased or high base number calcium oleate raw material weight+ Transforming agent gross weight)/grease gross weight × 100%.Transforming agent all counts non-newtonian fluid sulfenyl phenolate In calcium %.

Overbased and SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is prepared according to patent CN101423483.

Overbased and calcium sulfonate with high base number is prepared according to the method for patent CN101928239A.

It is limited that overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Lander Speciality Petrochemicals share Company.

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

High base number calcium salicylate is prepared according to the method for patent CN1345921.

High base number calcium oleate is prepared according to document (NLGI Spokeman, 2009,73 (2): 1-17) method.

Embodiment 1

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased calcium sulfenyl phenolate (total base number is 400mgKOH/g, 30kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4 octadecyl benzene Phenol (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12 hydroxy stearate Acid (2kg)；P-phthalic acid (3.5kg)；18-amine. (1.5kg)；MDI(0.7kg)；HVI500SN (100 DEG C of kinematic viscositys are 11mm to lubricating base oil²/ s, 17kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter overbased calcium sulfenyl phenolate and 30kg that 30kg total base number is 400mgKOH/g HVI150BS lubricating base oil, stirring；It is warmed up to 95 DEG C, adds the hydrogen that solid content is 20 weight % Calcium oxide suspension 9kg, stirs 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes； Add 3.5kg p-phthalic acid, stir 10 minutes；Add the HVI500SN lubricating base oil of 10kg And make material be down to 50 DEG C, constant temperature 10 minutes；Adding 2.8kg 4 octadecylphenol, temperature controls At 50 DEG C, stir 10 minutes；Add 1kg methanol, stir 10 minutes；Adding 2.8kg concentration is 20 The aqueous acetic acid of weight %, stirs 10 minutes；It is warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation； It is warmed up to 120 DEG C under stirring, keeps 45 minutes, dehydration；The HVI500SN adding 2kg lubricates base Plinth oil and 1.5kg 18-amine., stir 4 minutes, add the HVI500SN lubrication base being dissolved in 2kg 0.7kg MDI in oil, stirs 4 minutes, and added MDI with the ratio of the amount of the material of 18-amine. is 1:2,120 DEG C of constant temperature 20 minutes, finally it is warmed up to 200 DEG C of constant temperature 10 minutes.Then, it is cooled to 160 DEG C, Add remaining HVI500SN lubricating base oil；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, Degassing obtains finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %；12 hydroxyls Calcium stearate 2.4 weight %；P-phthalic acid calcium 4.8 weight %.

Embodiment 2

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number is 320mgKOH/g, 30kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 20kg)；4 octadecyl benzene Phenol (2.6kg)；N-butyl alcohol (1.2kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；Stearic acid (1.9kg)；Phthalic acid (3.5kg)；Lauryl amine (1.31kg)；MDI(0.89kg)；HVI500SN (100 DEG C of kinematic viscositys are 11mm to lubricating base oil²/ s, 27kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and the HVI150BS of 20kg that 30kg total base number is 320mgKOH/g Lubricating base oil, stirring；Be warmed up to 100 DEG C, add 0.2kg HVI500SN lubricating base oil and 0.131kg lauryl amine, stirs 8 minutes, adds the HVI500SN lubricating base oil being dissolved in 0.4kg In 0.089kg MDI, stir 8 minutes, added MDI with the ratio of the amount of the material of lauryl amine is 1:2,100 DEG C of constant temperature 10 minutes；At 85 DEG C, add the calcium hydroxide that solid content is 20 weight % and hang Turbid liquid 0.9kg, stirs 10 minutes, adds 0.19kg stearic acid, stirs 10 minutes, adds 0.35kg Phthalic acid, stirs 10 minutes；At 80 DEG C, constant temperature 10 minutes, add 1.2kg n-butyl alcohol and 2.6kg 4 octadecylphenol, temperature controls at 80 DEG C, stirs 10 minutes, and adding 2.8kg concentration is 20 weights The aqueous acetic acid of amount %, stirs 10 minutes, is warmed up to 90 DEG C, constant temperature 60 minutes, material retrogradation； At 85 DEG C, add the calcium hydroxide suspension 8.1kg that solid content is 20 weight %, stir 10 minutes, Add 1.71kg stearic acid, stir 10 minutes, add 3.15kg phthalic acid, stir 10 minutes； It is warmed up to 110 DEG C under stirring, keeps 60 minutes, dehydration；The HVI500SN adding 1.8kg lubricates base Plinth oil and 1.179kg lauryl amine, stir 8 minutes, adds the HVI500SN lubrication being dissolved in 3.6kg 0.801kg MDI in base oil, stirs 8 minutes, the amount of the material of added MDI and lauryl amine it Than being 1:2,100 DEG C of constant temperature 10 minutes；Finally it is warmed up to 230 DEG C of constant temperature 5 minutes.Then, addition is surplus Remaining HVI500SN lubricating base oil；Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing Obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.9 weight %；Stearic acid Calcium 2.3 weight %；Calcium phthalate 4.8 weight %.

Embodiment 3

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased calcium sulfenyl phenolate (total base number is 400mgKOH/g, 30kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 25kg)；4 octadecyl benzene Phenol (1.6kg)；DBSA (1.2kg)；Methanol (1kg)；Acetic acid (0.56kg)；Hydrogen-oxygen Change calcium (1.8kg)；12 hydroxy stearic acids (2kg)；M-phthalic acid (3.5kg)；18-amine. (1.66kg)； TDI(0.54kg)；(100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 22kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter overbased calcium sulfenyl phenolate and 25kg that 30kg total base number is 400mgKOH/g HVI150BS lubricating base oil, stirring；It is warmed up to 110 DEG C, adds the HVI500SN lubrication of 2kg Base oil and 1.66kg 18-amine., stir 4 minutes, adds the HVI500SN lubrication being dissolved in 2kg 0.54kg TDI in base oil, stirs 4 minutes, the ratio of added TDI and the amount of the material of 18-amine. For 1:2,110 DEG C of constant temperature 15 minutes；At 65 DEG C, constant temperature 10 minutes, add 1.6kg 4 octadecane Base phenol, temperature controls at 65 DEG C, stirs 10 minutes, adds 1.2kg DBSA, stirs Mix 10 minutes, add 1kg methanol, stir 10 minutes, add the vinegar that 2.8kg concentration is 20 weight % Aqueous acid, stirs 10 minutes, is warmed up to 100 DEG C, constant temperature 70 minutes, material retrogradation；At 90 DEG C Under, add the calcium hydroxide suspension 9kg that solid content is 20 weight %, stir 10 minutes, add 2kg 12 hydroxy stearic acids, stir 10 minutes, add 3.5kg M-phthalic acid, stir 10 minutes；Stirring Under be warmed up to 130 DEG C, keep 30 minutes, dehydration；Finally it is warmed up to 180 DEG C of constant temperature 20 minutes, so After, it is cooled to 160 DEG C, adds remaining HVI500SN lubricating base oil, treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %；12 hydroxyls Calcium stearate 2.4 weight %；M-phthalic acid calcium 4.8 weight %.

Embodiment 4

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number is 320mgKOH/g, 20kg)；High Base number calcium sulfonate (total base number is 360mgKOH/g, 10kg)；HVI150BS lubricating base oil (100 DEG C Kinematic viscosity is 31mm²/ s, 15kg)；4 octadecylphenol (1.8kg)；Boric acid (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)； 18-amine. (1.5kg)；MDI(0.7kg)；(100 DEG C of kinematic viscositys are HVI500SN lubricating base oil 11mm²/ s, 7kg).

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, calcium sulfenyl phenolate uses Total base number is the SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, and adds calcium sulfonate with high base number；With Boric acid replaces methanol, and its mesoboric acid adds after acetic acid；The consumption of each composition is as above.Assay is shown in Table 1。

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 52.1 weight %；Polyureas 3.5 weight %；Lubricating base oil 34.4 weight %；12 hydroxyls Calcium stearate 3.3 weight %；P-phthalic acid calcium 6.7 weight %.

Embodiment 5

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased calcium sulfenyl phenolate (total base number is 400mgKOH/g, 10kg)； Overbased calcium alkyl-salicylate (total base number is 320mgKOH/g, 20kg)；HVI150BS lubricating base oil (100 DEG C of kinematic viscositys are 31mm²/ s, 25kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12 hydroxy stearic acids (2kg)；4,4' biphenyl dicarboxylic acid (5.1kg)； 18-amine. (4.5kg)；MDI(2.1kg)；(100 DEG C of kinematic viscositys are HVI500SN lubricating base oil 11mm²/ s, 18.6kg).

Prepare lubricant composition according to the method for embodiment 1, except for the difference that, add high base number cycloalkanes Acid calcium, uses 4, and 4' biphenyl dicarboxylic acid replaces p-phthalic acid；Transforming agent is only 4 octadecylphenol And acetic acid, save the step adding methanol；The consumption of each composition is as above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 36.4 weight %；Polyureas 7.2 weight %；Lubricating base oil 47.6 weight %；12 hydroxyls Calcium stearate 2.3 weight %；4,4' biphenyl dicarboxylic acid calcium 6.5 weight %.

Embodiment 6

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number is 320mgKOH/g, 15kg)；High Base number calcium salicylate (total base number is 360mgKOH/g, 15kg)；Full synthetic oil poly-a-olefin oil PAO 40 (100 DEG C of kinematic viscositys are 41mm²/ s, 30kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)； 18-amine. (1.5kg)；MDI(0.7kg)；Full synthetic oil poly-a-olefin oil PAO 10 (100 DEG C of motions Viscosity is 11mm²/ s, 9kg)；Dithio dibutylphosphoric acid zinc (2kg)；Dibutyl dithio amino first Acid molybdenum (1kg)；Tungsten disulfide (2kg)；Two tungsten selenide (2kg)；Right, right ' di-iso-octyldiphenylamine (0.2kg).

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, calcium sulfenyl phenolate uses Total base number is the SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, and adds high base number calcium salicylate； Transforming agent is only 4 octadecylphenol and acetic acid, saves the step adding methanol；Use full synthetic oil gathers Alhpa olefin oil PAO 40 and PAO 10 replaces HVI150BS and HVI500SN respectively；And treat temperature It is cooled to 110 DEG C, adds the dithio dibutylphosphoric acid zinc of 2kg, stir 10 minutes, add 1kg Dibutyl dithiocaarbamate molybdenum, stir 10 minutes, add 2kg tungsten disulfide, stir 10 Minute, add two tungsten selenide of 2kg, stir 10 minutes, add the right of 0.2kg, right ' diisooctyl two Aniline, stirs 10 minutes, and then circulating filtration, homogenizing, degassing obtain finished product；The consumption of each composition As above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.8 weight %；Polyureas 2.5 weight %；Lubricating base oil 44.2 weight %；12 hydroxyls Calcium stearate 2.4 weight %；P-phthalic acid calcium 4.9 weight %；Dithio dibutylphosphoric acid zinc 2.3 weight Amount %；Dibutyl dithiocaarbamate molybdenum 1.1 weight %；Tungsten disulfide 2.3 weight %；Two tungsten selenide 2.3 weight %；Right, right ' di-iso-octyldiphenylamine 0.2 weight %.

Embodiment 7

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased calcium sulfenyl phenolate (total base number is 400mgKOH/g, 10kg)； High base number calcium oleate (total base number is 320mgKOH/g, 20kg)；HVI150BS lubricating base oil (100 DEG C Kinematic viscosity is 31mm²/ s, 15kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)； Calcium hydroxide (1.8kg)；12 hydroxy stearic acids (2kg)；2 methyl 1,4 phthalic acid (3.8kg)； 18-amine. (0.94kg)；Para-totuidine (0.38kg)；MDI(0.88kg)；HVI500SN lubricates base (100 DEG C of kinematic viscositys are 11mm to plinth oil²/ s, 33kg).

Prepare lubricant composition according to the method for embodiment 1, except for the difference that, add high base number oleic acid Calcium, transforming agent is only 4 octadecylphenol and acetic acid, saves the step adding methanol；Use 2 first Base 1,4 phthalic acid replaces p-phthalic acid；Monoamine, in addition to 18-amine., is additionally added para-totuidine, respectively The consumption of composition is as above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.1 weight %；Polyureas 2.4 weight %；Lubricating base oil 53.3 weight %；12 hydroxyls Calcium stearate 2.4 weight %；2 methyl 1,4 phthalic acid calcium 4.8 weight %.

Embodiment 8

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number is 320mgKOH/g, 8kg)；Non-cattle Pause height base number calcium sulfonate (15kg)；Overbased calcium alkyl-salicylate (total base number is 320mgKOH/g, 7kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 20kg)；4 octadecyl benzene Phenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (5.2kg)；12 hydroxy stearic acids (2kg)；Boron Acid (2.32kg)；P-phthalic acid (7.6kg)；18-amine. (0.84kg)；Lauryl amine (0.58kg)； MDI(0.78kg)；(100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 28kg)； Right, right ' di-iso-octyldiphenylamine (0.2kg).

The preparation of non-newtonian fluid calcium sulfonate with high base number: volume be 30L and with heating, stirring, Adding 8kg total base number in circulation, the normal-pressure reaction kettle cooled down is the calcium sulfonate with high base number of 350mgKOH/g It is 31mm with 100 DEG C of kinematic viscositys of 5kg²The HVI150BS lubricating base oil of/s, stirring, heating rises Warm to 80 DEG C, constant temperature 10 minutes；Adding 1.7kg DBSA, temperature controls on 80 DEG C of left sides The right side, stirs 10 minutes；Add acetic acid and the aqueous solution of acetic acid weight 4 times of 0.33kg, stir 10 Minute；Being warmed up to 85 DEG C, constant temperature 90 minutes, material retrogradation becomes smectic, obtains non-newtonian fluid sulfoacid calcium Standby.

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, calcium sulfenyl phenolate uses Total base number is the SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, and adds non-newtonian fluid high base number sulphur Acid calcium and overbased calcium alkyl-salicylate；Transforming agent is only 4 octadecylphenol and acetic acid, saves addition methanol Step；Add 12 hydroxy stearic acids to stir after 10 minutes, add boric acid, stir 10 minutes, so Rear addition p-phthalic acid, stirs 10 minutes；Monoamine, in addition to 18-amine., is additionally added lauryl amine；And And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right ' di-iso-octyldiphenylamine, stir 10 minutes, Then circulating filtration, homogenizing, degassing obtain finished product；The consumption of each composition is as above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 34.2 weight %；Polyureas 2.2 weight %；Lubricating base oil 49.2 weight %；12 hydroxyls Calcium stearate 2.2 weight %；Calcium pyroborate 2.4 weight %；P-phthalic acid calcium 9.6 weight %；Right, right ' Di-iso-octyldiphenylamine 0.2 weight %.

Embodiment 9

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased calcium sulfenyl phenolate (total base number is 400mgKOH/g, 8kg)；High Base number calcium sulfonate (total base number is 320mgKOH/g, 6kg)；(total base number is naphthenate with superhigh base number calcium 400mgKOH/g, 6kg)；High base number calcium salicylate (total base number is 360mgKOH/g, 5kg)；High Base number calcium oleate (total base number is 320mgKOH/g, 5kg)；HVI150BS lubricating base oil (100 DEG C Kinematic viscosity is 31mm²/ s, 15kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)； Calcium hydroxide (3kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)；Acetic acid (2kg)； 18-amine. (1.5kg)；MDI(0.7kg)；(100 DEG C of kinematic viscositys are HVI500SN lubricating base oil 11mm²/ s, 33kg).

Prepare lubricant composition according to the method for embodiment 1, except for the difference that, add sulfonate with high base number Calcium, naphthenate with superhigh base number calcium, high base number calcium salicylate and high base number calcium oleate, transforming agent is only 4 Octadecylphenol and acetic acid, save the step adding methanol；And add p-phthalic acid, stir 10 After minute, add acetic acid, stir 10 minutes；The consumption of each composition is as above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 36.0 weight %；Polyureas 2.4 weight %；Lubricating base oil 51.8 weight %；12 hydroxyls Calcium stearate 2.3 weight %；P-phthalic acid calcium 4.7 weight %；Calcium acetate 2.8 weight %.

Embodiment 10

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased calcium sulfenyl phenolate (total base number is 400mgKOH/g, 30kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4 octadecyl benzene Phenol (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12 hydroxy stearate Acid (2kg)；P-phthalic acid (3.5kg)；18-amine. (1.5kg)；MDI(0.7kg)；HVI500SN (100 DEG C of kinematic viscositys are 11mm to lubricating base oil²/ s, 17kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter overbased calcium sulfenyl phenolate and 30kg that 30kg total base number is 400mgKOH/g HVI150BS lubricating base oil, stirring；It is warmed up to 100 DEG C, adds the hydrogen that solid content is 20 weight % Calcium oxide suspension 9kg, stirs 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes； Add 3.5kg p-phthalic acid, stir 10 minutes；Add the HVI500SN lubricating base oil of 10kg And make material be down to 50 DEG C, constant temperature 10 minutes；Adding 2.8kg 4 octadecylphenol, temperature controls At 50 DEG C, stir 10 minutes；Add 1kg methanol, stir 10 minutes；Adding 2.8kg concentration is 20 The aqueous acetic acid of weight %, stirs 10 minutes；It is warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation； It is warmed up to 120 DEG C under stirring, keeps 45 minutes, dehydration.

Another volume be 30L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter HVI500SN lubricating base oil and the 1.5kg 18-amine. of 2kg, be warming up to 120 DEG C, stir 4 points Clock, adds the 0.7kg MDI dissolved with 2kg HVI500SN lubricating base oil, stirs 4 minutes, institute The mol ratio of the MDI added and 18-amine. is 1:2,120 DEG C of constant temperature 20 minutes, obtains polyureas.

Gained polyureas is all squeezed in a upper still, stir, be finally warmed up to 200 DEG C of constant temperature 10 Minute.Then, it is cooled to 160 DEG C, adds remaining HVI500SN lubricating base oil；Treat that temperature is cold But to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %；12 hydroxyls Calcium stearate 2.4 weight %；P-phthalic acid calcium 4.8 weight %.

Embodiment 11

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased calcium sulfenyl phenolate (total base number is 400mgKOH/g, 30kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4 octadecyl benzene Phenol (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12 hydroxy stearate Acid (2kg)；P-phthalic acid (3.5kg)；18-amine. (1.5kg)；MDI(0.7kg)；HVI500SN (100 DEG C of kinematic viscositys are 11mm to lubricating base oil²/ s, 17kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter overbased calcium sulfenyl phenolate and 30kg 100 DEG C motion that 30kg total base number is 400mgKOH/g Viscosity is 31mm²The HVI150BS lubricating base oil of/s, stirring, heat to 50 DEG C, constant temperature 10 minutes；Adding 2.8kg 4 octadecylphenol, temperature controls at about 50 DEG C, stirs 10 minutes； Add 1kg methanol, stir 10 minutes；Add the aqueous acetic acid that 2.8kg concentration is 20 weight %, Stir 10 minutes；It is warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation.

Another volume be 50L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering the HVI500SN lubricating base oil of 5kg, be warming up to 100 DEG C, adding solid content is 20 weight % Calcium hydroxide suspension 9kg, stirs 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes； Add 3.5kg p-phthalic acid, stir 10 minutes, obtain 12 hydroxy stearic acid calcium and p-phthalic acids Calcium.

The 3rd volume be 50L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter HVI500SN lubricating base oil and the 1.5kg 18-amine. of 2kg, stir 6 minutes, add and use 2kg The 0.7kg MDI that dissolves of HVI500SN lubricating base oil, stir 6 minutes, 120 DEG C of constant temperature 20 points Clock, obtains polyureas.

12 hydroxy stearic acid calcium and the p-phthalic acid calcium of gained are all squeezed in first still, stirring Uniformly, under stirring, it is warmed up to 120 DEG C, keeps 45 minutes, dehydration, gathering the 3rd reactor gained Urea is all squeezed in this still, stirs, and is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, cooling To 160 DEG C, add remaining HVI500SN lubricating base oil；Treat that temperature is cooled to 110 DEG C, circulation Filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %；12 hydroxyls Calcium stearate 2.4 weight %；P-phthalic acid calcium 4.8 weight %.

Embodiment 12

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Volume be 160L and with the normal-pressure reaction kettle A heating, stirring, circulate, cool down in add 30kg total base number is overbased calcium sulfenyl phenolate and the HVI150BS of 25kg of 400mgKOH/g (100 DEG C of kinematic viscositys are 31mm to lubricating base oil²/ s, lower same), stirring, heat to 60 DEG C, Constant temperature 10 minutes；Adding 2kg aphthenic acids and 1kg 4 octadecylphenol, temperature controls on 60 DEG C of left sides The right side, stirs 10 minutes；Add the 12.5kg butanol aqueous solution that concentration is 20%, stir 10 minutes； In 87 DEG C of constant temperature 70 minutes, material retrogradation.

Volume be 10L and with the normal-pressure reaction kettle B heating, stirring, circulate, cool down in add (100 DEG C of kinematic viscositys are 11mm to the HVI500SN lubricating base oil of 5kg²/ s, lower same), it is warming up to 90 DEG C, add the calcium hydroxide suspension 21kg that solid content is 20 weight %, stir 10 minutes, add The Palmic acid of 2.4kg, stirs 10 minutes, adds the biphenyl dicarboxylic acid of 4.2kg, the phosphoric acid of 1kg and 2kg Ethanedioic acid, stir 10 minutes, obtain calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and ethanedioic acid Calcium.

Volume be 10L and with the normal-pressure reaction kettle C heating, stirring, circulate, cool down in add The HVI500SN lubricating base oil of 5kg and 1kg MDI rapidly pre-warming to 90 DEG C, quickly stirring is lower adds 0.12kg ethylenediamine, stirs 4 minutes, adds 1.08kg 18-amine. and stirs 4 minutes, added MDI, The mol ratio of ethylenediamine and 18-amine. is 2:1:2,120 DEG C of constant temperature 20 minutes, obtains polyureas I.

Volume be 20L and with the normal-pressure reaction kettle D heating, stirring, circulate, cool down in add 10kg100 DEG C of kinematic viscosity is 11mm²The HVI500SN lubricating base oil of/s and 0.78kg MDI preheating To 90 DEG C, quickly stirring is lower adds 0.84kg 18-amine., stirs 4 minutes, quickly adds 0.19kg under stirring Ethylenediamine, stirs 4 minutes, adds 0.39kg MDI, added successively MDI, 18-amine., second two The mol ratio of amine and MDI is 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains polyureas II.

Gained calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and ethanedioic acid calcium are all squeezed into reactor A In, stir, under stirring, be warmed up to 120 DEG C, keep 30 minutes, dehydration, by gained polyureas I and Polyureas II all squeezes in reactor A, stirs, and is finally warmed up to 200 DEG C of constant temperature 5 minutes.So After, it is cooled to 150 DEG C, adds the HVI500SN lubricating base oil of 8kg；Treat that temperature is cooled to 110 DEG C, Circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 34.4 weight %；Calcium palmitate 2.7 weight %；Biphenyl dicarboxylic acid calcium 4.2 weight %；Phosphorus Acid calcium 1.6 weight %；Ethanedioic acid calcium 2.9 weight %；Polyureas 4.6 weight %；Lubricating base oil 49.6 weight Amount %.

Embodiment 13

The present embodiment is for illustrating lubricant composition prepared by the present invention.

It is 160L and with in the normal-pressure reaction kettle A heating, stirring, circulate, cool down at a volume Add overbased calcium sulfenyl phenolate and 10kg that 30kg total base number is 420mgKOH/g HVI150BS lubricating base oil, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 2kg DBSA, temperature controls at about 50 DEG C, stirs 10 minutes；Add 1kg methanol, stir Mix 10 minutes；Add the aqueous acetic acid that 2kg concentration is 20 weight %, stir 10 minutes；At 83 DEG C Constant temperature 80 minutes, material retrogradation.

Volume be 10L and with the normal-pressure reaction kettle B heating, stirring, circulate, cool down in add The HVI500SN lubricating base oil of 8kg, adds the hydroxide that solid content is 50 weight % at 85 DEG C Calcium suspension 8.0kg, stirs 10 minutes, adds the lauric acid of 2.4kg, stirs 10 minutes, adds The M-phthalic acid of 7.9kg, stirs 10 minutes, obtains calcium laurate and M-phthalic acid calcium.

Volume be 20L and with the normal-pressure reaction kettle C heating, stirring, circulate, cool down in add HVI500SN lubricating base oil and the 1.17kg MDI of 10kg are preheating to 80 DEG C, and quickly stirring is lower adds 0.84kg 18-amine., the mixture of 0.19kg ethylenediamine, added MDI, monoamine, the mol ratio of diamidogen For 3:2:2,120 DEG C of constant temperature 20 minutes, obtain polyureas.

Gained calcium laurate and M-phthalic acid calcium are all squeezed in reactor A, stirs, stirring Under be warmed up to 110 DEG C, keep 45 minutes, dehydration, gained polyureas is all squeezed in reactor A, Stir, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, the HVI500SN profit of 2kg is added Sliding base oil；Treating that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection knot Fruit is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 41.7 weight %；Calcium laurate 3.3 weight %；M-phthalic acid calcium 12.1 weight %； Polyureas 5.4 weight %；Lubricating base oil 37.5 weight %.

Embodiment 14

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased calcium sulfenyl phenolate (total base number is 400mgKOH/g, 30kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4 octadecyl benzene Phenol (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12 hydroxy stearate Acid (2kg)；P-phthalic acid (3.5kg)；18-amine. (1.5kg)；MDI(0.7kg)；HVI500SN (100 DEG C of kinematic viscositys are 11mm to lubricating base oil²/ s, 17kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter overbased calcium sulfenyl phenolate and 30kg that 30kg total base number is 400mgKOH/g HVI150BS lubricating base oil, stirring；It is warmed up to 50 DEG C, constant temperature 10 minutes；Add 2.8kg 4 Octadecylphenol, temperature controls at 50 DEG C, stirs 10 minutes；Add 1kg methanol, stir 10 Minute；Add the aqueous acetic acid that 2.8kg concentration is 20 weight %, stir 10 minutes；It is warmed up to 80 DEG C, Constant temperature 90 minutes, material retrogradation；It is warmed up to 100 DEG C, adds the hydroxide that solid content is 20 weight % Calcium suspension 9kg, stirs 10 minutes, adds 2kg 12 hydroxy stearic acid, stirs 10 minutes, adds 3.5kg p-phthalic acid, stirs 10 minutes；It is warmed up to 120 DEG C under stirring, keeps 45 minutes, dehydration； Add HVI500SN lubricating base oil and the 1.5kg 18-amine. of 2kg, stir 4 minutes, add molten 0.7kg MDI in the HVI500SN lubricating base oil of 2kg, stirs 4 minutes, added MDI It is 1:2 with the ratio of the amount of the material of 18-amine., 120 DEG C of constant temperature 20 minutes, finally it is warmed up to 200 DEG C of constant temperature 10 minutes.Then, it is cooled to 160 DEG C, adds remaining HVI500SN lubricating base oil；Treat temperature Being cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %；12 hydroxyls Calcium stearate 2.4 weight %；P-phthalic acid calcium 4.8 weight %.

Embodiment 15

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Lubricant composition is prepared, except for the difference that, by 4 octadecylphenol according to the method for embodiment 1 Replace with 18-amine., acetic acid is replaced with ethylene glycol monobutyl ether, methanol is replaced with methyl ethyl ketone.Inspection Test and the results are shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %；12 hydroxyls Calcium stearate 2.4 weight %；P-phthalic acid calcium 4.8 weight %.

Comparative example 1

Lubricant composition is prepared according to the method for embodiment 1, except for the difference that, overbased alkyl monosulfide Phenol calcium total base number is that the overbased sulfoacid calcium of 400mgKOH/g replaces, and the grease finished product obtained is each Performance data is shown in Table 1.

In the grease that this comparative example obtains, on the basis of grease weight, consist of: non-newtonian fluid sulphur Acid calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %；12 hydroxy stearic acids Calcium 2.4 weight %；P-phthalic acid calcium 4.8 weight %.

Table 1 each grease properties of sample data

Each indication test method: dropping point: GB/T 3498；Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T 269；Corrosion: GB/T 7326； Anticorrosive property: GB/T 5018；Water drenches number of dropouts: SH/T 0109；Salt spray test: SH/T 0081；Water resistant is sprayed: SH/T0643；Steel Net point oil: SH/T 0324；Surface hardened layer value: SH/T 0370 appendix A；Coefficient of friction: SH/T 0721；Tetra-ball machine test: SH/T 0202； Bearing lubrication life-span: ASTM D 3336.

Table 1 (Continued) each grease properties of sample data

Each indication test method: dropping point: GB/T 3498；Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T 269；Corrosion: GB/T 7326； Anticorrosive property: GB/T 5018；Water drenches number of dropouts: SH/T 0109；Salt spray test: SH/T 0081；Water resistant is sprayed: SH/T0643；Steel Net point oil: SH/T 0324；Surface hardened layer value: SH/T 0370 appendix A；Coefficient of friction: SH/T 0721；Tetra-ball machine test: SH/T 0202； Bearing lubrication life-span: ASTM D 3336.

It will be understood by those skilled in the art that Drawing cone in-degree is the least, grease thickening performance is more Good；Extending Drawing cone in-degree the least with the difference of Drawing cone in-degree, the mechanical stability of grease can be the best； Water pouring number of dropouts is the least, and the water-resistance of grease is the best；Salt spray test the highest grade, grease antirust And anticorrosive property is the best；Water resistant spraying value is the least, and the adhesiveness of grease and water-resistance are the best；Steel mesh divides Oil value is the least, and the colloid stability of grease is the best；The absolute value of Surface hardened layer value is the least, grease Storage stability is the best；Coefficient of friction is the least, and the abrasion resistance of grease is the best；PB, PD value is the biggest, The extreme pressure anti-wear of grease is the best.

Embodiment 1 and comparative example 1 are compared it can be seen that lubricant composition anti-of the present invention Rust and anticorrosive property, storage stability are substantially better than Composite calcium-sulfonate-batetrapolyurea polyurea grease.And, this Bright lubricant composition has that to be better than the viscous resistance of Composite calcium-sulfonate-batetrapolyurea polyurea grease, machinery stable Property, water-resistance, colloid stability, abrasion resistance, extreme pressure anti-wear and lubricating life.And, this Bright lubricant composition also has the heat-resisting quantity of excellence.

Embodiment 1 is compared with embodiment 10 and embodiment 11 respectively it can be seen that prepare in situ Lubricant composition, there is more preferable mechanical stability, water-resistance, colloid stability, abrasion resistance And lubricating life；Embodiment 1 and embodiment 11, embodiment 14 are compared it can be seen that advanced Row composite calcium and/or the reaction of polyurea compound, then convert, the lubricant composition prepared has more Good viscous resistance, mechanical stability, water-resistance, colloid stability, abrasion resistance and lubricating life；Will Embodiment 1 and embodiment 15 compare it can be seen that transforming agent is selected from DBSA, ring At least one in alkanoic acid, octadecyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water, Preparation lubricant composition, have more preferable viscous resistance, mechanical stability, water-resistance, colloid stabilize Property, abrasion resistance, extreme pressure anti-wear and lubricating life.

The lubricant composition of the present invention, has the most excellent with Composite calcium-sulfonate-batetrapolyurea polyurea grease Good antirust and anticorrosive property, and there is excellent storage stability, also have and be better than Composite calcium-sulfonate-batetrapolyurea The viscous resistance of polyurea grease, mechanical stability, water-resistance, colloid stability, abrasion resistance, extreme pressure Wear resistence and lubricating life, and also there is the performances such as excellent heat-resisting quantity.The grease of the present invention former Preparation technology is simple and environmentally-friendly for material, constant product quality.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.

It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (31)

1. a lubricant composition, described lubricant composition contains base oil and thickening agent, and it is special Levying and be, described thickening agent contains non-newtonian fluid calcium sulfenyl phenolate, the calcium salt of higher fatty acids and polyureas Compound, described thickening agent is also optionally with non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non- Newton body calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, little molecule mineral acid and/or rudimentary fat One or more in the calcium salt of fat acid, on the basis of the weight of described lubricant composition, base oil Content is 10 80 weight %, and the content of non-newtonian fluid calcium sulfenyl phenolate is 10 70 weight %, senior The content of the calcium salt of fatty acid is 1 20 weight %, and the content of polyurea compound is 0.5 30 weight %, The content of non-newtonian fluid sulfoacid calcium is 0-70 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 weight Amount %, the content of non-newtonian fluid calcium salicylate is 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, the content of the calcium salt of aromatic acid is 0-15 weight %, little molecule mineral acid and/or rudimentary fat The content of the calcium salt of fat acid is 0 15 weight %.

Lubricant composition the most according to claim 1, wherein, with the weight of lubricant composition On the basis of amount, the content of base oil is 20-70 weight %, and the content of non-newtonian fluid calcium sulfenyl phenolate is 20-65 weight %, the content of the calcium salt of higher fatty acids is 2-15 weight %, the content of polyurea compound For 1-20 weight %, the content of non-newtonian fluid sulfoacid calcium is 0-50 weight %, non-newtonian fluid calcium naphthenate Content be 0-50 weight %, the content of non-newtonian fluid calcium salicylate is 0-50 weight %, non-newtonian fluid The content of calcium oleate is 0-50 weight %, and the content of the calcium salt of aromatic acid is 2-10 weight %, little molecule without The content of the calcium salt of machine acid and/or lower fatty acid is 2-10 weight %.

Lubricant composition the most according to claim 1 and 2, wherein, described non-newtonian fluid sulfur Change alkyl phenol calcium to be obtained by the conversion of newton body calcium sulfenyl phenolate, described non-newtonian fluid sulfenyl phenolate The total base number of calcium is 250-450mgKOH/g；Described non-newtonian fluid sulfoacid calcium is to be turned by newton body sulfoacid calcium Change obtains, and the total base number of described non-newtonian fluid sulfoacid calcium is 250-450mgKOH/g；Described non newtonian Body calcium naphthenate is converted by newton body calcium naphthenate and obtains, the total alkali of described non-newtonian fluid calcium naphthenate Value is 250-450mgKOH/g；Described non-newtonian fluid calcium salicylate is to be converted by newton body calcium salicylate Arriving, the total base number of described non-newtonian fluid calcium salicylate is 250-450mgKOH/g；Described non-newtonian fluid Calcium oleate is converted by newton body calcium oleate and obtains, and the total base number of described non-newtonian fluid calcium oleate is 250-450mgKOH/g。

Lubricant composition the most according to claim 1 and 2, wherein, described higher fatty acids For fatty acid that carbon number is 8-20 or hydroxy fatty acid.

Lubricant composition the most according to claim 4, wherein, described higher fatty acids is selected from At least one in lauric acid, Palmic acid, stearic acid, 12-hydroxy stearic acid, eicosyl carboxylic acid.

Lubricant composition the most according to claim 1 and 2, wherein, described aromatic acid is for replacing Or unsubstituted aromatic acid, substituent group is the alkane of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno At least one in base or aryl, the molecular weight of described aromatic acid is less than or equal to 550.

7. according to the lubricant composition described in claim 6, wherein, described aromatic acid is selected from unsubstituted Or the substituted phthalic acid of C1-C5 alkyl, M-phthalic acid, p-phthalic acid, biphenyl diformazan At least one in acid, polyphenyls dioctyl phthalate.

Lubricant composition the most according to claim 1 and 2, wherein, little molecule mineral acid and The molecular weight of lower fatty acid is less than or equal to 250.

Lubricant composition the most according to claim 8, wherein, described little molecule mineral acid selects At least one in boric acid, phosphoric acid, sulphuric acid, described lower fatty acid selected from acetic acid, ethanedioic acid, third At least one in acid, malonic acid, butanoic acid, succinic acid.

Lubricant composition the most according to claim 1 and 2, wherein, described polyurea compound Structural formula be

Wherein, n is the integer of 03, R¹、R⁴It is alkyl, cycloalkyl or aryl, R²It it is alkylidene Or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.

11. lubricant compositions according to claim 10, wherein, polyurea compound is dimerization At least one in carbamide compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds.

12. lubricant compositions according to claim 10, wherein, R¹、R⁴It is phenyl or takes The phenyl in generation, or carbon number is the alkyl or cycloalkyl of 8 24；R²It is phenylene or biphenylene, or carbon Number is the alkylidene of 2 12；R³It is arlydene, alkylidene or the cycloalkylidene of 6 30.

13. lubricant compositions according to claim 12, wherein, R¹、R⁴It is phenyl or C1 C3 Alkyl or the phenyl of halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10 18；R²Be phenylene or Biphenylene, or carbon number is the alkylidene of 28；R³It is With-(CH₂)₆In- At least one.

The preparation method of lubricant composition described in any one, the party in 14. claim 1 13 Method includes: by thickening agent and part basis oil mix homogeneously, refine at 180 230 DEG C of constant temperature, adds remaining Amount base oil, adds necessary additive, obtains finished product, it is characterised in that described thickening agent contains non- Newton body calcium sulfenyl phenolate, the calcium salt of higher fatty acids and polyurea compound, described thickening agent is the most optional Ground is containing non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid One or more in the calcium salt of calcium oleate, the calcium salt of aromatic acid, little molecule mineral acid and/or lower fatty acid.

The preparation method of 15. 1 kinds of lubricant compositions, it is characterised in that the method includes:

(1) by containing newton body calcium sulfenyl phenolate, optional newton body and/or non-newtonian fluid sulfoacid calcium, Optional newton body and/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid salicylic acid Calcium and optional newton body and/or the high base number material of non-newtonian fluid calcium oleate and the mixing of part basis oil, To mixture；

(2) optionally carry out the reaction of at least part of composite calcium: add Calx or calcium hydroxide, add Higher fatty acids, optional aromatic acid, optional little molecule mineral acid and/or lower fatty acid, react； And/or optionally carry out the reaction of at least part of polyurea compound: add part basis oil and monoamine, or go back Add diamidogen, add diisocyanate and react；

(3) add transforming agent, heat up and treat material retrogradation；

(4) carry out remaining the reaction of composite calcium；

(5) heat up dehydration；

(6) carry out remaining the reaction of polyurea compound；

(7) it is warmed up to 180 230 DEG C of constant temperature refinings, adds surplus base oil, add necessary additive, Obtain finished product.

16. methods according to claim 15, wherein, in step (2), are carried out at least partly The reaction of composite calcium；And/or, carry out the reaction of at least part of polyurea compound.

17. according to the method described in claim 15 or 16, wherein, and step (2) and step (4) In, when carrying out the reaction of composite calcium, at 85-100 DEG C, add Calx or the suspension of calcium hydroxide, Add higher fatty acids, stir 5-20 minute, add optional aromatic acid, optional little molecule mineral acid And/or lower fatty acid, stir 5-20 minute.

18. according to the method described in claim 15 or 16, wherein, and step (2) and step (6) In, when carrying out the reaction of polyurea compound, add part basis oil, monoamine, optional diamidogen, two different After cyanate, 100 120 DEG C of constant temperature 10 30 minutes, wherein, monoamine, optional diamidogen, two different The amount of the material of cyanate meets following relation: the material of the amount of the material of diisocyanate × 2=monoamine Amount × 2 of the material of amount+diamidogen, or, diisocyanate excess, amount≤10% of excess.

19. according to the method described in claim 15 or 16, wherein, in step (3), at 50 80 DEG C, Transforming agent needed for addition reacts, after all transforming agents add, at 80 100 DEG C of constant temperature 60 90 Minute.

20. according to the method described in claim 15 or 16, wherein, in step (5), is warming up to 110-130 DEG C of dehydration.

21. according to the method described in claim 15 or 16, wherein, in step (7), is warmed up to 180 230 DEG C of constant temperature 5 30 minutes；Add surplus base oil, treat that temperature is cooled to 100 120 DEG C, add Enter the additive of necessity, stirring, circulating filtration, homogenizing, degassing.

22. according to the method described in claim 15 or 16, wherein, and described newton body sulfenyl phenolate Calcium is synthesis calcium sulfenyl phenolate, and the total base number of described newton body calcium sulfenyl phenolate is 250-450mgKOH/g；Described newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, described The total base number of newton body sulfoacid calcium is 250-450mgKOH/g；Described newton body calcium naphthenate is oil ring Alkanoic acid calcium and/or synthesis calcium naphthenate, the total base number of described newton body calcium naphthenate is 250-450mgKOH/g；Described newton body calcium salicylate is salicylate calcium, described newton body bigcatkin willow The total base number of acid calcium is 250-450mgKOH/g；Described newton body calcium oleate is natural calcium oleate and/or conjunction Becoming calcium oleate, the total base number of described newton body calcium oleate is 250-450mgKOH/g.

23. according to the method described in claim 15 or 16, wherein, described transforming agent selected from fatty alcohol, Fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, Phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate, aphthenic acids, C16-C24 alkyl phenol and At least one in water, the addition of transforming agent is the 2 30% of described high base number material gross weight.

24. methods according to claim 23, wherein, described transforming agent is selected from detergent alkylate In sulfonic acid, aphthenic acids, octadecyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water extremely Few one, the addition of transforming agent is the 6 22% of described high base number material gross weight.

25. according to the method described in claim 15 or 16, and wherein, the structural formula of described monoamine is R¹–NH₂、R⁴–NH₂, wherein, R¹、R⁴It is phenyl or C1 C3 alkyl or the phenyl of halogen substiuted, Or carbon number is the alkyl or cycloalkyl of 10 18.

26. methods according to claim 25, wherein, described monoamine is selected from aniline, m-chloro The aromatic amine of aniline, parachloroanilinum and/or para-totuidine and/or selected from lauryl amine, tetradecy lamine, cetylamine And/or the fatty amine of 18-amine..

27. according to the method described in claim 15 or 16, and wherein, the structural formula of described diamidogen is NH₂–R²–NH₂, wherein, R²Be carbon number be the alkylidene of 28, or phenylene or biphenylene.

28. methods according to claim 27, wherein, described diamidogen be selected from p-phenylenediamine, O-phenylenediamine, the aromatic amine of 4,4 ' benzidines and/or selected from ethylenediamine, propane diamine, 1,6 hexamethylene diamines Straight-chain fatty amine.

29. according to the method described in claim 15 or 16, wherein, and the structure of described diisocyanate For OCN R³NCO, R³Be carbon number be arlydene, alkylidene or the cycloalkylidene of 6 30.

30. methods according to claim 29, wherein, described diisocyanate is selected from toluene two Isocyanates, methyl diphenylene diisocyanate, six hexylidene diisocyanates, dicyclohexyl methyl hydride two At least one in isocyanates and an xylylene diisocyanate.

31. lubricant compositions prepared by the method described in any one in claim 15 30.