CN106032484A - Lubricating grease composition and preparation method thereof - Google Patents

Lubricating grease composition and preparation method thereof Download PDF

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Publication number
CN106032484A
CN106032484A CN201510105487.4A CN201510105487A CN106032484A CN 106032484 A CN106032484 A CN 106032484A CN 201510105487 A CN201510105487 A CN 201510105487A CN 106032484 A CN106032484 A CN 106032484A
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calcium
acid
weight
newtonian fluid
add
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CN106032484B (en
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何懿峰
孙洪伟
段庆华
张建荣
郑会
刘中其
孔锡奎
姜靓
陈政
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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-calcium sulfonate (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 naphthenate (0-70 wt%), calcium salicylate (0-70 wt%), 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 sulfoacid calcium, the calcium salt of higher fatty acids and polyurea compound, described thickening agent also optionally with Non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, little One or more in the calcium salt of molecule mineral acid and/or lower fatty acid, with described lubricant composition On the basis of weight, the content of base oil is 10 80 weight %, non-newtonian fluid calcium sulfenyl phenolate sulfonic acid 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 calcium naphthenate is 0-70 weight %, non- The content of newton 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 %, little molecule mineral acid and/or the calcium of lower fatty acid The content of salt 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 sulfoacid calcium is 20-65 weight %, the calcium salt of higher fatty acids Content be 2-15 weight %, the content of polyurea compound is 1-20 weight %, non-newtonian fluid aphthenic acids The content of calcium is 0-50 weight %, and the content of non-newtonian fluid calcium salicylate is 0-50 weight %, non newtonian The content of body calcium oleate is 0-50 weight %, and the content of the calcium salt of aromatic acid is 2-10 weight %, little molecule The content of the calcium salt of 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 sulfoacid calcium, the calcium salt of higher fatty acids and polyurea compound, described thickening agent also optionally with Non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, little One or more in the calcium salt of 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) containing newton body calcium sulfenyl phenolate, newton body and/or non-newtonian fluid sulfoacid calcium, or will contain There are newton body and/or non-newtonian fluid calcium sulfenyl phenolate, the high base number material of newton body sulfoacid calcium, and part Base oil mixes, and obtains mixture, and described high base number material is also optionally with newton body and/or non newtonian Body calcium naphthenate, newton body and/or non-newtonian fluid calcium salicylate and newton body and/or non-newtonian fluid calcium oleate In one or more；
(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.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the grease of embodiment 10 preparation.
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 calcium mahogany sulfonate And/or calcium alkylbenzenesulfonate, synthesis calcium sulfenyl phenolate, optional petroleum naphthenic acid calcium and/or synthesis cycloalkanes Acid calcium, optional salicylate calcium, optional natural calcium oleate and/or synthesis calcium oleate are raw material, with The polyurea compound that Shi Hanyou composite calcium thickening agent, isocyanates and amine reaction produce.
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 contain non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium, the calcium salt of higher fatty acids and Polyurea compound, thickening agent also optionally with non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, In the calcium salt of non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, little molecule mineral acid and/or lower fatty acid one Planting or multiple, 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 sulfoacid calcium 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 cycloalkanes The content of acid calcium is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 weight %, non-cattle The content of body calcium oleate is 0-70 weight %, and the content of the calcium salt of aromatic acid is 0-15 weight %, little point The content of the calcium salt of sub-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 sulfoacid calcium is 20-65 weight %, the calcium salt of higher fatty acids Content be 2-15 weight %, the content of polyurea compound is 1-20 weight %, non-newtonian fluid aphthenic acids The content of calcium is 0-50 weight %, and the content of non-newtonian fluid calcium salicylate is 0-50 weight %, non newtonian The content of body calcium oleate is 0-50 weight %, and the content of the calcium salt of aromatic acid is 2-10 weight %, little molecule The content of the calcium salt of 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 calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, One or more in the calcium salt of little molecule mineral acid and/or lower fatty acid are optional components, the present invention's Lubricant composition can include this component, it is also possible to do not include this component.
Non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid salicylic acid Calcium, non-newtonian fluid calcium oleate or a combination thereof thing are at infrared spectrum 873cm–1–886cm–1There is crystal formation carbon in place Acid calcium characteristic absorption peak.Non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is by newton body sulfoacid calcium and newton Body calcium sulfenyl phenolate is converted by transforming agent and obtains, non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium total Base number is 250 450mgKOH/g, preferably 300 400mgKOH/g；Non-newtonian fluid calcium naphthenate is Being obtained by the conversion of newton body calcium naphthenate, 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 sulfoacid calcium, newton body calcium sulfenyl phenolate, 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 sulphur Acid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate and the base number of non-newtonian fluid calcium oleate mixing Weight meansigma methods for the base number of each component.
In the present invention, higher fatty acids be carbon number be fatty acid or the hydroxyl fat of 8-20, preferably 10-18 Fat acid, such as in lauric acid, Palmic acid, stearic acid, 12-hydroxy stearic acid, eicosyl carboxylic acid At least one, 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 and 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.
Described lubricating 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, and thickening agent contains non-newtonian fluid calcium sulfenyl phenolate Sulfoacid calcium, the calcium salt of higher fatty acids and polyurea compound, thickening agent is also optionally with non-newtonian fluid Calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, little molecule are inorganic One or more in the calcium salt of 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 sulfoacid calcium, non-newtonian fluid calcium naphthenate, Non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, 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 sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid water Poplar acid calcium, non-newtonian fluid calcium oleate or a combination thereof thing, can be by newton body sulfoacid calcium, newton body sulfuration alkane Base phenol calcium, newton body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate or a combination thereof thing Respectively by transforming agent convert obtain, such as, by newton body sulfoacid calcium, newton body calcium sulfenyl phenolate, Optional newton body calcium naphthenate, optional newton body calcium salicylate, optional newton body calcium oleate and base Plinth oil Hybrid Heating to 50 80 DEG C, the transforming agent needed for addition reacts, after all transforming agents add, 80 100 DEG C of constant temperature 60 90 minutes, then heat to 110 130 DEG C of dehydrations.
In the present invention, " optional " refer to have this raw material can also not this raw material, such as, " appoint The newton body calcium naphthenate of choosing " i.e. refer to there is newton this raw material of body calcium naphthenate, it is also possible to do not have This raw material of newton body calcium naphthenate.
The third aspect, the invention provides the preparation method of a kind of lubricant composition, and the method includes:
(1) containing newton body calcium sulfenyl phenolate, newton body and/or non-newtonian fluid sulfoacid calcium, or will contain There are newton body and/or non-newtonian fluid calcium sulfenyl phenolate, the high base number material of newton body sulfoacid calcium, and part Base oil mixes, and obtains mixture, and described high base number material is also optionally with newton body and/or non newtonian Body calcium naphthenate, newton body and/or non-newtonian fluid calcium salicylate and newton body and/or non-newtonian fluid calcium oleate In one or more；
(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.
" optionally with " as it was previously stated, do not repeat them here.
In the present invention, newton body calcium sulfenyl phenolate, non-newtonian fluid calcium sulfenyl phenolate, newton body sulfonic acid Calcium, non-newtonian fluid sulfoacid calcium, newton body calcium naphthenate, non-newtonian fluid calcium naphthenate, newton body salicylic acid Calcium, non-newtonian fluid calcium salicylate, newton body calcium oleate, non-newtonian fluid calcium oleate, higher fatty acids, virtue Molecule mineral acid sour, little, lower fatty acid and base oil be not as it was previously stated, repeat them here.
In step of the present invention (1), " containing newton body calcium sulfenyl phenolate, newton body and/or non newtonian Body sulfoacid calcium, or containing newton body and/or non-newtonian fluid calcium sulfenyl phenolate, newton body sulfoacid calcium high-alkali Value material " i.e. refer to the calcium sulfenyl phenolate in high base number material and sulfoacid calcium at least one be newton body Type.
In step of the present invention (1), for the weight ratio of sulfoacid calcium and calcium sulfenyl phenolate without particular/special requirement, It is preferably 1:0.25 4.For the amount of other optional high base number materials without particular/special requirement, can basis Being actually needed the amount commonly used in the art that uses, high base number material gross weight is excellent with the weight ratio of part basis oil Elect 1:0.1 3 as.
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 alkyl monosulfide calcium phenolsulfonate in the lubricant composition prepared, non-newtonian fluid cycloalkanes The total content of acid calcium, non-newtonian fluid calcium salicylate and non-newtonian fluid calcium oleate all uses non-newtonian fluid alkyl monosulfide Phenol calcium sulfoacid calcium % represents, i.e.
Non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium %=(overbased or calcium sulfonate with high base number raw material weight Amount+overbased or SULFURIZED CALCIUM ALKYL PHENATE 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 sulfur Change in the content of alkyl phenol calcium sulfoacid 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 sulfoacid calcium (total base number is 400mgKOH/g, 24kg)；Superelevation alkali Value calcium sulfenyl phenolate (total base number is 400mgKOH/g, 6kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm2/ s, 30kg)；4 octadecylphenol (2.8kg)；Methanol (1kg)；Vinegar 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, 17kg).
A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 24kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number are The overbased calcium sulfenyl phenolate of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, Stirring；It is warmed up to 95 DEG C, adds the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 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, permanent Temperature 10 minutes, adds 2.8kg 4 octadecylphenol, and temperature controls, on 50 DEG C of right sides, to stir 10 minutes, Add 1kg methanol, stir 10 minutes, add the aqueous acetic acid that 2.8kg concentration is 20 weight %, Stir 10 minutes, be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation；120 DEG C it are warmed up under stirring, Keep 45 minutes, dehydration；Add HVI500SN lubricating base oil and the 1.5kg 18-amine. of 2kg, Stir 4 minutes, add the 0.7kg MDI in the HVI500SN lubricating base oil being dissolved in 2kg, stir Mixing 4 minutes, added MDI 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, is cooled to 160 DEG C, adds remaining HVI500SN Lubricating base oil, treats that temperature is cooled to 110 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Inspection 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 sulfoacid calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %； 12 hydroxy stearic acid calcium 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: overbased sulfoacid calcium (total base number is 400mgKOH/g, 6kg)；High base number sulfur Change alkyl phenol calcium (total base number is 320mgKOH/g, 24kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm2/ s, 20kg)；4 octadecylphenol (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 lubricating base oil (100 DEG C of kinematic viscositys For 11mm2/ s, 27kg).
A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 6kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 24kg total base number are The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g and the HVI150BS lubricating base oil of 20kg, stir Mix；It is warmed up to 100 DEG C, adds HVI500SN lubricating base oil and the 0.131kg lauryl amine of 0.2kg, Stir 8 minutes, add the 0.089kg MDI in the HVI500SN lubricating base oil being dissolved in 0.4kg, Stirring 8 minutes, the mol ratio of added MDI and lauryl amine is 1:2,100 DEG C of constant temperature 10 minutes；? At 85 DEG C, add the calcium hydroxide suspension 0.9kg that solid content is 20 weight %, stir 10 minutes； Add 0.19kg stearic acid, stir 10 minutes, add 0.35kg phthalic acid, stir 10 minutes； At 80 DEG C, constant temperature 10 minutes, add 1.2kg n-butyl alcohol and 2.6kg 4 octadecylphenol, temperature control System, at 80 DEG C, stirs 10 minutes, adds the aqueous acetic acid that 2.8kg concentration is 20 weight %, stirring 10 minutes, it is warmed up to 90 DEG C, constant temperature 60 minutes, material retrogradation；At 85 DEG C, adding solid content is The calcium hydroxide suspension 8.1kg of 20 weight %, stirs 10 minutes, adds 1.71kg stearic acid, stirs Mix 10 minutes, add 3.15kg phthalic acid, stir 10 minutes；110 DEG C it are warmed up under stirring, Keep 60 minutes, dehydration；Add HVI500SN lubricating base oil and the 1.179kg lauryl amine of 1.8kg, Stir 8 minutes, add the 0.801kg MDI in the HVI500SN lubricating base oil being dissolved in 3.6kg, Stirring 8 minutes, added MDI is 1:2 with the ratio of the amount of the material of lauryl amine, 100 DEG C of constant temperature 10 points Clock；Finally it is warmed up to 230 DEG C of constant temperature 5 minutes.Then, remaining HVI500SN lubrication base is added Oil；Treating 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 sulfoacid calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.9 weight %； Calcium stearate 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: calcium sulfonate with high base number (total base number is 320mgKOH/g, 24kg)；Overbased Calcium sulfenyl phenolate (total base number is 400mgKOH/g, 6kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm2/ s, 25kg)；4 octadecylphenol (1.6kg)；DBSA (1.2kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12 hydroxy stearic acids (2kg)；M-phthalic acid (3.5kg)；18-amine. (1.66kg)；TDI(0.54kg)；HVI500SN (100 DEG C of kinematic viscositys are 11mm to lubricating base oil2/ s, 22kg).
A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter 24kg total base number be the calcium sulfonate with high base number of 320mgKOH/g, 6kg total base number be 400mgKOH/g Overbased calcium sulfenyl phenolate and the HVI150BS lubricating base oil of 25kg, stirring；It is warmed up to 110 DEG C, add HVI500SN lubricating base oil and the 1.66kg 18-amine. of 2kg, stir 4 minutes, Add the 0.54kg TDI in the HVI500SN lubricating base oil being dissolved in 2kg, stir 4 minutes, institute The TDI added is 1:2 with the ratio of the amount of the material of 18-amine., 110 DEG C of constant temperature 15 minutes；At 65 DEG C, Constant temperature 10 minutes, adds 1.6kg 4 octadecylphenol, and temperature controls at 65 DEG C, stirs 10 minutes, Add 1.2kg DBSA, stir 10 minutes, add 1kg methanol, stir 10 minutes, Add the aqueous acetic acid that 2.8kg concentration is 20 weight %, stir 10 minutes, be warmed up to 100 DEG C, Constant temperature 70 minutes, material retrogradation；At 90 DEG C, add the calcium hydroxide that solid content is 20 weight % and hang Turbid liquid 9kg, stirs 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes, add 3.5kg M-phthalic acid, stirs 10 minutes；It is warmed up to 130 DEG C under stirring, keeps 30 minutes, dehydration；? After be warmed up to 180 DEG C of constant temperature 20 minutes, then, be cooled to 160 DEG C, add remaining HVI500SN Lubricating base oil, treats that temperature is cooled to 100 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Inspection 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 sulfoacid calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %； 12 hydroxy stearic acid calcium 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: calcium sulfonate with high base number (total base number is 320mgKOH/g, 12kg)；High base number sulfur Change alkyl phenol calcium (total base number is 320mgKOH/g, 6kg)；(total base number is naphthenate with superhigh base number calcium 400mgKOH/g, 12kg)；(100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil2/ 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 11mm to HVI500SN lubricating base oil2/ s, 7kg).
Preparing lubricant composition according to the method for embodiment 1, except for the difference that, sulfoacid calcium uses total base number For the calcium sulfonate with high base number of 320mgKOH/g, calcium sulfenyl phenolate uses total base number to be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, and add the naphthenate with superhigh base number that total base number is 400kgKOH/g Calcium；Transforming agent 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 sulfoacid calcium 52.1 weight %；Polyureas 3.5 weight %；Lubricating base oil 34.4 weight %； 12 hydroxy stearic acid calcium 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 sulfoacid calcium (total base number is 400mgKOH/g, 6kg)；Overbased Calcium sulfenyl phenolate (total base number is 400mgKOH/g, 12kg)；Overbased calcium salicylate (total alkali Value is 400mgKOH/g, 12kg)；(100 DEG C of kinematic viscositys are 31 to HVI150BS lubricating base oil mm2/ 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 11mm to HVI500SN lubricating base oil2/ s, 18.6kg).
Preparing lubricant composition according to the method for embodiment 1, except for the difference that, high base number material adds Overbased calcium salicylate, 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 It 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 sulfoacid calcium 36.4 weight %；Polyureas 7.2 weight %；Lubricating base oil 47.6 weight %； 12 hydroxy stearic acid calcium 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: overbased sulfoacid calcium (total base number is 400mgKOH/g, 6kg)；High base number sulfur Change alkyl phenol calcium (total base number is 320mgKOH/g, 18kg)；(total base number is overbased calcium oleate 400mgKOH/g, 6kg)；(100 DEG C of kinematic viscositys are 41 to full synthetic oil poly-a-olefin oil PAO 40 mm2/ 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)； (100 DEG C of kinematic viscositys are 11mm to full synthetic oil poly-a-olefin oil PAO 102/ s, 9kg)；Dithio two Butyl phosphoric acid zinc (2kg)；Dibutyl dithiocaarbamate 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 total base number and be The overbased calcium oleate of 400kgKOH/g；Transforming agent is only 4 octadecylphenol and acetic acid, saves Add the step of methanol；Full synthetic oil poly-a-olefin oil PAO 40 and PAO 10 is used to replace respectively HVI150BS and HVI500SN；And treat that temperature is cooled to 110 DEG C, add dithio two fourth of 2kg Base zinc phosphate, stirs 10 minutes, adds the dibutyl dithiocaarbamate molybdenum of 1kg, stirs 10 points Clock, adds the tungsten disulfide of 2kg, stirs 10 minutes, adds two tungsten selenide of 2kg, stirs 10 points Clock, adds the right of 0.2kg, right ' di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, equal Change, degassing obtains 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 sulfoacid calcium 37.8 weight %；Polyureas 2.5 weight %；Lubricating base oil 44.2 weight %； 12 hydroxy stearic acid calcium 2.4 weight %；P-phthalic acid calcium 4.9 weight %；Dithio dibutylphosphoric acid Zinc 2.3 weight %；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: calcium sulfonate with high base number (total base number is 320mgKOH/g, 6kg)；Overbased sulfur Change alkyl phenol calcium (total base number is 400mgKOH/g, 8kg)；(total base number is overbased calcium alkyl-salicylate 300mgKOH/g, 8kg)；High base number calcium salicylate (total base number is 300mgKOH/g, 8kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil2/ s, 15kg)；4 octadecyl benzene Phenol (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)；(100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil2/ s, 33kg).
Preparing lubricant composition according to the method for embodiment 1, except for the difference that, sulfoacid calcium uses total base number For the calcium sulfonate with high base number of 320mgKOH/g, add overbased calcium alkyl-salicylate and high base number bigcatkin willow simultaneously Acid calcium；Transforming agent is only 4 octadecylphenol and acetic acid, saves the step adding methanol；Use 2 Methyl 1,4 phthalic acid replaces p-phthalic acid；Monoamine, in addition to 18-amine., is additionally added para-totuidine； 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 sulfoacid calcium 37.1 weight %；Polyureas 2.4 weight %；Lubricating base oil 53.3 weight %； 12 hydroxy stearic acid calcium 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: calcium sulfonate with high base number (total base number is 320mgKOH/g, 6kg)；High base number vulcanizes Alkyl phenol calcium (total base number is 320mgKOH/g, 8kg)；(total base number is high base number calcium salicylate 360mgKOH/g, 8kg)；High base number calcium oleate (total base number is 400mgKOH/g, 8kg)；HVI150BS (100 DEG C of kinematic viscositys are 31mm to lubricating base oil2/ s, 20kg)；4 octadecylphenol (2.8kg)； Acetic acid (0.56kg)；Calcium hydroxide (5.2kg)；12 hydroxy stearic acids (2kg)；Boric 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 ' bis-different pungent Base diphenylamines (0.2kg).
Preparing lubricant composition according to the method for embodiment 1, except for the difference that, sulfoacid calcium uses total base number For the calcium sulfonate with high base number of 320mgKOH/g, calcium sulfenyl phenolate uses total base number to be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, add high base number calcium salicylate and high base number calcium oleate simultaneously；Convert Agent is only 4 octadecylphenol and acetic acid, saves the step adding methanol；Add 12 hydroxy stearic acids After stirring 10 minutes, add boric acid, stir 10 minutes, be subsequently adding p-phthalic acid, stir 10 Minute；Monoamine, in addition to 18-amine., is additionally added lauryl amine；And treat that temperature is cooled to 110 DEG C, add 0.2kg's is right, right ' di-iso-octyldiphenylamine, stirs 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 sulfoacid calcium 34.2 weight %；Polyureas 2.2 weight %；Lubricating base oil 49.2 weight %； 12 hydroxy stearic acid calcium 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: non-newtonian fluid calcium sulfonate with high base number (15kg)；Overbased calcium sulfenyl phenolate is (total Base number is 400mgKOH/g, 4kg)；Naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 4kg)；Overbased calcium salicylate (total base number is 400mgKOH/g, 4kg)；Overbased calcium oleate (total base number is 400mgKOH/g, 3kg)；(100 DEG C of kinematic viscositys are HVI150BS lubricating base oil 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 11mm to HVI500SN lubricating base oil2/ s, 33kg).
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 400mgKOH/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, overbased sulfoacid calcium is straight Connecing and use the non-newtonian fluid sulfoacid calcium prepared, high base number material increases calcium naphthenate, calcium salicylate and oil Acid calcium, transforming agent is only 4 octadecylphenol and acetic acid, saves the step adding methanol；And add After p-phthalic acid stirs 10 minutes, 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 sulfoacid calcium 36.0 weight %；Polyureas 2.4 weight %；Lubricating base oil 51.8 weight %； 12 hydroxy stearic acid calcium 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 sulfoacid calcium (total base number is 400mgKOH/g, 6kg)；Overbased Calcium sulfenyl phenolate (total base number is 400mgKOH/g, 24kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm2/ s, 30kg)；4 octadecylphenol (2.8kg)；Methanol (1kg)；Vinegar 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, 17kg).
A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 6kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 24kg total base number are The overbased calcium sulfenyl phenolate of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, Stirring, heats to 100 DEG C, adds the calcium hydroxide suspension 9kg that solid content is 20 weight %, Stir 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes；Add 3.5kg terephthaldehyde Acid, stirs 10 minutes；Cool to 50 DEG C, constant temperature 10 minutes；Add 2.8kg 4 octadecylphenol, Temperature controls at about 50 DEG C, stirs 10 minutes；Add 1kg methanol, stir 10 minutes；Add 2.8kg concentration is the aqueous acetic acid of 20 weight %, stirs 10 minutes；It is warmed up to 80 DEG C, constant temperature 90 Minute, material retrogradation；It is warmed up to 120 DEG C under stirring, keeps 30 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.Grease Infrared spectrum is shown in Fig. 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 sulfoacid calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %； 12 hydroxy stearic acid calcium 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 sulfoacid calcium (total base number is 400mgKOH/g, 24kg)；Superelevation alkali Value calcium sulfenyl phenolate (total base number is 400mgKOH/g, 6kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm2/ s, 30kg)；4 octadecylphenol (total acid number is 180mgKOH/g, 2.8kg)；Methanol (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)；HVI500SN lubrication base (100 DEG C of kinematic viscositys are 11mm to oil2/ s, 17kg).
A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 24kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number are Overbased calcium sulfenyl phenolate and 100 DEG C of kinematic viscositys of 30kg of 400mgKOH/g are 31mm2/s HVI150BS lubricating base oil, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 2.8kg 4 octadecylphenol, temperature controls at about 50 DEG C, stirs 10 minutes；Add 1kg methanol, stir Mix 10 minutes；Add the aqueous acetic acid that 2.8kg concentration is 20 weight %, stir 10 minutes；Heat 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 30 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 sulfoacid calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %； 12 hydroxy stearic acid calcium 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 10kg total base number be the calcium sulfonate with high base number of 350mgKOH/g, 20kg total base number be 400mgKOH/g Overbased calcium sulfenyl phenolate and HVI150BS lubricating base oil (100 DEG C of kinematic viscositys of 25kg For 31mm2/ s, lower same), stirring, heat to 60 DEG C, constant temperature 10 minutes；Add 2kg cycloalkanes Acid and 1kg 4 octadecylphenol, temperature controls at about 60 DEG C, stirs 10 minutes；Add concentration It is the 12.5kg butanol aqueous solution of 20%, stirs 10 minutes；87 DEG C of constant temperature 70 minutes, material became Thick.
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 sulfoacid calcium 34.4 weight %；Calcium palmitate 2.7 weight %；Biphenyl dicarboxylic acid calcium 4.2 Weight %；Calcium phosphate 1.6 weight %；Ethanedioic acid calcium 2.9 weight %；Polyureas 4.6 weight %；Lubrication base Plinth oil 49.6 weight %.
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 Adding 20kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 10kg total base number are The overbased calcium sulfenyl phenolate of 420mgKOH/g and the HVI150BS lubricating base oil of 10kg, Stirring, heats to 50 DEG C, constant temperature 10 minutes；Add 2kg DBSA, temperature control System, at about 50 DEG C, stirs 10 minutes；Add 1kg methanol, stir 10 minutes；Add 2kg concentration It is the aqueous acetic acid of 20 weight %, stirs 10 minutes；In 83 DEG C of 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 sulfoacid 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 sulfoacid calcium (total base number is 400mgKOH/g, 24kg)；Superelevation alkali Value calcium sulfenyl phenolate (total base number is 400mgKOH/g, 6kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm2/ s, 30kg)；4 octadecylphenol (2.8kg)；Methanol (1kg)；Vinegar 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, 17kg).
A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 24kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number are The overbased calcium sulfenyl phenolate of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, Stirring；It is warmed up to 50 DEG C, constant temperature 10 minutes, add 2.8kg 4 octadecylphenol, temperature controls On 50 DEG C of right sides, stirring 10 minutes, add 1kg methanol, stir 10 minutes, adding 2.8kg concentration is The aqueous acetic acid of 20 weight %, stirs 10 minutes, is warmed up to 80 DEG C, constant temperature 90 minutes, material Retrogradation；It is warmed up to 100 DEG C, adds the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes, add 3.5kg p-phthalic acid, Stir 10 minutes；It is warmed up to 120 DEG C under stirring, keeps 45 minutes, dehydration；Add the HVI500SN of 2kg Lubricating base oil and 1.5kg 18-amine., stir 4 minutes, adds the HVI500SN profit being dissolved in 2kg 0.7kg MDI in sliding base oil, stir 4 minutes, the amount of the material of added MDI and 18-amine. it Than being 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, 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 sulfoacid calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %； 12 hydroxy stearic acid calcium 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 butyl ether, methanol is replaced with methyl propyl ketone.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 sulfoacid calcium 37.5 weight %；Polyureas 2.5 weight %；Lubricating base oil 52.8 weight %； 12 hydroxy stearic acid calcium 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, extreme pressure anti-wear and Lubricating life；Embodiment 1 and embodiment 15 are compared it can be seen that transforming agent is selected from dodecane In base benzenesulfonic acid, aphthenic acids, octadecyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water At least one, the lubricant composition of preparation, there is more preferable viscous resistance, mechanical stability, water resistant Property, colloid stability, 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 sulfoacid calcium, the calcium of higher fatty acids Salt and polyurea compound, described thickening agent is also optionally with 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 described lubricant composition, the content of base oil is 10 80 weight %, the content of non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is 10 70 weight %, high The content of the calcium salt of level fatty acid is 1 20 weight %, and the content of polyurea compound is 0.5 30 weight %, The content of non-newtonian fluid 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 %.
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 %, non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium Content be 20-65 weight %, the content of the calcium salt of higher fatty acids is 2-15 weight %, polyureas chemical combination The content of thing is 1-20 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, non newtonian The content of body calcium salicylate is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, The content of the calcium salt of aromatic acid is 2-10 weight %, the calcium salt of little molecule mineral acid and/or lower fatty acid Content is 2-10 weight %.
Lubricant composition the most according to claim 1 and 2, wherein, described non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium to be obtained by newton body sulfoacid calcium and the conversion of newton body calcium sulfenyl phenolate, The total base number of described non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is 250 450mgKOH/g；Described non- Newton body calcium naphthenate is converted by newton body calcium naphthenate and obtains, described non-newtonian fluid calcium naphthenate Total base number is 250-450mgKOH/g；Described non-newtonian fluid calcium salicylate is to be turned by newton body calcium salicylate Change obtains, and the total base number of described non-newtonian fluid calcium salicylate is 250-450mgKOH/g；Described non-cattle The body calcium oleate that pauses 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, R2Be 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 In 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 sulfoacid calcium, the calcium salt of higher fatty acids and polyurea compound, described thickening Agent also optionally with non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, One or more in the calcium salt of 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) containing newton body calcium sulfenyl phenolate, newton body and/or non-newtonian fluid sulfoacid calcium, or will contain There are newton body and/or non-newtonian fluid calcium sulfenyl phenolate, the high base number material of newton body sulfoacid calcium, and part Base oil mixes, and obtains mixture, and described high base number material is also optionally with newton body and/or non newtonian Body calcium naphthenate, newton body and/or non-newtonian fluid calcium salicylate and newton body and/or non-newtonian fluid calcium oleate In one or more；
(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.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106590814A (en) * 2016-12-05 2017-04-26 新乡市瑞丰新材料股份有限公司 Preparation method of composite calcium sulfonate grease

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4181619A (en) * 1978-10-30 1980-01-01 Mobil Oil Corporation Antiwear composition
CN1252434A (en) * 1998-10-24 2000-05-10 燕化集团天津润滑油脂有限公司 Composite lithium- and calcium-base lubricating grease and its preparation
WO2002012418A2 (en) * 2000-08-10 2002-02-14 Shell Internationale Research Maatschappij B.V. Grease composition with improved rust prevention and abrasion resistance properties
CN101423483A (en) * 2008-06-20 2009-05-06 辽宁天合精细化工股份有限公司 High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof
CN102453598A (en) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof
CN102757845A (en) * 2011-04-28 2012-10-31 中国石油化工股份有限公司 Low-noise lithium-based lubricating grease composition and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4181619A (en) * 1978-10-30 1980-01-01 Mobil Oil Corporation Antiwear composition
CN1252434A (en) * 1998-10-24 2000-05-10 燕化集团天津润滑油脂有限公司 Composite lithium- and calcium-base lubricating grease and its preparation
WO2002012418A2 (en) * 2000-08-10 2002-02-14 Shell Internationale Research Maatschappij B.V. Grease composition with improved rust prevention and abrasion resistance properties
CN101423483A (en) * 2008-06-20 2009-05-06 辽宁天合精细化工股份有限公司 High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof
CN102453598A (en) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof
CN102757845A (en) * 2011-04-28 2012-10-31 中国石油化工股份有限公司 Low-noise lithium-based lubricating grease composition and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106590814A (en) * 2016-12-05 2017-04-26 新乡市瑞丰新材料股份有限公司 Preparation method of composite calcium sulfonate grease
CN106590814B (en) * 2016-12-05 2019-11-19 新乡市瑞丰新材料股份有限公司 A kind of preparation method of calcium sulfonate complex grease

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