CN108003964A - A kind of lubricating grease and preparation method thereof - Google Patents

A kind of lubricating grease and preparation method thereof Download PDF

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Publication number
CN108003964A
CN108003964A CN201610957939.6A CN201610957939A CN108003964A CN 108003964 A CN108003964 A CN 108003964A CN 201610957939 A CN201610957939 A CN 201610957939A CN 108003964 A CN108003964 A CN 108003964A
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China
Prior art keywords
acid
lubricating grease
weight
small molecule
base number
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Granted
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CN201610957939.6A
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CN108003964B (en
Inventor
何懿峰
郑会
孙洪伟
段庆华
白文娟
李华
姚立丹
杨海宁
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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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Priority to CN201610957939.6A priority Critical patent/CN108003964B/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
    • C07C273/1827—X being H
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26—Waterproofing or water resistance
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Abstract

The present invention relates to field of lubricant, discloses a kind of lubricating grease and preparation method thereof.The lubricating grease contains the salt of base oil, the compound shown at least one Formulas I, non-newtonian fluid high base number calcium and optional small molecule acid.The invention also discloses the method for preparing the lubricating grease, including：By newton body high base number calcium, transforming agent and Part I base oil Hybrid Heating, make material retrogradation；Products therefrom is mixed with hydroxy fatty acid, optional small molecule acid and source metal and carries out saponification, heating dehydration is carried out to the selectivity of product that saponification is obtained again, the compound of the group with one or more NHCONH structures is obtained in the presence of the selectivity of catalyst；Then products therefrom is refined, then is mixed with surplus base oil and optional additive.The invention also discloses the lubricating grease as made from the above method.The lubricating grease high comprehensive performance of the present invention, can be widely used for every profession and trade.

Description

A kind of lubricating grease and preparation method thereof
Technical field
The present invention relates to field of lubricant, and in particular, to a kind of lubricating grease and preparation method thereof.
Background technology
Calcium sulfonate with high base number is raw material production lubricating grease because it is with excellent high temperature performance, mechanical stability, glue Body stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, have caused domestic and international lubrication The extensive concern of fat industry.CN102417855A etc. introduces polyureas in sulfoacid calcium, improves lubricating life.CN103695137A Use overbased calcium alkyl-salicylate that the same excellent and more environmentally-friendly high base number ring of comprehensive performance can also be made for raw material etc. disclosing Alkanoic acid grease of calcium.CN103571588A etc. introduces polyureas in calcium naphthenate, further improves the comprehensive performance of lubricating grease. CN104450111A is prepared for the lubrication of excellent combination property using calcium sulfonate with high base number and overbased calcium alkyl-salicylate as raw material at the same time Fat, on this basis, CN104450114A etc. introduce the various aspects of performance that polyureas further improves lubricating grease.
Metal soap base grease particularly 12- hydroxy lithium stearates soap base grease is that annual output is maximum in the world at present A kind of lubricating grease, because it is widely used in every profession and trade with preferable comprehensive performance, but its dropping point is not high, mostly less than 200 DEG C, limit its scope applied.
Thickening agent in urea-base grease is gained the name because containing-NH-CO-NH- urea/ureido functional unity structures in its molecular structure, The number rolled into a ball according to urea/ureido functional can be divided into two urea fat (most common), triuret fat, four urea fat, six urea fat, eight urea fat etc., its shortcoming It is that mechanical stability is bad, it is bad to the sensitivity of metal class additive.
Although polyureas is combined with high base number series lubricating grease can improve the performance of high base number lubricating grease, both are physics Mixing, and and not up to optimum efficiency, be further improved.
The content of the invention
The purpose of the present invention is overcoming the deficiencies of the prior art and provide a kind of high-temperature behavior, mechanical stability and to metal The lubricating grease and its preparation method that the sensitivity of class additive is improved at the same time.
To achieve these goals, in a first aspect, the present invention provides a kind of lubricating grease, the lubricating grease contain base oil, The salt of compound, non-newtonian fluid high base number calcium and optional small molecule acid shown at least one Formulas I, the small molecule acid Salt be the salt of small molecule inorganic acid, at least one of salt of the salt of lower fatty acid and aromatic acid,
Wherein, R1For hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted virtue Base；R2For substituted or unsubstituted arlydene, substituted or unsubstituted alkylidene or substituted or unsubstituted cycloalkylidene；R3For Group with one or more-NHCONH- structures；Mn+The sun formed for IA races, Group IIA, Group IIIA or Group IVB metallic element Ion.
Second aspect, the present invention provides a kind of method for preparing the lubricating grease described in first aspect, this method includes：Will Compound, non-newtonian fluid high base number calcium, the salt of optional small molecule acid and the mixing of part basis oil shown at least one Formulas I are simultaneously Refined, then mixed with surplus base oil and optional additive.
The third aspect, the present invention provides a kind of method for preparing lubricating grease, this method includes：
(1) by newton body high base number calcium, transforming agent and Part I base oil Hybrid Heating, material retrogradation is made；
(2) it is with structural formula by step (1) products therefromHydroxy fatty acid, optionally Small molecule acid and source metal mixing carry out saponification, then the selectivity of product that saponification is obtained to carry out heating de- Water, in the presence of the selectivity of catalyst, makes the product that heating is dehydrated and polyisocyanates, amine and optional other isocyanide Acid esters is reacted to give the compound of the group with one or more-NHCONH- structures,
Alternatively, it is by structural formulaHydroxy fatty acid, optional small molecule acid, second Part basis oil and source metal mixing carry out saponification, then the selectivity of product that saponification is obtained to carry out heating de- Water, in the presence of the selectivity of catalyst, makes the product that heating is dehydrated and polyisocyanates, amine and optional other isocyanide Acid esters is reacted to give the compound of the group with one or more-NHCONH- structures, then by obtained product and step (1) products therefrom mixes；
Wherein, the small molecule acid is at least one of salt of small molecule inorganic acid, lower fatty acid and aromatic acid；
(3) step (2) products therefrom is refined, then is mixed with surplus base oil and optional additive.
Fourth aspect, the present invention provides the lubricating grease as made from the method described in the third aspect.
By the present invention in that by the use of by hydroxyl using soap grease and the chemical combined material of polyurea grease as thickening agent component so that High-temperature behavior, mechanical stability and the preferable lubricating grease of sensitivity to metal class additive are obtained, its performance is substantially better than The mechanical impurity of non-calcium-base grease and urea-base grease, can be widely used for every profession and trade.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of ESI mass spectrograms of the compound that embodiment obtains according to the present invention.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.
In first aspect, lubricating grease provided by the invention contains base oil, compound (the soap urea shown at least one Formulas I Compound), the salt of non-newtonian fluid high base number calcium and optional small molecule acid, the salt of the small molecule acid is inorganic for small molecule At least one of salt of the salt of acid, the salt of lower fatty acid and aromatic acid,
Wherein, R1For hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted virtue Base；R2For substituted or unsubstituted arlydene, substituted or unsubstituted alkylidene or substituted or unsubstituted cycloalkylidene；R3For Group with one or more-NHCONH- structures；Mn+The sun formed for IA races, Group IIA, Group IIIA or Group IVB metallic element Ion.
In the present invention, group is at least one in hydroxyl, halogen and carboxyl used by substitution.
Preferably, R1For the alkyl (or straight chained alkyl) of C1-C10 (C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10). It is highly preferred that R1For the straight chained alkyl of C3-C10 (C3, C4, C5, C6, C7, C8, C9 or C10).
Preferably, R2For C1-C20 (C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19 or C20) alkylidene (or straight-chain alkyl-sub).It is highly preferred that R2For C8-C15 (C8, C9, C10, C11, C12, C13, C14 or C15) straight-chain alkyl-sub.
Preferably, R3Structural formula beWherein, R3’Carbon number be 6- 30 (preferably 6-20) and be substituted or unsubstituted arlydene, substituted or unsubstituted alkylidene or substituted or unsubstituted Asia Cycloalkyl, R4For substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or have The group of one or more-NHCONH- structures.
It is highly preferred that R3’For(one end being connected with fatty acid chain can be either end), Or-CH2-(CH2)4-CH2-.It is highly preferred that R4For the straight chained alkyl of C6-C20 or with one or more The group of a-NHCONH- structures.
In the present invention, there is the group of one or more (such as 2,3,4,5,6 or 8)-NHCONH- structures (particularly R4) can be various conventional single urea functional groups or more urea functional groups.It will be appreciated to those of skill in the art that " group with one or more-NHCONH- structures " expression-NHCONH- involved in the present invention can have one or more, And the group of-NHCONH- both sides is (as it was previously stated, selected from substituted or unsubstituted (Asia) aryl, substituted or unsubstituted (Asia) alkane Base or substituted or unsubstituted (Asia) cycloalkyl) can be each identical or different.
It is highly preferred that R3In the groups of-NHCONH- structures both sides can be selected from：
Or-CH2-(CH2)0-16-CH2-。
Mn+Can be that (including metallic element is formed the various common cations that are formed of above-mentioned metallic element with oxygen element Cation), it is preferable that Mn+For Li+、Na+、K+、Ca2+、Sr2+、Ba2+、Al3+、Ti4+Or ZrO2+。
Most preferred embodiment according to the present invention, the structural formula of the compound are：
(wherein, R3And Mn+ As it was previously stated, and R3In-NHCONH- structures quantity in the range of 1-8).
In the present invention, as long as being that the mesh of the present invention can be achieved using above-claimed cpd as a part for grease thickener , wherein the content of base oil and thickening agent can be conventional selection.Preferably, using the gross weight of the lubricating grease as base Standard, the content of the base oil is 10-70 weight %, more preferably 20-65 weight %, is most preferably 30-55 weight %.It is preferred that Ground, on the basis of the gross weight of the lubricating grease, the content of the compound shown at least one Formulas I is 1-40 weight %, more excellent Elect 2-25 weight % as, be most preferably 5-20 weight %.Preferably, on the basis of the gross weight of the lubricating grease, non-newtonian fluid The content of high base number calcium is 10-75 weight %, is preferably 20-65 weight %, is most preferably 30-60 weight %.
In the present invention, as long as being that the mesh of the present invention can be achieved using above-claimed cpd as a part for grease thickener , the salt of the small molecule acid is the component selectively contained.Preferably, on the basis of the gross weight of the lubricating grease, small point The content of the salt of sub- acid is 0-20 weight %, more preferably 0.5-15 weight %, is most preferably 1-10 weight %.
The base oil can be various oil commonly used in the art, for example, in mineral oil, artificial oil and vegetable oil at least It is a kind of.The kinematic viscosity (being measured with reference to GB/T265-1988) of 100 DEG C of the base oil can be 2-100mm2/s。
Usually, the non-newtonian fluid high base number calcium is converted to obtain by newton body high base number calcium, the non-newtonian fluid The total base number of high base number calcium is 250-450mgKOH/g.The non-newtonian fluid high base number calcium can be non-newtonian fluid sulfonate with high base number Calcium, non-newtonian fluid overbased calcium alkyl-salicylate, non-newtonian fluid SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, non-newtonian fluid high base number calcium salicylate and At least one of non-newtonian fluid high base number calcium oleate.Non-newtonian fluid high base number calcium is in infrared spectrum 873-886cm-1Place occurs brilliant Type calcium carbonate characteristic absorption peak, total base number 250-450mgKOH/g, is preferably 300-400mgKOH/g.The non-newtonian fluid is high Base number calcium is to convert to obtain by transforming agent by newton body high base number calcium.And contain unformed carbonic acid in newton body high base number calcium Calcium, the 860-865cm in infrared spectrum-1There is characteristic absorption peak in place.The newton body high base number calcium can be oil high base number Calcium or synthesis high base number calcium or newton body calcium sulfonate with high base number, newton body overbased calcium alkyl-salicylate, newton body high base number At least one of sulfurized alkylphenol calcium, newton body high base number calcium salicylate, newton body high base number calcium oleate, its total base number is 250-450mgKOH/g, is preferably 300-400mgKOH/g, after changing into non-newtonian fluid high base number calcium, its base number is basically unchanged.
In the present invention, the salt of small molecule acid is the component selectively contained, and small molecule acid can be that this area is conventional Small molecule inorganic acid, lower fatty acid or aromatic acid, under preferable case, small molecule inorganic acid, lower fatty acid or aromatic acid Molecular weight is less than or equal to 210.Wherein, small molecule inorganic acid can be selected from least one of boric acid, phosphoric acid, nitric acid and sulfuric acid. Lower fatty acid can be structure such as R7-(COOH)PAt least one of shown compound, wherein, R7Can substitute or do not take The alkyl in generation, substituted or unsubstituted cycloalkyl or substituted or unsubstituted aryl, preferably alkyl, most preferably C1-C12 (C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12) alkyl；P can be the positive integer of 1-6, and preferably 1-3 is just Integer, is most preferably 1 or 2.It is further preferred that the lower fatty acid is selected from acetic acid, ethanedioic acid, propionic acid, malonic acid, fourth At least one of acid, succinic acid, azelaic acid, decanedioic acid etc..The aromatic acid can be the carboxylic acid with an aromatic rings, such as At least one of benzoic acid, terephthalic acid (TPA), M-phthalic acid and phthalic acid.Most preferably, the small molecule acid is Acetic acid and/or decanedioic acid.
In the present invention, the cation in the salt of the small molecule acid can be IA races, Group IIA, Group IIIA and Group IVB metal The cation that at least one of element is formed, is preferably Li+、Na+、K+、Ca2+、Sr2+、Ba2+、Al3+、Ti4+And ZrO2+In At least one, and and Mn+Can be identical or different.
The lubricating grease can also contain additive, and the content and species of additive are had no particular limits.With described On the basis of the gross weight of lubricating grease, the content of the additive can be preferably 0.5-15 weight %, most below 20 weight % Preferably 1-10 weight %.
The additive can be at least one of antioxidant, extreme pressure anti-wear additives and antirust agent.Wherein, antioxidant is preferred Can be at least one of diphenylamines, phenyl-α-naphthylamine and di-iso-octyldiphenylamine for arylamine kind antioxidant, preferably two is different Octyl diphenylamine.On the basis of the gross weight of lubricating grease, the content of antioxidant can be 0.01-5 weight %, be preferably 0.1- 2.5 weight %.
Extreme pressure anti-wear additives can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two thio dioxanes It is aminocarbamic acid lead, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethylene (PTFE), thio Molybdenum phosphate, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and oxygen Change at least one of zinc.On the basis of the gross weight of lubricating grease, the content of extreme pressure anti-wear additives can be 0.5-12 weight %, excellent Elect 0.8-8 weight % as.
Antirust agent can be barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl At least one of succinic acid.On the basis of the gross weight of lubricating grease, the content of antirust agent can be 0.01-4.5 weight %, excellent Elect 0.1-2 weight % as.
In second aspect, the method provided by the invention for preparing the lubricating grease described in first aspect includes：By at least one Compound, non-newtonian fluid high base number calcium, the salt of optional small molecule acid and part basis oil shown in Formulas I are mixed and refined System, then mixed with surplus base oil and optional additive.Shown in the salt of thickening agent small molecular acid and at least one Formulas I Compound can be mixed with base oil at the same time, can also be mixed step by step with base oil.Do not have to the condition for refining (constant temperature refining) It is special to require, it can be carried out according to conventional condition.Under preferable case, the condition of refining includes：Temperature is 140-230 DEG C, Time is 5-20min.
In the third aspect, the method provided by the invention for preparing lubricating grease includes：
(1) by newton body high base number calcium, transforming agent and Part I base oil Hybrid Heating, material retrogradation is made；
(2) it is with structural formula by step (1) products therefrom(R1And R2Under as it was previously stated, Hydroxy fatty acid, optional small molecule acid and source metal mixing together) carries out saponification, then the product that saponification is obtained Optionally carry out heating dehydration, in the presence of the selectivity of catalyst, make product and polyisocyanates, amine that heating is dehydrated with And optional other isocyanates is reacted to give the compound of the group with one or more-NHCONH- structures,
Alternatively, it is by structural formulaHydroxy fatty acid, optional small molecule acid, second Part basis oil and source metal mixing carry out saponification, then the selectivity of product that saponification is obtained to carry out heating de- Water, in the presence of the selectivity of catalyst, makes the product that heating is dehydrated and polyisocyanates, amine and optional other isocyanide Acid esters is reacted to give the compound of the group with one or more-NHCONH- structures, then by obtained product and step (1) products therefrom mixes；
Wherein, the small molecule acid is at least one of salt of small molecule inorganic acid, lower fatty acid and aromatic acid；
(3) step (2) products therefrom is refined, then is mixed with surplus base oil and optional additive.
In step (1), the transforming agent is preferably selected from fatty alcohol, aliphatic acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, carbon In sour calcium, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonates and water extremely Few one kind；It is more preferably selected from the fatty alcohol of C1-C5, the aliphatic acid of C1-C5, the aliphatic ketone of C1-C5, the fatty aldehyde of C1-C5, C1- The fatty amine of C5, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, the aryl phosphine of C6-C20 In acid, the aromatic amine of the diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, C7-C20, C8-C20 alkyl benzene sulphonates and water It is at least one；Still more preferably it is selected from dodecyl benzene sulfonic acid, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water At least one of.The addition of transforming agent is preferably the 2-30 weight % of newton body high base number calcium weight, more preferably 6-22 Weight %.
According to the third aspect of the invention we, in step (1), newton body high base number calcium and Part I base oil is mixed and added Heat arrives 50-90 DEG C, adds transforming agent, then when constant temperature 0.5-3 is small at 60-100 DEG C.Specifically, in step (1), by newton Body high base number calcium, Part I base oil Hybrid Heating are to 50-90 DEG C, preferably constant temperature 10-30 minutes, sequentially add required turn Agent is reacted, and is stirred 8-30 minutes, is reacted fully, all transforming agents heat up after adding, preferably after preferably adding every time When constant temperature 0.5-3 is small at 60-100 DEG C, make material retrogradation into smectic.
According to the third aspect of the invention we, step (1) is the step of preparing non-newtonian fluid high base number calcium, therefore, to newton The selection of body high base number calcium may refer to above.
According to the third aspect of the invention we, in step (2), the source metal can be oxide, the hydrogen of metal of metal At least one of alkoxide compound of oxide and metal (such as methoxy compound, ethoxy compound) (can be by Water is as solvent).The general formula of alkoxide compound can be Mn+(OR-)n(such as Zr4+(OR-)4、Na+(OR)-、Li+(OR)-Or Ca2+ (OR-)2), wherein, R can be C1-C10 alkyl, be preferably C2-C6 alkyl, as methyl, ethyl, n-propyl, normal-butyl, The tert-butyl group, n-pentyl or tertiary pentyl.Further, the source metal can be this area conventional containing available for saponification The compound of metallic element (such as IA races, Group IIA, Group IIIA or Group IVB metallic element), be preferably selected from lithium, sodium, potassium, calcium, At least one of oxide, hydroxide and alkoxide compound of at least one of strontium, barium, aluminium, titanium and zirconium metal, Such as, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum alkoxide, zirconium alkoxide be (such as Ethanol zirconium, zirconium iso-propoxide etc.), hydroxide (such as Zr (OH) of zirconium4With ZrO (OH)2At least one of).
Those skilled in the art know that saponification can carry out in reaction medium, can be the organic of routine Solvent (the various base oils used in such as lubricating grease), can also such as mineral oil, artificial oil, vegetable oil or their mixture There is provided by step (1) products therefrom.
It is highly preferred that in step (2), carry out saponification under conditions of 70-120 DEG C, reselection in 100-150 Heating dehydration is carried out at DEG C.It is further preferred that in step (2), saponification is carried out under conditions of 100-110 DEG C, then select Heating dehydration is carried out to selecting property at 115-150 DEG C.The time of saponification can be 60-180min.Heating dehydration is selection Property the step of carrying out, if it will be appreciated to those of skill in the art that saponification carries out at relatively high temperatures, and the thing after saponification Material is substantially free of water, then need not carry out heating dehydration.The time of heating dehydration can be 5-30min.
According to the third aspect of the invention we, it is not special to the molar ratio of hydroxy fatty acid, small molecule acid and source metal etc. Limitation, the mole (with elemental metal) of general control source metal is than the sum of mole of hydroxy fatty acid and small molecule acid High (such as high 1-10mol%).Relative to every mole of source metal (with elemental metal), the dosage of Part II base oil Can be 0.3-10kg.
According to the third aspect of the invention we, the catalyst is the material selectively used, for accelerating the progress of reaction. The catalyst can be the various materials that the hydroxyl that hydroxy fatty acid provides can be promoted to be reacted with isocyanates, it is preferable that The catalyst is organic amine (amine of such as C1-C20), in carbonate, the hydroxide of alkali metal, boron trifluoride, organic metal At least one.It is highly preferred that the catalyst is methylamine, ethamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, carbon At least one of sour sodium, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, boron trifluoride and organotin.
According to the third aspect of the invention we, the dosage of catalyst is not required particularly, for example, can be hydroxy aliphatic The 0.5-10 weight % of sour weight.
According to the third aspect of the invention we, isocyanates (polyisocyanates) and product (the i.e. hydroxy aliphatic of heating dehydration The metal salt of acid) molar ratio of hydroxyl that provides is usually 0.5-2.5：1.Heat up the product and isocyanates (more isocyanides being dehydrated Acid esters) reaction temperature can be 90-150 DEG C, the time can be 0.5-5h.
In the another embodiment of third aspect present invention, will heat up the product of dehydration and polyisocyanates, amine with And optional other isocyanates is reacted to give the compound of the group with one or more-NHCONH- structures.Its In, isocyanates in addition refers to the isocyanates in addition used, can be that (structural formula can be R to monoisocyanates4- N=C=O (wherein, R4For substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, such as preceding institute State), such as phenyl isocyanate, tolyl isocyanate, chlorophenyl isocyanate), or (such as two is different for polyisocyanates (structure can be O=C=N-R to cyanate3’- N=C=O, R3’For substituted or unsubstituted arlydene, substituted or unsubstituted Alkylidene or substituted or unsubstituted cycloalkylidene, R3’Carbon number be preferably 6-30, as previously described), can be diphenyl Methane diisocyanate, toluenediisocyanate, hexamethylene diisocyanate, dicyclohexylmethyl diisocyanate and isophthalic At least one of diformazan group diisocyanate), those skilled in the art can be selected according to the quantity of-NHCONH- structures Select.Amine is as the same, can be monoamine (general formula R5-NH2, wherein, R5Can for the alkyl of C8-C24, C8-C24 cycloalkyl or C6-C10 aryl, is preferably aniline, m-chloroaniline, parachloroanilinum, para-totuidine, n-octyl amine, lauryl amine (or lauryl amine), 14 At least one of amine, cetylamine and octadecylamine), or diamines (general formula NH2-R6-NH2, R6Can be for C2-C12's The arlydene of alkylidene or C6-C14, is preferably ethylenediamine, propane diamine, 1,6- hexamethylene diamines (or hexamethylene diamine), p-phenylenediamine, adjacent benzene At least one of diamines and 4,4 '-benzidine).In the present invention, the product of polyisocyanates and heating dehydration is provided After hydroxyl reaction, those skilled in the art, which have full knowledge that, how to utilize polyisocyanates (such as diisocyanate) and amine (such as Diamines) react to obtain the compound with one or more-NHCONH- structures.Specifically：
When preparing the compound with-NHCONH- structure, step (2) can include：In the selectivity of catalyst In the presence of, the product that will heat up dehydration is reacted with diisocyanate and monoamine successively.The production being dehydrated relative to every mole of heating The dosage of thing (in terms of hydroxyl), diisocyanate and monoamine can be each independently 0.5-1.5mol.
When preparing the compound with two-NHCONH- structures, step (2) can include：In the selectivity of catalyst In the presence of, the product that will heat up dehydration is reacted with diisocyanate, diamines and monoisocyanates successively.Relative to every mole of liter The product (in terms of hydroxyl) of temperature dehydration, the dosage of diisocyanate, diamines and monoisocyanates can be each independently 0.5- 1.5mol。
When preparing the compound with three-NHCONH- structures, step (2) can include：In the selectivity of catalyst In the presence of, will heat up the product of dehydration successively with Part I diisocyanate, diamines, Part II diisocyanate and monoamine Reaction.Relative to the product (in terms of hydroxyl) of every mole of heating dehydration, Part I diisocyanate, diamines, Part II The dosage of diisocyanate and monoamine can be each independently 0.5-1.5mol.Wherein, Part I diisocyanate and Two part diisocyanate can be identical or different.
When preparing the compound with four-NHCONH- structures, step (2) can include：In the selectivity of catalyst In the presence of, will heat up the product of dehydration successively with Part I diisocyanate, Part I diamines, Part II diisocyanate Ester, Part II diamines and monoisocyanates reaction.The product (in terms of hydroxyl) being dehydrated relative to every mole of heating, first Divide the dosage of diisocyanate, Part I diamines, Part II diisocyanate, Part II diamines and monoisocyanates can To be each independently 0.5-1.5mol.Wherein, Part I diisocyanate can be identical with Part II diisocyanate Or it is different, Part I diamines and Part II diamines are as the same.
The compound with six, eight or even multiple-NHCONH- structures can be obtained according to as above identical mode, This is no longer going to repeat them.
The method of lubricating grease produced according to the present invention, wherein, step (2) is to prepare the salt of soap carbamide compound and small molecule acid The step of, therefore, species and dosage of small molecule acid etc. can be with as it was previously stated, details are not described herein.In addition, base oil and addition The species and dosage of agent can also be with reference to foregoing teachings.
In step (3), to refine (constant temperature refining) condition do not require particularly, can according to routine condition into OK.Under preferable case, the condition of refining includes：Temperature is 140-230 DEG C (preferably 200-220 DEG C), time 5-20min.
It will be appreciated to those of skill in the art that the sum of the amount of each several part base oil and the amount of surplus base oil are institute The total amount of base oil, in of the invention, Part I base oil, Part II base oil and the weight ratio of surplus base oil are excellent Elect 1 as：0.1-5：0.1-5.
After being mixed with surplus base oil and optional additive, it can also in a conventional manner be filtered, be homogenized, be taken off The processing such as gas, to obtain lubricating grease finished product.
Fourth aspect, present invention also offers the lubricating grease as made from the method described in the third aspect.The method of the present invention system The lubricating grease obtained has excellent comprehensive performance.
The present invention will be described in detail by way of examples below.In the following Examples and Comparative Examples：
Non-newtonian fluid high base number calcium %=(overbased or high base number calcium raw material weight+transforming agent gross weight)/lubricating grease Gross weight × 100%, transforming agent are included in the content of non-newtonian fluid high base number calcium；
12- hydroxy stearic acids are purchased from Tongliao City prestige Ninghua work Co., Ltd；Overbased and overbased calcium alkyl-salicylate Raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd, can also be according to method system disclosed in CN101885677A It is standby；Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd.；Overbased sulfenyl phenolate Calcium raw material is purchased from Xinxiang Rui Feng Chemical Co., Ltd.s；Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industries Co., Ltd.
Embodiment 1
Raw material components：Overbased sulfoacid calcium (total base number 400mgKOH/g, 30kg)；150BS(30kg)；Aphthenic acids (pure acid number 120mgKOH/g, acid content 70%, 2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；12- hydroxy stearic acids (5kg)；One hydronium(ion) lithia (0.7kg)；Methyl diphenylene diisocyanate (MDI, 4.16kg)；Hexamethylene diamine (1.93kg)； Dibutyl tin (0.25kg)；Phenyl isocyanate (2kg)；Poly alpha olefin PAO10 (10kg)；Diisodecyl sebacate (DDS, 8kg)。
A volume for 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers For the overbased sulfoacid calcium and the HVI150BS lubricating base oils of 30kg of 400mgKOH/g, (100 DEG C of kinematic viscosity are 31mm2/ S, purchased from Karamay Petrochemical Company, similarly hereinafter), stirring, heats to 80 DEG C, constant temperature 10 minutes；2.8kg aphthenic acids is added, Temperature control stirs 10 minutes at 80 DEG C or so；1kg methanol is added, is stirred 10 minutes；Add the acetic acid and 2.24kg of 0.56kg Water, is stirred 10 minutes；It is warming up to 85 DEG C, constant temperature 90 minutes, material retrogradation；Add the 12- hydroxy stearic acids of 5kg, stirring 10min, mono- hydronium(ion) lithias of 0.7kg and 1kg water are slowly added thereto, and are warming up to 100 DEG C of draining saponification 1h, after be warming up to 150 DEG C, adding the PAO10 lubricating base oils of 10kg, (100 DEG C of kinematic viscosity are 10mm2/ s, purchased from Exxon Mobil Corporation, under 90 DEG C are cooled to together), adds MDI the and 0.25kg dibutyl tins of 4.16kg, reacts 60min, then add 1.93kg hexamethylene diamines, reaction After 60min, 2kg phenyl isocyanates are added, 30min is reacted, then heats to 220 DEG C, constant temperature 5min, add the DDS of 8kg (100 DEG C of kinematic viscosity are 6.8mm2/ s, purchased from one level ground lubricating oil branch company of Sinopec Chongqing) quench oil, stirring, is cooled to 100 DEG C of homogenizing degassings, obtain finished product.
In the lubricating grease that the present embodiment obtains, it can be calculated and learnt according to material amount, on the basis of lubricating grease weight, group Become：35.3 weight % of non-newtonian fluid sulfoacid calcium；50.8 weight % of lubricating base oil；13.9 weight % of lithium soap carbamido thickening agent. Each physicochemical property inspection result is shown in Table 1.
Embodiment 2
Raw material components：Overbased calcium alkyl-salicylate (total base number 360mgKOH/g, 40kg)；150BS(10kg)；Dodecyl Benzene sulfonic acid (2.8kg)；Isopropanol (1kg)；Acetic acid (0.56kg)；Ca(OH)2(0.25kg)；12- hydroxy stearic acids (2kg)；Two Methylenebis phenyl isocyanate (MDI, 1.67kg)；N-octyl amine (0.86kg)；Tripropyl amine (TPA) (0.2kg)；500SN(16kg).
A volume for 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add 40kg total alkalis It is worth the HVI150BS lubricating base oils of the overbased calcium alkyl-salicylate and 10kg for 360mgKOH/g, stirs, heat to 50 DEG C, Constant temperature 10 minutes；2.8kg dodecyl benzene sulfonic acid is added, temperature control stirs 10 minutes at 50 DEG C or so；Add 1kg isopropyls Alcohol, is stirred 10 minutes；The acetic acid and 2.24kg water of 0.56kg is added, is stirred 10 minutes；It is warming up to 95 DEG C, constant temperature 90 minutes, thing Expect retrogradation into smectic.
Another volume for 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle B in add 10kg (100 DEG C of kinematic viscosity are 10mm to 500SN lubricating base oils2/ s, purchased from Sinopec Yanshan Petrochemical company, similarly hereinafter) and 2kg 12- hydroxy stearic acids, stirring, become homogeneous system, at this time by the Ca (OH) of 0.25kg after being warming up to 95 DEG C2It is and dilute with 4 times of water The suspension released, is stirred 10 minutes；Be warming up to 100 DEG C of draining saponification 1h, after be warming up to 150 DEG C, be cooled to 90 DEG C, add Quick stirring 4 minutes of the MDI and 0.2kg tripropyl amine (TPA)s of 1.67kg, add 0.86kg n-octyl amines and stir 4 minutes, added MDI with just The molar ratio of octylame is 1:1,120 DEG C of constant temperature 20 minutes, then heats to 220 DEG C, constant temperature 5min, adds the 500SN chillings of 6kg Oil, stirring, is cooled to 100 DEG C of homogenizing, obtains calcium soap carbamido thickening agent.
B kettles resulting material is all squeezed into A kettles, is stirred evenly, is finally warming up to 200 DEG C of constant temperature 10 minutes.Then, turn Kettle cools down；Treat that temperature is cooled to 90 DEG C, circulating filtration, homogenizing, degassing obtain lubricating grease finished product.It can be calculated according to material amount Learn, on the basis of lubricating grease weight, the composition for the lubricating grease that the present embodiment obtains is：52.1 weight of non-newtonian fluid sulfoacid calcium Measure %；40.6 weight % of lubricating base oil；7.3 weight % of calcium soap carbamido thickening agent.Each physicochemical property inspection result is shown in Table 1.
A small amount of soap urea sample is prepared again by above-mentioned B kettles same method, is washed, filtered with petroleum ether (60-90 DEG C of boiling point) To precipitation, gained precipitation is after drying up to soap carbamide compound.Its Electrospray Ionization Mass Spectrometry spectrogram is shown in that Fig. 1 (is become using Fourier Change Ion cyclotron Resonance Mass Spectrometry (FT-ICR MS) to be tested to obtain, ion gun ESI-, sample is dissolved in toluene and methanol (volume Than for 1:1) solvent, concentration 0.01mg/mL, add 1 weight % ammonium hydroxide promote ionization, similarly hereinafter), at 678 it is visible most Strong peak is carboxylate anion peak, and the structure that soap carbamide compound is obtained with reference to further hydrogen spectrum and carbon spectrum analysis is as follows：
Embodiment 3
Raw material components：Overbased sulfurized alkylphenol calcium (total base number 420mgKOH/g, 22kg)；High base number calcium oleate (total base number 360mgKOH/g, 8kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oils2/ s, 30kg)；4- ten Eight alkylphenols (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12- hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；Aluminium isopropoxide (2.41kg)；Stearic acid (2.8kg)；Benzoic acid (1.2kg)；4# ethyl silicon oils (10kg).Two Methylenebis phenyl isocyanate (MDI, 1.67kg)；Ethylenediamine (0.4kg)；Toluenediisocyanate (TDI, 1.16kg)；Ten Eight amine (1.79kg)；Potassium carbonate (0.1kg)；
A volume for 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 22kg total base numbers The high base number calcium oleate and 30kg that overbased sulfurized alkylphenol calcium, 8kg total base numbers for 420mgKOH/g are 360mgKOH/g HVI150BS lubricating base oils, stirring；100 DEG C are heated to, adds 2.8kg stearic acid and 1.2kg benzoic acid, stirring is equal It is even, add 2.41kg aluminium isopropoxides and react 30min at 100 DEG C, add water 0.3kg, react 30min；50 DEG C are cooled to, perseverance Temperature 10 minutes, adds the 4- octadecylphenols of 2.8kg, and temperature control stirs 10 minutes at 50 DEG C, adds 2.8kg concentration and is The aqueous acetic acid of 20 weight %, stirs 10 minutes, is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation；It is 20 to add solid content The calcium hydroxide suspension 9kg of weight %, is stirred 10 minutes, adds the 12- hydroxy stearic acids of 2kg, is stirred 10 minutes, is added 3.5kg terephthalic acid (TPA)s, are stirred 10 minutes；110 DEG C are warming up under stirring, is kept for 45 minutes, dehydration；Add the MDI of 1.67kg With 0.1kg potassium carbonate, 2h is reacted, then adds 0.4kg ethylenediamines, after reacting 30min, adds 1.16kg toluenediisocyanates TDI, reacts 30min, adds 1.79kg octadecylamines, after reacting 30min, then heats to 180 DEG C, constant temperature 10min, adds (100 DEG C of kinematic viscosity are 31mm to the 150BS of 30kg2/ s) quench oil, stirring, is cooled to 80 DEG C of homogenizing degassings, obtains finished product.
In the lubricating grease that the present embodiment obtains, it can be calculated and learnt according to material amount, on the basis of lubricating grease weight, group Become：37.4 weight % of non-newtonian fluid high base number material；44.8 weight % of lubricating base oil；Composition metal soap carbamido thickening agent 17.8 weight %.Each physicochemical property testing result is shown in Table 1.
Embodiment 4
Overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 8kg)；(total base number is high base number calcium salicylate 320mgKOH/g, 12kg)；High base number calcium oleate (total base number 360mgKOH/g, 10kg)；HVI150BS lubricating base oils (100 DEG C kinematic viscosity is 31mm2/ s, 15kg)；4- octadecylphenols (2.8kg)；Acetic acid (0.56kg)；Zr(OH)4(3.9kg)； 12- hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；1, hexamethylene-diisocyanate (HDI, 1.12kg)；Lauryl amine (1.23kg)；Potassium hydroxide (KOH, 0.1kg)；Sulphur phosphorus fourth octyl group zinc salt (T202,2kg)；Zinc naphthenate (T704,2kg)；Two fourths Base aminodithioformic acid vulcanization oxygen molybdenum (T351,2kg)；Molybdenum disulfide (3kg)；Phenyl-α-naphthylamine (1kg)；HVI500SN moistens (100 DEG C of kinematic viscosity are 10mm to sliding base oil2/ s, 12kg).
A volume for 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 8kg total base numbers High base number calcium salicylate that overbased sulfurized alkylphenol calcium, 12kg total base numbers for 400mgKOH/g are 320mgKOH/g, 10kg total base numbers are the high base number calcium oleate of 360mgKOH/g and the HVI150BS lubricating base oils of 15kg, are stirred, heat temperature raising To 50 DEG C, constant temperature 10 minutes；The 4- octadecylphenols of 2.8kg are added, temperature control stirs 10 minutes at 50 DEG C；Add 2.8kg concentration is the aqueous acetic acid of 20 weight %, is stirred 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation；Add Enter the 12- hydroxy stearic acids and 3.5kg terephthalic acid (TPA)s of 2kg, stir 10min, add the Zr (OH) of 3.9kg4, it is warming up to 100 DEG C draining saponification 1h, after be warming up to 120 DEG C, the 500SN lubricating base oils for adding 10kg are cooled to 90 DEG C, add 1.12kg's The KOH of HDI and 0.1kg, reacts 60min, then adds 1.23kg lauryl amines, after reacting 60min, is warming up to 220 DEG C, constant temperature 5min, The 500SN quench oils of 2kg are added, stirring, is cooled to 100 DEG C, 2kg T202,2kg T704,2kg T351,3kg is added portionwise MoS2, 1kg phenyl-α-naphthylamines, after stirring evenly be homogenized, filter, degassing, go out kettle and obtain finished product.
It can be calculated and learnt according to material amount, grease composition is：41.3 weight % of non-newtonian fluid material, base oil 33.4 weight %, 12.9 2.5 2.5 2.5 weight of weight %, T351 of weight %, T704 of weight %, T202 of compound soap urea thickening agent Measure %, MoS23.7 weight %, 1.2 weight % of phenyl-α-naphthylamine.Each physicochemical property testing result is shown in Table 1.
Embodiment 5
Method according to embodiment 1 prepares lubricating grease, unlike, the 12- hydroxy stearic acids of 10kg are replaced with The 10- hydroxydecanoic acids of 6.26kg.The results are shown in Table 1.
Embodiment 6
Method according to embodiment 1 prepares lubricating grease, unlike, the 12- hydroxy stearic acids of 10kg are replaced with 12.33kg dihydroxy twenty diacids, while the dosage of follow-up MDI used, tripropyl amine (TPA) and n-octyl amine double.The results are shown in Table 1.
Comparative example 1
Method according to embodiment 1 prepares lubricating grease, unlike, it is different to be added without MDI, dibutyl tin hexamethylene diamine and phenyl Cyanate.The results are shown in Table 1.
Comparative example 2
Raw material components：Methyl diphenylene diisocyanate (MDI, 8.33kg)；N-octyl amine (8.6kg)；500SN(100kg).
Volume for 200L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 70kg HVI500SN lubricating base oils and 8.6kg n-octyl amines, become homogeneous system after being heated to 100 DEG C, stir 10 minutes, add 8.33kg MDI, are stirred 30 minutes, then heat to 180 DEG C of constant temperature 10 minutes, add the 500SN quench oils of 30kg, stirring drop Temperature, homogenizing, filtering, degassing, goes out kettle and obtains lithium base grease.Grease composition：85.5 weight % of base oil, 14.5 weight of thickening agent Measure %.Each physicochemical property of gained fat refers to table 1.
Comparative example 3
Raw material components：12- hydroxy stearic acids (10kg)；One hydronium(ion) lithia (1.4kg)；Diphenylmethane diisocyanate Ester (MDI, 8.33kg)；N-octyl amine (8.6kg)；500SN(100kg).
In a volume for 200L and with heating, stirring, the 500SN oil for circulating, 70kg being added in the reaction kettle of cooling (100 DEG C of kinematic viscosity are 11mm2/ s), the 12- hydroxy stearic acids of 10kg, stirring, become homogeneous system after being warming up to 80 DEG C, this When mono- hydronium(ion) lithias of 1.4kg and 5kg water are slowly added thereto, be warming up to 105 DEG C of draining saponification 2h, after be warming up to 115 DEG C, the MDI of 8.33kg is added, after stirring 20min, then adds 8.6kg n-octyl amines, after reacting 30min, after being warming up to 180 DEG C, constant temperature 10min, adds the 500SN quench oils of 30kg, stirring cooling, homogenizing, filtering, degassing, go out kettle and obtain finished product.Grease composition： 78.7 weight % of base oil, lithium thickening agent 8.0 weight %, two ureas, 13.3 weight %.
Comparative example 4
Method according to embodiment 1 prepares lubricating grease, unlike, it is added without dibutyl tin.The results are shown in Table 1.
Table 1
As can be seen from the above embodiments, lubricating grease of the invention has excellent comprehensive performance, particularly high-temperature behavior, Mechanical stability and the sensitivity to metal class additive.Specifically, dropping point is higher, illustrates that high-temperature behavior is preferable；60 tasks Cone penetration is small, illustrates that thickening ability is strong；It is 60 times small with 100,000 task cone penetration differences, illustrate that mechanical stability is good；Anticorrosion Property it is qualified, illustrate that anticorrosive property is good；Water leaching number of dropouts is small, illustrates that water-resistance is good；Stencil oil-dividing amount is small, illustrates colloid stability It is good；Bearing life is longer, illustrates that comprehensive performance is better；And 60 time and 10 ten thousand works higher added with dropping point after metal class additive It is good to the sensitivity of metal class additive to make the small explanation of cone penetration difference.
Especially, embodiment 1 obtains while has a part of the compound of lithium soap base and urea groups as thickening agent, and Comparative example 1 uses lithium soap based compound as thickening agent, and comparative example 2 uses urea-based compound as thickening agent, and comparative example 3-4 Unused catalyst causes thickening agent being simply mixed for lithium soap based compound and urea-based compound, is the machine of two kinds of lubricating grease Tool mixes, and from the results shown in Table 1, the performance of lubricating grease of the invention is far superior to simple soap base grease, urea groups The mixture of lubricating grease or soap base grease and urea-base grease.
In addition, embodiment 1 prepares lubricating grease using 12- hydroxy stearic acids, and embodiment 5-6 uses other hydroxy aliphatics Acid, from the performance test results as can be seen that performance more preferably lubricating grease can be obtained using currently preferred hydroxy fatty acid.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (16)

1. a kind of lubricating grease, it is characterised in that the lubricating grease contains base oil, the compound shown at least one Formulas I, non newtonian The salt of body high base number calcium and optional small molecule acid, the salt of the small molecule acid is the salt of small molecule inorganic acid, lower aliphatic At least one of the salt of acid and the salt of aromatic acid,
Wherein, R1For hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl；R2 For substituted or unsubstituted arlydene, substituted or unsubstituted alkylidene or substituted or unsubstituted cycloalkylidene；R3For with The group of one or more-NHCONH- structures；Mn+For IA races, Group IIA, Group IIIA or Group IVB metallic element formed sun from Son.
2. compound according to claim 1, wherein, R1For the alkyl of C1-C10；And/or
R2For the alkylidene of C1-C20；And/or
R3Structural formula beWherein, R3’Carbon number be 6-30 and for substitution or Unsubstituted arlydene, substituted or unsubstituted alkylidene or substituted or unsubstituted cycloalkylidene, R4For substitution or unsubstituted Alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or with one or more-NHCONH- structures Group；And/or
Mn+For Li+、Na+、K+、Ca2+、Sr2+、Ba2+、Al3+、Ti4+Or ZrO2+。
3. compound according to claim 1 or 2, wherein, group is in hydroxyl, halogen and carboxyl used by substitution It is at least one.
4. compound according to claim 2, wherein, R1For the straight chained alkyl of C3-C10；And/or
R2For the straight-chain alkyl-sub of C8-C15；And/or
R3’For Or-CH2-(CH2)4-CH2-；And/or
R4Straight chained alkyl for C6-C20 or the group with one or more-NHCONH- structures.
5. according to the compound described in any one in claim 1-4, wherein, the structural formula of the compound is：
And R3In-NHCONH- structures quantity in the range of 1-8.
6. lubricating grease according to claim 1, wherein, on the basis of the gross weight of the lubricating grease, the base oil Content is 10-70 weight %, is preferably 20-65 weight %, is most preferably 30-55 weight %；Chemical combination shown at least one Formulas I The content of thing is 1-40 weight %, is preferably 2-25 weight %, is most preferably 5-20 weight %；Non-newtonian fluid high base number calcium contains Measure as 10-75 weight %, preferably 20-65 weight %, most preferably 30-60 weight %；The content of the salt of small molecule acid is 0- 20 weight %, are preferably 0.5-15 weight %, are most preferably 1-10 weight %.
7. lubricating grease according to claim 1, wherein, the non-newtonian fluid high base number calcium is turned by newton body high base number calcium Change what is obtained, the total base number of the non-newtonian fluid high base number calcium is 250-450mgKOH/g.
8. lubricating grease according to claim 1, wherein, the molecular weight of small molecule inorganic acid, lower fatty acid or aromatic acid Less than or equal to 210.
9. the lubricating grease according to claim 1 or 8, wherein, the small molecule inorganic acid be selected from boric acid, phosphoric acid, nitric acid and At least one of sulfuric acid；The lower fatty acid is selected from acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid, azelaic acid At least one of with decanedioic acid；The aromatic acid is in benzoic acid, terephthalic acid (TPA), M-phthalic acid and phthalic acid It is at least one.
10. lubricating grease according to claim 1, wherein, the cation in the salt of the small molecule acid is IA races, Group IIA, The cation that at least one of Group IIIA and Group IVB metallic element are formed, is preferably Li+、Na+、K+、Ca2+、Sr2+、Ba2+、 Al3+、Ti4+And ZrO2+At least one of, and and Mn+It is identical or different.
11. prepare the method for the lubricating grease in claim 1-10 described in any one, it is characterised in that this method includes：Will Compound, non-newtonian fluid high base number calcium, the salt of optional small molecule acid and the mixing of part basis oil shown at least one Formulas I are simultaneously Refined, then mixed with surplus base oil and optional additive.
A kind of 12. method for preparing lubricating grease, it is characterised in that this method includes：
(1) by newton body high base number calcium, transforming agent and Part I base oil Hybrid Heating, material retrogradation is made；
(2) it is with structural formula by step (1) products therefromHydroxy fatty acid, optional small Molecule acid and source metal mixing carry out saponification, then the selectivity of product that saponification is obtained carry out heating dehydration, In the presence of the selectivity of catalyst, make the product that heating is dehydrated and polyisocyanates, amine and optional other isocyanates The compound of the group with one or more-NHCONH- structures is reacted to give,
Alternatively, it is by structural formulaHydroxy fatty acid, optional small molecule acid, Part II Base oil and source metal mixing carry out saponification, then the selectivity of product that saponification is obtained carry out heating dehydration, In the presence of the selectivity of catalyst, make the product that heating is dehydrated and polyisocyanates, amine and optional other isocyanates The compound of the group with one or more-NHCONH- structures is reacted to give, then by obtained product and step (1) Products therefrom mixes；
Wherein, the small molecule acid is at least one of salt of small molecule inorganic acid, lower fatty acid and aromatic acid；
(3) step (2) products therefrom is refined, then is mixed with surplus base oil and optional additive.
13. the method according to claim 11, wherein, in step (1), by newton body high base number calcium and Part I basis Oily Hybrid Heating adds transforming agent to 50-90 DEG C, then when constant temperature 0.5-3 is small at 60-100 DEG C.
14. according to the method for claim 12, wherein, in step (2), it is anti-that saponification is carried out under conditions of 70-120 DEG C Should, heating dehydration is carried out to reselection at 100-150 DEG C；
Alternatively, carrying out saponification under conditions of 100-110 DEG C, heating dehydration is carried out to reselection at 115-150 DEG C.
15. according to the method described in any one in claim 12-14, wherein, the catalyst is organic amine, carbonate, At least one of the hydroxide of alkali metal, boron trifluoride, organic metal, are preferably methylamine, ethamine, propylamine, dimethylamine, two In ethamine, trimethylamine, triethylamine, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, boron trifluoride and organotin At least one.
16. the lubricating grease as made from the method described in any one in claim 12-15.
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