CN108003978A - A kind of lubricating grease and preparation method thereof - Google Patents
A kind of lubricating grease and preparation method thereof Download PDFInfo
- Publication number
- CN108003978A CN108003978A CN201610957910.8A CN201610957910A CN108003978A CN 108003978 A CN108003978 A CN 108003978A CN 201610957910 A CN201610957910 A CN 201610957910A CN 108003978 A CN108003978 A CN 108003978A
- Authority
- CN
- China
- Prior art keywords
- acid
- lubricating grease
- small molecule
- weight
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/02—Mixtures of base-materials and thickeners
-
- 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
- C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
- C10M123/02—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a non-macromolecular compound
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
- C10M2207/1225—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic used as thickening agent
-
- 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
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
- C10M2207/1236—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic used as thickening agent
-
- 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
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
- C10M2207/1276—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic used as thickening agent
-
- 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
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
- C10M2207/1415—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic used as thickening agent
-
- 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
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/142—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
- C10M2207/1426—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic used as thickening agent
-
- 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
- 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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (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 base oil and thickening agent, and the thickening agent is provided as the compound shown in the salt of small molecule acid and at least one Formulas I.Preparing the method for lubricating grease includes：Thickening agent and part basis oil are mixed and refined, then is mixed with surplus base oil and optional additive；Or including by hydroxy fatty acid, small molecule acid, part basis oil and source metal mix carry out saponification, then the selectivity of product that saponification is obtained carry out heating dehydration；React products therefrom and polyisocyanates, amine and optional other isocyanates with；Products therefrom is refined, then is mixed with surplus base oil and optional additive.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 as to obtain high-temperature behavior, mechanical stability and the preferable lubricating grease of sensitivity to metal class additive.
Description
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
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.Complex soap lubricating grease is a kind of high dropping point grease, and dropping point is generally greater than 250 DEG C, can use
Under the higher operating mode of temperature, but many performance such as colloid stabilities, mechanical stability, service life etc. are not so good as lithium Ji Run
Consistent lubricant.
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.
CN1600843A discloses a kind of preparation method for preparing polyureas-lithium base grease, including：By C8-C24 organic amines
It is melted in base oil with isocyanates, is reacted after mixing respectively, at least one C10-C20 aliphatic acid is added after having reacted
Or small molecule acid is additionally added, after acid melts, add lithium hydroxide aqueous solution and reacted, 190-220 is warming up to after having reacted
DEG C, keep the temperature, cool down, homogenizing, this method enables urea groups, and the simultaneous reactions in a kettle generate with lithium base grease.It is however, logical
It is polyureas and aliphatic acid lithium soap Huo and the physical mixture of small molecule acid lithium soap to cross the product that the method for the mechanical mixture obtains,
It can be used as low-noise lubricating grease, its products characteristics is that dropping point is all omited than the lithium saponify or polyurea grease prepared under square one
It is low, and comprehensive performance (particularly high-temperature behavior, mechanical stability and the impression to metal class additive of the mixed grease
Property) not high, therefore high-temperature behavior, mechanical stability and equal to the sensitivity of metal class additive are made in same reaction kettle
Higher lubricating grease has prior Practical significance.
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 improves 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 and
Thickening agent, wherein, the thickening agent is provided as the compound shown in the salt of small molecule acid and at least one Formulas I, described small point
The salt of sub- acid is at least one of salt of the salt of small molecule inorganic 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 cation formed for IA races, Group IIA or Group IVB metallic element.
Second aspect, the present invention provides a kind of method for preparing the lubricating grease described in first aspect, this method includes：Will
Thickening agent and part basis oil are mixed and refined, then are 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) it is by structural formulaHydroxy fatty acid, small molecule acid, part basis oil and
Source metal mixing carry out saponification, then the selectivity of product that saponification is obtained carry out heating dehydration, the small molecule
Acid is at least one of small molecule inorganic acid, lower fatty acid and aromatic acid；
(2) in the presence of the selectivity of catalyst, step (1) products therefrom and polyisocyanates, amine and optional are made
Other isocyanates is reacted to give the compound of the group with one or more-NHCONH- structures；
(3) step (2) products therefrom is refined, then is mixed with surplus base oil and optional additive.
Fourth aspect, the present invention provides lubricating grease 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 better than metal
The lubricating grease of soap base grease and/or 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 and thickening agent, and the thickening agent is by small molecule acid
Salt and at least one Formulas I shown in compound (soap carbamide compound) provide, the salt of the small molecule acid is that small molecule is inorganic
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 cation formed for IA races, Group IIA or Group IVB metallic element.
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+Or ZrO2+。
Most preferred embodiment according to the present invention, the structural formula of the compound are：
(wherein, R3And Mn+
As previously described), for example, specific example can be：
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 50-95 weight %, more preferably 60-90 weight %, is most preferably 70-85 weight %.It is preferred that
Ground, on the basis of the gross weight of the lubricating grease, the content of the salt of small molecule acid is 1-30 weight %, more preferably 2-15 weights
% is measured, is most preferably 3-10 weight %.Preferably, on the basis of the gross weight of the lubricating grease, the change shown at least one Formulas I
The content of compound is 1-40 weight %, more preferably 2-25 weight %, is most preferably 5-20 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。
In the present invention, small molecule acid can be small molecule inorganic acid, lower fatty acid or the aromatic acid of this area routine, excellent
In the case of choosing, the molecular weight of small molecule inorganic acid, lower fatty acid or aromatic acid is less than or equal to 210.Wherein, small molecule inorganic acid
At least one of boric acid, phosphoric acid, nitric acid and sulfuric acid can be selected from.Lower fatty acid can be structure such as R7-(COOH)PIt is shown
At least one of compound, wherein, R7Can be substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl or substitution
Or unsubstituted aryl, be 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, be preferably the positive integer of 1-3, be most preferably 1 or 2.It is further preferred that institute
State at least one of lower fatty acid in acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid, azelaic acid, decanedioic acid etc.
Kind.The aromatic acid can be the carboxylic acid with an aromatic rings, such as benzoic acid, terephthalic acid (TPA), M-phthalic acid and adjacent benzene
At least one of dioctyl phthalate.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 in IA races, Group IIA and Group IVB metallic element
At least one formation cation, be preferably Li+、Na+、K+、Ca2+And ZrO2+At least one of, and and Mn+Can be identical
It is 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 thickening agent and
Part basis oil is mixed and refined, then is mixed with surplus base oil and optional additive.Thickening agent small molecular acid
Compound shown in salt and at least one Formulas I can be mixed with base oil at the same time, can also be mixed step by step with base oil.To refining
The condition of system (constant temperature refining) does not require particularly, can be carried out according to conventional condition.Under preferable case, the condition of refining
Including：Temperature is 140-230 DEG C, time 5-20min.
In the third aspect, the method provided by the invention for preparing lubricating grease includes：
(1) it is by structural formula(R1And R2As it was previously stated, similarly hereinafter) hydroxy fatty acid,
Small molecule acid, part basis oil and source metal mixing carry out saponification, then the selectivity of product that saponification is obtained into
Row heating dehydration, the small molecule acid is at least one of small molecule inorganic acid, lower fatty acid and aromatic acid；
(2) in the presence of the selectivity of catalyst, step (1) products therefrom and polyisocyanates, amine and optional are made
Other isocyanates is reacted to give the compound of the group with one or more-NHCONH- structures；
(3) step (2) products therefrom is refined, then is mixed with surplus base oil and optional additive.
According to the third aspect of the invention we, the source metal can be oxide, the hydroxide and gold of metal of metal
At least one of alkoxide compound (such as methoxy compound, ethoxy compound) of category (can be by water as molten
Agent).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 the first containing metal available for saponification of this area routine
The compound of plain (such as IA races, Group IIA or Group IVB metallic element), is preferably selected from least one of lithium, sodium, potassium, calcium and zirconium
At least one of oxide, hydroxide and alkoxide compound of metal, e.g., lithium hydroxide, sodium hydroxide, hydroxide
Potassium, calcium hydroxide, zirconium alkoxide (such as ethanol zirconium, zirconium iso-propoxide), hydroxide (such as Zr (OH) of zirconium4With ZrO (OH)2) in
At least one.
Those skilled in the art know that saponification can carry out in reaction medium (base oil), as it was previously stated,
The base oil can be the various base oils used in lubricating grease, such as mineral oil, artificial oil, vegetable oil or their mixing
Thing.
It is highly preferred that in step (1), under conditions of 70-120 DEG C, by hydroxy fatty acid, small molecule acid, part basis
Oil and source metal mixing carry out saponification, and heating dehydration is carried out to reselection at 100-150 DEG C.It is further preferred that
In step (1), under conditions of 100-110 DEG C, hydroxy fatty acid, small molecule acid, part basis oil and source metal are mixed into
Row saponification, carries out heating dehydration to reselection at 115-150 DEG C.The time of saponification can be 60-180min.
Heating dehydration for selectivity carry out the step of, if it will be appreciated to those of skill in the art that saponification at relatively high temperatures into
OK, the material and after saponification 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
Limitation, the mole (with elemental metal) of general control source metal are higher than the sum of the mole of hydroxy fatty acid and small molecule acid
(such as high 1-10mol%).Relative to every mole of source metal (with elemental metal), the dosage of part basis 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 step (1) products therefrom (i.e. hydroxy aliphatic
The metal salt of acid and the metal salt of small molecule acid) molar ratio of hydroxyl of offer is usually 0.5-2.5：1.Production obtained by step (1)
Thing and the temperature of isocyanates (polyisocyanates) reaction can be 90-150 DEG C, and the time can be 0.5-5h.
In the another embodiment of third aspect present invention, by step (1) products therefrom 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, polyisocyanates and step (1) products therefrom are 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, step (1) products therefrom is reacted with diisocyanate and monoamine successively.Relative to obtained by (1) the step of every mole
The dosage of product (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, step (1) products therefrom is reacted with diisocyanate, diamines and monoisocyanates successively.Relative to every mole
Step (1) products therefrom (in terms of hydroxyl), 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, by step (1) products therefrom successively with Part I diisocyanate, diamines, Part II diisocyanate and list
Amine reacts.Relative to every mole the step of (1) products therefrom (in terms of hydroxyl), Part I diisocyanate, diamines, second
Divide the dosage of diisocyanate and monoamine can be each independently 0.5-1.5mol.Wherein, Part I diisocyanate with
Part II 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, by step (1) products therefrom successively with Part I diisocyanate, Part I diamines, two isocyanide of Part II
Acid esters, Part II diamines and monoisocyanates reaction.Relative to every mole the step of (1) products therefrom (in terms of hydroxyl),
A part of diisocyanate, Part I diamines, Part II diisocyanate, the use of Part II diamines and monoisocyanates
Amount can be each independently 0.5-1.5mol.Wherein, Part I diisocyanate and Part II diisocyanate can be with
Identical or 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 (1) and step (2) they are the step of preparing thickening agent, because
This, species and dosage of small molecule acid etc. can be with as it was previously stated, details are not described herein.In addition, the species of base oil and additive
Can also be with reference to foregoing teachings with dosage.
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, time 5-20min.
It will be appreciated to those of skill in the art that the amount of part basis oil and the sum of the amount of surplus base oil are as used
Base oil total amount, in the present invention, part basis oil and the weight ratio of surplus base oil are preferably 1：0.1-5.
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, but is not intended to limit the present invention.12- hydroxy stearates
Acid is purchased from Tongliao City prestige Ninghua work Co., Ltd.
Embodiment 1
Raw material components：12- hydroxy stearic acids (10kg)；Decanedioic acid (5.38kg)；One hydronium(ion) lithia (3.7kg)；Two
Methylenebis phenyl isocyanate (MDI, 8.33kg)；N-octyl amine (4.3kg)；Tripropyl amine (TPA) (1kg)；500SN(100kg).
(a) preparation of thickening agent：A volume for 200L and with heating, stirring, circulation, cooling reaction kettle in plus
Entering the 500SN base oils of 70kg, (100 DEG C of kinematic viscosity are 11mm2/ s, purchased from Sinopec Yanshan Petrochemical company, similarly hereinafter),
The 12- hydroxy stearic acids and 5.38kg decanedioic acid of 10kg, stirring, is warming up to 80 DEG C, at this time by a hydronium(ion) lithia of 3.7kg
And 5kg water is slowly added thereto, be warming up to 105 DEG C of saponification 2h, after be warming up to 115 DEG C, add 8.33kg MDI and 1kg catalysis
Agent (tripropyl amine (TPA)), reacts 30min, then adds 4.3kg n-octyl amines, reacts 30min, and obtained product is used for step as thickening agent
(b), which is dissolved in petroleum ether, filtered, with petroleum ether filter residue 3 times, filter residue is returned using Fourier transform ion
Rotation resonance mass spectrum (FT-ICR MS) is tested (ion gun ESI-, sample is dissolved in toluene and methanol (volume ratio 1:1) it is molten
Agent, concentration 0.01mg/mL, the ammonium hydroxide for adding 1 weight % promote ionization, similarly hereinafter), gained ESI mass spectrograms are shown in Fig. 1, at 678
Visible highest peak is carboxylate anion peak, and soap carbamide compound in thickening agent is obtained with reference to further hydrogen spectrum and carbon spectrum analysis
Structure it is as follows：
(b) step (a) products therefrom is warming up to 180 DEG C, constant temperature 10min, adds the 500SN base oils of 30kg, stirred
Cooling, homogenizing, filtering, degassing, go out kettle and obtain single urea carboxylic acid lithium base grease.It can be calculated and learnt according to material amount, lubricated
The composition of fat is：77.8 weight % of base oil, 22.2 weight % of thickening agent；
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Embodiment 2
Raw material components：12- hydroxy stearic acids (5kg)；Acetic acid (6.99kg)；Calcium hydroxide (4.93kg)；Diphenyl methane
Diisocyanate (MDI, 4.16kg)；Hexamethylene diamine (1.93kg)；Dibutyl tin (0.5kg)；Phenyl isocyanate (1.98kg)；It is poly-
Alpha-olefin PAO10 (200kg)；Diisodecyl sebacate (DDS, 80kg).
(a) preparation of thickening agent：It is 500L and with heating, the reaction kettle A for stirring, circulating, cooling down in a volume
Add PAO10 oil (100 DEG C of kinematic viscosity 10mm of 100kg2/ s, purchased from Exxon Mobil Corporation), the 12- hydroxy stearates of 5kg
Acid, stirring, becomes homogeneous system after being warming up to 95 DEG C.
4.93kg calcium hydroxides are slowly added in 5kg water in another container B, are stirring evenly and then adding into 6.99kg vinegar
Acid, react 30min after it is spare.
Material in container B is slowly added into reaction kettle A, 100 DEG C of draining saponification 1h are warming up to after reacting 1h, rear heating
To 150 DEG C, the PAO10 for adding 100kg is cooled to 90 DEG C, adds MDI the and 0.5kg dibutyl tins of 4.16kg, reacts 60min,
Again plus 1.93kg hexamethylene diamines, after reacting 60min, 1.98kg phenyl isocyanates are added, react 30min, obtained product conduct
Thickening agent is used for step (b), which is dissolved in petroleum ether, after standing 5min, takes supernatant liquid to treat petroleum ether in container
After volatilization, residue is tested using Fourier Transform Ion cyclotron Resonance mass spectrum, gained ESI mass spectrograms combine further
Hydrogen spectrum and carbon spectrum analysis obtain soap carbamide compound in thickening agent structure it is as follows：
(b) step (a) products therefrom is warming up to 200 DEG C, constant temperature 5min, adds DDS (100 DEG C of kinematic viscosity of 80kg
For 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 grindings, obtains
Lubricating grease.It can be calculated and learnt according to material amount, grease composition：92.5 weight % of base oil, 7.5 weight % of thickening agent.
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Embodiment 3
Raw material components：12- hydroxy stearic acids (10kg)；Benzoic acid (2kg)；Sodium hydroxide (2kg)；Diphenyl methane two is different
Cyanate (MDI, 8.33kg)；Ethylenediamine (2kg)；Toluenediisocyanate (TDI, 5.8kg)；Octadecylamine (8.97kg)；Carbon
Sour potassium (0.1kg)；Methyl-silicone oil (70kg)；150BS(30kg).
(a) preparation of thickening agent：A volume for 200L and with heating, stirring, circulation, cooling reaction kettle in plus
Entering 70kg methyl-silicone oils, (201-100,25 DEG C of kinematic viscosity are 100mm2/ s, purchased from Beijing Zhong Dinghuaxin Trade Co., Ltd.s),
The 12- hydroxy stearic acids and 2kg benzoic acid of 10kg, stirring, is warming up to 90 DEG C, at this time that 2kg sodium hydroxides and 10kg water is slow
Be added thereto, be warming up to 105 DEG C of saponification 3h, after be warming up to 120 DEG C, add MDI the and 0.1kg catalyst (carbonic acid of 8.33kg
Potassium), 2h is reacted, then add 2kg ethylenediamines, after reacting 30min, the TDI of 5.8kg is added, 30min is reacted, adds 8.97kg ten
Eight amine, react 30min, and obtained product is used for step (b) as thickening agent, which is dissolved in petroleum ether, stand 5min
Afterwards, supernatant liquid is taken in container, and after petroleum ether volatilization, residue is used into Fourier Transform Ion cyclotron Resonance mass spectrum
(FT-ICR MS) is tested, and gained ESI mass spectrograms combine further hydrogen spectrum and carbon spectrum analysis obtains soap urea in thickening agent
The structure of compound is as follows：
(b) step (a) products therefrom is warming up to 180 DEG C, constant temperature 10min, adding the 150BS of 30kg, (100 DEG C of movements are viscous
Spend for 31mm2/ s, purchased from Karamay Petrochemical Company, similarly hereinafter) quench oil, stirring, is cooled to 80 DEG C of grindings, obtains three urea carboxylic acids
Oxygen sodium base grease.It can be calculated and learnt according to material amount, the composition of lubricating grease is：72.3 weight % of base oil, thickening agent
27.7 weight %；
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Embodiment 4
Raw material components：12- hydroxy stearic acids (10kg)；Terephthalic acid (TPA) (5.53kg)；ZrO(OH)2(7.05kg)；1,6-
Hexamethylene diisocyanate (HDI, 5.6kg)；Lauryl amine (6.17kg)；Potassium hydroxide (KOH, 0.1kg)；Sulphur phosphorus fourth octyl group zinc salt
(T202,2kg)；Zinc naphthenate (T704,2kg)；Dibutyl dithiocaarbamate vulcanization oxygen molybdenum (T351,2kg)；Molybdenum disulfide
(3kg)；Phenyl-α-naphthylamine (1kg)；Poly alpha olefin PAO6 (60kg)；150BS(20kg).
(a) preparation of thickening agent：A volume for 150L and with heating, stirring, circulation, cooling reaction kettle in plus
Enter 60kg PAO6 oil (100 DEG C of kinematic viscosity are 5.9mm2/ s, purchased from Exxon Mobil Corporation), the 12- hydroxy stearates of 10kg
The terephthalic acid (TPA) of acid and 5.53kg, stirring, after being warming up to 85 DEG C, at this time by the ZrO (OH) of 7.05kg2And 20kg water slowly adds
Enter wherein, be warming up to 110 DEG C of saponification 2h, then add the catalyst (KOH) of the HDI and 0.1kg of 5.6kg, react 30min, then
Add 6.17kg lauryl amines, react 40min, obtained product is used for step (b) as thickening agent, which is dissolved in petroleum ether
In, after standing 5min, supernatant liquid is taken in container, and after petroleum ether volatilization, residue is returned using Fourier transform ion
Rotation resonance mass spectrum (FT-ICR MS) is tested, and gained ESI mass spectrograms combine further hydrogen spectrum and carbon spectrum analysis is thickened
The structure of soap carbamide compound is as follows in agent：
(b) step (a) products therefrom is warming up to 200 DEG C, constant temperature 5min, adds the 150BS quench oils of 20kg, stirring drop
Temperature, the MoS of T351,3kg of T704,2kg of 100 DEG C of T202,2kg that 2kg is added portionwise2, 1kg phenyl-α-naphthylamines, stirring is equal
Homogenizing, filtering, degassing, go out kettle and obtain finished product after even.It can be calculated and learnt according to material amount, the composition of lubricating grease is：Basis
65.3 weight % of oil, 26.6 1.6 1.6 1.6 weight % of weight %, T351 of weight %, T704 of weight %, T202 of thickening agent,
MoS22.5 weight %, 0.8 weight % of phenyl-α-naphthylamine；
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Embodiment 5
Raw material components：12- hydroxy stearic acids (10kg)；Decanedioic acid (13.5kg)；One hydronium(ion) lithia (1.4kg)；Zr
(OH)4(10.6kg)；Methyl diphenylene diisocyanate (MDI, 8.33kg)；N-octyl amine (4.3kg)；Tripropyl amine (TPA) (1kg)；
500SN(120kg)。
(a) preparation of thickening agent：A volume for 300L and with heating, stirring, circulation, cooling reaction kettle in plus
Enter 70kg 500SN oil, the 12- hydroxy stearic acids and 13.5kg decanedioic acid of 10kg, stirring, is warming up to 80 DEG C, at this time by 1.4kg
The Zr (OH) of one hydronium(ion) lithia, 10.6kg4And 25kg water is slowly added thereto, be warming up to 105 DEG C of saponification 2h, after be warming up to
115 DEG C, MDI the and 1kg catalyst (tripropyl amine (TPA)) of 8.33kg is added, reacts 30min, then adds 4.3kg n-octyl amines, reacts 30min；
(b) step (a) products therefrom is warming up to 180 DEG C, constant temperature 10min, adds the 500SN quench oils of 50kg, stirred
Cooling, homogenizing, filtering, degassing, goes out kettle and obtains finished product.It can be calculated and learnt according to material amount, the composition of lubricating grease is：Base oil
73.5%, thickening agent 26.5%；
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Embodiment 6
Raw material components：12- hydroxy stearic acids (10kg)；Succinic acid (7.86kg)；One hydronium(ion) lithia (1.4kg)；Ca
(OH)2(4.93kg)；Methyl diphenylene diisocyanate (MDI, 8.33kg)；N-octyl amine (4.30kg)；Tripropyl amine (TPA) (1kg)；
500SN(220kg)。
(a) preparation of thickening agent：A volume for 400L and with heating, stirring, circulation, cooling reaction kettle in plus
Enter 500SN oil, the 12- hydroxy stearic acids of 10kg and the succinic acid of 7.86kg of 120kg, stirring, is warming up to 80 DEG C, at this time will
The Ca (OH) of mono- hydronium(ion) lithias of 1.4kg, 4.93kg2And 25kg water is slowly added thereto, 105 DEG C of saponification 2h are warming up to, after
115 DEG C are warming up to, adds MDI the and 1kg catalyst (tripropyl amine (TPA)) of 8.33kg, reacts 30min, then adds 4.30kg n-octyl amines, instead
Answer 30min,
(b) step (a) products therefrom is warming up to 180 DEG C, constant temperature 10min, adds the 500SN quench oils of 100kg, stirred
Cooling, homogenizing, filtering, degassing, goes out kettle and obtains finished product lubricating grease.It can be calculated and learnt according to material amount, the composition of lubricating grease
For：Base oil 86.9%, thickening agent 13.1%；
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Embodiment 7
Raw material components：12- hydroxy stearic acids (10kg)；Terephthalic acid (TPA) (2.76kg)；Zr(OH)4(2.65kg)；Ca
(OH)2(1.23kg)；Methyl diphenylene diisocyanate (MDI, 8.33kg)；N-octyl amine (4.30kg)；Tripropyl amine (TPA) (1kg)；
500SN(100kg)。
(a) preparation of thickening agent：A volume for 200L and with heating, stirring, circulation, cooling reaction kettle in plus
Enter 70kg 500SN oil, the 12- hydroxy stearic acids of 10kg and the terephthalic acid (TPA) of 2.76kg, stirring, is warming up to 80 DEG C, at this time will
The Zr (OH) of 2.65kg4、1.23kg Ca(OH)2And 10kg water is slowly added thereto, be warming up to 105 DEG C of saponification 2h, after be warming up to
115 DEG C, MDI the and 1kg catalyst (tripropyl amine (TPA)) of 8.33kg is added, reacts 30min, then adds 4.30kg n-octyl amines, reaction
30min,
(b) step (a) products therefrom is warming up to 180 DEG C, constant temperature 10min, adds the 500SN quench oils of 30kg, stirred
Cooling, homogenizing, filtering, degassing, goes out kettle and obtains finished product lubricating grease.It can be calculated and learnt according to material amount, the composition of lubricating grease
For：Base oil 78.3%, thickening agent 21.7%；
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Embodiment 8
Raw material components：12- hydroxy stearic acids (10kg)；Azelaic acid (3.13kg)；One hydronium(ion) lithia (1.4kg)；Zr
(OH)4(1.32kg)；Ca(OH)2(0.62kg)；Methyl diphenylene diisocyanate (MDI, 8.33kg)；N-octyl amine (4.30kg)；
Tripropyl amine (TPA) (1kg)；500SN(100kg).
(a) preparation of thickening agent：A volume for 200L and with heating, stirring, circulation, cooling reaction kettle in plus
Enter 500SN oil, the 12- hydroxy stearic acids of 10kg and the azelaic acid of 3.13kg of 70kg, stirring, is warming up to 80 DEG C, at this time will
Mono- hydronium(ion) lithias of 1.4kg, 1.32kg Zr (OH)4, 0.62kg Ca (OH)2And 5kg water is slowly added thereto, and is warming up to
105 DEG C of saponification 2h, after be warming up to 115 DEG C, add MDI the and 1kg catalyst (tripropyl amine (TPA)) of 8.33kg, react 30min, then add
4.30kg n-octyl amines, react 30min,
(b) step (a) products therefrom is warming up to 180 DEG C, constant temperature 10min, adds the 500SN quench oils of 30kg, stirred
Cooling, homogenizing, filtering, degassing, goes out kettle and obtains finished product lubricating grease.It can be calculated and learnt according to material amount, the composition of lubricating grease
For：Base oil 80.6%, thickening agent 19.4%；
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Embodiment 9
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 10
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 not added with MDI, tripropyl amine (TPA) and n-octyl amine.As a result such as table 1
It is shown.
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
500SN lubricating base oils and 8.60kg n-octyl amines, become homogeneous system after being heated to 100 DEG C, stir 10 minutes, add
The MDI of 8.33kg, is stirred 30 minutes, then heats to 180 DEG C of constant temperature 10 minutes, adds the 500SN quench oils of 30kg, stirring drop
Temperature, homogenizing, filtering, degassing, goes out kettle and obtains lubricating grease.It can be calculated and learnt according to material amount, the composition of lubricating grease is：Basis
Oil 85.5 weight %, 14.5 weight % of thickening agent.Gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in 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 (4.3kg)；500SN(100kg).
(a) preparation of thickening agent：A volume for 200L and with heating, stirring, circulation, cooling reaction kettle in plus
Enter 500SN oil, the 12- hydroxy stearic acids of 10kg of 70kg, stirring, becomes homogeneous system, at this time by 1.4kg after being warming up to 80 DEG C
A hydronium(ion) lithia and 5kg water be slowly added thereto, be warming up to 105 DEG C of saponification 2h, after be warming up to 115 DEG C, add
After the MDI stirrings 20min of 8.33kg, then add 4.3kg n-octyl amines, react 30min, obtained product is as thickening agent；
(b) step (a) products therefrom is warming up to 180 DEG C, constant temperature 10min, adds the 500SN quench oils of 30kg, stirred
Cooling, homogenizing, filtering, degassing, goes out kettle and obtains finished product.It can be calculated and learnt according to material amount, the composition of lubricating grease is：Basis
Oil 81.4 weight %, 18.6 weight % of thickening agent；
(c) gained lubricating grease is subjected to physical and chemical performance analysis, the results are shown in Table 1.
Comparative example 4
Polyureas-lithium base grease is prepared according to method disclosed in CN1600843A, it is specific as follows：
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).
The 500SN oils of 100kg are weighed into three parts, the MDI of 8.6kg n-octyl amines and 8.33kg is respectively put into 500SN oil
Middle heating melting, treats that temperature reaches 80 DEG C of hybrid reactions and stirs, and the 12- hydroxy stearic acids of 10kg are added after the reaction was complete, are treated
After melting and temperature adds the reaction of mono- hydronium(ion) lithias of 1.4kg at 91 DEG C, continues heating until temperature to 180 DEG C of constant temperature
200 DEG C are again heated to after 15min, 500SN quench oils is added, is cooled to room temperature twice of grinding.
Embodiment 11
Method according to embodiment 1 prepares lubricating grease, unlike, " a hydronium(ion) lithia " is replaced with into " hydroxide
Barium ", the physical and chemical performance analysis of gained lubricating grease the results are shown in Table 1.
Comparative example 5
Method according to embodiment 1 prepares lubricating grease, unlike, " a hydronium(ion) lithia " is replaced with into " isopropanol
Aluminium ", the physical and chemical performance analysis of gained lubricating grease 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, and as thickening agent, comparative example 2 uses urea-based compound as thickening agent, and comparative example 3 is not
Catalyst is used so that thickening agent being simply mixed for lithium soap based compound and urea-based compound, comparative example 4 with reference to it is existing
The method (CN1600843A) that polyureas-lithium base grease is prepared in same kettle prepares lubricating grease, is the machinery of two kinds of lubricating grease
Mixing, from the results shown in Table 1, the performance of lubricating grease of the invention are far superior to simple soap base grease, urea groups profit
The mixture of consistent lubricant or soap base grease and urea-base grease.
In addition, embodiment 1 prepares lubricating grease using 12- hydroxy stearic acids, and embodiment 9-10 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.
In addition, the performance for the lubricating grease that embodiment 1 is prepared using lithium hydroxide as source metal is distinguished better than embodiment 11 and comparative example 5
By lithium source replace with barium hydroxide and aluminium isopropoxide made from lubricating grease, illustrate to obtain using currently preferred source metal
Performance more preferably lubricating grease.
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 (14)
1. a kind of lubricating grease, which contains base oil and thickening agent, it is characterised in that the thickening agent is by small molecule acid
Compound shown in salt and at least one Formulas I provides, and the salt of the small molecule acid is salt, the rudimentary fat of small molecule inorganic acid
At least one of the salt of fat 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+The cation formed for IA races, Group IIA or Group IVB metallic element.
2. lubricating grease 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+Or ZrO2+。
3. lubricating grease according to claim 1 or 2, wherein, group is in hydroxyl, halogen and carboxyl used by substitution
It is at least one.
4. lubricating grease 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. lubricating grease according to claim 1, wherein, the structural formula of the compound is：
6. lubricating grease according to claim 1, wherein, on the basis of the gross weight of the lubricating grease, the base oil
Content is 50-95 weight %, is preferably 60-90 weight %, is most preferably 70-85 weight %；The content of the salt of small molecule acid is
1-30 weight %, are preferably 2-15 weight %, are most preferably 3-10 weight %；The content of compound shown at least one Formulas I
It is preferably 2-25 weight % for 1-40 weight %, is most preferably 5-20 weight %.
7. 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.
8. the lubricating grease according to claim 1 or 7, 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.
9. lubricating grease according to claim 1, wherein, the cation in the salt of the small molecule acid is IA races, Group IIA and
The cation that at least one of Group IVB metallic element is formed, is preferably Li+、Na+、K+、Ca2+And ZrO2+At least one of,
And and Mn+It is identical or different.
10. prepare the method for the lubricating grease in claim 1-9 described in any one, it is characterised in that this method includes：Will be thick
Agent and part basis oil are mixed and refined, then are mixed with surplus base oil and optional additive.
A kind of 11. method for preparing lubricating grease, it is characterised in that this method includes：
(1) it is by structural formulaHydroxy fatty acid, small molecule acid, part basis oil and metal
Source mixing carry out saponification, then the selectivity of product that saponification is obtained carry out heating dehydration, the small molecule acid is
At least one of small molecule inorganic acid, lower fatty acid and aromatic acid；
(2) in the presence of the selectivity of catalyst, step (1) products therefrom and polyisocyanates, amine and optionally in addition are made
Isocyanates be reacted to give the compound of the group with one or more-NHCONH- structures；
(3) step (2) products therefrom is refined, then is mixed with surplus base oil and optional additive.
12. the method according to claim 11, wherein, in step (1), under conditions of 70-120 DEG C, by hydroxy aliphatic
Acid, small molecule acid, part basis oil and source metal mixing carry out saponification, are risen at 100-150 DEG C to reselection
Temperature dehydration；
Alternatively, under conditions of 100-110 DEG C, hydroxy fatty acid, small molecule acid, part basis oil and source metal are mixed and carried out
Saponification, carries out heating dehydration to reselection at 115-150 DEG C.
13. the method according to claim 11 or 12, wherein, the catalyst is organic amine, carbonate, the hydrogen of alkali metal
At least one of oxide, boron trifluoride, organic metal, are preferably methylamine, ethamine, propylamine, dimethylamine, diethylamine, front three
At least one in amine, triethylamine, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, boron trifluoride and organotin
Kind.
14. the lubricating grease as made from the method described in any one in claim 11-13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610957910.8A CN108003978B (en) | 2016-10-27 | 2016-10-27 | Lubricating grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610957910.8A CN108003978B (en) | 2016-10-27 | 2016-10-27 | Lubricating grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108003978A true CN108003978A (en) | 2018-05-08 |
| CN108003978B CN108003978B (en) | 2021-03-12 |
Family
ID=62048321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610957910.8A Active CN108003978B (en) | 2016-10-27 | 2016-10-27 | Lubricating grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108003978B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868179A (en) * | 2019-02-26 | 2019-06-11 | 天津市金海利油脂有限公司 | A kind of manufacturing method of extreme pressure grease |
| CN111100732A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Soap urethane lubricating grease and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5854183A (en) * | 1996-04-26 | 1998-12-29 | Nippon Oil Co., Ltd. | Grease composition for constant-velocity joints |
| CN1414076A (en) * | 2002-10-09 | 2003-04-30 | 燕化集团天津润滑油脂有限公司 | High base number composite calcium sulfonate lubricating grease and its preparation method |
| CN1493673A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Preparation method of polyurea-composite calcium lubricating grease |
| CN101163781A (en) * | 2005-04-20 | 2008-04-16 | Ntn株式会社 | Grease composition, bearing prelubricated with grease, and rotation-transmitting apparatus with built-in one-way clutch |
| WO2008106345A1 (en) * | 2007-02-28 | 2008-09-04 | The Lubrizol Corporation | Alkali metal borate and lubricating compositions thereof |
-
2016
- 2016-10-27 CN CN201610957910.8A patent/CN108003978B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5854183A (en) * | 1996-04-26 | 1998-12-29 | Nippon Oil Co., Ltd. | Grease composition for constant-velocity joints |
| CN1414076A (en) * | 2002-10-09 | 2003-04-30 | 燕化集团天津润滑油脂有限公司 | High base number composite calcium sulfonate lubricating grease and its preparation method |
| CN1493673A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Preparation method of polyurea-composite calcium lubricating grease |
| CN101163781A (en) * | 2005-04-20 | 2008-04-16 | Ntn株式会社 | Grease composition, bearing prelubricated with grease, and rotation-transmitting apparatus with built-in one-way clutch |
| WO2008106345A1 (en) * | 2007-02-28 | 2008-09-04 | The Lubrizol Corporation | Alkali metal borate and lubricating compositions thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《化工百科全书》编辑委员会等: "《化工百科全书（第19卷）》", 30 September 1998, 化学工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100732A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Soap urethane lubricating grease and preparation method thereof |
| CN111100732B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Soap urethane lubricating grease and preparation method thereof |
| CN109868179A (en) * | 2019-02-26 | 2019-06-11 | 天津市金海利油脂有限公司 | A kind of manufacturing method of extreme pressure grease |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108003978B (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108003978A (en) | A kind of lubricating grease and preparation method thereof | |
| CN108003979A (en) | A kind of lubricating grease and preparation method thereof | |
| CN107986993A (en) | A kind of compound and lubricating grease and their preparation method with thickening power | |
| CN107986992A (en) | A kind of compound and lubricating grease and their preparation method with thickening power | |
| CN108003063A (en) | A kind of compound and lubricating grease and their preparation method with antioxygen and thickening | |
| CN104560318B (en) | A kind of polyurea grease of calcium naphthenate zirconium base six and preparation method thereof | |
| CN103571570B (en) | A kind of Calcium naphthenate base four polyurea grease and preparation method thereof | |
| CN104449956B (en) | A kind of high base number composite calcium-base polyurea grease and preparation method thereof | |
| CN108003965A (en) | A kind of lubricating grease and preparation method thereof | |
| CN108003066A (en) | A kind of compound and lubricating grease and their preparation method with thickening power | |
| CN103571571B (en) | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN108003065A (en) | A kind of compound and lubricating grease and their preparation method with thickening power | |
| CN108003064A (en) | A kind of compound and lubricating grease and their preparation method with thickening power | |
| CN104560320B (en) | A kind of composite calcium naphthenate calcium zirconium base polyurea grease and preparation method thereof | |
| CN104450109B (en) | A kind of polyurea grease of high base number composite calcium-base four and preparation method thereof | |
| CN104560317B (en) | A kind of complex calcium sulfonate calcium naphthenate zirconium base polyurea grease and preparation method thereof | |
| CN108003061A (en) | A kind of compound and lubricating grease and their preparation method with thickening power | |
| CN104450110B (en) | A kind of sulfoacid calcium Calcium naphthenate base polyurea grease and preparation method thereof | |
| CN104212611B (en) | A kind of Calcium naphthenate base polyurea grease and preparation method thereof | |
| CN108003964A (en) | A kind of lubricating grease and preparation method thereof | |
| CN104560273B (en) | A kind of complex calcium sulfonate calcium naphthenate zirconium base octa-polyurea lubricating grease and preparation method thereof | |
| CN104293452B (en) | A kind of Composite calcium naphthenate base polyurea grease and preparation method thereof | |
| CN103571588B (en) | A kind of Calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN104449961B (en) | A kind of sulfoacid calcium calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof | |
| CN104450112B (en) | A kind of polyurea grease of high base number composite calcium-base six and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |