CN104450113B - A kind of high base number composite calcium-base octa-polyurea lubricating grease and preparation method thereof - Google Patents
A kind of high base number composite calcium-base octa-polyurea lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high base number composite calcium-base octa-polyurea lubricating grease, it is characterised in that on the basis of lubricating grease weight, including following components：10 70 weight % non-newtonian fluid sulfoacid calcium calcium naphthenate；The calcium salt of 1 20 weight % higher fatty acids；1 15 weight % small molecule inorganic acid and/or the calcium salt of lower fatty acid；0.5 30 weight % polyurea compound；10 80 weight % base oil, wherein, the polyurea compound is eight polyurea compounds.The invention also discloses the preparation method of high base number composite calcium-base octa-polyurea lubricating grease and its high base number composite calcium-base octa-polyurea lubricating grease of preparation.The high base number composite calcium-base octa-polyurea lubricating grease of the present invention, with excellent anticorrosive property and heat-resisting quantity, but also there is the performances such as mechanical stability, water-resistance and adhesiveness better than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, resistance to saltfog, colloid stability, extreme pressure anti-wear, there is longer lubricating life.
Description
Technical field
The present invention relates to lubricating grease, in particular it relates to a kind of high base number composite calcium-base octa-polyurea lubricating grease and its preparation side
Method.
Background technology
Sulfoacid calcium is used as the detersive and the history of antirust agent existing decades of lubricating oil, is widely used in internal combustion engine lubrication
The additive of oil, the development of its technology mainly make its height alkalization, are exactly alkyl benzene sulphonate of the calcium carbonate with surface-active
Calcium or alkyl carboxylic acid calcium turn into a kind of colloidal dispersion system to be distributed in flux oil.Calcium sulfonate with high base number according to the mode of production not
It is same to be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate.Calcium mahogany sulfonate is to use oleum or SO3Sulfonation mineral lubricating oil produces
Accessory substance mahogany acid during white oil, through with Ca (OH)2React, the contour alkalization technology that is carbonated and obtain；Calcium alkylbenzenesulfonate is to use
Oleum or SO3The alkylbenzene of sulfonation synthesis, the alkyl benzene sulphonate of generation pass through and Ca (OH)2React, be carbonated contour alkalization skill
Art and obtain.
Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusivity, can
To be used as the detersive of lubricating oil, the additive of IC engine lubricating oil is widely used in, the development of its technology mainly makes its high-alkali
Change, calcium carbonate is exactly turned into a kind of colloidal dispersion system with the naphthenic acid calcium with surface-active to be distributed in flux oil.It is high
Base number calcium naphthenate mostly be the acidic components extracted in the distillate obtained from crude distillation, through with Ca (OH)2Reaction, carbonating
Contour alkalization technology and obtain, about prepare Patents have CN1465560 etc..
Using calcium sulfonate with high base number be raw material produce lubricating grease, because its have excellent high temperature performance, mechanical stability,
Colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, domestic and international profit is caused
The extensive concern of consistent lubricant industry, however, although high base number composite calcium sulfonate base grease has very excellent combination property, but
The high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, together
When, with requirement more and more higher of the people to environmental protection, in calcium sulfonate with high base number production process must through sulfonation process to ring
The pollution in border is also increasingly subject to the concern of people.Find a kind of performance it is similar with high base number composite calcium sulfonate base grease but can
Mitigating the lubricating grease of above mentioned problem turns into the big problem that people face at present.
The content of the invention
Similar with high base number composite calcium sulfonate base grease it is an object of the invention to provide a kind of performance, cost is low, prepares
Simple and environmentally-friendly lubricating grease of technique and preparation method thereof.
The present inventor has found under study for action, on the basis of lubricating grease weight, including following components：10-70 weight %
Non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium salt of 1-20 weight % higher fatty acids；1-15 weight % small molecule inorganic acid
And/or the calcium salt of lower fatty acid；0.5-30 weight % polyurea compound；10-80 weight % base oil, wherein, it is described poly-
Carbamide compound is eight polyurea compounds.The performance of the lubricating grease is similar with high base number composite calcium sulfonate base grease, and cost is low,
Preparation technology is simple and environmentally-friendly.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of polyureas of high base number composite calcium-base eight lubrication
Fat, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；1-20 weights
Measure the calcium salt of % higher fatty acids；1-15 weight % small molecule inorganic acid and/or the calcium salt of lower fatty acid；0.5-30 weights
Measure % polyurea compound；10-80 weight % base oil, wherein, the polyurea compound is eight polyurea compounds.
Preferably, on the basis of lubricating grease weight, including following components：20-65 weight % non-newtonian fluid sulfoacid calcium-ring
Alkanoic acid calcium；The calcium salt of 2-15 weight % higher fatty acids；2-10 weight % small molecule inorganic acid and/or the calcium of lower fatty acid
Salt；1-20 weight % eight polyurea compounds；20-70 weight % base oil.
Second aspect, the invention provides the preparation method of high base number composite calcium-base octa-polyurea lubricating grease as described above,
This method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, small molecule inorganic acid and/or rudimentary fat
Calcium salt, eight polyurea compounds and the part basis oil of fat acid are well mixed, and are refined in 180-230 DEG C of constant temperature, are added surplus basis
Oil, necessary additive is added, obtains finished product.
The third aspect, the invention provides a kind of preparation method of high base number composite calcium-base octa-polyurea lubricating grease, this method
Including：
（1）By newton body sulfoacid calcium, newton body calcium naphthenate and base oil Hybrid Heating, transforming agent is added, thing is treated in heating
Expect retrogradation；
（2）In step（1）Lime or calcium hydroxide are added in products therefrom, adds higher fatty acids, small molecule inorganic acid
And/or lower fatty acid is reacted, heat up dehydration after reaction；
（3）In step（2）Base oil and diisocyanate are added in gained mixture, then sequentially adds diamines, diamines
Reacted with monoamine；
（4）By step（3）Gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds base oil, adds necessary add
Add agent, obtain finished product.
Fourth aspect, the invention provides the polyureas of high base number composite calcium-base eight as made from method as described above to lubricate
Fat.
The present invention high base number composite calcium-base octa-polyurea lubricating grease, not only with Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease one
Sample, there is excellent anticorrosive property and heat-resisting quantity, but also the machinery with better than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease
The performance such as stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, there is the longer lubrication longevity
Life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, and product quality is stable.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 2.
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 invention provides a kind of high base number composite calcium-base octa-polyurea lubricating grease, this lubricating grease employs calcium mahogany sulfonate
And/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate be raw material, simultaneously containing composite calcium thickening agent,
Eight polyurea compounds caused by isocyanates and amine reaction.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of high base number composite calcium-base octa-polyurea lubricating grease, on the basis of lubricating grease weight,
Including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium salt of 1-20 weight % higher fatty acids；
1-15 weight % small molecule inorganic acid and/or the calcium salt of lower fatty acid；0.5-30 weight % polyurea compound；10-80 weights
% base oil is measured, wherein, the polyurea compound is eight polyurea compounds.
Preferably, on the basis of lubricating grease weight, including following components：20-65 weight % non-newtonian fluid sulfoacid calcium-ring
Alkanoic acid calcium；The calcium salt of 2-15 weight % higher fatty acids；2-10 weight % small molecule inorganic acid and/or the calcium of lower fatty acid
Salt；1-20 weight % eight polyurea compounds；20-70 weight % base oil.
Non-newtonian fluid sulfoacid calcium-the calcium naphthenate is in infrared spectrum 873cm-1-886cm-1There is crystal form calcium carbonate spy in place
Levy absworption peak, preferably total base number 250mgKOH/g-450mgKOH/g, 300mgKOH/g-400mgKOH/g.The non newtonian
Body sulfoacid calcium-calcium naphthenate is to convert to obtain by transforming agent by newton body sulfoacid calcium and newton body calcium naphthenate.And newton body
Contain unformed calcium carbonate in sulfoacid calcium, newton body calcium naphthenate, in infrared spectrum 860cm-1-865cm-1Place occurs unformed
Calcium carbonate characteristic absorption peak.The newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is
250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；The newton body calcium naphthenate is oil ring
Alkanoic acid calcium and/or synthesis calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-
400mgKOH/g.The base number of non-newtonian fluid sulfoacid calcium-calcium naphthenate is the base number and newton body calcium naphthenate of newton body sulfoacid calcium
Base number weight average value.
In the present invention, higher fatty acids is that carbon number is 8-20, preferably 10-16 straight chain fatty acid or hydroxy fatty acid, example
Such as at least one of laurate, palmitic acid, stearic acid, 12- hydroxy stearic acids, eicosyl carboxylic acid, preferably 12- hydroxyls are hard
Resin acid.
In the present invention, the molecular weight of small molecule inorganic acid or lower fatty acid is less than or equal to 150.Wherein, small molecule is inorganic
Acid can be selected from least one of boric acid, phosphoric acid, sulfuric acid etc., preferably boric acid and/or phosphoric acid；Lower fatty acid can be selected from
At least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid etc., preferably acetic acid.
In the present invention, eight polyurea compound preferably has following structure：
Wherein, R1Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-
18, aryl can be the phenyl of phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen substitution.
Wherein, R2Can be alkylidene or arlydene, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be with
It is phenylene or biphenylene.
Wherein, R3Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can
Think 6-30, preferably 6-20, R3More preferably At least one of.
Above-mentioned eight polyurea compound can use the thinkable various methods of those skilled in the art institute to obtain, such as can be with
It is prepared according to the CN103060068A methods recorded.
The lube base oil can be mineral oil, artificial oil, vegetable oil or their mixture, and 100 DEG C of motions are glutinous
Spend for 4-150mm2/ s, preferably 10-60mm2/s.Artificial oil can be poly-a-olefin oil（PAO）, Esters oil, alkyl-silicone oil, take
Hold in the palm artificial oil etc..
Various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the present invention.Its
In, the preferred arylamine kind antioxidant of antioxidant, account for 0.01-5%, the preferably 0.1-2.5% of lubricating grease gross weight, can be diphenylamines,
At least one of phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease
The 0.5-12% of gross weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two
Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethyl-ne
Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid
At least one of calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil
At least one of barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the preparation method of high base number composite calcium-base octa-polyurea lubricating grease as described above,
This method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, small molecule inorganic acid and/or rudimentary fat
Calcium salt, eight polyurea compounds and the part basis oil of fat acid are well mixed, and are refined in 180-230 DEG C of constant temperature, are added surplus basis
Oil, necessary additive is added, obtains finished product.
In the present invention, for non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, small molecule inorganic acid and/
Or calcium salt, eight polyurea compounds, base oil and the additive of lower fatty acid are as described above, will not be repeated here.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are used
Base oil total amount, in the present invention, part basis oil and the weight ratio preferably 1 of surplus base oil：0.1-5.
, can be by newton body sulfoacid calcium and newton body calcium naphthenate by turning for non-newtonian fluid sulfoacid calcium-calcium naphthenate
Agent converts to obtain, for example, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, adds
Required transforming agent is reacted, and after all transforming agents add, in 80-100 DEG C of constant temperature 60-90 minute, then heats to 100-
120 DEG C of dehydrations.
The third aspect, the invention provides a kind of preparation method of high base number composite calcium-base octa-polyurea lubricating grease, including：
（1）By newton body sulfoacid calcium, newton body calcium naphthenate and base oil Hybrid Heating, transforming agent is added, thing is treated in heating
Expect retrogradation；
（2）In step（1）Lime or calcium hydroxide are added in products therefrom, adds higher fatty acids, small molecule inorganic acid
And/or lower fatty acid is reacted, heat up dehydration after reaction；
（3）In step（2）Base oil and diisocyanate are added in gained mixture, then sequentially adds diamines, diamines
Reacted with monoamine；
（4）By step（3）Gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds base oil, adds necessary add
Add agent, obtain finished product.
Step（1）In, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add
Required transforming agent is reacted, after all transforming agents add, in 80-100 DEG C of constant temperature 60-90 minute.
In the present invention, for the weight ratio of newton body sulfoacid calcium and newton body calcium naphthenate without particular/special requirement, preferably 1：
0.25-4.Newton body sulfoacid calcium and the gross weight of newton body calcium naphthenate and the weight ratio of part basis oil are preferably 1：0.1-3.
The newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g-
450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；The newton body calcium naphthenate be petroleum naphthenic acid calcium and/or
Calcium naphthenate is synthesized, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.
The transforming agent be preferably selected from fatty alcohol, aliphatic acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid,
At least one of phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonates and water；It is more excellent
Choosing selected from C1-C5 fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine,
C1-C5 ether, boric acid, C1-C10 alkyl phosphonic acid, C2-C16 di alkyl phosphonic acid, C6-C20 arylphosphonic acid, C12-C24
At least one of diaryl phosphonic acids, C7-C20 aromatic alcohol, C7-C20 aromatic amine, C8-C20 alkyl benzene sulphonates and water；More
At least one further preferably in DBSA, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water
Kind.The addition of transforming agent is preferably the 2-30% of newton body sulfoacid calcium and newton body calcium naphthenate gross weight, more preferably newton
The 6-22% of body sulfoacid calcium and newton body calcium naphthenate gross weight.
In the present invention, fatty alcohol includes the fatty alcohol of straight chain, side chain and ring-type, aliphatic acid, aliphatic ketone, fatty aldehyde, fat
Amine is similarly.
Step（2）In, at 85-100 DEG C, the suspension of lime or calcium hydroxide is added, adds higher fatty acids, stirring
5-20 minutes, small molecule inorganic acid and/or lower fatty acid are added, stir 5-20 minutes, be warming up to 100-120 DEG C, preferably protect
30-60 minutes are held to realize dehydration.Wherein, higher fatty acids and small molecule inorganic acid and/or the addition sequence of lower fatty acid
It can exchange.
In the present invention, higher fatty acids, small molecule inorganic acid, lower fatty acid are as it was previously stated, will not be repeated here.
In the present invention, higher fatty acids and small molecule inorganic acid and/or the H of lower fatty acid+The amount and lime of total material
Or the OH contained by the suspension of calcium hydroxide-The amount of total material is equal, OH-Amount also can excessive 1-10%.
In the present invention, in terms of calcium hydroxide, the addition of the suspension of lime or calcium hydroxide is preferably newton body sulfonic acid
The 1-15% of calcium and newton body calcium naphthenate gross weight；With H+Material gauge, higher fatty acids and small molecule inorganic acid and/
Or the mol ratio of lower fatty acid is preferably 1：1-10.
In the present invention, the suspension of lime or calcium hydroxide refers to lime or calcium hydroxide formed in water it is suspended
Liquid, the solid content of suspension is preferably 10-60 weight %.
Step（3）In, in step（2）Base oil and diisocyanate are added in gained mixture, then sequentially adds two
Amine, diamines and monoamine are reacted, and are in step（2）Eight polyurea compounds are prepared in gained mixture.
The method of eight polyurea compounds is prepared without particular/special requirement, various methods commonly used in the art can be used.For example,
, can be in step in the present invention（2）Base oil and diisocyanate are added in gained mixture, adds diamines, 2-8 points of stirring
Clock, adds diamines again, stirs 2-8 minutes, adds monoamine, stirs 2-8 minutes, diisocyanate, diamines added by each time,
The mol ratio of diamines and monoamine is 4:2:1:2.
Step of the present invention（3）In, the diamines added twice can be the same or different, in order to easy to operate, preferably two
The diamines of secondary addition is identical.
The diisocyanate structure is OCN-R3- NCO, R3Can be that carbon number is 6-30, preferably 6-20 arlydene, Asia
Alkyl or cycloalkylidene, preferably Deng.
Such as the diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), 1,6- is sub-
Hexyl diisocyanate (HDI), dicyclohexylmethyl diisocyanate（HMDI）With an xylylene diisocyanate（XDI）Deng
At least one of.
The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, structural formula R1-NH2、R1’-NH2, R therein1、R1’Can
To be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, aryl can be phenyl or
Substituted phenyl, preferably phenyl or C1-C3 alkyl or the phenyl of halogen substitution.Preferable monoamine can be selected from aniline, m-chloro
Aniline, parachloroanilinum, the arylamine of para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, octadecylamine fatty amine.
The diamines can be fatty amine or arylamine, structural formula NH2-R2-NH2, R therein2Can be alkylidene or Asia
Aryl, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferable diamines can
Be selected from p-phenylenediamine, o-phenylenediamine, 4,4 '-benzidine aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6- oneself
The straight-chain fatty amine of diamines.
Step（4）In, first in 100-120 DEG C of constant temperature 10-20 minute, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minute；
Base oil is added, treats that temperature is cooled to 100-120 DEG C, adds necessary additive, is stirred, circulating filtration, homogenizing, degassing.
In the present invention, step（1）In base oil used total amount and step（3）In base oil used total amount and step
（4）In base oil used total amount weight ratio preferably 1：0.1-5：0.1-5.
Fourth aspect, present invention also offers high base number made from the preparation method provided as third aspect present invention is compound
Calcium base octa-polyurea lubricating grease.
Compared with the high base number composite calcium-base octa-polyurea lubricating grease as made from the preparation method that second aspect provides, third party
Face provide preparation method made from high base number composite calcium-base octa-polyurea lubricating grease have more preferable mechanical stability, water-resistance and
Adhesiveness, colloid stability, and there is longer lubricating life.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the following Examples and Comparative Examples：
Non-newtonian fluid sulfoacid calcium-calcium naphthenate %=（Overbased or calcium sulfonate with high base number raw material weight+overbased or high
Base number calcium naphthenate raw material weight+transforming agent gross weight）/ lubricating grease gross weight × 100%.Transforming agent is included in non-newtonian fluid sulphur
In the content of sour calcium-calcium naphthenate.
Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd, also may be used
To be prepared according to method disclosed in CN101885677A.
Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industries Co., Ltd.
Embodiment 1
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Boron
Acid（2.32kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 18kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；2.8kg aphthenic acids is added, temperature control exists
50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；80 DEG C are warming up to,
Constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, adds the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10
Minute；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；Add the boric acid aqueous solution that 9.28kg concentration is 25 weight %, stirring
10 minutes, 120 DEG C are warming up under stirring, is kept for 30 minutes, dehydration；Add 2kg HVI500SN lubricating base oils and
1.28kgMDI is quickly stirred 4 minutes, and 0.15kg ethylenediamines are added under quick stirring, stirring 4 minutes, are added again under quick stirring
Enter 0.08kg ethylenediamines, stir 4 minutes, add 0.69kg octadecylamines stirring 4 minutes, successively added MDI, ethylenediamine, second two
The ratio between amount of material of amine and octadecylamine is 4:2:1:2,120 DEG C of constant temperature 20 minutes, is finally warming up to 200 DEG C of constant temperature 10 minutes.
Then, 160 DEG C are cooled to, adds remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 110 DEG C, circulating filtration,
Change, degassing obtains finished product.Service check the results are shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
Embodiment 2
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Boron
Acid（2.32kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 18kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；2.8kg aphthenic acids is added, temperature control exists
50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；80 DEG C are warming up to,
Constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, adds the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10
Minute；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；Add the boric acid aqueous solution that 9.28kg concentration is 25 weight %, stirring
10 minutes, 120 DEG C are warming up under stirring, is kept for 30 minutes, dehydration.
Another volume be 30L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 2kg
HVI500SN lubricating base oils and 1.28kg MDI are quickly stirred 4 minutes, and quick stirring is lower to add 0.15kg ethylenediamines, stirs 4
Minute, 0.08kg ethylenediamines are added again under quick stirring, are stirred 4 minutes, add 0.69kg octadecylamines stirring 4 minutes, successively
Added MDI, ethylenediamine, the ratio between the amount of material of ethylenediamine and octadecylamine are 4:2:1:2,120 DEG C of constant temperature 20 minutes, obtains eight
Polyureas.
The polyureas of gained eight is all squeezed into a upper kettle, stirred, is finally warming up to 200 DEG C of constant temperature 10 minutes.So
Afterwards, 160 DEG C are cooled to, adds remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing,
Degassing obtains finished product.Service check the results are shown in Table 1, and infrared spectrum is shown in Fig. 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
The eight polyureas molecular structural formulas contained in component are：
Embodiment 3
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total alkali
It is worth for 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 20kg）；N-butanol
（2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；Stearic acid（1.9kg）；Boric acid（2.32kg）；Lauryl amine
（0.52kg）；Ethylenediamine（0.26kg）；MDI（1.42kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/
S, 28kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 20kg for being 320mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 80 DEG C, constant temperature 10 minutes；2.8kg n-butanols are added, temperature control exists
80 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；90 DEG C are warming up to,
Constant temperature 60 minutes, material retrogradation；The calcium hydroxide suspension 9kg that solid content is 20 weight % is added, is stirred 10 minutes；Add
1.9kg stearic acid, stir 10 minutes；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, is stirred 10 minutes, under stirring
120 DEG C are warming up to, is kept for 30 minutes, dehydration；Add 2kg HVI500SN lubricating base oils and 1.28kg MDI quickly stirrings 8
Minute, quick stirring is lower to add 0.17kg ethylenediamines, stirs 8 minutes, adds 0.09kg ethylenediamines again under quick stirring, stir
8 minutes, 0.52kg lauryl amines stirring 8 minutes is added, successively the amount of the material of added MDI, ethylenediamine, ethylenediamine and octadecylamine
The ratio between be 4:2:1:2,100 DEG C of constant temperature 10 minutes, is finally warming up to 230 DEG C of constant temperature 5 minutes.Then, add remaining
HVI500SN lubricating base oils；Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table
1。
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.6；The weight % of calcium stearate 2.3；The weight of line borate 2.7
Measure %.
Embodiment 4
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Total alkali
It is worth for 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 25kg）；Dodecyl
Benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；Ten
Eight amine（0.84kg）；Ethylenediamine（0.28kg）；TDI（1.08kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are
11mm2/ s, 23kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, sulfoacid calcium uses total
Base number is 320mgKOH/g calcium sulfonate with high base number；Aphthenic acids is replaced with DBSA simultaneously；MDI is replaced with TDI；Respectively
The dosage of composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
Embodiment 5
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids（Total acid
It is worth for 180mgKOH/g, 1.8kg）；Boric acid（1kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids
（2kg）；Boric acid（2.32kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN lubrication bases
Oil（100 DEG C of kinematic viscosity are 11mm2/ s, 7kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, sulfoacid calcium uses total
Base number is 320mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；Transforming agent is aphthenic acids, boric acid and acetic acid, and its mesoboric acid adds after acetic acid；The dosage of each composition is as above.Assay is shown in
Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 53.8；The weight % of eight polyureas 3.6；The weight % of lubricating base oil 35.4；The weight % of 12- hydroxy stearic acids calcium 3.4；Boric acid
The weight % of calcium 3.8.
Embodiment 6
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total alkali
It is worth for 400mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 25kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Boron
Acid（2.32kg）；Octadecylamine（2.07kg）；Ethylenediamine（0.69kg）；MDI（3.84kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 18.6kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, the dosage of each composition
As above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 7.5；The weight % of lubricating base oil 49.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
Embodiment 7
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 24kg）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO40（100 DEG C of kinematic viscosity are 41mm2/ s, 30kg）；Cycloalkanes
Acid（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；
Boric acid（2.32kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；Full synthetic oil poly ＆ Alpha ,-olefin oil
PAO10（100 DEG C of kinematic viscosity are 11mm2/ s, 9kg）；Two thio Acidic phosphates zinc（2kg）；Dialkyl dithio amino first
Sour molybdenum（1kg）；Tungsten disulfide（2kg）；Two tungsten selenides（2kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, calcium naphthenate uses
Total base number is 320mgKOH/g overbased calcium alkyl-salicylate；Replaced respectively using full synthetic oil poly ＆ Alpha ,-olefin oil PAO40 and PAO10
HVI150BS and HVI500SN；And treat that temperature is cooled to 110 DEG C, add 2kg two thio Acidic phosphates zinc, stir 10 points
Clock, 1kg molybdenum dialkyldithiocarbamacompositions are added, stirred 10 minutes, add 2kg tungsten disulfide, stirred 10 minutes, add
Enter 2kg two tungsten selenides, stir 10 minutes, add 0.2kg pair, right '-di-iso-octyldiphenylamine, stir 10 minutes, then follow
Ring filtering, homogenizing, degassing obtain finished product；The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.7；The weight % of eight polyureas 2.6；The weight % of lubricating base oil 45.2；The weight % of 12- hydroxy stearic acids calcium 2.5；Boric acid
The weight % of calcium 2.7；The two thio weight % of Acidic phosphates zinc 2.3；The weight % of molybdenum dialkyldithiocarbamacompositions 1.2；Tungsten disulfide
2.3 weight %；The weight % of two tungsten selenide 2.3；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 8
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total base number
For 400mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Boric acid
（2.32kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN lubricating base oils（100 DEG C of fortune
Kinetic viscosity is 11mm2/ s, 33kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, sulfoacid calcium uses total
Base number is 320mgKOH/g calcium sulfonate with high base number；The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.8；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.4；The weight % of 12- hydroxy stearic acids calcium 2.5；Boric acid
The weight % of calcium 2.8.
Embodiment 9
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number is
320mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 20kg）；Aphthenic acids（Total acid
It is worth for 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（5.2kg）；12- hydroxy stearic acids（2kg）；Boric acid
（2.32kg）；Phosphoric acid（3kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN lubrication bases
Oil（100 DEG C of kinematic viscosity are 11mm2/ s, 28kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, sulfoacid calcium uses total
Base number is 320mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；After adding boric acid stirring 10 minutes, phosphoric acid is added, is stirred 10 minutes, 120 DEG C are warming up under stirring, is kept for 30 minutes, is taken off
Water；And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulate
Filtering, homogenizing, degassing obtain finished product；The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 35.9；The weight % of eight polyureas 2.4；The weight % of lubricating base oil 51.6；The weight % of 12- hydroxy stearic acids calcium 2.3；Boric acid
The weight % of calcium 2.5；The weight % of calcium phosphate 5.1；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 10
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 15kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（3kg）；12- hydroxy stearic acids（2kg）；Boric acid
（2.32kg）；Acetic acid（2kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN lubrication bases
Oil（100 DEG C of kinematic viscosity are 11mm2/ s, 33kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, add boric acid stirring
After 10 minutes, acetic acid is added, is stirred 10 minutes, is then warming up to 120 DEG C under agitation, is kept for 30 minutes, dehydration；Each composition
Dosage is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 36.8；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 52.9；The weight % of 12- hydroxy stearic acids calcium 2.3；Boric acid
The weight % of calcium 2.6；The weight % of calcium acetate 2.9.
Embodiment 11
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 15kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Boric acid
（2.32kg）；Para-totuidine（0.34kg）；Ethylenediamine（0.28kg）；MDI（1.58kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 18kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, sulfoacid calcium uses total
Base number is 320mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；Octadecylamine is replaced using para-totuidine；The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
Embodiment 12
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 360mgKOH/g, 15kg）；Overbased calcium alkyl-salicylate（Total base number
For 360mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Detergent alkylate
Sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；18
Amine（0.63kg）；1,6- hexamethylene diamines（0.4kg）；MDI（1.17kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are
11mm2/ s, 33kg）.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, sulfoacid calcium uses total
Base number is 360mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 360mgKOH/g
Calcium；Aphthenic acids is replaced using DBSA；Ethylenediamine is replaced using 1,6- hexamethylene diamines；The dosage of each composition is as above.Inspection
Test and the results are shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
Embodiment 13
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Boron
Acid（2.32kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 18kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；2.8kg aphthenic acids is added, temperature control exists
50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；80 DEG C are warming up to,
Constant temperature 90 minutes, material retrogradation.
Another volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 5kg
HVI500SN lubricating base oils, 100 DEG C are warming up to, add the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10
Minute；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；Add the boric acid aqueous solution that 9.28kg concentration is 25 weight %, stirring
10 minutes, obtain 12- hydroxy stearic acids calcium and line borate.
The 3rd volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 2kg
HVI500SN lubricating base oils and 1.28kg MDI are quickly stirred 4 minutes, and quick stirring is lower to add 0.15kg ethylenediamines, stirs 4
Minute, 0.08kg ethylenediamines are added again under quick stirring, are stirred 4 minutes, add 0.69kg octadecylamines stirring 4 minutes, successively
Added MDI, ethylenediamine, the ratio between the amount of material of ethylenediamine and octadecylamine are 4:2:1:2,120 DEG C of constant temperature 20 minutes, obtains eight
Polyureas.
The 12- hydroxy stearic acids calcium and line borate of gained are all squeezed into first kettle, stirred, stirs lower heat up
To 120 DEG C, kept for 30 minutes, dehydration, eight polyureas obtained by the 3rd reactor are all squeezed into the kettle, stirred, most
After be warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, adds remaining HVI500SN lubricating base oils；Treat temperature
110 DEG C are cooled to, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
Embodiment 14
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, aphthenic acids is replaced
For phenol, acetic acid is replaced with into butyric acid.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
Embodiment 15
The present embodiment is used for the high base number composite calcium-base octa-polyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares high base number composite calcium-base octa-polyurea lubricating grease, unlike, aphthenic acids is replaced
For ketone, aqueous acetic acid is replaced with into ether.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.9；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；Boric acid
The weight % of calcium 2.7.
Comparative example 1
Method according to embodiment 1 prepares high base number composite calcium sulfonate base octa-polyurea lubricating grease, unlike, it is overbased
The overbased sulfoacid calcium that calcium naphthenate is 400mgKOH/g with total base number is replaced, and obtained each performance data of lubricating grease finished product is shown in
Table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight of non-newtonian fluid sulfoacid calcium 37.9
Measure %；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 54.5；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of line borate 2.7
Measure %.
Each lubricating grease properties of sample data of table 1
Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Water resistant is sprayed：SH/
T0643；Stencil oil-dividing：SH/T0324；Tetra-ball machine test：SH/T0202；The bearing lubrication life-span：ASTM D3336.
Table 1（It is continuous）Each lubricating grease properties of sample data
Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Water resistant is sprayed：SH/
T0643；Stencil oil-dividing：SH/T0324；Tetra-ball machine test：SH/T0202；The bearing lubrication life-span：ASTM D3336.
By embodiment 1 as can be seen that the high base number composite calcium-base octa-polyurea lubricating grease of the present invention compared with comparative example 1
The difference of extension work cone penetration and work cone penetration be less than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, it is far small that water drenches number of dropouts
In Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, salt spray test is better than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, and water resistant spraying value is small
In Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, Stencil oil-dividing value is much smaller than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, four-ball tester examination
Test value and be more than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, the bearing lubrication life-span is more than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, said
Mechanical stability, water-resistance and the adhesiveness of bright high base number composite calcium-base octa-polyurea lubricating grease of the invention, resistance to saltfog, colloid
Stability, extreme pressure anti-wear, lubricating life are superior to Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, and the high base number of the present invention is compound
Calcium base octa-polyurea lubricating grease has excellent anticorrosive property and heat-resisting quantity etc. as Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease
Performance.
By embodiment 1 respectively compared with embodiment 2 and embodiment 13 as can be seen that the high base number of preparation in situ is compound
Calcium base octa-polyurea lubricating grease, there is more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, and with longer
Lubricating life；By embodiment 1 respectively compared with embodiment 14 and embodiment 15 as can be seen that transforming agent is selected from dodecyl
At least one of benzene sulfonic acid, aphthenic acids, methanol, butanol, isopropanol, boric acid, acetic acid and water, the high base number composite calcium-base of preparation
Octa-polyurea lubricating grease, there is more preferable mechanical stability, water-resistance and adhesiveness, colloid stability.
It will be seen from figure 1 that lubricating grease prepared by embodiment 2 is in 873cm-1-886cm-1There is crystal form calcium carbonate feature in place
Absworption peak.Meanwhile in 3300cm-1-3323cm-1The peak at place is the stretching vibration absworption peak of-NH- in eight polyureas molecules.
The present invention high base number composite calcium-base octa-polyurea lubricating grease, not only with Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease one
Sample, there is excellent anticorrosive property and heat-resisting quantity, but also the machinery with better than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease
The performance such as stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, there is the longer lubrication longevity
Life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, and product quality is stable.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (25)
1. a kind of high base number composite calcium-base octa-polyurea lubricating grease, it is characterised in that on the basis of lubricating grease weight, including with the following group
Point：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium salt of 1-20 weight % higher fatty acids；1-15 weights
Measure % small molecule inorganic acid and/or the calcium salt of lower fatty acid；0.5-30 weight % polyurea compound；10-80 weight %
Base oil, wherein, the polyurea compound is eight polyurea compounds, and the non-newtonian fluid sulfoacid calcium-calcium naphthenate is infrared
Spectrogram 873cm-1-886cm-1There is crystal form calcium carbonate characteristic absorption peak in place.
2. lubricating grease according to claim 1, wherein, on the basis of lubricating grease weight, including following components：20-65 weights
Measure % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium salt of 2-15 weight % higher fatty acids；2-10 weight % small molecule
The calcium salt of inorganic acid and/or lower fatty acid；1-20 weight % eight polyurea compounds；20-70 weight % base oil.
3. lubricating grease according to claim 1 or 2, wherein, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is by newton body
Sulfoacid calcium and newton body calcium naphthenate convert what is obtained, and the total base number of the non-newtonian fluid sulfoacid calcium-calcium naphthenate is 250-
450mgKOH/g。
4. lubricating grease according to claim 1 or 2, wherein, the higher fatty acids is the straight chain fatty that carbon number is 8-20
Acid or hydroxy fatty acid.
5. lubricating grease according to claim 4, wherein, the higher fatty acids be selected from laurate, palmitic acid, stearic acid,
At least one of 12- hydroxy stearic acids, eicosyl carboxylic acid.
6. lubricating grease according to claim 1 or 2, wherein, the molecular weight of small molecule inorganic acid or lower fatty acid is less than
Equal to 150.
7. lubricating grease according to claim 6, wherein, the small molecule inorganic acid in boric acid, phosphoric acid, sulfuric acid extremely
Few one kind, the lower fatty acid are selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid.
8. lubricating grease according to claim 1 or 2, wherein, eight polyurea compound has following structure：
Wherein, R1It is alkyl, cycloalkyl or aryl, R2It is alkylidene or arlydene, R3It is arlydene, alkylidene or cycloalkylidene.
9. lubricating grease according to claim 8, wherein, R1Phenyl or substituted phenyl, or alkyl that carbon number is 8-24 or
Cycloalkyl；R2It is the alkylidene of phenylene or biphenylene or carbon number for 2-12；R3It is arlydene, the alkylidene that carbon number is 6-30
Or cycloalkylidene.
10. lubricating grease according to claim 9, wherein, R1It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or carbon
Count the alkyl or cycloalkyl for 10-18, R2It is phenylene or biphenylene, or carbon number is 2-8 alkylidene；R3It is selected from
With-(CH2)6At least one of-.
11. the preparation method of the high base number composite calcium-base octa-polyurea lubricating grease in claim 1-10 described in any one, it is special
Sign is that this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, small molecule inorganic acid and/
Or calcium salt, eight polyurea compounds and the part basis oil of lower fatty acid are well mixed, and are refined, are added in 180-230 DEG C of constant temperature
Surplus base oil, necessary additive is added, obtains finished product.
12. the preparation method of the high base number composite calcium-base octa-polyurea lubricating grease in claim 1-10 described in any one, it is special
Sign is that this method includes：
(1) by newton body sulfoacid calcium, newton body calcium naphthenate and base oil Hybrid Heating, transforming agent is added, heating treats that material becomes
It is thick；
(2) lime or calcium hydroxide are added in step (1) products therefrom, add higher fatty acids, small molecule inorganic acid and/or
Lower fatty acid is reacted, and heat up dehydration after reaction；
(3) base oil and diisocyanate are added in mixture obtained by step (2), then sequentially adds diamines, diamines and list
Amine is reacted；
(4) mixture obtained by step (3) is warming up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary addition
Agent, obtain finished product.
13. preparation method according to claim 12, wherein, in step (1), by newton body sulfoacid calcium, newton body cycloalkanes
Sour calcium, base oil Hybrid Heating add required transforming agent and reacted, after all transforming agents add, in 80- to 50-80 DEG C
100 DEG C of constant temperature 60-90 minutes.
14. preparation method according to claim 12, wherein, in step (2), at 85-100 DEG C, add lime or hydrogen
The suspension of calcium oxide, higher fatty acids is added, stir 5-20 minutes, added small molecule inorganic acid and/or lower fatty acid, stir
5-20 minutes are mixed, are warming up to 100-120 DEG C of dehydration.
15. preparation method according to claim 12, wherein, in step (3), added in mixture obtained by step (2)
Base oil and diisocyanate, diamines is added, stirs 2-8 minutes, add diamines again, stirred 2-8 minutes, add monoamine,
Stir 2-8 minutes, the mol ratio of diisocyanate, diamines, diamines and monoamine added by each time is 4:2:1:2.
16. preparation method according to claim 12, wherein, in step (4), first in 100-120 DEG C of 10-20 points of constant temperature
Clock, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minute；Base oil is added, treats that temperature is cooled to 100-120 DEG C, is added necessary
Additive, stirring, circulating filtration, homogenizing, degassing.
17. preparation method according to claim 12, wherein, the newton body sulfoacid calcium is calcium mahogany sulfonate and/or conjunction
Into sulfoacid calcium, the total base number of the newton body sulfoacid calcium is 250-450mgKOH/g；The newton body calcium naphthenate is oil ring
Alkanoic acid calcium and/or synthesis calcium naphthenate, the total base number of the newton body calcium naphthenate is 250-450mgKOH/g.
18. preparation method according to claim 12, wherein, the transforming agent be selected from fatty alcohol, aliphatic acid, aliphatic ketone,
Fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkane
At least one of base benzene sulfonic acid and water, the addition of transforming agent is newton body sulfoacid calcium and newton body calcium naphthenate gross weight
2-30%.
19. preparation method according to claim 18, wherein, the transforming agent be selected from DBSA, aphthenic acids,
At least one of methanol, isopropanol, butanol, boric acid, acetic acid and water, the addition of transforming agent is newton body sulfoacid calcium and newton
The 6-22% of body calcium naphthenate gross weight.
20. preparation method according to claim 12, wherein, the structural formula of the monoamine is R1-NH2, wherein, R1It is benzene
The phenyl of base, C1-C3 alkyl or halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.
21. preparation method according to claim 20, wherein, the monoamine is selected from aniline, m-chloroaniline, parachloroanilinum
And/or the arylamine of para-totuidine, and/or the fatty amine selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.
22. preparation method according to claim 12, wherein, the structural formula of the diamines is NH2-R2-NH2, wherein, R2It is
Carbon number is 2-8 alkylidene, or phenylene or biphenylene.
23. preparation method according to claim 22, wherein, the diamines is to be selected from p-phenylenediamine, o-phenylenediamine, 4,
The aromatic amine of 4 '-benzidine and/or selected from ethylenediamine, propane diamine, 1,6- hexamethylene diamines straight-chain fatty amine.
24. preparation method according to claim 12, wherein, the structure of the diisocyanate is OCN-R3- NCO, R3It is
Carbon number is 6-30 arlydene, alkylidene or cycloalkylidene.
25. preparation method according to claim 24, wherein, the diisocyanate is selected from toluene di-isocyanate(TDI), first
Base diphenyl diisocyanate, 1,6- hexylidene diisocyanates, dicyclohexylmethyl diisocyanate and an xyxylene two
At least one of isocyanates.
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| CN201310418852.8A CN104450113B (en) | 2013-09-13 | 2013-09-13 | A kind of high base number composite calcium-base octa-polyurea lubricating grease and preparation method thereof |
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| CN102417853B (en) * | 2010-09-27 | 2013-11-06 | 中国石油化工股份有限公司 | Calcium sulfonate octaurea lubricating grease and preparation method thereof |
| CN102453600B (en) * | 2010-10-22 | 2014-10-01 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based hexaurea grease |
| CN102453598B (en) * | 2010-10-22 | 2014-10-01 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based octaurea lubricating grease |
| CN102911761B (en) * | 2012-10-24 | 2014-04-30 | 中国石油化工股份有限公司 | High-temperature-resistant extreme pressure type lubricating grease composition and preparation method |
| CN103122266B (en) * | 2012-12-25 | 2014-03-05 | 乌鲁木齐市隆成实业有限公司 | Composite calcium-sulfonate-base lubricating grease and preparation method thereof |
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