CN104450115B - A kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof - Google Patents
A kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof Download PDFInfo
- Publication number
- CN104450115B CN104450115B CN201310419096.0A CN201310419096A CN104450115B CN 104450115 B CN104450115 B CN 104450115B CN 201310419096 A CN201310419096 A CN 201310419096A CN 104450115 B CN104450115 B CN 104450115B
- Authority
- CN
- China
- Prior art keywords
- calcium
- lubricating grease
- weight
- naphthenate
- sulfoacid
- 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.)
- Active
Links
- 0 CC(c1ccc(C)cc1)c1ccc(CCC2CCC(C*3CCC(C)CC3)CC2)cc1 Chemical compound CC(c1ccc(C)cc1)c1ccc(CCC2CCC(C*3CCC(C)CC3)CC2)cc1 0.000 description 2
Landscapes
- Lubricants (AREA)
Abstract
The invention discloses a kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea 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；0.5 30 weight % polyurea compound；10 80 weight % base oil, wherein, the polyurea compound is four polyurea compounds.The invention also discloses the preparation method of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease and its sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease of preparation.The sulfoacid calcium calcium naphthenate-based tetrapolyurea 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 calcium sulfonate tetra-polyurea lubricating grease, resistance to saltfog, colloid stability, extreme pressure anti-wear, with longer lubricating life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, and product quality is stable.
Description
Technical field
The present invention relates to lubricating grease, in particular it relates to a kind of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease and its preparation
Method.
Background technology
Sulfoacid calcium is used as the history of detersive and the antirust agent existing decades of lubricating oil, is widely used in internal combustion engine lubrication
The additive of oil, its technology development mainly makes its height alkalization, is 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 is produced
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 is passed 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, exactly calcium carbonate, which is distributed to the naphthenic acid calcium with surface-active in flux oil, turns into a kind of colloidal dispersion system.It is high
Base number calcium naphthenate mostly be the acidic components extracted from the distillate that crude distillation is obtained, 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, have caused domestic and international profit
The extensive concern of consistent lubricant industry, although however, sulfonate with high base number calcium-base grease has very excellent combination property, it is given birth to
Producing the high price and complicated preparation technology itself of raw material calcium sulfonate with high base number causes it not promoted rapidly, meanwhile, with
In requirement more and more higher of the people to environmental protection, calcium sulfonate with high base number production process must through dirt of the sulfonation process to environment
Dye is also increasingly subject to the concern of people.Find a kind of performance similar with sulfonate with high base number calcium-base grease but above-mentioned ask can be mitigated
The lubricating grease of topic turns into the big problem that people face at present.
The content of the invention
Similar with sulfonate with high base number calcium-base grease it is an object of the invention to provide a kind of performance, cost is low, preparation technology
Simple and environmentally-friendly lubricating grease 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；0.5-30 weight % polyurea compound；10-80 weight % base oil, wherein, institute
It is four polyurea compounds to state polyurea compound.The performance of the lubricating grease is similar with sulfonate with high base number calcium-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 calcium naphthenate-based tetrapolyurea lubricating grease,
On the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；0.5-30 weights
Measure % polyurea compound；10-80 weight % base oil, wherein, the polyurea compound is four 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；1-20 weight % four polyurea compounds；20-70 weight % base oil.
Second aspect, the invention provides the preparation side of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease as described above
Method, this method includes：Non-newtonian fluid sulfoacid calcium-calcium naphthenate, four polyurea compounds and part basis oil is well mixed,
180-230 DEG C of constant temperature refining, adds surplus base oil, adds necessary additive, obtain finished product.
The third aspect, the invention provides a kind of preparation method of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease, the party
Method includes：
（1）By the oily Hybrid Heating of newton body sulfoacid calcium, newton body calcium naphthenate and part basis, transforming agent, heating are added
Material retrogradation is treated, dehydration is further heated up；
（2）In step（1）Part basis oil and diisocyanate are added in products therefrom, diamines and list is then sequentially added
Amine is reacted；
（3）180-230 DEG C of constant temperature refining is warming up to, surplus base oil is added, adds necessary additive, obtain finished product.
Fourth aspect, moistens the invention provides the polyureas of sulfoacid calcium-Calcium naphthenate base four as made from method as described above
Consistent lubricant.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease of the present invention, not only as calcium sulfonate tetra-polyurea lubricating grease,
With excellent anticorrosive property and heat-resisting quantity, but also with better than calcium sulfonate tetra-polyurea lubricating grease mechanical stability,
The performance such as water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, with longer lubricating life.The present invention
Preparation of greases technique it is simple and environmentally-friendly, cost is low, and product quality is stable.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 2.
Embodiment
The embodiment to the present invention is described in detail below.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 sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease, this lubricating grease employs oil sulphur
Sour calcium and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, and isocyanates is contained simultaneously
Four polyurea compounds produced are reacted with amine.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease, using lubricating grease weight as base
Standard, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；0.5-30 weight % polyurea compound；
10-80 weight % base oil, wherein, the polyurea compound is four 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；1-20 weight % four polyurea compounds；20-70 weight % base oil.
Non-newtonian fluid sulfoacid calcium-the calcium naphthenate is in infrared spectrum 873cm-1-886cm-1It is special that crystal form calcium carbonate occurs in place
Absworption peak is levied, total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.The non newtonian
Body sulfoacid calcium-calcium naphthenate is to be obtained by newton body sulfoacid calcium and newton body calcium naphthenate by transforming agent conversion.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, four 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
To be phenylene or biphenylene.
Wherein, R3Can be arlydene, alkylidene or cycloalkylidene, arlydene, alkylidene or sub- cycloalkanes
The carbon number of base can be 6-30, preferably 6-20, R3More preferably In
It is at least one.
Above-mentioned four polyurea compound can be obtained using the thinkable various methods of those skilled in the art institute, for example can be with
Prepared according to the CN103060070A 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 accounts for the 0.01-5% of lubricating grease gross weight, preferably 0.1-2.5%, 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 side of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease as described above
Method, this method includes：Non-newtonian fluid sulfoacid calcium-calcium naphthenate, four polyurea compounds and part basis oil is well mixed,
180-230 DEG C of constant temperature refining, adds surplus base oil, adds necessary additive, obtain finished product.
In the present invention, for non-newtonian fluid sulfoacid calcium-calcium naphthenate, four polyurea compounds and base oil as described above,
This is repeated no more.
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.
For non-newtonian fluid sulfoacid calcium-calcium naphthenate, conversion can be passed through by newton body sulfoacid calcium, newton body calcium naphthenate
Agent conversion is obtained, for example, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, adding institute
The transforming agent needed is reacted, after all transforming agents are added, and in 80-100 DEG C of constant temperature 60-90 minutes, then heats to 100-120
DEG C dehydration.
The third aspect, the invention provides a kind of preparation method of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease, bag
Include：
（1）By the oily Hybrid Heating of newton body sulfoacid calcium, newton body calcium naphthenate and part basis, transforming agent, heating are added
Material retrogradation is treated, dehydration is further heated up；
（2）In step（1）Part basis oil and diisocyanate are added in products therefrom, diamines and list is then sequentially added
Amine is reacted；
（3）By step（2）Products therefrom is warming up to 180-230 DEG C of constant temperature refining, adds surplus base oil, adds necessary
Additive, obtains finished product.
Step（1）In, by newton body sulfoacid calcium, newton body calcium naphthenate, the oily Hybrid Heating of part basis to 50-80 DEG C,
Transforming agent needed for adding is reacted, after all transforming agents are added, and in 80-100 DEG C of constant temperature 60-90 minutes, is then heated to
100-120 DEG C of dehydration.
In the present invention, for newton body sulfoacid calcium and newton body calcium naphthenate weight ratio without particular/special requirement, preferably 1：
0.25-4.The weight ratio of newton body sulfoacid calcium and the gross weight of newton body calcium naphthenate and part basis oil is 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
Fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine selected from C1-C5,
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, in step（1）Part basis oil and diisocyanate are added in products therefrom, is then sequentially added
Diamines and monoamine are reacted, and are in step（1）Four polyurea compounds are prepared in products therefrom.
The method of four 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（1）Part basis oil and diisocyanate are added in products therefrom, is stirred 2-8 minutes, two are added
Amine, is stirred 2-8 minutes, adds monoamine, is stirred 2-8 minutes, and the mol ratio of diisocyanate, diamines and monoamine is 2:1:2.
The diisocyanate structure is OCN-R3- NCO, R3Can be that carbon number is 6-30, preferably
For 6-20 arlydene, alkylidene or cycloalkylidene, it is preferably Deng.
Such as described diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), 1,6- Asia
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, and structural formula is 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.It is preferred that 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, and structural formula is NH2-R2-NH2, R therein2Can be alkylidene or Asia
Aryl, the carbon number of alkylidene can be 2-12, and preferably 2-8, arlydene can be phenylene or biphenylene.It is preferred that diamines can
Be selected from p-phenylenediamine, o-phenylenediamine, 4, the aromatic amine of 4 '-benzidine and/or selected from ethylenediamine, propane diamine, 1,6- oneself
The straight-chain fatty amine of diamines.
Step（3）In, first in 100-120 DEG C of constant temperature 10-20 minutes, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minutes；
Surplus base oil is added, treats that temperature is cooled to 100-120 DEG C, necessary additive is added, stirring, takes off circulating filtration, homogenizing
Gas.
In the present invention, step（1）In base oil used and step（2）In base oil used and step（3）In basis used
The weight ratio preferably 1 of oil：0.1-5：0.1-5.
Fourth aspect, present invention also offers sulfoacid calcium-ring made from the preparation method provided as third aspect present invention
The polyurea grease of alkanoic acid calcium base four.
Compared with sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease as made from the preparation method that second aspect is provided, the
Three aspect provide preparation method made from sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease have more preferable mechanical stability,
Water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear, and with 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 height
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 sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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）；Boric acid（2.32kg）；Octadecylamine（1.08kg）；Ethylenediamine
（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 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；Add 16.24kg
Concentration is 14.3 weight % boric acid aqueous solution, stirs 10 minutes, is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation；Under stirring
120 DEG C are warming up to, is kept for 30 minutes, dehydration；2kg HVI500SN lubricating base oils and 1kgMDI is added, stirs 4 minutes, stirs
Mix lower addition 0.12kg ethylenediamines, stir 4 minutes, add 1.08kg octadecylamines, stir 4 minutes, added MDI, ethylenediamine with
The mol ratio of octadecylamine is 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, it is cooled to
160 DEG C, add remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing are obtained into
Product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 2
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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）；Boric acid（2.32kg）；Octadecylamine（1.08kg）；Ethylenediamine
（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 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；Add 16.24kg
Concentration is 14.3 weight % boric acid aqueous solution, stirs 10 minutes, is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation；Under stirring
120 DEG C are warming up to, is kept for 30 minutes, dehydration.
In another volume be 10L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg
HVI500SN lubricating base oils and 1kgMDI, are stirred 4 minutes, and stirring is lower to add 0.12kg ethylenediamines, stirs 4 minutes, adds
1.08kg octadecylamines, are stirred 4 minutes, and added MDI, ethylenediamine and octadecylamine mol ratio are 2:1:2,120 DEG C of 20 points of constant temperature
Clock, obtains four polyureas.
The polyureas of gained four is all squeezed into a upper kettle, stirred, 200 DEG C of constant temperature is finally warming up to 10 minutes.So
Afterwards, 160 DEG C are cooled to, remaining HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing,
Degassing obtains finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
The four polyureas molecular structural formulas contained in component are：
Embodiment 3
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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, 10kg）；Dodecyl
Benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Lauryl amine（0.88kg）；Ethylenediamine（0.14kg）；MDI
（1.18kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 38kg）.
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 10kg 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；Add 2.8kg DBSAs, temperature
Degree control is stirred 10 minutes at 80 DEG C or so；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；Plus
Enter the boric acid aqueous solution that 16.24kg concentration is 14.3 weight %, stir 10 minutes, be warming up to 90 DEG C, constant temperature 60 minutes, material becomes
It is thick；100 DEG C are warming up under stirring, is kept for 60 minutes, dehydration；2kg HVI500SN lubricating base oils and 1.18kgMDI is added,
Stirring 8 minutes, stirring is lower to add 0.14kg ethylenediamines, stirs 8 minutes, adds 0.88kg lauryl amines, stirs 8 minutes, added
MDI, ethylenediamine and lauryl amine mol ratio are 2:1:2,100 DEG C of constant temperature 10 minutes, is finally warming up to 230 DEG C of constant temperature 5 minutes.So
Afterwards, remaining HVI500SN lubricating base oils are added；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 is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 4
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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）；N-butanol
（2.8kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Octadecylamine（1.25kg）；Ethylenediamine（0.14kg）；TDI（0.81kg）；
HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 23kg）.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes
The calcium sulfonate with high base number for being 320mgKOH/g with total base number；Aphthenic acids is replaced with n-butanol simultaneously；MDI is replaced with TDI；And treat
Temperature is cooled to 110 DEG C, and then circulating filtration, homogenizing, degassing obtains finished product；The consumption of each composition is as above.Assay is shown in Table
1。
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 39.6；The weight % of four polyureas 2.6；The weight % of lubricating base oil 57.8.
Embodiment 5
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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, 2.8kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Octadecylamine（1.08kg）；Ethylenediamine
（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 7kg）；It is right, it is right '-two different
Octyl diphenylamine（0.4kg）.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes
The calcium sulfonate with high base number for being 320mgKOH/g with total base number, calcium naphthenate uses the high base number cycloalkanes that total base number is 320mgKOH/g
Sour calcium；And treat that temperature is cooled to 110 DEG C, add 0.4kg pair, right '-di-iso-octyldiphenylamine is stirred 10 minutes, then followed
Ring filtering, homogenizing, degassing obtain finished product；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 59.2；The weight % of four polyureas 3.6；The weight % of lubricating base oil 36.5；It is right, right ' weight of-di-iso-octyldiphenylamine 0.7
Measure %.
Embodiment 6
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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）；Boric acid（2.32kg）；Octadecylamine（3.24kg）；Ethylenediamine
（0.36kg）；MDI（3kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 18.6kg）.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, each composition
Consumption is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.8；The weight % of four polyureas 7.8；The weight % of lubricating base oil 50.4.
Embodiment 7
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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, 25kg）；Cycloalkanes
Acid（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Octadecylamine（1.08kg）；Ethylenediamine
（0.12kg）；MDI（1kg）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO10（100 DEG C of kinematic viscosity are 11mm2/ s, 23kg）；Two is thio
Acidic phosphates zinc（2kg）, molybdenum dialkyldithiocarbamacompositions（1kg）, tungsten disulfide（2kg）, two tungsten selenides（2kg）, it is right,
Right '-di-iso-octyldiphenylamine（0.2kg）.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate
Use the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g；Distinguished using full synthetic oil poly ＆ Alpha ,-olefin oil PAO40 and PAO10
Instead of HVI150BS and HVI500SN；And treat that temperature is cooled to 110 DEG C, add 2kg two thio Acidic phosphates zinc, stirring
10 minutes, 1kg molybdenum dialkyldithiocarbamacompositions are added, are stirred 10 minutes, 2kg tungsten disulfide is added, 10 points are stirred
Clock, adds 2kg two tungsten selenides, stirs 10 minutes, adds 0.2kg pair, and right '-di-iso-octyldiphenylamine is stirred 10 minutes,
Then circulating filtration, homogenizing, degassing obtain finished product；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.3；The weight % of four polyureas 2.4；The weight % of lubricating base oil 51.6；The two thio weight % of Acidic phosphates zinc 2.2；
The weight % of molybdenum dialkyldithiocarbamacompositions 1.1；The weight % of tungsten disulfide 2.1；The weight % of two tungsten selenide 2.1；It is different to p- two pungent
The weight % of base diphenylamines 0.2.
Embodiment 8
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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, 25kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Octadecylamine（1.08kg）；Ethylenediamine
（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 23kg）.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes
The calcium sulfonate with high base number for being 320mgKOH/g with total base number；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 9
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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, 25kg）；Aphthenic acids（Total acid
It is worth for 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Octadecylamine（1.08kg）；Ethylenediamine
（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 23kg）.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes
The calcium sulfonate with high base number for being 320mgKOH/g with total base number, calcium naphthenate uses the high base number cycloalkanes that total base number is 320mgKOH/g
Sour calcium；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 10
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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, 25kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Octadecylamine（1.03kg）；1,6- oneself two
Amine（0.22kg）；MDI（0.95kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 23kg）.
According to embodiment 1 method prepare sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, with 1,6- oneself
Diamines replaces ethylenediamine；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 11
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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, 25kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Octadecylamine（1.03kg）；P-phenylenediamine
（0.21kg）；MDI（0.96kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 23kg）.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes
The calcium sulfonate with high base number for being 320mgKOH/g with total base number, calcium naphthenate uses the high base number cycloalkanes that total base number is 320mgKOH/g
Sour calcium；Ethylenediamine is replaced with p-phenylenediamine；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 12
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea 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, 25kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；N-butanol（1kg）；Acetic acid（0.56kg）；Boric acid（2.32kg）；Octadecylamine（1.08kg）；
Ethylenediamine（0.12kg）；MDI（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 23kg）.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium makes
The calcium sulfonate with high base number for being 360mgKOH/g with total base number, calcium naphthenate uses the high base number cycloalkanes that total base number is 360mgKOH/g
Sour calcium；Transforming agent adds n-butanol, is added after aphthenic acids is added；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 13
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease for illustrating prepared by the present invention.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, by aphthenic acids
Phenol is replaced with, acetic acid is replaced with into butyric acid, boric acid is replaced with into acetone.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 14
The present embodiment is used for the sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease for illustrating prepared by the present invention.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease is prepared according to the method for embodiment 1, unlike, by aphthenic acids
Ketone is replaced with, aqueous acetic acid is replaced with into ether, boric acid aqueous solution is replaced with into ethamine.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 41.5；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Comparative example 1
The polyurea grease of calcium sulfonate with high base number base four is prepared as described in Example 1, unlike, naphthenate with superhigh base number
The overbased sulfoacid calcium that calcium 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 is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 41.5
Measure %；The weight % of four polyureas 2.6；The weight % of lubricating base oil 55.9.
Embodiment 1 and comparative example 1 are compared as can be seen that the polyureas of sulfoacid calcium-Calcium naphthenate base four of the present invention moistens
The difference of the extension work cone penetration of consistent lubricant and work cone penetration is less than calcium sulfonate tetra-polyurea lubricating grease, and it is far small that water drenches number of dropouts
In calcium sulfonate tetra-polyurea lubricating grease, salt spray test is better than calcium sulfonate tetra-polyurea lubricating grease, and water resistant spraying value is less than sulfoacid calcium
The polyurea grease of base four, Stencil oil-dividing value is less than calcium sulfonate tetra-polyurea lubricating grease, and tetra-ball machine test value is more than sulfoacid calcium base four
Polyurea grease, the bearing lubrication life-span is more than calcium sulfonate tetra-polyurea lubricating grease, illustrates sulfoacid calcium-Calcium naphthenate base of the present invention
Mechanical stability, water-resistance and the adhesiveness of four polyurea greases, resistance to saltfog, colloid stability, extreme pressure anti-wear, lubrication longevity
Life is superior to calcium sulfonate tetra-polyurea lubricating grease, and the sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease and sulfoacid calcium of the present invention
The polyurea grease of base four equally has the performances such as excellent anticorrosive property and heat-resisting quantity.
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.
Embodiment 1 and embodiment 2 are compared as can be seen that sulfoacid calcium-Calcium naphthenate base four polyureas in situ prepared
Lubricating grease, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear, and with longer
Lubricating life；Embodiment 1 is compared with embodiment 13 and embodiment 14 respectively as can be seen that transforming agent is selected from dodecane
At least one of base benzene sulfonic acid, aphthenic acids, methanol, butanol, isopropanol, boric acid, acetic acid and water, sulfoacid calcium-cycloalkanes of preparation
The sour polyurea grease of calcium base four, with more preferable mechanical stability, water-resistance and adhesiveness and colloid stability, and with longer
Lubricating life.
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 stretching vibration absworption peak that the peak at place is-NH- in four polyureas molecules.
Sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease of the present invention, not only as calcium sulfonate tetra-polyurea lubricating grease,
With excellent anticorrosive property and heat-resisting quantity, but also with better than calcium sulfonate tetra-polyurea lubricating grease mechanical stability,
The performance such as water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, with longer lubricating life.The present invention
Preparation of greases technique it is simple and environmentally-friendly, 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 (20)
1. a kind of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease, it is characterised in that on the basis of lubricating grease weight, including with
Lower component：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；0.5-30 weight % polyurea compound；10-80 weights
% base oil is measured, wherein, the polyurea compound is four polyurea compounds, and the non-newtonian fluid sulfoacid calcium-calcium naphthenate exists
Infrared spectrum 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；1-20 weight % four 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
What sulfoacid calcium and the conversion of newton body calcium naphthenate were obtained, 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, four polyurea compound has following structure：
Wherein, R1It is alkyl, cycloalkyl or aryl, R2It is alkylidene or arlydene, R3It is arlydene, alkylidene or cycloalkylidene.
5. lubricating grease according to claim 4, wherein, R1Phenyl or substituted phenyl, or carbon number for 8-24 alkyl or
Cycloalkyl；R2It is the alkylidene that phenylene or biphenylene or carbon number are 2-12；R3It is arlydene, alkylidene that carbon number is 6-30
Or cycloalkylidene.
6. lubricating grease according to claim 5, wherein, R1It is the phenyl of phenyl or C1-C3 alkyl or halogen substitution, or carbon
Number is 10-18 alkyl or cycloalkyl, R2It is phenylene or biphenylene, or the alkylidene that carbon number is 2-8；R3It is selected from - and-(CH2)6At least one of-.
7. the preparation method of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease in claim 1-6 described in any one, it is special
Levy and be, this method includes：Non-newtonian fluid sulfoacid calcium-calcium naphthenate, four polyurea compounds and part basis oil is well mixed,
In 180-230 DEG C of constant temperature refining, surplus base oil is added, necessary additive is added, obtains finished product.
8. the preparation method of sulfoacid calcium-calcium naphthenate-based tetrapolyurea lubricating grease in claim 1-6 described in any one, it is special
Levy and be, this method includes：
(1) by the oily Hybrid Heating of newton body sulfoacid calcium, newton body calcium naphthenate and part basis, transforming agent is added, thing is treated in heating
Expect retrogradation, further heat up dehydration；
(2) part basis oil and diisocyanate are added in step (1) products therefrom, diamines is then sequentially added and monoamine enters
Row reaction；
(3) step (2) is reacted into gained mixture and is warming up to 180-230 DEG C of constant temperature refining, added surplus base oil, add necessary
Additive, obtain finished product.
9. preparation method according to claim 8, wherein, in step (1), by newton body sulfoacid calcium, newton body aphthenic acids
The oily Hybrid Heating of calcium, part basis is to 50-80 DEG C, and the transforming agent needed for adding is reacted, after all transforming agents are added,
80-100 DEG C of constant temperature 60-90 minutes, then heats to 100-120 DEG C of dehydration.
10. preparation method according to claim 8, wherein, in step (2), part base is added in the product of step (1)
Plinth oil and diisocyanate, are stirred 2-8 minutes, add diamines, are stirred 2-8 minutes, add monoamine, are stirred 2-8 minutes, two isocyanides
The mol ratio of acid esters, diamines and monoamine is 2:1:2.
11. preparation method according to claim 8, wherein, in step (3), first in 100-120 DEG C of constant temperature 10-20 minutes,
Finally it is warming up to 180-230 DEG C of constant temperature 5-20 minutes；Surplus base oil is added, treats that temperature is cooled to 100-120 DEG C, is added necessary
Additive, stirring, circulating filtration, homogenizing, degassing.
12. preparation method according to claim 8, wherein, the newton body sulfoacid calcium is calcium mahogany sulfonate and/or synthesis
Sulfoacid calcium, the total base number of the newton body sulfoacid calcium is 250-450mgKOH/g；The newton body calcium naphthenate is oil cycloalkanes
Sour calcium and/or synthesis calcium naphthenate, the total base number of the newton body calcium naphthenate is 250-450mgKOH/g.
13. preparation method according to claim 8, wherein, the transforming agent is selected from fatty alcohol, aliphatic acid, aliphatic ketone, fat
Fat aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl
At least one of benzene sulfonic acid and water, the addition of transforming agent are the 2- of newton body sulfoacid calcium and newton body calcium naphthenate gross weight
30%.
14. preparation method according to claim 13, 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.
15. preparation method according to claim 8, wherein, the structural formula of the monoamine is R1-NH2, wherein, R1It is phenyl
Or C1-C3 alkyl or the phenyl of halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.
16. preparation method according to claim 15, wherein, the monoamine is to be 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.
17. preparation method according to claim 8, wherein, the structural formula of the diamines is NH2-R2-NH2, wherein, R2It is
Carbon number is 2-8 alkylidene, or phenylene or biphenylene.
18. preparation method according to claim 17, 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.
19. preparation method according to claim 8, wherein, the structure of the diisocyanate is OCN-R3- NCO, R3It is
Carbon number is 6-30 arlydene, alkylidene or cycloalkylidene.
20. preparation method according to claim 19, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310419096.0A CN104450115B (en) | 2013-09-13 | 2013-09-13 | A kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310419096.0A CN104450115B (en) | 2013-09-13 | 2013-09-13 | A kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104450115A CN104450115A (en) | 2015-03-25 |
| CN104450115B true CN104450115B (en) | 2017-09-29 |
Family
ID=52896874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310419096.0A Active CN104450115B (en) | 2013-09-13 | 2013-09-13 | A kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104450115B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824357A (en) * | 2010-05-27 | 2010-09-08 | 李墨菊 | High-performance complex calcium sulfonate grease and preparation method thereof |
| CN102417855B (en) * | 2010-09-27 | 2013-11-06 | 中国石油化工股份有限公司 | Calcium sulfonate tetra-polyurea lubricating grease and preparation method thereof |
| CN101935578B (en) * | 2010-10-11 | 2012-11-14 | 长沙众城石油化工有限责任公司 | Calcium sulfonate complex grease and preparation method thereof |
| 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 |
-
2013
- 2013-09-13 CN CN201310419096.0A patent/CN104450115B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104450115A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104450109B (en) | A kind of polyurea grease of high base number composite calcium-base four and preparation method thereof | |
| CN104449956B (en) | A kind of high base number composite calcium-base polyurea grease and preparation method thereof | |
| CN104450115B (en) | A kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof | |
| CN106032478B (en) | Lubricant composition and preparation method thereof | |
| CN104450111B (en) | A kind of complex calcium sulfonate calcium naphthenate base grease and preparation method thereof | |
| CN104560318B (en) | A kind of polyurea grease of calcium naphthenate zirconium base six and preparation method thereof | |
| CN104450116B (en) | A kind of sulfoacid calcium calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof | |
| CN104449961B (en) | A kind of sulfoacid calcium calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof | |
| CN104450110B (en) | A kind of sulfoacid calcium Calcium naphthenate base polyurea grease and preparation method thereof | |
| CN108003978A (en) | A kind of 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 | |
| CN104450113B (en) | A kind of high base number composite calcium-base octa-polyurea lubricating grease and preparation method thereof | |
| CN106032480B (en) | Lubricant composition and preparation method thereof | |
| CN104450114B (en) | A kind of complex calcium sulfonate calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof | |
| CN104560320B (en) | A kind of composite calcium naphthenate calcium zirconium base polyurea grease and preparation method thereof | |
| CN104449960B (en) | A kind of complex calcium sulfonate Calcium naphthenate base polyurea grease and preparation method thereof | |
| CN104449958B (en) | A kind of complex calcium sulfonate calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof | |
| CN104449957B (en) | A kind of complex calcium sulfonate calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof | |
| CN104560317B (en) | A kind of complex calcium sulfonate calcium naphthenate zirconium base polyurea grease and preparation method thereof | |
| CN106032484B (en) | Lubricant composition 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 | |
| CN104560270B (en) | A kind of polyurea grease of complex calcium sulfonate calcium naphthenate zirconium base four and preparation method thereof | |
| CN104560272B (en) | A kind of polyurea grease of complex calcium sulfonate calcium naphthenate zirconium base six and preparation method thereof | |
| CN104560316B (en) | A kind of polyurea grease of sulfoacid calcium calcium naphthenate zirconium base four and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |