CN104449956B - A kind of high base number composite calcium-base polyurea grease and preparation method thereof - Google Patents

A kind of high base number composite calcium-base polyurea grease and preparation method thereof Download PDF

Info

Publication number
CN104449956B
CN104449956B CN201310418395.2A CN201310418395A CN104449956B CN 104449956 B CN104449956 B CN 104449956B CN 201310418395 A CN201310418395 A CN 201310418395A CN 104449956 B CN104449956 B CN 104449956B
Authority
CN
China
Prior art keywords
calcium
acid
weight
base
preparation
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
Application number
CN201310418395.2A
Other languages
Chinese (zh)
Other versions
CN104449956A (en
Inventor
孙洪伟
何懿峰
段庆华
张建荣
刘中其
姜靓
陈政
郑会
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201310418395.2A priority Critical patent/CN104449956B/en
Publication of CN104449956A publication Critical patent/CN104449956A/en
Application granted granted Critical
Publication of CN104449956B publication Critical patent/CN104449956B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Lubricants (AREA)

Abstract

The invention discloses a kind of high base number composite calcium-base polyurea 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.The invention also discloses the preparation method of high base number composite calcium-base polyurea grease and its high base number composite calcium-base polyurea grease of preparation.The high base number composite calcium-base polyurea grease of the present invention, with excellent anticorrosive property and heat-resisting quantity, but also with performances such as the water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear for being better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, 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

A kind of high base number composite calcium-base polyurea grease and preparation method thereof
Technical field
The present invention relates to lubricating grease, in particular it relates to a kind of high base number composite calcium-base polyurea grease and preparation method thereof.
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, high base number composite calcium sulfonate base grease has very excellent combination property, 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, the requirement more and more higher with 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.The property of the lubricating grease Can be 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 high base number composite calcium-base polyureas 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.
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 % polyurea compound；20-70 weight % base oil.
Second aspect, should the invention provides the preparation method of high base number composite calcium-base polyurea grease as described above Method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, small molecule inorganic acid and/or lower aliphatic Calcium salt, polyurea compound and the part basis oil of acid are well mixed, and in 180-230 DEG C of constant temperature refining, add surplus base oil, plus Enter necessary additive, obtain finished product.
The third aspect, the invention provides a kind of preparation method of high base number composite calcium-base polyurea grease, this method bag Include：
（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, higher fatty acids, small molecule inorganic acid is added And/or lower fatty acid is reacted, heat up dehydration after reaction；
（3）In step（2）Base oil and monoamine are added in gained mixture, or is additionally added diamines, diisocyanate is added Reacted；
（4）By step（3）Gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds base oil, adds necessary add Plus agent, obtain finished product.
Fourth aspect, the invention provides the high base number composite calcium-base polyurea grease as made from method as described above.
The high base number composite calcium-base polyurea grease of the present invention, not only as Composite calcium-sulfonate-batetrapolyurea polyurea grease, tool There are excellent anticorrosive property and heat-resisting quantity, but also the water-resistance with better than Composite calcium-sulfonate-batetrapolyurea polyurea grease and adhesion The performances such as property, resistance to saltfog, colloid stability, extreme pressure anti-wear, with longer lubricating life.The system of the lubricating grease of the present invention Standby technique 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 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 high base number composite calcium-base polyurea 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, The polyurea compound that isocyanates and amine reaction are produced.
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 polyurea grease, on the basis of lubricating grease weight, bag Include 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.
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 % polyurea compound；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, 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, the polyurea compound can be polyurea compound commonly used in the art, for example may be used without particular/special requirement Think at least one of two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.Wherein dimerization Carbamide compound, four polyurea compounds, six polyurea compounds, the weight ratio of eight polyurea compounds can be arbitrary proportion.More preferably The polyurea compound is two polyurea compounds.
In the present invention, two polyurea compound preferably has following structure：
Wherein, R1、R1' can be the same or different, can be alkyl, cycloalkyl or aryl, the carbon of alkyl or cycloalkyl Number can be 8-24, and preferably 10-18, aryl can be phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen The phenyl of element substitution.
Wherein, R3Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R3More preferably With-(CH2)6At least one of-.
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, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R3More preferably With-(CH2)6At least one of-.
In the present invention, six 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, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R3More preferably With-(CH2)6At least one of-.
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 To be 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 With-(CH2)6At least one of-.
Above-mentioned polyurea compound can be obtained using the thinkable various methods of those skilled in the art institute, for example can be by Prepared according to CN103060069A, CN103060070A, CN103060068A, CN103060067A method 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, should the invention provides the preparation method of high base number composite calcium-base polyurea grease as described above Method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, small molecule inorganic acid and/or lower aliphatic Calcium salt, polyurea compound and the part basis oil of acid are well mixed, and in 180-230 DEG C of constant temperature refining, add surplus base oil, plus Enter necessary additive, obtain 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, polyurea compound, 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 conversion is obtained, for example, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, adding Required transforming agent 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 of dehydrations.
The third aspect, the invention provides a kind of preparation method of high base number composite calcium-base polyurea 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, higher fatty acids, small molecule inorganic acid is added And/or lower fatty acid is reacted, heat up dehydration after reaction；
（3）In step（2）Base oil and monoamine are added in gained mixture, or is additionally added diamines, diisocyanate is added Reacted；
（4）By step（3）Gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds base oil, adds necessary add Plus 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 was reacted, after all transforming agents are added, in 80-100 DEG C of constant temperature 60-90 minutes.
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, at 85-100 DEG C, the suspension of lime or calcium hydroxide is added, higher fatty acids, stirring is added 5-20 minutes, small molecule inorganic acid and/or lower fatty acid are added, is stirred 5-20 minutes, is warming up to 100-120 DEG C, preferably protects 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 excess 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 is that to refer to that lime or calcium hydroxide are formed in water suspended Liquid, the solid content of suspension is preferably 10-60 weight %.
Step（3）In, in step（2）Base oil and monoamine are added in gained mixture, or is additionally added diamines, two are added different Cyanate is reacted, and is in step（2）Polyurea compound is prepared in gained mixture, mixing polyureas can be prepared, also may be used To prepare single two polyurea compound, four polyurea compounds, six polyurea compounds or eight polyurea compounds.
The method of mixing polyureas is prepared without particular/special requirement, can be using the thinkable various sides of those skilled in the art institute Method, it is for instance possible to use United States Patent (USP) US3243372 method.
The method of two 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 monoamine are added in gained mixture, is stirred 2-8 minutes, is added and be dissolved in base Diisocyanate in plinth oil, is stirred 2-8 minutes, and the mol ratio of diisocyanate and monoamine is 1:2.
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（2）Base oil and diisocyanate are added in gained mixture, is stirred, diamines is added, stirs Mix 2-8 minutes, add monoamine, stir 2-8 minutes, the mol ratio of diisocyanate, diamines and monoamine is 2:1:2.
The method of six 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, is stirred, monoamine is added, stirs Mix 2-8 minutes, add diamines, stir 2-8 minute, add diisocyanate, stirring 2-8 minutes, successively two added isocyanides Acid esters, monoamine, the mol ratio of diamines and diisocyanate are 2:2:2:1.
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, is stirred, diamines is added, stirs Mix 2-8 minutes, add diamines again, stir 2-8 minute, add monoamine, stirring 2-8 minutes, successively added diisocyanate, The mol ratio of diamines, diamines and monoamine is 4:2:1:2.
The diisocyanate structure is OCN-R3- NCO, R3Can be carbon number be 6-30, preferably 6-20 arlydene, alkylidene or Cycloalkylidene, be preferably Deng.For example, the diisocyanate can be toluene di-isocyanate(TDI) (TDI), first Base diphenyl diisocyanate (MDI), 1,6- hexylidene diisocyanate (HDI), dicyclohexylmethyl diisocyanate （HMDI）With an xylylene diisocyanate（XDI）At least one of Deng.
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（4）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； Base oil is added, treats that temperature is cooled to 100-120 DEG C, necessary additive, stirring, circulating filtration, homogenizing, degassing is added.
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, is combined present invention also offers the high base number as made from the preparation method that third aspect present invention is provided Calcium base polyurea grease.
Compared with the high base number composite calcium-base polyurea grease as made from the preparation method that second aspect is provided, the third aspect High base number composite calcium-base polyurea grease made from the preparation method of offer has more preferable water-resistance and adhesiveness, colloid stable Property.
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 high base number composite calcium-base polyurea 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（1.5kg）；MDI（0.7kg）；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；80 DEG C are warming up to, Constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10 is added 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 1.5kg ten Eight amine, are stirred 4 minutes, add the 0.7kgMDI being dissolved in 2kg HVI500SN lubricating base oils, are stirred 4 minutes, added The ratio between amount of material of MDI and octadecylamine is 1:2,120 DEG C of constant temperature 20 minutes, is finally warming up to 200 DEG C of constant temperature 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 37.9；The weight % of two 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 polyurea 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（1.5kg）；MDI（0.7kg）；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；80 DEG C are warming up to, Constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10 is added 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.
In another volume be 20L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg HVI500SN lubricating base oils and 1.5kg octadecylamines, stir 4 minutes, add and be dissolved in 2kg HVI500SN lubricating base oils 0.7kg MDI, stir 4 minutes, the ratio between added MDI and the amount of material of octadecylamine be 1:2,120 DEG C of constant temperature 20 minutes, Obtain two polyureas.
The polyureas of gained two 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 37.9；The weight % of two 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 3
The present embodiment is used for the high base number composite calcium-base polyurea 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 （1.31kg）；MDI（0.89kg）；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, is stirred 10 minutes；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, is stirred 10 minutes, under stirring 100 DEG C are warming up to, is kept for 60 minutes, dehydration；2kg HVI500SN lubricating base oils and 1.31kg lauryl amines is added, 8 points are stirred Clock, adds the 0.89kg MDI being dissolved in 2kg HVI500SN lubricating base oils, stirs 8 minutes, added MDI and bay The ratio between amount of material of amine is 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 is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.9；The weight % of two 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 polyurea 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（1.66kg）；TDI（0.54kg）；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 polyurea grease, unlike, sulfoacid calcium uses total alkali It is worth the calcium sulfonate with high base number for 320mgKOH/g；Aphthenic acids is replaced with DBSA simultaneously；MDI is replaced with TDI；It is each into The consumption divided 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 37.9；The weight % of two 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 polyurea 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（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity For 11mm2/ s, 7kg）.
Method according to embodiment 1 prepares high base number composite calcium-base polyurea grease, unlike, sulfoacid calcium uses total alkali It is worth the calcium sulfonate with high base number for 320mgKOH/g, calcium naphthenate uses the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g； Transforming agent is aphthenic acids, boric acid and acetic acid, and its mesoboric acid is added after acetic acid；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 53.8；The weight % of two 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 polyurea 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（4.5kg）；MDI（2.1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ S, 18.6kg）.
Method according to embodiment 1 prepares high base number composite calcium-base polyurea grease, unlike, the consumption of each composition is such as On.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 37.9；The weight % of two 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 polyurea 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（1.5kg）；MDI（0.7kg）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO10（100 DEG C of kinematic viscosity are 11mm2/ s, 9kg）；Two thio Acidic phosphates zinc（2kg）；Molybdenum dialkyldithiocarbamacompositions（1kg）；Tungsten disulfide （2kg）；Two tungsten selenides（2kg）；To p- di-iso-octyldiphenylamine（0.2kg）.
Method according to embodiment 1 prepares high base number composite calcium-base polyurea 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, adds 1kg molybdenum dialkyldithiocarbamacompositions, stirs 10 minutes, adds 2kg tungsten disulfide, stirs 10 minutes, plus Enter 2kg two tungsten selenides, stir 10 minutes, add 0.2kg 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 38.7；The weight % of two 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；To the p- weight % of di-iso-octyldiphenylamine 0.2.
Embodiment 8
The present embodiment is used for the high base number composite calcium-base polyurea 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, 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）；Octadecylamine（0.94kg）；Para-totuidine（0.38kg）；MDI（0.88kg）；HVI500SN lubricating base oils（100℃ Kinematic viscosity is 11mm2/ s, 18kg）.
Method according to embodiment 1 prepares high base number composite calcium-base polyurea grease, unlike, sulfoacid calcium uses total alkali It is worth the calcium sulfonate with high base number for 320mgKOH/g；Monoamine is additionally added para-totuidine, the consumption of each composition is such as in addition to octadecylamine On.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 37.8；The weight % of two 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 polyurea 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（0.84kg）；Lauryl amine（0.58kg）；MDI（0.78kg）；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 polyurea grease, unlike, sulfoacid calcium uses total alkali It is worth the calcium sulfonate with high base number for 320mgKOH/g, calcium naphthenate uses the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g； After adding the stirring of 12- hydroxy stearic acids 10 minutes, boric acid is added, is stirred 10 minutes, phosphoric acid is then added, stirred 10 minutes；It is single Amine is additionally added to lauryl amine in addition to octadecylamine；And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, it is right '-two different pungent Base diphenylamines, is stirred 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The consumption of each composition is as above.Assay It 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 35.9；The weight % of two polyureas 2.4；The weight % of lubricating base oil 51.6；The weight % of 12- hydroxy stearic acids calcium 2.3；Boric acid Calcium weight 2.5%；The weight % of calcium phosphate 5.1；To the p- weight % of di-iso-octyldiphenylamine 0.2.
Embodiment 10
The present embodiment is used for the high base number composite calcium-base polyurea 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, 30kg）；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（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity For 11mm2/ s, 18kg）.
Method according to embodiment 1 prepares high base number composite calcium-base polyurea grease, unlike, add boric acid aqueous solution After stirring 10 minutes, acetic acid is added, is stirred 10 minutes, 120 DEG C are then warming up under agitation, is kept for 30 minutes, dehydration；It is each into The consumption divided 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 36.8；The weight % of two 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 polyurea 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（1.5kg）；MDI（0.7kg）；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（100 DEG C of kinematic viscosity are 31mm2/ s, similarly hereinafter）, stir, heat to 50 DEG C, 10 points of constant temperature Clock；2.8kg aphthenic acids is added, temperature control is stirred 10 minutes at 50 DEG C or so；Add the acetic acid that 2.8kg concentration is 20 weight % The aqueous solution, is stirred 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.
In another volume be 50L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 5kg HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, similarly hereinafter）, 100 DEG C are warming up to, addition solid content is 20 weights % calcium hydroxide suspension 9kg is measured, is stirred 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；Add 9.28kg Concentration is 25 weight % boric acid aqueous solution, stirs 10 minutes, obtains 12- hydroxy stearic acids calcium and line borate.
In the 3rd volume be 20L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg HVI500SN lubricating base oils and 1.5kg octadecylamines, stir 4 minutes, add and be dissolved in 2kg HVI500SN lubricating base oils 0.7kg MDI, stir 4 minutes, the ratio between added MDI and the amount of material of octadecylamine be 1:2,120 DEG C of constant temperature 20 minutes, is obtained To two polyureas.
The 12- hydroxy stearic acids calcium and line borate of gained are all squeezed into first kettle, stirred, stirring is lower to heat up To 120 DEG C, kept for 30 minutes, two polyureas obtained by the 3rd reactor are all squeezed into the kettle, stirred, most by dehydration After be warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, remaining HVI500SN lubricating base oils are added；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 is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.9；The weight % of two 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 polyurea grease for illustrating prepared by the present invention.
Volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add 10kg total base numbers be 350mgKOH/g calcium sulfonate with high base number, 20kg total base numbers is 400mgKOH/g naphthenate with superhigh base number calcium and 25kg100 DEG C Kinematic viscosity is 31mm2/ s HVI150BS lubricating base oils, stirring, heat to 60 DEG C, constant temperature 10 minutes；Add 3kg Aphthenic acids, temperature control is stirred 10 minutes at 60 DEG C or so；The 12.5kg butanol aqueous solution that concentration is 20% is added, 10 points are stirred Clock；In 87 DEG C of constant temperature 70 minutes, material retrogradation.
Volume be 60L and with heating, stirring, circulation, cooling normal-pressure reaction kettle B in add 5kg HVI500SN Lubricating base oil, is warming up to 90 DEG C, adds the calcium hydroxide suspension 28.9kg that solid content is 20 weight %, stirs 10 minutes, plus Enter 2.4kg palmitic acid, stir 10 minutes, add the ethanedioic acid of 4.78kg boric acid, 1kg phosphoric acid and 2kg, stir 10 points Clock, obtains calcium palmitate, line borate, calcium phosphate and ethanedioic acid calcium.
In volume be 20L and with heating, stirring, circulation, the normal-pressure reaction kettle C of cooling in add 5kg100 DEG C of motion viscous Spend for 11mm2/ s HVI500SN lubricating base oils and 1kg MDI rapidly pre-warmings is to 90 DEG C, and quick stirring is lower to add 0.12kg second Diamines, is stirred 4 minutes, is added 1.08kg octadecylamines and is stirred 4 minutes, and added MDI, ethylenediamine and octadecylamine mol ratio are 2: 1:2,120 DEG C of constant temperature 20 minutes, obtains four polyureas.
Volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle D in add 10kg100 DEG C motion Viscosity is 11mm2/ s HVI500SN lubricating base oils and 0.78kg MDI is preheating to 90 DEG C, and quick stirring is lower to add 0.84kg Octadecylamine, is stirred 4 minutes, and quick stirring is lower to add 0.19kg ethylenediamines, stirs 4 minutes, adds 0.39kg MDI, added successively MDI, octadecylamine, ethylenediamine and MDI mol ratio be 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.
Gained calcium palmitate, line borate, calcium phosphate and ethanedioic acid calcium are all squeezed into reactor A, stirred, is stirred Under be warming up to 120 DEG C, kept for 30 minutes, the polyureas of gained four and six polyureas are all squeezed into reactor A, stirred by dehydration, Finally it is warming up to 200 DEG C of constant temperature 5 minutes.Then, 150 DEG C are cooled to, 8kg HVI500SN lubricating base oils are added；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 is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 34.4；The weight % of calcium palmitate 2.7；The weight % of line borate 4.2；The weight % of calcium phosphate 1.6；The weight of ethanedioic acid calcium 2.9 Measure %；The weight % of four polyureas 2.3；The weight % of six polyureas 2.3；The weight % of lubricating base oil 49.6.
Embodiment 13
The present embodiment is used for the high base number composite calcium-base polyurea grease for illustrating prepared by the present invention.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add 20kg total alkalis Naphthenate with superhigh base number calcium that overbased sulfoacid calcium that value is 400mgKOH/g, 10kg total base numbers are 420mgKOH/g and 10kg100 DEG C of kinematic viscosity is 31mm2/ s HVI150BS lubricating base oils, stirring, heat to 50 DEG C, 10 points of constant temperature Clock；2kg DBSAs are added, temperature control is stirred 10 minutes at 50 DEG C or so；1kg methanol is added, 10 points are stirred Clock；The aqueous acetic acid that 2kg concentration is 20 weight % is added, is stirred 10 minutes；In 83 DEG C of constant temperature 80 minutes, material retrogradation.
Volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle B in add 8kg HVI500SN Lubricating base oil, the calcium hydroxide suspension 7.7kg that solid content is 50 weight % is added at 95 DEG C, is stirred 10 minutes, is added 2.4kg laurate, is stirred 10 minutes, adds 7.98kg butyric acid, is stirred 10 minutes, is obtained calcium laurate and calcium butyrate.
Volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle C in add 10kg100 DEG C motion Viscosity is 11mm2/ s HVI500SN lubricating base oils and 1.17kg MDI is preheating to 80 DEG C, and quick stirring is lower to add 0.84kg The mixture of octadecylamine, 0.19kg ethylenediamines, added MDI, monoamine, the mol ratio of diamines are 3:2:2,120 DEG C of 20 points of constant temperature Clock, obtains mixing polyureas.
Gained calcium laurate and calcium butyrate are all squeezed into reactor A, stirred, 110 DEG C, guarantor are warming up under stirring Hold 45 minutes, be dehydrated, gained mixing polyureas is all squeezed into reactor A, stirred, 200 DEG C of 5 points of constant temperature are finally warming up to Clock.Then, 2kg HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing are obtained 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 41.7；The weight % of calcium laurate 3.3；The weight % of calcium butyrate 12.1；The weight % of polyurea compound 5.4；Lubricating base oil 37.5 weight %.
Embodiment 14
The present embodiment is used for the high base number composite calcium-base polyurea grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares high base number composite calcium-base polyurea grease, unlike, aphthenic acids is replaced with Phenol, butyric acid is replaced with by acetic acid.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 37.9；The weight % of two 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 polyurea grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares high base number composite calcium-base polyurea grease, unlike, aphthenic acids is replaced with Ketone, ether is replaced with by aqueous acetic acid.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 37.9；The weight % of two 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 the polyurea grease of high base number composite calcium sulfonate base two, 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 is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 37.9 Measure %；The weight % of two 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.
Embodiment 1 and comparative example 1 are compared and can be seen that high base number composite calcium-base polyurea grease of the invention Water drenches number of dropouts and is much smaller than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and salt spray test is better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, resists Water spray value is less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and Stencil oil-dividing value is much smaller than Composite calcium-sulfonate-batetrapolyurea polyurea grease, four Ball machine test value is more than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and the bearing lubrication life-span is more than Composite calcium-sulfonate-batetrapolyurea polyurea grease, Illustrate the water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure of the high base number composite calcium-base polyurea grease of the present invention Wear resistence, lubricating life are superior to Composite calcium-sulfonate-batetrapolyurea polyurea grease, and the high base number composite calcium-base polyureas lubrication of the present invention Fat has the performances such as excellent anticorrosive property and heat-resisting quantity as Composite calcium-sulfonate-batetrapolyurea polyurea grease.
Embodiment 1 is compared with embodiment 2 and embodiment 11 respectively as can be seen that the high base number in situ prepared is combined Calcium base polyurea grease, with more preferable water-resistance and adhesiveness, colloid stability；By embodiment 1 respectively with embodiment 14 and Embodiment 15 is compared as can be seen that transforming agent is selected from DBSA, aphthenic acids, methanol, butanol, isopropanol, boron At least one of acid, acetic acid and water, the high base number composite calcium-base polyurea grease of preparation, with 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 stretching vibration absworption peak that the peak at place is-NH- in two polyureas molecules.
The high base number composite calcium-base polyurea grease of the present invention, not only as Composite calcium-sulfonate-batetrapolyurea polyurea grease, tool There are excellent anticorrosive property and heat-resisting quantity, but also the water-resistance with better than Composite calcium-sulfonate-batetrapolyurea polyurea grease and adhesion The performances such as property, resistance to saltfog, colloid stability, extreme pressure anti-wear, with longer lubricating life.The system of the lubricating grease of the present invention Standby technique 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 (26)

1. a kind of high base number composite calcium-base polyurea 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, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm-1-886cm-1There is crystal form calcium carbonate in place Characteristic absorption peak.
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 % polyurea compound；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, 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 is 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, the polyurea compound is two polyurea compounds, four polyureas At least one of compound, six polyurea compounds and eight polyurea compounds.
9. lubricating grease according to claim 8, wherein, the polyurea compound is two polyurea compounds, compound tool There is following structure：
Wherein, R1、R1’It is alkyl, cycloalkyl or aryl, R3It is arlydene, alkylidene or cycloalkylidene.
10. lubricating grease according to claim 9, wherein, R1、R1’It is phenyl or substituted phenyl, or carbon number is 8-24's Alkyl or cycloalkyl；R3It is 6-30 arlydene, alkylidene or cycloalkylidene.
11. lubricating grease according to claim 10, wherein, R1、R1’It is the benzene of phenyl, C1-C3 alkyl or halogen substitution Base, or the alkyl or cycloalkyl that carbon number is 10-18, R3It is With-(CH2)6At least one of-.
12. the preparation method of the high base number composite calcium-base polyurea grease in claim 1-11 described in any one, its feature It is, 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, polyurea compound and the part basis oil of lower fatty acid are well mixed, and in 180-230 DEG C of constant temperature refining, add surplus Base oil, adds necessary additive, obtains finished product.
13. the preparation method of the high base number composite calcium-base polyurea grease in claim 1-11 described in any one, its feature It is, 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 monoamine are added in mixture obtained by step (2), or is additionally added diamines, diisocyanate is added and carries out Reaction；
(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, obtains finished product.
14. preparation method according to claim 13, wherein, in step (1), by newton body sulfoacid calcium, newton body cycloalkanes Sour calcium, base oil Hybrid Heating are to 50-80 DEG C, and the transforming agent needed for adding is reacted, after all transforming agents are added, in 80- 100 DEG C of constant temperature 60-90 minutes.
15. preparation method according to claim 13, wherein, in step (2), at 85-100 DEG C, add lime or hydrogen The suspension of calcium oxide, adds higher fatty acids, stirs 5-20 minutes, adds small molecule inorganic acid and/or lower fatty acid, stirs Mix 5-20 minutes, be warming up to 100-120 DEG C of dehydration.
16. preparation method according to claim 13, wherein, in step (3), added in mixture obtained by step (2) Base oil and monoamine, are stirred 2-8 minutes, add diisocyanate, are stirred 2-8 minutes, mole of diisocyanate and monoamine Than for 1:2.
17. preparation method according to claim 13, wherein, in step (4), first in 100-120 DEG C of 10-20 points of constant temperature Clock, is finally warming up to 180-230 DEG C of constant temperature 5-20 minutes；Base oil is added, treats that temperature is cooled to 100-120 DEG C, is added necessary Additive, stirring, circulating filtration, homogenizing, degassing.
18. preparation method according to claim 13, 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.
19. preparation method according to claim 13, 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%.
20. preparation method according to claim 19, 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.
21. preparation method according to claim 13, wherein, the structural formula of the monoamine is R1-NH2、R1’-NH2, wherein, R1、R1’It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.
22. preparation method according to claim 21, 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.
23. preparation method according to claim 13, wherein, the structural formula of the diamines is NH2-R2-NH2, wherein, R2It is Carbon number is 2-8 alkylidene, or phenylene or biphenylene.
24. preparation method according to claim 23, 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.
25. preparation method according to claim 13, wherein, the structure of the diisocyanate is OCN-R3- NCO, R3It is Carbon number is 6-30 arlydene, alkylidene or cycloalkylidene.
26. preparation method according to claim 25, 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.
CN201310418395.2A 2013-09-13 2013-09-13 A kind of high base number composite calcium-base polyurea grease and preparation method thereof Active CN104449956B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310418395.2A CN104449956B (en) 2013-09-13 2013-09-13 A kind of high base number composite calcium-base polyurea grease and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310418395.2A CN104449956B (en) 2013-09-13 2013-09-13 A kind of high base number composite calcium-base polyurea grease and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104449956A CN104449956A (en) 2015-03-25
CN104449956B true CN104449956B (en) 2017-07-25

Family

ID=52896717

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310418395.2A Active CN104449956B (en) 2013-09-13 2013-09-13 A kind of high base number composite calcium-base polyurea grease and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104449956B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233967A (en) * 2018-11-09 2019-01-18 江苏澳润新材料有限公司 A kind of calcium sulfonate grease and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1414076A (en) * 2002-10-09 2003-04-30 燕化集团天津润滑油脂有限公司 High base number composite calcium sulfonate lubricating grease and its preparation method
CN1465560A (en) * 2002-06-28 2004-01-07 中国石油天然气股份有限公司 Process for preparing ultrahigh basicity calcium naphthenate
CN101885677A (en) * 2009-05-14 2010-11-17 中国石油化工股份有限公司 Preparation method for high-alkaline calcium naphthenate
CN102453599A (en) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 Composite calcium-sulfonate-based tetrapolyurea lubricating grease and preparation method thereof
CN102911761A (en) * 2012-10-24 2013-02-06 中国石油化工股份有限公司 High-temperature-resistant extreme pressure type lubricating grease composition and preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1465560A (en) * 2002-06-28 2004-01-07 中国石油天然气股份有限公司 Process for preparing ultrahigh basicity calcium naphthenate
CN1414076A (en) * 2002-10-09 2003-04-30 燕化集团天津润滑油脂有限公司 High base number composite calcium sulfonate lubricating grease and its preparation method
CN101885677A (en) * 2009-05-14 2010-11-17 中国石油化工股份有限公司 Preparation method for high-alkaline calcium naphthenate
CN102453599A (en) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 Composite calcium-sulfonate-based tetrapolyurea lubricating grease and preparation method thereof
CN102911761A (en) * 2012-10-24 2013-02-06 中国石油化工股份有限公司 High-temperature-resistant extreme pressure type lubricating grease composition and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
磺酸钙基脂晶型转化反应机理探讨;张林雅;《润滑与密封》;20060131(第01期);全文 *
高碱性环烷酸钙的合成与性能研究;李玲等;《石油炼制与化工》;20110430(第04期);全文 *

Also Published As

Publication number Publication date
CN104449956A (en) 2015-03-25

Similar Documents

Publication Publication Date Title
CN104449959B (en) A kind of high base number complex calcium lubricating grease and preparation method thereof
CN104449956B (en) A kind of high base number composite calcium-base polyurea grease and preparation method thereof
CN104560318B (en) A kind of polyurea grease of calcium naphthenate zirconium base six and preparation method thereof
CN104450109B (en) A kind of polyurea grease of high base number composite calcium-base four and preparation method thereof
CN108003978A (en) A kind of lubricating grease and preparation method thereof
CN104560320B (en) A kind of composite calcium naphthenate calcium zirconium base polyurea grease and preparation method thereof
CN104560317B (en) A kind of complex calcium sulfonate calcium naphthenate zirconium base polyurea grease and preparation method thereof
CN106032480B (en) Lubricant composition and preparation method thereof
CN104450110B (en) A kind of sulfoacid calcium Calcium naphthenate base polyurea 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
CN104449961B (en) A kind of sulfoacid calcium calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof
CN104449960B (en) A kind of complex calcium sulfonate Calcium naphthenate base polyurea grease and preparation method thereof
CN104560273B (en) A kind of complex calcium sulfonate calcium naphthenate zirconium base octa-polyurea lubricating grease and preparation method thereof
CN106032484B (en) Lubricant composition and preparation method thereof
CN104450116B (en) A kind of sulfoacid calcium calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof
CN104450115B (en) A kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating 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
CN104293452B (en) A kind of Composite calcium naphthenate base polyurea grease and preparation method thereof
CN104450114B (en) A kind of complex calcium sulfonate calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof
CN103571570A (en) Calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof
CN104212611B (en) A kind of Calcium naphthenate base polyurea grease and preparation method thereof
CN104560274B (en) A kind of sulfoacid calcium calcium naphthenate zirconium base polyurea grease and preparation method thereof
CN104212535B (en) A kind of calcium naphthenate base octa-polyurea lubricating grease 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