CN104450114B - A kind of complex calcium sulfonate calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof - Google Patents

A kind of complex calcium sulfonate calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof Download PDF

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CN104450114B
CN104450114B CN201310418904.1A CN201310418904A CN104450114B CN 104450114 B CN104450114 B CN 104450114B CN 201310418904 A CN201310418904 A CN 201310418904A CN 104450114 B CN104450114 B CN 104450114B
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calcium
acid
weight
lubricating grease
naphthenate
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CN104450114A (en
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何懿峰
孙洪伟
段庆华
张建荣
刘中其
姜靓
陈政
郑会
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Beijing General Fine Chemical Technology Development Co ltd
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a kind of complex calcium sulfonate 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;The calcium salt of 1 20 weight % higher fatty acids;The calcium salt of 1 15 weight % aromatic acid;0.5 30 weight % polyurea compound;10 80 weight % base oil;The optionally calcium salt of the small molecule inorganic acid also including 1 15 weight % and/or lower fatty acid, wherein, the polyurea compound is four polyurea compounds.Also disclose the preparation method of complex calcium sulfonate calcium naphthenate-based tetrapolyurea lubricating grease and its complex calcium sulfonate calcium naphthenate-based tetrapolyurea lubricating grease of preparation.The complex calcium sulfonate calcium naphthenate-based tetrapolyurea lubricating grease of the present invention, there is heat-resisting quantity, water-resistance and adhesiveness better than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, colloid stability, there is longer lubricating life.

Description

A kind of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof
Technical field
The present invention relates to lubricating grease, in particular it relates to a kind of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease and its Preparation method.
Background technology
Sulfoacid calcium is used as the detersive and the history of antirust agent existing decades of lubricating oil, is widely used in internal combustion engine lubrication The additive of oil, the development of its technology mainly make its height alkalization, are exactly alkyl benzene sulphonate of the calcium carbonate with surface-active Calcium or alkyl carboxylic acid calcium turn into a kind of colloidal dispersion system to be distributed in flux oil.Calcium sulfonate with high base number according to the mode of production not It is same to be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate.Calcium mahogany sulfonate is to use oleum or SO3Sulfonation mineral lubricating oil produces Accessory substance mahogany acid during white oil, through with Ca (OH)2React, the contour alkalization technology that is carbonated and obtain;Calcium alkylbenzenesulfonate is to use Oleum or SO3The alkylbenzene of sulfonation synthesis, the alkyl benzene sulphonate of generation pass through and Ca (OH)2React, be carbonated contour alkalization skill Art and obtain.
Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusivity, can To be used as the detersive of lubricating oil, the additive of IC engine lubricating oil is widely used in, the development of its technology mainly makes its high-alkali Change, calcium carbonate is exactly turned into a kind of colloidal dispersion system with the naphthenic acid calcium with surface-active to be distributed in flux oil.It is high Base number calcium naphthenate mostly be the acidic components extracted in the distillate obtained from crude distillation, through with Ca (OH)2Reaction, carbonating Contour alkalization technology and obtain, about prepare Patents have CN1465560 etc..
Using calcium sulfonate with high base number be raw material produce lubricating grease, because its have excellent high temperature performance, mechanical stability, Colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, domestic and international profit is caused The extensive concern of consistent lubricant industry, however, although high base number composite calcium sulfonate base grease has very excellent combination property, but The high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, together When, with requirement more and more higher of the people to environmental protection, in calcium sulfonate with high base number production process must through sulfonation process to ring The pollution in border is also increasingly subject to the concern of people.Find a kind of performance it is similar with high base number composite calcium sulfonate base grease but can Mitigating the lubricating grease of above mentioned problem turns into the big problem that people face at present.
The content of the invention
Similar with high base number composite calcium sulfonate base grease it is an object of the invention to provide a kind of performance, cost is low, prepares Simple and environmentally-friendly lubricating grease of technique and preparation method thereof.
The present inventor has found under study for action, on the basis of lubricating grease weight, including following components:10-70 weight % Non-newtonian fluid sulfoacid calcium-calcium naphthenate;The calcium salt of 1-20 weight % higher fatty acids;The calcium salt of 1-15 weight % aromatic acid; 0.5-30 weight % polyurea compound;10-80 weight % base oil;Optionally also including 1-15 weight % small molecule without The calcium salt of machine acid and/or lower fatty acid, wherein, the polyurea compound is four polyurea compounds.The performance of the lubricating grease and High base number composite calcium sulfonate base grease is similar, and cost is low, and preparation technology is simple and environmentally-friendly.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of complex calcium sulfonate-Calcium naphthenate base four Polyurea grease, on the basis of lubricating grease weight, including following components:10-70 weight % non-newtonian fluid sulfoacid calcium-aphthenic acids Calcium;The calcium salt of 1-20 weight % higher fatty acids;The calcium salt of 1-15 weight % aromatic acid;0.5-30 weight % polyurea compound; 10-80 weight % base oil;The optionally calcium of the small molecule inorganic acid also including 1-15 weight % and/or lower fatty acid Salt, 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;The calcium salt of 2-15 weight % higher fatty acids;The calcium salt of 2-10 weight % aromatic acid;1-20 weight % four polyureas Compound;20-70 weight % base oil;Optionally also include 2-10 weight % small molecule inorganic acid and/or lower fatty acid Calcium salt.
Second aspect, the invention provides the system of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease as described above Preparation Method, this method include:Non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, four are gathered Carbamide compound, part basis oil and the small molecule inorganic acid of selectivity and/or the calcium salt of lower fatty acid are well mixed, 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtain finished product.
The third aspect, the invention provides a kind of preparation method of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, This method includes:
(1)By newton body sulfoacid calcium, newton body calcium naphthenate and base oil Hybrid Heating, transforming agent is added, thing is treated in heating Expect retrogradation;
(2)In step(1)Lime or calcium hydroxide are added in products therefrom, adds higher fatty acids, aromatic acid and selection Property small molecule inorganic acid and/or lower fatty acid reacted, after reaction heat up dehydration;
(3)In step(2)Base oil and diisocyanate are added in gained mixture, then sequentially adds diamines and monoamine Reacted;
(4)By step(3)Gained mixture is warming up to 180-230 DEG C of constant temperature refining, cooling, adds base oil, addition must The additive wanted, obtains finished product.
Fourth aspect, the invention provides complex calcium sulfonate-Calcium naphthenate base four as made from method as described above to gather Urea grease.
Complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease of the present invention, not only moisten with the polyureas of Composite calcium-sulfonate-batetrapolyurea four Consistent lubricant is the same, has excellent anticorrosive property and resistance to saltfog, but also have and be better than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four Heat-resisting quantity, water-resistance and adhesiveness, colloid stability, the performance such as extreme pressure anti-wear, there is longer lubricating life.This hair Bright preparation of greases 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 specific embodiment part.
Brief description of the drawings
Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 2.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, this lubricating grease employs stone Oily sulfoacid calcium and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, simultaneously containing compound Calcium thickening agent, isocyanates and four polyurea compounds caused by amine reaction.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, with lubricating grease weight On the basis of, including following components:10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate;1-20 weight % higher fatty acids Calcium salt;The calcium salt of 1-15 weight % aromatic acid;0.5-30 weight % polyurea compound;10-80 weight % base oil;Selection Property also including 1-15 weight % small molecule inorganic acid and/or lower fatty acid calcium salt, 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;The calcium salt of 2-15 weight % higher fatty acids;The calcium salt of 2-10 weight % aromatic acid;1-20 weight % four polyureas Compound;20-70 weight % base oil;Optionally also include 2-10 weight % small molecule inorganic acid and/or lower fatty acid Calcium salt.
In the present invention, " optionally also including " refer to can include can not also include, i.e. small molecule inorganic acid and/ Or the calcium salt of lower fatty acid is optional component, can include in complex calcium sulfonate of the invention-calcium naphthenate base grease should Component, the component can not also be included.
Non-newtonian fluid sulfoacid calcium-the calcium naphthenate is in infrared spectrum 873cm-1-886cm-1There is crystal form calcium carbonate spy in place Levy absworption peak, preferably total base number 250mgKOH/g-450mgKOH/g, 300mgKOH/g-400mgKOH/g.The non newtonian Body sulfoacid calcium-calcium naphthenate is to convert to obtain by transforming agent by newton body sulfoacid calcium and newton body calcium naphthenate.And newton body Contain unformed calcium carbonate in sulfoacid calcium, newton body calcium naphthenate, in infrared spectrum 860cm-1-865cm-1Place occurs unformed Calcium carbonate characteristic absorption peak.The newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g;The newton body calcium naphthenate is oil ring Alkanoic acid calcium and/or synthesis calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g- 400mgKOH/g.The base number of non-newtonian fluid sulfoacid calcium-calcium naphthenate is the base number and newton body calcium naphthenate of newton body sulfoacid calcium Base number weight average value.
In the present invention, higher fatty acids is that carbon number is 8-20, preferably 10-16 straight chain fatty acid or hydroxy fatty acid, example Such as at least one of laurate, palmitic acid, stearic acid, 12- hydroxy stearic acids, eicosyl carboxylic acid, preferably 12- hydroxyls are hard Resin acid.
In the present invention, aromatic acid is the carboxylic acid that at least 1 carboxyl is joined directly together with aromatic ring, and aromatic acid can be substitution or not Substituted aromatic acid, its substituent can be in alkyl or aryl of alkyl, alkenyl, alkynyl, aryl, halo or perhalogeno etc. extremely Few one kind, the molecular weight of aromatic acid are less than or equal to 550.Aromatic acid is preferably binary aromatic acid, for example, unsubstituted or C1- can be selected from In the alkyl-substituted phthalic acids of C5, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid at least It is a kind of.Preferably phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, and methyl substituted biphenyl diformazan At least one of sour, multi-joint phthalic acid etc..
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, R3 is more preferably In It is at least one.
Above-mentioned four polyurea compound can use the thinkable various methods of those skilled in the art institute to obtain, such as can be with It is prepared according to the 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..
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.
Various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the present invention.Its In, the preferred arylamine kind antioxidant of antioxidant, account for 0.01-5%, the preferably 0.1-2.5% of lubricating grease gross weight, can be diphenylamines, At least one of phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease The 0.5-12% of gross weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethyl-ne Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid At least one of calcium and zinc oxide;Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil At least one of barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the system of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease as described above Preparation Method, this method include:Non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, four are gathered Carbamide compound, part basis oil and the small molecule inorganic acid of selectivity and/or the calcium salt of lower fatty acid are well mixed, 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtain finished product.
In the present invention, " selective small molecule inorganic acid and/or the calcium salt of lower fatty acid " refers to prepare composite sulfoacid The raw material of calcium-calcium naphthenate base grease can include the calcium salt of small molecule inorganic acid and/or lower fatty acid, can not also wrap Include the calcium salt of small molecule inorganic acid and/or lower fatty acid, i.e. the calcium salt of small molecule inorganic acid and/or lower fatty acid is Optional raw material or component.
In the present invention, for non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, small point Calcium salt, four polyurea compounds, base oil and the additive of sub- inorganic acid and/or lower fatty acid are as described above, no longer superfluous herein State.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are used Base oil total amount, in the present invention, part basis oil and the weight ratio preferably 1 of surplus base oil:0.1-5.
, can be by newton body sulfoacid calcium and newton body calcium naphthenate by turning for non-newtonian fluid sulfoacid calcium-calcium naphthenate Agent converts to obtain, for example, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, adds Required transforming agent is reacted, and after all transforming agents add, in 80-100 DEG C of constant temperature 60-90 minute, then heats to 100- 120 DEG C of dehydrations.
The third aspect, the invention provides a kind of preparation method of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, Including:
(1)By newton body sulfoacid calcium, newton body calcium naphthenate and base oil Hybrid Heating, transforming agent is added, thing is treated in heating Expect retrogradation;
(2)In step(1)Lime or calcium hydroxide are added in products therefrom, adds higher fatty acids, aromatic acid and selection Property small molecule inorganic acid and/or lower fatty acid reacted, after reaction heat up dehydration;
(3)In step(2)Base oil and diisocyanate are added in gained mixture, then sequentially adds diamines and monoamine Reacted;
(4)By step(3)Gained mixture is warming up to 180-230 DEG C of constant temperature refining, cooling, adds base oil, addition must The additive wanted, obtains finished product.
Step(1)In, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add Required transforming agent is reacted, after all transforming agents add, in 80-100 DEG C of constant temperature 60-90 minute.
In the present invention, for the weight ratio of newton body sulfoacid calcium and newton body calcium naphthenate without particular/special requirement, preferably 1: 0.25-4.Newton body sulfoacid calcium and the gross weight of newton body calcium naphthenate and the weight ratio of part basis oil are preferably 1:0.1-3.
The newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g- 450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g;The newton body calcium naphthenate be petroleum naphthenic acid calcium and/or Calcium naphthenate is synthesized, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.
The transforming agent be preferably selected from fatty alcohol, aliphatic acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, At least one of phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonates and water;It is more excellent Choosing selected from C1-C5 fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine, C1-C5 ether, boric acid, C1-C10 alkyl phosphonic acid, C2-C16 di alkyl phosphonic acid, C6-C20 arylphosphonic acid, C12-C24 At least one of diaryl phosphonic acids, C7-C20 aromatic alcohol, C7-C20 aromatic amine, C8-C20 alkyl benzene sulphonates and water;More At least one further preferably in DBSA, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water Kind.The addition of transforming agent is preferably the 2-30% of newton body sulfoacid calcium and newton body calcium naphthenate gross weight, more preferably newton The 6-22% of body sulfoacid calcium and newton body calcium naphthenate gross weight.
In the present invention, fatty alcohol includes the fatty alcohol of straight chain, side chain and ring-type, aliphatic acid, aliphatic ketone, fatty aldehyde, fat Amine is similarly.
Step(2)In, at 85-100 DEG C, the suspension of lime or calcium hydroxide is added, adds higher fatty acids, stirring 5-20 minutes, aromatic acid and the small molecule inorganic acid and/or lower fatty acid of selectivity are added, 5-20 minutes is stirred, is warming up to 100-120 DEG C, 30-60 minutes are preferably kept to realize dehydration.Wherein, higher fatty acids and aromatic acid, small molecule inorganic acid and/or The addition sequence of lower fatty acid can exchange.
In the present invention, " selective small molecule inorganic acid and/or lower fatty acid " refers to step(2)In can include it is small Molecule inorganic acid and/or lower fatty acid, small molecule inorganic acid and/or lower fatty acid can not also be included, i.e. small molecule without Machine acid and/or lower fatty acid are an optional raw materials.
In the present invention, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid are as it was previously stated, no longer superfluous herein State.
In the present invention, the H of higher fatty acids and the small molecule inorganic acid and/or lower fatty acid of aromatic acid and selectivity+ The amount of total material and the OH contained by the suspension of lime or calcium hydroxide-The amount of total material is equal, and OH- amount also can excessive 1- 10%。
In the present invention, in terms of calcium hydroxide, the addition of the suspension of lime or calcium hydroxide is preferably newton body sulfonic acid The 1-15% of calcium and newton body calcium naphthenate gross weight;With H+Material gauge, higher fatty acids and aromatic acid and selectivity it is small The mol ratio of molecule inorganic acid and/or lower fatty acid is preferably 1:1-10.
In the present invention, the suspension of lime or calcium hydroxide refers to lime or calcium hydroxide formed in water it is suspended Liquid, the solid content of suspension is preferably 10-60 weight %.
Step(3)In, in step(2)Base oil and diisocyanate are added in gained mixture, then sequentially adds two Amine and monoamine are reacted, and are in step(2)Four polyurea compounds are prepared in gained mixture.
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, stirs 2-8 minutes, adds two Amine, 2-8 minutes are stirred, add monoamine, stirred 2-8 minutes, 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 6-20 arlydene, Alkylidene or cycloalkylidene, it is preferably Deng. Such as the diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), 1,6- is sub- Hexyl diisocyanate (HDI), dicyclohexylmethyl diisocyanate(HMDI)With an xylylene diisocyanate(XDI)Deng At least one of.
The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, structural formula R1-NH2、R1’-NH2, R therein1、R1' can To be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, aryl can be phenyl or Substituted phenyl, preferably phenyl or C1-C3 alkyl or the phenyl of halogen substitution.Preferable monoamine can be selected from aniline, m-chloro Aniline, parachloroanilinum, the arylamine of para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, octadecylamine fatty amine.
The diamines can be fatty amine or arylamine, structural formula NH2-R2-NH2, R therein2Can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferable diamines can Be selected from p-phenylenediamine, o-phenylenediamine, 4,4 '-benzidine aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6- oneself The straight-chain fatty amine of diamines.
Step(4)In, first in 100-120 DEG C of constant temperature 10-20 minute, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minute; Base oil is added, treats that temperature is cooled to 100-120 DEG C, adds necessary additive, is stirred, circulating filtration, homogenizing, degassing.
In the present invention, step(1)In base oil used total amount and step(3)In base oil used total amount and step (4)In base oil used total amount weight ratio preferably 1:0.1-5:0.1-5.
Fourth aspect, present invention also offers composite sulfoacid made from the preparation method provided as third aspect present invention Calcium-calcium naphthenate-based tetrapolyurea lubricating grease.
With the preparation method that is provided as second aspect made from complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease phase Than complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease made from the preparation method that the third aspect provides has more preferable machine Tool stability, water-resistance and adhesiveness, colloid stability, and there is longer lubricating life.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the following Examples and Comparative Examples:
Non-newtonian fluid sulfoacid calcium-calcium naphthenate %=(Overbased or calcium sulfonate with high base number raw material weight+overbased or high Base number calcium naphthenate raw material weight+transforming agent gross weight)/ lubricating grease gross weight × 100%.Transforming agent is included in non-newtonian fluid sulphur In the content of sour calcium-calcium naphthenate.
Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd, also may be used To be prepared according to method disclosed in CN101885677A.
Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industries Co., Ltd.
Embodiment 1
The present embodiment is used for the complex calcium sulfonate-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);Methanol(1kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearates Acid(2kg);Terephthalic acid (TPA)(3.5kg);Octadecylamine(1.08kg);Ethylenediamine(0.12kg);MDI(1kg);HVI500SN lubricates Base oil(100 DEG C of kinematic viscosity are 11mm2/ s, 17kg).
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;1kg methanol is added, is stirred 10 minutes;It is water-soluble to add the acetic acid that 2.8kg concentration is 20 weight % Liquid, stir 10 minutes;It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation;100 DEG C are warming up to, addition solid content is 20 weight % Calcium hydroxide suspension 9kg, stir 10 minutes;2kg12- hydroxy stearic acids are added, are stirred 10 minutes;3.5kg is added to benzene Dioctyl phthalate, stir 10 minutes, 120 DEG C are warming up under stirring, kept for 30 minutes, dehydration;Add 2kg HVI500SN lubrication bases Oil and 1kg MDI, quick stirring 4 minutes, quick stirring is lower to add 0.12kg ethylenediamines, stirs 4 minutes, adds 1.08kg 18 Amine, stir 4 minutes, added MDI, ethylenediamine and octadecylamine mol ratio are 2:1:2,120 DEG C of constant temperature 20 minutes, finally heats up To 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, adds remaining HVI500SN lubricating base oils;Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.8;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.8.
Embodiment 2
The present embodiment is used for the complex calcium sulfonate-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);Methanol(1kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearates Acid(2kg);Terephthalic acid (TPA)(3.5kg);Octadecylamine(1.08kg);Ethylenediamine(0.12kg);MDI(1kg);HVI500SN lubricates Base oil(100 DEG C of kinematic viscosity are 11mm2/ s, 17kg).
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;1kg methanol is added, is stirred 10 minutes;It is water-soluble to add the acetic acid that 2.8kg concentration is 20 weight % Liquid, stir 10 minutes;It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation;100 DEG C are warming up to, addition solid content is 20 weight % Calcium hydroxide suspension 9kg, stir 10 minutes;2kg12- hydroxy stearic acids are added, are stirred 10 minutes;3.5kg is added to benzene Dioctyl phthalate, stir 10 minutes, 120 DEG C are warming up under stirring, kept for 30 minutes, dehydration;
Another volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 2kg HVI500SN lubricating base oils and 1kg MDI, are warming up to 120 DEG C, quick stirring 4 minutes, and quick stirring is lower to add 0.12kg second Diamines, stir 4 minutes, add 1.08kg octadecylamines, stir 4 minutes, added MDI, ethylenediamine and octadecylamine mol ratio are 2:1:2,120 DEG C of constant temperature 20 minutes, obtains four polyureas.
The polyureas of gained four is all squeezed into a upper kettle, stirred, is finally warming up to 200 DEG C of constant temperature 10 minutes.So Afterwards, 160 DEG C are cooled to, adds remaining HVI500SN lubricating base oils;Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, Degassing obtains finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.8;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.8.
A small amount of four polyureas is prepared again by the same method of above-mentioned steps 2, uses petroleum ether(60-90 DEG C of boiling point)Washing, is filtered To precipitation, gained precipitation produces four polyurea compounds after drying.
The four polyureas molecular structural formulas contained in component are:
Embodiment 3
The present embodiment is used for the complex calcium sulfonate-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, 20kg);N-butanol (3.8kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);Stearic acid(1.9kg);Phthalic acid(3.5kg);Lauryl amine (0.88kg);Ethylenediamine(0.14kg);MDI(1.18kg);HVI500SN lubricating base oils(100 DEG C of kinematic viscosity are 11mm2/ S, 27kg).
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The overbased calcium alkyl-salicylate 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;3.8kg n-butanols are added, temperature control exists 80 DEG C or so, stir 10 minutes;The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes;90 DEG C are warming up to, Constant temperature 60 minutes, material retrogradation;The calcium hydroxide suspension 9kg that solid content is 20 weight % is added, is stirred 10 minutes;Add 1.9kg stearic acid, stir 10 minutes;3.5kg phthalic acids are added, are stirred 10 minutes, 100 DEG C are warming up under stirring, are kept 60 minutes, dehydration;Add 2kg HVI500SN lubricating base oils and 1.18kg MDI, quick stirring 8 minutes, under quick stirring 0.14kg ethylenediamines are added, are stirred 8 minutes, add 0.88kg lauryl amines, are stirred 8 minutes, added MDI, ethylenediamine and bay The mol ratio of amine is 2:1:2,100 DEG C of constant temperature 10 minutes, is finally warming up to 230 DEG C of constant temperature 5 minutes.Then, add remaining HVI500SN lubricating base oils;Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1。
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.9;The weight % of calcium stearate 2.3;Phthalic acid The weight % of calcium 4.8.
Embodiment 4
The present embodiment is used for the complex calcium sulfonate-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);Dodecyl Benzene sulfonic acid(2.8kg);Methanol(1kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearic acids(2kg);Isophthalic Dioctyl phthalate(3.5kg);Octadecylamine(1.25kg);Ethylenediamine(0.14kg);TDI(0.81kg);HVI500SN lubricating base oils (100 DEG C of kinematic viscosity are 11mm2/ s, 22kg).
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, sulfonic acid Calcium uses the calcium sulfonate with high base number that total base number is 320mgKOH/g;It is different using DBSA, M-phthalic acid, toluene two Cyanate(TDI)Respectively instead of aphthenic acids, terephthalic acid (TPA), MDI;The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.8;The weight % of 12- hydroxy stearic acids calcium 2.4;Isophthalic The weight % of dioctyl phthalate calcium 4.8.
Embodiment 5
The present embodiment is used for the complex calcium sulfonate-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, 1.8kg);Boric acid(1kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearic acids (2kg);2- methyl isophthalic acids, 4- phthalic acids(3.8kg);Octadecylamine(1.08kg);Ethylenediamine(0.12kg);MDI(1kg); HVI500SN lubricating base oils(100 DEG C of kinematic viscosity are 11mm2/ s, 7kg).
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, sulfonic acid Calcium uses the high base number that total base number is 320mgKOH/g using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate Calcium naphthenate;Methanol is replaced with boric acid;With 2- methyl isophthalic acids, 4- phthalic acids replace terephthalic acid (TPA);The dosage of each composition is as above. Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 52.1;The weight % of four polyureas 3.5;The weight % of lubricating base oil 34.4;The weight % of 12- hydroxy stearic acids calcium 3.3;2- first The weight % of base -1,4- phthalic acids calcium 6.7.
Embodiment 6
The present embodiment is used for the complex calcium sulfonate-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);Calcium hydroxide(1.8kg);12- hydroxy stearic acids(2kg);4, 4'- biphenyl dicarboxylic acids(5.1kg);Octadecylamine(3.24kg);Ethylenediamine(0.36kg);MDI(3kg);HVI500SN lubrication bases Oil(100 DEG C of kinematic viscosity are 11mm2/ s, 18.6kg).
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, use 4,4'- biphenyl dicarboxylic acids replace terephthalic acid (TPA);Transforming agent is only aphthenic acids and acetic acid, saves the step of adding methanol;Respectively into The dosage divided is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 36.4;The weight % of four polyureas 7.2;The weight % of lubricating base oil 47.6;The weight % of 12- hydroxy stearic acids calcium 2.3;4, The weight % of 4'- biphenyl dicarboxylic acids calcium 6.5.
Embodiment 7
The present embodiment is used for the complex calcium sulfonate-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, 30kg);Cycloalkanes Acid(Total acid number is 180mgKOH/g, 2.8kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearic acids(2kg); Terephthalic acid (TPA)(3.5kg);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, 9kg);Two thio Acidic phosphates zinc(2kg);Dialkyl dithio amino first Sour molybdenum(1kg);Tungsten disulfide(2kg);Two tungsten selenides(2kg);It is right, right '-di-iso-octyldiphenylamine(0.2kg).
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, cycloalkanes Sour calcium uses the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g;Transforming agent is only aphthenic acids and acetic acid, saves addition first The step of alcohol;HVI150BS and HVI500SN is replaced respectively using full synthetic oil poly & Alpha ,-olefin oil PAO40 and PAO10;And treat Temperature is cooled to 110 DEG C, adds 2kg two thio Acidic phosphates zinc, stirs 10 minutes, adds 1kg dialkyl dithio Carbamic acid molybdenum, stir 10 minutes, add 2kg tungsten disulfide, stir 10 minutes, add 2kg two tungsten selenides, stir 10 points Clock, 0.2kg pair is added, right '-di-iso-octyldiphenylamine, is stirred 10 minutes, then circulating filtration, homogenizing, degassing obtains into Product;The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.8;The weight % of four polyureas 2.5;The weight % of lubricating base oil 44.2;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.9;The two thio weight % of Acidic phosphates zinc 2.3;The weight % of molybdenum dialkyldithiocarbamacompositions 1.1;Two The weight % of tungsten sulfide 2.3;The weight % of two tungsten selenide 2.3;It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 8
The present embodiment is used for the complex calcium sulfonate-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, 15kg);Aphthenic acids(Always Acid number is 180mgKOH/g, 2.8kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearic acids(2kg);To benzene Dioctyl phthalate(3.5kg);Octadecylamine(1.08kg);Ethylenediamine(0.12kg);MDI(1kg);HVI500SN lubricating base oils(100℃ Kinematic viscosity is 11mm2/ s, 33kg).
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, sulfonic acid Calcium uses the calcium sulfonate with high base number that total base number is 320mgKOH/g;Transforming agent is only aphthenic acids and acetic acid, saves and adds methanol Step;The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.1;The weight % of four polyureas 2.4;The weight % of lubricating base oil 53.3;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.8.
Embodiment 9
The present embodiment is used for the complex calcium sulfonate-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, 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);Terephthalic acid (TPA)(7.6kg);Octadecylamine(1.08kg);Ethylenediamine(0.12kg);MDI(1kg);HVI500SN moistens Sliding base 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 complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, sulfonic acid Calcium uses the high base number that total base number is 320mgKOH/g using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate Calcium naphthenate;Transforming agent is only aphthenic acids and acetic acid, saves the step of adding methanol;Add 12- hydroxy stearic acids and stir 10 points Zhong Hou, boric acid is added, stirred 10 minutes, then add terephthalic acid (TPA), stirred 10 minutes;And treat that temperature is cooled to 110 DEG C, 0.2kg pair is added, right '-di-iso-octyldiphenylamine, is stirred 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product;Respectively The dosage of composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 34.2;The weight % of four polyureas 2.2;The weight % of lubricating base oil 49.2;The weight % of 12- hydroxy stearic acids calcium 2.2;Boric acid The weight % of calcium 2.4;The weight % of terephthalic acid (TPA) calcium 9.6;It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 10
The present embodiment is used for the complex calcium sulfonate-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, 15kg);Aphthenic acids (Total acid number is 180mgKOH/g, 2.8kg);Acetic acid(0.56kg);Calcium hydroxide(3kg);12- hydroxy stearic acids(2kg);To benzene Dioctyl phthalate(3.5kg);Acetic acid(2kg);Octadecylamine(1.08kg);Ethylenediamine(0.12kg);MDI(1kg);HVI500SN lubricates base Plinth oil(100 DEG C of kinematic viscosity are 11mm2/ s, 33kg).
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, conversion Agent is only aphthenic acids and acetic acid, saves the step of adding methanol;And after adding terephthalic acid (TPA) stirring 10 minutes, add second Acid, stir 10 minutes, be then warming up to 120 DEG C under agitation, kept for 30 minutes, dehydration;The dosage of each composition is as above.Examine knot Fruit is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 36.0;The weight % of four polyureas 2.4;The weight % of lubricating base oil 51.8;The weight % of 12- hydroxy stearic acids calcium 2.3;To benzene The weight % of dioctyl phthalate calcium 4.7;The weight % of calcium acetate 2.8.
Embodiment 11
The present embodiment is used for the complex calcium sulfonate-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, 30kg);Aphthenic acids(Always Acid number is 180mgKOH/g, 2.8kg);Methanol(1kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearic acids (2kg);Terephthalic acid (TPA)(3.5kg);Para-totuidine(0.61kg);Ethylenediamine(0.17kg);MDI(1.42kg);HVI500SN Lubricating base oil(100 DEG C of kinematic viscosity are 11mm2/ s, 17kg);It is right, right '-di-iso-octyldiphenylamine(0.2kg).
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, sulfonic acid Calcium uses the high base number that total base number is 320mgKOH/g using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate Calcium naphthenate;Octadecylamine is replaced using para-totuidine;And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, it is right '-two different Octyl diphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product;The dosage of each composition is as above.Examine knot Fruit is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.4;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.7;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.8;It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 12
The present embodiment is used for the complex calcium sulfonate-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, 15kg);Detergent alkylate Sulfonic acid(2.8kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearic acids(2kg);Terephthalic acid (TPA) (3.5kg);Octadecylamine(1.03kg);1,6- hexamethylene diamines(0.22kg);MDI(0.95kg);HVI500SN lubricating base oils(100 DEG C kinematic viscosity is 11mm2/ s, 33kg);It is right, right '-di-iso-octyldiphenylamine(0.2kg).
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, sulfonic acid Calcium uses the high base number that total base number is 360mgKOH/g using the calcium sulfonate with high base number that total base number is 360mgKOH/g, calcium naphthenate Calcium naphthenate;Aphthenic acids is replaced using DBSA;Transforming agent is only DBSA and acetic acid, saves addition The step of methanol;Ethylenediamine is replaced using 1,6- hexamethylene diamines;And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, right '- Di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product;The dosage of each composition is as above.Inspection Test and the results are shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.0;The weight % of four polyureas 2.4;The weight % of lubricating base oil 53.2;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.8;It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 13
The present embodiment is used for the complex calcium sulfonate-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);Methanol(1kg);Acetic acid(0.56kg);Calcium hydroxide(1.8kg);12- hydroxy stearates Acid(2kg);Terephthalic acid (TPA)(3.5kg);Octadecylamine(1.08kg);Ethylenediamine(0.12kg);MDI(1kg);HVI500SN lubricates Base oil(100 DEG C of kinematic viscosity are 11mm2/ s, 17kg).
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;1kg methanol is added, is stirred 10 minutes;It is water-soluble to add the acetic acid that 2.8kg concentration is 20 weight % Liquid, stir 10 minutes;It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.
Another volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 5kg HVI500SN lubricating base oils, 100 DEG C are warming up to, add the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10 Minute;2kg12- hydroxy stearic acids are added, are stirred 10 minutes;3.5kg terephthalic acid (TPA)s are added, stirs 10 minutes, obtains 12- hydroxyls Base calcium stearate and terephthalic acid (TPA) calcium.
The 3rd volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 2kg HVI500SN lubricating base oils and 1kg MDI, quick stirring 4 minutes, quick stirring is lower to add 0.12kg ethylenediamines, stirs 6 points Clock, 1.08kg octadecylamines are added, stirred 4 minutes, added MDI, ethylenediamine and octadecylamine mol ratio are 2:1:2,120 DEG C of perseverances Temperature 20 minutes, obtains four polyureas.
The 12- hydroxy stearic acids calcium of gained and terephthalic acid (TPA) calcium are all squeezed into first kettle, stirred, is stirred Under be warming up to 120 DEG C, kept for 30 minutes, dehydration, four polyureas obtained by the 3rd reactor all squeezed into the kettle, stirring is equal It is even, finally it is warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, adds remaining HVI500SN lubricating base oils;Treat Temperature is cooled to 110 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.8;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.8.
Embodiment 14
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, by ring Alkanoic acid replaces with phenol, and acetic acid is replaced with into butyric acid, and methanol is replaced with into acetone.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.8;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.8.
Embodiment 15
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, unlike, by ring Alkanoic acid replaces with ketone, and aqueous acetic acid is replaced with into ether, and methanol is replaced with into ethamine.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be:Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.8;The weight % of 12- hydroxy stearic acids calcium 2.4;To benzene The weight % of dioctyl phthalate calcium 4.8.
Comparative example 1
The polyurea grease of Composite calcium-sulfonate-batetrapolyurea four is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number The overbased sulfoacid calcium that calcium is 400mgKOH/g with total base number replaces, and obtained each performance data of lubricating grease finished product is shown in Table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be:The weight of non-newtonian fluid sulfoacid calcium 37.5 Measure %;The weight % of four polyureas 2.5;The weight % of lubricating base oil 52.8;The weight % of 12- hydroxy stearic acids calcium 2.4;Terephthalic acid (TPA) calcium 4.8 weight %.
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;Steel
Net point oil: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:GB/T269;Corrosion:GB/T7326;Anticorrosion 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;Four
Ball machine is tested:SH/T0202;Ball bearing lubricating life:ASTM D3336.
By embodiment 1 as can be seen that complex calcium sulfonate-Calcium naphthenate base four of the present invention is gathered compared with comparative example 1 The dropping point of urea grease is higher than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, and water leaching number of dropouts is much smaller than the polyureas of Composite calcium-sulfonate-batetrapolyurea four Lubricating grease, Stencil oil-dividing value are much smaller than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, and the bearing lubrication life-span is much larger than complex calcium sulfonate The polyurea grease of base four, illustrate heat-resisting quantity, the water-resistance of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease of the present invention The polyurea grease of Composite calcium-sulfonate-batetrapolyurea four, and the composite sulfoacid of the present invention are superior to adhesiveness, colloid stability, lubricating life Calcium-calcium naphthenate-based tetrapolyurea lubricating grease has excellent anticorrosive property and resisted as the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four The performance such as salt fog.
By embodiment 1 respectively compared with embodiment 2 and embodiment 13 as can be seen that the composite sulfoacid in situ prepared Calcium-calcium naphthenate-based tetrapolyurea lubricating grease, there is more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, and have There is longer lubricating life;By embodiment 1 respectively compared with embodiment 5 and embodiment 6 as can be seen that transforming agent is selected from ten At least one of dialkyl benzene sulfonic acids, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water, the composite sulfoacid of preparation Calcium-calcium naphthenate-based tetrapolyurea lubricating grease, there is more preferable water-resistance and adhesiveness, colloid stability, and there is longer profit The sliding life-span.
It will be seen from figure 1 that lubricating grease prepared by embodiment 2 is in 873cm-1-886cm-1There is crystal form calcium carbonate feature in place Absworption peak.Meanwhile in 3300cm-1-3323cm-1The peak at place is the stretching vibration absworption peak of-NH- in four polyureas molecules.
Complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease of the present invention, not only moisten with the polyureas of Composite calcium-sulfonate-batetrapolyurea four Consistent lubricant is the same, has excellent anticorrosive property and resistance to saltfog, but also have and be better than the polyurea grease of Composite calcium-sulfonate-batetrapolyurea four Heat-resisting quantity, water-resistance and adhesiveness, the performance such as colloid stability, there is longer lubricating life.The lubricating grease of the present invention Preparation technology 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 (26)

  1. A kind of 1. complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease, it is characterised in that 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- The calcium salt of 15 weight % aromatic acid;0.5-30 weight % polyurea compound;10-80 weight % base oil;Optionally also include 1-15 weight % small molecule inorganic acid and/or the calcium salt of lower fatty acid, wherein, the polyurea compound is four polyureas chemical combination Thing, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm-1-886cm-1There is the suction of crystal form calcium carbonate feature in place Receive peak.
  2. 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;The calcium of 2-10 weight % aromatic acid Salt;1-20 weight % four polyurea compounds;20-70 weight % base oil;Optionally also include 2-10 weight % small molecule The calcium salt of inorganic acid and/or lower fatty acid.
  3. 3. lubricating grease according to claim 1 or 2, wherein, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is by newton body Sulfoacid calcium and newton body calcium naphthenate convert what is obtained, and the total base number of the non-newtonian fluid sulfoacid calcium-calcium naphthenate is 250- 450mgKOH/g。
  4. 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. 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. 6. lubricating grease according to claim 1 or 2, wherein, the aromatic acid is substituted or unsubstituted aromatic acid, substituent For alkyl, alkenyl, alkynyl, aryl, halo at least one of alkyl or aryl, the molecular weight of the aromatic acid is less than or equal to 550。
  7. 7. lubricating grease according to claim 6, wherein, the aromatic acid is selected from the alkyl-substituted neighbours of unsubstituted or C1-C5 At least one of phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid.
  8. 8. 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.
  9. 9. lubricating grease according to claim 8, wherein, R1Phenyl or substituted phenyl, or alkyl that carbon number is 8-24 or Cycloalkyl;R2It is the alkylidene of phenylene or biphenylene or carbon number for 2-12;R3It is arlydene, the alkylidene that carbon number is 6-30 Or cycloalkylidene.
  10. 10. lubricating grease according to claim 9, wherein, R1It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or carbon Count the alkyl or cycloalkyl for 10-18, R2It is phenylene or biphenylene, or carbon number is 2-8 alkylidene;R3It is selected fromWithAt least one of.
  11. 11. 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.
  12. 12. lubricating grease according to claim 11, wherein, the small molecule inorganic acid is in boric acid, phosphoric acid, sulfuric acid At least one, the lower fatty acid are selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid.
  13. 13. the preparation side of complex calcium sulfonate-calcium naphthenate-based tetrapolyurea lubricating grease in claim 1-12 described in any one Method, it is characterised in that this method includes:
    (1)By newton body sulfoacid calcium, newton body calcium naphthenate and base oil Hybrid Heating, transforming agent is added, heating treats that material becomes It is thick;
    (2)In step(1)Lime or calcium hydroxide are added in products therefrom, adds higher fatty acids, aromatic acid and selectivity Small molecule inorganic acid and/or lower fatty acid are reacted, and heat up dehydration after reaction;
    (3)In step(2)Base oil and diisocyanate are added in gained mixture, diamines is then sequentially added and monoamine is carried out Reaction;
    (4)By step(3)Gained mixture is warming up to 180-230 DEG C of constant temperature refining, cooling, adds base oil, adds necessary Additive, obtain finished product.
  14. 14. preparation method according to claim 13, wherein, step(1)In, by newton body sulfoacid calcium, newton body cycloalkanes Sour calcium, base oil Hybrid Heating add required transforming agent and reacted, after all transforming agents add, in 80- to 50-80 DEG C 100 DEG C of constant temperature 60-90 minutes.
  15. 15. preparation method according to claim 13, wherein, step(2)In, at 85-100 DEG C, add lime or hydrogen The suspension of calcium oxide, higher fatty acids is added, stir 5-20 minutes, add aromatic acid and the small molecule inorganic acid of selectivity And/or lower fatty acid, 5-20 minutes are stirred, are warming up to 100-120 DEG C of dehydration.
  16. 16. preparation method according to claim 13, wherein, step(3)In, in step(2)Added in gained mixture Base oil and diisocyanate, 2-8 minutes are stirred, add diamines, stir 2-8 minutes, add monoamine, stir 2-8 minutes, two is different The mol ratio of cyanate, diamines and monoamine is 2:1:2.
  17. 17. preparation method according to claim 13, wherein, step(4)In, first in 100-120 DEG C of 10-20 points of constant temperature Clock, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minute;Base oil is added, treats that temperature is cooled to 100-120 DEG C, is added necessary Additive, stirring, circulating filtration, homogenizing, degassing.
  18. 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. 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. 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. 21. preparation method according to claim 13, wherein, the structural formula of the monoamine is R1-NH2, wherein, R1It is benzene The phenyl of base, C1-C3 alkyl or halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.
  22. 22. preparation method according to claim 21, wherein, the monoamine is selected from aniline, m-chloroaniline, parachloroanilinum And/or the arylamine of para-totuidine, and/or the fatty amine selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.
  23. 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. 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. 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. 26. preparation method according to claim 25, wherein, the diisocyanate is selected from toluene di-isocyanate(TDI), two Phenyl methylidene group diisocyanate, 1,6- hexylidene diisocyanates, dicyclohexylmethyl diisocyanate and an xyxylene At least one of diisocyanate.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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