CN106032480B - Lubricant composition and preparation method thereof - Google Patents

Lubricant composition and preparation method thereof Download PDF

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Publication number
CN106032480B
CN106032480B CN201510106344.5A CN201510106344A CN106032480B CN 106032480 B CN106032480 B CN 106032480B CN 201510106344 A CN201510106344 A CN 201510106344A CN 106032480 B CN106032480 B CN 106032480B
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calcium
acid
weight
newtonian fluid
content
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CN106032480A (en
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段庆华
何懿峰
孙洪伟
刘中其
姜靓
郑会
陈政
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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 present invention relates to lubricating grease fields, disclose a kind of lubricant composition, contain base oil and thickening agent, thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium, the calcium salt and polyurea compound of higher fatty acids, also optionally contain non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, one of calcium salt of small molecule inorganic acid and/or lower fatty acid is a variety of, the content of base oil is 10-80 weight %, the content of non-newtonian fluid sulfurized alkylphenol calcium is 10-70 weight %, the content of the calcium salt of higher fatty acids is 1-20 weight %, the content of polyurea compound is 0.5-30 weight %, the content of remaining optional components is respectively 0-70 weight %, 0-70 weight %, 0-70 weight %, 0-70 weight % , 0-15 weight %, 0-15 weight %.Also disclose preparation method.Lubricant composition of the invention has excellent performance.

Description

Lubricant composition and preparation method thereof
Technical field
The present invention relates to a kind of lubricant compositions and preparation method thereof.
Background technique
SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusion Property, it is used as the detersive of lubricating oil, is widely used in modulation medium and high classes I. C. engine oil, is particularly suitable for supercharged diesel engine For oil to reduce the carbon deposit of top land and the additive of marine cylinder oil, technology development mainly makes its height alkalization, be exactly Calcium carbonate, which is distributed in flux oil with the sulfurized alkylphenol calcium with surface-active, becomes a kind of colloidal dispersion system.High base number Sulfurized alkylphenol calcium is that alkyl phenol is reacted with CaO, vulcanized, carbonated contour alkalization technology and obtain, and the correlation in relation to preparation is specially Benefit has CN101423483 etc..
It is that raw material produces lubricating grease using calcium sulfonate with high base number, because it is with excellent antirust and anticorrosive property, from investment Since market, the extensive concern of domestic and international lubricating grease industry is caused, however, although high base number composite calcium sulfonate base grease has Very excellent antirust and anticorrosive property, but hardening is easy in storage process, and its raw materials for production calcium sulfonate with high base number is high Price and complicated preparation process itself cause it not promoted rapidly, meanwhile, the requirement with people to environmental protection is got over Come higher, necessary sulfonation process is also increasingly subject to the concern of people to the pollution of environment in calcium sulfonate with high base number production process. It finds a kind of antirust and anticorrosive property is similar with high base number composite calcium sulfonate base grease but can reduce the lubrication of the above problem Rouge becomes the big problem that people face at present.
Summary of the invention
The object of the present invention is to provide one kind to have good antirust and anticorrosive property, storage good security and its raw material system Standby simple process, lubricating grease of environmental protection and preparation method thereof.
The present inventor has found that sulfurized alkylphenol calcium may hold at high temperature due to containing active sulfur under study for action Elemental sulfur easily is precipitated and generates corrosion, therefore, when as detersive, the antirust and anticorrosive property of sulfurized alkylphenol calcium are far below Sulfoacid calcium, but when sulfurized alkylphenol calcium is prepared lubricating grease as thickening agent, but it can get and high base number composite calcium sulfonate Ji Run Consistent lubricant quite even preferably antirust and anticorrosive property, and storage good security.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of lubricant composition, the lubricating grease Composition contains base oil and thickening agent, and the thickening agent contains the calcium salt of non-newtonian fluid sulfurized alkylphenol calcium, higher fatty acids And polyurea compound, the thickening agent also optionally contain non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid water Poplar acid calcium, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid one of calcium salt or A variety of, on the basis of the weight of the lubricant composition, the content of base oil is 10-80 weight %, and non-newtonian fluid vulcanizes alkane The content of base phenol calcium is 10-70 weight %, and the content of the calcium salt of higher fatty acids is 1-20 weight %, the content of polyurea compound For 0.5-30 weight %, the content of non-newtonian fluid sulfoacid calcium is 0-70 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 Weight %, the content of non-newtonian fluid calcium salicylate are 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, virtue The content of the calcium salt of acid is 0-15 weight %, and the content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is 0-15 weight Measure %.
Preferably, on the basis of the weight of lubricant composition, the content of base oil is 20-70 weight %, non-newtonian fluid The content of sulfurized alkylphenol calcium is 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, polyurea compound Content be 1-20 weight %, the content of non-newtonian fluid sulfoacid calcium is 0-50 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, the content of non-newtonian fluid calcium salicylate are 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight Measure %, the content of the calcium salt of aromatic acid is 2-10 weight %, and the content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is 2- 10 weight %.
Second aspect, the present invention provides the preparation methods of lubricant composition as described above, this method comprises: by thick Agent and part basis oil are uniformly mixed, and refine in 180-230 DEG C of constant temperature, surplus base oil is added, necessary additive is added, Finished product is obtained, the thickening agent contains the calcium salt and polyurea compound of non-newtonian fluid sulfurized alkylphenol calcium, higher fatty acids, described Thickening agent is also optionally containing non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid oil Sour calcium, the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid one of calcium salt or a variety of.
The third aspect, the present invention provides a kind of preparation methods of lubricant composition, this method comprises:
(1) newton body sulfurized alkylphenol calcium, optional newton body and/or non-newtonian fluid sulfoacid calcium, optional ox will be contained Body and/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid calcium salicylate and optional newton body and/ Or high base number material and part basis the oil mixing of non-newtonian fluid calcium oleate, obtain mixture；
(2) reaction of at least partly composite calcium is optionally carried out: addition lime or calcium hydroxide, addition higher fatty acids, Optional aromatic acid, optional small molecule inorganic acid and/or lower fatty acid, are reacted；And/or it optionally carries out at least partly The reaction of polyurea compound: being added part basis oil and monoamine, or be additionally added diamines, and diisocyanate is added and is reacted；
(3) transforming agent is added, heats up to material retrogradation；
(4) reaction of remaining composite calcium is carried out；
(5) heating dehydration；
(6) reaction of remaining polyurea compound is carried out；
(7) 180-230 DEG C of constant temperature refinings are warming up to, surplus base oil is added, necessary additive is added, obtains finished product.
Fourth aspect, the present invention provides the lubricant compositions as made from method as described above.
Lubricant composition of the invention has the antirust quite even more excellent with Composite calcium-sulfonate-batetrapolyurea polyurea grease And anticorrosive property, and there is excellent storage stability, also there is the viscous resistance better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, machine Tool stability, water-resistance, colloid stability, abrasion resistance, extreme pressure anti-wear and lubricating life, and also there is excellent high temperature resistant The performances such as property.The feed preparation process of lubricating grease of the invention is simple and environmentally-friendly, stable product quality.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of lubricant composition, this lubricant composition uses synthesis sulfurized alkylphenol calcium, And optional calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, optional petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, optionally Salicylate calcium, optional natural calcium oleate and/or synthesis calcium oleate be raw material, contain composite calcium thickening agent, different simultaneously The polyurea compound that cyanate and amine reaction generate.
The present invention also provides the preparation methods of foregoing grease composition.
On the one hand, the present invention provides a kind of lubricant composition, lubricant composition contains base oil and thickening agent, thick Agent contains the calcium salt and polyurea compound of non-newtonian fluid sulfurized alkylphenol calcium, higher fatty acids, and thickening agent also optionally contains Non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, aromatic acid calcium salt, small One of calcium salt of molecule inorganic acid and/or lower fatty acid is a variety of, on the basis of the weight of lubricant composition, basis The content of oil is 10-80 weight %, and the content of non-newtonian fluid sulfurized alkylphenol calcium is 10-70 weight %, the calcium of higher fatty acids The content of salt is 1-20 weight %, and the content of polyurea compound is 0.5-30 weight %, and the content of non-newtonian fluid sulfoacid calcium is 0- 70 weight %, the content of non-newtonian fluid calcium naphthenate are 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 weight % is measured, the content of non-newtonian fluid calcium oleate is 0-70 weight %, and the content of the calcium salt of aromatic acid is 0-15 weight %, and small molecule is inorganic The content of the calcium salt of acid and/or lower fatty acid is 0-15 weight %.
Preferably, on the basis of the weight of lubricant composition, the content of base oil is 20-70 weight %, non-newtonian fluid The content of sulfurized alkylphenol calcium is 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, polyurea compound Content be 1-20 weight %, the content of non-newtonian fluid sulfoacid calcium is 0-50 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, the content of non-newtonian fluid calcium salicylate are 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight Measure %, the content of the calcium salt of aromatic acid is 2-10 weight %, and the content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is 2- 10 weight %.
In the present invention, " optionally containing " refers to can be containing the component or without containing the component, that is, non-newtonian fluid Sulfoacid calcium, newton body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule inorganic acid And/or one of calcium salt of lower fatty acid or it is a variety of be optional component, may include in lubricant composition of the invention The component can not also include the component.
Non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid salicylic acid Calcium, non-newtonian fluid calcium oleate or combinations thereof object are in infrared spectrum 873cm-1-886cm-1There is crystal form calcium carbonate characteristic absorption in place Peak.Non-newtonian fluid sulfurized alkylphenol calcium is converted by newton body sulfurized alkylphenol calcium, non-newtonian fluid sulfurized alkylphenol calcium Total base number be 250-450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid sulfoacid calcium is by newton body sulfoacid calcium What conversion obtained, the total base number of non-newtonian fluid sulfoacid calcium is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non newtonian Body calcium naphthenate is converted by newton body calcium naphthenate, and the total base number of non-newtonian fluid calcium naphthenate is 250- 450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid calcium salicylate is converted by newton body calcium salicylate, The total base number of non-newtonian fluid calcium salicylate is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid calcium oleate It is to be converted by newton body calcium oleate, the total base number of non-newtonian fluid calcium oleate is 250-450mgKOH/g, preferably 300- 400mgKOH/g.And newton body sulfurized alkylphenol calcium, newton body sulfoacid calcium, newton body calcium naphthenate, newton body calcium salicylate, ox Contain unformed calcium carbonate in body calcium oleate, in infrared spectrum 860cm-1-865cm-1There is unformed calcium carbonate feature and inhales in place Receive peak.Newton body sulfurized alkylphenol calcium is synthesis sulfurized alkylphenol calcium, total base number 250-450mgKOH/g, preferably 300- 400mgKOH/g；Newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, total base number 250-450mgKOH/g, Preferably 300-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, total base number are 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body calcium salicylate is salicylate calcium, and total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body calcium oleate be natural calcium oleate and/or synthesis calcium oleate, Its total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g.Non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulphur The base number for the high base number material that sour calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate and non-newtonian fluid calcium oleate mix For the weight average value of the base number of each component.
In the present invention, higher fatty acids can be that carbon number is 8-20, preferably the fatty acid of 10-18 or hydroxy fatty acid, Such as can be at least one of lauric acid, palmitinic acid, stearic acid, 12- hydroxy stearic acid, eicosyl carboxylic acid, preferably 12- hydroxy stearic acid.
In the present invention, aromatic acid is the carboxylic acid that at least 1 carboxyl and aromatic ring are connected directly, and aromatic acid can be substituted or not Substituted aromatic acid, substituent group can be in alkyl, alkenyl, alkynyl, aryl, halogenated or perhalogeno alkyl or aryl etc. extremely The molecular weight of few one kind, aromatic acid is preferably smaller than equal to 550.Aromatic acid is preferably binary aromatic acid, for example, can selected from unsubstituted or The alkyl-substituted phthalic acid of C1-C5, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, in multi-joint phthalic acid extremely Few one kind.Preferably phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid and methyl substituted biphenyl two At least one of formic acid, multi-joint phthalic acid etc..
In the present invention, the molecular weight of small molecule inorganic acid or lower fatty acid is less than or equal to 250.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, polyurea compound can be polyurea compound commonly used in the art, for example, polyureas without particular/special requirement The structural formula of compound can be
Wherein, n is preferably 0-3 integer.
Wherein, R1、R4It can be the same or different, can be alkyl, naphthenic base or aryl, the carbon of alkyl or cycloalkyl Number can be 8-24, preferably 10-18, and aryl can be phenyl or substituted phenyl, preferably the alkyl of phenyl or C1-C3 or The phenyl that halogen replaces.
Wherein, R2It can 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, R3It can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R3More preferably In It is at least one.
In the present invention, single polyureas can be used, mixing polyureas also can be used, for example, polyurea compound can be two At least one of polyurea compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds.
Above-mentioned polyurea compound can be obtained using the thinkable various methods of those skilled in the art institute, such as can be by The method preparation recorded according to CN103060069A, CN103060070A, CN103060068A, CN103060067A, US3243372 It obtains.
In the present invention, base oil can be mineral oil, synthetic oil, vegetable oil or their mixture, 100 DEG C of dynamic viscosities For 4-150mm2/ s, preferably 10-60mm2/s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, Fischer-Tropsch Synthetic oil etc..
Various additives can also be contained in lubricant composition of the invention, such as antioxidant, extreme pressure anti-wear additives, antirust agent Etc..Wherein, the preferred arylamine kind antioxidant of antioxidant, accounts for the 0.01-5% of lubricating grease total weight, preferably 0.1-2.5%, can be with It is diphenylamines, phenyl-α-at least one of naphthylamines and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme-pressure anti-wear Agent accounts for the 0.5-12% of lubricating grease total weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl group Carbamic acid molybdenum, two thio dialkyl amido lead formates, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, two sulphur Change molybdenum, polytetrafluoroethylene (PTFE), thiophosphoric acid molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, At least one of fluorographite, calcium carbonate and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease total weight, preferably 0.1- 2%, it can be in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid It is at least one.
Second aspect, the present invention provides the preparation methods of lubricant composition as described above, this method comprises: by thick Agent and part basis oil are uniformly mixed, and refine in 180-230 DEG C of constant temperature, surplus base oil is added, necessary additive is added, Finished product is obtained, thickening agent contains the calcium salt and polyurea compound of non-newtonian fluid sulfurized alkylphenol calcium, higher fatty acids, and thickening agent is also Optionally contain non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, virtue One of the calcium salt or a variety of of the calcium salt of acid, small molecule inorganic acid and/or lower fatty acid.
In the present invention, " optionally containing " is as previously mentioned, details are not described herein.
In the present invention, for non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non- Newton body calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, small molecule inorganic acid and/or low Calcium salt, polyurea compound, base oil and the additive of grade fatty acid are as described above, details are not described herein.
It will be understood by those skilled in the art that the sum of the amount of part basis oil and the amount of surplus base oil are used Base oil total amount, in the present invention, the weight ratio of part basis oil and surplus base oil is preferably 1:0.1-5.
For non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid bigcatkin willow Sour calcium, non-newtonian fluid calcium oleate or combinations thereof object, can be by newton body sulfurized alkylphenol calcium, newton body sulfoacid calcium, newton body ring Alkanoic acid calcium, newton body calcium salicylate, newton body calcium oleate or combinations thereof object pass through transforming agent respectively and convert to obtain, for example, by ox Pause body sulfurized alkylphenol calcium, optional newton body sulfoacid calcium, optional newton body calcium naphthenate, optional newton body salicylic acid Calcium, optional newton body calcium oleate and base oil Hybrid Heating are added required transforming agent and are reacted to 50-80 DEG C, own After transforming agent adds, 80-100 DEG C constant temperature 60-90 minutes, then heat to 110-130 DEG C of dehydration.
In the present invention, " optional " refer to can there is the raw material or no raw material, for example, " optional newton body Sulfoacid calcium ", which refers to, can this raw material of newton body sulfoacid calcium, can also not have this raw material of newton body sulfoacid calcium.
The third aspect, the present invention provides a kind of preparation methods of lubricant composition, this method comprises:
(1) newton body sulfurized alkylphenol calcium, optional newton body and/or non-newtonian fluid sulfoacid calcium, optional ox will be contained Body and/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid calcium salicylate and optional newton body and/ Or high base number material and part basis the oil mixing of non-newtonian fluid calcium oleate, obtain mixture；
(2) reaction of at least partly composite calcium is optionally carried out: addition lime or calcium hydroxide, addition higher fatty acids, Optional aromatic acid, optional small molecule inorganic acid and/or lower fatty acid, are reacted；And/or it optionally carries out at least partly The reaction of polyurea compound: being added part basis oil and monoamine, or be additionally added diamines, and diisocyanate is added and is reacted；
(3) transforming agent is added, heats up to material retrogradation；
(4) reaction of remaining composite calcium is carried out；
(5) heating dehydration；
(6) reaction of remaining polyurea compound is carried out；
(7) 180-230 DEG C of constant temperature refinings are warming up to, surplus base oil is added, necessary additive is added, obtains finished product.
" optional " as previously mentioned, details are not described herein.
In the present invention, newton body sulfurized alkylphenol calcium, newton body sulfoacid calcium, non-newtonian fluid sulfoacid calcium, newton body aphthenic acids Calcium, non-newtonian fluid calcium naphthenate, newton body calcium salicylate, non-newtonian fluid calcium salicylate, newton body calcium oleate, non-newtonian fluid oleic acid Calcium, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid and base oil are as previously mentioned, details are not described herein.
In step (1) of the present invention, " optional newton body and/or non-newtonian fluid sulfoacid calcium " refers to that sulfoacid calcium is optional Component, sulfoacid calcium can be newton body sulfoacid calcium, or non-newtonian fluid sulfoacid calcium.Remaining is same.
In step (1) of the present invention, the weight ratio of high base number material total weight and part basis oil is preferably 1:0.1-3.
In step (2) of the present invention, " optionally carrying out the reaction of at least partly composite calcium " i.e. include three kinds of situations: (i) not Carry out the reaction of composite calcium, that is, the reaction in step (2) without composite calcium only carries out whole composite calciums in step (4) Reaction, converted that is, transforming agent is first added in the method for the present invention, carry out the reaction of composite calcium after conversion again；(ii) into The reaction of row part composite calcium carries out the reaction of part composite calcium in step (2), carry out again in step (4) remaining multiple The reaction for closing calcium carries out part that is, the method for the present invention carries out the reaction of part composite calcium before conversion again in post-conversion The reaction of composite calcium；(iii) reaction for carrying out whole composite calciums, i.e., carry out the reaction of whole composite calciums, no in step (2) It carries out step (4), that is, the method for the present invention first carries out the reaction of composite calcium, then is converted.
In step (2) of the present invention, " optionally carrying out the reaction of at least partly polyurea compound " includes three kinds of situations: (i) without the reaction of polyurea compound, that is, the reaction in step (2) without polyurea compound, only in step (6) into The reaction of the whole polyurea compound of row, is converted that is, transforming agent is first added in the method for the present invention, is carried out again after conversion The reaction of polyurea compound；(ii) reaction for carrying out part polyurea compound, i.e., carry out part polyurea compound in step (2) Reaction, the reaction of remaining polyurea compound is carried out again in step (6), that is, the method for the present invention carry out portion before conversion The reaction for dividing polyurea compound, carries out the reaction of part polyurea compound again in post-conversion；(iii) whole polyurea compounds are carried out Reaction, i.e., the reaction of whole polyurea compounds is carried out in the step (2), without step (6), that is, side of the present invention Method first carries out the reaction of polyurea compound, then is converted.
This field is generally transforming agent to be first added to be converted, then carry out composite calcium and polyureas when preparing lubricating grease The reaction of compound, when such as preparing sulfoacid calcium base polyurea grease.But the present inventor has found under study for action, according to above-mentioned The case where reaction of the progress composite calcium of step (2) (ii) or (iii), and/or the carry out polyureas chemical combination according to above-mentioned steps (2) The case where reaction of object (ii) or (iii), carry out method of the invention, i.e., first carry out the reaction of all or part of composite calcium and/ Or polyurea compound reaction, then converted, it can further improve the performance of lubricating grease obtained.This may be due to elder generation All or part of composite calcium reaction and/or the reaction of polyurea compound are carried out, can preferably be vulcanized the newton body of oily Alkyl phenol calcium is converted into the non-newtonian fluid sulfurized alkylphenol calcium of smectic.It is therefore preferred that being carried out at least partly multiple in step (2) Close the reaction of calcium；And/or carry out the reaction of at least partly polyurea compound.That is, it is preferred that first carrying out all or part of composite calcium It reacts and/or first carries out all or part of polyurea compound reaction, then converted.
In step (2) of the present invention and step (4), when carrying out the reaction of composite calcium, it is preferable that at 85-100 DEG C, be added Higher fatty acids is added in the suspension of lime or calcium hydroxide, stirs 5-20 minutes, and optional aromatic acid, optional small point is added Sub- inorganic acid and/or lower fatty acid stir 5-20 minutes.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, higher fatty acids and optional aromatic acid and optional small molecule inorganic acid and/or lower fatty acid H+OH contained by the amount and lime of total material or the suspension of calcium hydroxide-The amount of total material is equal, OH-Amount can also be excessive 1-10%.
In the present invention, in terms of calcium hydroxide, the additional amount of the suspension of lime or calcium hydroxide is preferably high base number material The 1-15% of total weight；With H+Substance meter, higher fatty acids and optional aromatic acid and optional small molecule inorganic acid and/ Or the molar ratio of lower fatty acid is preferably 1:1-10.
In the present invention, the suspension of lime or calcium hydroxide refers to that lime or calcium hydroxide are formed suspended in water Liquid, the solid content of suspension are preferably 10-60 weight %.
In step (2) of the present invention and step (6), when carrying out the reaction of polyurea compound, single polyureas can be prepared, it can also Polyureas is mixed with preparation.The method of polyurea compound is prepared without particular/special requirement, those skilled in the art can be used commonly each Kind of method, for example, can using CN103060069A, CN103060070A as described above, CN103060068A, The method preparation that CN103060067A, US3243372 are recorded.Preferably, part basis oil, monoamine, optional diamines, two is added After isocyanates, 100-120 DEG C constant temperature 10-30 minutes, wherein monoamine, optional diamines, diisocyanate substance amount Meet following relationship: amount × 2 of amount+diamines substance of the amount of the substance of diisocyanate × 2=monoamine substance, or, two Isocyanates is excessive, excessive amount≤10%.
The structure of the diisocyanate is OCN-R3- NCO, R3Can be carbon number is 6-30, preferably 6-20 arlydene, Alkylidene or cycloalkylidene, preferably Deng. For example, the diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), six it is sub- oneself In group diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI) and xylylene diisocyanate (XDI) etc. At least one.
The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, structural formula R1–NH2、R4–NH2, R therein1、R4It can be with It is alkyl, naphthenic base or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, and aryl can be phenyl or take The phenyl that the phenyl in generation, preferably phenyl or C1-C3 alkyl or halogen replace.Preferred monoamine can be selected from aniline, chlorobenzene The arylamine of amine, parachloroanilinum and/or 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, wherein R2It can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferred diamines can Be selected from p-phenylenediamine, o-phenylenediamine, 4,4 '-benzidines aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6-oneself The straight-chain fatty amine of diamines.
In step (3) of the present invention, it is preferable that at 50-80 DEG C, required transforming agent is added in preferred constant temperature 10-30 minutes It is reacted, is stirred 8-12 minutes after preferably adding every kind of transforming agent, after all transforming agents add, in 80-100 DEG C of constant temperature 60- 90 minutes.
Transforming agent be preferably selected from fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, In carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonate, C16-C24 alkyl phenol and water at least It is a kind of；It is more preferably selected from the fatty alcohol of C1-C5, the fatty acid of C1-C5, the aliphatic ketone of C1-C5, the fatty aldehyde of C1-C5, C1-C5 Fatty amine, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, C6-C20 arylphosphonic acid, The diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate, C16-C22 alkane At least one of base phenol and water；Still more preferably selected from dodecyl benzene sulfonic acid, aphthenic acids, octadecyl phenol, methanol, different At least one of propyl alcohol, butanol, boric acid, acetic acid and water.The additional amount of transforming agent is preferably the 2-of high base number material total weight 30%, more preferably the 6-22% of high base number material total weight.
In the present invention, fatty alcohol includes straight chain, branch and cricoid fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fat Amine is similarly.
In step (5) of the present invention, it is preferable that be warming up to 110-130 DEG C, preferably remain 30-60 minutes to realize dehydration.
In step (7) of the present invention, it is preferable that be warming up to 180-230 DEG C of constant temperature 5-30 minutes；Surplus base oil is added, to Temperature is cooled to 100-120 DEG C, and necessary additive is added, stirring, circulating filtration, homogenizing, degassing.
In the present invention, in step (1) in the total amount of base oil used and step (2) and (6) total amount of base oil used and The weight ratio of the total amount of base oil used is preferably 1:0.1-5:0.1-5 in step (7).
Fourth aspect, the present invention also provides grease compositions made from the preparation method provided as third aspect present invention Object.
Compared with the lubricant composition made from the preparation method provided as second aspect, preparation side that the third aspect provides Lubricant composition made from method has better mechanical stability, water-resistance, colloid stability, abrasion resistance and lubrication longevity Life.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In the following Examples and Comparative Examples:
Non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulfoacid calcium, non-newtonian fluid ring in lubricant composition obtained The total content of alkanoic acid calcium, non-newtonian fluid calcium salicylate and non-newtonian fluid calcium oleate uses non-newtonian fluid sulfurized alkylphenol calcium % table Show, that is,
Non-newtonian fluid sulfurized alkylphenol calcium %=(overbased or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER raw material weight+superelevation alkali Value or calcium sulfonate with high base number raw material weight+overbased or overbased calcium alkyl-salicylate raw material weight+overbased or high base number water Poplar acid calcium raw material weight+overbased or high base number calcium oleate raw material weight+transforming agent total weight)/lubricating grease total weight × 100%.Transforming agent is included in non-newtonian fluid sulfurized alkylphenol calcium %.
Overbased and SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is prepared according to patent CN101423483.
Overbased and calcium sulfonate with high base number is prepared according to the method for patent CN101928239A.
Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd.
Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industry Co., Ltd.
High base number calcium salicylate is prepared according to the method for patent CN1345921.
High base number calcium oleate is prepared according to document (NLGI Spokeman, 2009,73 (2): 1-17) method.
Embodiment 1
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 30kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 30kg)；4-octadecylphenols (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；Octadecylamine (1.5kg)； MDI(0.7kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 17kg).
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfurized alkylphenol calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stirring；95 DEG C are warming up to, The calcium hydroxide suspension 9kg that solid content is 20 weight % is added, stirs 10 minutes；12-hydroxy stearic acid of 2kg, stirring is added 10 minutes；3.5kg terephthalic acid (TPA) is added, stirs 10 minutes；The HVI500SN lubricating base oil of 10kg is added and drops material To 50 DEG C, constant temperature 10 minutes；4-octadecylphenol of 2.8kg is added, temperature is controlled at 50 DEG C, stirred 10 minutes；1kg is added Methanol stirs 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 minutes；80 DEG C are warming up to, perseverance Temperature 90 minutes, material retrogradation；It is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration；The HVI500SN lubrication base of 2kg is added Oil and 1.5kg octadecylamine stir 4 minutes, add the 0.7kg MDI being dissolved in the HVI500SN lubricating base oil of 2kg, stir 4 minutes, the ratio between amount of substance of added MDI and octadecylamine was 1:2,120 DEG C constant temperature 20 minutes, be finally warming up to 200 DEG C of perseverances Temperature 10 minutes.Then, 160 DEG C are cooled to, remaining HVI500SN lubricating base oil is added；110 DEG C are cooled to temperature, circulation Filtering, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.5 weight %；2.5 weight % of polyureas；52.8 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；To benzene two 4.8 weight % of calcium formate.
Embodiment 2
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 30kg)；HVI150BS lubrication base (100 DEG C of kinematic viscosity are 31mm to oil2/ s, 20kg)；4-octadecylphenols (2.6kg)；N-butanol (1.2kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；Stearic acid (1.9kg)；Phthalic acid (3.5kg)；Lauryl amine (1.31kg)；MDI (0.89kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 27kg).
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g and the HVI150BS lubricating base oil of 20kg, stirring；100 DEG C are warming up to, The HVI500SN lubricating base oil and 0.131kg lauryl amine of 0.2kg is added, stirs 8 minutes, adds and be dissolved in 0.4kg's 0.089kg MDI in HVI500SN lubricating base oil is stirred 8 minutes, and the ratio between added MDI and the amount of substance of lauryl amine are 1:2,100 DEG C constant temperature 10 minutes；At 85 DEG C, the calcium hydroxide suspension 0.9kg that solid content is 20 weight %, stirring 10 is added Minute, 0.19kg stearic acid is added, stirs 10 minutes, 0.35kg phthalic acid is added, stirs 10 minutes；At 80 DEG C, constant temperature 10 minutes, 1.2kg n-butanol and 2.6kg4-octadecylphenol is added, temperature is controlled at 80 DEG C, stirred 10 minutes, is added 2.8kg concentration is the aqueous acetic acid of 20 weight %, stirs 10 minutes, is warming up to 90 DEG C, constant temperature 60 minutes, material retrogradation；? At 85 DEG C, the calcium hydroxide suspension 8.1kg that solid content is 20 weight % is added, stirs 10 minutes, 1.71kg stearic acid is added, 3.15kg phthalic acid is added in stirring 10 minutes, stirs 10 minutes；It is warming up to 110 DEG C under stirring, is kept for 60 minutes, dehydration； The HVI500SN lubricating base oil and 1.179kg lauryl amine of 1.8kg is added, stirs 8 minutes, adds and be dissolved in 3.6kg's 0.801kg MDI in HVI500SN lubricating base oil is stirred 8 minutes, and the ratio between added MDI and the amount of substance of lauryl amine are 1:2,100 DEG C constant temperature 10 minutes；Finally being warming up to 230 DEG C, constant temperature for 5 minutes.Then, remaining HVI500SN lubrication base is added Oil；120 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.5 weight %；2.5 weight % of polyureas；52.9 weight % of lubricating base oil；2.3 weight % of calcium stearate；Calcium phthalate 4.8 weight %.
Embodiment 3
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 30kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 25kg)；4-octadecylphenols (1.6kg)；Dodecyl benzene sulfonic acid (1.2kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)；M-phthalic acid (3.5kg)；Octadecylamine (1.66kg)；TDI(0.54kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 22kg)。
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfurized alkylphenol calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 25kg, stirring；It is warming up to 110 DEG C, the HVI500SN lubricating base oil and 1.66kg octadecylamine of 2kg is added, stirs 4 minutes, adds and be dissolved in 2kg's 0.54kg TDI in HVI500SN lubricating base oil is stirred 4 minutes, and the ratio between added TDI and the amount of substance of octadecylamine are 1:2,110 DEG C constant temperature 15 minutes；At 65 DEG C, constant temperature 10 minutes, 4-octadecylphenol of 1.6kg is added, temperature is controlled 65 DEG C, it stirs 10 minutes, 1.2kg dodecyl benzene sulfonic acid is added, stir 10 minutes, 1kg methanol is added, stir 10 minutes, be added 2.8kg concentration is the aqueous acetic acid of 20 weight %, stirs 10 minutes, is warming up to 100 DEG C, constant temperature 70 minutes, material retrogradation；? At 90 DEG C, the calcium hydroxide suspension 9kg that solid content is 20 weight % is added, stirs 10 minutes, 2kg12-hydroxy stearate is added Acid stirs 10 minutes, and 3.5kg M-phthalic acid is added, and stirs 10 minutes；It is warming up to 130 DEG C under stirring, is kept for 30 minutes, takes off Water；It is finally warming up to 180 DEG C of constant temperature 20 minutes, then, is cooled to 160 DEG C, remaining HVI500SN lubricating base oil is added, to Temperature is cooled to 100 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.5 weight %；2.5 weight % of polyureas；52.8 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；Isophthalic two 4.8 weight % of calcium formate.
Embodiment 4
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 20kg)；Calcium sulfonate with high base number is (total Base number is 360mgKOH/g, 10kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 15kg)；4-ten eight Alkylphenol (1.8kg)；Boric acid (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)；It is right Phthalic acid (3.5kg)；Octadecylamine (1.5kg)；MDI(0.7kg)；(100 DEG C of kinematic viscosity are HVI500SN lubricating base oil 11mm2/ s, 7kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfurized alkylphenol calcium is using total base number The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, and increase calcium sulfonate with high base number；Methanol is replaced with boric acid, wherein boric acid exists It is added after acetic acid；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 52.1 weight %；3.5 weight % of polyureas；34.4 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 3.3 weight %；To benzene two 6.7 weight % of calcium formate.
Embodiment 5
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 10kg)；Overbased calcium alkyl-salicylate (total base number 320mgKOH/g, 20kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 25kg)；4– Octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)；4,4'- biphenyl Dioctyl phthalate (5.1kg)；Octadecylamine (4.5kg)；MDI(2.1kg)；(100 DEG C of kinematic viscosity are HVI500SN lubricating base oil 11mm2/ s, 18.6kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, overbased calcium alkyl-salicylate is increased, is used 4,4'- biphenyl dicarboxylic acid replaces terephthalic acid (TPA)；Transforming agent is only 4-octadecylphenols and acetic acid, saves the step that methanol is added Suddenly；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 36.4 weight %；7.2 weight % of polyureas；47.6 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.3 weight %；4,4'– 6.5 weight % of biphenyl dicarboxylic acid calcium.
Embodiment 6
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 15kg)；High base number calcium salicylate (total base number 360mgKOH/g, 15kg)；(100 DEG C of kinematic viscosity are 41mm to the poly- α of full synthetic oil-alkene oil PAO 402/ s, 30kg)；4-octadecylphenols (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)； Terephthalic acid (TPA) (3.5kg)；Octadecylamine (1.5kg)；MDI(0.7kg)；The poly- α of full synthetic oil-alkene oil PAO 10 (100 DEG C of movements Viscosity is 11mm2/ s, 9kg)；Two thio dibutylphosphoric acid zinc (2kg)；Dibutyl dithiocaarbamate molybdenum (1kg)；Curing Tungsten (2kg)；Two tungsten selenides (2kg)；It is right, right '-di-iso-octyldiphenylamine (0.2kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfurized alkylphenol calcium is using total base number The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, and increase high base number calcium salicylate；Transforming agent is only 4-octadecyl benzene Phenol and acetic acid save the step of methanol is added；It is replaced respectively using the poly- α of full synthetic oil-alkene oil PAO 40 and PAO 10 HVI150BS and HVI500SN；And 110 DEG C are cooled to temperature, the two thio dibutylphosphoric acid zinc of 2kg are added, stirs 10 points The dibutyl dithiocaarbamate molybdenum of 1kg is added in clock, stirs 10 minutes, and the tungsten disulfide of 2kg is added, and stirs 10 minutes, adds Enter two tungsten selenides of 2kg, stir 10 minutes, pair of 0.2kg is added, right '-di-iso-octyldiphenylamine is stirred 10 minutes, then followed Ring filtering, homogenizing, degassing obtain finished product；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.8 weight %；2.5 weight % of polyureas；44.2 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；To benzene two 4.9 weight % of calcium formate；Two thio 2.3 weight % of dibutylphosphoric acid zinc；1.1 weight % of dibutyl dithiocaarbamate molybdenum； 2.3 weight % of tungsten disulfide；Two tungsten selenides, 2.3 weight %；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine.
Embodiment 7
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 10kg)；High base number calcium oleate (total base number 320mgKOH/g, 20kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 15kg)；4– Octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)；2-methyl-1, 4-phthalic acids (3.8kg)；Octadecylamine (0.94kg)；Para-totuidine (0.38kg)；MDI(0.88kg)；HVI500SN lubricates base (100 DEG C of kinematic viscosity are 11mm to plinth oil2/ s, 33kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, increase high base number calcium oleate, transforming agent Only 4-octadecylphenols and acetic acid save the step of methanol is added；It is replaced using 2-- 1,4-phthalic acids of methyl to benzene two Formic acid；Monoamine is additionally added para-totuidine other than octadecylamine, and the dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.1 weight %；2.4 weight % of polyureas；53.3 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；2-first 4.8 weight % of base-1,4-phthalic acid calcium.
Embodiment 8
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 8kg)；Non-newtonian fluid high base number sulphur Sour calcium (15kg)；Overbased calcium alkyl-salicylate (total base number 320mgKOH/g, 7kg)；HVI150BS lubricating base oil (100 DEG C of fortune Kinetic viscosity is 31mm2/ s, 20kg)；4-octadecylphenols (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (5.2kg)；12– Hydroxy stearic acid (2kg)；Boric acid (2.32kg)；Terephthalic acid (TPA) (7.6kg)；Octadecylamine (0.84kg)；Lauryl amine (0.58kg)； MDI(0.78kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 28kg)；It is right, right '-diisooctyl two Aniline (0.2kg).
The preparation of non-newtonian fluid calcium sulfonate with high base number: in a volume being 30L and with heating, stirring, circulation, cooling 100 DEG C of kinematic viscosity of calcium sulfonate with high base number and 5kg that 8kg total base number is 350mgKOH/g are added in normal-pressure reaction kettle is 31mm2The HVI150BS lubricating base oil of/s, stirring, heats to 80 DEG C, constant temperature 10 minutes；1.7kg dodecyl is added Benzene sulfonic acid, temperature are controlled at 80 DEG C or so, are stirred 10 minutes；The acetic acid and 4 times of acetic acid weight of aqueous solution of 0.33kg is added, stirs It mixes 10 minutes；85 DEG C are warming up to, constant temperature 90 minutes, it is spare to obtain non-newtonian fluid sulfoacid calcium at smectic for material retrogradation.
Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfurized alkylphenol calcium is using total base number The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, and increase non-newtonian fluid calcium sulfonate with high base number and overbased calcium alkyl-salicylate； Transforming agent is only 4-octadecylphenols and acetic acid, saves the step of methanol is added；12-hydroxy stearic acids are added to stir 10 minutes Afterwards, boric acid is added, stirs 10 minutes, terephthalic acid (TPA) is then added, stirs 10 minutes；Monoamine is additionally added other than octadecylamine Lauryl amine；And 110 DEG C are cooled to temperature, is added pair of 0.2kg, right '-di-iso-octyldiphenylamine stirs 10 minutes, then Circulating filtration, homogenizing, degassing obtain finished product；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 34.2 weight %；2.2 weight % of polyureas；49.2 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.2 weight %；Line borate 2.4 weight %；9.6 weight % of terephthalic acid (TPA) calcium；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine.
Embodiment 9
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 8kg)；Calcium sulfonate with high base number is (total Base number is 320mgKOH/g, 6kg)；Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 6kg)；High base number calcium salicylate (total base number 360mgKOH/g, 5kg)；High base number calcium oleate (total base number 320mgKOH/g, 5kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 15kg)；4-octadecylphenols (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (3kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；Acetic acid (2kg)；Octadecylamine (1.5kg)；MDI (0.7kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 33kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, increase calcium sulfonate with high base number, superelevation alkali It is worth calcium naphthenate, high base number calcium salicylate and high base number calcium oleate, transforming agent is only 4-octadecylphenols and acetic acid, saves and adds The step of entering methanol；And terephthalic acid (TPA) is added, after ten minutes, acetic acid is added in stirring, stirs 10 minutes；The dosage of each ingredient As above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 36.0 weight %；2.4 weight % of polyureas；51.8 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.3 weight %；To benzene two 4.7 weight % of calcium formate；2.8 weight % of calcium acetate.
Embodiment 10
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 30kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 30kg)；4-octadecylphenols (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；Octadecylamine (1.5kg)； MDI(0.7kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 17kg).
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfurized alkylphenol calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stirring；It is warming up to 100 DEG C, the calcium hydroxide suspension 9kg that solid content is 20 weight % is added, stirs 10 minutes；12-hydroxy stearic acid of 2kg is added, Stirring 10 minutes；3.5kg terephthalic acid (TPA) is added, stirs 10 minutes；The HVI500SN lubricating base oil of 10kg is added and makes object Material is down to 50 DEG C, constant temperature 10 minutes；4-octadecylphenol of 2.8kg is added, temperature is controlled at 50 DEG C, stirred 10 minutes；It is added 1kg methanol stirs 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 minutes；80 DEG C are warming up to, Constant temperature 90 minutes, material retrogradation；It is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration.
It in another volume is 30L and with being added 2kg's in heating, stirring, circulation, cooling normal-pressure reaction kettle HVI500SN lubricating base oil and 1.5kg octadecylamine are warming up to 120 DEG C, stir 4 minutes, are added with 2kg HVI500SN lubrication The 0.7kg MDI of base oil dissolution, is stirred 4 minutes, and the molar ratio of added MDI and octadecylamine is 1:2, and 120 DEG C of constant temperature 20 divide Clock obtains polyureas.
Gained polyureas is all squeezed into a upper kettle, is stirred evenly, is finally warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, remaining HVI500SN lubricating base oil is added；110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing Obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.5 weight %；2.5 weight % of polyureas；52.8 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；To benzene two 4.8 weight % of calcium formate.
Embodiment 11
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 30kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 30kg)；4-octadecylphenols (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；Octadecylamine (1.5kg)； MDI(0.7kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 17kg).
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle It is 31mm for 100 DEG C of kinematic viscosity of overbased sulfurized alkylphenol calcium and 30kg of 400mgKOH/g2The HVI150BS of/s lubricates Base oil, stirring, heats to 50 DEG C, constant temperature 10 minutes；4-octadecylphenol of 2.8kg is added, temperature is controlled at 50 DEG C Left and right is stirred 10 minutes；1kg methanol is added, stirs 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs It mixes 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.
It in another volume is 50L and with being added 5kg's in heating, stirring, circulation, cooling normal-pressure reaction kettle HVI500SN lubricating base oil is warming up to 100 DEG C, and the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10 is added Minute；12-hydroxy stearic acid of 2kg is added, stirs 10 minutes；3.5kg terephthalic acid (TPA) is added, stirs 10 minutes, obtains 12- Hydroxy stearic acid calcium and terephthalic acid (TPA) calcium.
It in third volume is 50L and with being added 2kg's in heating, stirring, circulation, cooling normal-pressure reaction kettle HVI500SN lubricating base oil and 1.5kg octadecylamine stir 6 minutes, add and are dissolved with the HVI500SN lubricating base oil of 2kg 0.7kg MDI, stir 6 minutes, 120 DEG C constant temperature 20 minutes, obtain polyureas.
Resulting 12-hydroxy stearic acid calcium and terephthalic acid (TPA) calcium are all squeezed into first kettle, stirred evenly, is stirred Under be warming up to 120 DEG C, kept for 45 minutes, dehydration all squeezes into third reaction kettle resulting polyureas in the kettle, and stirring is It is even, finally it is warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, remaining HVI500SN lubricating base oil is added；To Temperature is cooled to 110 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.5 weight %；2.5 weight % of polyureas；52.8 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；To benzene two 4.8 weight % of calcium formate.
Embodiment 12
The present embodiment is for illustrating lubricant composition prepared by the present invention.
It is 160L in volume and is with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle A (100 DEG C of kinematic viscosity are the HVI150BS lubricating base oil of the overbased sulfurized alkylphenol calcium of 400mgKOH/g and 25kg 31mm2/ s, similarly hereinafter), stirring heats to 60 DEG C, constant temperature 10 minutes；2kg aphthenic acids and 1kg 4-octadecyl benzene is added Phenol, temperature are controlled at 60 DEG C or so, are stirred 10 minutes；The 12.5kg butanol aqueous solution that concentration is 20% is added, stirs 10 minutes； 87 DEG C constant temperature 70 minutes, material retrogradation.
In volume for 10L and with heating, the HVI500SN for stirring, recycling, 5kg being added in the normal-pressure reaction kettle B of cooling (100 DEG C of kinematic viscosity are 11mm to lubricating base oil2/ s, similarly hereinafter), 90 DEG C are warming up to, the hydrogen-oxygen that solid content is 20 weight % is added Change calcium suspension 21kg, stir 10 minutes, be added the palmitinic acid of 2.4kg, stir 10 minutes, be added 4.2kg biphenyl dicarboxylic acid, The phosphoric acid of 1kg and the ethanedioic acid of 2kg stir 10 minutes, obtain calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and ethanedioic acid calcium.
In volume for 10L and with heating, the HVI500SN for stirring, recycling, 5kg being added in the normal-pressure reaction kettle C of cooling Lubricating base oil and 1kg MDI rapidly pre-warming are quickly added with stirring 0.12kg ethylenediamine to 90 DEG C, stir 4 minutes, are added 1.08kg octadecylamine stirs 4 minutes, and the molar ratio of added MDI, ethylenediamine and octadecylamine are 2:1:2, and 120 DEG C of constant temperature 20 divide Clock obtains polyureas I.
It in volume is 20L and with 10kg100 DEG C of movement is added in heating, stirring, circulation, cooling normal-pressure reaction kettle D Viscosity is 11mm2The HVI500SN lubricating base oil and 0.78kg MDI of/s is preheating to 90 DEG C, is quickly added with stirring 0.84kg Octadecylamine stirs 4 minutes, is quickly added with stirring 0.19kg ethylenediamine, stirs 4 minutes, and 0.39kg MDI is added, successively added MDI, octadecylamine, ethylenediamine and MDI molar ratio be 2:2:2:1,120 DEG C constant temperature 20 minutes, obtain polyureas II.
Gained calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and ethanedioic acid calcium are all squeezed into reaction kettle A, stirring is equal It is even, it is warming up to 120 DEG C under stirring, is kept for 30 minutes, gained polyureas I and polyureas II are all squeezed into reaction kettle A, stirred by dehydration It mixes uniformly, being finally warming up to 200 DEG C, constant temperature for 5 minutes.Then, 150 DEG C are cooled to, the HVI500SN lubricating base oil of 8kg is added； 110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 34.4 weight %；2.7 weight % of calcium palmitate；4.2 weight % of biphenyl dicarboxylic acid calcium；1.6 weight % of calcium phosphate；Ethanedioic acid calcium 2.9 weight %；4.6 weight % of polyureas；49.6 weight % of lubricating base oil.
Embodiment 13
The present embodiment is for illustrating lubricant composition prepared by the present invention.
It in a volume is 160L and with 30kg total alkali is added in heating, stirring, circulation, cooling normal-pressure reaction kettle A Value is the overbased sulfurized alkylphenol calcium of 420mgKOH/g and the HVI150BS lubricating base oil of 10kg, stirring, heat temperature raising To 50 DEG C, constant temperature 10 minutes；2kg dodecyl benzene sulfonic acid is added, temperature is controlled at 50 DEG C or so, stirred 10 minutes；1kg is added Methanol stirs 10 minutes；The aqueous acetic acid that 2kg concentration is 20 weight % is added, stirs 10 minutes；Divide in 83 DEG C of constant temperature 80 Clock, material retrogradation.
In volume for 10L and with heating, the HVI500SN for stirring, recycling, 8kg being added in the normal-pressure reaction kettle B of cooling The calcium hydroxide suspension 8.0kg that solid content is 50 weight % is added at 85 DEG C, stirs 10 minutes, is added for lubricating base oil The lauric acid of 2.4kg stirs 10 minutes, and the M-phthalic acid of 7.9kg is added, and stirs 10 minutes, obtains calcium laurate and isophthalic Dioctyl phthalate calcium.
In volume for 20L and with heating, the HVI500SN for stirring, recycling, 10kg being added in the normal-pressure reaction kettle C of cooling Lubricating base oil and 1.17kg MDI are preheating to 80 DEG C, be quickly added with stirring 0.84kg octadecylamine, 0.19kg ethylenediamine it is mixed Close object, added MDI, monoamine, diamines molar ratio be 3:2:2,120 DEG C constant temperature 20 minutes, obtain polyureas.
Gained calcium laurate and M-phthalic acid calcium are all squeezed into reaction kettle A, stirred evenly, is warming up under stirring It 110 DEG C, is kept for 45 minutes, gained polyureas is all squeezed into reaction kettle A, stirred evenly, is finally warming up to 200 DEG C of perseverances by dehydration Temperature 5 minutes.Then, the HVI500SN lubricating base oil of 2kg is added；110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing Obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 41.7 weight %；3.3 weight % of calcium laurate；12.1 weight % of M-phthalic acid calcium；5.4 weight % of polyureas；Lubricating base oil 37.5 weight %.
Embodiment 14
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 30kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 30kg)；4-octadecylphenols (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12-hydroxy stearic acids (2kg)；Terephthalic acid (TPA) (3.5kg)；Octadecylamine (1.5kg)； MDI(0.7kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 17kg).
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfurized alkylphenol calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stirring；50 DEG C are warming up to, Constant temperature 10 minutes；4-octadecylphenol of 2.8kg is added, temperature is controlled at 50 DEG C, stirred 10 minutes；1kg methanol is added, stirs It mixes 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 minutes；80 DEG C are warming up to, constant temperature 90 divides Clock, material retrogradation；100 DEG C are warming up to, the calcium hydroxide suspension 9kg that solid content is 20 weight % is added, stirs 10 minutes, adds Enter 12-hydroxy stearic acid of 2kg, stir 10 minutes, 3.5kg terephthalic acid (TPA) is added, stirs 10 minutes；120 are warming up under stirring DEG C, it is kept for 45 minutes, dehydration；The HVI500SN lubricating base oil and 1.5kg octadecylamine of 2kg is added, stirs 4 minutes, adds The 0.7kg MDI being dissolved in the HVI500SN lubricating base oil of 2kg is stirred 4 minutes, the substance of added MDI and octadecylamine Amount the ratio between be 1:2,120 DEG C constant temperature 20 minutes, be finally warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, is added surplus Remaining HVI500SN lubricating base oil；110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection result It is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.5 weight %；2.5 weight % of polyureas；52.8 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；To benzene two 4.8 weight % of calcium formate.
Embodiment 15
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Lubricant composition is prepared according to the method for embodiment 1, unlike, 4-octadecylphenols are replaced with 18 Amine, replaces with ethylene glycol monobutyl ether for acetic acid, and methanol is replaced with methyl ethyl ketone.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 37.5 weight %；2.5 weight % of polyureas；52.8 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；To benzene two 4.8 weight % of calcium formate.
Comparative example 1
Lubricant composition is prepared according to the method for embodiment 1, unlike, overbased sulfurized alkylphenol calcium total alkali Value is replaced by the overbased sulfoacid calcium of 400mgKOH/g, 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, composition are as follows: 37.5 weight of non-newtonian fluid sulfoacid calcium Measure %；2.5 weight % of polyureas；52.8 weight % of lubricating base oil；12-hydroxy stearic acid calcium, 2.4 weight %；Terephthalic acid (TPA) calcium 4.8 weight %.
Each lubricating grease properties of sample data of table 1
Each indication test method: dropping point: GB/T 3498；Work cone penetration and extension work cone penetration: GB/T 269；It is rotten Erosion: GB/T 7326；Anticorrosive property: GB/T 5018；Water drenches number of dropouts: SH/T 0109；Salt spray test: SH/T 0081；Water resistant It is spraying: SH/T0643；Stencil oil-dividing: SH/T 0324；Surface hardened layer value: 0370 appendix A of SH/T；Coefficient of friction: SH/T 0721；Tetra-ball machine test: SH/T 0202；The bearing lubrication service life: ASTM D 3336.
Each lubricating grease properties of sample data of 1 (Continued) of table
Each indication test method: dropping point: GB/T 3498；Work cone penetration and extension work cone penetration: GB/T 269；It is rotten Erosion: GB/T 7326；Anticorrosive property: GB/T 5018；Water drenches number of dropouts: SH/T 0109；Salt spray test: SH/T 0081；Water resistant It is spraying: SH/T0643；Stencil oil-dividing: SH/T 0324；Surface hardened layer value: 0370 appendix A of SH/T；Coefficient of friction: SH/T 0721；Tetra-ball machine test: SH/T 0202；The bearing lubrication service life: ASTM D 3336.
It will be understood by those skilled in the art that work cone penetration is smaller, grease thickening performance is better；Extend work The difference for making cone penetration and the cone penetration that works is smaller, and the mechanical stability of lubricating grease can be better；Water leaching number of dropouts is smaller, lubricating grease Water-resistance it is better；Salt spray test higher grade, and the antirust and anticorrosive property of lubricating grease are better；Water resistant is worth smaller, lubrication by spraying The adhesiveness and water-resistance of rouge are better；Stencil oil-dividing value is smaller, and the colloid stability of lubricating grease is better；Surface hardened layer value it is absolute It is worth smaller, the storage stability of lubricating grease is better；Coefficient of friction is smaller, and the abrasion resistance of lubricating grease is better；PB, PD value are bigger, The extreme pressure anti-wear of lubricating grease is better.
Embodiment 1 and comparative example 1 are compared to antirust and anticorrosion as can be seen that lubricant composition of the invention Property, storage stability be substantially better than Composite calcium-sulfonate-batetrapolyurea polyurea grease.It is better than moreover, lubricant composition of the invention has The viscous resistance of Composite calcium-sulfonate-batetrapolyurea polyurea grease, mechanical stability, water-resistance, colloid stability, abrasion resistance, extreme-pressure anti-wear Property and lubricating life.Moreover, lubricant composition of the invention also has excellent heat-resisting quantity.
Embodiment 1 is compared with embodiment 10 and embodiment 11 to the lubricating grease group as can be seen that being prepared in situ respectively Object is closed, there is better mechanical stability, water-resistance, colloid stability, abrasion resistance and lubricating life；By embodiment 1 and in fact Apply example 11, embodiment 14 is compared as can be seen that first carry out the reaction of composite calcium and/or polyurea compound, then converted, Lubricant composition obtained has better viscous resistance, mechanical stability, water-resistance, colloid stability, abrasion resistance and profit The sliding service life；Embodiment 1 and embodiment 15 are compared as can be seen that transforming agent is selected from dodecyl benzene sulfonic acid, aphthenic acids, ten At least one of eight alkyl phenols, methanol, isopropanol, butanol, boric acid, acetic acid and water, the lubricant composition of preparation have more Good viscous resistance, mechanical stability, water-resistance, colloid stability, abrasion resistance, extreme pressure anti-wear and lubricating life.
Lubricant composition of the invention has the antirust quite even more excellent with Composite calcium-sulfonate-batetrapolyurea polyurea grease And anticorrosive property, and there is excellent storage stability, also there is the viscous resistance better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, machine Tool stability, water-resistance, colloid stability, abrasion resistance, extreme pressure anti-wear and lubricating life, and also there is excellent high temperature resistant The performances such as property.The feed preparation process of lubricating grease of the invention is simple and environmentally-friendly, stable product quality.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
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 also be regarded as the disclosure of the present invention.

Claims (33)

1. a kind of lubricant composition, the lubricant composition contains base oil and thickening agent, which is characterized in that the thickening Agent contains the calcium salt and polyurea compound of non-newtonian fluid sulfurized alkylphenol calcium, higher fatty acids, and the thickening agent also optionally contains Have non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, aromatic acid calcium salt, One of calcium salt of small molecule inorganic acid and/or lower fatty acid is a variety of, using the weight of the lubricant composition as base Standard, the content of base oil are 10-80 weight %, and the content of non-newtonian fluid sulfurized alkylphenol calcium is 10-70 weight %, higher aliphatic The content of the calcium salt of acid is 1-20 weight %, and the content of polyurea compound is 0.5-30 weight %, and non-newtonian fluid sulfoacid calcium contains Amount is 0-70 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0- 70 weight %, the content of non-newtonian fluid calcium oleate are 0-70 weight %, and the content of the calcium salt of aromatic acid is 0-15 weight %, small molecule The content of the calcium salt of inorganic acid and/or lower fatty acid is 0-15 weight %.
2. lubricant composition according to claim 1, wherein on the basis of the weight of lubricant composition, base oil Content be 20-70 weight %, the content of non-newtonian fluid sulfurized alkylphenol calcium is 20-65 weight %, the calcium salt of higher fatty acids Content be 2-15 weight %, the content of polyurea compound is 1-20 weight %, and the content of non-newtonian fluid sulfoacid calcium is that 0-50 is weighed % is measured, the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, and the content of non-newtonian fluid calcium salicylate is 0-50 weight %, non- The content of newton body calcium oleate is 0-50 weight %, and the content of the calcium salt of aromatic acid is 2-10 weight %, small molecule inorganic acid and/or The content of the calcium salt of lower fatty acid is 2-10 weight %.
3. lubricant composition according to claim 1 or 2, wherein the non-newtonian fluid sulfurized alkylphenol calcium is by ox Pause what body sulfurized alkylphenol calcium converted, the total base number of the non-newtonian fluid sulfurized alkylphenol calcium is 250-450mgKOH/g； The non-newtonian fluid sulfoacid calcium is converted by newton body sulfoacid calcium, and the total base number of the non-newtonian fluid sulfoacid calcium is 250- 450mgKOH/g；The non-newtonian fluid calcium naphthenate is converted by newton body calcium naphthenate, the non-newtonian fluid cycloalkanes The total base number of sour calcium is 250-450mgKOH/g；The non-newtonian fluid calcium salicylate is to convert to obtain by newton body calcium salicylate , the total base number of the non-newtonian fluid calcium salicylate is 250-450mgKOH/g；The non-newtonian fluid calcium oleate is by newton body What calcium oleate converted, the total base number of the non-newtonian fluid calcium oleate is 250-450mgKOH/g.
4. lubricant composition according to claim 1 or 2, wherein the higher fatty acids is the rouge that carbon number is 8-20 Fat acid.
5. lubricant composition according to claim 1 or 2, wherein the higher fatty acids is the hydroxyl that carbon number is 8-20 Base fatty acid.
6. lubricant composition according to claim 4, wherein the higher fatty acids is selected from lauric acid, palmitinic acid, hard At least one of resin acid, 12- hydroxy stearic acid, eicosyl carboxylic acid.
7. lubricant composition according to claim 1 or 2, wherein the aromatic acid is substituted or unsubstituted aromatic acid, Substituent group is at least one of alkyl, alkenyl, alkynyl, aryl and halogenated alkyl or aryl, and the molecular weight of the aromatic acid is small In equal to 550.
8. lubricant composition according to claim 7, wherein the halogenated alkyl or aryl is the alkyl of perhalogeno Or aryl.
9. lubricant composition according to claim 7, wherein the aromatic acid is selected from unsubstituted or C1-C5 alkyl and takes At least one of the phthalic acid in generation, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid.
10. lubricant composition according to claim 1 or 2, wherein the molecule of small molecule inorganic acid and lower fatty acid Amount is less than or equal to 250.
11. lubricant composition according to claim 10, wherein the small molecule inorganic acid is selected from boric acid, phosphoric acid, sulphur At least one of acid, the lower fatty acid in acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid at least It is a kind of.
12. lubricant composition according to claim 1 or 2, wherein the structural formula of the polyurea compound is
Wherein, n is 0-3 integer, R1、R4It is alkyl, naphthenic base or aryl, R2It is alkylidene or arlydene, R3It is arlydene, Asia Alkyl or cycloalkylidene.
13. lubricant composition according to claim 12, wherein polyurea compound is two polyurea compounds, four polyureas At least one of compound, six polyurea compounds and eight polyurea compounds.
14. lubricant composition according to claim 13, wherein R1、R4It is phenyl or substituted phenyl or carbon number is 8-24 alkyl or cycloalkyl；R2It is the alkylidene that phenylene or biphenylene or carbon number are 2-12；R3Be carbon number be 6-30 Arlydene, alkylidene or cycloalkylidene.
15. lubricant composition according to claim 14, wherein R1、R4It is the alkyl or halogen of phenyl C1-C3 The alkyl or cycloalkyl that the phenyl or carbon number that element replaces are 10-18；R2It is phenylene or biphenylene or carbon number is 2-8 Alkylidene；R3It is With-(CH2)6In at least It is a kind of.
16. the preparation method of lubricant composition described in any one of claim 1-15, this method comprises: by thickening agent It is uniformly mixed with part basis oil, is refined in 180-230 DEG C of constant temperature, surplus base oil is added, necessary additive is added, obtains Finished product, which is characterized in that the thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium, the calcium salt of higher fatty acids and polyureas chemical combination Object, the thickening agent also optionally contain non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non- Newton body calcium oleate, the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid one of calcium salt or a variety of.
17. a kind of preparation method of lubricant composition, which is characterized in that this method comprises:
(1) newton body sulfurized alkylphenol calcium, optional newton body and/or non-newtonian fluid sulfoacid calcium, optional newton body will be contained And/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid calcium salicylate and optional newton body and/or non- The high base number material and part basis oil of newton body calcium oleate mix, and obtain mixture；
(2) it optionally carries out the reaction of at least partly composite calcium: lime or calcium hydroxide is added, higher fatty acids, optionally is added Aromatic acid, optional small molecule inorganic acid and/or lower fatty acid, reacted；And/or optionally carry out at least partly polyureas The reaction of compound: being added part basis oil and monoamine, or be additionally added diamines, and diisocyanate is added and is reacted；
(3) transforming agent is added, heats up to material retrogradation；
(4) reaction of remaining composite calcium is carried out；
(5) heating dehydration；
(6) reaction of remaining polyurea compound is carried out；
(7) 180-230 DEG C of constant temperature refinings are warming up to, surplus base oil is added, necessary additive is added, obtains finished product；
On the basis of the weight of the lubricant composition, the content of base oil is 10-80 weight %, non-newtonian fluid alkyl monosulfide The content of phenol calcium is 10-70 weight %, and the content of the calcium salt of higher fatty acids is 1-20 weight %, and the content of polyurea compound is 0.5-30 weight %, the content of non-newtonian fluid sulfoacid calcium are 0-70 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 weight % is measured, the content of non-newtonian fluid calcium salicylate is 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, aromatic acid The content of calcium salt be 0-15 weight %, the content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is 0-15 weight %.
18. according to the method for claim 17, wherein in step (2), carry out the reaction of at least partly composite calcium；With/ Or, carrying out the reaction of at least partly polyurea compound.
19. method described in 7 or 18 according to claim 1, wherein in step (2) and step (4), carry out the reaction of composite calcium When, at 85-100 DEG C, the suspension of lime or calcium hydroxide is added, higher fatty acids is added, stirs 5-20 minutes, is added and appoints The aromatic acid of choosing, optional small molecule inorganic acid and/or lower fatty acid stir 5-20 minutes.
20. method described in 7 or 18 according to claim 1, wherein in step (2) and step (6), carry out polyurea compound When reaction, be added part basis oil, monoamine, optional diamines, after diisocyanate, 100-120 DEG C constant temperature 10-30 minutes, Wherein, monoamine, optional diamines, diisocyanate the amount of substance meet following relationship: amount × 2 of the substance of diisocyanate Amount × 2 of amount+diamines substance of the substance of=monoamine, or, diisocyanate is excessive, excessive amount≤10%.
21. method described in 7 or 18 according to claim 1, wherein in step (3), at 50-80 DEG C, required transforming agent is added Reacted, after all transforming agents add, 80-100 DEG C constant temperature 60-90 minutes.
22. method described in 7 or 18 according to claim 1, wherein in step (5), be warming up to 110-130 DEG C of dehydration.
23. method described in 7 or 18 according to claim 1, wherein in step (7), be warming up to 5-30 points of 180-230 DEG C of constant temperature Clock；Be added surplus base oil, be cooled to 100-120 DEG C to temperature, necessary additive be added, stir, circulating filtration, homogenizing, Degassing.
24. method described in 7 or 18 according to claim 1, wherein the newton body sulfurized alkylphenol calcium is synthesis alkyl monosulfide Phenol calcium, the total base number of the newton body sulfurized alkylphenol calcium are 250-450mgKOH/g；The newton body sulfoacid calcium is petroleum sulphur Sour calcium and/or calcium alkylbenzenesulfonate, the total base number of the newton body sulfoacid calcium are 250-450mgKOH/g；The newton body aphthenic acids Calcium is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and the total base number of the newton body calcium naphthenate is 250-450mgKOH/g； The newton body calcium salicylate is salicylate calcium, and the total base number of the newton body calcium salicylate is 250-450mgKOH/g； The newton body calcium oleate is natural calcium oleate and/or synthesis calcium oleate, and the total base number of the newton body calcium oleate is 250- 450mgKOH/g。
25. method described in 7 or 18 according to claim 1, wherein the transforming agent be selected from fatty alcohol, fatty acid, aliphatic ketone, Fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, C8-C20 benzene sulfonamide At least one of acid, aphthenic acids, C16-C24 alkyl phenol and water, the additional amount of transforming agent are the high base number material total weight 2-30%.
26. according to the method for claim 25, wherein the transforming agent is selected from dodecyl benzene sulfonic acid, aphthenic acids, 18 At least one of alkyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water, the additional amount of transforming agent are the high base number The 6-22% of material total weight.
27. method described in 7 or 18 according to claim 1, wherein the structural formula of the monoamine is R1–NH2、R4–NH2, wherein R1、R4It is the phenyl that phenyl C1-C3 alkyl or halogen replace or the alkyl or cycloalkyl that carbon number is 10-18.
28. according to the method for claim 27, wherein the monoamine be selected from aniline, m-chloroaniline, parachloroanilinum and/ Or para-totuidine aromatic amine and/or fatty amine selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.
29. method described in 7 or 18 according to claim 1, wherein the structural formula of the diamines is NH2–R2–NH2, wherein R2It is The alkylidene or phenylene or biphenylene that carbon number is 2-8.
30. according to the method for claim 29, wherein the diamines is selected from p-phenylenediamine, o-phenylenediamine, 4,4 '-connection The aromatic amine of phenylenediamine and/or selected from ethylenediamine, propane diamine, 1,6-hexamethylene diamines straight-chain fatty amine.
31. method described in 7 or 18 according to claim 1, wherein the structure of the diisocyanate is OCN-R3- NCO, R3It is Arlydene, alkylidene or the cycloalkylidene that carbon number is 6-30.
32. according to the method for claim 31, wherein the diisocyanate is selected from toluene di-isocyanate(TDI), diphenyl Methane diisocyanate, six hexylidene diisocyanates, dicyclohexyl methyl hydride diisocyanate and xyxylene diisocyanate At least one of ester.
33. lubricant composition made from the method as described in any one of claim 17-32.
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