CN106032484B - Lubricant composition and preparation method thereof - Google Patents
Lubricant composition and preparation method thereof Download PDFInfo
- Publication number
- CN106032484B CN106032484B CN201510105487.4A CN201510105487A CN106032484B CN 106032484 B CN106032484 B CN 106032484B CN 201510105487 A CN201510105487 A CN 201510105487A CN 106032484 B CN106032484 B CN 106032484B
- Authority
- CN
- China
- Prior art keywords
- calcium
- acid
- weight
- newtonian fluid
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Lubricants (AREA)
Abstract
Lubricant composition and preparation method thereof.The present invention relates to lubricating grease fields, disclose a kind of lubricant composition, lubricant composition contains base oil and thickening agent, thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, the calcium salt and polyurea compound of higher fatty acids, thickening agent also optionally contains non-newtonian fluid calcium naphthenate, calcium salicylate, 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, on the basis of the weight of lubricant composition, the content of base oil is 10-80%, non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content is 10-70%, the content of the calcium salt of higher fatty acids is 1-20%, the content of polyurea compound is 0.5-30%, the content of remaining optional components is respectively 0-70%, 0-70%, 0-70%, 0-15%, 0-15%.Also disclose the preparation method of lubricant composition.Lubricant composition of the invention has excellent performance.
Description
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 non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, higher aliphatic
Acid calcium salt and polyurea compound, the thickening agent also optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate,
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, with
On the basis of the weight of the lubricant composition, the content of base oil is 10-80 weight %, non-newtonian fluid sulfurized alkylphenol calcium-
The content of sulfoacid 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 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 %.
Preferably, on the basis of the weight of lubricant composition, the content of base oil is 20-70 weight %, non-newtonian fluid
Sulfurized alkylphenol calcium-sulfoacid calcium content is 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, is gathered
The content of carbamide compound is 1-20 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, non-newtonian fluid salicylic acid
The content of calcium is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, and the content of the calcium salt of aromatic acid is 2-10
The content of the calcium salt of weight %, 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 polyureas of non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, higher fatty acids
Close object, the thickening agent also optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate,
One of calcium salt of the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid is a variety of.
The third aspect, the present invention provides a kind of preparation methods of lubricant composition, this method comprises:
(1) will contain newton body sulfurized alkylphenol calcium, newton body and/or non-newtonian fluid sulfoacid calcium, or containing newton body and/
Or non-newtonian fluid sulfurized alkylphenol calcium, the high base number material of newton body sulfoacid calcium and the mixing of part basis oil, mixture is obtained,
The high base number material also optionally contains newton body and/or non-newtonian fluid calcium naphthenate, newton body and/or non-newtonian fluid bigcatkin willow
Sour calcium and one of newton body and/or non-newtonian fluid calcium oleate or a variety of;
(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.
Detailed description of the invention
Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 10.
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 calcium mahogany sulfonate and/or conjunction
At sulfoacid calcium, synthesis sulfurized alkylphenol calcium, optional petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, optional synthesis bigcatkin willow
Sour calcium, optional natural calcium oleate and/or synthesis calcium oleate are raw material, contain composite calcium thickening agent, isocyanates and amine simultaneously
React the polyurea compound generated.
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-sulfoacid calcium, higher fatty acids, and thickening agent is also appointed
Selection of land contain non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule without
One of calcium salt of machine acid and/or lower fatty acid is a variety of, and on the basis of the weight of lubricant composition, base oil contains
Amount is 10-80 weight %, and non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content is 10-70 weight %, higher fatty acids
The content of calcium salt is 1-20 weight %, and the content of polyurea compound is 0.5-30 weight %, the content of non-newtonian fluid calcium naphthenate
For 0-70 weight %, 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
Measure %, the content of the calcium salt of aromatic 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 %.
Preferably, on the basis of the weight of lubricant composition, the content of base oil is 20-70 weight %, non-newtonian fluid
Sulfurized alkylphenol calcium-sulfoacid calcium content is 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, is gathered
The content of carbamide compound is 1-20 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, non-newtonian fluid salicylic acid
The content of calcium is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, and the content of the calcium salt of aromatic acid is 2-10
The content of the calcium salt of weight %, 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
Calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule inorganic acid and/or lower aliphatic
One of calcium salt of acid or it is a variety of be optional component, may include the component in lubricant composition of the invention, can also be with
It does not include the component.
Non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non newtonian
Body calcium oleate or combinations thereof object is in infrared spectrum 873cm–1–886cm–1There is crystal form calcium carbonate characteristic absorption peak in place.Non-newtonian fluid
Sulfurized alkylphenol calcium-sulfoacid calcium is to convert to obtain by transforming agent by newton body sulfoacid calcium and newton body sulfurized alkylphenol calcium, non-
Newton body sulfurized alkylphenol calcium-sulfoacid calcium total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g;Non- ox
The body calcium naphthenate that pauses 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 sulfoacid calcium, newton body sulfurized alkylphenol 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.It is non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, non-
The base number of newton body calcium naphthenate, non-newtonian fluid calcium salicylate and the mixing of non-newtonian fluid calcium oleate is the weight of the base number of each component
Weighted average.
In the present invention, higher fatty acids is that carbon number is 8-20, the preferably fatty acid of 10-18 or hydroxy fatty acid, such as the moon
At least one of cinnamic acid, palmitinic acid, stearic acid, 12- hydroxy stearic acid, eicosyl carboxylic acid, preferably 12- hydroxy stearate
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 and 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, arlydene, alkylidene or cycloalkylidene
Carbon number can be 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.
The lubricating 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-sulfoacid calcium, higher fatty acids,
Thickening agent also optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, aromatic acid calcium
One of calcium salt of salt, small molecule inorganic acid and/or lower fatty acid is a variety of.
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-sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid water
Poplar acid calcium, non-newtonian fluid calcium oleate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid
Calcium salt, polyurea compound, base oil and additive 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-sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-
Newton body calcium oleate or combinations thereof object, can by newton body sulfoacid calcium, newton body sulfurized alkylphenol calcium, newton body calcium naphthenate,
Non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate or combinations thereof object pass through transforming agent respectively and convert to obtain, for example, by newton body
Sulfoacid calcium, newton body sulfurized alkylphenol calcium, optional newton body calcium naphthenate, optional newton body calcium salicylate, optional ox
Body calcium oleate and base oil Hybrid Heating are added required transforming agent and are reacted, all transforming agents add to 50-80 DEG C
Afterwards, 80-100 DEG C constant temperature 60-90 minutes, then heat to 110-130 DEG C of dehydrations.
In the present invention, " optional " refer to can there is the raw material or no raw material, for example, " optional newton body
Calcium naphthenate ", which refers to, can this raw material of newton body calcium naphthenate, can also not have this raw material of newton body calcium naphthenate.
The third aspect, the present invention provides a kind of preparation methods of lubricant composition, this method comprises:
(1) will contain newton body sulfurized alkylphenol calcium, newton body and/or non-newtonian fluid sulfoacid calcium, or containing newton body and/
Or non-newtonian fluid sulfurized alkylphenol calcium, the high base number material of newton body sulfoacid calcium and the mixing of part basis oil, mixture is obtained,
The high base number material also optionally contains newton body and/or non-newtonian fluid calcium naphthenate, newton body and/or non-newtonian fluid bigcatkin willow
Sour calcium and one of newton body and/or non-newtonian fluid calcium oleate or a variety of;
(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.
" optionally containing " is as previously mentioned, details are not described herein.
In the present invention, newton body sulfurized alkylphenol calcium, non-newtonian fluid sulfurized alkylphenol calcium, newton body sulfoacid calcium, non newtonian
Body sulfoacid calcium, newton body calcium naphthenate, non-newtonian fluid calcium naphthenate, newton body calcium salicylate, non-newtonian fluid calcium salicylate, newton
For example preceding institute of body calcium oleate, non-newtonian fluid calcium oleate, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid and base oil
It states, details are not described herein.
In step (1) of the present invention, " containing newton body sulfurized alkylphenol calcium, newton body and/or non-newtonian fluid sulfoacid calcium, or
High base number material containing newton body and/or non-newtonian fluid sulfurized alkylphenol calcium, newton body sulfoacid calcium " refers to high base number material
In sulfurized alkylphenol calcium and at least one of sulfoacid calcium be newton figure.
In step (1) of the present invention, for sulfoacid calcium and sulfurized alkylphenol calcium weight ratio without particular/special requirement, preferably 1:
0.25–4.For other optional high base number materials amount without particular/special requirement, can be according to actual needs using commonly used in the art
Amount, 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 sulfenyl phenolate-sulfoacid calcium in lubricant composition obtained, non-newtonian fluid calcium naphthenate, non-ox
The total content of body calcium salicylate and non-newtonian fluid calcium oleate uses non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium % to indicate,
That is,
Non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium %=(overbased or calcium sulfonate with high base number raw material weight+superelevation
Base number or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER raw material weight+overbased or overbased calcium alkyl-salicylate raw material weight+overbased or
High base number calcium salicylate raw material weight+overbased or high base number calcium oleate raw material weight+transforming agent total weight)/lubricating grease is total
Weight × 100%.Transforming agent is included in non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content.
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.
(NLGI Spokeman, 2009,73 (2): 1-17) prepared by method according to document for high base number calcium oleate.
Embodiment 1
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 24kg);Overbased sulfurized alkylphenol calcium
(total base number 400mgKOH/g, 6kg);(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 30kg);4-ten
Eight alkylphenols (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 HVI500SN lubricating base oil
11mm2/ s, 17kg).
It in a volume is 160L and with 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle
For the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number be 400mgKOH/g overbased sulfurized alkylphenol calcium and
The HVI150BS lubricating base oil of 30kg, stirring;95 DEG C are warming up to, the calcium hydroxide suspension that solid content is 20 weight % is added
9kg is stirred 10 minutes;12-hydroxy stearic acid of 2kg is added, stirs 10 minutes, 3.5kg terephthalic acid (TPA) is added, stirs 10 points
Clock;The HVI500SN lubricating base oil of 10kg is added and material is made to be down to 50 DEG C, constant temperature 10 minutes, 4-octadecane of 2.8kg is added
Base phenol, temperature control are stirred 10 minutes on 50 DEG C of right sides, and 1kg methanol is added, stirs 10 minutes, and addition 2.8kg concentration is 20 weights
The aqueous acetic acid of % is measured, stirs 10 minutes, is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation;120 DEG C are warming up under stirring,
It is kept for 45 minutes, dehydration;The HVI500SN lubricating base oil and 1.5kg octadecylamine of 2kg is added, stirs 4 minutes, adds and be dissolved in
0.7kg MDI in the HVI500SN lubricating base oil of 2kg is stirred 4 minutes, the amount of the substance of added MDI and octadecylamine it
Than for 1:2,120 DEG C constant temperature 20 minutes;It is finally warming up to 200 DEG C of constant temperature 10 minutes, then, is cooled to 160 DEG C, is added remaining
HVI500SN lubricating base oil is cooled to 110 DEG C to temperature, 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 sulfenyl phenolate
37.5 weight % of calcium-sulfoacid calcium;2.5 weight % of polyureas;52.8 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.4 weight
Measure %;4.8 weight % of terephthalic acid (TPA) calcium.
Embodiment 2
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 6kg);SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is (total
Base number is 320mgKOH/g, 24kg);(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 20kg);4-ten eight
Alkylphenol (2.6kg);N-butanol (1.2kg);Acetic acid (0.56kg);Calcium hydroxide (1.8kg);Stearic acid (1.9kg);Adjacent benzene
Dioctyl phthalate (3.5kg);Lauryl amine (1.31kg);MDI(0.89kg);(100 DEG C of kinematic viscosity are HVI500SN lubricating base oil
11mm2/ s, 27kg).
It in a volume is 160L and with 6kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle
For the overbased sulfoacid calcium of 400mgKOH/g, 24kg total base number be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and 20kg
HVI150BS lubricating base oil, stirring;100 DEG C are warming up to, the HVI500SN lubricating base oil and 0.131kg of 0.2kg is added
Lauryl amine stirs 8 minutes, adds the 0.089kg MDI being dissolved in the HVI500SN lubricating base oil of 0.4kg, stirs 8 points
The molar ratio of clock, added MDI and lauryl amine be 1:2,100 DEG C constant temperature 10 minutes;At 85 DEG C, addition solid content is 20 weights
The calcium hydroxide suspension 0.9kg of % is measured, is stirred 10 minutes;0.19kg stearic acid is added, stirs 10 minutes, it is adjacent that 0.35kg is added
Phthalic acid stirs 10 minutes;At 80 DEG C, constant temperature 10 minutes, 1.2kg n-butanol and 4-octadecylphenol of 2.6kg is added,
Temperature is controlled at 80 DEG C, is stirred 10 minutes, and the aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 minutes, heating
To 90 DEG C, constant temperature 60 minutes, material retrogradation;At 85 DEG C, the calcium hydroxide suspension that solid content is 20 weight % is added
8.1kg is stirred 10 minutes, and 1.71kg stearic acid is added, and is stirred 10 minutes, and 3.15kg phthalic acid is added, and is stirred 10 minutes;
It is warming up to 110 DEG C under stirring, is kept for 60 minutes, dehydration;HVI500SN lubricating base oil and the 1.179kg laurel of 1.8kg is added
Amine stirs 8 minutes, adds the 0.801kg MDI being dissolved in the HVI500SN lubricating base oil of 3.6kg, stirs 8 minutes, institute
The ratio between amount of substance of the MDI and lauryl amine that add be 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 lubricating base oil is added;120 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing are obtained into
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 sulfenyl phenolate
37.5 weight % of calcium-sulfoacid calcium;2.5 weight % of polyureas;52.9 weight % of lubricating base oil;2.3 weight % of calcium stearate;It is adjacent
4.8 weight % of phthalic acid calcium.
Embodiment 3
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: calcium sulfonate with high base number (total base number 320mgKOH/g, 24kg);Overbased sulfurized alkylphenol calcium
(total base number 400mgKOH/g, 6kg);(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 25kg);4-ten
Eight alkylphenols (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 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle
The overbased sulfurized alkylphenol calcium and 25kg that calcium sulfonate with high base number, 6kg total base number for 320mgKOH/g are 400mgKOH/g
HVI150BS lubricating base oil, stirring;110 DEG C are warming up to, the HVI500SN lubricating base oil and 1.66kg 18 of 2kg is added
Amine stirs 4 minutes, adds the 0.54kg TDI being dissolved in the HVI500SN lubricating base oil of 2kg, stirs 4 minutes, added
The ratio between amount of substance of TDI and octadecylamine be 1:2,110 DEG C constant temperature 15 minutes;At 65 DEG C, constant temperature 10 minutes, 1.6kg is added
4-octadecylphenols, temperature are controlled at 65 DEG C, are stirred 10 minutes, and 1.2kg dodecyl benzene sulfonic acid is added, stirs 10 minutes,
1kg methanol is added, stirs 10 minutes, the aqueous acetic acid that 2.8kg concentration is 20 weight % is added, 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
It mixes 10 minutes;12-hydroxy stearic acid of 2kg is added, stirs 10 minutes, 3.5kg M-phthalic acid is added, stirs 10 minutes;Stirring
Under be warming up to 130 DEG C, kept for 30 minutes, dehydration;It is finally warming up to 180 DEG C of constant temperature 20 minutes, then, is cooled to 160 DEG C, is added
Remaining HVI500SN lubricating base oil is cooled to 100 DEG C to temperature, and circulating filtration, homogenizing, degassing obtain finished product.Examine knot
Fruit 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 sulfenyl phenolate
37.5 weight % of calcium-sulfoacid calcium;2.5 weight % of polyureas;52.8 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.4 weight
Measure %;4.8 weight % of M-phthalic acid calcium.
Embodiment 4
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: calcium sulfonate with high base number (total base number 320mgKOH/g, 12kg);SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is (total
Base number is 320mgKOH/g, 6kg);Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 12kg);HVI150BS lubrication
(100 DEG C of kinematic viscosity are 31mm to base oil2/ s, 15kg);4-octadecylphenols (1.8kg);Boric acid (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, 7kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfoacid calcium is using total base number
The calcium sulfonate with high base number of 320mgKOH/g, the high base number sulfenyl phenolate that sulfurized alkylphenol calcium is 320mgKOH/g using total base number
Calcium, and increase the naphthenate with superhigh base number calcium that total base number is 400kgKOH/g;Transforming agent replaces methanol with boric acid, wherein boric acid
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 sulfenyl phenolate
52.1 weight % of calcium-sulfoacid calcium;3.5 weight % of polyureas;34.4 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 3.3 weight
Measure %;6.7 weight % of terephthalic acid (TPA) calcium.
Embodiment 5
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 6kg);Overbased sulfurized alkylphenol calcium
(total base number 400mgKOH/g, 12kg);Overbased calcium salicylate (total base number 400mgKOH/g, 12kg);HVI150BS
(100 DEG C of kinematic viscosity are 31mm to lubricating base oil2/ s, 25kg);4-octadecylphenols (2.8kg);Acetic acid (0.56kg);Hydrogen
Calcium oxide (1.8kg);12-hydroxy stearic acids (2kg);4,4'- biphenyl dicarboxylic acid (5.1kg);Octadecylamine (4.5kg);MDI
(2.1kg);(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 18.6kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, high base number material increases overbased water
Poplar acid calcium replaces terephthalic acid (TPA) using 4,4'- biphenyl dicarboxylic acid;Transforming agent is only 4-octadecylphenols and acetic acid, is saved
The step of methanol is added;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 sulfenyl phenolate
36.4 weight % of calcium-sulfoacid calcium;7.2 weight % of polyureas;47.6 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.3 weight
Measure %;6.5 weight % of 4,4'- biphenyl dicarboxylic acid calcium.
Embodiment 6
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 6kg);SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is (total
Base number is 320mgKOH/g, 18kg);Overbased calcium oleate (total base number 400mgKOH/g, 6kg);Poly- α-the alkene of full synthetic oil
(100 DEG C of kinematic viscosity are 41mm to hydrocarbon ils PAO 402/ s, 30kg);4-octadecylphenols (2.8kg);Acetic acid (0.56kg);Hydrogen
Calcium oxide (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 the poly- α of full synthetic oil-alkene oil PAO 102/ s, 9kg);Two thio dibutylphosphoric acid zinc (2kg);
Dibutyl dithiocaarbamate molybdenum (1kg);Tungsten disulfide (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 the overbased calcium oleate that total base number is 400kgKOH/g;Turn
Agent is only 4-octadecylphenols and acetic acid, saves the step of methanol is added;Use the poly- α of full synthetic oil-alkene oil PAO 40
HVI150BS and HVI500SN is replaced respectively with PAO 10;And 110 DEG C are cooled to temperature, two thio two fourths of 2kg are added
Base trbasic zinc phosphate stirs 10 minutes, and the dibutyl dithiocaarbamate molybdenum of 1kg is added, and stirs 10 minutes, two sulphur of 2kg are added
Change tungsten, stir 10 minutes, two tungsten selenides of 2kg are added, stirs 10 minutes, pair of 0.2kg, right '-diisooctyl hexichol is added
Amine stirs 10 minutes, and 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 sulfenyl phenolate
37.8 weight % of calcium-sulfoacid calcium;2.5 weight % of polyureas;44.2 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.4 weight
Measure %;4.9 weight % of terephthalic acid (TPA) calcium;Two thio 2.3 weight % of dibutylphosphoric acid zinc;Dibutyl dithiocaarbamate molybdenum
1.1 weight %;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: calcium sulfonate with high base number (total base number 320mgKOH/g, 6kg);Overbased sulfurized alkylphenol calcium is (total
Base number is 400mgKOH/g, 8kg);Overbased calcium alkyl-salicylate (total base number 300mgKOH/g, 8kg);High base number calcium salicylate
(total base number 300mgKOH/g, 8kg);(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 15kg);4-ten
Eight alkylphenols (2.8kg);Acetic acid (0.56kg);Calcium hydroxide (1.8kg);12-hydroxy stearic acids (2kg);2-methyl-1,4-
Phthalic acid (3.8kg);Octadecylamine (0.94kg);Para-totuidine (0.38kg);MDI(0.88kg);HVI500SN lubrication base
(100 DEG C of kinematic viscosity are 11mm to oil2/ s, 33kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfoacid calcium is using total base number
The calcium sulfonate with high base number of 320mgKOH/g, while increasing overbased calcium alkyl-salicylate and high base number calcium salicylate;Transforming agent is only
4-octadecylphenols and acetic acid save the step of methanol is added;Terephthaldehyde is replaced using 2-- 1,4-phthalic acids of methyl
Acid;Monoamine is additionally added para-totuidine other than octadecylamine;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 sulfenyl phenolate
37.1 weight % of calcium-sulfoacid calcium;2.4 weight % of polyureas;53.3 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.4 weight
Measure %;2-- 1,4-phthalic acid of methyl calcium, 4.8 weight %.
Embodiment 8
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: calcium sulfonate with high base number (total base number 320mgKOH/g, 6kg);SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total alkali
Value is 320mgKOH/g, 8kg);High base number calcium salicylate (total base number 360mgKOH/g, 8kg);High base number calcium oleate (total alkali
Value is 400mgKOH/g, 8kg);(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 20kg);4-octadecanes
Base phenol (2.8kg);Acetic acid (0.56kg);Calcium hydroxide (5.2kg);12-hydroxy stearic acids (2kg);Boric acid (2.32kg);It is right
Phthalic acid (7.6kg);Octadecylamine (0.84kg);Lauryl amine (0.58kg);MDI(0.78kg);HVI500SN lubricating base oil
(100 DEG C of kinematic viscosity are 11mm2/ s, 28kg);It is right, right '-di-iso-octyldiphenylamine (0.2kg).
Lubricant composition is prepared according to the method for embodiment 1, unlike, sulfoacid calcium is using total base number
The calcium sulfonate with high base number of 320mgKOH/g, the high base number sulfenyl phenolate that sulfurized alkylphenol calcium is 320mgKOH/g using total base number
Calcium, while increasing high base number calcium salicylate and high base number calcium oleate;Transforming agent is only 4-octadecylphenols and acetic acid, is saved
The step of methanol is added;The stirring of 12-hydroxy stearic acids is added after ten minutes, boric acid is added, stirs 10 minutes, is then added to benzene
Dioctyl phthalate stirs 10 minutes;Monoamine is additionally added lauryl amine other than octadecylamine;And 110 DEG C are cooled to temperature, is added
Pair of 0.2kg, right '-di-iso-octyldiphenylamine stir 10 minutes, and then circulating filtration, homogenizing, degassing obtain finished product;Each ingredient
Dosage it 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 sulfenyl phenolate
34.2 weight % of calcium-sulfoacid calcium;2.2 weight % of polyureas;49.2 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.2 weight
Measure %;2.4 weight % of line borate;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: non-newtonian fluid calcium sulfonate with high base number (15kg);(total base number is for overbased sulfurized alkylphenol calcium
400mgKOH/g, 4kg);Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 4kg);Overbased calcium salicylate is (total
Base number is 400mgKOH/g, 4kg);Overbased calcium oleate (total base number 400mgKOH/g, 3kg);HVI150BS lubrication base
(100 DEG C of kinematic viscosity are 31mm to 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).
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 400mgKOH/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, overbased sulfoacid calcium is directly using preparation
Good non-newtonian fluid sulfoacid calcium, it is only 4-octadecanes that high base number material, which increases calcium naphthenate, calcium salicylate and calcium oleate, transforming agent,
Base phenol and acetic acid save the step of methanol is added;And terephthalic acid (TPA) stirring is added after ten minutes, acetic acid, stirring is added
10 minutes;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 sulfenyl phenolate
36.0 weight % of calcium-sulfoacid calcium;2.4 weight % of polyureas;51.8 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.3 weight
Measure %;4.7 weight % of terephthalic acid (TPA) calcium;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 sulfoacid calcium (total base number 400mgKOH/g, 6kg);Overbased sulfurized alkylphenol calcium
(total base number 400mgKOH/g, 24kg);(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 30kg);4–
Octadecylphenol (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);(the 100 DEG C of movements of HVI500SN lubricating base oil
Viscosity is 11mm2/ s, 17kg).
It in a volume is 160L and with 6kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle
For the overbased sulfoacid calcium of 400mgKOH/g, 24kg total base number be 400mgKOH/g overbased sulfurized alkylphenol calcium and
The HVI150BS lubricating base oil of 30kg, stirring heat to 100 DEG C, and the calcium hydroxide that solid content is 20 weight % is added
Suspension 9kg is stirred 10 minutes;12-hydroxy stearic acid of 2kg is added, stirs 10 minutes;3.5kg terephthalic acid (TPA) is added, stirs
It mixes 10 minutes;Cool to 50 DEG C, constant temperature 10 minutes;4-octadecylphenol of 2.8kg is added, temperature is controlled at 50 DEG C or so, stirred
It mixes 10 minutes;1kg methanol is added, stirs 10 minutes;The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 points
Clock;It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation;It is warming up to 120 DEG C under stirring, is kept for 30 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.The infrared spectrum of lubricating grease is shown in Fig. 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfenyl phenolate
37.5 weight % of calcium-sulfoacid calcium;2.5 weight % of polyureas;52.8 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.4 weight
Measure %;4.8 weight % of terephthalic acid (TPA) calcium.
Embodiment 11
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 24kg);Overbased sulfurized alkylphenol calcium
(total base number 400mgKOH/g, 6kg);(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 30kg);4-ten
Eight alkylphenols (total acid number 180mgKOH/g, 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);HVI500SN lubricates base
(100 DEG C of kinematic viscosity are 11mm to plinth oil2/ s, 17kg).
It in a volume is 160L and with 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle
For the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number be 400mgKOH/g overbased sulfurized alkylphenol calcium and
100 DEG C of kinematic viscosity of 30kg are 31mm2The HVI150BS lubricating base oil of/s, stirring, heats to 50 DEG C, constant temperature 10 divides
Clock;2.8kg4-octadecylphenol is added, temperature is controlled at 50 DEG C or so, stirred 10 minutes;1kg methanol is added, stirs 10 points
Clock;The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 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 30 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 sulfenyl phenolate
37.5 weight % of calcium-sulfoacid calcium;2.5 weight % of polyureas;52.8 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.4 weight
Measure %;4.8 weight % of terephthalic acid (TPA) calcium.
Embodiment 12
The present embodiment is for illustrating lubricant composition prepared by the present invention.
It is 160L in volume and is with 10kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle A
The calcium sulfonate with high base number of 350mgKOH/g, the overbased sulfurized alkylphenol calcium that 20kg total base number is 400mgKOH/g and 25kg
(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, similarly hereinafter), stirring heats to 60 DEG C, constant temperature 10 divides
Clock;2kg aphthenic acids and 4-octadecylphenol of 1kg is added, temperature is controlled at 60 DEG C or so, stirred 10 minutes;Concentration, which is added, is
20% 12.5kg butanol aqueous solution 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 sulfenyl phenolate
34.4 weight % of calcium-sulfoacid calcium;2.7 weight % of calcium palmitate;4.2 weight % of biphenyl dicarboxylic acid calcium;1.6 weight % of calcium phosphate;
2.9 weight % of ethanedioic acid calcium;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 20kg total alkali is added in heating, stirring, circulation, cooling normal-pressure reaction kettle A
Overbased sulfurized alkylphenol calcium that overbased sulfoacid calcium that value is 400mgKOH/g, 10kg total base number are 420mgKOH/g and
The HVI150BS lubricating base oil of 10kg, stirring, heats to 50 DEG C, constant temperature 10 minutes;2kg detergent alkylate sulphur is added
Acid, temperature are controlled at 50 DEG C or so, are stirred 10 minutes;1kg methanol is added, stirs 10 minutes;Addition 2kg concentration is 20 weight %
Aqueous acetic acid, stir 10 minutes;83 DEG C constant temperature 80 minutes, 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 sulfenyl phenolate
41.7 weight % of calcium-sulfoacid calcium;3.3 weight % of calcium laurate;12.1 weight % of M-phthalic acid calcium;5.4 weight % of polyureas;
37.5 weight % of lubricating base oil.
Embodiment 14
The present embodiment is for illustrating lubricant composition prepared by the present invention.
Raw material components: overbased sulfoacid calcium (total base number 400mgKOH/g, 24kg);Overbased sulfurized alkylphenol calcium
(total base number 400mgKOH/g, 6kg);(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 30kg);4-ten
Eight alkylphenols (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 HVI500SN lubricating base oil
11mm2/ s, 17kg).
It in a volume is 160L and with 24kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle
For the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number be 400mgKOH/g overbased sulfurized alkylphenol calcium 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 control is stirred 10 minutes on 50 DEG C of right sides, and 1kg methanol is added, and is stirred 10 minutes, and it is 20 weight %'s that 2.8kg concentration, which is added,
Aqueous acetic acid stirs 10 minutes, is warming up to 80 DEG C, and constant temperature 90 minutes, material retrogradation;100 DEG C are warming up to, solid content, which is added, is
The calcium hydroxide suspension 9kg of 20 weight % is stirred 10 minutes;12-hydroxy stearic acid of 2kg is added, stirs 10 minutes, is added
3.5kg terephthalic acid (TPA) stirs 10 minutes;It is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration;It is added 2kg's
HVI500SN lubricating base oil and 1.5kg octadecylamine stir 4 minutes, add and be dissolved in the HVI500SN lubricating base oil of 2kg
0.7kg MDI, stir 4 minutes, the ratio between amount of substance of added MDI and octadecylamine is 1:2,120 DEG C constant temperature 20 minutes;Most
After be warming up to 200 DEG C of constant temperature 10 minutes, then, be cooled to 160 DEG C, remaining HVI500SN lubricating base oil be added, to temperature
110 DEG C are cooled to, 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 sulfenyl phenolate
37.5 weight % of calcium-sulfoacid calcium;2.5 weight % of polyureas;52.8 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.4 weight
Measure %;4.8 weight % of terephthalic acid (TPA) calcium.
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 butyl ether for acetic acid, and methanol is replaced with methyl propyl 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 sulfenyl phenolate
37.5 weight % of calcium-sulfoacid calcium;2.5 weight % of polyureas;52.8 weight % of lubricating base oil;12-hydroxy stearic acid calcium, 2.4 weight
Measure %;4.8 weight % of terephthalic acid (TPA) calcium.
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, extreme pressure
Wear resistence and lubricating life;Embodiment 1 and embodiment 15 are compared as can be seen that transforming agent is selected from detergent alkylate sulphur
At least one of acid, aphthenic acids, octadecyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water, the lubricating grease of preparation
Composition has better viscous resistance, mechanical stability, water-resistance, colloid stability, abrasion resistance, extreme pressure anti-wear and profit
The sliding service 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-sulfoacid calcium, higher fatty acids, and the thickening agent is also
Optionally containing non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule
One of calcium salt of inorganic acid and/or lower fatty acid is a variety of, on the basis of the weight of the lubricant composition, basis
The content of oil is 10-80 weight %, and non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content is 10-70 weight %, advanced rouge
The content of the calcium salt of fat acid is 1-20 weight %, and the content of polyurea compound is 0.5-30 weight %, non-newtonian fluid calcium naphthenate
Content be 0-70 weight %, 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 %, the content of the calcium salt of aromatic acid are 0-15 weight %, and the calcium salt of small molecule inorganic acid and/or lower fatty acid contains
Amount 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 %, non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium content be 20-65 weight %, higher aliphatic
The content of the calcium salt of acid is 2-15 weight %, and the content of polyurea compound is 1-20 weight %, and non-newtonian fluid calcium naphthenate contains
Amount is 0-50 weight %, and the content of non-newtonian fluid calcium salicylate is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50
Weight %, the content of the calcium salt of aromatic acid are 2-10 weight %, and the content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is
2-10 weight %.
3. lubricant composition according to claim 1 or 2, wherein the non-newtonian fluid sulfurized alkylphenol calcium-sulfonic acid
Calcium is converted by newton body sulfoacid calcium and newton body sulfurized alkylphenol calcium, the non-newtonian fluid sulfurized alkylphenol calcium-sulphur
The total base number of sour calcium is 250-450mgKOH/g;The non-newtonian fluid calcium naphthenate is to convert to obtain by newton body calcium naphthenate
, the total base number of the non-newtonian fluid calcium naphthenate is 250-450mgKOH/g;The non-newtonian fluid calcium salicylate is by newton
Body calcium salicylate converts, and the total base number of the non-newtonian fluid calcium salicylate is 250-450mgKOH/g;The non newtonian
Body calcium oleate is converted by newton body calcium oleate, and 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-C5Alkyl replaces
Phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, at least one of 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 phenyl or C1–C3Alkyl or halogen take
The alkyl or cycloalkyl that the phenyl or carbon number in generation are 10-18;R2It is the alkylene that phenylene or biphenylene or carbon number are 2-8
Base;R3It is
With-(CH2)6At least one 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 contain non-newtonian fluid sulfurized alkylphenol calcium-sulfoacid calcium, higher fatty acids calcium salt and
Polyurea compound, the thickening agent is also optionally containing 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.
17. a kind of preparation method of lubricant composition, which is characterized in that this method comprises:
(1) newton body sulfurized alkylphenol calcium, newton body and/or non-newtonian fluid sulfoacid calcium will be contained, or contain newton body and/or non-
Newton body sulfurized alkylphenol calcium, the high base number material of newton body sulfoacid calcium and the mixing of part basis oil, obtain mixture, described
High base number material also optionally contains newton body and/or non-newtonian fluid calcium naphthenate, newton body and/or non-newtonian fluid calcium salicylate
With one of newton body and/or non-newtonian fluid calcium oleate or a variety of;
(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
Phenol calcium-sulfoacid calcium content is 10-70 weight %, and the content of the calcium salt of higher fatty acids is 1-20 weight %, polyurea compound
Content be 0.5-30 weight %, the content of non-newtonian fluid calcium naphthenate is 0-70 weight %, and non-newtonian fluid calcium salicylate contains
Amount is 0-70 weight %, and 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 %,
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-C20Benzene sulfonamide
Acid, aphthenic acids, C16-C24At least one of 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 phenyl or C1–C3The alkyl or cycloalkyl that the phenyl or carbon number that alkyl or halogen replace are 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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510105487.4A CN106032484B (en) | 2015-03-11 | 2015-03-11 | Lubricant composition and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510105487.4A CN106032484B (en) | 2015-03-11 | 2015-03-11 | Lubricant composition and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106032484A CN106032484A (en) | 2016-10-19 |
CN106032484B true CN106032484B (en) | 2019-01-08 |
Family
ID=57150375
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510105487.4A Active CN106032484B (en) | 2015-03-11 | 2015-03-11 | Lubricant composition and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106032484B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106590814B (en) * | 2016-12-05 | 2019-11-19 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of calcium sulfonate complex grease |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4181619A (en) * | 1978-10-30 | 1980-01-01 | Mobil Oil Corporation | Antiwear composition |
CN1252434A (en) * | 1998-10-24 | 2000-05-10 | 燕化集团天津润滑油脂有限公司 | Composite lithium- and calcium-base lubricating grease and its preparation |
WO2002012418A3 (en) * | 2000-08-10 | 2002-04-25 | Shell Int Research | Grease composition with improved rust prevention and abrasion resistance properties |
CN101423483A (en) * | 2008-06-20 | 2009-05-06 | 辽宁天合精细化工股份有限公司 | High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof |
CN102453598A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof |
CN102757845A (en) * | 2011-04-28 | 2012-10-31 | 中国石油化工股份有限公司 | Low-noise lithium-based lubricating grease composition and preparation method thereof |
-
2015
- 2015-03-11 CN CN201510105487.4A patent/CN106032484B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4181619A (en) * | 1978-10-30 | 1980-01-01 | Mobil Oil Corporation | Antiwear composition |
CN1252434A (en) * | 1998-10-24 | 2000-05-10 | 燕化集团天津润滑油脂有限公司 | Composite lithium- and calcium-base lubricating grease and its preparation |
WO2002012418A3 (en) * | 2000-08-10 | 2002-04-25 | Shell Int Research | Grease composition with improved rust prevention and abrasion resistance properties |
CN101423483A (en) * | 2008-06-20 | 2009-05-06 | 辽宁天合精细化工股份有限公司 | High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof |
CN102453598A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof |
CN102757845A (en) * | 2011-04-28 | 2012-10-31 | 中国石油化工股份有限公司 | Low-noise lithium-based lubricating grease composition and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN106032484A (en) | 2016-10-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106032488B (en) | Lubricant composition and preparation method thereof | |
CN106032486B (en) | Lubricant composition and preparation method thereof | |
CN106032482B (en) | Lubricant composition and preparation method thereof | |
CN106032484B (en) | Lubricant composition and preparation method thereof | |
CN106032478B (en) | Lubricant composition and preparation method thereof | |
CN106032483B (en) | A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof | |
CN106032480B (en) | Lubricant composition and preparation method thereof | |
CN106032481B (en) | Lubricant composition and preparation method thereof | |
CN106032485B (en) | Lubricant composition and preparation method thereof | |
CN104560318B (en) | A kind of polyurea grease of calcium naphthenate zirconium base six and preparation method thereof | |
CN106032477B (en) | Lubricant composition and preparation method thereof | |
CN104450109B (en) | A kind of polyurea grease of high base number composite calcium-base four and preparation method thereof | |
CN104449956B (en) | A kind of high base number composite calcium-base polyurea grease and preparation method thereof | |
CN106032487B (en) | Lubricant composition and preparation method thereof | |
CN106032479B (en) | Lubricant composition and preparation method thereof | |
CN104560273B (en) | A kind of complex calcium sulfonate calcium naphthenate zirconium base octa-polyurea lubricating grease and preparation method thereof | |
CN104560320B (en) | A kind of composite calcium naphthenate calcium zirconium base polyurea grease and preparation method thereof | |
CN104450113B (en) | A kind of high base number composite calcium-base octa-polyurea lubricating grease and preparation method thereof | |
CN104450112B (en) | A kind of polyurea grease of high base number composite calcium-base six and preparation method thereof | |
CN104560272B (en) | A kind of polyurea grease of complex calcium sulfonate calcium naphthenate zirconium base six and preparation method thereof | |
CN104449958B (en) | A kind of complex calcium sulfonate calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof | |
CN104560270B (en) | A kind of polyurea grease of complex calcium sulfonate calcium naphthenate zirconium base four and preparation method thereof | |
CN104560325B (en) | A kind of polyurea grease of composite calcium naphthenate calcium zirconium base six and preparation method thereof | |
CN104449957B (en) | A kind of complex calcium sulfonate calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof | |
CN104449960B (en) | A kind of complex calcium sulfonate Calcium naphthenate base polyurea grease and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |