CN104560278B - A kind of sulfoacid calcium calcium naphthenate zirconium base lubricating grease and preparation method thereof - Google Patents
A kind of sulfoacid calcium calcium naphthenate zirconium base lubricating grease and preparation method thereof Download PDFInfo
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- CN104560278B CN104560278B CN201310522896.5A CN201310522896A CN104560278B CN 104560278 B CN104560278 B CN 104560278B CN 201310522896 A CN201310522896 A CN 201310522896A CN 104560278 B CN104560278 B CN 104560278B
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Abstract
The invention discloses a kind of sulfoacid calcium calcium naphthenate zirconium base lubricating grease, including following components：10 70 weight % non-newtonian fluid sulfoacid calcium calcium naphthenate；The zirconates of 1 10 weight % higher fatty acids；1 15 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；10 80 weight % base oil, wherein, the zirconates of the higher fatty acids is formed by higher fatty acids and component A reactions, the zirconates of the small molecule inorganic acid and/or lower fatty acid is to be formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, and the component A is at least one of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide.The invention also discloses sulfoacid calcium calcium naphthenate zirconium base preparation of greases method and its sulfoacid calcium calcium naphthenate zirconium base lubricating grease of preparation.The lubricating grease of the present invention, there is more preferable mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and extreme pressure anti-wear.
Description
Technical field
The present invention relates to lubricating grease, in particular it relates to a kind of sulfoacid calcium-calcium naphthenate zirconium base lubricating grease and its preparation side
Method.
Background technology
Sulfoacid calcium is used as the detersive and the history of antirust agent existing decades of lubricating oil, is widely used in internal combustion engine lubrication
The additive of oil, the development of its technology mainly make its height alkalization, are exactly alkyl benzene sulphonate of the calcium carbonate with surface-active
Calcium or alkyl carboxylic acid calcium turn into a kind of colloidal dispersion system to be distributed in flux oil.Calcium sulfonate with high base number according to the mode of production not
It is same to be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate.Calcium mahogany sulfonate is to use oleum or SO3Sulfonation mineral lubricating oil produces
Accessory substance mahogany acid during white oil, through with Ca (OH)2React, the contour alkalization technology that is carbonated and obtain；Calcium alkylbenzenesulfonate is to use
Oleum or SO3The alkylbenzene of sulfonation synthesis, the alkyl benzene sulphonate of generation pass through and Ca (OH)2React, be carbonated contour alkalization skill
Art and obtain.
Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusivity, can
To be used as the detersive of lubricating oil, the additive of IC engine lubricating oil is widely used in, the development of its technology mainly makes its high-alkali
Change, calcium carbonate is exactly turned into a kind of colloidal dispersion system with the naphthenic acid calcium with surface-active to be distributed in flux oil.It is high
Base number calcium naphthenate mostly be the acidic components extracted in the distillate obtained from crude distillation, through with Ca (OH)2Reaction, carbonating
Contour alkalization technology and obtain, about prepare Patents have CN1465560 etc..
Using calcium sulfonate with high base number be raw material produce lubricating grease, because its have excellent high temperature performance, mechanical stability,
Colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, domestic and international profit is caused
The extensive concern of consistent lubricant industry, however, although sulfonate with high base number calcium-base grease has very excellent combination property, but it is given birth to
The high price and complicated preparation technology itself for producing raw material calcium sulfonate with high base number cause it not promoted rapidly, meanwhile, with
Requirement more and more higher of the people to environmental protection, in calcium sulfonate with high base number production process must through dirt of the sulfonation process to environment
Dye is also increasingly subject to the concern of people.It is similar with sulfonate with high base number calcium-base grease but above-mentioned ask can be avoided to find a kind of performance
The lubricating grease of topic turns into the big problem that people face at present.
Zirconium belongs to Group IVB as a kind of transition metal, positioned at the 5th cycle.Zirconium-containing compound has excellent lubrication
Effect, is often used as lubricating additive, if CN101113382 and JP1973038444 is using the oxide of zirconium as lubricant addition
Agent improves abrasiveness；WO2007143414 and US20060063682, which describes zirconium tetrafluoride, to be turned into as wear reducing additive
One of component of lubricant；It is resistance to heavy well that US20060254823 has found that the lubricant containing 2 ethyl hexanoic acid zirconates is shown
Load and abrasion resistance；US20050043189 has found that fluozirconate such as fluorine zirconic acid aluminium can be used in lubricant as oxidation retarder
In；DE102004021812 has found that the inorganic salts such as zirconium carbonate, sulfonic acid zirconium or basic zirconium phosphate are added to inside lubricating grease and can improved
Abrasion resistance.
The content of the invention
It is an object of the invention to provide a kind of mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and
Extreme pressure anti-wear is preferable, and cost is low, simple and environmentally-friendly lubricating grease of preparation technology and preparation method thereof.
The present inventor has found under study for action, on the basis of lubricating grease weight, including following components：10-70 weight %
Non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 weight % small molecule inorganic acid
And/or the zirconates of lower fatty acid；10-80 weight % base oil, wherein, the zirconates of the higher fatty acids is by advanced fat
Fat acid forms with component A reactions, the zirconates of the small molecule inorganic acid and/or lower fatty acid be by small molecule inorganic acid with/
Or lower fatty acid forms with component A reactions, the component A is in the hydroxide and zirconium alkoxide of the oxide of zirconium, zirconium
It is at least one.The lubricating grease has preferable mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and pole
Wear resistence is pressed, and cost is low, preparation technology is simple and environmentally-friendly.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of sulfoacid calcium-calcium naphthenate zirconium base lubrication
Fat, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；1-10 weights
Measure the zirconates of % higher fatty acids；1-15 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；10-80 weight %
Base oil, wherein, the zirconates of the higher fatty acids is formed by higher fatty acids and component A reactions, the small molecule without
The zirconates of machine acid and/or lower fatty acid is to be formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, described
Component A is at least one of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide.
Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid sulfoacid calcium-ring
Alkanoic acid calcium；The zirconates of 2-6 weight % higher fatty acids；2-10 weight % small molecule inorganic acid and/or the zirconium of lower fatty acid
Salt；20-70 weight % base oil.
Preferably, the component A is the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, in terms of zirconium, zirconium
Oxide and/or the mol ratio of hydroxide and zirconium alkoxide be 1：0.1-10, more preferably 1：0.5-5.
Second aspect, should the invention provides sulfoacid calcium as described above-calcium naphthenate zirconium base preparation of greases method
Method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid and/or lower aliphatic
Zirconates and the part basis oil of acid are well mixed, are refined in 180-230 DEG C of constant temperature, add surplus base oil, add necessary add
Add agent, obtain finished product.
The third aspect, the invention provides a kind of sulfoacid calcium-calcium naphthenate zirconium base preparation of greases method, this method bag
Include：
（1）Newton body sulfoacid calcium, newton body calcium naphthenate, part basis oil and transforming agent are mixed, heating treats that material becomes
It is thick；
（2）In step（1）Component A is added in products therefrom, add higher fatty acids and small molecule inorganic acid and/or
Lower fatty acid is reacted, and heat up dehydration after reaction, and the component A is oxide, the hydroxide and alkoxy of zirconium of zirconium
At least one of zirconium；
（3）By step（2）Reaction gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds surplus base oil, adds
Necessary additive, obtains finished product.
Fourth aspect, the invention provides the sulfoacid calcium as made from method as described above-calcium naphthenate zirconium base lubricating grease.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease of the present invention, compared to calcium sulfonate grease, there is preferably machinery peace
Qualitative, water-resistance and adhesiveness, resistance to saltfog, colloid stability and extreme pressure anti-wear.The preparation of greases technique of the present invention
Simple and environmentally-friendly, cost is low, and product quality is stable.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of sulfoacid calcium-calcium naphthenate zirconium base lubricating grease, this lubricating grease employs calcium mahogany sulfonate
And/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, simultaneously containing compound zirconium thickening agent.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides sulfoacid calcium-calcium naphthenate zirconium base lubricating grease, on the basis of lubricating grease weight, including
Following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15
Weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；10-80 weight % base oil, wherein, higher fatty acids
Zirconates is formed by higher fatty acids and component A reactions, and the zirconates of small molecule inorganic acid and/or lower fatty acid is by small molecule
Inorganic acid and/or lower fatty acid form with component A reactions, and component A is oxide, the hydroxide and zirconium alkoxide of zirconium of zirconium
At least one of.
Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid sulfoacid calcium-ring
Alkanoic acid calcium；The zirconates of 2-6 weight % higher fatty acids；2-10 weight % small molecule inorganic acid and/or the zirconium of lower fatty acid
Salt；20-70 weight % base oil；It is highly preferred that on the basis of lubricating grease weight, including following components：30-55 weight %'s is non-
Newton body sulfoacid calcium-calcium naphthenate；The zirconates of 2.2-4.5 weight % higher fatty acids；3-8 weight % small molecule inorganic acid
And/or the zirconates of lower fatty acid；30-60 weight % base oil.
Non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm-1-886cm-1There is the suction of crystal form calcium carbonate feature in place
Receive peak, preferably total base number 250mgKOH/g-450mgKOH/g, 300mgKOH/g-400mgKOH/g.Non-newtonian fluid sulfonic acid
Calcium-calcium naphthenate is to convert to obtain by transforming agent by newton body sulfoacid calcium and newton body calcium naphthenate.And newton body sulfoacid calcium,
Contain unformed calcium carbonate in newton body calcium naphthenate, in infrared spectrum 860cm-1-865cm-1It is special that unformed calcium carbonate occurs in place
Levy absworption peak.Newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g-
450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis
Calcium naphthenate, its total base number are 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid
The base number of sulfoacid calcium-calcium naphthenate is averaged for the weight of the base number and the base number of newton body calcium naphthenate of newton body sulfoacid calcium
Value.
In the present invention, higher fatty acids is that carbon number is 8-20, preferably 10-16 straight chain fatty acid or hydroxy fatty acid, example
Such as at least one of laurate, palmitic acid, stearic acid, 12- hydroxy stearic acids, eicosyl carboxylic acid, preferably 12- hydroxyls are hard
Resin acid.
In the present invention, the molecular weight of small molecule inorganic acid or lower fatty acid is less than or equal to 150.Wherein, small molecule is inorganic
Acid can be selected from least one of boric acid, phosphoric acid, sulfuric acid etc., preferably boric acid and/or phosphoric acid；Lower fatty acid can be selected from
At least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid etc., preferably acetic acid.
The present inventor has been surprisingly found that under study for action, when the oxide and/or hydroxide and alcoxyl that component A is zirconium
During the mixture of base zirconium, i.e., when the raw material of zirconium is the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, one can be entered
Step improves mechanical stability, water-resistance and adhesiveness, colloid stability and the extreme pressure anti-wear of lubricating grease, and therefore, component A is preferred
The mixture of oxide and/or hydroxide and zirconium alkoxide for zirconium, wherein, in terms of zirconium, the oxide and/or hydroxide of zirconium
The mol ratio of thing and zirconium alkoxide is preferably 1：0.1-10, more preferably 1：0.2-8, it is still more preferably 1：0.5-5, in zirconium
Oxide and/or the preferred molar ratio of hydroxide and zirconium alkoxide in the case of, can further improve the machine of lubricating grease
Tool stability, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear.
In the present invention, the oxide and/or hydroxide of zirconium are preferably selected from ZrO2、ZrO(OH)2、Zr(OH)4And they
At least one of hydrate.ZrO(OH)2Hydrate can be brand-new wet hydrogen zirconium oxide, it can pass through ZrOX2·
8H2O（X is F, Cl, Br or I）Or ZrO (NO3)2·2H2O etc. reacts with alkali to be obtained, wherein, alkali can be NaOH, KOH, dense ammonia
Water etc., preferably ZrOCl2·8H2O and NaOH reacts.
In the present invention, the formula of zirconium alkoxide can be Zr (OR1)4, R1Can be C1-C10 alkyl, preferably C2-C6
Alkyl；It is highly preferred that zirconium alkoxide in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and n-amyl alcohol zirconium extremely
Few one kind.
The lube base oil can be mineral oil, artificial oil, vegetable oil or their mixture, and 100 DEG C of motions are glutinous
Spend for 4-60mm2/ s, preferably 10-30mm2/s.Artificial oil can be poly ＆ Alpha ,-olefin oil（PAO）, Esters oil, alkyl-silicone oil, Fischer-Tropsch
Artificial oil etc..
Various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the present invention.Its
In, the preferred arylamine kind antioxidant of antioxidant, account for 0.01-5%, the preferably 0.1-2.5% of lubricating grease gross weight, can be diphenylamines,
At least one of phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease
The 0.5-12% of gross weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two
Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethyl-ne
Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid
At least one of calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil
At least one of barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, should the invention provides sulfoacid calcium as described above-calcium naphthenate zirconium base preparation of greases method
Method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid and/or lower aliphatic
Zirconates and the part basis oil of acid are well mixed, are refined in 180-230 DEG C of constant temperature, add surplus base oil, add necessary add
Add agent, obtain finished product.
In the present invention, for non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid and/
Or zirconates, base oil and the additive of lower fatty acid are as described above, will not be repeated here.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are used
Base oil total amount, in the present invention, part basis oil and the weight ratio preferably 1 of surplus base oil：0.1-5.
For non-newtonian fluid sulfoacid calcium-calcium naphthenate, conversion can be passed through by newton body sulfoacid calcium, newton body calcium naphthenate
Agent converts to obtain, for example, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, adds institute
The transforming agent needed is reacted, and after all transforming agents add, in 60-90 DEG C of constant temperature 60-90 minute, then heats to 100-120
DEG C dehydration.
The third aspect, the invention provides a kind of sulfoacid calcium-calcium naphthenate zirconium base preparation of greases method, including：
（1）Newton body sulfoacid calcium, newton body calcium naphthenate, part basis oil and transforming agent are mixed, heating treats that material becomes
It is thick；
（2）In step（1）Component A is added in products therefrom, add higher fatty acids and small molecule inorganic acid and/or
Lower fatty acid is reacted, and heat up dehydration after reaction, and the component A is oxide, the hydroxide and alkoxy of zirconium of zirconium
At least one of zirconium；
（3）By step（2）Reaction gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds surplus base oil, adds
Necessary additive, obtains finished product.
Step（1）In, by newton body sulfoacid calcium, newton body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C,
It is preferred that constant temperature 10-30 minutes, add required transforming agent and reacted, 8-12 minutes are stirred after preferably adding every kind of transforming agent,
After all transforming agents add, in 60-90 DEG C of constant temperature 60-90 minute.
Step of the present invention（1）In, it is excellent for the weight ratio of newton body sulfoacid calcium and newton body calcium naphthenate without particular/special requirement
Elect 1 as：0.25-4.Newton body sulfoacid calcium and the gross weight of newton body calcium naphthenate and the weight ratio of part basis oil are preferably 1：
0.1-3。
In the present invention, newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/
G-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or conjunction
Into calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.
The transforming agent be preferably selected from fatty alcohol, aliphatic acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid,
At least one of phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonates and water；It is more excellent
Choosing selected from C1-C5 fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine,
C1-C5 ether, boric acid, C1-C10 alkyl phosphonic acid, C2-C16 di alkyl phosphonic acid, C6-C20 arylphosphonic acid, C12-C24
At least one of diaryl phosphonic acids, C7-C20 aromatic alcohol, C7-C20 aromatic amine, C8-C20 alkyl benzene sulphonates and water；More
At least one further preferably in DBSA, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water
Kind.The addition of transforming agent is preferably the 2-30% of newton body sulfoacid calcium and newton body calcium naphthenate gross weight, more preferably newton
The 6-22% of body sulfoacid calcium and newton body calcium naphthenate gross weight.
In the present invention, fatty alcohol includes the fatty alcohol of straight chain, side chain and ring-type, aliphatic acid, aliphatic ketone, fatty aldehyde, fat
Amine is similarly.
As it was previously stated, the present inventor has been surprisingly found that under study for action, step（2）In, when the oxide that component A is zirconium
And/or during the mixture of hydroxide and zirconium alkoxide, i.e., the raw material of zirconium is the oxide and/or hydroxide and alkoxy of zirconium
During the mixture of zirconium, can further improve mechanical stability, water-resistance and the adhesiveness of obtained lubricating grease, colloid stability and
Extreme pressure anti-wear, it is therefore preferred that step（2）In, at 85-100 DEG C, component A is added, adds higher fatty acids, stirs 5-
20 minutes, small molecule inorganic acid and/or lower fatty acid are added, 5-20 minutes is stirred, is warming up to 100-120 DEG C, preferably keeps
30-60 minutes, dehydration, the component A is the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, in terms of zirconium, zirconium
Oxide and/or the mol ratio of hydroxide and zirconium alkoxide be preferably 1：0.1-10, more preferably 1：0.2-8, more enter one
Step is preferably 1：0.5-5.Wherein, higher fatty acids can be handed over the addition sequence of small molecule inorganic acid and/or lower fatty acid
Change.
In the present invention, higher fatty acids, small molecule inorganic acid, lower fatty acid, the oxide of zirconium, zirconium hydroxide and
Zirconium alkoxide is as it was previously stated, will not be repeated here.
In the present invention, higher fatty acids and small molecule inorganic acid and/or the H of lower fatty acid+The amount of total material is equal to complete
Portion neutralizes the H needed for the hydroxide and zirconium alkoxide of the oxide of zirconium, zirconium+Molal quantity, but the hydrogen-oxygen of the oxide of zirconium, zirconium
Compound and zirconium alkoxide can excessive 1-10% relative to higher fatty acids and small molecule inorganic acid and/or lower fatty acid.
In the present invention, the addition of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide is preferably newton body sulfoacid calcium
With the 1-15% of newton body calcium naphthenate gross weight；With H+Material gauge, higher fatty acids and small molecule inorganic acid and/or
The mol ratio of lower fatty acid is preferably 1：1-10.
Step（3）In, it is warming up to 180-230 DEG C of constant temperature 5-20 minute；Surplus base oil is added, treats that temperature is cooled to 100-
120 DEG C, necessary additive is added, is stirred, circulating filtration, homogenizing, degassing.
In the present invention, step（1）In part basis used oil and step（3）The weight ratio preferably 1 of middle surplus base oil：
0.1-5。
Fourth aspect, present invention also offers sulfoacid calcium-ring made from the preparation method provided as third aspect present invention
Alkanoic acid calcium zirconium base lubricating grease.
Compared with the sulfoacid calcium as made from the preparation method that second aspect provides-calcium naphthenate zirconium base lubricating grease, third party
Face provide preparation method made from sulfoacid calcium-calcium naphthenate zirconium base lubricating grease have more preferable mechanical stability, water-resistance and
Adhesiveness, colloid stability and extreme pressure anti-wear.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the following Examples and Comparative Examples：
Non-newtonian fluid sulfoacid calcium-calcium naphthenate %=（Overbased or calcium sulfonate with high base number raw material weight+overbased or high
Base number calcium naphthenate raw material weight+transforming agent gross weight）/ lubricating grease gross weight × 100%.Transforming agent is included in non-newtonian fluid sulphur
In the content of sour calcium-calcium naphthenate.
The zirconates of higher fatty acids and the content of the zirconates of small molecule inorganic acid and/or lower fatty acid, according to added
Higher fatty acids and small molecule inorganic acid and/or the oxide of lower fatty acid and zirconium, the hydroxide and alcoxyl of zirconium entered
The amount that base zirconium reacts generation zirconates completely calculates.
Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd, also may be used
To be prepared according to method disclosed in CN101885677A.
Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industries Co., Ltd.
Embodiment 1
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)4（3.9kg）；12- hydroxy stearic acids（2kg）；Boron
Acid（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 18kg）.
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control exists
50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；60 DEG C are warming up to,
Constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, adds the Zr (OH) that solid content is 20 weight %4Suspension 19.5kg, stirring
10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, is stirred
Mix 10 minutes, 110 DEG C are warming up under stirring, kept for 45 minutes, dehydration；It is warming up to 200 DEG C of constant temperature 10 minutes.Then, add
18kg HVI500SN lubricating base oils, treat that temperature is cooled to 110 DEG C, 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, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 2
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 420mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total alkali
It is worth for 420mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Ethanol zirconium（5.6kg）；ZrO(OH)2（0.58kg）；12- hydroxyls
Base stearic acid（2kg）；Boric acid（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 18kg）.
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 6kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 420mgKOH/g for 420mgKOH/g overbased sulfoacid calcium, 24kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 65 DEG C, constant temperature 20 minutes；2.8kg aphthenic acids is added, temperature control exists
65 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；75 DEG C are warming up to,
Constant temperature 75 minutes, material retrogradation；85 DEG C are warming up to, successively adds the ZrO (OH) of 5.6kg ethanol zirconium and solid content for 20 weight %2
Suspension 2.9kg, in terms of zirconium, ZrO (OH)2Mol ratio with ethanol zirconium is 1：5, stir 10 minutes；It is hard to add 2kg12- hydroxyls
Resin acid, stir 10 minutes；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, stirs 10 minutes, is warming up under stirring
100 DEG C, kept for 60 minutes, dehydration；It is warming up to 230 DEG C of constant temperature 5 minutes.Then, 18kg HVI500SN lubricating base oils are added,
Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 3
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total alkali
It is worth for 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 20kg）；Butanol
（2.8kg）；Acetic acid（0.56kg）；Zirconium-n-butylate（3.13kg）；Zr(OH)4（2.6kg）；Stearic acid（1.9kg）；Boric acid
（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 28kg）.
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 20kg for being 320mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 80 DEG C, constant temperature 10 minutes；2.8kg butanol is added, temperature control is 80
DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；90 DEG C are warming up to, perseverance
Temperature 60 minutes, material retrogradation；Successively add the Zr (OH) of 3.13kg zirconium-n-butylates and solid content for 20 weight %4Suspension 13kg,
In terms of zirconium, Zr (OH)4Mol ratio with zirconium-n-butylate is 1：0.5, stir 10 minutes；1.9kg stearic acid is added, stirs 10 points
Clock；The boric acid aqueous solution that 9.28kg concentration is 25 weight % is added, is stirred 10 minutes, 120 DEG C are warming up under stirring, is kept for 30 points
Clock, dehydration；It is warming up to 180 DEG C of constant temperature 20 minutes.Then, 160 DEG C are cooled to, adds 28kg HVI500SN lubricating base oils,
Treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.3；The weight % of lubricating base oil 55.0；The weight % of zirconyl stearate 2.6；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 4
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 33kg）；Overbased calcium alkyl-salicylate（Total alkali
It is worth for 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 20kg）；Dodecyl
Benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Zirconium-n-propylate（4.0kg）；Zr(OH)4（2.0kg）；12- hydroxy stearic acids（2kg）；
Boric acid（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 28kg）.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses
Total base number is 320mgKOH/g overbased calcium alkyl-salicylate；Aphthenic acids is replaced with DBSA；Add Zr (OH)4When also
Add zirconium-n-propylate, in terms of zirconium, Zr (OH)4Mol ratio with zirconium-n-propylate is 1：1；The dosage of each composition is as above.Assay
It is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 44.0；The weight % of lubricating base oil 49.8；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.4；The weight % of boric acid oxygen zirconium 3.8.
Embodiment 5
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids（Total acid
It is worth for 180mgKOH/g, 1.8kg）；Butanol（1.0kg）；Acetic acid（0.56kg）；Zr(OH)4（3.9kg）；12- hydroxy stearic acids
（2kg）；Boric acid（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 7kg）；It is right, it is right '-two different
Octyl diphenylamine（0.4kg）.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium uses total
Base number is 320mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；Transforming agent is three kinds, adds butanol after aphthenic acids is added, then adds acetic acid；And treat that temperature is cooled to 110 DEG C,
0.4kg pair is added, right '-di-iso-octyldiphenylamine, after stirring 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；
The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 54.0；The weight % of lubricating base oil 35.6；The weight % of 12- hydroxy stearic acid oxygen zirconium 3.8；The weight % of boric acid oxygen zirconium 5.9；
It is right, right ' weight % of-di-iso-octyldiphenylamine 0.7.
Embodiment 6
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total alkali
It is worth for 400mgKOH/g, 24kg）；Poly alpha olefine synthetic oil PAO40（100 DEG C of kinematic viscosity are 41mm2/ s, 30kg）；Dodecane
Base benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Zr(OH)4（3.9kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；
Poly alpha olefine synthetic oil PAO10（100 DEG C of kinematic viscosity are 11mm2/ s, 18kg）.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, use dodecyl
Benzene sulfonic acid replaces aphthenic acids；Use poly alpha olefine synthetic oil PAO40（100 DEG C of kinematic viscosity are 41mm2/s）Closed with poly alpha olefin
Into oily PAO10（100 DEG C of kinematic viscosity are 11mm2/s）Respectively instead of HVI150BS（100 DEG C of kinematic viscosity are 31mm2/s）With
HVI500SN（100 DEG C of kinematic viscosity are 11mm2/s）；The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 7
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)4（3.9kg）；12- hydroxy stearic acids（2kg）；Boric acid
（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 18kg）.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses
Total base number is 320mgKOH/g overbased calcium alkyl-salicylate；The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 8
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total base number
For 400mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)4（3.9kg）；12- hydroxy stearic acids（2kg）；Boric acid
（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 18kg）.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium uses total
Base number is 320mgKOH/g calcium sulfonate with high base number；The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1
Embodiment 9
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number is
320mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids（Total acid
It is worth for 180mgKOH/g, 1.8kg）；Methanol（1.0kg）；Acetic acid（0.56kg）；Zr(OH)4（3.9kg）；12- hydroxy stearic acids
（2kg）；Boric acid（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 33kg）.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium uses total
Base number is 320mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；Transforming agent is three kinds, adds methanol after aphthenic acids is added, then adds acetic acid；The dosage of each composition is as above.Examine knot
Fruit is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 10
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 15kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Dodecane
Base benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Zr(OH)4（6.3kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；
Phosphoric acid（1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 33kg）；It is right, right '-diisooctyl hexichol
Amine（0.2kg）.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, use dodecyl
Benzene sulfonic acid replaces aphthenic acids；Phosphoric acid is additionally added after boric acid is added, then heat up dehydration again；And treat that temperature is cooled to 110 DEG C,
0.2kg pair is added, right '-di-iso-octyldiphenylamine, after stirring 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；
The dosage of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 37.0；The weight % of lubricating base oil 53.3；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of boric acid oxygen zirconium 4.0；
The weight % of zirconium phosphate oxygen 2.9；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 11
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 360mgKOH/g, 15kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（2.8kg）；Acetic acid（0.56kg）；Zr(OH)4（6.6kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；Acetic acid
（2kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 18kg）；It is right, right '-di-iso-octyldiphenylamine
（0.2kg）.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, sulfoacid calcium uses total
Base number is 360mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；Acetic acid is additionally added after boric acid is added, then heat up dehydration again；And treat that temperature is cooled to 110 DEG C, add 0.2kg pair,
Right '-di-iso-octyldiphenylamine, after stirring 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The dosage of each composition is such as
On.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 36.5；The weight % of lubricating base oil 52.6；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of boric acid oxygen zirconium 4.0；
The weight % of zirconyl acetate 4.1；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 12
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)4（3.9kg）；12- hydroxy stearic acids（2kg）；Boron
Acid（2.32kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 18kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control exists
50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；60 DEG C are warming up to,
Constant temperature 90 minutes, material retrogradation.
Another volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 7kg
HVI500SN lubricating base oils, the Zr (OH) that solid content is 20 weight % is added at 100 DEG C4Suspension 19.5kg, stir 10 points
Clock；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；Add the boric acid aqueous solution that 9.28kg concentration is 25 weight %, stirring 10
Minute, obtain 12- hydroxy stearic acid oxygen zirconiums and boric acid oxygen zirconium.
Gained 12- hydroxy stearic acid oxygen zirconiums and boric acid oxygen zirconium are all squeezed into a upper kettle, stirs, is risen under stirring
Temperature is kept for 45 minutes to 110 DEG C, dehydration；It is warming up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubrications base is added
Plinth oil, treats that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 13
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, aphthenic acids is replaced
For phenol, acetic acid is replaced with into butyric acid.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 14
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, aphthenic acids is replaced
For methyl propyl ketone, aqueous acetic acid is replaced with into butyl ether.Assay is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；The weight % of boric acid oxygen zirconium 4.1.
Embodiment 15
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 4, unlike, at Zr (OH)4Just
In the case that the total mole number of propyl alcohol zirconium is constant, Zr (OH) is adjusted4Mol ratio with zirconium-n-propylate is 1：0.1.Gained fat it is each
Physicochemical property is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 44.0；The weight % of lubricating base oil 49.8；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.4；The weight % of boric acid oxygen zirconium 3.8.
Embodiment 16
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 4, unlike, at Zr (OH)4Just
In the case that the total mole number of propyl alcohol zirconium is constant, Zr (OH) is adjusted4Mol ratio with zirconium-n-propylate is 1：10.Each reason of gained fat
Change performance and be shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 44.0；The weight % of lubricating base oil 49.8；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.4；The weight % of boric acid oxygen zirconium 3.8.
Embodiment 17
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 4, unlike, zirconium-n-propylate is replaced
It is changed to equimolar Zr (OH)4.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 44.0；The weight % of lubricating base oil 49.8；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.4；The weight % of boric acid oxygen zirconium 3.8.
Embodiment 18
The present embodiment is used for the sulfoacid calcium-calcium naphthenate zirconium base lubricating grease for illustrating prepared by the present invention.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease is prepared according to the method for embodiment 4, unlike, by Zr (OH)4Replace
For equimolar zirconium-n-propylate.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 44.0；The weight % of lubricating base oil 49.8；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.4；The weight % of boric acid oxygen zirconium 3.8.
Comparative example 1
Method according to embodiment 1 prepares calcium sulfonate grease, unlike, naphthenate with superhigh base number calcium is replaced with
Total base number is 400mgKOH/g overbased sulfoacid calcium, Zr used (OH)4With Ca (OH)2Instead of, while adjust dosage and make respectively
Component content is consistent with embodiment 1.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight of non-newtonian fluid sulfoacid calcium 38.2
Measure %；The weight % of lubricating base oil 55.0；The weight % of 12- hydroxy stearic acids calcium 2.7；The weight % of line borate 4.1.
Comparative example 2
Method according to embodiment 5 prepares calcium sulfonate grease, unlike, overbased calcium alkyl-salicylate is replaced with always
Base number is 320mgKOH/g calcium sulfonate with high base number, Zr used (OH)4With Ca (OH)2Instead of, while adjust dosage and make each composition
Content is consistent with embodiment 5.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight of non-newtonian fluid sulfoacid calcium 54.0
Measure %；The weight % of lubricating base oil 35.6；The weight % of 12- hydroxy stearic acids calcium 3.8；The weight % of line borate 5.9；It is right, it is right '-two different pungent
The weight % of base diphenylamines 0.7.
Each lubricating grease properties of sample data of table 1
Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Water resistant is sprayed：SH/
T0643；Stencil oil-dividing：SH/T0324；Tetra-ball machine test：SH/T0202.
Table 1（It is continuous）Each lubricating grease properties of sample data
Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Water resistant is sprayed：SH/
T0643；Stencil oil-dividing：SH/T0324；Tetra-ball machine test：SH/T0202.
By embodiment 1 compared with comparative example 1, by embodiment 5 compared with comparative example 2, it can be seen that the present invention
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease extend work cone penetration with work cone penetration difference be less than sulfoacid calcium base lubrication
Fat, water leaching number of dropouts are much smaller than calcium sulfonate grease, and salt spray test is better than calcium sulfonate grease, and water resistant spraying value is less than sulphur
Sour calcium-base grease, Stencil oil-dividing value are less than calcium sulfonate grease, and tetra-ball machine test value is more than calcium sulfonate grease, explanation
Mechanical stability, water-resistance and adhesiveness, resistance to saltfog, the colloid peace of sulfoacid calcium-calcium naphthenate zirconium base lubricating grease of the present invention
Qualitative and extreme pressure anti-wear is superior to calcium sulfonate grease.
By embodiment 1 as can be seen that sulfoacid calcium-calcium naphthenate zirconium base the lubrication in situ prepared compared with embodiment 12
Fat, there is more preferable mechanical stability, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear；By embodiment 1 respectively with
Embodiment 13 and embodiment 14 are compared as can be seen that transforming agent is selected from DBSA, aphthenic acids, methanol, isopropyl
At least one of alcohol, butanol, boric acid, acetic acid and water, sulfoacid calcium-calcium naphthenate zirconium base lubricating grease of preparation, have more preferable
Mechanical stability, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear；By embodiment 4 respectively with embodiment 15 and real
Example 16 is applied to be compared as can be seen that the oxide and/or the mol ratio of hydroxide and zirconium alkoxide of zirconium are 1：0.5-5, system
Standby sulfoacid calcium-calcium naphthenate zirconium base lubricating grease, there is more preferable mechanical stability, water-resistance and adhesiveness, colloid stability
And extreme pressure anti-wear；By embodiment 4 respectively compared with embodiment 17 and embodiment 18 as can be seen that the raw material of zirconium is zirconium
The mixture of oxide and/or hydroxide and zirconium alkoxide, sulfoacid calcium-calcium naphthenate zirconium base lubricating grease of preparation, have more
Mechanical stability, water-resistance and adhesiveness well, colloid stability and extreme pressure anti-wear.
Sulfoacid calcium-calcium naphthenate zirconium base lubricating grease of the present invention, compared to calcium sulfonate grease, there is preferably machinery peace
Qualitative, water-resistance and adhesiveness, resistance to saltfog, colloid stability and extreme pressure anti-wear.The preparation of greases technique of the present invention
Simple and environmentally-friendly, cost is low, and product quality is stable.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (21)
1. a kind of sulfoacid calcium-calcium naphthenate zirconium base lubricating grease, it is characterised in that on the basis of lubricating grease weight, including with the following group
Point：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 weights
Measure % small molecule inorganic acid and/or the zirconates of lower fatty acid；10-80 weight % base oil, wherein, the higher aliphatic
The zirconates of acid is formed by higher fatty acids and component A reactions, and the zirconates of the small molecule inorganic acid and/or lower fatty acid is
Formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, the component A is oxide, the hydroxide of zirconium of zirconium
At least one of thing and zirconium alkoxide, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm-1-886cm-1
There is crystal form calcium carbonate characteristic absorption peak in place.
2. lubricating grease according to claim 1, wherein, on the basis of lubricating grease weight, including following components：20-60 weights
Measure % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 2-6 weight % higher fatty acids；2-10 weight % small molecule
The zirconates of inorganic acid and/or lower fatty acid；20-70 weight % base oil.
3. lubricating grease according to claim 1, wherein, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is by newton body sulphur
Sour calcium and newton body calcium naphthenate convert what is obtained, and the total base number of the non-newtonian fluid sulfoacid calcium-calcium naphthenate is 250-
450mgKOH/g。
4. lubricating grease according to claim 1 or 2, wherein, the higher fatty acids is the straight chain fatty that carbon number is 8-20
Acid or hydroxy fatty acid.
5. lubricating grease according to claim 4, wherein, the higher fatty acids be selected from laurate, palmitic acid, stearic acid,
At least one of 12- hydroxy stearic acids, eicosyl carboxylic acid.
6. lubricating grease according to claim 1 or 2, wherein, the molecular weight of small molecule inorganic acid or lower fatty acid is less than
Equal to 150.
7. lubricating grease according to claim 6, wherein, the small molecule inorganic acid in boric acid, phosphoric acid, sulfuric acid extremely
Few one kind, the lower fatty acid are selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid.
8. lubricating grease according to claim 1 or 2, wherein, the component A be zirconium oxide and/or hydroxide with
The mixture of zirconium alkoxide, in terms of zirconium, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：0.1-10.
9. lubricating grease according to claim 8, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium
Mol ratio be 1：0.5-5.
10. lubricating grease according to claim 1 or 2, wherein, the oxide and/or hydroxide of zirconium are selected from ZrO2、ZrO
(OH)2、Zr(OH)4And at least one of their hydrate.
11. lubricating grease according to claim 1 or 2, wherein, the formula of the zirconium alkoxide is Zr (OR1)4, R1For C1-
C10 alkyl.
12. lubricating grease according to claim 11, wherein, the zirconium alkoxide is selected from ethanol zirconium, zirconium-n-propylate, n-butanol
At least one of zirconium, zirconium tert-butoxide and n-amyl alcohol zirconium.
13. sulfoacid calcium-calcium naphthenate zirconium base preparation of greases method in claim 1-12 described in any one, its feature
It is, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, small molecule inorganic acid and/or
Zirconates and the part basis oil of lower fatty acid are well mixed, are refined in 180-230 DEG C of constant temperature, add surplus base oil, added
Necessary additive, obtains finished product.
14. sulfoacid calcium-calcium naphthenate zirconium base preparation of greases method in claim 1-12 described in any one, its feature
It is, this method includes：
(1) newton body sulfoacid calcium, newton body calcium naphthenate, part basis oil and transforming agent are mixed, material retrogradation is treated in heating；
(2) component A is added in step (1) products therefrom, adds higher fatty acids and small molecule inorganic acid and/or rudimentary
Aliphatic acid is reacted, and heat up dehydration after reaction, and the component A is in the hydroxide and zirconium alkoxide of the oxide of zirconium, zirconium
At least one；
(3) step (2) is reacted into gained mixture and is warming up to 180-230 DEG C of constant temperature refining, added surplus base oil, add necessary
Additive, obtain finished product.
15. according to the method for claim 14, wherein, in step (1), by newton body sulfoacid calcium, newton body calcium naphthenate,
Part basis oil Hybrid Heating adds required transforming agent and reacted, after all transforming agents add, in 60-90 to 50-80 DEG C
DEG C constant temperature 60-90 minutes.
16. according to the method for claim 14, wherein, in step (2), at 85-100 DEG C, component A is added, is added high
Level aliphatic acid, stirs 5-20 minutes, adds small molecule inorganic acid and/or lower fatty acid, stirs 5-20 minutes, is warming up to 100-
120 DEG C of dehydrations, the component A is the oxide and/or the mixture of hydroxide and zirconium alkoxide of zirconium, in terms of zirconium, the oxygen of zirconium
Compound and/or the mol ratio of hydroxide and zirconium alkoxide are 1：0.1-10.
17. the method according to claim 11, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium
Mol ratio be 1：0.5-5.
18. according to the method for claim 14, wherein, in step (3), it is warming up to 180-230 DEG C of constant temperature 5-20 minute；Add
Enter surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassing.
19. according to the method for claim 14, wherein, the newton body sulfoacid calcium is calcium mahogany sulfonate and/or synthesis sulphur
Sour calcium, the total base number of the newton body sulfoacid calcium is 250-450mgKOH/g；The newton body calcium naphthenate is petroleum naphthenic acid
Calcium and/or synthesis calcium naphthenate, the total base number of the newton body calcium naphthenate is 250-450mgKOH/g.
20. according to the method for claim 14, wherein, the transforming agent is selected from fatty alcohol, aliphatic acid, aliphatic ketone, fat
Aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkylbenzenes
At least one of sulfonic acid and water, the addition of transforming agent are the 2- of newton body sulfoacid calcium and newton body calcium naphthenate gross weight
30%.
21. according to the method for claim 20, wherein, the transforming agent is selected from DBSA, aphthenic acids, first
At least one of alcohol, isopropanol, butanol, boric acid, acetic acid and water, the addition of transforming agent is newton body sulfoacid calcium and newton body
The 6-22% of calcium naphthenate gross weight.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453600A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based hexapolyurea lubricating grease and preparation method thereof |
| CN102911761A (en) * | 2012-10-24 | 2013-02-06 | 中国石油化工股份有限公司 | High-temperature-resistant extreme pressure type lubricating grease composition and preparation method |
| CN103060067A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
-
2013
- 2013-10-29 CN CN201310522896.5A patent/CN104560278B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453600A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based hexapolyurea lubricating grease and preparation method thereof |
| CN103060067A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
| CN102911761A (en) * | 2012-10-24 | 2013-02-06 | 中国石油化工股份有限公司 | High-temperature-resistant extreme pressure type lubricating grease composition and preparation method |
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