CN104513690B - Composite calcium-zirconium-based lubricating grease and preparation method thereof - Google Patents
Composite calcium-zirconium-based lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention discloses composite calcium-zirconium-based lubricating grease which comprises following components, on the basis of the weight of the lubricating grease, by weight, 5-50% of a composite calcium-zirconium-based thickening agent and 50-95% of basic oil, wherein the composite calcium-zirconium-based thickening agent is a calcium-zirconium soap generated through a reaction among a component A, a component B and a component C. The component A is a mixture composed of a higher fatty acid and an aromatic acid. The component B is an oxide and/or a hydroxide of calcium. The component C is at least one of an oxide of zirconium, a hydroxide of zirconium and alkoxyl zirconium. The invention also discloses a preparation method of the composite calcium-zirconium-based lubricating grease. Compared with zirconium-based lubricating grease, the composite calcium-zirconium-based lubricating grease is better in high-temperature resistance, mechanical stability, water resistance, adhesivity, salt fog resistance, colloid stability and extreme-pressure wear resistance. The lubricating grease is simple in the preparation method, is low in cost and is stable in quality.
Description
Technical field
The present invention relates to grease, in particular it relates to a kind of composite calcium zirconio grease and preparation method thereof.
Background technology
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, and such as CN101113382 and JP1973038444 adds the oxide of zirconium as lubricant
Agent improves abrasiveness；WO2007143414 and US20060063682 describe zirconium tetrafluoride can be become 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 shows
Load and abrasion resistance；US20050043189 has found that fluozirconate such as fluorine zirconic acid aluminum can be used in lubricant as oxidation retarder
In；DE102004021812 has found the inorganic salts such as zirconium carbonate, sulfonic acid zirconium or zirconium phosphate are added to inside grease and can be improved
Abrasion resistance.
There is US4189387 as the patent that thickening agent prepares zirconio grease using zirconates, thickening agent is by organic hypophosphorous acid
Or the reaction of monocarboxylic acid and zirconium hydroxide is obtained, obtained grease has a preferable extreme pressure anti-wear, but grease its
His performance still awaits further improving.
The content of the invention
It is an object of the invention to provide a kind of heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, glue
Body stability, extreme pressure anti-wear are preferable, low cost, composite calcium zirconio grease of preparation process is simple and preparation method thereof.
The present inventor has found under study for action, on the basis of grease weight, including following components：5-50 weight %
Composite calcium zirconio thickening agent；The base oil of 50-95 weight %, wherein, the composite calcium zirconio thickening agent is by component A, component
The calcium zirconium soap that B and the reaction of component C are generated, wherein, component A is higher fatty acids and the mixture of aromatic acid, and component B is
The oxide and/or hydroxide of calcium, component C is the oxide of zirconium, in the hydroxide of zirconium and zirconium alkoxide at least
It is a kind of.There is the grease preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid to stabilize
Property, extreme pressure anti-wear, and low cost, preparation process is simple.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of composite calcium zirconio grease, to lubricate
On the basis of fat weight, including following components：The composite calcium zirconio thickening agent of 5-50 weight %；The base oil of 50-95 weight %, its
In, the composite calcium zirconio thickening agent is that the calcium zirconium soap for generating is reacted by component A, component B and component C, wherein, component A
For higher fatty acids and the mixture of aromatic acid, oxide and/or hydroxide of component B for calcium, component C are zirconium
At least one in oxide, the hydroxide and zirconium alkoxide of zirconium.
Preferably, on the basis of grease weight, including following components：The composite calcium zirconio thickening agent of 8-35 weight %；
The base oil of 65-92 weight %；It is highly preferred that on the basis of grease weight, including following components：10-25 weight % it is compound
Calcium zirconio thickening agent；The base oil of 75-90 weight %.
Preferably, in the composite calcium zirconio thickening agent, the mol ratio of calcium and zirconium is 1：0.1-10, more preferably 1：
0.25-4。
Preferably, oxide and/or hydroxide and the mixture of zirconium alkoxide of component C for 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, the invention provides a kind of composite calcium zirconio preparation of greases method, methods described includes：
（1）Component A, component B and component C are mixed in base oil, intensification draining saponification, wherein, component A is height
The mixture of level fatty acid and aromatic acid, oxide and/or hydroxide of component B for calcium, oxidation of component C for zirconium
At least one in thing, the hydroxide and zirconium alkoxide of zirconium；
（2）By step（1）Reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds surplus base oil, cold
But, necessary additive is added, obtains finished product.
Preferably, step（1）In, the mol ratio of calcium and zirconium is 1：0.1-10, more preferably 1：0.25-4.
Preferably, step（1）In, by component A and base oil Hybrid Heating to 60-90 DEG C, add component B and component
C, in 90-120 DEG C of draining saponification, wherein, oxide and/or hydroxide and the mixture of zirconium alkoxide of component C for zirconium, with
Zirconium meter, the oxide and/or hydroxide of zirconium are 1 with the mol ratio of zirconium alkoxide：0.1-10, more preferably 1：0.5-5.
The composite calcium zirconio grease of the present invention, compares zirconio grease, stable with more preferable heat-resisting quantity, machinery
Property, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, especially when calcium in grease and the mol ratio of zirconium
For 1：0.25-4；The raw material for preparing the zirconium of composite calcium zirconio thickening agent is the oxide and/or hydroxide and zirconium alkoxide of zirconium
Mixture；In terms of zirconium, the oxide and/or hydroxide of zirconium are 1 with the mol ratio of zirconium alkoxide：During 0.5-5, composite calcium zirconium
The heat-resisting quantity of base grease, mechanical stability, water-resistance and adhesiveness, colloid stability can be greatly improved.This
Bright preparation of greases process is simple, low cost, product quality are stable.The grease of the present invention can be widely used for high speed, weight
The bearing lubrication such as load running, oil drilling.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of composite calcium zirconio grease, on the basis of grease weight, including with the following group
Point：The composite calcium zirconio thickening agent of 5-50 weight %；The base oil of 50-95 weight %, wherein, the composite calcium zirconio thickening agent is
The calcium zirconium soap for generating is reacted by component A, component B and component C, wherein, component A is the mixing of higher fatty acids and aromatic acid
Thing, oxide and/or hydroxide of component B for calcium, component C are oxide, the hydroxide of zirconium and the alkane of zirconium
At least one in epoxide zirconium.
Preferably, on the basis of grease weight, including following components：The composite calcium zirconio thickening agent of 8-35 weight %；
The base oil of 65-92 weight %；It is highly preferred that on the basis of grease weight, including following components：10-25 weight % it is compound
Calcium zirconio thickening agent；The base oil of 75-90 weight %.
According to the present invention, although the composite calcium zirconio grease with said components, you can realize the purpose of the present invention, i.e.,
There is grease preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure to resist
Mill property, but work as in composite calcium zirconio thickening agent, the mol ratio of calcium and zirconium is 1：0.1-10, more preferably 1：During 0.25-4, can enter
One step improves heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, colloid stability and the extreme pressure anti-wear of grease.Cause
This, in the composite calcium zirconio thickening agent of the present invention, the mol ratio of calcium and zirconium is preferably 1：0.1-10, more preferably 1：0.25-4.
The present inventor has been surprisingly found that under study for action, when component C is the oxide and/or hydroxide and alcoxyl of zirconium
During the mixture of base zirconium, i.e., when the raw material of zirconium is the mixture of oxide and/or hydroxide and zirconium alkoxide of zirconium, one can be entered
Step improves heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, colloid stability and the extreme pressure anti-wear of grease, therefore,
Component C is preferably the oxide and/or hydroxide of zirconium and the mixture of zirconium alkoxide, wherein, in terms of zirconium, the oxide of zirconium
And/or hydroxide is preferably 1 with the mol ratio of zirconium alkoxide：0.1-10, more preferably 1：0.2-8, still more preferably for
1：0.5-5, in the case of the oxide and/or hydroxide of zirconium with the preferred molar ratio of zirconium alkoxide, further can carry
The heat-resisting quantity of high remperature grease, mechanical stability, water-resistance and adhesiveness, colloid stability.
In the present invention, the oxide and/or hydroxide of calcium can be CaO, Ca (OH)2；The oxide and/or hydrogen-oxygen of zirconium
Compound is preferably selected from ZrO2、ZrO(OH)2、Zr(OH)4And at least one in their hydrate.ZrO(OH)2Hydrate
Can be the wet hydrogen zirconium oxide of brand-new, which can pass through ZrOX2·8H2O（X is F, Cl, Br or I）Or ZrO (NO3)2·2H2O etc.
Obtain with alkali reaction, wherein, alkali can be NaOH, KOH, strong aqua ammonia etc., preferred ZrOCl2·8H2O and NaOH reacts.
In the present invention, the formula of zirconium alkoxide can be Zr (OR1)4, R1Can be the alkyl of C1-C10, preferably C2-C6
Alkyl；It is highly preferred that zirconium alkoxide in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and the n-amyl alcohol zirconium extremely
Few one kind.
In the present invention, 100 DEG C of kinematic viscositys of base oil are preferably 2-150mm2/ s, more preferably 5-100mm2/ s, more enters one
Step is preferably 8-50mm2/ s, base oil can be at least one in mineral oil, artificial oil and vegetable oil, and artificial oil can be
Poly ＆ Alpha ,-olefin oil（PAO）, Esters oil, alkyl-silicone oil, Fischer-Tropsch synthesis oil etc..
In the present invention, higher fatty acids can be that carbon number is 8-24, the straight chain fatty acid or hydroxy aliphatic of preferred 10-20
Acid, at least be more preferably selected from lauric acid, Oleic acid, Palmic acid, stearic acid, 12- hydroxy stearic acids and eicosyl carboxylic acid
Kind, it is still more preferably 12- hydroxy stearic acids.
In the present invention, the carboxylic acid that aromatic acid is at least 1 carboxyl to be joined directly together with aromatic ring, aromatic acid can be replaced or not
Substituted aromatic acid, its substituent group can be in alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, fluoro or perfluoro etc. extremely
Few one kind.Aromatic acid is preferably binary aromatic acid, for example, can be selected from substituted or unsubstituted phthalic acid, M-phthalic acid, right
At least one in phthalic acid, biphenyl dicarboxylic acid and multi-joint phthalic acid.
In the present invention, higher fatty acids are preferably 1 with the mol ratio of aromatic acid：0.5-7, more preferably 1：1-4.
In the present invention, H contained by higher fatty acids and aromatic acid+Molal quantity sum be equal to all oxides of neutralization calcium, calcium
Hydroxide, the oxide of zirconium, the hydroxide of zirconium and the H needed for zirconium alkoxide+Molal quantity, but oxide, the calcium of calcium
Hydroxide, the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide can excess 1- relative to higher fatty acids and aromatic acid
10%。
Various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent etc. can also be contained in grease of the present invention.Its
In, the preferred arylamine kind antioxidant of antioxidant accounts for the 0.01-5% of grease gross weight, preferred 0.1-2.5%, can be diphenylamines,
At least one in phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for grease
The 0.5-12% of gross weight, preferred 0.8-8%, can be dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, two
Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum bisuphide, polytetrafluoroethyl-ne
Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, carbonic acid
At least one in calcium and Zinc Oxide；Antirust agent accounts for the 0.01-4.5% of grease gross weight, preferred 0.1-2%, can be oil
At least one in barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides a kind of composite calcium zirconio preparation of greases method, the method includes：
（1）Component A, component B and component C are mixed in base oil, intensification draining saponification, wherein, component A is senior fat
Fat acid and the mixture of aromatic acid, oxide and/or hydroxide of component B for calcium, oxide, the hydrogen-oxygen of zirconium of component C for zirconium
At least one in compound and zirconium alkoxide；
（2）By step（1）Reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds surplus base oil, cold
But, necessary additive is added, obtains finished product.
According to the present invention, composite calcium zirconio grease is prepared while in accordance with said method, you can realize the purpose of the present invention,
The composite calcium zirconio grease for preparing has preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, salt fog resistance
Property, colloid stability, extreme pressure anti-wear, but step（1）In, when the mol ratio of calcium and zirconium is 1：0.1-10, more preferably 1：
During 0.25-4, heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, the colloid peace of obtained grease is can further improve
Qualitative and extreme pressure anti-wear.Therefore, step of the present invention（1）In, the mol ratio of calcium and zirconium is preferably 1：0.1-10, more preferably 1：
0.25-4。
Step of the present invention（1）In, base oil can be made first to mix with component A, it is also possible to make base oil first and component B and group
Divide C mixing；Higher fatty acids and aromatic acid can be dehydrated with component B and the reaction of component C in base oil simultaneously, it is also possible to anti-respectively
Should be dehydrated.It is preferred that by base oil and component A Hybrid Heating to 60-90 DEG C, adding component B and component C, intensification draining saponification.
As it was previously stated, the present inventor has been surprisingly found that under study for action, step（1）In, when component C is the oxide of zirconium
And/or hydroxide and zirconium alkoxide mixture when, i.e. oxide and/or hydroxide and alkoxyl of the raw material of zirconium for zirconium
During the mixture of zirconium, heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, the glue of obtained grease is can further improve
Body stability and extreme pressure anti-wear, it is therefore preferred that step（1）In, by component A and base oil Hybrid Heating to 60-90 DEG C,
Component B and component C are added, in 90-120 DEG C of draining saponification, wherein, oxide and/or hydroxide and alcoxyl of component C for zirconium
The mixture of base zirconium, in terms of zirconium, the oxide and/or hydroxide of zirconium are preferably 1 with the mol ratio of zirconium alkoxide：0.1-10,
More preferably 1：0.2-8, is still more preferably 1：0.5-5.
Step of the present invention（1）In, the weight ratio preferably 1 of the total amount of higher fatty acids and aromatic acid and part basis oil：5-
50。
Step of the present invention（1）In, higher fatty acids are preferably 1 with the mol ratio of aromatic acid：0.5-7, more preferably 1：1-4.
Higher fatty acids, aromatic acid, the oxide of calcium, the hydroxide of calcium, the oxide of zirconium, the hydroxide of zirconium and alcoxyl
Base zirconium is as it was previously stated, will not be described here.
The oxide of higher fatty acids and aromatic acid and calcium, the hydroxide of calcium, the oxide of zirconium, the hydroxide of zirconium and alkane
The mol ratio of epoxide zirconium is as it was previously stated, will not be described here.
Step of the present invention（2）In, it is warmed up to 180-230 DEG C of constant temperature 5-20 minute；Surplus base oil is added, treats that temperature is cooled down
To 80-130 DEG C, necessary additive is added, finished product is obtained.
Base oil and additive are as it was previously stated, will not be described here.
In the present invention, step（1）In part basis oil used and step（2）The weight ratio preferably 1 of middle surplus base oil：
0.5-5。
Embodiment
The present invention is further illustrated for below example, but and is not so limited the present invention.
Embodiment 1
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
By 150g HVI500SN lubricating base oils（100 DEG C of kinematic viscositys are 10mm2/ s, similarly hereinafter）, 48g12- hydroxy stearates
During acid and 26.6g phthalic acids add normal oleosterin kettle, stirring is heated to 75 DEG C, by 31.5g zirconium-n-propylates, 3.6g Ca
(OH)2With 15.3g Zr (OH)4The mol ratio for being successively added thereto reaction, calcium and zirconium is 1：4, in terms of zirconium, Zr (OH)4With positive third
The mol ratio of alcohol zirconium is 1：1,105 DEG C of draining saponification are warming up to, 200 DEG C of constant temperature is then heated to 10 minutes, plus 200g
HVI500SN lubricating base oils, stirring cooling, treat that temperature is cooled to 110 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Inspection
The results are shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 21.6
Weight %, 78.4 weight % of base oil.
Embodiment 2
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
By 400g HVI150BS lubricating base oils（100 DEG C of kinematic viscositys are 30mm2/ s, similarly hereinafter）, 48g12- hydroxy stearates
During acid and 80g M-phthalic acids add normal oleosterin kettle, stirring is heated to 90 DEG C, by 17g Ca (OH)2、8.9g Zr(OH)4With
It is 1 that 76g ethanol zirconium is successively added thereto the mol ratio of reaction, calcium and zirconium：1.5, in terms of zirconium, Zr (OH)4With ethanol zirconium mole
Than for 1：5,120 DEG C of draining saponification are warming up to, 230 DEG C of constant temperature is then heated to 5 minutes, plus 600g HVI150BS lubrication bases
Oil, stirring cooling, treats that temperature is cooled to 120 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 15.1
Weight %, 84.9 weight % of base oil.
Embodiment 3
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
By 500g full synthetic oil poly ＆ Alpha ,-olefin oil PAO10（100 DEG C of kinematic viscositys are 10mm2/ s, similarly hereinafter）, 45.5g Hard Fat
During acid and 26.6g p-phthalic acids add normal oleosterin kettle, stirring is heated to 60 DEG C, by 12.3g zirconium-n-butylates, 9.1g ZrO
(OH)2With 10.7g Ca (OH)2The mol ratio for being successively added thereto reaction, calcium and zirconium is 1：0.67, in terms of zirconium, ZrO (OH)2With
The mol ratio of zirconium-n-butylate is 1：0.5,90 DEG C of draining saponification are warming up to, 180 DEG C of constant temperature is then heated to 20 minutes, plus 500g complete
Artificial oil poly ＆ Alpha ,-olefin oil PAO10, stirring cooling, treats that temperature is cooled to 100 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.
Assay is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：8 weight of composite calcium zirconio thickening agent
Amount %, 92 weight % of base oil.
Embodiment 4
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
By 12.1g ZrOCl2·8H2O is dissolved in 60g water, and 40 aqueous solutions containing 3.1g NaOH are slowly added into above-mentioned
ZrOCl2Aqueous solution in, quick stirring obtains white precipitate, is filtrated to get precipitation, and precipitation massive laundering is washed standby afterwards.
By 400g full synthetic oil poly ＆ Alpha ,-olefin oil PAO40（100 DEG C of kinematic viscositys are 40mm2/s）, 48g12- hydroxy stearates
Acid and 116g4, during 4 '-biphenyl dicarboxylic acid adds normal oleosterin kettle, stirring is heated to 80 DEG C, by 28.9g zirconium tert-butoxides, above-mentioned
Precipitation and 33.2g Ca (OH)2The mol ratio for being successively added thereto reaction, calcium and zirconium is 1：0.25, in terms of zirconium, Zr (OH)4And uncle
The mol ratio of butanol zirconium is 1：2,110 DEG C of draining saponification are warming up to, 205 DEG C of constant temperature is then heated to 8 minutes, plus 600g quench oils
Plexol 201（100 DEG C of kinematic viscositys are 3mm2/s）, stirring cooling treats that temperature is cooled to 105 DEG C, circulating filtration,
Change, degassing obtains finished product.Assay is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 16.3
Weight %, 83.7 weight % of base oil.
Embodiment 5
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
Method according to embodiment 1 prepares composite calcium zirconio grease, except for the difference that, at Ca (OH)2、ZrO(OH)2Just
The gross weight of propanol zirconium is constant, in the case that the mol ratio of calcium and zirconium is constant, adjusts ZrO (OH)2With the mol ratio of zirconium-n-propylate
For 1：0.1.Each physicochemical property of gained fat is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 21.6
Weight %, 78.4 weight % of base oil.
Embodiment 6
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
Method according to embodiment 1 prepares composite calcium zirconio grease, except for the difference that, at Ca (OH)2、ZrO(OH)2Just
The gross weight of propanol zirconium is constant, in the case that the mol ratio of calcium and zirconium is constant, adjusts ZrO (OH)2With the mol ratio of zirconium-n-propylate
For 1：10.Each physicochemical property of gained fat is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 21.6
Weight %, 78.4 weight % of base oil.
Embodiment 7
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
Method according to embodiment 1 prepares composite calcium zirconio grease, except for the difference that, calcium and zirconium raw material total consumption not
Become, in the case that the mol ratio of calcium and zirconium is constant, zirconium-n-propylate is replaced with into Zr (OH)4.Each physicochemical property of gained fat is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 21.6
Weight %, 78.4 weight % of base oil.
Embodiment 8
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
Method according to embodiment 1 prepares composite calcium zirconio grease, except for the difference that, calcium and zirconium raw material total consumption not
Become, in the case that the mol ratio of calcium and zirconium is constant, by Zr (OH)4Replace with zirconium-n-propylate.Each physicochemical property of gained fat is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 21.6
Weight %, 78.4 weight % of base oil.
Embodiment 9
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
Method according to embodiment 1 prepares composite calcium zirconio grease, keeps 12- hydroxy stearic acids with phthalic acid
Mol ratio, Zr (OH)4Constant with the mol ratio of zirconium-n-propylate, except for the difference that, the mol ratio for adjusting calcium and zirconium is 1：0.1, it is each to use
Amount is adjusted accordingly to keep thickening agent proportion constant.Each physicochemical property of gained fat is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 21.6
Weight %, 78.4 weight % of base oil.
Embodiment 10
The present embodiment is used for the composite calcium zirconio grease for illustrating present invention preparation.
Method according to embodiment 1 prepares composite calcium zirconio grease, keeps 12- hydroxy stearic acids with phthalic acid
Mol ratio, Zr (OH)4Constant with the mol ratio of zirconium-n-propylate, except for the difference that, the mol ratio for adjusting calcium and zirconium is 1：10, each consumption
It is adjusted accordingly to keep thickening agent proportion constant.Each physicochemical property of gained fat is shown in Table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Composite calcium zirconio thickening agent 21.6
Weight %, 78.4 weight % of base oil.
Comparative example 1
Method according to embodiment 1 prepares Composite zirconium-based grease, and holding 12- hydroxy stearic acids are rubbed with phthalic acid
You compare, Zr (OH)4It is constant with the mol ratio of zirconium-n-propylate, except for the difference that, by Ca (OH)2Replace with Zr (OH)4And zirconium-n-propylate,
Each consumption is adjusted accordingly to keep thickening agent proportion constant.Each physicochemical property of gained fat is shown in Table 1.
In the grease that this comparative example is obtained, on the basis of grease weight, consist of：Compound 21.6 weight of zirconio thickening agent
Amount %, 78.4 weight % of base oil.
Comparative example 2
Method according to embodiment 1 prepares calcium-base grease, keeps the mol ratio of 12- hydroxy stearic acids and phthalic acid
It is constant, except for the difference that, by Zr (OH)4Ca (OH) is replaced with zirconium-n-propylate2, consumption simultaneously adjusts accordingly to keep thickening agent institute
Account for constant rate.Each physicochemical property of gained fat is shown in Table 1.
In the product that this comparative example is obtained, consist of：21.6 weight % of composite calcium-base thickening agent, 78.4 weight % of base oil.
Embodiment 1 and comparative example 1 are compared as can be seen that the dropping point of the composite calcium zirconio grease of the present invention is far high
In Composite zirconium-based grease and complex calcium lubricating grease, the difference for extending work cone penetration with work cone penetration is much smaller than compound zirconium
Base grease and complex calcium lubricating grease, water drench number of dropouts and are much smaller than Composite zirconium-based grease and complex calcium lubricating grease, salt fog
Test is much smaller than Composite zirconium-based grease and composite calcium better than Composite zirconium-based grease and complex calcium lubricating grease, Stencil oil-dividing value
Base grease, tetra-ball machine test PB、PDValue is more than Composite zirconium-based grease and complex calcium lubricating grease, tetra-ball machine test D40 60Value
Less than Composite zirconium-based grease and complex calcium lubricating grease, heat-resisting quantity, the machine of the composite calcium zirconio grease of the present invention are illustrated
Tool stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear be superior to Composite zirconium-based grease and
Complex calcium lubricating grease.
Embodiment 1 is compared oxide and/or hydroxide as can be seen that zirconium respectively with embodiment 5 and embodiment 6
Thing is 1 with the mol ratio of zirconium alkoxide：0.5-5, the composite calcium zirconio grease of preparation, with more preferable heat-resisting quantity, machinery
Stability, water-resistance and adhesiveness, colloid stability；Embodiment 1 is compared with embodiment 7 and embodiment 8 respectively can be with
Find out, the raw material for preparing the zirconium of composite calcium zirconio thickening agent is the mixing of oxide and/or hydroxide with zirconium alkoxide of zirconium
Thing, the composite calcium zirconio grease of preparation are pacified with more preferable heat-resisting quantity, mechanical stability, water-resistance and adhesiveness, colloid
Qualitative and extreme pressure anti-wear；Embodiment 1 is compared with embodiment 9 and embodiment 10 respectively as can be seen that calcium and zirconium rub
You are than being 1：0.25-4, the composite calcium zirconio grease of preparation, with more preferable heat-resisting quantity, mechanical stability, water-resistance and
Adhesiveness, colloid stability and extreme pressure anti-wear.
1 each grease properties of sample data of table
Each indication test method：Dropping point：GB/T3498；Work cone penetration and prolongation work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Stencil oil-dividing：SH/
T0324；Tetra-ball machine test（PB、PD）：SH/T0202；Tetra-ball machine test（D40 60）：SH/T0204.
The composite calcium zirconio grease of the present invention, compares zirconio grease and complex calcium lubricating grease, with preferably resistance to
High temperatures, mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, especially work as grease
The mol ratio of middle calcium and zirconium is 1：0.25-4；The raw material for preparing the zirconium of composite calcium zirconio thickening agent is the oxide and/or hydrogen of zirconium
The mixture of oxide and zirconium alkoxide；In terms of zirconium, the oxide and/or hydroxide of zirconium are 1 with the mol ratio of zirconium alkoxide：
During 0.5-5, the heat-resisting quantity of composite calcium zirconio grease, mechanical stability, water-resistance and adhesiveness, colloid stability can be obtained
To being greatly improved.The preparation of greases process is simple of the present invention, low cost, product quality are stable.The grease of the present invention can
It is widely used in the bearing lubrication such as high speed, heavy load operating, oil drilling.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various 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 specific 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 compound mode of energy is no longer separately illustrated.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as which is without prejudice to this
The thought of invention, which should equally be considered as content disclosed in this invention.
Claims (23)
1. a kind of composite calcium zirconio grease, it is characterised in that on the basis of grease weight, including following components：5-50 weights
The composite calcium zirconio thickening agent of amount %；The base oil of 50-95 weight %, wherein, the composite calcium zirconio thickening agent is by component
The calcium zirconium soap that the reaction of A, component B and component C is generated, wherein, component A is the mixture of higher fatty acids and aromatic acid, described
Oxide and/or hydroxide of component B for calcium, component C is the oxide of zirconium, in the hydroxide and zirconium alkoxide of zirconium
At least one；The higher fatty acids are the straight chain fatty acid or hydroxy fatty acid that carbon number is 8-24；The aromatic acid is at least 1
The carboxylic acid that individual carboxyl is joined directly together with aromatic ring.
2. grease according to claim 1, wherein, on the basis of grease weight, including following components：8-35 weights
The composite calcium zirconio thickening agent of amount %；The base oil of 65-92 weight %.
3. grease according to claim 2, wherein, on the basis of grease weight, including following components：10-25 weights
The composite calcium zirconio thickening agent of amount %；The base oil of 75-90 weight %.
4. the grease according to any one in claim 1-3, wherein, in the composite calcium zirconio thickening agent, calcium and
The mol ratio of zirconium is 1：0.1-10.
5. grease according to claim 4, wherein, in the composite calcium zirconio thickening agent, the mol ratio of calcium and zirconium is
1：0.25-4.
6. the grease according to any one in claim 1-3, wherein, oxide and/or hydrogen of component C for zirconium
The mixture of oxide and zirconium alkoxide, in terms of zirconium, the oxide and/or hydroxide of zirconium are 1 with the mol ratio of zirconium alkoxide：
0.1-10。
7. grease according to claim 6, wherein, in terms of zirconium, the oxide and/or hydroxide of zirconium and zirconium alkoxide
Mol ratio be 1：0.5-5.
8. the grease according to any one in claim 1-3, wherein, the oxide and/or hydroxide of zirconium are selected from
ZrO2、ZrO(OH)2、Zr(OH)4And at least one in their hydrate.
9. the grease according to any one in claim 1-3, wherein, the formula of the zirconium alkoxide is Zr (OR1)4,
R1For the alkyl of C1-C10.
10. grease according to claim 9, wherein, the zirconium alkoxide is selected from ethanol zirconium, zirconium-n-propylate, n-butyl alcohol
At least one in zirconium, zirconium tert-butoxide and n-amyl alcohol zirconium.
11. greases according to any one in claim 1-3, wherein, 100 DEG C of kinematic viscositys of the base oil are 2-
150mm2/s。
12. greases according to any one in claim 1-3, wherein, the base oil is selected from mineral oil, artificial oil
With at least one in vegetable oil.
13. greases according to claim 1, wherein, the higher fatty acids are selected from lauric acid, Oleic acid, Palmic acid, hard
At least one in fat acid, 12- hydroxy stearic acids and eicosyl carboxylic acid.
14. greases according to any one in claim 1-3, wherein, the aromatic acid is binary aromatic acid.
15. greases according to claim 14, wherein, the aromatic acid selected from substituted or unsubstituted phthalic acid,
At least one in M-phthalic acid, p-phthalic acid, biphenyl dicarboxylic acid and multi-joint phthalic acid.
16. greases according to any one in claim 1-3, wherein, the higher fatty acids and the aromatic acid
Mol ratio is 1：0.5-7.
Composite calcium zirconio preparation of greases method in 17. claim 1-16 described in any one, it is characterised in that described
Method includes：
(1) component A, component B and component C are mixed in base oil, intensification draining saponification, wherein, component A is senior fat
Fat acid and the mixture of aromatic acid, oxide and/or hydroxide of component B for calcium, component C for zirconium oxide,
At least one in the hydroxide and zirconium alkoxide of zirconium, the higher fatty acids are the straight chain fatty acid or hydroxyl that carbon number is 8-24
Base fatty acid；The aromatic acid is the carboxylic acid that at least one carboxyl is joined directly together with aromatic ring；
(2) step (1) is reacted into gained mixture and is warmed up to 180-230 DEG C of constant temperature refining, added surplus base oil, cool down, plus
Enter necessary additive, obtain finished product.
18. methods according to claim 17, wherein, in step (1), the mol ratio of calcium and zirconium is 1：0.1-10.
19. methods according to claim 18, wherein, in step (1), the mol ratio of calcium and zirconium is 1：0.25-4.
20. methods according to any one in claim 17-19, wherein, in step (1), by component A and basis
Oily Hybrid Heating to 60-90 DEG C, adds component B and component C, in 90-120 DEG C of draining saponification, wherein, oxidation of component C for zirconium
The mixture of thing and/or hydroxide and zirconium alkoxide, in terms of zirconium, oxide and/or hydroxide and the zirconium alkoxide of zirconium
Mol ratio is 1：0.1-10.
21. methods according to claim 20, wherein, in terms of zirconium, the oxide and/or hydroxide of zirconium and zirconium alkoxide
Mol ratio be 1：0.5-5.
22. methods according to any one in claim 17-19, wherein, the higher fatty acids and the aromatic acid
Mol ratio is 1：0.5-7.
23. methods according to any one in claim 17-19, wherein, in step (2), be warmed up to 180-230 DEG C it is permanent
Warm 5-20 minutes；Surplus base oil is added, treats that temperature is cooled to 80-130 DEG C, added necessary additive, obtain finished product.
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| CN106032485B (en) * | 2015-03-11 | 2019-03-08 | 中国石油化工股份有限公司 | Lubricant composition and preparation method thereof |
| CN108949302B (en) * | 2018-08-16 | 2021-08-06 | 四川瑞荣科技有限公司 | Wear-resistant antifriction gear lubricating oil and preparation method thereof |
| CN111100722B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Composite calcium-based lubricating grease and preparation method thereof |
| CN111100730B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Metal soap-based lubricating grease and preparation method thereof |
| CN112795422B (en) * | 2019-10-28 | 2023-04-07 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
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