CN104560268B - A kind of composite calcium naphthenate calcium zirconium base lubricating grease and preparation method thereof - Google Patents
A kind of composite calcium naphthenate calcium zirconium base lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of composite calcium naphthenate calcium zirconium base lubricating grease, including following components：10 70 weight % non-newtonian fluid calcium naphthenate；The zirconates of 1 10 weight % higher fatty acids；The zirconates of 1 15 weight % aromatic acid；10 80 weight % base oil；Small molecule inorganic acid and/or the zirconates of lower fatty acid optionally also including 1 15 weight %, wherein, the zirconates of higher fatty acids, the zirconates of aromatic acid, the zirconates of small molecule inorganic acid and/or lower fatty acid are formed by higher fatty acids, aromatic acid, small molecule inorganic acid and/or lower fatty acid and component A reactions respectively, and component A is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium.The invention also discloses preparation of greases method and its lubricating grease of preparation.The lubricating grease of the present invention, with the performance such as excellent mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear.
Description
Technical field
The present invention relates to lubricating grease, in particular it relates to a kind of composite calcium naphthenate calcium zirconium base lubricating grease and preparation method thereof.
Background technology
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, exactly calcium carbonate, which is distributed to the naphthenic acid calcium with surface-active in flux oil, turns into a kind of colloidal dispersion system.It is high
Base number calcium naphthenate mostly be the acidic components extracted from the distillate that crude distillation is obtained, 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, have caused domestic and international profit
The extensive concern of consistent lubricant industry, although however, sulfonate with high base number calcium-base grease has very excellent combination property, it is given birth to
Producing the high price and complicated preparation technology itself of raw material calcium sulfonate with high base number causes it not promoted rapidly, meanwhile, with
In requirement more and more higher of the people to environmental protection, 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.Find a kind of performance similar with sulfonate with high base number calcium-base grease but above-mentioned ask can be avoided
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, such as CN101113382 and JP1973038444 add the oxide of zirconium as lubricant
Agent improves abrasiveness；WO2007143414 and US20060063682, which describe 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 better than sulfonate with high base number calcium-base grease it is an object of the invention to provide a kind of performance, cost is low, preparation technology letter
Single, environmental protection lubricating grease 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 calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；The zirconates of 1-15 weight % aromatic acid；10-80 weights
Measure % base oil；Small molecule inorganic acid and/or the zirconates of lower fatty acid optionally also including 1-15 weight %, wherein,
The zirconates of the higher fatty acids is to be formed by higher fatty acids with component A reactions, and the zirconates of the aromatic acid is by aromatic acid and group
A reactions are divided to form, the zirconates of the small molecule inorganic acid and/or lower fatty acid is by small molecule inorganic acid and/or rudimentary fat
Fat acid is formed with component A reactions, and the component A is at least one of oxide, the hydroxide of zirconium and zirconium alkoxide of zirconium.
Mechanical stability, water-resistance and the adhesiveness of the lubricating grease, resistance to saltfog, colloid stability, extreme pressure anti-wear are better than high base number
Calcium sulfonate grease, 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 composite calcium naphthenate calcium zirconium base lubricating grease,
On the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid calcium naphthenate；1-10 weight %'s is senior
The zirconates of aliphatic acid；The zirconates of 1-15 weight % aromatic acid；10-80 weight % base oil；Optionally also include 1-15 weight %
Small molecule inorganic acid and/or lower fatty acid zirconates, wherein, the zirconates of the higher fatty acids be by higher fatty acids with
Component A reactions are formed, and the zirconates of the aromatic acid is to be reacted to form by aromatic acid and component A, the small molecule inorganic acid and/or rudimentary
The zirconates of aliphatic acid is to be formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, and the component A is the oxygen of zirconium
At least one of compound, the hydroxide of zirconium and zirconium alkoxide.
Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid calcium naphthenate；
The zirconates of 2-6 weight % higher fatty acids；The zirconates of 2-10 weight % aromatic acid；20-70 weight % base oil；Optionally
The zirconates of small molecule inorganic acid and/or lower fatty acid also including 2-10 weight %.
Preferably, the component A is the oxide of zirconium and/or the mixture of hydroxide and zirconium alkoxide, in terms of zirconium, zirconium
Oxide and/or hydroxide and zirconium alkoxide mol ratio be 1：0.1-10, more preferably 1：0.5-5.
Second aspect, the invention provides composite calcium naphthenate calcium zirconium base preparation of greases method as described above, the party
Method includes：By non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid and part basis oil and selectivity
Small molecule inorganic acid and/or the zirconates of lower fatty acid be well mixed, in the refining of 180-230 DEG C of constant temperature, add surplus basis
Oil, adds necessary additive, obtains finished product.
The third aspect, the invention provides a kind of composite calcium naphthenate calcium zirconium base preparation of greases method, this method includes：
（1）Newton body calcium naphthenate, part basis oil and transforming agent are mixed, material retrogradation is treated in heating；
（2）In step（1）Component A is added in products therefrom, small point of higher fatty acids, aromatic acid and selectivity is added
Sub- inorganic acid and/or lower fatty acid are reacted, and heat up dehydration after reaction, and the component A is oxide, the hydrogen-oxygen of zirconium of zirconium
At least one of compound and zirconium alkoxide；
（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 composite calcium naphthenate calcium zirconium base lubricating grease as made from method as described above.
The composite calcium naphthenate calcium zirconium base lubricating grease of the present invention, compared to complex calcium sulfonate grease, with more preferable machinery
The performance such as stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear.The system of the lubricating grease of the present invention
Standby technique is simple and environmentally-friendly, and cost is low, and product quality is stable.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.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 composite calcium naphthenate calcium zirconium base lubricating grease, this lubricating grease employ petroleum naphthenic acid calcium or
Synthesis calcium naphthenate is 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 a kind of composite calcium naphthenate calcium zirconium base lubricating grease, on the basis of lubricating grease weight, including
Following components：10-70 weight % non-newtonian fluid calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 weight %'s
The zirconates of aromatic acid；10-80 weight % base oil；Optionally also including 1-15 weight % small molecule inorganic acid and/or rudimentary
The zirconates of aliphatic acid, wherein, the zirconates of higher fatty acids is to be formed by higher fatty acids with component A reactions, and the zirconates of aromatic acid is
Formed by aromatic acid and component A reaction, the zirconates of small molecule inorganic acid and/or lower fatty acid be by small molecule inorganic acid and/or
Lower fatty acid is formed with component A reactions, and component A is at least one in the oxide of zirconium, the hydroxide and zirconium alkoxide of zirconium
Kind.
Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid calcium naphthenate；
The zirconates of 2-6 weight % higher fatty acids；The zirconates of 2-10 weight % aromatic acid；20-70 weight % base oil；Optionally
The zirconates of small molecule inorganic acid and/or lower fatty acid also including 2-10 weight %；It is highly preferred that using lubricating grease weight as base
Standard, including following components：30-55 weight % non-newtonian fluid calcium naphthenate；The zirconates of 2.2-4.5 weight % higher fatty acids；
The zirconates of 3-8 weight % aromatic acid；30-60 weight % base oil；Optionally also include 3-8 weight % small molecule inorganic acid
And/or the zirconates of lower fatty acid.
In the present invention, " optionally also including " refer to can include can not also include, i.e. small molecule inorganic acid and/
Or the zirconates of lower fatty acid is optional component, the component can be included in composite calcium naphthenate calcium zirconium base lubricating grease of the invention,
The component can not also be included.
Non-newtonian fluid calcium naphthenate is in infrared spectrum 873cm-1-886cm-1There is crystal form calcium carbonate characteristic absorption peak in place, always
Base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid calcium naphthenate be by
Newton body calcium naphthenate is obtained by transforming agent conversion.And contain unformed calcium carbonate in newton body calcium naphthenate, in INFRARED SPECTRUM
Figure 86 0cm-1-865cm-1There is unformed calcium carbonate characteristic absorption peak in place.Newton body calcium naphthenate be petroleum naphthenic acid calcium and/
Or synthesis calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g, is turned
It is melted into after non-newtonian fluid calcium naphthenate, its base number is constant.
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 carboxylic acid that aromatic acid is at least 1 carboxyl to be joined directly together with aromatic ring, aromatic acid can be substitution or not
Substituted aromatic acid, its substituent can be in alkyl or aryl of alkyl, alkenyl, alkynyl, aryl, halo or perhalogeno etc. extremely
Few one kind, the molecular weight of aromatic acid is less than or equal to 550.Aromatic acid is preferably binary aromatic acid, for example, unsubstituted or C1- can be selected from
In the alkyl-substituted phthalic acids of C5, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid at least
It is a kind of.Preferably phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, and methyl substituted biphenyl diformazan
At least one of sour, multi-joint phthalic acid etc..
In the present invention, 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., the raw material of zirconium for zirconium oxide and/or hydroxide and zirconium alkoxide mixture when, one can be entered
Step improves mechanical stability, water-resistance and the adhesiveness of lubricating grease, colloid stability, and therefore, component A is preferably the oxide of zirconium
And/or the mixture of hydroxide and zirconium alkoxide, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium
Mol ratio be preferably 1：0.1-10, more preferably 1：0.2-8, is still more preferably 1：0.5-5, zirconium oxide and/
Or in the case of the preferred molar ratio of hydroxide and zirconium alkoxide, can further improve the mechanical stability of lubricating grease, resist
Aqueous and adhesiveness, colloid stability.
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 accounts for the 0.01-5% of lubricating grease gross weight, preferably 0.1-2.5%, can be diphenylamines,
At least one of phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease
The 0.5-12% of gross weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two
Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethyl-ne
Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid
At least one of calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil
At least one of barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides composite calcium naphthenate calcium zirconium base preparation of greases method as described above, the party
Method includes：By non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid and part basis oil and selectivity
Small molecule inorganic acid and/or the zirconates of lower fatty acid be well mixed, in the refining of 180-230 DEG C of constant temperature, add surplus basis
Oil, adds necessary additive, obtains finished product.
It is inorganic for non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid, small molecule in the present invention
Zirconates, base oil and the additive of acid and/or 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 calcium naphthenate, it can be obtained by newton body calcium naphthenate by transforming agent conversion, for example, by ox
Body calcium naphthenate, the base oil Hybrid Heating of pausing are to 50-80 DEG C, and the transforming agent needed for adding is reacted, and all transforming agents are added
Afterwards, in 60-90 DEG C of constant temperature 60-90 minutes, 100-120 DEG C of dehydration is then heated to.
The third aspect, the invention provides a kind of composite calcium naphthenate calcium zirconium base preparation of greases method, this method includes：
（1）Newton body calcium naphthenate, part basis oil and transforming agent are mixed, material retrogradation is treated in heating；
（2）In step（1）Component A is added in products therefrom, small point of higher fatty acids, aromatic acid and selectivity is added
Sub- inorganic acid and/or lower fatty acid are reacted, and heat up dehydration after reaction, and the component A is oxide, the hydrogen-oxygen of zirconium of zirconium
At least one of compound and zirconium alkoxide；
（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 calcium naphthenate, the oily Hybrid Heating of part basis to 50-80 DEG C, preferably constant temperature 10-30
Minute, the transforming agent needed for adding is reacted, and is preferably added and is stirred 8-12 minutes after every kind of transforming agent, all transforming agents are added
Afterwards, in 60-90 DEG C of constant temperature 60-90 minutes.
Step of the present invention（1）In, the weight ratio preferably 1 of newton body calcium naphthenate and part basis oil：0.1-3.
In the present invention, newton body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and 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
Fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine selected from C1-C5,
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 calcium naphthenate weight, more preferably newton body calcium naphthenate weight
6-22%。
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 hydroxide and zirconium alkoxide mixture when, i.e., the raw material of zirconium be zirconium oxide and/or hydroxide and alkoxy
During the mixture of zirconium, mechanical stability, water-resistance and adhesiveness, the colloid stability of obtained lubricating grease are can further improve,
It is therefore preferred that step（2）In, at 85-100 DEG C, component A is added, higher fatty acids is added, stirred 5-20 minutes, is added
The small molecule inorganic acid and/or lower fatty acid of aromatic acid and selectivity, stir 5-20 minutes, are warming up to 100-120 DEG C, excellent
Choosing keep 30-60 minute, dehydration, the component A be zirconium oxide and/or hydroxide and zirconium alkoxide mixture, with
Zirconium meter, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are preferably 1：0.1-10, more preferably 1：0.2-8,
Still more preferably it is 1：0.5-5.Wherein, the addition of higher fatty acids and aromatic acid, small molecule inorganic acid and/or lower fatty acid
Order can be exchanged.
In the present invention, " selective small molecule inorganic acid and/or lower fatty acid " refers to step（2）In can include it is small
Molecule inorganic acid and/or lower fatty acid, can not also include small molecule inorganic acid and/or lower fatty acid, i.e. small molecule without
Machine acid and/or lower fatty acid are an optional raw materials.
In the present invention, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid, the oxide of zirconium, the hydrogen-oxygen of zirconium
Compound and zirconium alkoxide are as it was previously stated, will not be repeated here.
In the present invention, the H of higher fatty acids and the small molecule inorganic acid and/or lower fatty acid of aromatic acid and selectivity+
The amount of total material is equal to the H needed for the oxide, the hydroxide of zirconium and the zirconium alkoxide that all neutralize zirconium+Molal quantity, but zirconium
Oxide, the hydroxide of zirconium and zirconium alkoxide relative to higher fatty acids and aromatic acid and selectivity small molecule it is inorganic
Acid and/or lower fatty acid can excess 1-10%.
In the present invention, the addition of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide is preferably newton body aphthenic acids
The 1-15% of calcium weight；With H+Material gauge, the small molecule inorganic acid of higher fatty acids and aromatic acid and selectivity and/or low
The mol ratio of level aliphatic acid is preferably 1：1-10.
Step（3）In, it is warming up to 180-230 DEG C of constant temperature 5-20 minutes；Surplus base oil is added, treats that temperature is cooled to 100-
120 DEG C, add necessary additive, stirring, circulating filtration, homogenizing, degassing.
In the present invention, step（1）In part basis oil used and step（3）The weight ratio preferably 1 of middle surplus base oil：
0.1-5。
Fourth aspect, present invention also offers composite calcium naphthenate made from the preparation method provided as third aspect present invention
Calcium zirconium base lubricating grease.
Compared with the composite calcium naphthenate calcium zirconium base lubricating grease as made from the preparation method that second aspect is provided, the third aspect is carried
Composite calcium naphthenate calcium zirconium base lubricating grease made from the preparation method of confession have more preferable mechanical stability, water-resistance and adhesiveness,
Colloid stability.
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 calcium naphthenate %=（Overbased or overbased calcium alkyl-salicylate raw material weight+transforming agent gross weight）/ profit
Consistent lubricant gross weight × 100%.Transforming agent is included in the content of non-newtonian fluid calcium naphthenate.
The zirconates of the zirconates of higher fatty acids, the zirconates of aromatic acid and small molecule inorganic acid and/or lower fatty acid contains
Amount, according to the higher fatty acids added, the oxide of aromatic acid and small molecule inorganic acid and/or lower fatty acid and zirconium, zirconium
Hydroxide and zirconium alkoxide react completely generation zirconates amount calculate.
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 sulfoacid calcium 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 composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；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）；Terephthalic acid (TPA)（3.5kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 17kg）.
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers
The HVI150BS lubricating base oils of naphthenate with superhigh base number calcium and 30kg for 400mgKOH/g, stirring, heat to 50 DEG C,
Constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control is stirred 10 minutes at 50 DEG C or so；It is 20 weights to add 2.8kg concentration
% aqueous acetic acid is measured, is stirred 10 minutes；It is warming up to 60 DEG C, constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, is added solid
Content is 20 weight % Zr (OH)4Suspension 19.5kg, is stirred 10 minutes；2kg12- hydroxy stearic acids are added, 10 points are stirred
Clock；3.5kg terephthalic acid (TPA)s are added, stirring is warming up to 110 DEG C, kept for 45 minutes under stirring, dehydration；It is warming up to 200 DEG C of constant temperature
10 minutes.Then, 17kg HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing
Obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.7
Weight %；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of terephthalic acid (TPA) oxygen zirconium 6.5.
Embodiment 2
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Naphthenate with superhigh base number calcium（Total base number is 420mgKOH/g, 30kg）；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（5.5kg）；Zr(OH)4（0.65kg）；12- hydroxy stearic acids（2kg）；Phthalic acid（3.5kg）；HVI500SN moistens
Sliding base oil（100 DEG C of kinematic viscosity are 11mm2/ s, 17kg）.
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers
The HVI150BS lubricating base oils of naphthenate with superhigh base number calcium and 30kg for 420mgKOH/g, stirring, heat to 65 DEG C,
Constant temperature 20 minutes；2.8kg aphthenic acids is added, temperature control is stirred 10 minutes at 65 DEG C or so；It is 20 weights to add 2.8kg concentration
% aqueous acetic acid is measured, is stirred 10 minutes；It is warming up to 75 DEG C, constant temperature 75 minutes, material retrogradation；85 DEG C are warming up to, is successively added
5.5kg ethanol zirconium and the Zr (OH) that solid content is 20 weight %4Suspension 3.25kg, in terms of zirconium, Zr (OH)4With mole of ethanol zirconium
Than for 1：5, stir 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；3.5kg phthalic acids are added, are stirred,
100 DEG C are warming up under stirring, is kept for 60 minutes, dehydration；It is warming up to 230 DEG C of constant temperature 5 minutes.Then, add 17kg's
HVI500SN lubricating base oils；Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table
1。
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.7
Weight %；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of terephthalic acid (TPA) oxygen zirconium 6.5.
Embodiment 3
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；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）；M-phthalic acid（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity
For 11mm2/ s, 28kg）.
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers
The HVI150BS lubricating base oils of naphthenate with superhigh base number calcium and 20kg for 400mgKOH/g, stirring, heat to 80 DEG C,
Constant temperature 10 minutes；2.8kg butanol is added, temperature control is stirred 10 minutes at 80 DEG C or so；It is 20 weight % to add 2.8kg concentration
Aqueous acetic acid, stir 10 minutes；It is warming up to 90 DEG C, constant temperature 60 minutes, material retrogradation；Successively add 3.13kg zirconium-n-butylates
With the Zr (OH) that solid content is 20 weight %4Suspension 13kg, in terms of zirconium, Zr (OH)4Mol ratio with zirconium-n-butylate is 1：0.5,
Stirring 10 minutes；1.9kg stearic acid is added, is stirred 10 minutes；3.5kg M-phthalic acids are added, stirring is warming up under stirring
120 DEG C, kept for 30 minutes, dehydration；It is warming up to 180 DEG C of constant temperature 20 minutes.Then, 28kg HVI500SN lubrication bases are added
Oil；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 is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.8
Weight %；The weight % of lubricating base oil 53.2；The weight % of zirconyl stearate 2.5；The weight % of terephthalic acid (TPA) oxygen zirconium 6.5.
Embodiment 4
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 39kg）；HVI150BS lubricating base oils
（100 DEG C of kinematic viscosity are 31mm2/ s, 20kg）；DBSA（2.8kg）；Acetic acid（0.56kg）；Zirconium-n-propylate
（4.0kg）；Zr(OH)4（2.0kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；HVI500SN lubrication bases
Oil（100 DEG C of kinematic viscosity are 11mm2/ s, 28kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, use DBSA
Instead of aphthenic acids；Add Zr (OH)4When be additionally added zirconium-n-propylate, in terms of zirconium, Zr (OH)4Mol ratio with zirconium-n-propylate is 1：1；
And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, right '-di-iso-octyldiphenylamine after stirring 10 minutes, is then circulated
Filtering, homogenizing, degassing obtain finished product；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 43.7
Weight %；The weight % of lubricating base oil 49.5；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.2；The weight % of terephthalic acid (TPA) oxygen zirconium 4.4；
It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 5
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；HVI150BS lubricating base oils
（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；
Zr(OH)4（3.9kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 7kg）.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, the consumption of each composition is such as
On.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 52.6
Weight %；The weight % of lubricating base oil 34.7；The weight % of 12- hydroxy stearic acid oxygen zirconium 3.7；The weight % of terephthalic acid (TPA) oxygen zirconium 9.0.
Embodiment 6
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；Poly alpha olefine synthetic oil
PAO40（100 DEG C of kinematic viscosity are 40mm2/ s, 30kg）；DBSA（2.8kg）；Acetic acid（0.56kg）；Zr(OH)4
（3.9kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；Poly alpha olefine synthetic oil PAO10（100 DEG C of motions are viscous
Spend for 11mm2/ s, 17kg）.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, use detergent alkylate sulphur
Acid replaces aphthenic acids；Use poly alpha olefine synthetic oil PAO40（100 DEG C of kinematic viscosity are 40mm2/s）And poly alpha olefine synthetic oil
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 consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.7
Weight %；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of terephthalic acid (TPA) oxygen zirconium 6.5.
Embodiment 7
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased calcium alkyl-salicylate（Total base number is 320mgKOH/g, 30kg）；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）；2- methyl isophthalic acids, 4- phthalic acids（3.8kg）；HVI500SN lubrication bases
Oil（100 DEG C of kinematic viscosity are 11mm2/ s, 16.7kg）.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses total alkali
It is worth the overbased calcium alkyl-salicylate for 320mgKOH/g；2- methyl isophthalic acids are used, 4- phthalic acids replace terephthalic acid (TPA)；The use of each composition
Amount is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.7
Weight %；The weight % of lubricating base oil 52.8；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；2- methyl isophthalic acids, 4- phthalic acid oxygen zirconiums
6.8 weight %.
Embodiment 8
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased calcium alkyl-salicylate（Total base number is 360mgKOH/g, 30kg）；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）；4,4'- biphenyl dicarboxylic acids（5.1kg）；HVI500SN lubricating base oils
（100 DEG C of kinematic viscosity are 11mm2/ s, 20kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）；Two thio dialkyl amido first
Sour molybdenum（4kg）；Selenium disulfide（4kg）；Benzotriazole（0.4kg）.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses total alkali
It is worth the overbased calcium alkyl-salicylate for 360mgKOH/g；Terephthalic acid (TPA) is replaced with 4,4'- biphenyl dicarboxylic acids；And treat that temperature is cooled down
To 110 DEG C, 0.2kg pair is added, right '-di-iso-octyldiphenylamine is stirred 10 minutes, adds 4kg two thio dialkyl amidos
Formic acid molybdenum, is stirred 10 minutes, adds 4kg selenium disulfide, is stirred 10 minutes, adds 0.4kg benzotriazole, stirs 10 points
Clock, then circulating filtration, homogenizing, degassing obtains finished product；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 32.9
Weight %；The weight % of lubricating base oil 49.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.3；The weight of 4,4'- biphenyl dicarboxylic acid oxygen zirconium 7.2
Measure %；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2；The two thio weight % of dialkyl amido formic acid molybdenum 3.9；Selenium disulfide 3.9
Weight %；The weight % of benzotriazole 0.4.
Embodiment 9
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；HVI150BS lubricating base oils
（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；
Zr(OH)4（3.9kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 32kg）.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, the consumption of each composition is such as
On.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.7
Weight %；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of terephthalic acid (TPA) oxygen zirconium 6.5.
Embodiment 10
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased calcium alkyl-salicylate（Total base number is 360mgKOH/g, 30kg）；HVI150BS lubricating base oils
（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；DBSA（2.8kg）；Acetic acid（0.56kg）；Zr(OH)4
（7.1kg）；12- hydroxy stearic acids（2kg）；Boric acid（2.32kg）；Terephthalic acid (TPA)（3.5kg）；HVI500SN lubricating base oils
（100 DEG C of kinematic viscosity are 11mm2/ s, 15kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses total alkali
It is worth the overbased calcium alkyl-salicylate for 360mgKOH/g；Aphthenic acids is replaced using DBSA；Adding 12- hydroxy stearates
Boric acid is additionally added after acid, terephthalic acid (TPA) is then added；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 consumption of each composition is as above.
Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.0
Weight %；The weight % of lubricating base oil 49.9；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of line borate 4.0；Terephthalic acid (TPA)
The weight % of oxygen zirconium 6.3；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 11
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Overbased calcium alkyl-salicylate（Total base number is 360mgKOH/g, 30kg）；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（6.5kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)（3.5kg）；Acetic acid（2kg）；HVI500SN lubricates base
Plinth oil（100 DEG C of kinematic viscosity are 11mm2/ s, 14kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses total alkali
It is worth the overbased calcium alkyl-salicylate for 360mgKOH/g；Acetic acid is additionally added after terephthalic acid (TPA) is added, then heat up dehydration again；And
And treat that temperature is cooled to 110 DEG C, 0.2kg pair is added, right '-di-iso-octyldiphenylamine after stirring 10 minutes, is then circulated throughout
Filter, homogenizing, degassing obtain finished product；The consumption of each composition is as above.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.1
Weight %；The weight % of lubricating base oil 48.9；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of terephthalic acid (TPA) oxygen zirconium 4.8；Second
The sour weight % of oxygen zirconium 6.4；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 12
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Raw material components：Naphthenate with superhigh base number calcium（Total base number is 400mgKOH/g, 30kg）；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）；Terephthalic acid (TPA)（3.5kg）；HVI500SN lubricating base oils（100℃
Kinematic viscosity is 11mm2/ s, 17kg）.
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base numbers
The HVI150BS lubricating base oils of naphthenate with superhigh base number calcium and 30kg for 400mgKOH/g, stirring, heat to 50 DEG C,
Constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control is stirred 10 minutes at 50 DEG C or so；It is 20 weights to add 2.8kg concentration
% aqueous acetic acid is measured, is stirred 10 minutes；It is warming up to 60 DEG C, 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, add the Zr (OH) that solid content is 20 weight % at 100 DEG C4Suspension 19.5kg, stirs 10 points
Clock；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；3.5kg terephthalic acid (TPA)s are added, stirs 10 minutes, obtains 12- hydroxyls
Zirconyl stearate and terephthalic acid (TPA) oxygen zirconium.
Gained 12- hydroxy stearic acid oxygen zirconiums and terephthalic acid (TPA) oxygen zirconium are all squeezed into a upper kettle, stirs, stirs
Mix down and be warming up to 110 DEG C, kept for 45 minutes, dehydration；It is warming up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN is added
Lubricating base oil；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.7
Weight %；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of terephthalic acid (TPA) oxygen zirconium 6.5.
Embodiment 13
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, aphthenic acids is replaced with into benzene
Phenol, butyric acid is replaced with by acetic acid.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.7
Weight %；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of terephthalic acid (TPA) oxygen zirconium 6.5.
Embodiment 14
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 1, unlike, aphthenic acids is replaced with into first
Base propyl group ketone, butyl ether is replaced with by aqueous acetic acid.Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 37.7
Weight %；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；The weight % of terephthalic acid (TPA) oxygen zirconium 6.5.
Embodiment 15
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 4, unlike, at Zr (OH)4With positive third
In the case that the total mole number of alcohol zirconium is constant, Zr (OH) is adjusted4Mol ratio with zirconium-n-propylate is 1：0.1.Each reason of gained fat
Change performance and be shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 43.7
Weight %；The weight % of lubricating base oil 49.5；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.2；The weight % of terephthalic acid (TPA) oxygen zirconium 4.4；
It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 16
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 4, unlike, at Zr (OH)4With positive third
In the case that the total mole number of alcohol zirconium is constant, Zr (OH) is adjusted4Mol ratio with zirconium-n-propylate is 1：10.Each physics and chemistry of gained fat
Performance is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 43.7
Weight %；The weight % of lubricating base oil 49.5；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.2；The weight % of terephthalic acid (TPA) oxygen zirconium 4.4；
It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 17
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 4, unlike, zirconium-n-propylate is replaced with
Equimolar Zr (OH)4.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 43.7
Weight %；The weight % of lubricating base oil 49.5；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.2；The weight % of terephthalic acid (TPA) oxygen zirconium 4.4；
It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 18
The present embodiment is used for the composite calcium naphthenate calcium zirconium base lubricating grease for illustrating prepared by the present invention.
Composite calcium naphthenate calcium zirconium base lubricating grease is prepared according to the method for embodiment 4, unlike, by Zr (OH)4Replace with
Equimolar zirconium-n-propylate.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid calcium naphthenate 43.7
Weight %；The weight % of lubricating base oil 49.5；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.2；The weight % of terephthalic acid (TPA) oxygen zirconium 4.4；
It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Comparative example 1
Method according to embodiment 1 prepares complex calcium sulfonate grease, unlike, naphthenate with superhigh base number calcium is replaced
It is 400mgKOH/g overbased sulfoacid calcium, Zr (OH) used to be changed to total base number4With Ca (OH)2Instead of while adjusting consumption
Make each component content consistent with embodiment 1.Each physicochemical property of gained fat is shown in Table 1.
In the lubricating grease that this comparative example is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 37.7
Measure %；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acids calcium 2.6；The weight % of terephthalic acid (TPA) calcium 6.5.
Comparative example 2
Method according to embodiment 5 prepares calcium sulfonate grease, unlike, naphthenate with superhigh base number calcium is replaced with
Total base number is 400mgKOH/g overbased sulfoacid calcium, Zr (OH) used4With Ca (OH)2Instead of while adjusting consumption makes respectively
Component 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 is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 52.6
Measure %；The weight % of lubricating base oil 34.7；The weight % of 12- hydroxy stearic acids calcium 3.7；The weight % of terephthalic acid (TPA) calcium 9.0.
Each lubricating grease properties of sample data of table 1
Each indication test method：Outward appearance：Range estimation；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；It is anti-
Water spray：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：Outward appearance：Range estimation；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；It is anti-
Water spray：SH/T0643；Stencil oil-dividing：SH/T0324；Tetra-ball machine test：SH/T0202.
Embodiment 1 is compared with comparative example 1, embodiment 5 is compared with comparative example 2, it can be seen that the present invention
Composite calcium naphthenate calcium zirconium base lubricating grease extension work cone penetration with work cone penetration difference be less than Composite calcium-sulfonate-batetrapolyurea profit
Consistent lubricant, water drenches number of dropouts and is much smaller than complex calcium sulfonate grease, and salt spray test is better than complex calcium sulfonate grease, water resistant spray
Haze value is less than complex calcium sulfonate grease, and Stencil oil-dividing value is less than complex calcium sulfonate grease, and tetra-ball machine test value is more than
Complex calcium sulfonate grease, illustrates the mechanical stability of composite calcium naphthenate calcium zirconium base lubricating grease of the present invention, water-resistance and viscous
Attached property, resistance to saltfog, colloid stability, extreme pressure anti-wear are superior to complex calcium sulfonate grease.
Embodiment 1 and embodiment 12 are compared and can be seen that the composite calcium naphthenate calcium zirconium base lubricating grease in situ prepared,
With more preferable mechanical stability, water-resistance and adhesiveness, colloid stability；By embodiment 1 respectively with embodiment 13 and implement
Example 14 is compared as can be seen that transforming agent is selected from DBSA, aphthenic acids, methanol, isopropanol, butanol, boric acid, vinegar
Acid and at least one of water, the composite calcium naphthenate calcium zirconium base lubricating grease of preparation, with more preferable mechanical stability, water-resistance and
Adhesiveness, colloid stability；Embodiment 4 is compared to the oxidation as can be seen that zirconium with embodiment 15 and embodiment 16 respectively
The mol ratio of thing and/or hydroxide and zirconium alkoxide is 1：0.5-5, the composite calcium naphthenate calcium zirconium base lubricating grease of preparation, has
More preferable mechanical stability, water-resistance and adhesiveness, colloid stability；By embodiment 4 respectively with embodiment 17 and embodiment 18
It is compared as can be seen that the raw material of zirconium is the oxide of zirconium and/or the mixture of hydroxide and zirconium alkoxide, preparation is answered
Calcium naphthenate zirconium base lubricating grease is closed, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability.
The composite calcium naphthenate calcium zirconium base lubricating grease of the present invention, compared to complex calcium sulfonate grease, with more preferable machinery
The performance such as stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear.The system of the lubricating grease of the present invention
Standby technique is simple and environmentally-friendly, and 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 (23)
1. a kind of composite calcium naphthenate calcium zirconium base lubricating grease, it is characterised in that on the basis of lubricating grease weight, including following components：
10-70 weight % non-newtonian fluid calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 weight % aromatic acid
Zirconates；10-80 weight % base oil；Optionally also include 1-15 weight % small molecule inorganic acid and/or lower aliphatic
The zirconates of acid, wherein, the zirconates of the higher fatty acids is to be formed by higher fatty acids with component A reactions, the zirconium of the aromatic acid
Salt is to be formed by aromatic acid with component A reactions, and the zirconates of the small molecule inorganic acid and/or lower fatty acid is inorganic by small molecule
Acid and/or lower fatty acid are formed with component A reactions, and the component A is oxide, the hydroxide and zirconium alkoxide of zirconium of zirconium
At least one of, the non-newtonian fluid calcium naphthenate is in infrared spectrum 873cm-1-886cm-1There is crystal form calcium carbonate feature in place
Absworption peak.
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 calcium naphthenate；The zirconates of 2-6 weight % higher fatty acids；The zirconates of 2-10 weight % aromatic acid；20-
70 weight % base oil；Small molecule inorganic acid and/or the zirconates of lower fatty acid optionally also including 2-10 weight %.
3. lubricating grease according to claim 1, wherein, the non-newtonian fluid calcium naphthenate is turned by newton body calcium naphthenate
Change what is obtained, the total base number of the non-newtonian fluid 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 aromatic acid is substituted or unsubstituted aromatic acid, substituent
For at least one of alkyl, alkenyl, alkynyl, aryl, the alkyl or aryl of halo, the molecular weight of the aromatic acid is less than or equal to
550。
7. according to the lubricating grease described in claim 6, wherein, the aromatic acid is selected from the alkyl-substituted neighbours of unsubstituted or C1-C5
At least one of phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid.
8. lubricating grease according to claim 1 or 2, wherein, the molecular weight of small molecule inorganic acid and lower fatty acid is less than
Equal to 150.
9. lubricating grease according to claim 8, wherein, the small molecule inorganic acid in boric acid, phosphoric acid, sulfuric acid extremely
Few one kind, the lower fatty acid is selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid.
10. lubricating grease according to claim 1 or 2, wherein, the component A for 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.
11. lubricating grease according to claim 10, wherein, in terms of zirconium, the oxide and/or hydroxide and alkoxy of zirconium
The mol ratio of zirconium is 1：0.5-5.
12. 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)4At least one of and their hydrate.
13. lubricating grease according to claim 1 or 2, wherein, the formula of the zirconium alkoxide is Zr (OR1)4, R1For C1-
C10 alkyl.
14. lubricating grease according to claim 13, 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.
15. the composite calcium naphthenate calcium zirconium base preparation of greases method in claim 1-14 described in any one, its feature exists
In this method includes：By non-newtonian fluid calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid and part basis oil, with
And the small molecule inorganic acid of selectivity and/or the zirconates of lower fatty acid are well mixed, in 180-230 DEG C of constant temperature refining, add
Surplus base oil, adds necessary additive, obtains finished product.
16. the composite calcium naphthenate calcium zirconium base preparation of greases method in claim 1-14 described in any one, its feature exists
In this method includes：
(1) newton body calcium naphthenate, part basis oil and transforming agent are mixed, material retrogradation is treated in heating；
(2) in step (1) products therefrom add component A, add higher fatty acids, aromatic acid and selectivity small molecule without
Machine acid and/or lower fatty acid are reacted, and heat up dehydration after reaction, and the component A is oxide, the hydroxide of zirconium of zirconium
At least one of with zirconium alkoxide；
(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.
17. method according to claim 16, wherein, it is in step (1), newton body calcium naphthenate, part basis oil is mixed
Conjunction is heated to 50-80 DEG C, and the transforming agent needed for adding is reacted, after all transforming agents are added, in 60-90 DEG C of constant temperature 60-90
Minute.
18. method according to claim 16, wherein, in step (2), at 85-100 DEG C, component A is added, is added high
Level aliphatic acid, is stirred 5-20 minutes, adds the small molecule inorganic acid and/or lower fatty acid of aromatic acid and selectivity, stirs 5-
20 minutes, 100-120 DEG C of dehydration is warming up to, the component A is the mixing of the oxide and/or hydroxide and zirconium alkoxide of zirconium
Thing, in terms of zirconium, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：0.1-10.
19. method according to claim 18, wherein, in terms of zirconium, the oxide and/or hydroxide and zirconium alkoxide of zirconium
Mol ratio be 1：0.5-5.
20. method according to claim 16, wherein, in step (3), it is warming up to 180-230 DEG C of constant temperature 5-20 minutes；Plus
Enter surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stirring, circulating filtration, homogenizing, degassing.
21. method according to claim 16, wherein, the newton body calcium naphthenate is petroleum naphthenic acid calcium and/or conjunction
Into calcium naphthenate, the total base number of the newton body calcium naphthenate is 250-450mgKOH/g.
22. method according to claim 16, 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 2-30% of newton body calcium naphthenate weight.
23. method according to claim 22, 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 calcium naphthenate weight
6-22%.
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| CN102453599A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium-sulfonate-based tetrapolyurea lubricating grease and preparation method thereof |
| CN103031184A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Composite zirconium-based tetraurea lubrication grease and its preparation method |
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