CN104450111B - A kind of complex calcium sulfonate calcium naphthenate base grease and preparation method thereof - Google Patents
A kind of complex calcium sulfonate calcium naphthenate base grease and preparation method thereof Download PDFInfo
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- CN104450111B CN104450111B CN201310418643.3A CN201310418643A CN104450111B CN 104450111 B CN104450111 B CN 104450111B CN 201310418643 A CN201310418643 A CN 201310418643A CN 104450111 B CN104450111 B CN 104450111B
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Abstract
The invention discloses a kind of complex calcium sulfonate calcium naphthenate base grease, on the basis of lubricating grease weight, including following components：10 70 weight % non-newtonian fluid sulfoacid calcium calcium naphthenate；The calcium salt of 1 20 weight % higher fatty acids；The calcium salt of 1 15 weight % aromatic acid；10 80 weight % base oil；Small molecule inorganic acid and/or the calcium salt of lower fatty acid optionally also including 1 15 weight %.The invention also discloses complex calcium sulfonate Calcium naphthenate base preparation of greases method and its complex calcium sulfonate calcium naphthenate base grease of preparation.The complex calcium sulfonate calcium naphthenate base grease of the present invention, with excellent anticorrosive property and heat-resisting quantity, but also there is the performances such as mechanical stability, water-resistance and adhesiveness better than complex calcium sulfonate grease, resistance to saltfog, colloid stability, extreme pressure anti-wear.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, and product quality is stable.
Description
Technical field
The present invention relates to lubricating grease, in particular it relates to a kind of complex calcium sulfonate-calcium naphthenate base grease and its preparation side
Method.
Background technology
Sulfoacid calcium is used as the history of detersive and the antirust agent existing decades of lubricating oil, is widely used in internal combustion engine lubrication
The additive of oil, its technology development mainly makes its height alkalization, is exactly alkyl benzene sulphonate of the calcium carbonate with surface-active
Calcium or alkyl carboxylic acid calcium turn into a kind of colloidal dispersion system to be distributed in flux oil.Calcium sulfonate with high base number according to the mode of production not
It is same to be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate.Calcium mahogany sulfonate is to use oleum or SO3Sulfonation mineral lubricating oil is produced
Accessory substance mahogany acid during white oil, through with Ca (OH)2React, the contour alkalization technology that is carbonated and obtain；Calcium alkylbenzenesulfonate is to use
Oleum or SO3The alkylbenzene of sulfonation synthesis, the alkyl benzene sulphonate of generation is passed through and Ca (OH)2React, be carbonated contour alkalization skill
Art and obtain.
Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusivity, can
To be used as the detersive of lubricating oil, the additive of IC engine lubricating oil is widely used in, the development of its technology mainly makes its high-alkali
Change, 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, high base number composite calcium sulfonate base grease has very excellent combination property,
The high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, together
When, the requirement more and more higher with people to environmental protection, in calcium sulfonate with high base number production process must through sulfonation process to ring
The pollution in border is also increasingly subject to the concern of people.Find a kind of performance it is similar with high base number composite calcium sulfonate base grease but can
Mitigating the lubricating grease of above mentioned problem turns into the big problem that people face at present.
The content of the invention
Similar with high base number composite calcium sulfonate base grease it is an object of the invention to provide a kind of performance, cost is low, prepares
Simple and environmentally-friendly lubricating grease of technique and preparation method thereof.
The present inventor has found under study for action, on the basis of lubricating grease weight, including following components：10-70 weight %
Non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium salt of 1-20 weight % higher fatty acids；The calcium salt of 1-15 weight % aromatic acid；
10-80 weight % base oil；Small molecule inorganic acid and/or the calcium of lower fatty acid optionally also including 1-15 weight %
Salt.The performance of the lubricating grease is similar with high base number composite calcium sulfonate base grease, and cost is low, and preparation technology is simple and environmentally-friendly.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of complex calcium sulfonate-Calcium naphthenate base profit
Consistent lubricant, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；1-20
The calcium salt of weight % higher fatty acids；The calcium salt of 1-15 weight % aromatic acid；10-80 weight % base oil；Optionally also wrap
Include 1-15 weight % small molecule inorganic acid and/or the calcium salt of lower fatty acid.
Preferably, on the basis of lubricating grease weight, including following components：20-65 weight % non-newtonian fluid sulfoacid calcium-ring
Alkanoic acid calcium；The calcium salt of 2-15 weight % higher fatty acids；The calcium salt of 2-10 weight % aromatic acid；20-70 weight % base oil；
Small molecule inorganic acid and/or the calcium salt of lower fatty acid optionally also including 2-10 weight %.
Second aspect, the invention provides complex calcium sulfonate as described above-Calcium naphthenate base preparation of greases method,
This method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, part basis oil,
And the small molecule inorganic acid of selectivity and/or the calcium salt of lower fatty acid are well mixed, in 180-230 DEG C of constant temperature refining, plus
Enter surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides a kind of complex calcium sulfonate-Calcium naphthenate base preparation of greases method, this method
Including：
（1）By the oily Hybrid Heating of newton body sulfoacid calcium, newton body calcium naphthenate and part basis, transforming agent, heating are added
Treat material retrogradation；
（2）In step（1）Lime or calcium hydroxide are added in products therefrom, higher fatty acids, aromatic acid and selection is added
Property small molecule inorganic acid and/or lower fatty acid reacted, after reaction heat up dehydration；
（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 complex calcium sulfonate as made from method as described above-Calcium naphthenate base lubrication
Fat.
Complex calcium sulfonate-calcium naphthenate base grease of the present invention, not only as complex calcium sulfonate grease, has
Excellent anticorrosive property and heat-resisting quantity, but also mechanical stability, water-resistance with better than complex calcium sulfonate grease
With the performance such as adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear.The preparation of greases technique of the present invention is simple, ring
Protect, cost is low, product quality is stable.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Fig. 1 is the infrared spectrum and the infrared spectrum of overbased calcium alkyl-salicylate raw material of lubricating grease prepared by embodiment 2.
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 complex calcium sulfonate-calcium naphthenate base grease, this lubricating grease employs mahogany acid
Calcium and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, are thickened simultaneously containing composite calcium
Agent.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of complex calcium sulfonate-calcium naphthenate base grease, using lubricating grease weight as base
Standard, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium of 1-20 weight % higher fatty acids
Salt；The calcium salt of 1-15 weight % aromatic acid；10-80 weight % base oil；Optionally also including 1-15 weight % small molecule without
The calcium salt of machine acid and/or lower fatty acid.
Preferably, on the basis of lubricating grease weight, including following components：20-65 weight % non-newtonian fluid sulfoacid calcium-ring
Alkanoic acid calcium；The calcium salt of 2-15 weight % higher fatty acids；The calcium salt of 2-10 weight % aromatic acid；20-70 weight % base oil；
Small molecule inorganic acid and/or the calcium salt of lower fatty acid optionally also including 2-10 weight %.
In the present invention, " optionally also including " refer to can include can not also include, i.e. small molecule inorganic acid and/
Or the calcium salt of lower fatty acid is optional component, can include in complex calcium sulfonate-calcium naphthenate base grease of the invention should
Component, can not also include the component.
Non-newtonian fluid sulfoacid calcium-the calcium naphthenate is in infrared spectrum 873cm-1-886cm-1It is special that crystal form calcium carbonate occurs in place
Absworption peak is levied, total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.The non newtonian
Body sulfoacid calcium-calcium naphthenate is to be obtained by newton body sulfoacid calcium and newton body calcium naphthenate by transforming agent conversion.And newton body
Contain unformed calcium carbonate in sulfoacid calcium, newton body calcium naphthenate, in infrared spectrum 860cm-1-865cm-1Place occurs unformed
Calcium carbonate characteristic absorption peak.The newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is
250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；The newton body calcium naphthenate is oil ring
Alkanoic acid calcium and/or synthesis calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-
400mgKOH/g.The base number of non-newtonian fluid sulfoacid calcium-calcium naphthenate is the base number and newton body calcium naphthenate of newton body sulfoacid calcium
Base number weight average value.
In the present invention, higher fatty acids is that carbon number is 8-20, preferably 10-16 straight chain fatty acid or hydroxy fatty acid, example
Such as at least one of laurate, palmitic acid, stearic acid, 12- hydroxy stearic acids, eicosyl carboxylic acid, preferably 12- hydroxyls are hard
Resin acid.
In the present invention, the 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..
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 4-150mm2/ s, preferably 10-60mm2/s.Artificial oil can be poly-a-olefin oil（PAO）, Esters oil, alkyl-silicone oil, take
Hold in the palm artificial oil 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.
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 complex calcium sulfonate as described above-Calcium naphthenate base preparation of greases method,
This method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, part basis oil,
And the small molecule inorganic acid of selectivity and/or the calcium salt of lower fatty acid are well mixed, in 180-230 DEG C of constant temperature refining, plus
Enter surplus base oil, add necessary additive, obtain finished product.
In the present invention, " selective small molecule inorganic acid and/or the calcium salt of lower fatty acid " refers to prepare composite sulfoacid
The raw material of calcium-calcium naphthenate base grease can include the calcium salt of small molecule inorganic acid and/or lower fatty acid, can not also wrap
Include the calcium salt of small molecule inorganic acid and/or lower fatty acid, i.e. the calcium salt of small molecule inorganic acid and/or lower fatty acid is individual
Optional raw material or component.
In the present invention, for non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, small point
Calcium salt, base oil and the additive of sub- inorganic 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 sulfoacid calcium-calcium naphthenate, conversion can be passed through by newton body sulfoacid calcium, newton body calcium naphthenate
Agent conversion is obtained, for example, by newton body ring sulfoacid calcium, newton body alkanoic acid calcium, base oil Hybrid Heating to 50-80 DEG C, adding institute
The transforming agent needed is reacted, after all transforming agents are added, and in 80-100 DEG C of constant temperature 60-90 minutes, then heats to 100-120
DEG C dehydration.
The third aspect, the invention provides a kind of complex calcium sulfonate-Calcium naphthenate base preparation of greases method, including：
（1）By the oily Hybrid Heating of newton body sulfoacid calcium, newton body calcium naphthenate and part basis, transforming agent, heating are added
Treat material retrogradation；
（2）In step（1）Lime or calcium hydroxide are added in products therefrom, higher fatty acids, aromatic acid and selection is added
Property small molecule inorganic acid and/or lower fatty acid reacted, after reaction heat up dehydration；
（3）By step（2）Products therefrom is warming up to 180-230 DEG C of constant temperature refining, adds surplus base oil, adds necessary
Additive, obtains finished product.
Step（1）In, by newton body sulfoacid calcium, newton body calcium naphthenate, the oily Hybrid Heating of part basis to 50-80 DEG C,
Transforming agent needed for adding was reacted, after all transforming agents are added, in 80-100 DEG C of constant temperature 60-90 minutes.
In the present invention, for newton body sulfoacid calcium and newton body calcium naphthenate weight ratio without particular/special requirement, preferably 1：
0.25-4.The weight ratio of newton body sulfoacid calcium and the gross weight of newton body calcium naphthenate and part basis oil is preferably 1：0.1-3.
The newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g-
450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；The newton body calcium naphthenate be petroleum naphthenic acid calcium and/or
Calcium naphthenate is synthesized, 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 sulfoacid calcium and newton body calcium naphthenate gross weight, more preferably newton
The 6-22% of body sulfoacid calcium and newton body calcium naphthenate gross weight.
In the present invention, fatty alcohol includes the fatty alcohol of straight chain, side chain and ring-type, aliphatic acid, aliphatic ketone, fatty aldehyde, fat
Amine is similarly.
Step（2）In, at 85-100 DEG C, the suspension of lime or calcium hydroxide is added, higher fatty acids, stirring is added
5-20 minutes, the small molecule inorganic acid and/or lower fatty acid of aromatic acid and selectivity are added, stirs 5-20 minutes, is warming up to
100-120 DEG C, preferably keep realize dehydration within 30-60 minutes；Wherein, higher fatty acids and aromatic acid, small molecule inorganic acid and/or
The addition sequence of lower fatty acid 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 as it was previously stated, no longer go to live in the household of one's in-laws on getting married herein
State.
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 and the OH contained by the suspension of lime or calcium hydroxide-The amount of total material is equal, OH-Amount also can excess 1-
10%。
In the present invention, in terms of calcium hydroxide, the addition of the suspension of lime or calcium hydroxide is preferably newton body sulfonic acid
The 1-15% of calcium and newton body calcium naphthenate gross weight；With H+Material gauge, higher fatty acids and aromatic acid and selectivity it is small
The mol ratio of molecule inorganic acid and/or lower fatty acid is preferably 1：1-10.
In the present invention, the suspension of lime or calcium hydroxide is that to refer to that lime or calcium hydroxide are formed in water suspended
Liquid, the solid content of suspension is preferably 10-60 weight %.
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 base oil used and step（3）In base oil used weight ratio preferably 1：0.1-
5。
Fourth aspect, present invention also offers composite sulfoacid made from the preparation method provided as third aspect present invention
Calcium-calcium naphthenate base grease.
Compared with the complex calcium sulfonate as made from the preparation method that second aspect is provided-calcium naphthenate base grease, the 3rd
Complex calcium sulfonate-calcium naphthenate base grease made from the preparation method that aspect is provided has more preferable mechanical stability, water resistant
Property and adhesiveness, colloid stability and extreme pressure anti-wear.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the following Examples and Comparative Examples：
Non-newtonian fluid sulfoacid calcium-calcium naphthenate %=（Overbased or calcium sulfonate with high base number raw material weight+overbased or height
Base number calcium naphthenate raw material weight+transforming agent gross weight）/ lubricating grease gross weight × 100%.Transforming agent is included in non-newtonian fluid sulphur
In the content of sour calcium-calcium naphthenate.
Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd, also may be used
To be prepared according to method disclosed in CN101885677A.
Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industries Co., Ltd.
Embodiment 1
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；It is right
Phthalic acid（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 17kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；2.8kg aphthenic acids is added, temperature control exists
50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；80 DEG C are warming up to,
Constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10 is added
Minute；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；3.5kg terephthalic acid (TPA)s are added, stirs 10 minutes, is risen under stirring
Temperature is kept for 45 minutes to 110 DEG C, dehydration；It is warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, adds 17kg's
HVI500SN lubricating base oils；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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.4；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of terephthalic acid (TPA) calcium 5.0
Measure %.
Embodiment 2
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 420mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total alkali
It is worth for 420mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 1.8kg）；Acetic acid（0.56kg）；Boric acid（1kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearates
Acid（2kg）；Phthalic acid（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 17kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 6kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 420mgKOH/g for 420mgKOH/g overbased sulfoacid calcium, 24kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 60 DEG C, constant temperature 10 minutes；1.8kg aphthenic acids is added, temperature control exists
60 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；Add 5kg concentration
For 20 weight % boric acid aqueous solution, stir 10 minutes；It is warming up to 85 DEG C, constant temperature 75 minutes, material retrogradation；Adding solid content is
20 weight % calcium hydroxide suspension 9kg, is stirred 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；Add
3.5kg phthalic acids, are stirred 10 minutes, and 100 DEG C are warming up under stirring, are kept for 60 minutes, dehydration；It is warming up to 180 DEG C of constant temperature
20 minutes.Then, 17kg HVI500SN lubricating base oils are added；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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.4；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of calcium phthalate 5.0
Measure %.
Embodiment 3
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total alkali
It is worth for 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 20kg）；Butanol
（1.8kg）；Acetic acid（0.56kg）；Boric acid（1kg）；Calcium hydroxide（1.8kg）；Stearic acid（1.9kg）；M-phthalic acid
（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 28kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The overbased calcium alkyl-salicylate and 20kg for being 320mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 80 DEG C, constant temperature 10 minutes；1.8kg butanol is added, temperature control is 80
DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；Adding 5kg concentration is
20 weight % boric acid aqueous solution, is stirred 10 minutes；It is warming up to 90 DEG C, constant temperature 60 minutes, material retrogradation；It is 20 to add solid content
Weight % calcium hydroxide suspension 9kg, is stirred 10 minutes；1.9kg stearic acid is added, is stirred 10 minutes；Add 3.5kg isophthalic
Dioctyl phthalate, is stirred 10 minutes, and 120 DEG C are warming up under stirring, is kept for 30 minutes, dehydration；It is warming up to 230 DEG C of constant temperature 5 minutes.So
Afterwards, 28kg HVI500SN lubricating base oils are added；Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing obtain finished product.
Assay is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.4；The weight % of lubricating base oil 54.3；The weight % of calcium stearate 2.3；The weight % of M-phthalic acid calcium 5.0.
Embodiment 4
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 33kg）；Overbased calcium alkyl-salicylate（Total alkali
It is worth for 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 20kg）；Dodecyl
Benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA)
（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 28kg）, right, right '-di-iso-octyldiphenylamine
（0.2kg）.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, calcium naphthenate makes
The overbased calcium alkyl-salicylate for being 320mgKOH/g with total base number；Aphthenic acids is replaced with DBSA simultaneously；And treat temperature
Degree is cooled to 110 DEG C, adds 0.2kg pair, after right '-di-iso-octyldiphenylamine is stirred 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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 39.6；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2；The weight % of terephthalic acid (TPA) calcium 4.0,
It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 5
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids（Total acid
It is worth for 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；To benzene two
Formic acid（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 7kg）.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, sulfoacid calcium is used
Total base number is 320mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 54.0；The weight % of lubricating base oil 35.6；The weight % of 12- hydroxy stearic acids calcium 3.4；The weight of terephthalic acid (TPA) calcium 7.0
Measure %.
Embodiment 6
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total alkali
It is worth for 400mgKOH/g, 24kg）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO40（100 DEG C of kinematic viscosity are 41mm2/ s, 30kg）；Ten
Dialkyl benzene sulfonic acids（2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Terephthaldehyde
Acid（3.5kg）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO10（100 DEG C of kinematic viscosity are 11mm2/ s, 17kg）.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, use dodecane
Base benzene sulfonic acid replaces aphthenic acids；Use full synthetic oil poly ＆ Alpha ,-olefin oil PAO40（100 DEG C of kinematic viscosity are 41mm2/s）And PAO10
（100 DEG C of kinematic viscosity are 11mm2/s）Respectively instead of HVI150BS（100 DEG C of kinematic viscosity are 31mm2/s）And HVI500SN（100
DEG C kinematic viscosity is 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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.4；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of terephthalic acid (TPA) calcium 5.0
Measure %.
Embodiment 7
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（2.2kg）；12- hydroxy stearic acids（10kg）；2- first
Base-Isosorbide-5-Nitrae-phthalic acid（2.2kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 20kg）.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, calcium naphthenate makes
The overbased calcium alkyl-salicylate for being 320mgKOH/g with total base number；Using 2- methyl isophthalic acids, 4- phthalic acids replace terephthalic acid (TPA)；Respectively
The consumption of 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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 34.5；The weight % of lubricating base oil 51.7；The weight % of 12- hydroxy stearic acids calcium 11.0；2- methyl isophthalic acids, 4- benzene diformazans
The sour weight % of calcium 2.8.
Embodiment 8
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total base number
For 400mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；4,4'-
Biphenyl dicarboxylic acid（5.1kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 20kg）, it is right, it is right '-two different
Octyl diphenylamine（0.2kg）；Two thio dialkyl amido formic acid molybdenums（4kg）；Selenium disulfide（4kg）；Benzotriazole
（0.4kg）.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, sulfoacid calcium is used
Total base number is 320mgKOH/g calcium sulfonate with high base number；Terephthalic acid (TPA) is replaced using 4,4'- biphenyl dicarboxylic acids；And treat temperature
110 DEG C are cooled to, 0.2kg pair is added, right '-di-iso-octyldiphenylamine is stirred 10 minutes, adds 4kg two thio dialkyl group
Carbamic acid molybdenum, is stirred 10 minutes, adds 4kg selenium disulfide, is stirred 10 minutes, adds 0.4kg benzotriazole, stirring
10 minutes, then circulating filtration, homogenizing, degassing obtained 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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 33.4；The weight % of lubricating base oil 50.0；The weight % of 12- hydroxy stearic acids calcium 2.1；4,4'- biphenyl dicarboxylic acid calcium
5.9 weight %；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2；The two thio weight % of dialkyl amido formic acid molybdenum 4.0；Curing
The weight % of selenium 4.0；The weight % of benzotriazole 0.4.
Embodiment 9
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number is
320mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 15kg）；Aphthenic acids（Total acid
It is worth for 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；To benzene two
Formic acid（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 32kg）.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, sulfoacid calcium is used
Total base number is 320mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.4；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of terephthalic acid (TPA) calcium 5.0
Measure %.
Embodiment 10
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 15kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Dodecane
Base benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（3.3kg）；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, it is right '-two different
Octyl diphenylamine（0.2kg）.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, use dodecyl
Benzene sulfonic acid replaces aphthenic acids；And 12- hydroxy stearic acids are being added, after stirring 10 minutes, addition boric acid, stirring 10 minutes, so
After add terephthalic acid (TPA)；And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, right '-di-iso-octyldiphenylamine stirring
After 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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.2；The weight % of lubricating base oil 51.5；The weight % of 12- hydroxy stearic acids calcium 2.5；The weight % of line borate 2.7；To benzene
The weight % of dioctyl phthalate calcium 4.9；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 11
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 15kg）；Overbased calcium alkyl-salicylate（Total base number
For 320mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids（Always
Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（3kg）；12- hydroxy stearic acids（2kg）；To benzene two
Formic acid（3.5kg）；Acetic acid（2kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 14kg）, it is right, right '-
Di-iso-octyldiphenylamine（0.2kg）.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, sulfoacid calcium is used
Total base number is 320mgKOH/g calcium sulfonate with high base number, and calcium naphthenate uses the high base number aphthenic acids that total base number is 320mgKOH/g
Calcium；And terephthalic acid (TPA) is being added, after stirring 10 minutes, acetic acid is being added, stirs 10 minutes, be then warming up under agitation
110℃；And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, after right '-di-iso-octyldiphenylamine is stirred 10 minutes, then
Circulating filtration, 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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.5；The weight % of lubricating base oil 50.8；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of terephthalic acid (TPA) calcium 5.0
Measure %；The weight % of calcium acetate 3.1；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.
Embodiment 12
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always
Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm2/ s, 30kg）；Aphthenic acids
（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；It is right
Phthalic acid（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm2/ s, 17kg）.
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers
The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers
HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；2.8kg aphthenic acids is added, temperature control exists
50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；80 DEG C are warming up to,
Constant temperature 90 minutes, material retrogradation.
Another volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 7kg
HVI500SN lubricating base oils, the calcium hydroxide suspension 9kg that solid content is 20 weight % is added at 100 DEG C, 10 points are stirred
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
Calcium stearate and terephthalic acid (TPA) calcium.
The 12- hydroxy stearic acids calcium and terephthalic acid (TPA) calcium of gained are all squeezed into a upper kettle, stirred, is stirred
Under be warming up to 110 DEG C, kept for 45 minutes, dehydration, be finally warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C, addition are cooled to
Remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Examine knot
Fruit is shown in Table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.4；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of terephthalic acid (TPA) calcium 5.0
Measure %.
Embodiment 13
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, aphthenic acids is replaced
Phenol is changed to, acetic acid is replaced with into butyric 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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.4；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of terephthalic acid (TPA) calcium 5.0
Measure %.
Embodiment 14
The present embodiment is used for the complex calcium sulfonate-calcium naphthenate base grease for illustrating prepared by the present invention.
Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base grease, unlike, aphthenic acids is replaced
Ketone is changed to, acetic acid is replaced with into ether.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 sulfoacid calcium-cycloalkanes
The sour weight % of calcium 38.4；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight of terephthalic acid (TPA) calcium 5.0
Measure %.
Comparative example 1
Method according to embodiment 1 prepares complex calcium sulfonate grease, unlike, naphthenate with superhigh base number calcium is with always
Base number replaces for 400mgKOH/g overbased sulfoacid calcium, and obtained each performance data of lubricating grease finished product 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 38.4
Measure %；The weight % of lubricating base oil 54.2；The weight % of 12- hydroxy stearic acids calcium 2.4；The weight % of terephthalic acid (TPA) calcium 5.0.
Each lubricating grease properties of sample data of table 1
Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Water resistant is sprayed：SH/
T0643；Stencil oil-dividing：SH/T0324；Tetra-ball machine test：SH/T0202.
Table 1（It is continuous）Each lubricating grease properties of sample data
Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：
GB/T7326；Anticorrosive property：GB/T5018；Water drenches number of dropouts：SH/T0109；Salt spray test：SH/T0081；Water resistant is sprayed：SH/
T0643；Stencil oil-dividing：SH/T0324；Tetra-ball machine test：SH/T0202.
Embodiment 1 and comparative example 1 are compared as can be seen that complex calcium sulfonate-Calcium naphthenate base of the present invention lubricates
The difference of the extension work cone penetration of fat and work cone penetration is less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and it is far small that water drenches number of dropouts
In complex calcium sulfonate grease, salt spray test is better than complex calcium sulfonate grease, and water resistant spraying value is less than complex calcium sulfonate
Base grease, Stencil oil-dividing value is much smaller than complex calcium sulfonate grease, and tetra-ball machine test value lubricates more than Composite calcium-sulfonate-batetrapolyurea
Fat, illustrates complex calcium sulfonate-mechanical stability, water-resistance and the adhesiveness of calcium naphthenate base grease, the salt fog resistance of the present invention
Property, colloid stability, extreme pressure anti-wear be superior to complex calcium sulfonate grease, and complex calcium sulfonate-aphthenic acids of the present invention
Calcium-base grease has the performances such as excellent anticorrosive property and heat-resisting quantity as complex calcium sulfonate grease.
Embodiment 1 and embodiment 12 are compared as can be seen that the complex calcium sulfonate-Calcium naphthenate base in situ prepared is moistened
Consistent lubricant, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear；Embodiment 1 is distinguished
Be compared with embodiment 13 and embodiment 14 as can be seen that transforming agent be selected from DBSA, it is aphthenic acids, methanol, different
At least one of propyl alcohol, butanol, boric acid, acetic acid and water, complex calcium sulfonate-calcium naphthenate base grease of preparation, with more
Mechanical stability, water-resistance and adhesiveness well, colloid stability and extreme pressure anti-wear.
It will be seen from figure 1 that lubricating grease prepared by embodiment 2 is in 873cm-1-886cm-1There is crystal form calcium carbonate feature in place
Absworption peak.The absworption peak of unformed calcium carbonate is 863cm in overbased calcium alkyl-salicylate raw material-1, into fat after its absworption peak be
874cm-1。
Complex calcium sulfonate-calcium naphthenate base grease of the present invention, not only as complex calcium sulfonate grease, has
Excellent anticorrosive property and heat-resisting quantity, but also mechanical stability, water-resistance with better than complex calcium sulfonate grease
With the performance such as adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear.The preparation of greases technique of the present invention is simple, ring
Protect, cost is low, product quality is stable.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these 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 (17)
1. a kind of complex calcium sulfonate-calcium naphthenate base grease, it is characterised in that on the basis of lubricating grease weight, including it is following
Component：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium salt of 1-20 weight % higher fatty acids；1-15 weights
Measure the calcium salt of % aromatic acid；10-80 weight % base oil；Optionally also include 1-15 weight % small molecule inorganic acid
And/or the calcium salt of lower fatty acid, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm-1-886cm-1Place goes out
Existing crystal form calcium carbonate characteristic absorption peak.
2. lubricating grease according to claim 1, wherein, on the basis of lubricating grease weight, including following components：20-65 weights
Measure % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium salt of 2-15 weight % higher fatty acids；2-10 weight % aromatic acid
Calcium salt；20-70 weight % base oil；Optionally also include 2-10 weight % small molecule inorganic acid and/or lower aliphatic
The calcium salt of acid.
3. lubricating grease according to claim 1 or 2, wherein, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is by newton body
What sulfoacid calcium and the conversion of newton body calcium naphthenate were obtained, the total base number of the non-newtonian fluid sulfoacid calcium-calcium naphthenate is 250-
450mgKOH/g。
4. lubricating grease according to claim 1 or 2, wherein, the higher fatty acids is the straight chain fatty that carbon number is 8-20
Acid or hydroxy fatty acid.
5. lubricating grease according to claim 4, wherein, the higher fatty acids be selected from laurate, palmitic acid, stearic acid,
At least one of 12- hydroxy stearic acids, eicosyl carboxylic acid.
6. lubricating grease according to claim 1 or 2, wherein, the aromatic acid is substituted or unsubstituted aromatic acid, substituent
At least one of alkyl or aryl for alkyl, alkenyl, alkynyl, aryl, halo or perhalogeno, the molecular weight of the aromatic acid is small
In 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, point of the small molecule inorganic acid or the lower fatty acid
Son amount is less than or 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. complex calcium sulfonate-Calcium naphthenate base preparation of greases method in claim 1-9 described in any one, it is special
Levy and be, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, part
The calcium salt of the small molecule inorganic acid and/or lower fatty acid of base oil and selectivity is well mixed, in 180-230 DEG C of constant temperature
Refining, adds surplus base oil, adds necessary additive, obtains finished product.
11. complex calcium sulfonate-Calcium naphthenate base preparation of greases method in claim 1-9 described in any one, it is special
Levy and be, this method includes：
(1) by the oily Hybrid Heating of newton body sulfoacid calcium, newton body calcium naphthenate and part basis, transforming agent is added, thing is treated in heating
Expect retrogradation；
(2) lime or calcium hydroxide are added in step (1) products therefrom, higher fatty acids, aromatic acid and selectivity is added
Small molecule inorganic acid and/or lower fatty acid are reacted, and heat up dehydration after reaction；
(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.
12. preparation method according to claim 11, wherein, in step (1), by newton body sulfoacid calcium, newton body cycloalkanes
The oily Hybrid Heating of sour calcium, part basis is to 50-80 DEG C, and the transforming agent needed for adding is reacted, after all transforming agents are added,
80-100 DEG C of constant temperature 60-90 minutes.
13. preparation method according to claim 11, wherein, in step (2), at 85-100 DEG C, add lime or hydrogen
The suspension of calcium oxide, adds higher fatty acids, stirs 5-20 minutes, adds the small molecule inorganic acid of aromatic acid and selectivity
And/or lower fatty acid, stir 5-20 minutes, be warming up to 100-120 DEG C of dehydration.
14. preparation method according to claim 11, wherein, in step (3), it is warming up to 180-230 DEG C of 5-20 points of constant temperature
Clock；Add surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stirring, circulating filtration, homogenizing,
Degassing.
15. preparation method according to claim 11, wherein, the newton body sulfoacid calcium is calcium mahogany sulfonate and/or conjunction
Into sulfoacid calcium, the total base number of the newton body sulfoacid calcium is 250-450mgKOH/g；The newton body calcium naphthenate is oil ring
Alkanoic acid calcium and/or synthesis calcium naphthenate, the total base number of the newton body calcium naphthenate is 250-450mgKOH/g.
16. preparation method according to claim 11, wherein, the transforming agent be selected from fatty alcohol, aliphatic acid, aliphatic ketone,
Fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkane
At least one of base benzene sulfonic acid and water, the addition of transforming agent is newton body sulfoacid calcium and newton body calcium naphthenate gross weight
2-30%.
17. preparation method according to claim 16, wherein, the transforming agent be selected from DBSA, aphthenic acids,
At least one of methanol, isopropanol, butanol, boric acid, acetic acid and water, the addition of transforming agent is newton body sulfoacid calcium and newton
The 6-22% of body calcium naphthenate gross weight.
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| CN101824357A (en) * | 2010-05-27 | 2010-09-08 | 李墨菊 | High-performance complex calcium sulfonate grease and preparation method thereof |
| CN101935578A (en) * | 2010-10-11 | 2011-01-05 | 长沙众城石油化工有限责任公司 | Calcium sulfonate complex grease and preparation method thereof |
| CN102911761A (en) * | 2012-10-24 | 2013-02-06 | 中国石油化工股份有限公司 | High-temperature-resistant extreme pressure type lubricating grease composition and preparation method |
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| CN101824357A (en) * | 2010-05-27 | 2010-09-08 | 李墨菊 | High-performance complex calcium sulfonate grease and preparation method thereof |
| CN101935578A (en) * | 2010-10-11 | 2011-01-05 | 长沙众城石油化工有限责任公司 | Calcium sulfonate complex grease and preparation method thereof |
| CN102911761A (en) * | 2012-10-24 | 2013-02-06 | 中国石油化工股份有限公司 | High-temperature-resistant extreme pressure type lubricating grease composition and preparation method |
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