CN104560276B

CN104560276B - A kind of complex calcium sulfonate calcium naphthenate zirconium base lubricating grease and preparation method thereof

Info

Publication number: CN104560276B
Application number: CN201310520493.7A
Authority: CN
Inventors: 何懿峰; 孙洪伟; 段庆华; 张建荣; 刘中其; 姜靓; 陈政; 郑会
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-10-29
Filing date: 2013-10-29
Publication date: 2017-11-03
Anticipated expiration: 2033-10-29
Also published as: CN104560276A

Abstract

The invention discloses a kind of complex calcium sulfonate calcium naphthenate zirconium base lubricating grease, including：10 70 weight % non-newtonian fluid sulfoacid calcium 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

A kind of complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease and preparation method thereof

Technical field

The present invention relates to lubricating grease, in particular it relates to a kind of complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease and its preparation 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, 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 an object of the invention to provide a kind of mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and Extreme pressure anti-wear is preferable, and cost is low, simple and environmentally-friendly lubricating grease of preparation technology and preparation method thereof

The present inventor has found under study for action, on the basis of lubricating grease weight, including following components：10-70 weight % Non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；The zirconates of 1-15 weight % aromatic acid； 10-80 weight % base oil；Small molecule inorganic acid and/or the zirconium of lower fatty acid optionally also including 1-15 weight % Salt, wherein, the zirconates of the higher fatty acids is to be formed by higher fatty acids with component A reactions, the zirconates of the aromatic acid be by Aromatic acid and component A reaction are formed, the zirconates of the small molecule inorganic acid and/or lower fatty acid be by small molecule inorganic acid and/ Or lower fatty acid and component A reaction are formed, the component A is the oxide of zirconium, in the hydroxide and zirconium alkoxide of zirconium It is at least one.The lubricating grease has preferable mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability and pole Wear resistence is pressed, and cost is low, preparation technology is simple and environmentally-friendly.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of complex calcium sulfonate-calcium naphthenate zirconium base Lubricating grease, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；1- The zirconates of 10 weight % higher fatty acids；The zirconates of 1-15 weight % aromatic acid；10-80 weight % base oil；Optionally also The zirconates of small molecule inorganic acid and/or lower fatty acid including 1-15 weight %, wherein, the zirconates of the higher fatty acids is Formed by higher fatty acids with component A reactions, the zirconates of the aromatic acid is to be formed by aromatic acid with component A reactions, the small molecule The zirconates of inorganic acid and/or lower fatty acid is to be formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, institute State at least one of oxide, the hydroxide of zirconium and zirconium alkoxide that component A is zirconium.

Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid sulfoacid calcium-ring Alkanoic acid calcium；The zirconates of 2-6 weight % higher fatty acids；The zirconates of 2-10 weight % aromatic acid；20-70 weight % base oil；Choosing Also include to selecting property 2-10 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid.

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 complex calcium sulfonate as described above-calcium naphthenate zirconium base preparation of greases side Method, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid and part base The zirconates of the small molecule inorganic acid and/or lower fatty acid of plinth oil and selectivity is well mixed, in 180-230 DEG C of constant temperature refining System, adds surplus base oil, adds necessary additive, obtains finished product.

The third aspect, the invention provides a kind of complex calcium sulfonate-calcium naphthenate zirconium base preparation of greases method, the party Method includes：

（1）Newton body sulfoacid calcium, newton body calcium naphthenate, part basis oil and transforming agent are mixed, heating treats that material becomes It is thick；

（2）In step（1）Component A is added in products therefrom, 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 complex calcium sulfonate as made from method as described above-calcium naphthenate zirconium base profit Consistent lubricant.

Complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease of the present invention, compared to complex calcium sulfonate grease, with more preferable Mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, the performance such as extreme pressure anti-wear.The lubrication of the present invention The preparation technology of fat 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 complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, this lubricating grease employs oil sulphur Sour calcium and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, it is simultaneously thick containing compound zirconium 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 zirconium base lubricating grease, using lubricating grease weight as base Standard, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconium of 1-10 weight % higher fatty acids Salt；The zirconates of 1-15 weight % aromatic acid；10-80 weight % base oil；Optionally also including 1-15 weight % small molecule without The zirconates of machine acid and/or lower fatty acid, wherein, the zirconates of higher fatty acids be reacted by higher fatty acids and component A and Into the zirconates of aromatic acid is to be formed by aromatic acid with component A reactions, and the zirconates of small molecule inorganic acid and/or lower fatty acid is by small Molecule inorganic acid and/or lower fatty acid are formed with component A reactions, and component A is oxide, the hydroxide and alcoxyl of zirconium of zirconium At least one of base zirconium.

Preferably, on the basis of lubricating grease weight, including following components：20-60 weight % non-newtonian fluid sulfoacid calcium-ring Alkanoic acid calcium；The zirconates of 2-6 weight % higher fatty acids；The zirconates of 2-10 weight % aromatic acid；20-70 weight % base oil；Choosing Also include to selecting property 2-10 weight % small molecule inorganic acid and/or the zirconates of lower fatty acid；It is highly preferred that with lubricating grease weight On the basis of amount, including following components：30-55 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；2.2-4.5 weight %'s is senior The zirconates of aliphatic acid；The zirconates of 3-8 weight % aromatic acid；30-60 weight % base oil；Optionally also include 3-8 weight %'s The zirconates of small molecule inorganic acid and/or 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 sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1There is the suction of crystal form calcium carbonate feature in place Peak is received, total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid sulfonic acid Calcium-calcium naphthenate is to be obtained by newton body sulfoacid calcium and newton body calcium naphthenate by transforming agent conversion.And newton body sulfoacid calcium, Contain unformed calcium carbonate in newton body calcium naphthenate, in infrared spectrum 860cm^-1-865cm^-1It is special that unformed calcium carbonate occurs in place Levy absworption peak.Newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g- 450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis Calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Non-newtonian fluid The base number of sulfoacid calcium-calcium naphthenate is averaged for the base number of newton body sulfoacid calcium with the weight of the base number of newton body calcium naphthenate 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..

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.

In the present invention, for non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid, small point Zirconates, 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 sulfoacid calcium, newton body calcium naphthenate, 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 60-90 DEG C of constant temperature 60-90 minutes, then heats to 100-120 DEG C dehydration.

Step（1）In, by newton body sulfoacid calcium, newton body calcium naphthenate, the oily Hybrid Heating of part basis to 50-80 DEG C, It is preferred that constant temperature 10-30 minutes, the transforming agent needed for adding is reacted, stirring 8-12 minutes after every kind of transforming agent are preferably added, After all transforming agents are added, in 60-90 DEG C of constant temperature 60-90 minutes.

Step of the present invention（1）In, for newton body sulfoacid calcium and newton body calcium naphthenate weight ratio without particular/special requirement, it is excellent Elect 1 as：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。

In the present invention, newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/ G-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or conjunction Into calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.

The transforming agent be preferably selected from fatty alcohol, aliphatic acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, At least one of phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8-C20 alkyl benzene sulphonates and water；It is more excellent 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.

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 sulfoacid calcium With the 1-15% of newton body calcium naphthenate gross weight；With H⁺Material gauge, higher fatty acids and aromatic acid and selective small point The mol ratio of sub- inorganic acid and/or lower fatty acid is preferably 1：1-10.

Step（3）In, it is warming up to 180-230 DEG C of constant temperature 5-20 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 sulfoacid made from the preparation method provided as third aspect present invention Calcium-calcium naphthenate zirconium base lubricating grease.

Compared with the complex calcium sulfonate as made from the preparation method that second aspect is provided-calcium naphthenate zirconium base lubricating grease, the Three aspect provide preparation method made from complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease 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 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.

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 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 zirconium base lubricating grease for illustrating prepared by the present invention.

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Always Base number is 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 30kg）；Aphthenic acids （Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；It is right Phthalic acid（3.5kg）；HVI500SN lubricating base oils（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 24kg total base numbers The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control exists 50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；It is warming up to 60 DEG C, constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, the Zr (OH) that solid content is 20 weight % is added₄Suspension 19.5kg, Stirring 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；3.5kg terephthalic acid (TPA)s are added, stirring rises 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, 17kg HVI500SN lubrication bases are added Plinth 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 sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.7；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；Terephthalic acid (TPA) oxygen zirconium 6.5 Weight %.

Embodiment 2

Raw material components：Overbased sulfoacid calcium（Total base number is 420mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total alkali It is worth for 420mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 30kg）；Aphthenic acids （Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Ethanol zirconium（5.5kg）；Zr(OH)₄（0.65kg）；12- hydroxyls Stearic acid（2kg）；Phthalic acid（3.5kg）；HVI500SN lubricating base oils（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 6kg total base numbers The naphthenate with superhigh base number calcium and 30kg for being 420mgKOH/g for 420mgKOH/g overbased sulfoacid calcium, 24kg total base numbers HVI150BS lubricating base oils, stirring, heat to 65 DEG C, constant temperature 20 minutes；2.8kg aphthenic acids is added, temperature control exists 65 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；75 DEG C are warming up to, Constant temperature 75 minutes, material retrogradation；85 DEG C are warming up to, the Zr (OH) of 5.5kg ethanol zirconium and solid content for 20 weight % is successively added₄ Suspension 3.25kg, in terms of zirconium, Zr (OH)₄Mol ratio with ethanol zirconium is 1：5, stir 10 minutes；Add 2kg12- hydroxyls hard Resin acid, is stirred 10 minutes；3.5kg phthalic acids are added, stirring is warming up to 100 DEG C, kept for 60 minutes under stirring, dehydration；Rise Temperature was to 230 DEG C of constant temperature 5 minutes.Then, 17kg HVI500SN lubricating base oils are added；Treat that temperature is cooled to 120 DEG C, be circulated throughout Filter, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

Embodiment 3

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 24kg）；Overbased calcium alkyl-salicylate（Total alkali It is worth for 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 20kg）；Butanol （2.8kg）；Acetic acid（0.56kg）；Zirconium-n-butylate（3.13kg）；Zr(OH)₄（2.6kg）；Stearic acid（1.9kg）；M-phthalic acid （3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 28kg）.

A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The 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；2.8kg butanol is added, temperature control is 80 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；It is warming up to 90 DEG C, perseverance Temperature 60 minutes, material retrogradation；Successively add the Zr (OH) of 3.13kg zirconium-n-butylates and solid content for 20 weight %₄Suspension 13kg, In terms of zirconium, Zr (OH)₄Mol ratio with zirconium-n-butylate is 1：0.5, stir 10 minutes；1.9kg stearic acid is added, 10 points are stirred Clock；3.5kg M-phthalic acids are added, stirring is warming up to 120 DEG C, kept for 30 minutes under stirring, dehydration；It is warming up to 180 DEG C of constant temperature 20 minutes.Then, 28kg HVI500SN lubricating base oils are added；Treat that temperature is cooled to 100 DEG C, it is circulating filtration, homogenizing, de- It is so incensed that 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 37.8；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

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 33kg）；Overbased calcium alkyl-salicylate（Total alkali It is worth for 320mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 20kg）；Dodecyl Benzene sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Zirconium-n-propylate（4.0kg）；Zr(OH)₄（2.0kg）；12- hydroxy stearic acids（2kg）； Terephthalic acid (TPA)（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 28kg）；It is right, it is right '-two different Octyl diphenylamine（0.2kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, calcium naphthenate Use the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g；Aphthenic acids is replaced with DBSA；Add Zr (OH)₄ When 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, Addition 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 sulfoacid calcium-cycloalkanes The sour weight % of calcium 43.7；The weight % of lubricating base oil 49.5；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.2；Terephthalic acid (TPA) oxygen zirconium 4.4 Weight %；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 5

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）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；Terephthaldehyde 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 zirconium base lubricating grease, unlike, sulfoacid calcium makes The calcium sulfonate with high base number for being 320mgKOH/g with total base number, calcium naphthenate uses the high base number cycloalkanes that total base number is 320mgKOH/g Sour 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 52.6；The weight % of lubricating base oil 34.7；The weight % of 12- hydroxy stearic acid oxygen zirconium 3.7；Terephthalic acid (TPA) oxygen zirconium 9.0 Weight %.

Embodiment 6

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total alkali It is worth for 400mgKOH/g, 24kg）；Poly alpha olefine synthetic oil PAO40（100 DEG C of kinematic viscosity are 40mm²/ s, 30kg）；Dodecane Base benzene sulfonic acid（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 kinematic viscosity are 11mm²/ s, 17kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, use 12 Alkyl benzene sulphonate replaces aphthenic acids；Use poly alpha olefine synthetic oil PAO40（100 DEG C of kinematic viscosity are 40mm²/s）With poly- α-alkene Hydrocarbon artificial oil 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 of kinematic viscosity are 11mm²/s）；The consumption of each composition is as above.Assay is shown in Table 1.

Embodiment 7

Raw material components：Overbased sulfoacid calcium（Total base number is 400mgKOH/g, 6kg）；Overbased calcium alkyl-salicylate（Total base number For 320mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 30kg）；Aphthenic acids（Always Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；2- first Base -1,4- phthalic acids（3.8kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 16.7kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, calcium naphthenate Use the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g；2- methyl isophthalic acids are used, 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 37.7；The weight % of lubricating base oil 52.8；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.7；2- methyl isophthalic acids, 4- benzene diformazans The sour weight % of oxygen zirconium 6.8.

Embodiment 8

Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 6kg）；Naphthenate with superhigh base number calcium（Total base number For 400mgKOH/g, 24kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 30kg）；Aphthenic acids（Always Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；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 zirconium base lubricating grease, unlike, sulfoacid calcium makes The calcium sulfonate with high base number for being 320mgKOH/g with total base number；Terephthalic acid (TPA) is replaced with 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 32.9；The weight % of lubricating base oil 49.2；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.3；4,4'- biphenyl dicarboxylic acid oxygen The weight % of zirconium 7.2；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2；The two thio weight % of dialkyl amido formic acid molybdenum 3.9；Two sulphur Change the weight % of selenium 3.9；The weight % of benzotriazole 0.4.

Embodiment 9

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）；Zr(OH)₄（3.9kg）；12- hydroxy stearic acids（2kg）；Terephthaldehyde Acid（3.5kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ s, 32kg）.

Embodiment 10

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）；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, it is right '-two different Octyl diphenylamine（0.2kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, use 12 Alkyl benzene sulphonate replaces aphthenic acids；Boric acid is additionally added after 12- hydroxy stearic acids are added, terephthalic acid (TPA) is then added；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 sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.0；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；It is right The weight % of phthalic acid oxygen zirconium 6.3；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 11

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）；Zr(OH)₄（6.5kg）；12- hydroxy stearic acids（2kg）；To benzene Dioctyl phthalate（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 zirconium base lubricating grease, unlike, sulfoacid calcium makes The calcium sulfonate with high base number for being 320mgKOH/g with total base number, calcium naphthenate uses the high base number cycloalkanes that total base number is 320mgKOH/g Sour calcium；Acetic acid is additionally added after terephthalic acid (TPA) is added, then heat up dehydration again；And treat that temperature is cooled to 110 DEG C, addition 0.2kg pair, right '-di-iso-octyldiphenylamine, after stirring 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；It is each into The consumption divided 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 37.1；The weight % of lubricating base oil 48.9；The weight % of 12- hydroxy stearic acid oxygen zirconium 2.6；Terephthalic acid (TPA) oxygen zirconium 4.8 Weight %；The weight % of zirconyl acetate 6.4；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 12

A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 30 minutes；2.8kg aphthenic acids is added, temperature control exists 50 DEG C or so, stir 10 minutes；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；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.

Embodiment 13

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, by aphthenic acids Phenol is replaced with, acetic acid is replaced with into butyric acid.Assay is shown in Table 1.

Embodiment 14

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, by aphthenic acids Methyl propyl ketone is replaced with, aqueous acetic acid is replaced with into butyl ether.Assay is shown in Table 1.

Embodiment 15

Method according to embodiment 4 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, at Zr (OH)₄ With the total mole number of zirconium-n-propylate it is constant in the case of, adjust Zr (OH)₄Mol ratio with zirconium-n-propylate is 1：0.1.Gained fat Each physicochemical property be shown in Table 1.

Embodiment 16

Method according to embodiment 4 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, at Zr (OH)₄ With the total mole number of zirconium-n-propylate it is constant in the case of, adjust Zr (OH)₄Mol ratio with zirconium-n-propylate is 1：10.Gained fat Each physicochemical property is shown in Table 1.

Embodiment 17

Method according to embodiment 4 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, by normal propyl alcohol Zirconium replaces with equimolar Zr (OH)₄.Each physicochemical property of gained fat is shown in Table 1.

Embodiment 18

Method according to embodiment 4 prepares complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, unlike, by Zr (OH)₄ Replace with equimolar zirconium-n-propylate.Each physicochemical property of gained fat is shown in Table 1.

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, overbased calcium alkyl-salicylate is replaced with always Base number is 320mgKOH/g calcium sulfonate with high base number, Zr (OH) used₄With Ca (OH)₂Instead of while adjusting consumption makes each composition Content is consistent with embodiment 5.Each physicochemical property of gained fat is shown in Table 1.

In the lubricating grease that this comparative example 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.

Embodiment 1 is compared with comparative example 1, embodiment 5 is compared with comparative example 2, it can be seen that the present invention Complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease extension work cone penetration with work cone penetration difference be less than composite sulfoacid Calcium-base grease, water drenches number of dropouts and is less than complex calcium sulfonate grease, and salt spray test is better than complex calcium sulfonate grease, resists Water spray value is less than complex calcium sulfonate grease, and Stencil oil-dividing value is less than complex calcium sulfonate grease, tetra-ball machine test value More than complex calcium sulfonate grease, illustrate complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease of the present invention mechanical stability, Water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear are superior to complex calcium sulfonate grease.

Embodiment 1 and embodiment 12 are compared as can be seen that the complex calcium sulfonate-calcium naphthenate zirconium base in situ prepared Lubricating grease, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability；By embodiment 1 respectively with embodiment 13 With embodiment 14 be compared as can be seen that transforming agent be selected from DBSA, aphthenic acids, methanol, isopropanol, butanol, At least one of boric acid, acetic acid and water, complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease of preparation, with more preferable machinery Stability, water-resistance and adhesiveness, colloid stability；Embodiment 4 is compared with embodiment 15 and embodiment 16 respectively can To find out, the oxide and/or hydroxide of zirconium and the mol ratio of zirconium alkoxide are 1：0.5-5, complex calcium sulfonate-ring of preparation Alkanoic acid calcium zirconium base lubricating grease, with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability；Embodiment 4 is distinguished It is compared with embodiment 17 and embodiment 18 as can be seen that the raw material of zirconium is the oxide and/or hydroxide and alcoxyl of zirconium The mixture of base zirconium, complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease of preparation, with more preferable mechanical stability, water-resistance With adhesiveness, colloid stability.

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

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

1. a kind of complex calcium sulfonate-calcium naphthenate zirconium base lubricating grease, it is characterised in that on the basis of lubricating grease weight, including with Lower component：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 1-10 weight % higher fatty acids；1-15 The zirconates of weight % aromatic acid；10-80 weight % base oil；Optionally also include 1-15 weight % small molecule inorganic acid And/or the zirconates of lower fatty acid, wherein, the zirconates of the higher fatty acids is to be formed by higher fatty acids with component A reactions, The zirconates of the aromatic acid 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 Formed by small molecule inorganic acid and/or lower fatty acid with component A reactions, the component A is oxide, the hydroxide of zirconium of zirconium At least one of thing and zirconium alkoxide, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1 There is crystal form calcium carbonate characteristic absorption peak in place.

2. lubricating grease according to claim 1, wherein, on the basis of lubricating grease weight, including following components：20-60 weights Measure % non-newtonian fluid sulfoacid calcium-calcium naphthenate；The zirconates of 2-6 weight % higher fatty acids；2-10 weight % aromatic acid Zirconates；20-70 weight % base oil；Optionally also include 2-10 weight % small molecule inorganic acid and/or lower aliphatic The zirconates of acid.

3. lubricating grease according to claim 1, wherein, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is by newton body sulphur What sour 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 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. complex calcium sulfonate-calcium naphthenate zirconium base preparation of greases method in claim 1-14 described in any one, its It is characterised by, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the zirconates of higher fatty acids, the zirconates of aromatic acid and The zirconates of the small molecule inorganic acid and/or lower fatty acid of part basis oil and selectivity is well mixed, at 180-230 DEG C Constant temperature is refined, and adds surplus base oil, is added necessary additive, is obtained finished product.

16. complex calcium sulfonate-calcium naphthenate zirconium base preparation of greases method in claim 1-14 described in any one, its It is characterised by, this method includes：

(1) newton body sulfoacid calcium, newton body calcium naphthenate, part basis oil and transforming agent are mixed, material retrogradation is treated in heating；

(2) 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, in step (1), by newton body sulfoacid calcium, newton body calcium naphthenate, Part basis oil Hybrid Heating is 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 constant temperature 60-90 minutes.

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 sulfoacid calcium is calcium mahogany sulfonate and/or synthesis sulphur Sour calcium, the total base number of the newton body sulfoacid calcium is 250-450mgKOH/g；The newton body calcium naphthenate is petroleum naphthenic acid Calcium and/or synthesis calcium naphthenate, the total base number of the newton body calcium naphthenate is 250-450mgKOH/g.

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- of newton body sulfoacid calcium and newton body calcium naphthenate gross weight 30%.

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 sulfoacid calcium and newton body The 6-22% of calcium naphthenate gross weight.