CN104449958B

CN104449958B - A kind of complex calcium sulfonate calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof

Info

Publication number: CN104449958B
Application number: CN201310418853.2A
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: 2013-09-13
Filing date: 2013-09-13
Publication date: 2017-11-28
Anticipated expiration: 2033-09-13
Also published as: CN104449958A

Abstract

The invention discloses a kind of complex calcium sulfonate calcium naphthenate base octa-polyurea lubricating 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；0.5 30 weight % polyurea compound；10 80 weight % base oil；The optionally calcium salt of the small molecule inorganic acid also including 1 15 weight % and/or lower fatty acid, wherein, the polyurea compound is eight polyurea compounds.Also disclose the preparation method of complex calcium sulfonate calcium naphthenate base octa-polyurea lubricating grease and its complex calcium sulfonate calcium naphthenate base octa-polyurea lubricating grease of preparation.The lubricating grease of the present invention, there is the performances such as mechanical stability, water-resistance and adhesiveness better than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, resistance to saltfog, extreme pressure anti-wear, there is longer lubricating life.

Description

A kind of complex calcium sulfonate-calcium naphthenate base octa-polyurea 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 base octa-polyurea lubricating grease and its Preparation method.

Background technology

Sulfoacid calcium is used as the detersive and the history of antirust agent existing decades of lubricating oil, is widely used in internal combustion engine lubrication The additive of oil, the development of its technology mainly make its height alkalization, are exactly alkyl benzene sulphonate of the calcium carbonate with surface-active Calcium or alkyl carboxylic acid calcium turn into a kind of colloidal dispersion system to be distributed in flux oil.Calcium sulfonate with high base number according to the mode of production not It is same to be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate.Calcium mahogany sulfonate is to use oleum or SO₃Sulfonation mineral lubricating oil produces Accessory substance mahogany acid during white oil, through with Ca (OH)₂React, the contour alkalization technology that is carbonated and obtain；Calcium alkylbenzenesulfonate is to use Oleum or SO₃The alkylbenzene of sulfonation synthesis, the alkyl benzene sulphonate of generation pass through and Ca (OH)₂React, be carbonated contour alkalization skill Art and obtain.

Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusivity, can To be used as the detersive of lubricating oil, the additive of IC engine lubricating oil is widely used in, the development of its technology mainly makes its high-alkali Change, calcium carbonate is exactly turned into a kind of colloidal dispersion system with the naphthenic acid calcium with surface-active to be distributed in flux oil.It is high Base number calcium naphthenate mostly be the acidic components extracted in the distillate obtained from crude distillation, through with Ca (OH)₂Reaction, carbonating Contour alkalization technology and obtain, about prepare Patents have CN1465560 etc..

Using calcium sulfonate with high base number be raw material produce lubricating grease, because its have excellent high temperature performance, mechanical stability, Colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, domestic and international profit is caused The extensive concern of consistent lubricant industry, however, although high base number composite calcium sulfonate base grease has very excellent combination property, but 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, with requirement more and more higher of the 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； 0.5-30 weight % polyurea compound；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, wherein, the polyurea compound is eight polyurea compounds.The performance of the lubricating grease and High base number composite calcium sulfonate base grease is similar, 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 eight Polyurea grease, on the basis of lubricating grease weight, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-aphthenic acids Calcium；The calcium salt of 1-20 weight % higher fatty acids；The calcium salt of 1-15 weight % aromatic acid；0.5-30 weight % polyurea compound； 10-80 weight % base oil；The optionally calcium of the small molecule inorganic acid also including 1-15 weight % and/or lower fatty acid Salt, wherein, the polyurea compound is eight polyurea compounds.

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；1-20 weight % eight polyureas Compound；20-70 weight % base oil；Optionally also include 2-10 weight % small molecule inorganic acid and/or lower fatty acid Calcium salt.

Second aspect, the invention provides the system of complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease as described above Preparation Method, this method include：Non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, eight are gathered Carbamide compound, part basis oil and the small molecule inorganic acid of selectivity and/or the calcium salt of lower fatty acid are well mixed, 180-230 DEG C of constant temperature refining, adds surplus base oil, adds necessary additive, obtain finished product.

The third aspect, the invention provides a kind of preparation method of complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, This method includes：

（1）By newton body sulfoacid calcium, newton body calcium naphthenate and base oil Hybrid Heating, transforming agent is added, thing is treated in heating Expect retrogradation；

（2）In step（1）Lime or calcium hydroxide are added in products therefrom, adds higher fatty acids, aromatic acid and selection Property small molecule inorganic acid and/or lower fatty acid reacted, after reaction heat up dehydration；

（3）In step（2）Base oil and diisocyanate are added in gained mixture, then sequentially adds diamines, diamines Reacted with monoamine；

（4）By step（3）Gained mixture is warming up to 180-230 DEG C of constant temperature refining, adds base oil, adds necessary add Add agent, obtain finished product.

Fourth aspect, the invention provides complex calcium sulfonate-Calcium naphthenate base eight as made from method as described above to gather Urea grease.

Complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease of the present invention, not only moisten with the polyureas of Composite calcium-sulfonate-batetrapolyurea eight Consistent lubricant is the same, has excellent anticorrosive property, colloid stability and heat-resisting quantity, but also have and be better than Composite calcium-sulfonate-batetrapolyurea eight The performance such as mechanical stability, water-resistance and the adhesiveness of polyurea grease, resistance to saltfog, extreme pressure anti-wear, has longer profit The sliding life-span.The preparation of greases technique of the present invention 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 specific embodiment part.

Brief description of the drawings

Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 2.

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The invention provides a kind of complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, this lubricating grease employs stone Oily sulfoacid calcium and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, simultaneously containing compound Calcium thickening agent, isocyanates and eight polyurea compounds caused by amine reaction.

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 octa-polyurea lubricating grease, with lubricating grease weight On the basis of, including following components：10-70 weight % non-newtonian fluid sulfoacid calcium-calcium naphthenate；1-20 weight % higher fatty acids Calcium salt；The calcium salt of 1-15 weight % aromatic acid；0.5-30 weight % polyurea compound；10-80 weight % base oil；Selection Property also including 1-15 weight % small molecule inorganic acid and/or lower fatty acid calcium salt, wherein, the polyurea compound is Eight polyurea compounds.

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 of the invention-calcium naphthenate base grease should Component, the component can not also be included.

Non-newtonian fluid sulfoacid calcium-the calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1There is crystal form calcium carbonate spy in place Levy absworption peak, preferably total base number 250mgKOH/g-450mgKOH/g, 300mgKOH/g-400mgKOH/g.The non newtonian Body sulfoacid calcium-calcium naphthenate is to convert to obtain by transforming agent by newton body sulfoacid calcium and newton body calcium naphthenate.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, aromatic acid is the carboxylic acid that at least 1 carboxyl is joined directly together with aromatic ring, and 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 are 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, eight polyurea compound preferably has following structure：

Wherein, R¹Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10- 18, aryl can be the phenyl of phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen substitution.

Wherein, R²Can be alkylidene or arlydene, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be with It is phenylene or biphenylene.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R³More preferably In It is at least one.

Above-mentioned eight polyurea compound can use the thinkable various methods of those skilled in the art institute to obtain, such as can be with It is prepared according to the CN103060068A methods recorded.

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, account for 0.01-5%, the preferably 0.1-2.5% of lubricating grease gross weight, can be diphenylamines, At least one of phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease The 0.5-12% of gross weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, polytetrafluoroethyl-ne Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid At least one of calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil At least one of barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.

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 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, eight polyurea compounds, base oil and the additive of sub- inorganic acid and/or lower fatty acid are as described above, no longer superfluous herein State.

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.

, can be by newton body sulfoacid calcium and newton body calcium naphthenate by turning for non-newtonian fluid sulfoacid calcium-calcium naphthenate Agent converts to obtain, for example, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, adds Required transforming agent is reacted, and after all transforming agents add, in 80-90 DEG C of constant temperature 60-90 minute, then heats to 100- 120 DEG C of dehydrations.

The third aspect, the invention provides a kind of preparation method of complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, Including：

Step（1）In, by newton body sulfoacid calcium, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add Required transforming agent is reacted, after all transforming agents add, in 80-100 DEG C of constant temperature 60-90 minute.

In the present invention, for the weight ratio of newton body sulfoacid calcium and newton body calcium naphthenate without particular/special requirement, preferably 1： 0.25-4.Newton body sulfoacid calcium and the gross weight of newton body calcium naphthenate and the weight ratio of part basis oil are preferably 1：0.1-3.

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 Choosing selected from C1-C5 fatty alcohol, C1-C5 aliphatic acid, C1-C5 aliphatic ketone, C1-C5 fatty aldehyde, C1-C5 fatty amine, C1-C5 ether, boric acid, C1-C10 alkyl phosphonic acid, C2-C16 di alkyl phosphonic acid, C6-C20 arylphosphonic acid, C12-C24 At least one of diaryl phosphonic acids, C7-C20 aromatic alcohol, C7-C20 aromatic amine, C8-C20 alkyl benzene sulphonates and water；More At least one further preferably in DBSA, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water Kind.The addition of transforming agent is preferably the 2-30% of newton body sulfoacid calcium and newton body calcium naphthenate gross weight, more preferably newton The 6-22% of body sulfoacid calcium and newton body calcium naphthenate gross weight.

In the present invention, fatty alcohol includes the fatty alcohol of straight chain, side chain and ring-type, aliphatic acid, aliphatic ketone, fatty aldehyde, fat Amine is similarly.

Step（2）In, at 85-100 DEG C, the suspension of lime or calcium hydroxide is added, adds higher fatty acids, stirring 5-20 minutes, aromatic acid and the small molecule inorganic acid and/or lower fatty acid of selectivity are added, 5-20 minutes is stirred, is warming up to 100-120 DEG C, 30-60 minutes are preferably kept to realize dehydration.Wherein, higher fatty acids and aromatic acid, small molecule inorganic acid and/or The addition sequence of lower fatty acid can exchange.

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, small molecule inorganic acid and/or lower fatty acid can not also be included, 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 are as it was previously stated, no longer superfluous 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 excessive 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 refers to lime or calcium hydroxide formed in water it is suspended Liquid, the solid content of suspension is preferably 10-60 weight %.

Step（3）In, in step（2）Base oil and diisocyanate are added in gained mixture, then sequentially adds two Amine, diamines and monoamine are reacted, and are in step（2）Eight polyurea compounds are prepared in gained mixture.

The method of eight polyurea compounds is prepared without particular/special requirement, various methods commonly used in the art can be used.For example, , can be in step in the present invention（2）Base oil and diisocyanate are added in gained mixture, adds diamines, 2-8 points of stirring Clock, adds diamines again, stirs 2-8 minutes, adds monoamine, stirs 2-8 minutes, diisocyanate, diamines added by each time, The mol ratio of diamines and monoamine is 4:2:1:2.

Step of the present invention（3）In, the diamines added twice can be the same or different, in order to easy to operate, preferably two The diamines of secondary addition is identical.

The diisocyanate structure is OCN-R³- NCO, R³Can be that carbon number is 6-30, preferably 6-20 arlydene, Alkylidene or cycloalkylidene, preferably Deng. Such as the diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), 1,6- is sub- Hexyl diisocyanate (HDI), dicyclohexylmethyl diisocyanate（HMDI）With an xylylene diisocyanate（XDI）Deng At least one of.

The monoamine can be fatty amine, aliphatic cyclic amine or arylamine, structural formula R¹-NH₂、R^1’-NH₂, R therein¹、R^1’Can To be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, aryl can be phenyl or Substituted phenyl, preferably phenyl or C1-C3 alkyl or the phenyl of halogen substitution.Preferable monoamine can be selected from aniline, m-chloro Aniline, parachloroanilinum, the arylamine of para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, octadecylamine fatty amine.

The diamines can be fatty amine or arylamine, structural formula NH₂-R²-NH₂, R therein²Can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferable diamines can Be selected from p-phenylenediamine, o-phenylenediamine, 4,4 '-benzidine aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6- oneself The straight-chain fatty amine of diamines.

Step（4）In, first in 100-120 DEG C of constant temperature 10-20 minute, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minute； Base oil is added, treats that temperature is cooled to 100-120 DEG C, adds necessary additive, is stirred, circulating filtration, homogenizing, degassing.

In the present invention, step（1）In base oil used total amount and step（3）In base oil used total amount and step （4）In base oil used total amount weight ratio preferably 1：0.1-5：0.1-5.

Fourth aspect, present invention also offers composite sulfoacid made from the preparation method provided as third aspect present invention Calcium-calcium naphthenate base octa-polyurea lubricating grease.

With the preparation method that is provided as second aspect made from complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease phase Than complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease made from the preparation method that the third aspect provides has more preferable machine Tool stability, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, and there is longer lubricating life.

Embodiment

The present invention is further illustrated for following embodiment, but and is not so limited the present invention.

In the following Examples and Comparative Examples：

Non-newtonian fluid sulfoacid calcium-calcium naphthenate %=（Overbased or calcium sulfonate with high base number raw material weight+overbased or high Base number calcium naphthenate raw material weight+transforming agent gross weight）/ lubricating grease gross weight × 100%.Transforming agent is included in non-newtonian fluid sulphur In the content of sour calcium-calcium naphthenate.

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 octa-polyurea 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）；Methanol（1kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearates Acid（2kg）；Terephthalic acid (TPA)（3.5kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN Lubricating base oil（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 be separately added into 24kg total Naphthenate with superhigh base number calcium that overbased sulfoacid calcium that base number is 400mgKOH/g, 6kg total base numbers are 400mgKOH/g and 30kg HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 2.8kg aphthenic acids, temperature Control is stirred 10 minutes at 50 DEG C or so；1kg methanol is added, is stirred 10 minutes；Add the acetic acid that 2.8kg concentration is 20 weight % The aqueous solution, stir 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, addition solid content is 20 weights % calcium hydroxide suspension 9kg is measured, is stirred 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；Add 3.5kg pairs Phthalic acid, stir 10 minutes, 120 DEG C are warming up under stirring, kept for 30 minutes, dehydration；Add 2kg HVI500SN lubrication bases Plinth oil and 1.28kg MDI, quick stirring 4 minutes, quick stirring is lower to add 0.15kg ethylenediamines, stirs 4 minutes, quick stirring Under add 0.08kg ethylenediamines again, stir 4 minutes, add 0.69kg octadecylamines, stir 4 minutes, successively added MDI, second The mol ratio of diamines, ethylenediamine and octadecylamine is 4:2:1:2,120 DEG C of constant temperature 20 minutes, is finally warming up to 200 DEG C of constant temperature 10 and divides Clock.Then, 160 DEG C are cooled to, adds remaining 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 obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 52.8；The weight % of 12- hydroxy stearic acids calcium 2.4；To benzene The weight % of dioctyl phthalate calcium 4.8.

Embodiment 2

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in be separately added into 24kg total Naphthenate with superhigh base number calcium that overbased sulfoacid calcium that base number is 400mgKOH/g, 6kg total base numbers are 400mgKOH/g and 30kg HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 2.8kg aphthenic acids, temperature Control is stirred 10 minutes at 50 DEG C or so；1kg methanol is added, is stirred 10 minutes；Add the acetic acid that 2.8kg concentration is 20 weight % The aqueous solution, stir 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation；100 DEG C are warming up to, addition solid content is 20 weights % calcium hydroxide suspension 9kg is measured, is stirred 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；Add 3.5kg pairs Phthalic acid, stir 10 minutes, 120 DEG C are warming up under stirring, kept for 30 minutes, dehydration.

Another volume be 30L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 2kg HVI500SN lubricating base oils and 1.28kg MDI, quick stirring 4 minutes, quick stirring is lower to add 0.15kg ethylenediamines, stirring 4 Minute, 0.08kg ethylenediamines are added again under quick stirring, are stirred 4 minutes, addition 0.69kg octadecylamines, stirring 4 minutes, successively Added MDI, ethylenediamine, the mol ratio of ethylenediamine and octadecylamine are 4:2:1:2,120 DEG C of constant temperature 20 minutes, obtains eight polyureas.

The polyureas of gained eight is all squeezed into a upper kettle, stirred, is finally warming up to 200 DEG C of constant temperature 10 minutes.So Afterwards, 160 DEG C are cooled to, adds remaining HVI500SN lubricating base oils；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, Degassing obtains finished product.Assay is shown in Table 1.

A small amount of eight polyureas is prepared again by the same method of above-mentioned steps 2, uses petroleum ether（60-90 DEG C of boiling point）Washing, is filtered To precipitation, gained precipitation produces eight polyurea compounds after drying.

The eight polyureas molecular structural formulas contained in component are：

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）；N-butanol （3.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；Stearic acid（1.9kg）；Phthalic acid（3.5kg）；Lauryl amine （0.52kg）；Ethylenediamine（0.26kg）；MDI（1.42kg）；HVI500SN lubricating base oils（100 DEG C of kinematic viscosity are 11mm²/ S, 27kg）.

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in be separately added into 24kg total Naphthenate with superhigh base number calcium that overbased sulfoacid calcium that base number is 400mgKOH/g, 6kg total base numbers are 320mgKOH/g and 20kg HVI150BS lubricating base oils, stirring, heat to 80 DEG C, constant temperature 10 minutes；Add 3.8kg n-butanols, temperature Control is stirred 10 minutes at 80 DEG C or so；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, is stirred 10 minutes；Heating To 90 DEG C, constant temperature 60 minutes, material retrogradation；The calcium hydroxide suspension 9kg that solid content is 20 weight % is added, is stirred 10 minutes； 1.9kg stearic acid is added, is stirred 10 minutes；3.5kg phthalic acids are added, stirs 10 minutes, 100 DEG C is warming up under stirring, Kept for 60 minutes, dehydration；2kg HVI500SN lubricating base oils and 1.42kg MDI is added, quick stirring 8 minutes, is quickly stirred Lower addition 0.18kg ethylenediamines are mixed, are stirred 4 minutes, 0.08kg ethylenediamines is added again under quick stirring, stirs 4 minutes, add 0.52kg lauryl amines, stir 8 minutes, the mol ratio of added MDI, ethylenediamine, ethylenediamine and octadecylamine is 4 successively:2:1:2, 100 DEG C of constant temperature 10 minutes, is finally warming up to 230 DEG C of constant temperature 5 minutes.Then, remaining HVI500SN lubricating base oils are added；Treat Temperature is cooled to 120 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 52.9；The weight % of calcium stearate 2.3；Phthalic acid The weight % of calcium 4.8.

Embodiment 4

Raw material components：Calcium sulfonate with high base number（Total base number is 320mgKOH/g, 24kg）；Naphthenate with superhigh base number calcium（Total alkali It is worth for 400mgKOH/g, 6kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 25kg）；Dodecyl Benzene sulfonic acid（2.8kg）；Methanol（1kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Isophthalic Dioctyl phthalate（3.5kg）；Octadecylamine（0.84kg）；Ethylenediamine（0.28kg）；TDI（1.08kg）；HVI500SN lubricating base oils （100 DEG C of kinematic viscosity are 11mm²/ s, 22kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, sulfonic acid Calcium uses the calcium sulfonate with high base number that total base number is 320mgKOH/g；It is different using DBSA, M-phthalic acid, toluene two Cyanate（TDI）Respectively instead of aphthenic acids, terephthalic acid (TPA), MDI；The dosage of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 52.8；The weight % of 12- hydroxy stearic acids calcium 2.4；Isophthalic The weight % of dioctyl phthalate calcium 4.8.

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, 1.8kg）；Boric acid（1kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids （2kg）；2- methyl isophthalic acids, 4- phthalic acids（3.8kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）； 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 octa-polyurea lubricating grease, unlike, sulfonic acid Calcium uses the high base number that total base number is 320mgKOH/g using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate Calcium naphthenate；Methanol is replaced with boric acid；With 2- methyl isophthalic acids, 4- phthalic acids replace terephthalic acid (TPA)；The dosage of each composition is as above. Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 52.1；The weight % of eight polyureas 3.5；The weight % of lubricating base oil 34.4；The weight % of 12- hydroxy stearic acids calcium 3.3；2- first The weight % of base -1,4- phthalic acids calcium 6.7.

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）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 25kg）；Aphthenic acids （Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；4, 4'- biphenyl dicarboxylic acids（5.1kg）；Octadecylamine（2.07kg）；Ethylenediamine（0.69kg）；MDI（3.84kg）；HVI500SN lubricates base Plinth oil（100 DEG C of kinematic viscosity are 11mm²/ s, 18.6kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, use 4,4'- biphenyl dicarboxylic acids replace terephthalic acid (TPA)；Transforming agent is only aphthenic acids and acetic acid, saves the step of adding methanol；Respectively into The dosage divided is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 36.4；The weight % of eight polyureas 7.2；The weight % of lubricating base oil 47.6；The weight % of 12- hydroxy stearic acids calcium 2.3；4, The weight % of 4'- biphenyl dicarboxylic acids calcium 6.5.

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）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO40（100 DEG C of kinematic viscosity are 41mm²/ s, 30kg）；Cycloalkanes Acid（Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）； Terephthalic acid (TPA)（3.5kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；Full synthetic oil poly alpha olefin Oily PAO10（100 DEG C of kinematic viscosity are 11mm²/ s, 9kg）；Two thio Acidic phosphates zinc（2kg）；Dialkyl dithio amino Formic acid molybdenum（1kg）；Tungsten disulfide（2kg）；Two tungsten selenides（2kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, cycloalkanes Sour calcium uses the overbased calcium alkyl-salicylate that total base number is 320mgKOH/g；Transforming agent is only aphthenic acids and acetic acid, saves addition first The step of alcohol；HVI150BS and HVI500SN is replaced respectively using full synthetic oil poly ＆ Alpha ,-olefin oil PAO40 and PAO10；And treat Temperature is cooled to 110 DEG C, adds 2kg two thio Acidic phosphates zinc, stirs 10 minutes, adds 1kg dialkyl dithio Carbamic acid molybdenum, stir 10 minutes, add 2kg tungsten disulfide, stir 10 minutes, add 2kg two tungsten selenides, stir 10 points Clock, 0.2kg pair is added, right '-di-iso-octyldiphenylamine, is stirred 10 minutes, then circulating filtration, homogenizing, degassing obtains into Product；The dosage of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.8；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 44.2；The weight % of 12- hydroxy stearic acids calcium 2.4；To benzene The weight % of dioctyl phthalate calcium 4.9；The two thio weight % of Acidic phosphates zinc 2.3；The weight % of molybdenum dialkyldithiocarbamacompositions 1.1；Two The weight % of tungsten sulfide 2.3；The weight % of two tungsten selenide 2.3；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

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, 15kg）；Aphthenic acids（Always Acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；To benzene Dioctyl phthalate（3.5kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN lubricating base oils （100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, sulfonic acid Calcium uses the calcium sulfonate with high base number that total base number is 320mgKOH/g；Transforming agent is only aphthenic acids and acetic acid, saves and adds methanol Step；The dosage of each composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.1；The weight % of eight polyureas 2.4；The weight % of lubricating base oil 53.3；The weight % of 12- hydroxy stearic acids calcium 2.4；To benzene The weight % of dioctyl phthalate calcium 4.8.

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, 20kg）；Aphthenic acids（Total acid It is worth for 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（5.2kg）；12- hydroxy stearic acids（2kg）；Boric acid （2.32kg）；Terephthalic acid (TPA)（7.6kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN Lubricating base oil（100 DEG C of kinematic viscosity are 11mm²/ s, 28kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, sulfonic acid Calcium uses the high base number that total base number is 320mgKOH/g using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate Calcium naphthenate；Transforming agent is only aphthenic acids and acetic acid, saves the step of adding methanol；Add 12- hydroxy stearic acids and stir 10 points Zhong Hou, boric acid is added, stirred 10 minutes, then add terephthalic acid (TPA), stirred 10 minutes；And treat that temperature is cooled to 110 DEG C, 0.2kg pair is added, right '-di-iso-octyldiphenylamine, is stirred 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；Respectively The dosage of composition is as above.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 34.2；The weight % of eight polyureas 2.2；The weight % of lubricating base oil 49.2；The weight % of 12- hydroxy stearic acids calcium 2.2；Boric acid The weight % of calcium 2.4；The weight % of terephthalic acid (TPA) calcium 9.6；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

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, 15kg）；Aphthenic acids （Total acid number is 180mgKOH/g, 2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（3kg）；12- hydroxy stearic acids（2kg）；To benzene Dioctyl phthalate（3.5kg）；Acetic acid（2kg）；Octadecylamine（0.69kg）；Ethylenediamine（0.23kg）；MDI（1.28kg）；HVI500SN moistens Sliding base oil（100 DEG C of kinematic viscosity are 11mm²/ s, 33kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, conversion Agent is only aphthenic acids and acetic acid, saves the step of adding methanol；And after adding terephthalic acid (TPA) stirring 10 minutes, add second Acid, stir 10 minutes, be then warming up to 120 DEG C under agitation, kept for 30 minutes, dehydration；The dosage of each composition is as above.Examine knot Fruit is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 36.0；The weight % of eight polyureas 2.4；The weight % of lubricating base oil 51.8；The weight % of 12- hydroxy stearic acids calcium 2.3；To benzene The weight % of dioctyl phthalate calcium 4.7；The weight % of calcium acetate 2.8.

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）；Methanol（1kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids （2kg）；Terephthalic acid (TPA)（3.5kg）；Para-totuidine（0.34kg）；Ethylenediamine（0.28kg）；MDI（1.58kg）；HVI500SN Lubricating base oil（100 DEG C of kinematic viscosity are 11mm²/ s, 17kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, sulfonic acid Calcium uses the high base number that total base number is 320mgKOH/g using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate Calcium naphthenate；Octadecylamine is replaced using para-totuidine；And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, it is right '-two different Octyl diphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The dosage of each composition is as above.Examine knot Fruit is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.4；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 52.7；The weight % of 12- hydroxy stearic acids calcium 2.4；To benzene The weight % of dioctyl phthalate calcium 4.8；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 12

Raw material components：Calcium sulfonate with high base number（Total base number is 360mgKOH/g, 15kg）；Overbased calcium alkyl-salicylate（Total base number For 360mgKOH/g, 15kg）；HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, 15kg）；Detergent alkylate Sulfonic acid（2.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；12- hydroxy stearic acids（2kg）；Terephthalic acid (TPA) （3.5kg）；Octadecylamine（0.63kg）；1,6- hexamethylene diamines（0.4kg）；MDI（1.17kg）；HVI500SN lubricating base oils（100℃ Kinematic viscosity is 11mm²/ s, 33kg）；It is right, right '-di-iso-octyldiphenylamine（0.2kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, sulfonic acid Calcium uses the high base number that total base number is 360mgKOH/g using the calcium sulfonate with high base number that total base number is 360mgKOH/g, calcium naphthenate Calcium naphthenate；Aphthenic acids is replaced using DBSA；Transforming agent is only DBSA and acetic acid, saves addition The step of methanol；Ethylenediamine is replaced using 1,6- hexamethylene diamines；And treat that temperature is cooled to 110 DEG C, add 0.2kg pair, right '- Di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassing obtains finished product；The dosage of each composition is as above.Inspection Test and the results are shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.0；The weight % of eight polyureas 2.4；The weight % of lubricating base oil 53.2；The weight % of 12- hydroxy stearic acids calcium 2.4；To benzene The weight % of dioctyl phthalate calcium 4.8；It is right, right ' weight % of-di-iso-octyldiphenylamine 0.2.

Embodiment 13

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in be separately added into 24kg total Naphthenate with superhigh base number calcium that overbased sulfoacid calcium that base number is 400mgKOH/g, 6kg total base numbers are 400mgKOH/g and 30kg HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 2.8kg aphthenic acids, temperature Control is stirred 10 minutes at 50 DEG C or so；1kg methanol is added, is stirred 10 minutes；Add the acetic acid that 2.8kg concentration is 20 weight % The aqueous solution, stir 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.

Another volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 5kg HVI500SN lubricating base oils, 100 DEG C are warming up to, add the calcium hydroxide suspension 9kg that solid content is 20 weight %, stirring 10 Minute；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；3.5kg terephthalic acid (TPA)s are added, stirs 10 minutes, obtains 12- hydroxyls Base calcium stearate and terephthalic acid (TPA) calcium.

The 3rd volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 2kg HVI500SN lubricating base oils and 1.28kg MDI, quick stirring 4 minutes, quick stirring is lower to add 0.15kg ethylenediamines, stirring 4 Minute, 0.08kg ethylenediamines are added again under quick stirring, are stirred 4 minutes, addition 0.69kg octadecylamines, stirring 4 minutes, successively Added MDI, ethylenediamine, the mol ratio of ethylenediamine and octadecylamine are 4:2:1:2,120 DEG C of constant temperature 20 minutes, obtains eight polyureas.

The 12- hydroxy stearic acids calcium of gained and terephthalic acid (TPA) calcium are all squeezed into first kettle, stirred, is stirred Under be warming up to 120 DEG C, kept for 30 minutes, dehydration, eight polyureas obtained by the 3rd reactor all squeezed into the kettle, stirring is equal It is even, finally it is warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, adds remaining HVI500SN lubricating base oils；Treat Temperature is cooled to 110 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

Embodiment 14

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, by ring Alkanoic acid replaces with phenol, and acetic acid is replaced with into butyric acid, and methanol is replaced with into acetone.Assay is shown in Table 1.

Embodiment 15

Method according to embodiment 1 prepares complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, unlike, by ring Alkanoic acid replaces with ketone, and aqueous acetic acid is replaced with into ether, and methanol is replaced with into ethamine.Assay is shown in Table 1.

Comparative example 1

Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number The overbased sulfoacid calcium that calcium is 400mgKOH/g with total base number replaces, and obtained each performance data of lubricating grease finished product is shown in Table 1.

In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：The weight of non-newtonian fluid sulfoacid calcium 37.5 Measure %；The weight % of eight polyureas 2.5；The weight % of lubricating base oil 52.8；The weight % of 12- hydroxy stearic acids calcium 2.4；Terephthalic acid (TPA) calcium 4.8 weight %.

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；The bearing lubrication life-span：ASTM D3336.

Table 1（It is continuous）Each lubricating grease properties of sample data

By embodiment 1 as can be seen that complex calcium sulfonate-Calcium naphthenate base eight of the present invention is gathered compared with comparative example 1 The difference of the extension work cone penetration of urea grease and work cone penetration is less than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, water leaching stream Vector is much smaller than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, and salt spray test is better than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, water resistant Spraying value is less than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, and tetra-ball machine test value is more than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, The bearing lubrication life-span is much larger than Composite calcium-sulfonate-batetrapolyurea octa-polyurea lubricating grease, illustrates complex calcium sulfonate-Calcium naphthenate base of the present invention Mechanical stability, water-resistance and the adhesiveness of octa-polyurea lubricating grease, resistance to saltfog, extreme pressure anti-wear, lubricating life are superior to again Close calcium sulfonate octaurea lubricating grease, and the complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease and composite sulfoacid of the present invention Calcium base octa-polyurea lubricating grease equally has the performances such as excellent anticorrosive property, colloid stability and heat-resisting quantity.

By embodiment 1 respectively compared with embodiment 2 and embodiment 13 as can be seen that the composite sulfoacid in situ prepared Calcium-calcium naphthenate base octa-polyurea lubricating grease, there is more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, extreme pressure Wear resistence, and there is longer lubricating life；Embodiment 1 can be seen compared with embodiment 14 and embodiment 15 respectively Go out, transforming agent in DBSA, aphthenic acids, methanol, isopropanol, butanol, boric acid, acetic acid and water at least one Kind, complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease of preparation, there is more preferable mechanical stability, water-resistance and adhesion Property, colloid stability, extreme pressure anti-wear, and there is longer lubricating life.

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.Meanwhile in 3300cm^-1-3323cm^-1The peak at place is the stretching vibration absworption peak of-NH- in eight polyureas molecules.

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

A kind of 1. complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease, it is characterised in that on the basis of lubricating grease weight, bag Include 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；0.5-30 weight % polyurea compound；10-80 weight % base oil；Optionally The calcium salt of small molecule inorganic acid and/or lower fatty acid also including 1-15 weight %, wherein, the polyurea compound is eight poly- Carbamide compound, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1There is crystal form calcium carbonate in place 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；1-20 weight % eight polyurea compounds；20-70 weight % base oil；Optionally also including 2-10 weight % The calcium salt of small molecule inorganic acid and/or lower fatty acid.
3. lubricating grease according to claim 1 or 2, wherein, the non-newtonian fluid sulfoacid calcium-calcium naphthenate is by newton body Sulfoacid calcium and newton body calcium naphthenate convert what is obtained, and its 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 alkyl, alkenyl, alkynyl, aryl, halo at least one of alkyl or aryl, 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, eight polyurea compound has following structure：

Wherein, R¹It is alkyl, cycloalkyl or aryl, R²It is alkylidene or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.
9. lubricating grease according to claim 8, wherein, R¹Phenyl or substituted phenyl, or alkyl that carbon number is 8-24 or Cycloalkyl；R²It is the alkylidene of phenylene or biphenylene or carbon number for 2-12；R³It is arlydene, the alkylidene that carbon number is 6-30 Or cycloalkylidene.
10. lubricating grease according to claim 9, wherein, R¹It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or carbon Count the alkyl or cycloalkyl for 10-18, R²It is phenylene or biphenylene, or carbon number is 2-8 alkylidene；R³It is selected from With-(CH₂)₆At least one of-.
11. lubricating grease according to claim 1 or 2, wherein, the molecular weight of small molecule inorganic acid or lower fatty acid is less than Equal to 150.
12. lubricating grease according to claim 11, wherein, the small molecule inorganic acid is in boric acid, phosphoric acid, sulfuric acid At least one, the lower fatty acid are selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid.
13. the preparation side of complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease in claim 1-12 described in any one Method, it is characterised in that this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, aromatic acid calcium Salt, eight polyurea compounds, part basis oil and the small molecule inorganic acid of selectivity and/or the calcium salt of lower fatty acid mix Uniformly, refined in 180-230 DEG C of constant temperature, add surplus base oil, add necessary additive, obtain finished product.
14. the preparation side of complex calcium sulfonate-calcium naphthenate base octa-polyurea lubricating grease in claim 1-12 described in any one Method, it is characterised in that this method includes：

(1) by newton body sulfoacid calcium, newton body calcium naphthenate and base oil Hybrid Heating, transforming agent is added, heating treats that material becomes It is thick；

(2) lime or calcium hydroxide are added in step (1) products therefrom, adds higher fatty acids, aromatic acid and selectivity Small molecule inorganic acid and/or lower fatty acid are reacted, and heat up dehydration after reaction；

(3) base oil and diisocyanate are added in mixture obtained by step (2), then sequentially adds diamines, diamines and list Amine is reacted；

(4) mixture obtained by step (3) is warming up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary addition Agent, obtain finished product.
15. preparation method according to claim 14, wherein, in step (1), by newton body sulfoacid calcium, newton body cycloalkanes Sour calcium, base oil Hybrid Heating add required transforming agent and reacted, after all transforming agents add, in 80- to 50-80 DEG C 100 DEG C of constant temperature 60-90 minutes.
16. preparation method according to claim 14, wherein, in step (2), at 85-100 DEG C, add lime or hydrogen The suspension of calcium oxide, higher fatty acids is added, stir 5-20 minutes, add aromatic acid and the small molecule inorganic acid of selectivity And/or lower fatty acid, 5-20 minutes are stirred, are warming up to 100-120 DEG C of dehydration.
17. preparation method according to claim 14, wherein, in step (3), added in mixture obtained by step (2) Base oil and diisocyanate, diamines is added, stirs 2-8 minutes, add diamines again, stirred 2-8 minutes, add monoamine, Stir 2-8 minutes, the mol ratio of diisocyanate, diamines, diamines and monoamine added by each time is 4:2:1:2.
18. preparation method according to claim 14, wherein, in step (4), first in 100-120 DEG C of 10-20 points of constant temperature Clock, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minute；Base oil is added, treats that temperature is cooled to 100-120 DEG C, is added necessary Additive, stirring, circulating filtration, homogenizing, degassing.
19. preparation method according to claim 14, 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.
20. preparation method according to claim 14, 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%.
21. preparation method according to claim 20, 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.
22. preparation method according to claim 14, wherein, the structural formula of the monoamine is R¹-NH₂, wherein, R¹It is benzene The phenyl of base, C1-C3 alkyl or halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.
23. preparation method according to claim 22, wherein, the monoamine is selected from aniline, m-chloroaniline, parachloroanilinum And/or the arylamine of para-totuidine, and/or the fatty amine selected from lauryl amine, tetradecy lamine, cetylamine and/or octadecylamine.
24. preparation method according to claim 14, wherein, the structural formula of the diamines is NH₂-R²-NH₂, wherein, R²It is Carbon number is 2-8 alkylidene, or phenylene or biphenylene.
25. preparation method according to claim 24, wherein, the diamines is to be selected from p-phenylenediamine, o-phenylenediamine, 4, The aromatic amine of 4 '-benzidine and/or selected from ethylenediamine, propane diamine, 1,6- hexamethylene diamines straight-chain fatty amine.
26. preparation method according to claim 14, wherein, the structure of the diisocyanate is OCN-R³- NCO, R³It is Carbon number is 6-30 arlydene, alkylidene or cycloalkylidene.
27. preparation method according to claim 26, wherein, the diisocyanate is selected from toluene di-isocyanate(TDI), first Base diphenyl diisocyanate, 1,6- hexylidene diisocyanates, dicyclohexylmethyl diisocyanate and an xyxylene two At least one of isocyanates.