CN104449960B

CN104449960B - A kind of complex calcium sulfonate Calcium naphthenate base polyurea grease and preparation method thereof

Info

Publication number: CN104449960B
Application number: CN201310419090.3A
Authority: CN
Inventors: 何懿峰; 孙洪伟; 刘中其; 段庆华; 张建荣; 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: 2017-11-03
Anticipated expiration: 2033-09-13
Also published as: CN104449960A

Abstract

The invention discloses a kind of complex calcium sulfonate Calcium naphthenate base polyurea 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；Small molecule inorganic acid and/or the calcium salt of lower fatty acid optionally also including 1 15 weight %.Also disclose the preparation method of complex calcium sulfonate Calcium naphthenate base polyurea grease and its complex calcium sulfonate Calcium naphthenate base polyurea grease of preparation.The complex calcium sulfonate Calcium naphthenate base polyurea grease of the present invention, with excellent anticorrosive property and heat-resisting quantity, the performances such as mechanical stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear with better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, with longer lubricating life.

Description

A kind of complex calcium sulfonate-Calcium naphthenate base polyurea 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 polyurea grease and its system 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, high base number composite calcium sulfonate base grease has very excellent combination property, The high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, together When, the requirement more and more higher with people to environmental protection, in calcium sulfonate with high base number production process must through sulfonation process to ring The pollution in border is also increasingly subject to the concern of people.Find a kind of performance it is similar with high base number composite calcium sulfonate base grease but can Mitigating the lubricating grease of above mentioned problem turns into the big problem that people face at present.

The content of the invention

Similar with high base number composite calcium sulfonate base grease it is an object of the invention to provide a kind of performance, cost is low, prepares Simple and environmentally-friendly lubricating grease of technique and preparation method thereof.

The present inventor has found under study for action, on the basis of lubricating grease weight, including following components：10-70 weight % Non-newtonian fluid sulfoacid calcium-calcium naphthenate；The calcium salt of 1-20 weight % higher fatty acids；The calcium salt of 1-15 weight % aromatic acid； 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.The performance of the lubricating grease is similar with high base number composite calcium sulfonate base grease, and cost Low, preparation technology is simple and environmentally-friendly.

Therefore, to achieve these goals, on the one hand, poly- the invention provides a kind of complex calcium sulfonate-Calcium naphthenate base Urea 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；Small molecule inorganic acid and/or the calcium salt of lower fatty acid optionally also including 1-15 weight %.

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 % polyureas chemical combination Thing；20-70 weight % base oil；The optionally small molecule inorganic acid and/or lower fatty acid also including 2-10 weight % Calcium salt.

Second aspect, the invention provides the preparation of complex calcium sulfonate as described above-Calcium naphthenate base polyurea grease Method, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, polyureas The calcium salt of compound, the small molecule inorganic acid of part basis oil and selectivity and/or lower fatty acid is well mixed, in 180- 230 DEG C of constant temperature refinings, add surplus base oil, add necessary additive, obtain finished product.

The third aspect, should the invention provides a kind of preparation method of complex calcium sulfonate-Calcium naphthenate base polyurea grease 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, higher fatty acids, aromatic acid and selection is added Property small molecule inorganic acid and/or lower fatty acid reacted, after reaction heat up dehydration；

（3）In step（2）Base oil and monoamine are added in gained mixture, or is additionally added diamines, diisocyanate is added Reacted；

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

Fourth aspect, the invention provides the complex calcium sulfonate as made from method as described above-Calcium naphthenate base polyureas Lubricating grease.

Complex calcium sulfonate-Calcium naphthenate base polyurea grease of the present invention, not only with Composite calcium-sulfonate-batetrapolyurea polyurea grease Equally, with excellent anticorrosive property and heat-resisting quantity, but also the machinery with better than Composite calcium-sulfonate-batetrapolyurea polyurea grease The performance such as stability, water-resistance and adhesiveness, resistance to saltfog, colloid stability, extreme pressure anti-wear, with the longer lubrication longevity Life.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 embodiment part.

Brief description of the drawings

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

Embodiment

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

The invention provides a kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease, this lubricating grease employs oil Sulfoacid calcium and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, and composite calcium is contained simultaneously The polyurea compound that thickening agent, isocyanates and amine reaction are produced.

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 polyurea grease, using lubricating grease weight as Benchmark, 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；Selectivity The calcium salt of small molecule inorganic acid and/or lower fatty acid of the ground also including 1-15 weight %.

In the present invention, " optionally also including " refer to can include can not also include, i.e. small molecule inorganic acid and/ Or the calcium salt of lower fatty acid is optional component, can include in complex calcium sulfonate-calcium naphthenate base grease of the invention should Component, can not also include the component.

Non-newtonian fluid sulfoacid calcium-the calcium naphthenate is in infrared spectrum 873cm^-1-886cm^-1It is special that crystal form calcium carbonate occurs in place Absworption peak is levied, total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.The non newtonian Body sulfoacid calcium-calcium naphthenate is to be obtained by newton body sulfoacid calcium and newton body calcium naphthenate by transforming agent conversion.And newton body Contain unformed calcium carbonate in sulfoacid calcium, newton body calcium naphthenate, in infrared spectrum 860cm^-1-865cm^-1Place occurs unformed Calcium carbonate characteristic absorption peak.The newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；The newton body calcium naphthenate is oil ring Alkanoic acid calcium and/or synthesis calcium naphthenate, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g- 400mgKOH/g.The base number of non-newtonian fluid sulfoacid calcium-calcium naphthenate is the base number and newton body calcium naphthenate of newton body sulfoacid calcium Base number weight average value.

In the present invention, higher fatty acids is that carbon number is 8-20, preferably 10-16 straight chain fatty acid or hydroxy fatty acid, example Such as at least one of laurate, palmitic acid, stearic acid, 12- hydroxy stearic acids, eicosyl carboxylic acid, preferably 12- hydroxyls are hard Resin acid.

In the present invention, the carboxylic acid that aromatic acid is at least 1 carboxyl to be joined directly together with aromatic ring, aromatic acid can be substitution or not Substituted aromatic acid, its substituent can be in alkyl or aryl of alkyl, alkenyl, alkynyl, aryl, halo or perhalogeno etc. extremely Few one kind, the molecular weight of aromatic acid is less than or equal to 550.Aromatic acid is preferably binary aromatic acid, for example, unsubstituted or C1- can be selected from In the alkyl-substituted phthalic acids of C5, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid at least It is a kind of.Preferably phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, and methyl substituted biphenyl diformazan At least one of sour, multi-joint phthalic acid etc..

In the present invention, the polyurea compound can be polyurea compound commonly used in the art, for example may be used without particular/special requirement Think at least one of two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.Wherein dimerization Carbamide compound, four polyurea compounds, six polyurea compounds, the weight ratio of eight polyurea compounds can be arbitrary proportion.More preferably The polyurea compound is two polyurea compounds.

In the present invention, two polyurea compound preferably has following structure：

Wherein, R¹、R^1’It can be the same or different, can be alkyl, cycloalkyl or aryl, the carbon of alkyl or cycloalkyl Number can be 8-24, and preferably 10-18, aryl can be phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen The phenyl of element substitution.

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.

In the present invention, four 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 To be phenylene or biphenylene.

In the present invention, six polyurea compound preferably has following structure：

In the present invention, eight polyurea compound preferably has following structure：

Above-mentioned polyurea compound can be obtained using the thinkable various methods of those skilled in the art institute, for example can be by Prepared according to CN103060069A, CN103060070A, CN103060068A, CN103060067A method 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 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, " selective small molecule inorganic acid and/or the calcium salt of lower fatty acid " refers to prepare composite sulfoacid The raw material of calcium-calcium naphthenate base grease can include the calcium salt of small molecule inorganic acid and/or lower fatty acid, can not also wrap Include the calcium salt of small molecule inorganic acid and/or lower fatty acid, i.e. the calcium salt of small molecule inorganic acid and/or lower fatty acid is individual Optional raw material or component.

In the present invention, for non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, small point Calcium salt, polyurea compound, 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.

, can be by newton body sulfoacid calcium and newton body calcium naphthenate by turning for non-newtonian fluid sulfoacid calcium-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 Required transforming agent is reacted, after all transforming agents are added, and in 80-100 DEG C of constant temperature 60-90 minutes, then heats to 100- 120 DEG C of dehydrations.

The third aspect, the invention provides a kind of preparation method of complex calcium sulfonate-Calcium naphthenate base polyurea grease, bag Include：

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 was reacted, after all transforming agents are added, in 80-100 DEG C of constant temperature 60-90 minutes.

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

The newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total base number is 250mgKOH/g- 450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g；The newton body calcium naphthenate be petroleum naphthenic acid calcium and/or Calcium naphthenate is synthesized, its total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.

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

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

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

In the present invention, " selective small molecule inorganic acid and/or lower fatty acid " refers to step（2）In can include it is small Molecule inorganic acid and/or lower fatty acid, can not also include small molecule inorganic acid and/or lower fatty acid, i.e. small molecule without Machine acid and/or lower fatty acid are an optional raw materials.

In the present invention, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid as it was previously stated, no longer go to live in the household of one's in-laws on getting married herein State.

In the present invention, the H of higher fatty acids and the small molecule inorganic acid and/or lower fatty acid of aromatic acid and selectivity⁺ The amount of total material and the OH contained by the suspension of lime or calcium hydroxide^-The amount of total material is equal, OH^-Amount also can excess 1- 10%。

In the present invention, in terms of calcium hydroxide, the addition of the suspension of lime or calcium hydroxide is preferably newton body sulfonic acid The 1-15% of calcium and newton body calcium naphthenate gross weight；With H⁺Material gauge, higher fatty acids and aromatic acid and selectivity it is small The mol ratio of molecule inorganic acid and/or lower fatty acid is preferably 1：1-10.

In the present invention, the suspension of lime or calcium hydroxide is that to refer to that lime or calcium hydroxide are formed in water suspended Liquid, the solid content of suspension is preferably 10-60 weight %.

Step（3）In, in step（2）Base oil and monoamine are added in gained mixture, or is additionally added diamines, two are added different Cyanate is reacted, and is in step（2）Polyurea compound is prepared in gained mixture, mixing polyureas can be prepared, also may be used To prepare single two polyurea compound, four polyurea compounds, six polyurea compounds or eight polyurea compounds.

The method of mixing polyureas is prepared without particular/special requirement, can be using the thinkable various sides of those skilled in the art institute Method, it is for instance possible to use United States Patent (USP) US3243372 method.

The method of two 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 monoamine are added in gained mixture, is stirred 2-8 minutes, is added and be dissolved in base Diisocyanate in plinth oil, is stirred 2-8 minutes, and the mol ratio of diisocyanate and monoamine is 1:2.

The method of four 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, is stirred, diamines is added, stirs Mix 2-8 minutes, add monoamine, stir 2-8 minutes, the mol ratio of diisocyanate, diamines and monoamine is 2:1:2.

The method of six 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, is stirred, monoamine is added, stirs Mix 2-8 minutes, add diamines, stir 2-8 minute, add diisocyanate, stirring 2-8 minutes, successively two added isocyanides Acid esters, monoamine, the mol ratio of diamines and diisocyanate are 2:2:2:1.

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, is stirred, diamines is added, stirs Mix 2-8 minutes, add diamines again, stir 2-8 minute, add monoamine, stirring 2-8 minutes, successively added diisocyanate, The mol ratio of diamines, diamines and monoamine is 4:2:1:2.

The diisocyanate structure is OCN-R³- NCO, R³Can be that carbon number is 6-30, preferably 6-20 arlydene, Asia Alkyl or cycloalkylidene, be preferably Deng. For example, the diisocyanate can be toluene di-isocyanate(TDI) (TDI), and 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, and structural formula is 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.It is preferred that 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, and structural formula is NH₂-R²-NH₂, R therein²Can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, and preferably 2-8, arlydene can be phenylene or biphenylene.It is preferred that diamines can Be selected from p-phenylenediamine, o-phenylenediamine, the aromatic amine of 4,4 '-benzidine 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 minutes, finally it is warming up to 180-230 DEG C of constant temperature 5-20 minutes； Base oil is added, treats that temperature is cooled to 100-120 DEG C, necessary additive, stirring, circulating filtration, homogenizing, degassing is added.

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 polyurea grease.

Compared with the complex calcium sulfonate as made from the preparation method that second aspect is provided-Calcium naphthenate base polyurea grease, Complex calcium sulfonate-Calcium naphthenate base polyurea grease made from the preparation method that the third aspect is provided, which has preferably, to be had more preferably Mechanical stability, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, and with 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 height Base number calcium naphthenate raw material weight+transforming agent gross weight）/ lubricating grease gross weight × 100%.Transforming agent is included in non-newtonian fluid sulphur In the content of sour calcium-calcium naphthenate.

Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd, also may be used To be prepared according to method disclosed in CN101885677A.

Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..

Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industries Co., Ltd.

Embodiment 1

The present embodiment is used for the complex calcium sulfonate-Calcium naphthenate base polyurea 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（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of fortune Kinetic viscosity is 11mm²/ s, 17kg）.

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；2.8kg aphthenic acids is added, temperature control exists 50 DEG C or so, stir 10 minutes；1kg methanol is added, is stirred 10 minutes；Add 2.8kg concentration water-soluble for 20 weight % acetic acid Liquid, is stirred 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 weight % Calcium hydroxide suspension 9kg, stir 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；3.5kg is added to benzene Dioctyl phthalate, is stirred 10 minutes, and 120 DEG C are warming up under stirring, is kept for 30 minutes, dehydration；Add 2kg HVI500SN lubrication bases Oil and 1.5kg octadecylamines, stir 4 minutes, add the 0.7kg MDI being dissolved in 2kg HVI500SN lubricating base oils, stir 4 minutes, the ratio between added MDI and the amount of material of octadecylamine were 1:2,120 DEG C of constant temperature 20 minutes, is finally warming up to 200 DEG C of perseverances Temperature 10 minutes.Then, 160 DEG C are cooled to, remaining HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulation Filtering, 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 37.5；The weight % of two 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 add 24kg total base numbers The naphthenate with superhigh base number calcium and 30kg for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；2.8kg aphthenic acids is added, temperature control exists 50 DEG C or so, stir 10 minutes；1kg methanol is added, is stirred 10 minutes；Add 2.8kg concentration water-soluble for 20 weight % acetic acid Liquid, is stirred 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 weight % Calcium hydroxide suspension 9kg, stir 10 minutes；2kg12- hydroxy stearic acids are added, are stirred 10 minutes；3.5kg is added to benzene Dioctyl phthalate, is stirred 10 minutes, and 120 DEG C are warming up under stirring, is kept for 30 minutes, dehydration；

In another volume be 30L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg HVI500SN lubricating base oils and 1.5kg octadecylamines, are warming up to 120 DEG C, stir 4 minutes, add and are lubricated with 2kg HVI500SN The 0.7kg MDI of base oil dissolving, are stirred 4 minutes, and added MDI and the mol ratio of octadecylamine are 1:2,120 DEG C of 20 points of constant temperature Clock, obtains two polyureas.

The polyureas of gained two is all squeezed into a upper kettle, stirred, 200 DEG C of constant temperature is finally warming up to 10 minutes.So Afterwards, 160 DEG C are cooled to, remaining HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, Degassing obtains 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）；N-butanol （3.8kg）；Acetic acid（0.56kg）；Calcium hydroxide（1.8kg）；Stearic acid（1.9kg）；Phthalic acid（3.5kg）；Lauryl amine （1.31kg）；MDI（0.89kg）；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 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；3.8kg n-butanols are added, temperature control exists 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；90 DEG C are warming up to, Constant temperature 60 minutes, material retrogradation；The calcium hydroxide suspension 9kg that solid content is 20 weight % is added, is stirred 10 minutes；Add 1.9kg stearic acid, is stirred 10 minutes；3.5kg phthalic acids are added, are stirred 10 minutes, 100 DEG C, holding are warming up under stirring 60 minutes, dehydration；2kg HVI500SN lubricating base oils and 1.31kg lauryl amines is added, is stirred 8 minutes, is added and be dissolved in 4kg HVI500SN lubricating base oils in 0.89kg MDI, stir 8 minutes, the ratio between added MDI and the amount of material of lauryl amine For 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 lubrications base is added Plinth oil；Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 37.5；The weight % of two 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（1.66kg）；TDI（0.54kg）；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 polyurea grease, unlike, sulfoacid calcium Use the calcium sulfonate with high base number that total base number is 320mgKOH/g；Aphthenic acids is replaced with DBSA simultaneously；With isophthalic two Formic acid replaces terephthalic acid (TPA)；MDI is replaced with TDI；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 37.5；The weight % of two 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）；Terephthalic acid (TPA)（3.5kg）；Octadecylamine（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of motions Viscosity is 11mm²/ s, 7kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-Calcium naphthenate base polyurea grease, unlike, sulfoacid calcium Using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate uses the high base number ring that total base number is 320mgKOH/g Alkanoic acid calcium；Transforming agent is aphthenic acids, boric acid and acetic acid, and its mesoboric acid is added after acetic acid；The consumption of each composition is as above.Examine knot Fruit is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 52.1；The weight % of two polyureas 3.5；The weight % of lubricating base oil 34.4；The weight % of 12- hydroxy stearic acids calcium 3.3；To benzene The weight % of dioctyl phthalate 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（4.5kg）；MDI（2.1kg）；HVI500SN lubricating base oils（100 DEG C of motions are viscous Spend for 11mm²/ s, 18.6kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-Calcium naphthenate base polyurea grease, unlike, using 4, 4'- biphenyl dicarboxylic acids replace terephthalic acid (TPA)；Transforming agent is only aphthenic acids and acetic acid, the step of saving addition methanol；Each composition Consumption 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 36.4；The weight % of two 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（1.5kg）；MDI（0.7kg）；Full synthetic oil poly ＆ Alpha ,-olefin oil PAO10（100 DEG C of motions Viscosity is 11mm²/ s, 9kg）；Two thio Acidic phosphates zinc（2kg）；Molybdenum dialkyldithiocarbamacompositions（1kg）；Curing Tungsten（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 polyurea grease, unlike, aphthenic acids 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 methanol The step of；HVI150BS and HVI500SN is replaced respectively using full synthetic oil poly ＆ Alpha ,-olefin oil PAO40 and PAO10；And treat temperature Degree is cooled to 110 DEG C, adds 2kg two thio Acidic phosphates zinc, stirs 10 minutes, adds 1kg dialkyl dithio ammonia Base formic acid molybdenum, is stirred 10 minutes, adds 2kg tungsten disulfide, is stirred 10 minutes, adds 2kg two tungsten selenides, stirs 10 points Clock, adds 0.2kg pair, and right '-di-iso-octyldiphenylamine is stirred 10 minutes, then circulating filtration, homogenizing, degassing is obtained into 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 37.8；The weight % of two 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）；2- first Base -1,4- phthalic acids（3.8kg）；Octadecylamine（0.94kg）；Para-totuidine（0.38kg）；MDI（0.88kg）；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 polyurea grease, unlike, sulfoacid calcium Use the calcium sulfonate with high base number that total base number is 320mgKOH/g；Transforming agent is only aphthenic acids and acetic acid, saves the step for adding methanol Suddenly；Using 2- methyl isophthalic acids, 4- phthalic acids replace terephthalic acid (TPA)；Monoamine is additionally added para-totuidine in addition to octadecylamine, respectively 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 two polyureas 2.4；The weight % of lubricating base oil 53.3；The weight % of 12- hydroxy stearic acids calcium 2.4；2- first The weight % of base -1,4- phthalic acids 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（0.84kg）；Lauryl amine（0.58kg）；MDI（0.78kg）；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 polyurea grease, unlike, sulfoacid calcium Using the calcium sulfonate with high base number that total base number is 320mgKOH/g, calcium naphthenate uses the high base number ring that total base number is 320mgKOH/g Alkanoic acid calcium；Transforming agent is only aphthenic acids and acetic acid, the step of saving addition methanol；12- hydroxy stearic acids are added to stir 10 minutes Afterwards, boric acid is added, is stirred 10 minutes, terephthalic acid (TPA) is then added, stirred 10 minutes；And treat that temperature is cooled to 110 DEG C, plus Enter 0.2kg pair, right '-di-iso-octyldiphenylamine is stirred 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 34.2；The weight % of two 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（1.5kg）；MDI（0.7kg）；HVI500SN lubricating base oils（100 DEG C of motions Viscosity is 11mm²/ s, 33kg）.

Method according to embodiment 1 prepares complex calcium sulfonate-Calcium naphthenate base polyurea grease, unlike, transforming agent Only aphthenic acids and acetic acid, save the step of adding methanol；And after adding terephthalic acid (TPA) stirring 10 minutes, acetic acid is added, Stirring 10 minutes, is then warming up to 120 DEG C under agitation, is kept for 30 minutes, dehydration；The consumption of each composition is as above.Assay It 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 36.0；The weight % of two 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

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 24kg total base numbers The naphthenate with superhigh base number calcium and 30kg100 for being 400mgKOH/g for 400mgKOH/g overbased sulfoacid calcium, 6kg total base numbers DEG C kinematic viscosity is 31mm²/ s 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 2.8kg dense Spend for 20 weight % aqueous acetic acid, stirring 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.

In another volume be 50L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 5kg HVI500SN lubricating base oils, are warming up to 100 DEG C, 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.

In the 3rd volume be 20L and with heating, stirring, circulation, the normal-pressure reaction kettle of cooling in add 2kg HVI500SN lubricating base oils and 1.5kg octadecylamines, are stirred 6 minutes, are added and are dissolved with 2kg HVI500SN lubricating base oils 0.7kg MDI, stir 6 minutes, 120 DEG C of constant temperature 20 minutes obtains two polyureas.

The 12- hydroxy stearic acids calcium and terephthalic acid (TPA) calcium of gained are all squeezed into first kettle, stirred, is stirred Under be warming up to 120 DEG C, kept for 30 minutes, dehydration all squeezes into two polyureas obtained by the 3rd reactor in the kettle, and 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, remaining HVI500SN lubricating base oils are added；Treat Temperature is cooled to 110 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

Embodiment 12

Volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add 10kg total base numbers be 350mgKOH/g calcium sulfonate with high base number, 20kg total base numbers for 400mgKOH/g naphthenate with superhigh base number calcium and 25kg HVI150BS lubricating base oils（100 DEG C of kinematic viscosity are 31mm²/ s, similarly hereinafter）, stir, heat to 60 DEG C, 10 points of constant temperature Clock；3kg aphthenic acids is added, temperature control is stirred 10 minutes at 60 DEG C or so；Add concentration water-soluble for 20% 12.5kg butanol Liquid, is stirred 10 minutes；In 87 DEG C of constant temperature 70 minutes, material retrogradation.

Volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle B in add 5kg HVI500SN Lubricating base oil（100 DEG C of kinematic viscosity are 11mm²/ s, similarly hereinafter）, 90 DEG C are warming up to, the hydrogen-oxygen that solid content is 20 weight % is added Change calcium suspension 21kg, stir 10 minutes, add 2.4kg palmitic acid, stir 10 minutes, addition 4.2kg biphenyl dicarboxylic acid, 1kg phosphoric acid and 2kg ethanedioic acid, stir 10 minutes, obtain calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and ethanedioic acid calcium.

Volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle C in add 5kg HVI500SN Lubricating base oil and 1kg MDI rapidly pre-warmings are to 90 DEG C, and quick stirring is lower to add 0.12kg ethylenediamines, stirs 4 minutes, adds 1.08kg octadecylamines are stirred 4 minutes, and added MDI, ethylenediamine and octadecylamine mol ratio are 2:1:2,120 DEG C of 20 points of constant temperature Clock, obtains four polyureas.

Volume be 30L and with heating, stirring, circulation, cooling normal-pressure reaction kettle D in add 10kg100 DEG C motion Viscosity is 11mm²/ s HVI500SN lubricating base oils and 0.78kg MDI is preheating to 90 DEG C, and quick stirring is lower to add 0.84kg Octadecylamine, is stirred 4 minutes, and quick stirring is lower to add 0.19kg ethylenediamines, stirs 4 minutes, adds 0.39kg MDI, added successively MDI, octadecylamine, ethylenediamine and MDI mol ratio be 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.

Gained calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and ethanedioic acid calcium are all squeezed into reactor A, stirring is equal It is even, 120 DEG C are warming up under stirring, is kept for 30 minutes, the polyureas of gained four and six polyureas are all squeezed into reactor A, stirred by dehydration Mix uniform, be finally warming up to 200 DEG C of constant temperature 5 minutes.Then, 150 DEG C are cooled to, 8kg HVI500SN lubricating base oils are added； Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, constitute and be：Non-newtonian fluid sulfoacid calcium-cycloalkanes The sour weight % of calcium 34.4；The weight % of calcium palmitate 2.7；The weight % of biphenyl dicarboxylic acid calcium 4.2；The weight % of calcium phosphate 1.6；Ethanedioic acid calcium 2.9 weight %；The weight % of four polyureas 2.3；The weight % of six polyureas 2.3；The weight % of lubricating base oil 49.6.

Embodiment 13

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle A in add 20kg total alkalis Naphthenate with superhigh base number calcium and 10kg that overbased sulfoacid calcium that value is 400mgKOH/g, 10kg total base numbers are 420mgKOH/g HVI150BS lubricating base oils, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 2kg DBSAs, temperature Degree control is stirred 10 minutes at 50 DEG C or so；1kg methanol is added, is stirred 10 minutes；Add the acetic acid that 2kg concentration is 20 weight % The aqueous solution, is stirred 10 minutes；In 83 DEG C of constant temperature 80 minutes, material retrogradation.

Volume be 10L and with heating, stirring, circulation, cooling normal-pressure reaction kettle B in add 8kg HVI500SN Lubricating base oil, the calcium hydroxide suspension 8.0kg that solid content is 50 weight % is added at 85 DEG C, is stirred 10 minutes, is added 2.4kg laurate, is stirred 10 minutes, adds 7.9kg M-phthalic acid, is stirred 10 minutes, is obtained calcium laurate and isophthalic Dioctyl phthalate calcium.

Volume be 20L and with heating, stirring, circulation, cooling normal-pressure reaction kettle C in add 10kg HVI500SN Lubricating base oil and 1.17kg MDI are preheating to 80 DEG C, quick stirring is lower add 0.84kg octadecylamines, 0.19kg ethylenediamines it is mixed Compound, added MDI, monoamine, the mol ratio of diamines are 3:2:2,120 DEG C of constant temperature 20 minutes, obtains mixing polyureas.

Gained calcium laurate and M-phthalic acid calcium are all squeezed into reactor A, stirred, is warming up under stirring 110 DEG C, kept for 45 minutes, gained mixing polyureas is all squeezed into reactor A, stirs, be finally warming up to 200 by dehydration DEG C constant temperature 5 minutes.Then, 2kg HVI500SN lubricating base oils are added；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, Degassing obtains 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 41.7；The weight % of calcium laurate 3.3；The weight % of M-phthalic acid calcium 12.1；The weight % of polyurea compound 5.4；Lubrication The weight % of base oil 37.5.

Embodiment 14

Method according to embodiment 1 prepares complex calcium sulfonate-Calcium naphthenate base polyurea grease, unlike, by cycloalkanes 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 polyurea grease, unlike, by cycloalkanes 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

The polyurea grease of Composite calcium-sulfonate-batetrapolyurea two 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 is replaced, and obtained each performance data of lubricating grease finished product is shown in Table 1.

In the lubricating grease that this comparative example is obtained, on the basis of lubricating grease weight, constitute and be：The weight of non-newtonian fluid sulfoacid calcium 37.5 Measure %；The weight % of two 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 %.

Embodiment 1 and comparative example 1 are compared as can be seen that complex calcium sulfonate-Calcium naphthenate base polyureas of the present invention The difference of the extension work cone penetration of lubricating grease and work cone penetration is less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and water drenches number of dropouts Much smaller than Composite calcium-sulfonate-batetrapolyurea polyurea grease, salt spray test is better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and water resistant spraying value is small In Composite calcium-sulfonate-batetrapolyurea polyurea grease, Stencil oil-dividing value is much smaller than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and tetra-ball machine test is big In Composite calcium-sulfonate-batetrapolyurea polyurea grease, the bearing lubrication life-span is more than Composite calcium-sulfonate-batetrapolyurea polyurea grease, illustrates the present invention's Mechanical stability, water-resistance and the adhesiveness of complex calcium sulfonate-Calcium naphthenate base polyurea grease, resistance to saltfog, colloid are stabilized Property, extreme pressure anti-wear, lubricating life be superior to Composite calcium-sulfonate-batetrapolyurea polyurea grease, and complex calcium sulfonate-cycloalkanes of the present invention Sour calcium base polyurea grease has the property such as excellent anticorrosive property and heat-resisting quantity as Composite calcium-sulfonate-batetrapolyurea polyurea grease Energy.

Embodiment 1 is compared with embodiment 2 and embodiment 11 respectively as can be seen that the composite sulfoacid in situ prepared Calcium-Calcium naphthenate base polyurea grease, resists with more preferable mechanical stability, water-resistance and adhesiveness, colloid stability, extreme pressure Mill property, and with longer lubricating life；Embodiment 1 is compared with embodiment 14 and embodiment 15 respectively and be can be seen that Transforming agent is selected from least one of DBSA, aphthenic acids, methanol, butanol, isopropanol, boric acid, acetic acid and water, system Standby complex calcium sulfonate-Calcium naphthenate base polyurea grease, with more preferable mechanical stability, water-resistance and adhesiveness, colloid Stability, extreme pressure anti-wear, and with longer lubricating life.

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；Steel

Net point oil：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

Each indication test method：Dropping point：GB/T3498；Work cone penetration and extension work cone penetration：GB/T269；Corrosion：GB/ T7326；

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 stretching vibration absworption peak that the peak at place is-NH- in two 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

1. a kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease, it is characterised in that 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；1- The calcium salt of 15 weight % aromatic acid；0.5-30 weight % polyurea compound；10-80 weight % base oil；Optionally also The calcium salt of small molecule inorganic acid and/or lower fatty acid including 1-15 weight %, the non-newtonian fluid sulfoacid calcium-calcium naphthenate In infrared spectrum 873cm^-1-886cm^-1There 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：20-65 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 % polyurea compound；20-70 weight % base oil；It is optionally also small including 2-10 weight % The calcium salt of 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 What sulfoacid calcium and the conversion of newton body calcium naphthenate were obtained, the total base number of the non-newtonian fluid sulfoacid calcium-calcium naphthenate is 250- 450mgKOH/g。

4. lubricating grease according to claim 1 or 2, wherein, the higher fatty acids is the straight chain fatty that carbon number is 8-20 Acid or hydroxy fatty acid.

5. lubricating grease according to claim 4, wherein, the higher fatty acids be selected from laurate, palmitic acid, stearic acid, At least one of 12- hydroxy stearic acids, eicosyl carboxylic acid.

6. lubricating grease according to claim 1 or 2, wherein, the aromatic acid is substituted or unsubstituted aromatic acid, substituent 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 polyurea compound is two polyurea compounds, four polyureas At least one of compound, six polyurea compounds and eight polyurea compounds.

9. lubricating grease according to claim 8, wherein, the polyurea compound is two polyurea compounds, compound tool There is following structure：

Wherein, R¹、R^1’It is alkyl, cycloalkyl or aryl, R³It is arlydene, alkylidene or cycloalkylidene.

10. lubricating grease according to claim 9, wherein, R¹、R^1’It is phenyl or substituted phenyl, or carbon number is 8-24's Alkyl or cycloalkyl；R³It is 6-30 arlydene, alkylidene or cycloalkylidene.

11. lubricating grease according to claim 10, wherein, R¹、R^1’It is the benzene of phenyl, C1-C3 alkyl or halogen substitution Base, or the alkyl or cycloalkyl that carbon number is 10-18, R³It is With- (CH₂)₆At least one of-.

12. 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.

13. lubricating grease according to claim 12, wherein, the small molecule inorganic acid is in boric acid, phosphoric acid, sulfuric acid At least one, the lower fatty acid is selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid.

14. the preparation method of complex calcium sulfonate-Calcium naphthenate base polyurea grease in claim 1-13 described in any one, Characterized in that, this method includes：By non-newtonian fluid sulfoacid calcium-calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, The calcium salt of polyurea compound, the small molecule inorganic acid of part basis oil and selectivity and/or lower fatty acid is well mixed, In 180-230 DEG C of constant temperature refining, surplus base oil is added, necessary additive is added, obtains finished product.

15. the preparation method of complex calcium sulfonate-Calcium naphthenate base polyurea grease in claim 1-13 described in any one, Characterized 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, higher fatty acids, aromatic acid and selectivity is added Small molecule inorganic acid and/or lower fatty acid are reacted, and heat up dehydration after reaction；

(3) base oil and monoamine are added in mixture obtained by step (2), or is additionally added diamines, diisocyanate is added and carries out Reaction；

(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, obtains finished product.

16. preparation method according to claim 15, wherein, in step (1), by newton body sulfoacid calcium, newton body cycloalkanes Sour calcium, base oil Hybrid Heating are to 50-80 DEG C, and the transforming agent needed for adding is reacted, after all transforming agents are added, in 80- 100 DEG C of constant temperature 60-90 minutes.

17. preparation method according to claim 15, wherein, in step (2), at 85-100 DEG C, add lime or hydrogen The suspension of calcium oxide, adds higher fatty acids, stirs 5-20 minutes, adds the small molecule inorganic acid of aromatic acid and selectivity And/or lower fatty acid, stir 5-20 minutes, be warming up to 100-120 DEG C of dehydration.

18. preparation method according to claim 15, wherein, in step (3), added in mixture obtained by step (2) Base oil and monoamine, are stirred 2-8 minutes, add diisocyanate, are stirred 2-8 minutes, mole of diisocyanate and monoamine Than for 1:2.

19. preparation method according to claim 15, wherein, in step (4), first in 100-120 DEG C of 10-20 points of constant temperature Clock, is finally warming up to 180-230 DEG C of constant temperature 5-20 minutes；Base oil is added, treats that temperature is cooled to 100-120 DEG C, is added necessary Additive, stirring, circulating filtration, homogenizing, degassing.

20. preparation method according to claim 15, 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.

21. preparation method according to claim 15, 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%.

22. preparation method according to claim 21, 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.

23. preparation method according to claim 15, wherein, the structural formula of the monoamine is R¹-NH₂、R^1’-NH₂, wherein, R¹、R^1’It is the phenyl of phenyl, C1-C3 alkyl or halogen substitution, or the alkyl or cycloalkyl that carbon number is 10-18.

24. preparation method according to claim 23, wherein, the monoamine is to be 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.

25. preparation method according to claim 15, wherein, the structural formula of the diamines is NH₂-R²-NH₂, wherein, R²It is Carbon number is 2-8 alkylidene, or phenylene or biphenylene.

26. preparation method according to claim 25, 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.

27. preparation method according to claim 15, wherein, the structure of the diisocyanate is OCN-R³- NCO, R³It is Carbon number is 6-30 arlydene, alkylidene or cycloalkylidene.

28. preparation method according to claim 27, 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.