CN104212611B - A kind of Calcium naphthenate base polyurea grease and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of Calcium naphthenate base polyurea grease, it is characterised in that on the basis of grease weight, including following components: the non-newtonian fluid calcium naphthenate of 20 60 weight %；The polyurea compound of 0.5 25 weight %；The base oil of 25 70 weight %, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the characteristic absorption peak of aragonite calcium carbonate.The invention also discloses the preparation method of Calcium naphthenate base polyurea grease and the Calcium naphthenate base polyurea grease of preparation thereof.The Calcium naphthenate base polyurea grease of the present invention, not only as sulfonic acid calcio polyurea grease, there is excellent anticorrosive property and resistance to saltfog, but also there is performances such as being better than the heat-resisting quantity of sulfonic acid calcio polyurea grease, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, there is longer lubricating life.The preparation of greases technique of the present invention is simple and environmentally-friendly, low cost, constant product quality.

Description

A kind of Calcium naphthenate base polyurea grease and preparation method thereof

Technical field

The present invention relates to grease, in particular it relates to a kind of Calcium naphthenate base polyurea grease and preparation method thereof.

Background technology

Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusibility, can To be used as the detersive of lubricating oil, being widely used in the additive of IC engine lubricating oil, the development of its technology mainly makes it high-alkali Change, it is simply that calcium carbonate is distributed in flux oil become a kind of colloidal dispersion system with the naphthenic acid calcium with surface activity.High Mostly base number calcium naphthenate is from the distillate that crude distillation obtains the acidic components extracted, warp and Ca (OH)₂Reaction, carbonating Contour alkalization technology and obtain, about preparation Patents have CN1465560 etc..

Utilize calcium sulfonate with high base number for raw material production grease, because of its have excellence high temperature performance, mechanical stability, Colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, caused profit both at home and abroad The extensive concern of consistent lubricant industry, but, although high base number composite calcium sulfonate base grease has the most 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, with Time, along with people are more and more higher to the requirement of environmental conservation, 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 similar with calcium sulfonate with high base number but the problems referred to above can be avoided Grease become the big problem that people face at present.

Summary of the invention

It is an object of the invention to provide a kind of performance similar with sulfonate with high base number grease of calcium, low cost, preparation technology letter Singly, grease of environmental protection and preparation method thereof.

The present inventor finds under study for action, on the basis of grease weight, including following components: 20-60 weight % Non-newtonian fluid calcium naphthenate；The polyurea compound of 0.5-25 weight %；The base oil of 25-70 weight %, wherein, described non newtonian The infrared spectrum of body calcium naphthenate has the characteristic absorption peak of aragonite calcium carbonate.The performance of this grease and calcium sulfonate with high base number Grease is similar to, and low cost, and preparation technology is simple and environmentally-friendly.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of Calcium naphthenate base polyurea grease, its It is characterised by, on the basis of grease weight, including following components: the non-newtonian fluid calcium naphthenate of 20-60 weight %；0.5-25 The polyurea compound of weight %；The base oil of 25-70 weight %, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has The characteristic absorption peak of aragonite calcium carbonate.

Preferably, on the basis of grease weight, including following components: the non-newtonian fluid calcium naphthenate of 30-55 weight %； 1.5-15 the polyurea compound of weight %；The base oil of 35-60 weight %.

Second aspect, the invention provides the preparation method of Calcium naphthenate base polyurea grease as above, its feature Being, the method includes: by non-newtonian fluid calcium naphthenate, polyurea compound and part basis oil mix homogeneously, at 180-230 DEG C Constant temperature is refined, cooling, adds surplus base oil, adds necessary additive, obtains finished product.

The third aspect, the invention provides the preparation method of a kind of Calcium naphthenate base polyurea grease, it is characterised in that should Method includes:

(1) by newton body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, enter One step heats up and is dehydrated, and then lowers the temperature；

(2) in step (1) products therefrom, add part basis oil and monoamine, or be additionally added diamidogen, add two Carbimide .s Ester reacts；

(3) step (2) products therefrom is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add Necessary additive, obtains finished product.

Fourth aspect, the invention provides the Calcium naphthenate base polyurea grease prepared by method as above.

The Calcium naphthenate base polyurea grease of the present invention, not only as sulfonic acid calcio polyurea grease, has excellent Anticorrosive property and resistance to saltfog, but also have be better than the heat-resisting quantity of sulfonic acid calcio polyurea grease, water-resistance and adhesiveness, The performance such as colloid stability, extreme pressure anti-wear, has longer lubricating life.The preparation of greases technique of the present invention is simple, Environmental protection, low cost, constant product quality.

Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.

Accompanying drawing explanation

Fig. 1 is the infrared analysis spectrogram of the calcium carbonate in the overbased calcium alkyl-salicylate of embodiment 2.

Fig. 2 is the infrared analysis spectrogram of the calcium carbonate in the grease of embodiment 2 preparation.

Fig. 3 is that the XRD crystal formation of the calcium carbonate in the grease of embodiment 2 preparation measures.

Detailed description of the invention

Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.

The invention provides a kind of Calcium naphthenate base polyurea grease, this grease have employed petroleum naphthenic acid calcium or conjunction One-tenth calcium naphthenate is raw material, contains isocyanates and the polyurea compound of amine reaction generation simultaneously.

Present invention also offers above-mentioned preparation of greases method.

On the one hand, the invention provides a kind of Calcium naphthenate base polyurea grease, on the basis of grease weight, including with Lower component: the non-newtonian fluid calcium naphthenate of 20-60 weight %；The polyurea compound of 0.5-25 weight %；The basis of 25-70 weight % Oil, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the characteristic absorption peak of aragonite calcium carbonate.

Preferably, on the basis of grease weight, including following components: the non-newtonian fluid calcium naphthenate of 30-55 weight %； 1.5-15 the polyurea compound of weight %；The base oil of 35-60 weight %.

The infrared absorption peak of the mainly carbonate that calcium carbonate occurs in infrared spectrum, is divided into 4 regions: ν 1- 1450cm^-1；ν2-1080cm^-1；ν3-870cm^-1With ν 4-710cm^-1.ν 1 bands of a spectrum are carbonate (CO₃ ^2-) antisymmetric stretching vibration suction Receiving peak, ν 2 bands of a spectrum are carbonate symmetrical stretching vibration absworption peaks, and ν 3 bands of a spectrum are the out-of-plane bending vibration absworption peaks of carbonate, and ν 4 composes Band is the in-plane bending vibration absworption peak of carbonate.It is said that in general, calcium carbonate can be distinguished by the difference of these absworption peaks Crystal form.The characteristic absorption of different crystal forms calcium carbonate is as follows: ν 3 bands of a spectrum of calcite type are 876cm^-1Left and right, ν 4 bands of a spectrum are 712cm^-1Left and right；ν 2 bands of a spectrum of aragonitic are 1082cm^-1Left and right, ν 3 bands of a spectrum are 856cm^-1Left and right, ν 4 bands of a spectrum are 712cm^-1With 700cm^-1(weak)；Vaterite-type ν 3 bands of a spectrum are 876cm^-1Left and right, ν 4 bands of a spectrum are 745cm^-1Left and right；Amorphous ν 3 bands of a spectrum are 860cm^-1Left and right.Environment residing for calcium carbonate is different, the peak position of its infrared band slightly difference.

Described non-newtonian fluid calcium naphthenate is at infrared spectrum 1082cm^-1Left and right, 856cm^-1Left and right, 712cm^-1Left and right, 700cm^-1There is the characteristic absorption peak of aragonite calcium carbonate in place, and total base number is 250mgKOH/g-500mgKOH/g, preferably 300mgKOH/g-450mgKOH/g.Described non-newtonian fluid calcium naphthenate is to be converted by transforming agent by newton body calcium naphthenate Arrive.And containing unformed calcium carbonate in newton body calcium naphthenate, at infrared spectrum 1076cm^-1Left and right, 860cm^-1At left and right with or without Sizing calcium carbonate characteristic absorption peak.Described newton body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, its total base number For 250mgKOH/g-500mgKOH/g, preferably 300mgKOH/g-450mgKOH/g, after changing into non-newtonian fluid calcium naphthenate, its Base number is constant.

In the present invention, described polyurea compound, without particular/special requirement, can be polyurea compound commonly used in the art, such as may be used Think at least one in 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 Described polyurea compound is two polyurea compounds.

In the present invention, described two polyurea compounds preferably have a structure that

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

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R³More preferably (CH₂)₆In At least one.

In the present invention, described four polyurea compounds preferably have a structure that

Wherein, R¹Can 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 substiuted.

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.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R³More preferably (CH₂)₆In At least one.

In the present invention, described six polyurea compounds preferably have a structure that

Wherein, R¹Can 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 substiuted.

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.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R³More preferably (CH₂)₆In At least one.

In the present invention, described eight polyurea compounds preferably have a structure that

Wherein, R¹Can 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 substiuted.

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.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can Think 6-30, preferably 6-20, R³More preferably (CH₂)₆In At least one.

Above-mentioned polyurea compound can use the thinkable various methods of those skilled in the art institute to obtain, such as can be by The method recorded according to CN103060069A, CN103060070A, CN103060068A, CN103060067A prepares.

Described lube base oil can be mineral oil, artificial oil, vegetable oil or their mixture, and 100 DEG C of motions are glutinous Degree is 4-150mm²/ s, preferably 10-60mm²/s.Artificial oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, Fischer-Tropsch Artificial oil etc..

Grease of the present invention can also contain various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent etc..Its In, antioxidant preferred arylamine kind antioxidant, account for the 0.01-5% of grease gross weight, preferably 0.1-2.5%, can be diphenylamines, At least one in phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for grease The 0.5-12% of gross weight, preferably 0.8-8%, can be dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, two Sulfur is for dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum bisuphide, polytetrafluoroethyl-ne Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium sulfide, fluorographite, carbonic acid At least one in calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of grease gross weight, preferably 0.1-2%, can be oil At least one in barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.

Second aspect, the invention provides the preparation method of Calcium naphthenate base polyurea grease as above, the method Including: by non-newtonian fluid calcium naphthenate, polyurea compound and part basis oil mix homogeneously, refine at 180-230 DEG C of constant temperature, cold But, add surplus base oil, add necessary additive, obtain finished product.

In the present invention, for non-newtonian fluid calcium naphthenate, polyurea compound and base oil as it has been described above, the most superfluous at this State.

It will be understood by those skilled in the art that the amount of part basis oil is used with the amount sum of surplus base oil The total amount of base oil, in the present invention, part basis oil is preferably 1:0.1-0.5 with the weight ratio of surplus base oil.

For non-newtonian fluid calcium naphthenate, can be obtained, such as, by cattle by transforming agent conversion by newton body calcium naphthenate Body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, the transforming agent needed for addition reacts, and all transforming agents add After, more than 90 DEG C and less than or equal to 110 DEG C, preferably 95-110 DEG C, constant temperature 40-100 minute, then heat to 150-170 DEG C Dehydration.

The third aspect, the invention provides the another kind of preparation method of Calcium naphthenate base polyurea grease as above, Including:

(1) by newton body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, enter One step heats up and is dehydrated, and then lowers the temperature；

(2) in step (1) products therefrom, add part basis oil and monoamine, or be additionally added diamidogen, add two Carbimide .s Ester reacts；

(3) it is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain Finished product.

In step (1), by newton body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, the conversion needed for addition Agent is reacted, after all transforming agents add, more than 90 DEG C and less than or equal to 110 DEG C, and preferably 95-110 DEG C, constant temperature 40-100 Minute, it is warming up to 150-170 DEG C of dehydration, is then cooled to 100-120 DEG C.

Newton body calcium naphthenate is preferably 1:0.1-1 with the weight ratio of part basis oil.

Described newton body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total base number is 250mgKOH/g- 500mgKOH/g, preferably 300mgKOH/g-450mgKOH/g.

Described transforming agent is selected from water, fatty alcohol, aliphatic ether, fatty acid, aphthenic acids, fatty aldehyde, aliphatic ketone, fatty amine, ring At least one in alkanamine, cyclic alkanol, cycloalkanes ether, carbon dioxide, aromatic alcohol, aromatic amine and alkyl benzene sulphonate, be preferably selected from water, Isopropanol, methanol, ethanol, propanol, n-butyl alcohol, ketone, formaldehyde, glycol dimethyl ether, acetic acid, propanoic acid, butanoic acid, aphthenic acids, hard At least one in fat acid, 12-hydroxy stearic acid and DBSA.More preferably A, B, C tri-class material, A class material For at least one in ethanol, propanol, butanol and 12-hydroxy stearic acid, B class material be in acetic acid, propanoic acid and butanoic acid at least One, C class material is water, and feed postition be preferably A class material prior to B class material add, be i.e. initially charged ethanol, propanol, At least one in butanol and 12-hydroxy stearic acid, after mixing homogeneously with newton body calcium naphthenate, add acetic acid, propanoic acid and At least one in butanoic acid, for the addition sequence of C class material water without particular/special requirement, can first add, can add later, it is also possible to A class material or B class material add together.

The addition of transforming agent is the 4-32% of newton body calcium naphthenate weight, preferably 15-25%.When transforming agent be preferably A, B, C tri-class material, A class material is at least one in ethanol, propanol, butanol and 12-hydroxy stearic acid, B class material be acetic acid, At least one in propanoic acid and butanoic acid, when C class material is water, A class material is preferably with the weight ratio of B class material with C class material 1:0.1-10:1-10, more preferably 1:0.5-8:1-8.For the concrete material selected in A class material and B class material and each thing Amount ratio between matter is without particular/special requirement, as long as total amount can obtain more preferable effect within the above range.

In step (2), step (1) products therefrom adds part basis oil and monoamine, or is additionally added diamidogen, add two Isocyanates reacts, and is i.e. to prepare polyurea compound in step (1) products therefrom, can prepare mixing polyureas, it is possible to To prepare single two polyurea compounds, four polyurea compounds, six polyurea compounds or eight polyurea compounds.

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

Prepare the method for two polyurea compounds without particular/special requirement, various methods commonly used in the art can be used.Such as, exist In the present invention, base oil and monoamine can be added in step (1) products therefrom, stir 2-8 minute, add and be dissolved in basis Diisocyanate in oil, stirs 2-8 minute, and diisocyanate is 1:2 with the mol ratio of monoamine.

Prepare the method for four polyurea compounds without particular/special requirement, various methods commonly used in the art can be used.Such as, exist In the present invention, base oil and diisocyanate can be added in step (1) products therefrom, stir, add diamidogen, stirring 2-8 minute, adding monoamine, stir 2-8 minute, diisocyanate, diamidogen are 2:1:2 with the mol ratio of monoamine.

Prepare the method for six polyurea compounds without particular/special requirement, various methods commonly used in the art can be used.Such as, exist In the present invention, base oil and diisocyanate can be added in step (1) products therefrom, stir, add monoamine, stirring 2-8 minute, add diamidogen, stir 2-8 minute, add diisocyanate, stir 2-8 minute, two added successively Carbimide .s Ester, monoamine, diamidogen are 2:2:2:1 with the mol ratio of diisocyanate.

Prepare the method for eight polyurea compounds without particular/special requirement, various methods commonly used in the art can be used.Such as, exist In the present invention, base oil and diisocyanate can be added in step (1) products therefrom, stir, add diamidogen, stirring 2-8 minute, again add diamidogen, stir 2-8 minute, add monoamine, stir 2-8 minute, successively added by diisocyanate, two The mol ratio of amine, diamidogen and monoamine is 4:2:1:2.

Described diisocyanate structure is OCN-R³-NCO, R³Can be carbon number be the arlydene of 6-30, preferably 6-20, Asia Alkyl or cycloalkylidene, be preferably ——(CH₂)₆Deng. Such as, described diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), and 1,6-is sub- Hexyl diisocyanate (HDI), dicyclohexylmethyl diisocyanate (HMDI) and an xylylene diisocyanate (XDI) etc. In at least one.

Described 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 substiuted.Preferably monoamine can be selected from aniline, m-chloro Aniline, parachloroanilinum, the arylamine of para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, the fatty amine of 18-amine..

Described diamidogen 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, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferably diamidogen 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 two The straight-chain fatty amine of amine.

In step (3), first 100-120 DEG C of constant temperature 10-20 minute, finally it is warmed up to 180-230 DEG C of constant temperature 5-20 minute； It is cooled to 150-160 DEG C, adds surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stirring, follow Ring filtration, homogenizing, degassing.

In the present invention, in part basis oil used by part basis oil used by step (1) and step (2) and step (3) The weight ratio of surplus base oil is preferably 1:0.1-1:0.1-1.

Fourth aspect, the Calcium naphthenate base that the preparation method that present invention also offers is provided by third aspect present invention prepares Polyurea grease.

Compared with the Calcium naphthenate base polyurea grease that the preparation method provided by second aspect prepares, the third aspect provides Preparation method prepare Calcium naphthenate base polyurea grease have more preferable heat-resisting quantity, water-resistance and adhesiveness, colloid peace Qualitative and extreme pressure anti-wear.

Embodiment

The present invention is further illustrated for below example, but and is not so limited the present invention.

In the following Examples and Comparative Examples:

Non-newtonian fluid calcium naphthenate %=(is overbased or overbased calcium alkyl-salicylate raw materials quality+transforming agent gross mass)/profit Consistent lubricant gross mass × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium naphthenate.

In embodiment, overbased limited from Xinjiang Lander Speciality Petrochemicals share with overbased calcium alkyl-salicylate raw material Company, it is also possible to prepare according to method disclosed in CN101885677A.

In comparative example, calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..

Embodiment 1

The present embodiment is for illustrating Calcium naphthenate base polyurea grease prepared by the present invention.

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add 30kg total base number Naphthenate with superhigh base number calcium and 30kg100 DEG C of kinematic viscosity for 320mgKOH/g are 31mm²The HVI150BS lubrication base of/s Oil, stirring, heat to 80 DEG C, constant temperature 10 minutes；Adding 1.8kg n-butyl alcohol, temperature controls at about 80 DEG C, stirs 10 points Clock；Add 1.56kg n-butyric acie and 3.2kg water, stir 10 minutes；In 95 DEG C of constant temperature 100 minutes, material retrogradation；Stirring is lower to heat up To 160 DEG C, keep 60 minutes, dehydration, cool to 120 DEG C；10kg100 DEG C of kinematic viscosity of addition is 11mm²/ s's The 10.7kg 18-amine. that HVI500SN lubricating base oil dissolves, stirs 6 minutes, adds with 5kg HVI500SN lubricating base oil The 5kg MDI dissolved, stirs 6 minutes, 120 DEG C of constant temperature 20 minutes, is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, it is cooled to 160 DEG C, add HVI500SN lubricating base oil 15kg；Treating that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing are become Product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid calcium naphthenate 30.6%；Two polyureas 14.4%；Lubricating base oil 55.0%.

Embodiment 2

The present embodiment is for illustrating Calcium naphthenate base polyurea grease prepared by the present invention.

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add 33kg total base number Overbased calcium alkyl-salicylate and 15kg100 DEG C of kinematic viscosity for 400mgKOH/g are 31mm²The HVI150BS lubricating base oil of/s, Stirring, heats to 60 DEG C, constant temperature 10 minutes；Adding 0.56kg ethanol, temperature controls at about 60 DEG C, stirs 10 minutes； Add 3.36kg propanoic acid and 3.36kg water, stir 10 minutes；In 100 DEG C of constant temperature 70 minutes, material retrogradation；It is warmed up under stirring 150 DEG C, keep 60 minutes, dehydration, cool to 110 DEG C；5kg100 DEG C of kinematic viscosity of addition is 11mm²The HVI500SN profit of/s The 0.76kg lauryl amine that sliding base oil dissolves, stirs 2 minutes, adds with the dissolving of 5kg HVI500SN lubricating base oil 0.34kg HDI, stirs 2 minutes, 110 DEG C of constant temperature 15 minutes, is finally warmed up to 180 DEG C of constant temperature 20 minutes.Then, 150 it are cooled to DEG C, add HVI500SN lubricating base oil 10kg；Treating that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection Test and the results are shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid calcium naphthenate 50.2%；Two polyureas 1.5%；Lubricating base oil 48.3%.

Embodiment 3

The present embodiment is for illustrating Calcium naphthenate base polyurea grease prepared by the present invention.

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add 30kg total base number Naphthenate with superhigh base number calcium and 30kg100 DEG C of kinematic viscosity for 450mgKOH/g are 31mm²The HVI150BS lubrication base of/s Oil, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 0.2kg normal propyl alcohol, 0.2kg n-butyl alcohol and 3.2kg water, temperature control System, at about 50 DEG C, stirs 10 minutes；Add 2.96kg acetic acid, stir 10 minutes；In 110 DEG C of constant temperature 40 minutes, material retrogradation； It is warmed up to 170 DEG C under stirring, keeps 60 minutes, dehydration, cool to 100 DEG C；3kg100 DEG C of kinematic viscosity of addition is 11mm²/s HVI500SN lubricating base oil dissolve 3.51kg para-totuidine, stir 8 minutes, add with 3kg HVI500SN lubrication base The 3.09kg XDI that plinth oil dissolves, stirs 8 minutes, 100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, It is cooled to 155 DEG C, adds HVI500SN lubricating base oil 6kg；Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, deaerate To finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid calcium naphthenate 40.7%；Two polyureas 8.0%；Lubricating base oil 51.3%.

Embodiment 4

The present embodiment is for illustrating Calcium naphthenate base polyurea grease prepared by the present invention.

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add 30kg total base number Naphthenate with superhigh base number calcium and 30kg100 DEG C of kinematic viscosity for 320mgKOH/g are 31mm²The HVI150BS lubrication base of/s Oil, stirring, heat to 80 DEG C, constant temperature 10 minutes；Adding 1.8kg n-butyl alcohol, temperature controls at about 80 DEG C, stirs 10 points Clock；Add 1.56kg n-butyric acie and 3.2kg water, stir 10 minutes；In 95 DEG C of constant temperature 100 minutes, material retrogradation；Stirring is lower to heat up To 160 DEG C, keep 60 minutes, dehydration.

Another volume be 50L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in addition 10kg100 DEG C kinematic viscosity is 11mm²The 10.7kg 18-amine. that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, adds use The 5kg MDI that 5kg HVI500SN lubricating base oil dissolves, stirs 6 minutes, 120 DEG C of constant temperature 20 minutes, obtains two polyureas.

Two polyureas of gained are all squeezed in a upper still, stirs, be finally warmed up to 200 DEG C of constant temperature 10 minutes. Then, it is cooled to 160 DEG C, adds HVI500SN lubricating base oil 15kg；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, Degassing obtains finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid calcium naphthenate 30.6%；Two polyureas 14.4%；Lubricating base oil 55.0%.

Embodiment 5

The present embodiment is for illustrating Calcium naphthenate base polyurea grease prepared by the present invention.

Volume be 160L and with the normal-pressure reaction kettle A heating, stirring, circulate, cool down in add 30kg total base number be Overbased calcium alkyl-salicylate and the 25kg100 DEG C of kinematic viscosity of 300mgKOH/g are 31mm²The HVI150BS lubricating base oil of/s, stirs Mix, heat to 60 DEG C, constant temperature 10 minutes；Adding 0.28kg ethanol and 0.28kg normal propyl alcohol, temperature controls at about 60 DEG C, Stir 10 minutes；Add 1.4kg acetic acid, 1.4kg n-butyric acie and 3.92kg water, stir 10 minutes；110 DEG C of constant temperature 70 minutes, Material retrogradation；It is warmed up to 150 DEG C under stirring, keeps 60 minutes, dehydration.

Volume be 10L and with the normal-pressure reaction kettle B heating, stirring, circulate, cool down in add 5kg100 DEG C of motion viscous Degree is 11mm²The HVI500SN lubricating base oil of/s and 1kg MDI rapidly pre-warming to 90 DEG C, quickly stirring is lower adds 0.12kg second Diamidogen, stirs 4 minutes, adds 1.08kg 18-amine. and stirs 4 minutes, and added MDI, ethylenediamine are 2 with the mol ratio of 18-amine.: 1:2,120 DEG C of constant temperature 20 minutes, obtain four polyureas.

Volume be 20L and with the normal-pressure reaction kettle C heating, stirring, circulate, cool down in add 10kg100 DEG C of motion Viscosity is 11mm²HVI500SN lubricating base oil and the 0.78kg MDI of/s are preheating to 90 DEG C, quickly add 0.84kg under stirring 18-amine., stirs 4 minutes, and quickly stirring is lower adds 0.19kg ethylenediamine, stirs 4 minutes, adds 0.39kg MDI, added successively MDI, 18-amine., the mol ratio of ethylenediamine and MDI be 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtain six polyureas.

Gained four polyureas and six polyureas are all squeezed in reactor A, stirs, be finally warmed up to 200 DEG C of constant temperature 5 points Clock.Then, it is cooled to 150 DEG C, adds 8kg lubricating base oil 500SN；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, de- It is so incensed that finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid calcium naphthenate 38.8%；Four polyureas 2.6%；Six polyureas 2.6%；Lubricating base oil 56.0%.

Embodiment 6

The present embodiment is for illustrating Calcium naphthenate base polyurea grease prepared by the present invention.

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add 30kg total base number Naphthenate with superhigh base number calcium and 10kg100 DEG C of kinematic viscosity for 420mgKOH/g are 31mm²The HVI150BS lubrication base of/s Oil, stirring, heat to 50 DEG C, constant temperature 10 minutes；Adding 0.56kg normal propyl alcohol and 2.8kg water, temperature controls on 50 DEG C of left sides The right side, stirs 10 minutes；Add 1kg acetic acid, 1kg propanoic acid and 0.8kg n-butyric acie, stir 10 minutes；110 DEG C of constant temperature 40 minutes, Material retrogradation；It is warmed up to 170 DEG C under stirring, keeps 60 minutes, dehydration.

Volume be 20L and with the normal-pressure reaction kettle C heating, stirring, circulate, cool down in add 10kg100 DEG C of motion Viscosity is 11mm²HVI500SN lubricating base oil and the 1.17kg MDI of/s are preheating to 80 DEG C, quickly add 0.84kg under stirring 18-amine., the mixture of 0.19kg ethylenediamine, added MDI, monoamine, the mol ratio of diamidogen are 3:2:2,120 DEG C of constant temperature 20 points Clock, obtains mixing polyureas.

Gained polyurea compound is all squeezed in a upper still, stir, be finally warmed up to 200 DEG C of constant temperature 5 minutes. Then, it is cooled to 160 DEG C, adds 8kg lubricating base oil 500SN；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing Obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid calcium naphthenate 51.7%；Polyurea compound 3.5%；Lubricating base oil 44.8%.

Embodiment 7

The present embodiment is for illustrating Calcium naphthenate base polyurea grease prepared by the present invention.

Prepare Calcium naphthenate base polyurea grease according to the method for embodiment 1, except for the difference that, be initially charged the positive fourth of 1.56kg Acid, temperature controls at about 80 DEG C, stirs 10 minutes, adds 1.8kg n-butyl alcohol and 3.2kg water, stirs 10 minutes.Inspection knot Fruit is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid calcium naphthenate 30.6%；Two polyureas 14.4%；Lubricating base oil 55.0%.

Embodiment 8

The present embodiment is for illustrating Calcium naphthenate base polyurea grease prepared by the present invention.

Prepare Calcium naphthenate base polyurea grease according to the method for embodiment 1, except for the difference that, 1.8kg n-butyl alcohol is replaced For 3.2kg ketone, 1.56kg n-butyric acie and 3.2kg water are replaced with 3.36kg aphthenic acids.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid calcium naphthenate 30.6%；Two polyureas 14.4%；Lubricating base oil 55.0%.

Comparative example 1

Prepare sulfonate with high base number calcio dimerization urea grease, except for the difference that, overbased calcium alkyl-salicylate as described in Example 1 Replacing with the calcium sulfonate with high base number that total base number is 320mgKOH/g, each performance data of grease finished product obtained is shown in Table 1.

In the grease that this comparative example obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfoacid calcium 30.6%； Two polyureas 14.4%；Lubricating base oil 55.0%.

Table 1 each grease properties of sample data

Each indication test method: dropping point: GB/T3498；Drawing cone in-degree: GB/T269；Corrosion: GB/T7326；Anticorrosion Property: GB/T5018；Water drenches number of dropouts: SH/T0109；Stencil oil-dividing: SH/T0324；Tetra-ball machine test: SH/T0202；Ball bearing Lubricating life: ASTM D3336.

Embodiment 1 and comparative example 1 are compared it can be seen that the dropping point of Calcium naphthenate base polyurea grease of the present invention Far above sulfonic acid calcio polyurea grease, water drenches number of dropouts and is much smaller than sulfonic acid calcio polyurea grease, and Stencil oil-dividing value is much smaller than Sulfonic acid calcio polyurea grease, tetra-ball machine test value is more than sulfonic acid calcio polyurea grease, and the bearing lubrication life-span is much larger than sulfonic acid Calcio polyurea grease, illustrates the heat-resisting quantity of Calcium naphthenate base polyurea grease, water-resistance and the adhesiveness of the present invention, colloid Stability, extreme pressure anti-wear, lubricating life are superior to sulfonic acid calcio polyurea grease, and the Calcium naphthenate base polyureas profit of the present invention Consistent lubricant has the performances such as excellent anticorrosive property and resistance to saltfog as sulfonic acid calcio polyurea grease.

Embodiment 1 and embodiment 4 are compared it can be seen that the Calcium naphthenate base polyurea grease of preparation in situ, have There are more preferable heat-resisting quantity, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear；Embodiment 1 is carried out with embodiment 7 Comparison, it can be seen that A class material is prior to the addition of B class material, the Calcium naphthenate base polyurea grease of preparation in transforming agent, has more Heat-resisting quantity, water-resistance and adhesiveness well, colloid stability, and there is longer lubricating life；By embodiment 1 and embodiment 8 compare it can be seen that transforming agent is A, B, C tri-class material, and A class material is ethanol, propanol, butanol and 12-hydroxy stearate At least one in acid, B class material is at least one in acetic acid, propanoic acid and butanoic acid, and C class material is water, the aphthenic acids of preparation Calcio polyurea grease, has more preferable heat-resisting quantity, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear, has Longer lubricating life.

It will be seen from figure 1 that the ν of the calcium carbonate in the overbased calcium alkyl-salicylate of embodiment 2₂Bands of a spectrum are at 1076- 1077cm^-1Left and right, ν₃Bands of a spectrum are 860cm^-1Left and right.Illustrate as amorphous calcium carbonate.

Figure it is seen that containing 1082cm in the infrared spectrum of calcium carbonate in the grease of embodiment 2 preparation^-1Left Right, 855cm^-1Left and right, 700cm^-1Left and right, 713cm^-1The absworption peaks such as left and right, for the characteristic absorption peak of aragonite calcium carbonate, explanation Amorphous calcium carbonate in overbased calcium alkyl-salicylate converts for aragonite calcium carbonate.

From figure 3, it can be seen that embodiment 2 preparation grease in calcium carbonate XRD crystal formation measure, angle 26 °, 27 °, 46 °, 33.5 °, 36 °, 38 °, have intensity peak near 43 °, consistent with aragonite standard spectrogram, after illustrating to convert, sample is deposited At aragonite calcium carbonate.

The Calcium naphthenate base polyurea grease of the present invention, not only as sulfonic acid calcio polyurea grease, has excellent Anticorrosive property and resistance to saltfog, but also have be better than the heat-resisting quantity of sulfonic acid calcio polyurea grease, water-resistance and adhesiveness, The performance such as colloid stability, extreme pressure anti-wear, has longer lubricating life.The preparation of greases technique of the present invention is simple, Environmental protection, low cost, constant product quality.

The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, but, the present invention is not limited to above-mentioned reality Execute the detail in mode, in the technology concept of the present invention, technical scheme can be carried out multiple letter Monotropic type, these simple variant belong to protection scope of the present invention.

It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can The compound mode of energy illustrates the most separately.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this The thought of invention, it should be considered as content disclosed in this invention equally.

Claims (20)

1. a Calcium naphthenate base polyurea grease, it is characterised in that on the basis of grease weight, including following components: 20- The non-newtonian fluid calcium naphthenate of 60 weight %；The polyurea compound of 0.5-25 weight %；The base oil of 25-70 weight %, wherein, The infrared spectrum of described non-newtonian fluid calcium naphthenate has the characteristic absorption peak of aragonite calcium carbonate.

Grease the most according to claim 1, wherein, on the basis of grease weight, including following components: 30-55 weight The non-newtonian fluid calcium naphthenate of amount %；1.5-15 the polyurea compound of weight %；The base oil of 35-60 weight %.

Grease the most according to claim 1 and 2, wherein, described non-newtonian fluid calcium naphthenate is by newton body aphthenic acids Calcium conversion obtains, and its total base number is 250-500mgKOH/g.

Grease the most according to claim 1 and 2, wherein, described polyurea compound is two polyurea compounds.

Grease the most according to claim 4, wherein, described polyurea compound has a structure that

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

Grease the most according to claim 5, wherein, R¹、R^1’It is phenyl or substituted phenyl, or carbon number is the alkane of 8-24 Base or cycloalkyl；R³It is the arlydene of 6-30, alkylidene or cycloalkylidene.

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

8. the preparation method of Calcium naphthenate base polyurea grease described in any one in claim 1-7, it is characterised in that should Method includes: by non-newtonian fluid calcium naphthenate, polyurea compound and part basis oil mix homogeneously, refine at 180-230 DEG C of constant temperature System, cooling, add surplus base oil, add necessary additive, obtain finished product.

9. the preparation method of Calcium naphthenate base polyurea grease described in any one in claim 1-7, it is characterised in that should Method includes:

(1) by newton body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, further Heat up dehydration, then lowers the temperature；

(2) in step (1) products therefrom, add part basis oil and monoamine, add diisocyanate and react；

(3) it is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain finished product.

Preparation method the most according to claim 9, wherein, in step (1), by newton body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, the transforming agent needed for addition reacts, after all transforming agents add, more than 90 DEG C and be less than Equal to 110 DEG C of constant temperature 40-100 minute, it is warming up to 150-170 DEG C of dehydration, is then cooled to 100-120 DEG C.

11. preparation methoies according to claim 9, wherein, in step (2), add part base in the product of step (1) Plinth oil and monoamine, stir 2-8 minute, add diisocyanate, stir 2-8 minute, diisocyanate and the mol ratio of monoamine For 1:2.

12. preparation methoies according to claim 9, wherein, in step (3), first 100-120 DEG C of constant temperature 10-20 minute, Finally it is warmed up to 180-230 DEG C of constant temperature 5-20 minute；It is cooled to 150-160 DEG C, adds surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stirring, circulating filtration, homogenizing, degassing.

13. preparation methoies according to claim 9, wherein, described newton body calcium naphthenate be petroleum naphthenic acid calcium and/or Synthesis calcium naphthenate, its total base number is 250-500mgKOH/g.

14. preparation methoies according to claim 9, wherein, described transforming agent is selected from water, fatty alcohol, aliphatic ether, fat Acid, aphthenic acids, fatty aldehyde, aliphatic ketone, fatty amine, cycloalkanes amine, cyclic alkanol, cycloalkanes ether, carbon dioxide, aromatic alcohol, aromatic amine and At least one in alkyl benzene sulphonate, the addition of transforming agent is the 4-32% of newton body calcium naphthenate weight.

15. preparation methoies according to claim 14, wherein, described transforming agent is A, B, C tri-class material, and A class material is At least one in ethanol, propanol, butanol and 12-hydroxy stearic acid, B class material is at least in acetic acid, propanoic acid and butanoic acid Kind, C class material is water, and the addition of transforming agent is the 15-25% of newton body calcium naphthenate weight.

16. preparation methoies according to claim 15, wherein, A class material adds prior to B class material.

17. preparation methoies according to claim 9, wherein, the structural formula of described monoamine is R¹-NH₂、R^1’-NH₂, wherein, R¹、R^1’It is phenyl or C1-C3 alkyl or the phenyl of halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18.

18. preparation methoies according to claim 17, wherein, described monoamine is selected from aniline, m-chloroaniline, parachloroanilinum And/or the arylamine of para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine and/or the fatty amine of 18-amine..

19. preparation methoies according to claim 9, wherein, the structure of described diisocyanate is OCN-R³-NCO, R³It is Carbon number is the arlydene of 6-30, alkylidene or cycloalkylidene.

20. preparation methoies according to claim 19, wherein, described diisocyanate is selected from toluene di-isocyanate(TDI), first Base diphenyl diisocyanate, 1,6-hexylidene diisocyanate, dicyclohexylmethyl diisocyanate and an xyxylene two At least one in isocyanates.