CN104212610B

CN104212610B - A kind of calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof

Info

Publication number: CN104212610B
Application number: CN201310214066.6A
Authority: CN
Inventors: 孙洪伟; 郑会; 董禄虎; 何懿峰; 段庆华; 张建荣; 陈政; 刘中其; 姜靓
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: 2013-05-31
Filing date: 2013-05-31
Publication date: 2016-08-10
Anticipated expiration: 2033-05-31
Also published as: CN104212610A

Abstract

The invention discloses a kind of calcium naphthenate-based tetrapolyurea lubricating 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, and described polyurea compound is four polyurea compounds.The invention also discloses the preparation method of calcium naphthenate-based tetrapolyurea lubricating grease and the calcium naphthenate-based tetrapolyurea lubricating grease of preparation thereof.The calcium naphthenate-based tetrapolyurea lubricating grease of the present invention, there is excellent anticorrosive property and resistance to saltfog, but also there is performances such as being better than the heat-resisting quantity of calcium sulfonate tetra-polyurea lubricating 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-based tetrapolyurea lubricating grease and preparation method thereof

Technical field

The present invention relates to grease, in particular it relates to a kind of calcium naphthenate-based tetrapolyurea lubricating 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, and described polyurea compound is four polyureas chemical combination Thing.The performance of this grease is similar with sulfonate with high base number grease of calcium, 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-based tetrapolyurea lubricating grease, It is characterized in that, on the basis of grease weight, including following components: the non-newtonian fluid calcium naphthenate of 20-60 weight %；0.5- The polyurea compound of 25 weight %；The base oil of 25-70 weight %, wherein, the infrared spectrum tool of described non-newtonian fluid calcium naphthenate Having the characteristic absorption peak of aragonite calcium carbonate, described polyurea compound is four polyurea compounds.

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

Second aspect, the invention provides the preparation method of calcium naphthenate-based tetrapolyurea lubricating grease as above, and it is special Levying and be, the method includes: by non-newtonian fluid calcium naphthenate, four polyurea compounds and part basis oil mix homogeneously, at 180- 230 DEG C of constant temperature refinings, cooling, add surplus base oil, add necessary additive, obtain finished product.

The third aspect, the invention provides the preparation method of a kind of calcium naphthenate-based tetrapolyurea lubricating grease, it is characterised in that The 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 diisocyanate, be then sequentially added into diamidogen and list Amine 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.

Fourth aspect, the invention provides the calcium naphthenate-based tetrapolyurea lubricating grease prepared by method as above.

The calcium naphthenate-based tetrapolyurea lubricating grease of the present invention, not only as calcium sulfonate tetra-polyurea lubricating grease, has excellent Good anticorrosive property and resistance to saltfog, but also have be better than the heat-resisting quantity of calcium sulfonate tetra-polyurea lubricating grease, water-resistance and The performances such as adhesiveness, colloid stability, extreme pressure anti-wear, have longer lubricating life.The preparation of greases work of the present invention Skill is simple and environmentally-friendly, 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-based tetrapolyurea lubricating grease, this grease have employed petroleum naphthenic acid calcium or Synthesis calcium naphthenate is raw material, contains isocyanates and four polyurea compounds 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-based tetrapolyurea lubricating grease, 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 of 25-70 weight % Plinth oil, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the characteristic absorption peak of aragonite calcium carbonate, described polyureas Compound is four polyurea compounds.

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 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 be 6- 30, preferably 6-20, R³More preferably Extremely Few one.

Above-mentioned four polyurea compounds can use the thinkable various methods of those skilled in the art institute to obtain, the most permissible The method recorded according to CN103060070A 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-based tetrapolyurea lubricating grease as above, the party Method includes: by non-newtonian fluid calcium naphthenate, four polyurea compounds 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.

In the present invention, for non-newtonian fluid calcium naphthenate, four polyurea compounds 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 side of calcium naphthenate-based tetrapolyurea lubricating grease as above Method, including:

(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.

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 diisocyanate, is then sequentially added into Diamidogen and monoamine react, and are i.e. to prepare four polyurea compounds in step (1) products therefrom.

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, part basis oil and diisocyanate can be added in step (1) products therefrom, stir 2-8 minute, add two Amine, stirs 2-8 minute, adds monoamine, stirs 2-8 minute, and diisocyanate, diamidogen are 2:1:2 with the mol ratio of monoamine.

Described diisocyanate structure is OCN-R³-NCO, R³Can be carbon number be 6-30, preferably 6-20 arlydene, Alkylidene or cycloalkylidene, be preferably Such as Described diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), hexamethylene Diisocyanate (HDI), in dicyclohexylmethyl diisocyanate (HMDI) and an xylylene diisocyanate (XDI) etc. 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 Four polyurea greases.

Compared with the calcium naphthenate-based tetrapolyurea lubricating grease that the preparation method provided by second aspect prepares, the third aspect carries The calcium naphthenate-based tetrapolyurea lubricating grease that the preparation method of confession prepares has more preferable heat-resisting quantity, water-resistance and adhesiveness, glue Body stability 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-based tetrapolyurea lubricating 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 7.15kg MDI that HVI500SN lubricating base oil dissolves, stirs 6 minutes, adds 0.86kg ethylenediamine, stirs 6 minutes, adds 5kg100 DEG C of kinematic viscosity is 11mm²The 7.69kg 18-amine. that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, and 120 DEG C 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, adds HVI500SN lubrication base Oil 15kg；Treating 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 30.6%；Four polyureas 14.4%；Lubricating base oil 55.0%.

Embodiment 2

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 0.45kg HDI that sliding base oil dissolves, stirs 2 minutes, adds 0.15kg p-phenylenediamine, stirs 2 minutes, addition 5kg100 DEG C kinematic viscosity is 11mm²The 0.5kg lauryl amine that the HVI500SN lubricating base oil of/s dissolves, stirs 2 minutes, 110 DEG C of constant temperature 15 minutes, finally it is warmed up to 180 DEG C of constant temperature 20 minutes.Then, it is cooled to 150 DEG C, adds HVI500SN lubricating base oil 10kg； Treating that temperature is cooled to 100 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 50.2%；Four polyureas 1.5%；Lubricating base oil 48.3%.

Embodiment 3

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 3.74kg XDI, stir 8 minutes, addition 0.74kg propane diamine, stir 8 minutes, add Entering with 3kg100 DEG C of kinematic viscosity is 11mm²The 2.13kg para-totuidine that the HVI500SN lubricating base oil of/s dissolves, stirs 8 points Clock, 100 DEG C of constant temperature 10 minutes, finally it is warmed up to 230 DEG C of constant temperature 5 minutes.Then, it is cooled to 155 DEG C, adds HVI500SN lubrication Base oil 6kg；Treating that temperature is cooled to 120 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 40.7%；Four polyureas 8.0%；Lubricating base oil 51.3%.

Embodiment 4

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 7.15kgMDI that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, adds 0.86kg second Diamidogen, stirs 6 minutes, and adding 5kg100 DEG C of kinematic viscosity is 11mm²The 7.69kg that the HVI500SN lubricating base oil of/s dissolves 18-amine., stirs 6 minutes, 120 DEG C of constant temperature 20 minutes, obtains four polyureas.

Four 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.

Embodiment 5

Prepare calcium naphthenate-based tetrapolyurea lubricating 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.

Embodiment 6

Prepare calcium naphthenate-based tetrapolyurea lubricating grease according to the method for embodiment 1, except for the difference that, 1.8kg n-butyl alcohol is replaced It is changed to 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.

Comparative example 1

Prepare sulfonate with high base number calcio four polyurea 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%； Four 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 lubricates Life-span: ASTM D3336.

Embodiment 1 and comparative example 1 are compared it can be seen that the dripping of calcium naphthenate-based tetrapolyurea lubricating grease of the present invention Point is far above calcium sulfonate tetra-polyurea lubricating grease, and water drenches number of dropouts much smaller than calcium sulfonate tetra-polyurea lubricating grease, Stencil oil-dividing value Much smaller than calcium sulfonate tetra-polyurea lubricating grease, tetra-ball machine test value is more than calcium sulfonate tetra-polyurea lubricating grease, bearing lubrication life-span Much larger than calcium sulfonate tetra-polyurea lubricating grease, the heat-resisting quantity of the calcium naphthenate-based tetrapolyurea lubricating grease of the present invention, water resistant are described Property and adhesiveness, colloid stability, extreme pressure anti-wear, lubricating life are superior to calcium sulfonate tetra-polyurea lubricating grease, and the present invention Calcium naphthenate-based tetrapolyurea lubricating grease there is as calcium sulfonate tetra-polyurea lubricating grease excellent anticorrosive property and salt fog resistance The performances such as property.

Embodiment 1 and embodiment 4 are compared it can be seen that the calcium naphthenate-based tetrapolyurea lubricating grease of preparation in situ, There is more preferable heat-resisting quantity, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear, and there is the longer lubrication longevity Life；Embodiment 1 and embodiment 5 are compared it can be seen that A class material adds prior to B class material in transforming agent, the ring of preparation Alkanoic acid calcio four polyurea grease, has more preferable water-resistance and adhesiveness, colloid stability, and has the longer lubrication longevity Life；Embodiment 1 and embodiment 6 are compared it can be seen that transforming agent is A, B, C tri-class material, A class material be ethanol, third At least one in alcohol, butanol and 12-hydroxy stearic acid, B class material is at least one in acetic acid, propanoic acid and butanoic acid, C class thing Matter is water, the calcium naphthenate-based tetrapolyurea lubricating grease of preparation, has more preferable heat-resisting quantity, water-resistance and adhesiveness, colloid peace Qualitative and extreme pressure anti-wear, and there is 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 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

1. a calcium naphthenate-based tetrapolyurea lubricating 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 %, its In, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the characteristic absorption peak of aragonite calcium carbonate, described polyurea compound It is four polyurea compounds.

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 %；Four polyurea compounds of 1.5-15 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 four polyurea compounds have a structure that

Wherein, R¹It is alkyl, cycloalkyl or aryl, R²It is alkylidene or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.

Grease the most according to claim 4, wherein, R¹Phenyl or substituted phenyl, or alkyl that carbon number is 8-24 or Cycloalkyl；R²It is phenylene or biphenylene or carbon number is the alkylidene of 2-12；R³Be carbon number be the arlydene of 6-30, alkylidene Or cycloalkylidene.

Grease the most according to claim 5, wherein, R¹It is phenyl or C1-C3 alkyl or the phenyl of halogen substiuted, or carbon Number is the alkyl or cycloalkyl of 10-18, R²It is phenylene or biphenylene, or carbon number is the alkylidene of 2-8；R³It is selected from With-(CH₂)₆At least one in-.

7. the preparation method of calcium naphthenate-based tetrapolyurea lubricating grease described in any one in claim 1-6, it is characterised in that The method includes: by non-newtonian fluid calcium naphthenate, four polyurea compounds and part basis oil mix homogeneously, 180-230 DEG C of perseverance Temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.

8. the preparation method of calcium naphthenate-based tetrapolyurea lubricating grease described in any one in claim 1-6, it is characterised in that The 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 diisocyanate, be then sequentially added into diamidogen and monoamine enters Row reaction；

(3) step (2) reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add Enter the additive of necessity, obtain finished product.

Preparation method the most according to claim 8, 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.

Preparation method the most according to claim 8, wherein, in step (2), adds part base in the product of step (1) Plinth oil and diisocyanate, stir 2-8 minute, adds diamidogen, stirs 2-8 minute, adds monoamine, stirs 2-8 minute, two isocyanides Acid esters, diamidogen are 2:1:2 with the mol ratio of monoamine.

11. preparation methoies according to claim 8, 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.

12. preparation methoies according to claim 8, wherein, described newton body calcium naphthenate be petroleum naphthenic acid calcium and/or Synthesis calcium naphthenate, its total base number is 250-500mgKOH/g.

13. preparation methoies according to claim 8, 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.

14. preparation methoies according to claim 13, 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.

15. preparation methoies according to claim 14, wherein, A class material adds prior to B class material.

16. preparation methoies according to claim 8, wherein, the structural formula of described monoamine is R¹-NH₂, wherein, R¹It it is phenyl Or C1-C3 alkyl or the phenyl of halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18.

17. preparation methoies according to claim 16, 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..

18. preparation methoies according to claim 8, wherein, the structural formula of described diamidogen is NH₂-R²-NH₂, wherein, R²It is Carbon number is the alkylidene of 2-8, or phenylene or biphenylene.

19. preparation methoies according to claim 18, wherein, described diamidogen be selected from p-phenylenediamine, o-phenylenediamine, 4,4- The aromatic amine of benzidine and/or selected from ethylenediamine, propane diamine, the straight-chain fatty amine of 1,6-hexamethylene diamine.

20. preparation methoies according to claim 8, wherein, the structure of described diisocyanate is OCN-R³-NCO, R³It is Carbon number is the arlydene of 6-30, alkylidene or cycloalkylidene.

21. preparation methoies according to claim 20, 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.