CN102417853A - Calcium sulfonate octaurea lubricating grease and preparation method thereof - Google Patents
Calcium sulfonate octaurea lubricating grease and preparation method thereof Download PDFInfo
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- CN102417853A CN102417853A CN201010292876XA CN201010292876A CN102417853A CN 102417853 A CN102417853 A CN 102417853A CN 201010292876X A CN201010292876X A CN 201010292876XA CN 201010292876 A CN201010292876 A CN 201010292876A CN 102417853 A CN102417853 A CN 102417853A
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Abstract
The invention provides calcium sulfonate octaurea lubricating grease and a preparation method thereof. The lubricating grease comprises the following components by weight percent: 10-70% of non-Newtonian calcium sulfonate, 0.5-30% of octaurea and 10-80% of lube base oil. The preparation method comprises the following steps of: converting Newtonian calcium sulfonate and reacting with diisocyanate, diamine and monoamine. The lubricating grease has excellent extreme pressure anti-wear property, ultra-long lubricating life, good adhesivity, water resistance, colloid stability, high dropping point, heat stability, corrosion resistance, salt fog resistance and other performances.
Description
Technical field
The present invention relates to lubricant, definite a kind of calcium sulphonate base eight polyurea greases and preparation method thereof of saying so.
Background technology
Calcium sulphonate is used as the purification agent of lubricating oil and the history that rust-preventive agent has decades; Be widely used in the additive of IC engine lubricating oil; Its technical development mainly is to make its high alkalization, is distributed to lime carbonate to become a kind of colloidal dispersion system in the thinning oil with having surface-active alkyl benzene calcium sulfonate or alkyl carboxylic acid calcium exactly.Calcium sulfonate with high base number can be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate according to mode of production difference.Calcium mahogany sulfonate is with oleum or SO
3By product oil sulfonic acid when the sulfonation mineral lubricating oils is produced white oil, warp and Ca (OH)
2Height such as reaction, carbonating alkalizes technology and gets; Calcium alkylbenzenesulfonate is with oleum or SO
3Sulfonation synthetic korenyl, the alkyl benzene sulphonate(ABS) warp of generation and Ca (OH)
2Height such as reaction, carbonating alkalizes technology and gets.
As far back as the 1950's; Sproule etc. are at patent US 2; Ethylsulfonic acid calcium with calcium mahogany sulfonate and lower molecular weight in 535,101 makes calcium sulfonate grease as viscosifying agent multiviscosisty MO by a certain percentage jointly, and dropping point can reach about 205 ℃; High more than general quicklime grease, but thickening ability is less.Six the seventies have patent such as US 3,242 in succession; 079, US 3,376, and 222, US 3; 816,310, US 4,261; 840 grades have reported and have made newton's body calcium sulphonate be transformed into the method for the non-newtonian fluid with thixotropic property, and have introduced the height alkalization technology of calcium sulphonate, have processed the high alkaline calcium sulfonate base grease.But these early stage calcium sulfonate greases are than thickness, and temperature pumping property difference has hindered its application.The eighties mid-term; Muir etc. are at patent US 4; Reported in 560,489 that with the improved overbased Calcium Sulfonate Complex Grease of boric acid, its composition and performance and former complex calcium sulfonate are very different; Not only overcome temperature pumping property difference and aging hardened shortcoming, and had excellent high temperature performance, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion.Hauled oneself willingly into since the market, cause the extensive concern of domestic and international railway grease industry, have the patented technology of high base number composite calcium sulfonate base grease to deliver successively, like US 5,126,062, US 4,597,880, US 5,308,514, US 5,338,467 etc.
The industrial application of complex calcium sulfonate grease still is in the starting stage at home; Domestic also have TP to describe this type preparation of greases method; Wherein CN 1152949 provides a kind of compound method that contains the high base number composite calcium sulfonate base grease of organic carbamide compound, and used organic urea is two polyureas, though performances such as its lubricating life increase than prior art; But character such as extreme pressure anti-wear and prior art difference are little, all are still waiting further raising.
Summary of the invention
The invention provides a kind of calcium sulphonate base eight polyurea greases, it is raw material that this railway grease has adopted calcium mahogany sulfonate or calcium alkylbenzenesulfonate, contains eight polyurea compounds that the reaction of isocyanic ester and amine produces simultaneously.
The present invention also provides above-mentioned preparation of greases method.
Overbased calcium sulphonate base eight polyurea greases provided by the invention are benchmark with railway grease weight, comprise following component:
1) non-newtonian fluid calcium sulphonate 10-70%, preferred 20-60%, most preferably 30-50%;
2) eight polyureas 0.5-30%, preferred 1-20%, most preferably 2-10%;
3) lubricating base oil, 10-80%, preferred 20-70%, most preferably 30-60%.
Said non-newtonian fluid calcium sulphonate is at infrared spectrum 881-886cm
-1The charateristic avsorption band of calcite type calcium carbonate appears in the place, and newton's body calcium sulphonate 862-863cm in infrared spectrum
-1There is the charateristic avsorption band of unformed lime carbonate at the place.The non-newtonian fluid calcium sulphonate is transformed through transforming agent by newton's body calcium sulphonate and obtains, and said newton's body calcium sulphonate is calcium mahogany sulfonate or calcium alkylbenzenesulfonate, and its total basicnumber is 250-450mgKOH/g, preferred 300-400mgKOH/g.
Said eight polyureas have following structure:
R wherein
1Can be alkyl, naphthenic base or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, and is preferred 10～18, and aryl can be phenyl or substituted phenyl, preferred phenyl or C1～C3 alkyl or the substituted phenyl of halogen.
R wherein
2Can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2～12, and is preferred 2～8, and arylidene can be phenylene or biphenylene.
R wherein
3Can be that carbon number is 6～30, preferred 6～20 arylidene, alkylidene group or cycloalkylidene, at least a in preferred tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and the hexylidene.
Said lubricant base can be MO, synthetic oil, vegetables oil or their mixture, and 100 ℃ of kinematic viscosities are 4-60mm
2/ s, preferred 10-30mm
2/ s.Synthetic oil can be poly-a-olefin oil (PAO), ester class oil, alkyl-silicone oil, Fischer-Tropsch synthesis oil etc.
Can also contain various additives in the railway grease of the present invention, like oxidation inhibitor, anti-wear agent rust-preventive agent or the like.The preferred arylamine kind antioxidant of oxidation inhibitor wherein accounts for the 0.1-5% of railway grease gross weight, and preferred 0.2-1% can be pentanoic, PA, di-iso-octyldiphenylamine or their mixture, preferred di-iso-octyldiphenylamine.
The preparation method of said calcium sulphonate base eight polyurea greases comprises:
(1) newton's body calcium sulphonate, part base oil and transforming agent are mixed, heats, treat that the material retrogradation becomes smectic, the dehydration that heats up, cooling;
(2) adding is dissolved in the vulcabond in the part base oil; Adding diamines earlier reacts; Add diamines once more and react, add monoamine at last again and react, the mol ratio of the added vulcabond of each time, diamines, diamines and monoamine is 4: 2: 1: 2;
(3) be warmed up to 200-220 ℃ of constant temperature refining, cooling adds the surplus base oil, adds necessary additive, obtains finished product.
Specifically, in the step (1), newton's body calcium sulphonate, part base oil Hybrid Heating are arrived 50-80 ℃; Add required transforming agent successively and react, preferably add the back at every turn and stirred about 10 minutes, react fully; All transforming agents add the back and heat up, preferably at 80-90 ℃ of constant temperature 60-90 minute, when reaction system is a smectic by the oily retrogradation; Be warming up to 100-120 ℃, preferred 105-110 ℃ of dehydration treated to be cooled to below 105 ℃ after water has taken off.
Said newton's body calcium sulphonate is calcium mahogany sulfonate or calcium alkylbenzenesulfonate, and its total basicnumber is 250-450mgKOH/g, preferred 300-400mgKOH/g.
Said transforming agent is selected from Fatty Alcohol(C12-C14 and C12-C18), lipid acid, alkanone, alkanoic, aliphatic amide, cycloalkanes amine, cycloalkanol, the ether of C1-C5, and boric acid, phosphonic acids; Carbonic acid gas, phenol, aromatic alcohol; Aromatic amine; The C8-C20 alkyl benzene sulphonate(ABS), one or more in the water etc., preferred Witco 1298 Soft Acid, acetic acid and water.The add-on of transforming agent is the 2-30% of newton's body calcium sulphonate weight, preferred 6-22%.
In the step (2); Adding is dissolved in the vulcabond in the part base oil in the product of step (1), stirs, and adds diamines; Reacted 2-8 minute; Added once more diamine reactant 2-8 minute, and added monoamine reaction 2-8 minute, the mol ratio of the added vulcabond of each time, diamines, diamines and monoamine is 4: 2: 1: 2.
Said vulcabond structure is OCN-R
3-NCO, R
3Can be that carbon number is 6～30, preferred 6～20 arylidene, alkylidene group or cycloalkylidene, preferred tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene, hexylidene etc.For example said vulcabond can be tolylene diisocyanate (TDI); Methyldiphenyl group diisocyanate (MDI), hexamethylene vulcabond (HDI); Dicyclohexyl methyl vulcabond (HMDI), or at least a in the xylylene vulcabond (XDI) etc.
Said monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R wherein
1Can be alkyl, naphthenic base or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, and is preferred 10～18, and aryl can be phenyl or substituted phenyl, preferred phenyl or C1～C3 alkyl or the substituted phenyl of halogen.Preferred monoamine can be the arylamine that is selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.
Said diamines can be aliphatic amide or arylamine, and structural formula is NH
2-R
2-NH
2, R wherein
2Can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2～12, and is preferred 2～8, and arylidene can be phenylene or biphenylene.Preferred diamines can be to be selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine and/or be selected from quadrol, tn, 1, the straight-chain fatty amine of 6-hexanediamine.
In the step (3), the product of step 2 is heated up, preferred 100-120 ℃ constant temperature 10-20 minute, be warmed up to 200-220 ℃ of constant temperature 5-10 minute at last; Be cooled to 150-160 ℃, add the surplus lubricating base oil, treat that temperature is cooled to 100-120 ℃, add necessary additive, stir, circulating filtration, homogenizing, the degassing obtain finished product.
The present invention compared with prior art has fabulous extreme pressure anti-wear and overlength lubricating life, simultaneously, also has performances such as good adhesivity, water resisting property, colloid stability, high dropping point, heat-resistant quality, non-corrosibility, resistance to salt(spray)fog.This product preparation process is simple, constant product quality.
Description of drawings
Fig. 1 is the infrared analysis spectrogram of eight polyureas in the railway grease of embodiment 1 preparation.As can be seen from the figure, 3310～3323cm
-1The peak at place is in the eight polyureas molecules-the stretching vibration absorption peak of NH-, and 1630cm
-1The peak at place is in the eight polyureas molecules-vibration absorption peak of CO-.
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of eight polyureas in the railway grease of embodiment 1 preparation.As can be seen from the figure, the peak about δ=155HZ is in the eight polyureas molecules-chemical shift of CO-.
Fig. 3 is the electrospray ionization mass spectrum analysis of spectra of eight polyureas in the railway grease of embodiment 1 preparation.As can be seen from the figure, the mass-to-charge ratio of sample is 1721.4m/z, and the relative molecular mass of this and eight polyurea compounds matches.
The separation method of eight polyureas: elder generation with sherwood oil (60～90 ℃ of boiling points) washing, filters railway grease to obtain deposition, the dilute acetic acid solution immersion that precipitates with 5% is not stopped to stir in 5～10 minutes, to no longer producing CO
2Bubble filters, and filter residue cleans with big water gaging, no longer produces foam to filtrating, and uses rare NaHCO of 1% again
3Solution soaking gained deposition is filtered, and filter residue cleans with big water gaging, to the pH value of filtrating be 7 o'clock, gained precipitates and after drying, promptly gets eight polyureas.
Embodiment
Embodiment 1
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI (1.28kg); 500SN (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
At a volume is that to add the 30kg total basicnumber be that overbased calcium sulphonate and 100 ℃ of kinematic viscosity of 15kg of 400mgKOH/g are 31mm for 110L and have in heating, stirring, circulation, the refrigerative normal-pressure reaction kettle
2The HVI150BS lubricating base oil of/s stirs, and heats to 60 ℃, constant temperature 10 minutes; Add the 2.8kg Witco 1298 Soft Acid, temperature is controlled at about 65 ℃, stirs 10 minutes; The aqueous solution that the acetic acid of adding 0.56kg and acetic acid weight are 4 times stirred 10 minutes; Add 2.32kg boric acid and with 6 times of consoluet BASs of hot water, stir, 80 ℃ of constant temperature 90 minutes, the material retrogradation became smectic; Be warmed up to 110 ℃ under stirring, kept 60 minutes, dehydration; Cooling to 90 ℃ of addings uses 5kg100 ℃ of kinematic viscosity to be 11mm
2The HVI500SN lubricating base oil dissolved 1.28kg MDI of/s stirred 4 minutes fast, stirred fast down to add the 0.15kg quadrol, stirred 4 minutes; Stir fast and add the 0.08kg quadrol down once more; Stirred 4 minutes, and added the 0.69kg stearylamine and stirred 4 minutes, the mol ratio of added successively MDI, quadrol, quadrol and stearylamine is 4: 2: 1: 2; 120 ℃ of constant temperature 20 minutes is warmed up to 200 ℃ of constant temperature 5 minutes at last.Then, be cooled to 160 ℃, add 28kg lubricating base oil 500SN; Treat that temperature is cooled to 110 ℃, after adding 0.2kg stirred 10 minutes to right-di-iso-octyldiphenylamine, circulating filtration, homogenizing, the degassing obtained finished product.Assay is seen table 1.
In the railway grease that present embodiment obtains, be benchmark, consist of: non-newtonian fluid calcium sulphonate 41.3% with railway grease weight; Eight polyureas 2.6%; Lubricating base oil 55.9%; To right-di-iso-octyldiphenylamine 0.2%.
The eight polyureas molecular structural formulas that contain in the component are:
Embodiment 2
Feed composition: (total basicnumber is 420mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI (1.28kg); 500SN (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases, and the total basicnumber of the different overbased calcium sulphonate that is to use is 420mgKOH/g, and each performance data of railway grease finished product that obtains is seen table 1.
Embodiment 3
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Laurylamine (0.52kg) 0.6%; Quadrol (0.26kg); MDI (1.42kg); 500SN (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases, and the different aliphatic amides that are to use are laurylamine, and each performance data of railway grease finished product that obtains is seen table 1.
Embodiment 4
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg; Quadrol (0.28kg); TDI (1.08kg); 500SN (33kg); PA (0.2kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases, and the different vulcabond that is to use is tolylene diisocyanate (TDI), and oxidation inhibitor is PA, and each performance data of railway grease finished product that obtains is seen table 1.
Embodiment 5
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg; Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI (1.28kg); 500SN (7kg); To right-di-iso-octyldiphenylamine (0.4kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases; The amount of different is 500SN is 7kg; Thereby make each material rate take place than about-face, that uses in addition is 0.4kg to right-di-iso-octyldiphenylamine, and each performance data of railway grease finished product that obtains is seen table 1.
In the railway grease that present embodiment obtains, be benchmark, consist of: non-newtonian fluid calcium sulphonate 59.0% with railway grease weight; Eight polyureas 3.7%; Lubricating base oil 36.6%; To right-di-iso-octyldiphenylamine 0.7%.
Embodiment 6
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (2.07kg); Quadrol (0.69kg; MDI (3.84kg); 500SN (28.6kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases; The consumption of different is stearylamine, quadrol, MDI and 500SN changes to some extent; The weight fraction of eight polyureas that reaction generates is 7.6%, and each performance data of railway grease finished product that obtains is seen table 1.
In the railway grease that present embodiment obtains, be benchmark, consist of: non-newtonian fluid calcium sulphonate 41.5% with railway grease weight; Eight polyureas 7.6%; Lubricating base oil 50.7%; To right-di-iso-octyldiphenylamine 0.2%.
Embodiment 7
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); PAO 40 (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg; Quadrol (0.23kg); MDI (1.28kg); PAO 10 (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases, and (100 ℃ of kinematic viscosity are 11mm to the different full synthetic oil poly & Alpha ,-olefin oil PAO 10 that is to use
2/ s) (100 ℃ of kinematic viscosity are 41mm with PAO 40
2/ s) replacing 500SN and 150BS respectively, each performance data of railway grease finished product that obtains is seen table 1.
Embodiment 8
Feed composition: (total basicnumber is 320mgKOH/g to calcium sulfonate with high base number, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI (1.28kg); 500SN (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares calcium sulfonate with high base number base eight polyurea greases, and the total basicnumber of the different calcium sulfonate with high base number that is to use is 320mgKOH/g, and each performance data of railway grease finished product that obtains is seen table 1.
Embodiment 9
Feed composition: (total basicnumber is 360mgKOH/g to calcium sulfonate with high base number, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI (1.28kg); 500SN (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares calcium sulfonate with high base number base eight polyurea greases, and the total basicnumber of the different calcium sulfonate with high base number that is to use is 360mgKOH/g, and each performance data of railway grease finished product that obtains is seen table 1.
Embodiment 10
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.78kg); 1,6-hexanediamine (0.34kg); MDI (1.08kg); 500SN (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases, and different is to use 1, and the 6-hexanediamine replaces quadrol, and each performance data of railway grease finished product that obtains is seen table 1.
Embodiment 11
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.79kg); Ursol D (0.32kg); MDI (1.10kg); 500SN (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases, and the different Ursol D that are to use replace quadrol, and each performance data of railway grease finished product that obtains is seen table 1.
Embodiment 12
Feed composition: (total basicnumber is 400mgKOH/g to overbased calcium sulphonate, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI (1.28kg); 500SN (33kg).
Method by instance 1 prepares overbased calcium sulphonate base eight polyurea greases, and different is not add oxidation inhibitor to right-di-iso-octyldiphenylamine, and each performance data of railway grease finished product that obtains is seen table 1.
In the railway grease that present embodiment obtains, be benchmark, consist of: non-newtonian fluid calcium sulphonate 41.5% with railway grease weight; Eight polyureas 2.6%; Lubricating base oil 55.9%.
Comparative Examples 1
Feed composition: (total basicnumber is 320mgKOH/g to calcium sulfonate with high base number, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); 500SN (35.2kg); To right-di-iso-octyldiphenylamine (0.2kg).
At a volume is that to add the 30kg total basicnumber be that calcium sulfonate with high base number and 100 ℃ of kinematic viscosity of 15kg of 320mgKOH/g are 31mm for 110L and have in heating, stirring, circulation, the refrigerative normal-pressure reaction kettle
2The HVI150BS lubricating base oil of/s stirs, and heats to 60 ℃, constant temperature 10 minutes; Add the 2.8kg Witco 1298 Soft Acid, temperature is controlled at about 65 ℃, stirs 10 minutes; The aqueous solution that the acetic acid of adding 0.56kg and acetic acid weight are 4 times stirred 10 minutes; Add 2.32kg boric acid and with 6 times of consoluet BASs of hot water, stir, 80 ℃ of constant temperature 90 minutes, the material retrogradation became smectic; Be warmed up to 110 ℃ under stirring, kept 60 minutes, dehydration; Be warmed up to 200 ℃ of constant temperature 5 minutes at last.Be cooled to 160 ℃, add 35.2kg lubricating base oil 500SN; Treat that temperature is cooled to 110 ℃, after adding 0.2kg stirred 10 minutes to right-di-iso-octyldiphenylamine, circulating filtration, homogenizing, the degassing obtained finished product.Assay is seen table 1.
Comparative Examples 2
Feed composition: (total basicnumber is 320mgKOH/g to calcium sulfonate with high base number, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI (0.7kg); 500SN (33kg); To right-di-iso-octyldiphenylamine (0.2kg).
Method by instance 1 prepares calcium sulfonate with high base number base two polyurea greases, and the total basicnumber of newton's body calcium sulphonate is 320mgKOH/g and does not contain diamines in the reactant, and each performance data of railway grease finished product that obtains is seen table 1.
Each railway grease properties of sample data of table 1
Continuous table
Claims (22)
1. calcium sulphonate base eight polyurea greases are benchmark with railway grease weight, comprise following component:
1) non-newtonian fluid calcium sulphonate 10-70%; 2) eight polyureas 0.5-30%; 3) lubricating base oil, 10-80%.
2. according to the described railway grease of claim 1, be benchmark wherein, comprise following component with railway grease weight:
1) non-newtonian fluid calcium sulphonate 20-60%; 2) eight polyureas 1-20%; 3) lubricating base oil 20-70%.
3. according to the described railway grease of claim 1, wherein said non-newtonian fluid calcium sulphonate is transformed by newton's body calcium sulphonate and obtains, and its total basicnumber is 250-450mgKOH/g.
4. according to the described railway grease of claim 1, said newton's body calcium sulphonate is calcium mahogany sulfonate or calcium alkylbenzenesulfonate, and its total basicnumber is 300-400mgKOH/g.
5. according to the described railway grease of claim 1, wherein, said eight polyureas have following structure:
Wherein, R
1Be alkyl, naphthenic base or aryl, R
2Be alkylidene group or arylidene, R
3Be arylidene, alkylidene group or cycloalkylidene.
6. according to the described railway grease of claim 5, wherein, R
1Be phenyl or substituted phenyl, or carbon number is 8～24 alkyl or cycloalkyl; R
2Be that phenylene or biphenylene or carbon number are 2～12 alkylidene group; R
3Be that carbon number is 6～30 arylidene, alkylidene group or cycloalkylidene.
7. according to the described railway grease of claim 6, wherein, R
1Be phenyl or C1～C3 alkyl or the substituted phenyl of halogen, or carbon number is 10～18 alkyl or cycloalkyl, R
2Be phenylene or biphenylene, or carbon number is 2～8 alkylidene group; R
3Be selected from least a in tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and the hexylidene.
8. the preparation method of said calcium sulphonate base eight polyurea greases of one of claim 1～7 comprises:
(1) newton's body calcium sulphonate, part base oil and transforming agent are mixed, heats, treat that the material retrogradation becomes smectic, the dehydration that heats up, cooling;
(2) adding is dissolved in the vulcabond in the part base oil; Adding diamines earlier reacts; Add diamines once more and react, add monoamine at last again and react, the mol ratio of the added vulcabond of each time, diamines, diamines and monoamine is 4: 2: 1: 2;
(3) be warmed up to 200-220 ℃ of constant temperature refining, cooling adds the surplus base oil, adds necessary additive, obtains finished product.
9. according to the described preparation method of claim 8, in the step (1), newton's body calcium sulphonate, part base oil Hybrid Heating are arrived 50-80 ℃; Adding required transforming agent successively reacts; All transforming agents add the back and heat up, at 80-90 ℃ of constant temperature 60-90 minute, when the reaction system retrogradation is a smectic; Be warming up to 100-120 ℃ of dehydration, treat that water has taken off the back cooling.
10. according to the described preparation method of claim 8, in the step (2), adding is dissolved in the vulcabond in the part base oil in the product of step (1), adds diamines, reacts 2-8 minute, adds once more diamine reactant 2-8 minute, adds monoamine reaction 2-8 minute,
11. according to the described preparation method of claim 8, in the step (3), the product intensification to step 2 at 100-120 ℃ of constant temperature 10-20 minute, is warmed up to 200-220 ℃ of constant temperature 5-10 minute at last; Be cooled to 150-160 ℃, add the surplus lubricating base oil, treat that temperature is cooled to 100-120 ℃, add necessary additive, stir circulating filtration, homogenizing, the degassing.
12. according to the described preparation method of claim 8, said newton's body calcium sulphonate is calcium mahogany sulfonate or calcium alkylbenzenesulfonate, its total basicnumber is 250-450mgKOH/g.
13. according to the described preparation method of claim 8; Said transforming agent is selected from Fatty Alcohol(C12-C14 and C12-C18), lipid acid, alkanone, alkanoic, aliphatic amide, cycloalkanes amine, cycloalkanol, the ether of C1-C5; And in the boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate(ABS), water one or more, the add-on of transforming agent is the 2-30% of newton's body calcium sulphonate weight.
14. according to the described preparation method of claim 8, said transforming agent is selected from Witco 1298 Soft Acid, acetic acid, water, the add-on of transforming agent is the 6-22% of newton's body calcium sulphonate weight.
15. according to the described preparation method of claim 8, wherein, said monoamine structural formula is R
1-NH
2, R wherein
1Be alkyl, naphthenic base or aryl, the carbon number of alkyl or cycloalkyl is 8～24, and aryl is phenyl or substituted phenyl.
16. according to the described preparation method of claim 15, R wherein
1Be phenyl or C1～C3 alkyl or the substituted phenyl of halogen, or carbon number is 10～18 alkyl or cycloalkyl.
17. according to the described preparation method of claim 8, wherein, said monoamine is the arylamine that is selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide and/or para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.
18. according to the described preparation method of claim 8, wherein, said diamines structural formula is NH
2-R
2-NH
2, R wherein
2Be alkylidene group or arylidene, the carbon number of alkylidene group is 2～12, and arylidene is phenylene or biphenylene.
19. according to the described preparation method of claim 8, wherein, said diamines is selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine, and/or be selected from quadrol, tn, 1, the straight-chain fatty amine of 6-hexanediamine.
20. according to the described preparation method of claim 8, wherein, said vulcabond structure is OCN-R
3-NCO, R
3Be that carbon number is 6～30 arylidene, alkylidene group or cycloalkylidene.
21. according to the described preparation method of claim 20, wherein, R
3Be that carbon number is 6～20 arylidene, alkylidene group or cycloalkylidene.
22. according to the described preparation method of claim 8, wherein, said vulcabond is selected from tolylene diisocyanate; The methyldiphenyl group diisocyanate, the hexamethylene vulcabond; Dicyclohexyl methyl vulcabond, or at least a in the xylylene vulcabond.
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| CN103571588A (en) * | 2012-07-30 | 2014-02-12 | 中国石油化工股份有限公司 | Calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof |
| CN104450113A (en) * | 2013-09-13 | 2015-03-25 | 中国石油化工股份有限公司 | High-base number composite calcium-based urea octamer grease and preparation method thereof |
| CN104450116A (en) * | 2013-09-13 | 2015-03-25 | 中国石油化工股份有限公司 | Calcium sulfonate-calcium naphthenate-based urea octamer grease and preparation method thereof |
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| CN104560318A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Calcium naphthenate zirconium-based hexurea lubricating grease and preparation method thereof |
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| CN104560318A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Calcium naphthenate zirconium-based hexurea lubricating grease and preparation method thereof |
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