CN102453600B - Composite calcium sulfonate-based hexaurea grease - Google Patents
Composite calcium sulfonate-based hexaurea grease Download PDFInfo
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Abstract
The invention provides composite calcium sulfonate-based hexaurea grease and a preparation method thereof. The composite calcium sulfonate-based hexaurea grease comprises: by weight, 10 to 70% of non-Newtonian calcium sulfonate, 1 to 10% of higher fatty acid calcium, 1 to 15% of low-molecular inorganic acid calcium or organic acid calcium, 0.5 to 30% of hexaurea, and 10 to 80% of lubricating base oil. The composite calcium sulfonate-based hexaurea grease is characterized in that petroleum calcium sulfonate or synthetic calcium sulfonate is utilized as a raw material and the composite calcium sulfonate-based hexaurea grease also contains a composite calcium densifier and a hexaurea compound. The composite calcium sulfonate-based hexaurea grease has excellent extreme pressure abrasion resistance, a very long lubricating life, excellent adhesiveness, good water resistance, colloid stability, a high dropping point, thermal stability, corrosion resistance, and salt spray resistance.
Description
Technical field
The present invention relates to lubricant, definite a kind of complex calcium sulfonate base six polyurea greases and preparation method thereof that say.
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 internal combustion (IC) engine lubricating oil, its technical development is mainly to make its high alkalization, exactly calcium carbonate is distributed to and in thinning oil, becomes a kind of colloidal dispersion system with having surface-active alkyl benzene calcium sulfonate or alkyl carboxylic acid calcium.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 sulfonation mineral lubricating oils is produced white oil, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtaining; Calcium alkylbenzenesulfonate is with oleum or SO
3the alkylbenzene that sulfonation is synthetic, alkyl benzene sulphonate (ABS) warp and Ca (OH) of generation
2reaction, the contour alkalization technology of carbonating and obtaining.
As far back as the 1950's, Sproule etc. are at patent US2,535, the ethylsulfonic acid calcium of calcium mahogany sulfonate and lower molecular weight of usining in 101 makes calcium sulfonate grease as viscosifying agent multiviscosisty mineral oil by a certain percentage jointly, dropping point can reach 205 ℃ of left and right, high more than general quicklime grease, but thickening ability is less.Six the seventies, in succession there is patent as US3,242,079, US3,376,222, US3,816,310, US4,261,840 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 made high alkaline calcium sulfonate base grease.But these early stage calcium sulfonate greases are compared with thickness, temperature pumping is poor has hindered its application.The eighties mid-term, Muir etc. are at patent US4,560, in 489, reported by 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 the shortcoming of the poor and aging sclerosis of temperature pumping, and there is excellent high temperature performance, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion.Since putting goods on the market, cause the extensive concern of domestic and international lubricating grease industry, there is successively the patented technology of high base number composite calcium sulfonate base grease to deliver, as US5,126,062, US4,597,880, US5,308,514, US5,338,467 etc.
The industrial application of complex calcium sulfonate grease is still in the starting stage at home, domestic also have technical literature to describe this class preparation of greases method, wherein CN1152949 provides a kind of synthetic method of the high base number composite calcium sulfonate base grease containing organic carbamide compound, organic urea used is two polyureas, although the performances such as its lubricating life increase compared with prior art, but the performances such as extreme pressure anti-wear and prior art difference are little, all need further raising.
Summary of the invention
The invention provides a kind of complex calcium sulfonate base six polyurea greases, it is raw material that this lubricating grease has adopted calcium mahogany sulfonate or calcium alkylbenzenesulfonate, contains composite calcium viscosifying agent and six polyurea compounds simultaneously.
The present invention also provides above-mentioned preparation of greases method.
Calcium sulphonate base six polyurea greases provided by the invention, take lubricating grease weight as benchmark, comprise following component:
1) non-newtonian fluid calcium sulphonate 10-70%, preferably 20-60%, most preferably 30-55%;
2) higher fatty acid calcium 1-10%, preferably 2-6%, most preferably 2.2-4.2%;
3) small molecules mineral acid calcium or calcium of organic acid 1-15%, preferably 2-10%, most preferably 3-8%;
4) six polyureas 0.5-30%, preferably 1-20%, most preferably 2-10%;
5) lubricating base oil, 10-80%, preferably 20-70%, most preferably 30-60%.
Described non-newtonian fluid calcium sulphonate is at infrared spectrum 881-886cm
-1there is the charateristic avsorption band of calcite type calcium carbonate in place, and newton's body calcium sulphonate 862-863cm in infrared spectrum
-1there is the charateristic avsorption band of unformed calcium carbonate at place.Non-newtonian fluid calcium sulphonate is transformed and is obtained by transforming agent by newton's body calcium sulphonate, and described newton's body calcium sulphonate is calcium mahogany sulfonate or calcium alkylbenzenesulfonate, and its total basicnumber is 250-450mgKOH/g, preferably 300-400mgKOH/g.
Said higher fatty acid calcium is that carbon number is 8-20, straight chain fatty acid calcium or the hydroxy fatty acid calcium of preferred 10-16, one or more mixtures in calcium laurate, calcium palmitate, calcium stearate, 12-oxystearic acid calcium, eicosyl calcium carboxylates for example, preferably 12-oxystearic acid calcium.
Mineral acid or organic acid molecular weight in said small molecules mineral acid calcium or calcium of organic acid are less than or equal to 150, can be one or more the mixture in lime acetate, oxalic acid calcium, calcium propionate, propanedioic acid calcium, Calcium Butyrate, calcium succinate, lime borate, calcium phosphate, calcium sulfate etc., preferred boric acid calcium and/or calcium phosphate.
Described six polyureas have following structure:
R wherein
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, preferably 10～18, and aryl can be the phenyl of phenyl or replacement, the phenyl that preferably phenyl or C1～C3 alkyl or halogen replace.
R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2～12, preferably 2～8, and arylidene can be phenylene or biphenylene.
R wherein
3can be that carbon number is 6～30, preferably 6～20 arylidene, alkylidene group or cycloalkylidene, preferably at least one in tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and hexylidene.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 ℃ of kinematic viscosities are 4-60mm
2/ s, preferably 10-30mm
2/ s.Synthetic oil can be poly & Alpha ,-olefin oil (PAO), ester class oil, alkyl-silicone oil, Fischer-Tropsch synthesis oil etc.
In lubricating grease of the present invention, can also contain various additives, as oxidation inhibitor, anti-wear agent rust-preventive agent etc.The preferred arylamine kind antioxidant of oxidation inhibitor wherein, accounts for the 0.1-5% of lubricating grease gross weight, and preferably 0.2-1%, can be pentanoic, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or their mixture, preferably di-iso-octyldiphenylamine.
The preparation method of described complex calcium sulfonate base six polyurea greases, comprising:
(1) newton's body calcium sulphonate, part base oil and transforming agent are mixed, heated, make material retrogradation become smectic;
(2) add lime or calcium hydroxide, add respectively higher fatty acid and small molecules acid, cooling after the dehydration that heats up;
(3) add the vulcabond being dissolved in part base oil, add successively monoamine to react, add diamines to react again, then add vulcabond to react, wherein the mol ratio of each added vulcabond, monoamine, diamines and vulcabond is 2:2:2:1;
(4) be warmed up to 200-220 ℃ of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
Specifically, in step (1), newton's body calcium sulphonate, part base oil Hybrid Heating are arrived to 50-90 ℃, preferably constant temperature 10-30 minute, adds required transforming agent to react successively, preferably adds rear stirring about 10 minutes at every turn, react fully, all transforming agents add rear intensification, preferably at 85-100 ℃ of constant temperature 0.5-3 hour, make material retrogradation become smectic.
Described newton's body calcium sulphonate is calcium mahogany sulfonate or calcium alkylbenzenesulfonate, its total basicnumber 250-450mgKOH/g, preferably 300-400mgKOH/g.
Described transforming agent is selected from fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, cycloalkanes amine, cycloalkanol, the ether of C1-C5, and boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate (ABS), one or more in water etc., preferably 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, preferably 6-22%.
In step (2), at 85-100 ℃ of suspension liquid that adds lime or calcium hydroxide, at 85-100 ℃, add higher fatty acid, stir 5-20 minute, add small molecules mineral acid or organic acid, stir 5-20 minute, be warmed up to 105-120 ℃, preferably keep 30-60 minute, dehydration, cools to 90-105 ℃;
Said higher fatty acid is that carbon number is 8-20, preferably straight chain fatty acid or the hydroxy fatty acid of 10-16, for example one or more mixtures in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, preferably 12-oxystearic acid.
Said small molecules mineral acid or organic acid molecular weight are less than or equal to 150, can be one or more mixture, preferred boric acid and/or the phosphoric acid in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid, boric acid, phosphoric acid, sulfuric acid etc.
Higher fatty acid and small molecules mineral acid are or/and organic acid H
+the OH that total amount of substance and calcium hydroxide are contained
-total amount of substance equates.
In step (3), in the product of step (2), add successively the vulcabond being dissolved in part base oil, stir, add monoamine, reaction 2-8 minute, adds diamine reactant 2-8 minute, then adds the vulcabond being dissolved in part base oil, reaction 2-8 minute, the mol ratio of each added vulcabond, monoamine, diamines and vulcabond is 2:2:2:1.
Said vulcabond structure is OCN-R
3-NCO, R
3can be that carbon number is 6～30, preferably 6～20 arylidene, alkylidene group or cycloalkylidene, preferred tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene, hexylidene etc.For example described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl group diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), dicyclohexyl methyl vulcabond (HMDI), or at least one in an 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, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, preferably 10～18, and aryl can be the phenyl of phenyl or replacement, the phenyl that preferably phenyl or C1～C3 alkyl or halogen replace.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, preferably 2～8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from the aromatic amine of Ursol D, O-Phenylene Diamine, 4,4 '-benzidine and/or be selected from quadrol, propylene diamine, 1, the straight-chain fatty amine of 6-hexanediamine.
In step (4), the product of step (3) is heated up, preferably 100-120 ℃ of constant temperature 10-20 minute, is finally warmed up to 200-220 ℃ of constant temperature 5-10 minute; Be cooled to 150-160 ℃, add surplus lubricating base oil, treat that temperature is cooled to 100-120 ℃, add necessary additive, stir circulating filtration, homogenizing, the degassed finished product that obtains.
Lubricating grease of the present invention compared with prior art, has fabulous extreme pressure anti-wear and overlength lubricating life, meanwhile, also has the 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.
Accompanying drawing explanation
Fig. 1 is the infrared analysis spectrogram of six polyureas in the lubricating grease of embodiment 1 preparation.As can be seen from the figure, 3310～3323cm
-1the peak at place is in six polyureas molecules-the stretching vibration absorption peak of NH-, and 1630cm
-1the peak at place is in six polyureas molecules-vibration absorption peak of CO-.
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of six polyureas in the lubricating grease of embodiment 1 preparation.As can be seen from the figure, the peak of δ=155HZ left and right is in six polyureas molecules-chemical shift of CO-.
The separation method of six polyureas: first, by sherwood oil for lubricating grease (60～90 ℃ of boiling points) washing, filtration is precipitated, does not stop precipitation in 5～10 minutes to stir with 5% dilute acetic acid solution immersion, to no longer producing CO
2bubble, filters, and filter residue cleans with large water gaging, no longer produces foam to filtrate, then uses rare NaHCO of 1%
3solution soaking gained precipitation, filters, and filter residue cleans with large water gaging, to filtrate pH value be 7 o'clock, gained precipitates and obtains after drying six polyureas.
Embodiment
Embodiment 1
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in to add 30kg total basicnumber be that overbased calcium sulphonate and the 15kg100 ℃ of kinematic viscosity of 400mgKOH/g is 31mm
2the HVI150BS lubricating base oil of/s, stirs, and heats to 80 ℃, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature is controlled at 80 ℃ of left and right, stirs 10 minutes; The aqueous solution that adds 4 times of the acetic acid of 0.56kg and acetic acid weight, stirs 10 minutes; Be warmed up to 85 ℃, constant temperature 90 minutes, material retrogradation becomes smectic; Add 1.8kgCa (OH)
2and with 4 times of water-reducible suspension liquids, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 2.32kg boric acid and with 6 times of consoluet boric acid solution of hot water, stir, under stirring, being warmed up to 110 ℃, keeping dehydration 60 minutes; Cool to 90 ℃ and add 0.78kg MDI rapid stirring 4 minutes, under rapid stirring, add 0.84kg stearylamine, stir 4 minutes, under rapid stirring, add 0.19kg quadrol, stir 4 minutes, add 0.39kg MDI, the mol ratio of added MDI, stearylamine, quadrol and MDI is 2:2:2:1 successively, 120 ℃ of constant temperature 20 minutes, is finally warmed up to 200 ℃ of constant temperature 5 minutes.Then, be cooled to 160 ℃, adding 100 ℃ of kinematic viscosity that account for lubricating grease weight 33kg is 11mm
2the HVI500SN lubricating base oil of/s; Treat that temperature is cooled to 110 ℃, add to account for lubricating grease weight 0.2kg p-di-iso-octyldiphenylamine was stirred after 10 minutes circulating filtration, homogenizing, the degassed finished product that obtains.Assay is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 37.8%; Six polyureas 2.5%; Lubricating base oil 54.4%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%; To p-di-iso-octyldiphenylamine 0.2%.
The six polyureas molecular structural formulas that contain in component are:
Embodiment 2
Feed composition: overbased calcium sulphonate (total basicnumber is 420mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, the total basicnumber of the overbased calcium sulphonate that different is uses is 420mgKOH/g, and each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 3
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Amino dodecane (0.66kg); Quadrol (0.21kg); MDI (1.33kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, different is that the aliphatic amide using is amino dodecane, and each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 4
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1kg); Quadrol (0.22kg); TDI (0.97kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, different is that the vulcabond using is tolylene diisocyanate (TDI), and each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 5
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); 500SN (7kg); To p-di-iso-octyldiphenylamine (0.4kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, the amount of different is 500SN is 7kg, thereby make each material rate that larger change occur, use is 0.4kg to p-di-iso-octyldiphenylamine in addition, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 53.4%; Six polyureas 3.5%; Lubricating base oil 35.2%; 12-oxystearic acid calcium 3.4%; Lime borate 3.8%; To p-di-iso-octyldiphenylamine 0.6%.
Embodiment 6
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (2.52kg); Quadrol (0.56kg); MDI (3.51kg); 500SN (28.6kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, the amount of different is stearylamine, quadrol, MDI and 500SN is respectively 2.52kg, 0.56kg, 3.51kg and 28.6kg, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 37.1%; Six polyureas 7.3%; Lubricating base oil 50.4%; 12-oxystearic acid calcium 2.4%; Lime borate 2.6%; To p-di-iso-octyldiphenylamine 0.2%.
Embodiment 7
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); PAO40 (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); PAO10 (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, different is that (100 ℃ of kinematic viscosity are 11mm to use full synthetic oil poly & Alpha ,-olefin oil PAO10
2/ s) and PAO40 (100 ℃ of kinematic viscosity are 41mm
2/ s) replace respectively 500SN and 150BS, each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 8
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare high base number composite calcium sulfonate base six polyurea greases, the total basicnumber of the overbased calcium sulphonate that different is uses is 320mgKOH/g, and each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 9
Feed composition: calcium sulfonate with high base number (total basicnumber is 360mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare high base number composite calcium sulfonate base six polyurea greases, the total basicnumber of the calcium sulfonate with high base number that different is uses is 360mgKOH/g, and each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 10
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); 500SN (33kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, different is not contain oxidation inhibitor to p-di-iso-octyldiphenylamine, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 37.8%; Six polyureas 2.5%; Lubricating base oil 54.4%; 12-oxystearic acid calcium 2.5%; Lime borate 2.8%.
Embodiment 11
Feed composition: calcium sulfonate with high base number (total basicnumber is 360mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(5.2kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Phosphoric acid (3kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 9, prepare high base number composite calcium sulfonate base six polyurea greases, different is to have increased phosphoric acid, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 35.9%; Six polyureas 2.4%; Lubricating base oil 51.6%; 12-oxystearic acid calcium 2.3%; Lime borate 2.5%; Calcium phosphate 5.1%; To p-di-iso-octyldiphenylamine (0.2kg) 0.2%.
Embodiment 12
Feed composition: calcium sulfonate with high base number (total basicnumber is 360mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(3kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Acetic acid (2kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI (1.17kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 9, prepare high base number composite calcium sulfonate base six polyurea greases, different is to have increased acetic acid, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 36.8%; Six polyureas 2.4%; Lubricating base oil 52.8%; 12-oxystearic acid calcium 2.3%; Lime borate 2.6%; Lime acetate 2.9%; To p-di-iso-octyldiphenylamine (0.2kg) 0.2%.
Embodiment 13
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Para-totuidine (0.43kg); Quadrol (0.25kg); MDI (1.52kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, different is to replace stearylamine with para-totuidine, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 37.8%; Six polyureas 2.5%; Lubricating base oil 54.4%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%; To p-di-iso-octyldiphenylamine 0.2%.
Embodiment 14
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.78kg); 1,6-hexanediamine (0.34kg); MDI (1.08kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased complex calcium sulfonate base six polyurea greases, different is to replace quadrol with 1,6-hexanediamine, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 37.8%; Six polyureas 2.5%; Lubricating base oil 54.4%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%; To p-di-iso-octyldiphenylamine 0.2%.
Comparative example 1
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); 500SN (35.2kg); To p-di-iso-octyldiphenylamine (0.2kg).
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in to add 30kg total basicnumber be that calcium sulfonate with high base number and the 15kg100 ℃ of kinematic viscosity of 320mgKOH/g is 31mm
2the HVI150BS lubricating base oil of/s, stirs, and heats to 80 ℃, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature is controlled at 80 ℃ of left and right, stirs 10 minutes; The aqueous solution that adds 4 times of the acetic acid of 0.56kg and acetic acid weight, stirs 10 minutes; 85 ℃ of constant temperature 90 minutes, material retrogradation became smectic; Under stirring, be warmed up to 110 ℃, keep 60 minutes, dehydration; Finally be warmed up to 200 ℃ of constant temperature 5 minutes.Be cooled to 160 ℃, add the lubricating base oil 500SN that accounts for lubricating grease weight 35.2kg; Treat that temperature is cooled to 110 ℃, add to account for lubricating grease weight 0.2kg p-di-iso-octyldiphenylamine was stirred after 10 minutes circulating filtration, homogenizing, the degassed finished product that obtains.Assay is in Table 1.
Comparative example 2
Feed composition: calcium sulfonate with high base number (320mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH) 2 (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI (0.7kg); 500SN (33kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare high base number composite calcium sulfonate base two polyurea greases, the total basicnumber of newton's body calcium sulphonate in reactant that different is is 320mgKOH/g and containing diamines, each performance data of lubricating grease finished product obtaining is in Table 1.
Each lubricating grease properties of sample data of table 1
Continued
Claims (25)
1. complex calcium sulfonate base six polyurea greases, take lubricating grease weight as benchmark, comprise following component:
1) non-newtonian fluid calcium sulphonate 10-70%; 2) higher fatty acid calcium 1-10%; 3) small molecules mineral acid calcium or calcium of organic acid 1-15%; 4) six polyureas 0.5-30%; 5) lubricating base oil 10-80%; It is characterized in that, described complex calcium sulfonate base six polyurea greases are prepared by following methods:
(1) newton's body calcium sulphonate, part base oil and transforming agent are mixed, heated, make material retrogradation become smectic;
(2) add lime or calcium hydroxide, add respectively higher fatty acid and small molecules acid, cooling after the dehydration that heats up;
(3) add the vulcabond being dissolved in part base oil, add successively monoamine to react, add diamines to react again, then add vulcabond to react, the mol ratio of vulcabond, monoamine, diamines and vulcabond that wherein each time adds is 2: 2: 2: 1;
(4) be warmed up to 200-220 ℃ of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
2. according to lubricating grease claimed in claim 1, wherein take lubricating grease weight as benchmark, comprise following component:
1) non-newtonian fluid calcium sulphonate 20-60%; 2) higher fatty acid calcium 2-6%; 3) small molecules mineral acid calcium or calcium of organic acid 2-10%; 4) six polyureas 1-20%; 5) lubricating base oil 20-70%.
3. according to lubricating grease claimed in claim 1, wherein said non-newtonian fluid calcium sulphonate is transformed and is obtained by newton's body calcium sulphonate, and its total basicnumber is 250-450mgKOH/g.
4. according to lubricating grease claimed in claim 1, said higher fatty acid calcium is that carbon number is the straight chain fatty acid of 8-20 or the calcium salt of hydroxy fatty acid.
5. according to lubricating grease claimed in claim 1, said higher fatty acid calcium is selected from the calcium salt of one or more mixtures in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.
6. according to lubricating grease claimed in claim 1, mineral acid or organic acid molecular weight in said small molecules mineral acid calcium or calcium of organic acid are less than or equal to 150.
7. according to lubricating grease claimed in claim 1, said small molecules mineral acid calcium or calcium of organic acid are selected from the calcium salt of one or more mixtures in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid, boric acid, phosphoric acid, sulfuric acid.
8. according to lubricating grease claimed in claim 1, wherein, said six polyureas have following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
9. according to lubricating grease claimed in claim 8, wherein, R
1the phenyl of phenyl or replacement, or the carbon number alkyl or cycloalkyl that is 8～24; R
2that phenylene or biphenylene or carbon number are 2～12 alkylidene group; R
3that carbon number is 6～30 arylidene, alkylidene group or cycloalkylidene.
10. according to lubricating grease claimed in claim 9, wherein, R
1the phenyl that phenyl or C1～C3 alkyl or halogen replace, or carbon number be 10～18 alkyl or cycloalkyl, R
2phenylene or biphenylene, or the carbon number alkylidene group that is 2～8; R
3be selected from least one in tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and hexylidene.
11. according to lubricating grease claimed in claim 1, in step (1), newton's body calcium sulphonate, part base oil Hybrid Heating is arrived to 50-80 ℃, add successively required transforming agent to react, all transforming agents add rear intensification, and at 80-90 ℃ of constant temperature 60-90 minute, making material retrogradation is smectic.
12. according to lubricating grease claimed in claim 1, in step (2), at 85-100 ℃ of suspension liquid that adds lime or calcium hydroxide, at 85-100 ℃, add higher fatty acid, stir 5-20 minute, add small molecules mineral acid or organic acid, stir 5-20 minute, be warmed up to 105-120 ℃, dehydration, cools to 90-105 ℃.
13. according to lubricating grease claimed in claim 1, in step (3), in the product of step (2), add successively the vulcabond being dissolved in part base oil, add monoamine, reaction 2-8 minute, add diamine reactant 2-8 minute, then add the vulcabond being dissolved in part base oil, reaction 2-8 minute.
14. according to lubricating grease claimed in claim 1, in step (4), the product of step (3) is heated up, and at 100-120 ℃ of constant temperature 10-20 minute, is finally warmed up to 200-220 ℃ of constant temperature 5-10 minute; Be cooled to 150-160 ℃, add surplus lubricating base oil, treat that temperature is cooled to 100-120 ℃, add necessary additive, stir circulating filtration, homogenizing, degassed.
15. according to lubricating grease claimed in claim 1, and described newton's body calcium sulphonate is calcium mahogany sulfonate or calcium alkylbenzenesulfonate, and its total basicnumber is 250-450mgKOH/g.
16. according to lubricating grease claimed in claim 1, said transforming agent is selected from fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, cycloalkanes amine, cycloalkanol, the ether of C1-C5, and one or more in boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate (ABS), water, the add-on of transforming agent is the 2-30% of newton's body calcium sulphonate weight.
17. according to lubricating grease claimed in claim 1, and said transforming agent is selected from Witco 1298 Soft Acid, acetic acid, water, and the add-on of transforming agent is the 6-22% of newton's body calcium sulphonate weight.
18. according to lubricating grease claimed in claim 1, and wherein, said monoamine structural formula is R
1-NH
2, R wherein
1be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl is 8～24, and aryl is the phenyl of phenyl or replacement.
19. according to the lubricating grease described in claim 18, R wherein
1the phenyl that phenyl or C1～C3 alkyl or halogen replace, or the carbon number alkyl or cycloalkyl that is 10～18.
20. according to lubricating grease claimed in claim 1, and wherein, said monoamine is the arylamine that is selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide and/or para-totuidine, and/or be selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.
21. according to lubricating grease claimed in claim 1, and 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.
22. according to lubricating grease claimed in claim 1, and wherein, said diamines is selected from the aromatic amine of Ursol D, O-Phenylene Diamine, 4,4 '-benzidine, and/or is selected from quadrol, propylene diamine, 1, the aliphatic amide of 6-hexanediamine.
23. according to lubricating grease claimed in claim 1, and wherein, said vulcabond structure is OCN-R
3-NCO, R
3that carbon number is 6～30 arylidene, alkylidene group or cycloalkylidene.
24. according to the lubricating grease described in claim 23, wherein, and R
3that carbon number is 6～20 arylidene, alkylidene group or cycloalkylidene.
25. according to lubricating grease claimed in claim 1, and wherein, described vulcabond is selected from tolylene diisocyanate, methyldiphenyl group diisocyanate, hexamethylene vulcabond, dicyclohexyl methyl vulcabond, or at least one in an xylylene vulcabond.
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| CN103627497B (en) * | 2012-08-28 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of Composite calcium naphthenate base six polyurea grease and preparation method thereof |
| CN103695137B (en) * | 2012-09-27 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of Composite calcium naphthenate base lubricating grease and preparation method thereof |
| CN103695138B (en) * | 2012-09-27 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of Composite calcium naphthenate base six polyurea grease and preparation method thereof |
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| CN104560317B (en) * | 2013-10-29 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of complex calcium sulfonate calcium naphthenate zirconium base polyurea grease and preparation method thereof |
| CN104560325B (en) * | 2013-10-29 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of polyurea grease of composite calcium naphthenate calcium zirconium base six and preparation method thereof |
| CN104560278B (en) * | 2013-10-29 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of sulfoacid calcium calcium naphthenate zirconium base lubricating grease and preparation method thereof |
| CN104560272B (en) * | 2013-10-29 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of polyurea grease of complex calcium sulfonate calcium naphthenate zirconium base six and preparation method thereof |
| CN104560271B (en) * | 2013-10-29 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of calcium naphthenate zirconium base polyurea grease and preparation method thereof |
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