CN104449961A - Calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof - Google Patents
Calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof Download PDFInfo
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- CN104449961A CN104449961A CN201310419098.XA CN201310419098A CN104449961A CN 104449961 A CN104449961 A CN 104449961A CN 201310419098 A CN201310419098 A CN 201310419098A CN 104449961 A CN104449961 A CN 104449961A
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- HZQQAWTXWSAPIV-UHFFFAOYSA-N CC1C(C)=C(C)C=CC1 Chemical compound CC1C(C)=C(C)C=CC1 HZQQAWTXWSAPIV-UHFFFAOYSA-N 0.000 description 1
- 0 CC1CC*CC1 Chemical compound CC1CC*CC1 0.000 description 1
- QRMPKOFEUHIBNM-UHFFFAOYSA-N CC1CCC(C)CC1 Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 1
- AFZZYIJIWUTJFO-UHFFFAOYSA-N CCc1cccc(CC)c1 Chemical compound CCc1cccc(CC)c1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 1
- UDHAWRUAECEBHC-UHFFFAOYSA-N Cc(cc1)ccc1I Chemical compound Cc(cc1)ccc1I UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 1
- GWHJZXXIDMPWGX-UHFFFAOYSA-N Cc1ccc(C)c(C)c1 Chemical compound Cc1ccc(C)c(C)c1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses calcium sulfonate-calcium naphthenate-based urea hexamer grease. The calcium sulfonate-calcium naphthenate-based urea hexamer grease comprises, by weight, 10-70% of non-Newtonian calcium sulfonate-calcium naphthenate, 0.5-30% of a polyurea compound and 10-80% of base oil, wherein the polyurea compound is a urea hexamer compound. The invention also discloses a preparation method of the calcium sulfonate-calcium naphthenate-based urea hexamer grease and the calcium sulfonate-calcium naphthenate-based urea hexamer grease obtained by the preparation method. The calcium sulfonate-calcium naphthenate-based urea hexamer grease has excellent corrosion resistance and high temperature resistance. Compared with the calcium sulfonate-based urea hexamer grease, the calcium sulfonate-calcium naphthenate-based urea hexamer grease has better mechanical stability, water resistance, adhesion resistance, salt mist resistance, extreme pressure antiwear property and colloid stability and a longer service life. The preparation method has simple processes, environmental friendliness, a low cost and stable product quality.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of calcium sulphonate-Calcium naphthenate base six polyurea grease and preparation method thereof.
Background technology
Calcium sulphonate is used as the history that the purification agent of lubricating oil and rust-preventive agent have decades, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed 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
3sulfonation mineral lubricating oils produces by product mahogany acid during white oil, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtaining; Calcium alkylbenzenesulfonate is with oleum or SO
3the alkylbenzene of sulfonation synthesis, alkyl benzene sulphonate (ABS) warp and Ca (OH) of generation
2reaction, the contour alkalization technology of carbonating and obtaining.
Overbased calcium alkyl-salicylate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffustivity, the purification agent of lubricating oil can be used as, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active naphthenic acid calcium.Mostly overbased calcium alkyl-salicylate is the acidic components extracted from the distillate that crude distillation obtains, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtain, about the Patents prepared has CN1465560 etc.
Utilize calcium sulfonate with high base number for raw material production lubricating grease, because it has 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, but, although sulfonate with high base number quicklime grease has very excellent over-all properties, 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, simultaneously, along with the requirement of people to environment protection is more and more higher, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment also received day by day to the concern of people.Find a kind of performance and sulfonate with high base number quicklime grease is similar but the lubricating grease that can alleviate the problems referred to above becomes the large problem that people face at present.
Summary of the invention
The object of this invention is to provide a kind of performance and sulfonate with high base number quicklime grease is similar, cost is low, and preparation technology is simple, the lubricating grease of environmental protection and preparation method thereof.
The present inventor finds under study for action, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight, wherein, described polyurea compound is six polyurea compounds.Performance and the sulfonate with high base number quicklime grease of this lubricating grease are similar, and cost is low, and preparation technology is simple, environmental protection.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of Calcium naphthenate base six polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight, wherein, described polyurea compound is six polyurea compounds.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; Six polyurea compounds of 1-20 % by weight; The base oil of 20-70 % by weight.
Second aspect, the invention provides the preparation method of calcium sulphonate-Calcium naphthenate base six polyurea grease as above, the method comprises: non-newtonian fluid calcium sulphonate-calcium naphthenate, six polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides a kind of preparation method of calcium sulphonate-Calcium naphthenate base six polyurea grease, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, heat up dehydration further;
(2) in step (1) products therefrom, add part basis oil and vulcabond, then add monoamine, diamines and vulcabond successively and react;
(3) step (2) reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds surplus base oil, add necessary additive, obtain finished product.
Fourth aspect, the invention provides calcium sulphonate-Calcium naphthenate base six polyurea grease obtained by method as above.
Calcium sulphonate-Calcium naphthenate base six polyurea grease of the present invention, not only the same with calcium sulphonate base six polyurea grease, there is excellent non-corrosibility and high thermal resistance, but also there is the performance such as mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear being better than calcium sulphonate base six polyurea grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 2.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of calcium sulphonate-Calcium naphthenate base six polyurea grease, this lubricating grease have employed calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate be raw material, simultaneously containing isocyanic ester and amine reaction produce six polyurea compounds.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of calcium sulphonate-Calcium naphthenate base six polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight, wherein, described polyurea compound is six polyurea compounds.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; Four polyurea compounds of 1-20 % by weight; The base oil of 20-70 % by weight.
Described non-newtonian fluid calcium sulphonate-calcium naphthenate is at infrared spectrum 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place, total basicnumber is 250mgKOH/g-450mgKOH/g, preferred 300mgKOH/g-400mgKOH/g.Described non-newtonian fluid calcium sulphonate-calcium naphthenate is obtained by transforming agent conversion by newton's body calcium sulphonate and newton's body calcium naphthenate.And containing unformed calcium carbonate in newton's body calcium sulphonate, newton's body calcium naphthenate, at infrared spectrum 860cm
-1-865cm
-1there is unformed calcium carbonate charateristic avsorption band in place.Described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.The base number of non-newtonian fluid calcium sulphonate-calcium naphthenate is the weight mean value of the base number of newton's body calcium sulphonate and the base number of newton's body calcium naphthenate.
In the present invention, described six polyurea compounds preferably have following structure:
Wherein, R
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, and be preferably 10-18, aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.
Wherein, R
3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R
3be more preferably
in at least one.
Above-mentioned six polyurea compounds can adopt the thinkable various method of those skilled in the art institute to obtain, and the method such as can recorded according to CN103060067A prepares.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 DEG C of kinematic viscosities are 4-150mm
2/ s, is preferably 10-60mm
2/ s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Can also various additive be contained, as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc. in lubricating grease of the present invention.Wherein, the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.01-5% of lubricating grease gross weight, preferred 0.1-2.5%, can be at least one in pentanoic, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of lubricating grease gross weight, preferred 0.8-8% can be at least one in dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenumdisulphide, tetrafluoroethylene, thiophosphoric acid molybdenum, clorafin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, calcium carbonate and zinc oxide; Rust-preventive agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferred 0.1-2%, can be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the preparation method of calcium sulphonate-Calcium naphthenate base six polyurea grease as above, the method comprises: non-newtonian fluid calcium sulphonate-calcium naphthenate, six polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
In the present invention, described above for non-newtonian fluid calcium sulphonate-calcium naphthenate, six polyurea compounds and base oil, do not repeat them here.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are the total amount of base oil used, in the present invention, part basis oil is preferably 1:0.1-5 with the weight ratio of surplus base oil.
For non-newtonian fluid calcium sulphonate-calcium naphthenate, can be obtained by transforming agent conversion by newton's body calcium sulphonate, newton's body calcium naphthenate, such as, by newton's body calcium sulphonate, newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.
The third aspect, the invention provides a kind of preparation method of calcium sulphonate-Calcium naphthenate base six polyurea grease, comprising:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, heat up dehydration further;
(2) in step (1) products therefrom, add part basis oil and vulcabond, then add monoamine, diamines and vulcabond successively and react;
(3) step (2) products therefrom is warmed up to 180-230 DEG C of constant temperature refining, adds surplus base oil, add necessary additive, obtain finished product.
In step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent and react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.
In the present invention, for the weight ratio of newton's body calcium sulphonate and newton's body calcium naphthenate without particular requirement, be preferably 1:0.25-4.The gross weight of newton's body calcium sulphonate and newton's body calcium naphthenate and the weight ratio of part basis oil are preferably 1:0.1-3.
Described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.
Described transforming agent is preferably selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water; More preferably at least one in the fatty alcohol of C1-C5, the lipid acid of C1-C5, the aliphatic ketone of C1-C5, the alkanoic of C1-C5, the aliphatic amide of C1-C5, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, the arylphosphonic acid of C6-C20, the diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate (ABS) and water is selected from; Further be preferably selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water.The add-on of transforming agent is preferably the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight, is more preferably the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
In the present invention, fatty alcohol comprises the fatty alcohol of straight chain, side chain and ring-type, and lipid acid, aliphatic ketone, alkanoic, aliphatic amide are in like manner.
In step (2), in step (1) products therefrom, add part basis oil and vulcabond, then adding monoamine, diamines and vulcabond successively and react, is namely prepare six polyurea compounds in step (1) products therefrom.
Prepare the method for six polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, part basis oil and vulcabond can be added in the product of step (1), add monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, add the vulcabond be dissolved in part basis oil again, stir 2-8 minute, the mol ratio of vulcabond, monoamine, diamines and vulcabond added by each time is 2:2:2:1.
In step of the present invention (2), the vulcabond added for twice can be the same or different, and in order to easy to operate, the vulcabond that preferably twice adds is identical.
Described vulcabond structure is OCN-R
3-NCO, R
3can be carbon number be 6-30, the arylidene of preferred 6-20, alkylidene group or cycloalkylidene, be preferably
deng.Such as described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), at least one in dicyclohexylmethyl vulcabond (HMDI) and an xylylene diisocyanate (XDI) etc.
Described monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R
1 '-NH
2, R wherein
1, R
1 'can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.Preferred monoamine can be the arylamine being 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.
Described 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, preferred 2-8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from Ursol D, O-Phenylene Diamine, 4, the aromatic amine of 4 '-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
In step (3), first at 100-120 DEG C of constant temperature 10-20 minute, be finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
In the present invention, in step (1), in base oil used and step (2), in base oil used and step (3), the weight ratio of base oil used is preferably 1:0.1-5:0.1-5.
Fourth aspect, calcium sulphonate-Calcium naphthenate base six polyurea grease that the preparation method that present invention also offers is provided by third aspect present invention obtains.
Compared with calcium sulphonate-Calcium naphthenate base six polyurea grease obtained with the preparation method provided by second aspect, calcium sulphonate-Calcium naphthenate base six polyurea grease that the preparation method that the third aspect provides obtains has better mechanical stability, water resisting property and adhesivity and colloid stability.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following Examples and Comparative Examples:
Overbased or calcium sulfonate with high base number raw material weight+the overbased or overbased calcium alkyl-salicylate raw material weight+transforming agent gross weight of non-newtonian fluid calcium sulphonate-calcium naphthenate %=()/lubricating grease gross weight × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium sulphonate-calcium naphthenate.
Overbased and overbased calcium alkyl-salicylate raw material, also can according to method preparation disclosed in CN101885677A purchased from Xinjiang Land Fine Petrochemical Co., Ltd.
Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Naphthenic acid is purchased from Jinzhou Tie Chen petrochemical complex limited liability company.
Embodiment 1
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Add the boric acid aqueous solution that 16.24kg concentration is 14.3 % by weight, stir 10 minutes, be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 120 DEG C under stirring, keep 30 minutes, dehydration; Add HVI500SN lubricating base oil and the 0.78kg MDI of 2kg, stir 4 minutes, 0.84kg stearylamine is added under rapid stirring, stir 4 minutes, under rapid stirring, add 0.19kg quadrol, stir 4 minutes, add the 0.39kg MDI be dissolved in the HVI500SN lubricating base oil of 2kg, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1, and 120 DEG C of constant temperature 20 minutes, is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 2
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Add the boric acid aqueous solution that 16.24kg concentration is 14.3 % by weight, stir 10 minutes, be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 120 DEG C under stirring, keep 30 minutes, dehydration.
Another volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add HVI500SN lubricating base oil and the 0.78kg MDI of 2kg, stir 4 minutes, 0.84kg stearylamine is added under rapid stirring, stir 4 minutes, 0.19kg quadrol is added under rapid stirring, stir 4 minutes, add the 0.39kg MDI be dissolved in the HVI500SN lubricating base oil of 2kg, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.
Gained six polyureas is all squeezed in a upper still, stirs, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
The six polyureas molecular structural formulas contained in component are:
Embodiment 3
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 10kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Lauryl amine (0.66kg); Quadrol (0.21kg); MDI(1.33kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 38kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 320mgKOH/g and the HVI150BS lubricating base oil of 10kg, stir, heat to 80 DEG C, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature controls at about 80 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Add the boric acid aqueous solution that 16.24kg concentration is 14.3 % by weight, stir 10 minutes, be warmed up to 90 DEG C, constant temperature 60 minutes, material retrogradation; Be warmed up to 100 DEG C under stirring, keep 60 minutes, dehydration; Add HVI500SN lubricating base oil and the 0.89kg MDI of 2kg, stir 8 minutes, 0.66kg lauryl amine is added under rapid stirring, stir 8 minutes, under rapid stirring, add 0.21kg quadrol, stir 8 minutes, add the 0.44kg MDI be dissolved in the HVI500SN lubricating base oil of 2kg, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1, and 100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, remaining HVI500SN lubricating base oil is added; Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 4
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Propyl carbinol (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1kg); Quadrol (0.22kg); TDI(0.97kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg);
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; Replace naphthenic acid with propyl carbinol simultaneously; MDI is replaced with TDI; And treat that temperature is cooled to 110 DEG C, add the phenyl-a-naphthylamine of 0.2kg, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 39.6 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 57.8 % by weight.
Embodiment 5
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 7kg); Right, right '-di-iso-octyldiphenylamine (0.4kg).
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; And treat that temperature is cooled to 110 DEG C, add the right of 0.4kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 59.2 % by weight; Six polyureas 3.6 % by weight; Lubricating base oil 36.5 % by weight; Right, right '-di-iso-octyldiphenylamine 0.7 % by weight.
Embodiment 6
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (2.52kg); Quadrol (0.56kg); MDI(3.51kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, the consumption of each composition is as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.8 % by weight; Six polyureas 7.8 % by weight; Lubricating base oil 50.4 % by weight.
Embodiment 7
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); Full synthetic oil poly & Alpha ,-olefin oil PAO40(100 DEG C of kinematic viscosity is 41mm
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); Full synthetic oil poly & Alpha ,-olefin oil PAO10(100 DEG C of kinematic viscosity is 11mm
2/ s, 23kg); Dithio Acidic phosphates zinc (2kg), molybdenum dialkyldithiocarbamacompositions (1kg), tungsten disulfide (2kg), two tungsten selenide (2kg), right, right '-di-iso-octyldiphenylamine (0.2kg).
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Full synthetic oil poly & Alpha ,-olefin oil PAO40 and PAO10 is used to replace HVI150BS and HVI500SN respectively; And treat that temperature is cooled to 110 DEG C, add the dithio Acidic phosphates zinc of 2kg, stir 10 minutes, add the molybdenum dialkyldithiocarbamacompositions of 1kg, stir 10 minutes, add the tungsten disulfide of 2kg, stir 10 minutes, add two tungsten selenide of 2kg, stir 10 minutes, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 38.3 % by weight; Six polyureas 2.4 % by weight; Lubricating base oil 51.6 % by weight; Dithio Acidic phosphates zinc 2.2 % by weight; Molybdenum dialkyldithiocarbamacompositions 1.1 % by weight; Tungsten disulfide 2.1 % by weight; Two tungsten selenide 2.1 % by weight; To p-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 8
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 9
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 10
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 15kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.78kg); 1,6-hexanediamine (0.40kg); MDI(1.26kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, replace quadrol with 1,6-hexanediamine; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 11
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 15kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.79kg); Ursol D (0.32kg); MDI(1.10kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Quadrol is replaced with Ursol D; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 12
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 360mgKOH/g, 15kg); Overbased calcium alkyl-salicylate (total basicnumber is 360mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Propyl carbinol (1kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 360mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 360mgKOH/g; Transforming agent adds propyl carbinol, adds after adding naphthenic acid; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 13
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with phenol, acetic acid is replaced with butyric acid, boric acid is replaced with acetone.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 14
Calcium sulphonate-Calcium naphthenate base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium sulphonate-Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with ketone, aqueous acetic acid is replaced with ether, boric acid aqueous solution is replaced with ethamine.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Comparative example 1
Calcium sulfonate with high base number base six polyurea grease is prepared by the method for embodiment 1, unlike, naphthenate with superhigh base number calcium total basicnumber is that the overbased calcium sulphonate of 400mgKOH/g replaces, and each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate 41.5 % by weight; Six polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Table 1 each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643; Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.
Table 1(continues) each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643; Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.
Embodiment 1 and comparative example 1 are compared and can find out, the prolongation Drawing cone in-degree of calcium sulphonate-Calcium naphthenate base six polyurea grease of the present invention and the difference of Drawing cone in-degree are much smaller than calcium sulphonate base six polyurea grease, water drenches number of dropouts much smaller than calcium sulphonate base six polyurea grease, salt-fog test is better than calcium sulphonate base six polyurea grease, water resistant spraying value is less than calcium sulphonate base six polyurea grease, Stencil oil-dividing value is much smaller than calcium sulphonate base six polyurea grease, tetra-ball machine test value is greater than calcium sulphonate base six polyurea grease, the bearing lubrication life-span is greater than calcium sulphonate base six polyurea grease, the mechanical stability of calcium sulphonate-Calcium naphthenate base six polyurea grease of the present invention is described, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear, lubricating life is all better than calcium sulphonate base six polyurea grease, and calcium sulphonate-Calcium naphthenate base six polyurea grease of the present invention is the same with calcium sulphonate base six polyurea grease has the performances such as excellent non-corrosibility and high thermal resistance.
Embodiment 1 and embodiment 2 are compared and can find out, calcium sulphonate-Calcium naphthenate base six polyurea grease prepared by original position, there is better mechanical stability, water resisting property and adhesivity and colloid stability; Embodiment 1 is compared can find out with embodiment 13 and embodiment 14 respectively, transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, butanols, Virahol, boric acid, acetic acid and water, calcium sulphonate-Calcium naphthenate base six polyurea grease of preparation, there is better mechanical stability, water resisting property and adhesivity, colloid stability, and there is longer lubricating life.
As can be seen from Figure 1, the lubricating grease of embodiment 2 preparation is at 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place.Meanwhile, at 3300cm
-1-3323cm
-1the peak at place is the stretching vibration absorption peak of-NH-in six polyureas molecules.
Calcium sulphonate-Calcium naphthenate base six polyurea grease of the present invention, not only the same with calcium sulphonate base six polyurea grease, there is excellent non-corrosibility and high thermal resistance, but also there is the performance such as mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear being better than calcium sulphonate base six polyurea grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (21)
1. calcium sulphonate-Calcium naphthenate base six polyurea grease, is characterized in that, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight, wherein, described polyurea compound is six polyurea compounds.
2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; Six polyurea compounds of 1-20 % by weight; The base oil of 20-70 % by weight.
3. lubricating grease according to claim 1 and 2, wherein, described non-newtonian fluid calcium sulphonate-calcium naphthenate is transformed by newton's body calcium sulphonate and newton's body calcium naphthenate and obtains, and the total basicnumber of described non-newtonian fluid calcium sulphonate-calcium naphthenate is 250-450mgKOH/g.
4. lubricating grease according to claim 1 and 2, wherein, described six polyurea compounds have following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
5. lubricating grease according to claim 4, wherein, R
1be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8-24; R
2be phenylene or biphenylene or carbon number be the alkylidene group of 2-12; R
3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.
6. lubricating grease according to claim 5, wherein, R
1be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18, R
2be phenylene or biphenylene, or carbon number is the alkylidene group of 2-8; R
3be selected from
in at least one.
7. the preparation method of calcium sulphonate-Calcium naphthenate base six polyurea grease in claim 1-6 described in any one, it is characterized in that, the method comprises: non-newtonian fluid calcium sulphonate-calcium naphthenate, six polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
8. a preparation method for calcium sulphonate-Calcium naphthenate base six polyurea grease, it is characterized in that, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, heat up dehydration further;
(2) in step (1) products therefrom, add part basis oil and vulcabond, then add monoamine, diamines and vulcabond successively and react;
(3) step (2) products therefrom is warmed up to 180-230 DEG C of constant temperature refining, adds surplus base oil, add necessary additive, obtain finished product.
9. preparation method according to claim 8, wherein, in step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.
10. preparation method according to claim 8, wherein, in step (2), in the product of step (1), add part basis oil and vulcabond, add monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, then add the vulcabond be dissolved in part basis oil, stir 2-8 minute, the mol ratio of vulcabond, monoamine, diamines and vulcabond added by each time is 2:2:2:1.
11. preparation methods according to claim 8, wherein, in step (3), first at 100-120 DEG C of constant temperature 10-20 minute, are finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
12. preparation methods according to claim 8, wherein, described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and the total basicnumber of described newton's body calcium sulphonate is 250-450mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and the total basicnumber of described newton's body calcium naphthenate is 250-450mgKOH/g.
13. preparation methods according to claim 8, wherein, described transforming agent is selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water, and the add-on of transforming agent is the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
14. preparation methods according to claim 13, wherein, described transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water, and the add-on of transforming agent is the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
15. preparation methods according to claim 8, wherein, the structural formula of described monoamine is R
1-NH
2, wherein, R
1be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18.
16. preparation methods according to claim 15, wherein, described monoamine is the arylamine being 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.
17. preparation methods according to claim 8, wherein, the structural formula of described diamines is NH
2-R
2-NH
2, wherein, R
2the alkylidene group of to be carbon number be 2-8, or phenylene or biphenylene.
18. preparation methods according to claim 17, wherein, described diamines is selected from Ursol D, O-Phenylene Diamine, 4, the aromatic amine of 4 '-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
19. preparation methods according to claim 8, wherein, the structure of described vulcabond is OCN-R
3-NCO, R
3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.
20. preparation methods according to claim 19, wherein, described vulcabond is selected from least one in tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
21. calcium sulphonate-Calcium naphthenate base six polyurea greases obtained by the method in claim 8-20 described in any one.
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