CN103627495A - Composite calcium naphthenate base di-polyurea lubricating grease and preparation method thereof - Google Patents
Composite calcium naphthenate base di-polyurea lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a composite calcium naphthenate base di-polyurea lubricating grease and a preparation method thereof. The composite calcium naphthenate base di-polyurea lubricating grease comprises, by weight, 1) 10-70% of non-Newtonian calcium naphthenate, 2) 1-10% of a calcium salt of a higher fatty acid, 3) 1-15% of a calcium salt of a small molecule inorganic acid and/or a fatty acid, 4) 0.5-30% of di-polyurea, and 5) 10-80% of a lubricating base oil. According to the present invention, the petroleum calcium naphthenate or the synthetic calcium naphthenate is adopted as the raw material, the lubricating grease contains the composite calcium thickener and the di-polyurea compound, and the lubricating grease further has characteristics of excellent extreme pressure wear resistance, ultra-long lubrication life, excellent adhesion, excellent water resistance, excellent colloidal stability, high dropping point, thermal stability, corrosion resistance and the like.
Description
Technical field
The present invention relates to lubricant, definite a kind of compound calcium naphthenate base two polyurea greases and preparation method thereof that say.
Background technology
High base number calcium naphthenate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffustivity, the purification agent that can be used as lubricating oil, 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 naphthenic acid calcium.The acidic components that extract the distillate mostly high base number calcium naphthenate is to obtain from crude distillation, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtain, the relevant Patents of preparing has CN 1465560 etc.
What to utilize calcium sulfonate with high base number be raw material production lubricating grease has excellent high temperature performance because of it, 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, yet, although high base number composite calcium sulfonate base 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 people are more and more higher to the requirement of environment protection, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment is also received to people's concern day by day.Find a kind of performance and high base number composite calcium sulfonate similar but can avoid the lubricating grease of the problems referred to above to become the large problem that people face at present.
Summary of the invention
The invention provides a kind of compound calcium naphthenate base two polyurea greases, it is raw material that this lubricating grease has adopted petroleum naphthenic acid calcium or synthetic calcium naphthenate, contains composite calcium viscosifying agent and two polyurea compounds simultaneously.
The present invention also provides above-mentioned preparation of greases method.
Calcium naphthenate base two polyurea greases provided by the invention, take lubricating grease weight as benchmark, comprise following component:
1) non-newtonian fluid calcium naphthenate 10%-70%, preferably 20%-60%, most preferably 30%-55%;
2) the calcium salt calcium 1%-10% of higher fatty acid, preferably 2%-6%, most preferably 2.2%-4.2%;
3) the calcium salt 1%-15% of small molecules mineral acid and/or lipid acid, preferably 2%-10%, most preferably 3%-8%;
4) two 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 naphthenate is at infrared spectrum 873cm
-1-886cm
-1place occurs that crystal form calcium carbonate charateristic avsorption band, total basicnumber are 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Described non-newtonian fluid calcium naphthenate is to be transformed and obtained by transforming agent by newton's body calcium naphthenate.And in newton's body calcium naphthenate, contain unformed carbonic acid calcium, 860cm in infrared spectrum
-1-865cm
-1there is charateristic avsorption band in place.Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthetic calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, and preferably 300mgKOH/g-400mgKOH/g, changes into after non-newtonian fluid calcium naphthenate, and its base number is constant.
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.
The molecular weight of said small molecules mineral acid and/or lipid acid is less than or equal to 150, said small molecules mineral acid is selected from one or more the mixture in boric acid, phosphoric acid, sulfuric acid, and said small molecules lipid acid is selected from one or more the mixture in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.
Said two polyureas have following structure:
R wherein
1, R
3can be the same or different, can be alkyl, cycloalkyl or aryl, and 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 that carbon number is 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, preferably at least one in methylene phenyl, phenylbenzene methylene radical, dicyclohexyl methylene radical, phenylenedimethylidyne and hexylidene.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 ° of C kinematic viscosities are 4mm
2/ s-150mm
2/ s, preferably 10mm
2/ s-60mm
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, extreme pressure anti-wear additives, 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.Extreme pressure anti-wear additives can be dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenyl thiophosphatephosphorothioate, 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 can be barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
The preparation method of described compound calcium naphthenate base two polyurea greases, comprising:
(1) in reactor A, newton's body calcium naphthenate, part base oil and transforming agent are mixed, heated, make material retrogradation;
(2) in aforesaid reaction vessel, add lime or calcium hydroxide, add respectively higher fatty acid and small molecules acid, dehydration heats up;
(3) in the product of reactor A or in reactor B, add part base oil, monoamine and vulcabond to react, wherein vulcabond is 1:2 with the ratio of the amount of substance of monoamine;
(4) mixing of materials in reactor A is even, or mix after the material of reactor A and B is merged, be warmed up to 200 ° of C-220 ° of C constant temperature refinings, cooling, add surplus base oil, add necessary additive, obtain finished product.
Specifically, preparation method of the present invention can complete in a reactor, also can use two reactors.
Specifically, in step (1), by newton's body calcium naphthenate, part base oil Hybrid Heating to 50 ° C-90 ° C, preferably constant temperature is 10 minutes-30 minutes, adds successively required transforming agent to react, and preferably adds rear stirring about 10 minutes at every turn, react fully, all transforming agents add rear intensification, preferably, 85 ° of C-100 ° of C constant temperature 0.5 hour-3 hours, make material retrogradation.
Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthetic calcium naphthenate, 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 one or more in calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate (ABS), water etc., preferably Witco 1298 Soft Acid, C16-C62 naphthenic acid, methyl alcohol, butanols, acetic acid and water.The add-on of transforming agent is the 2%-30% of newton's body calcium naphthenate weight, preferably 6%-22%.
In step (2), the suspension liquid that adds lime or calcium hydroxide at 85 ° of C-100 ° of C, at 85 ° of C-100 ° of C, add higher fatty acid, stir 5 minutes-20 minutes, add small molecules mineral acid and/or lipid acid, stir 5 minutes-20 minutes, be warmed up to 105 ° of C-120 ° of C, preferably keep 30 minutes-60 minutes dehydration;
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.
The molecular weight of said small molecules mineral acid and/or lipid acid is less than or equal to 150, said small molecules mineral acid is selected from one or more the mixture in boric acid, phosphoric acid, sulfuric acid, and said small molecules lipid acid is selected from one or more the mixture in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.
The H of higher fatty acid and small molecules mineral acid and/or lipid acid
+the OH that total amount of substance and calcium hydroxide are contained
-total amount of substance equates, the OH that calcium hydroxide is contained
-total amount of substance also can excessive 1-10%.
In step (3), in the product of step (2) or in another reactor, add part base oil, monoamine and vulcabond to react, wherein vulcabond is 1:2 with the ratio of the amount of substance of monoamine, and monoamine and vulcabond can first be dissolved in part base oil.
Said vulcabond structure is OCN-R
2-NCO, R
2can be that carbon number is 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, preferably at least one in methylene phenyl, phenylbenzene methylene radical, dicyclohexyl methylene radical, phenylenedimethylidyne and hexylidene.For example described vulcabond can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), 1, hexamethylene-diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), or at least one in the vulcabond such as xylylene diisocyanate (XDI).
Said monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R
3-NH
2, R wherein
1, R
3can 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.
In step (4), the product of step (2) and step (3) is mixed to rear intensification, preferably 100 ° of C-120 ° of C constant temperature is 10 minutes-20 minutes, is finally warmed up to 200 ° of C-220 ° of C constant temperature 5 minutes-10 minutes; Be cooled to 150 ° of C-160 ° of C, add surplus lubricating base oil, treat that temperature is cooled to 100 ° of C-120 ° of C, add necessary additive, stir circulating filtration, homogenizing, the degassed finished product that obtains.
Lubricating grease of the present invention compared with prior art, has good extreme pressure anti-wear and long 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 spectrum of the lubricating grease of embodiment 1 preparation.As can be seen from the figure, 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 in two polyureas molecules-the stretching vibration absorption peak of NH-.
Embodiment
In embodiment, the method for calculation of each component concentration are as follows:
Overbased or the high base number calcium naphthenate raw materials quality+transforming agent total mass of non-newtonian fluid calcium naphthenate %=()/lubricating grease total mass.Transforming agent all counts in the content of non-newtonian fluid calcium naphthenate.
In embodiment, overbased and high base number calcium naphthenate raw material is from Xinjiang Land Fine Petrochemical Co., Ltd, also can be according to the preparation method of a CN101885677A(highly basic calcium naphthenate) disclosed method preparation.
In comparative example, calcium sulfonate with high base number raw material is purchased from Jinzhou Hui Fatianhe Chemical Co., Ltd..
Embodiment 1
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(30kg); Naphthenic acid (pure acid number 120mgKOH/g, acid content 70%, 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(18kg).
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in to add 30kg total basicnumber be that naphthenate with superhigh base number calcium and 100 ° of C kinematic viscosity of 30kg of 400mgKOH/g are 31mm
2the HVI150BS lubricating base oil of/s, stirs, and heats to 80 ° of C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature is controlled at 80 ° of C 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 ° of C, constant temperature 30 minutes, material retrogradation; 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 3 times of hot water dissolvings' boric acid solution, stir, under stirring, being warmed up to 110 ° of C, keeping dehydration 60 minutes; Cool to 90 ° of C and add 0.7kg MDI rapid stirring 4 minutes, add 1.5kg stearylamine to stir 4 minutes, added MDI is 1:2 with the ratio of the amount of substance of stearylamine, and 120 ° of C constant temperature 20 minutes, is finally warmed up to 200 ° of C constant temperature 5 minutes.Then, be cooled to 160 ° of C, adding 100 ° of C kinematic viscosity that account for lubricating grease weight 18kg is 11mm
2the HVI500SN lubricating base oil of/s; Treat that temperature is cooled to 110 ° of C, 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 naphthenate 37.9%; Two polyureas 2.5%; Lubricating base oil 54.5%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%.
The two polyureas molecular structural formulas that contain in component are:
Embodiment 2
Naphthenate with superhigh base number calcium (total basicnumber is 420mgKOH/g, 30kg); 150BS(30kg); Naphthenic acid (pure acid number 100mgKOH/g, acid content 60%, 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(18kg).
A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in to add 30kg total basicnumber be that naphthenate with superhigh base number calcium and 100 ° of C kinematic viscosity of 30kg of 420mgKOH/g are 31mm
2the HVI150BS lubricating base oil of/s, stirs, and heats to 50 ° of C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature is controlled at 50 ° of C 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 95 ° of C, constant temperature 90 minutes, material retrogradation; 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 10 times of consoluet boric acid solution of hot water, stir, under stirring, being warmed up to 110 ° of C, keeping dehydration 60 minutes.
Another volume be 30L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in to add 18kg100 ° of C kinematic viscosity be 11mm
2the HVI500SN lubricating base oil of/s and 1.5kg stearylamine are warming up to 110 ° of C, stir 4 minutes, add 0.7kg MDI to stir 4 minutes, and added MDI is 1:2 with the ratio of the amount of substance of stearylamine, and 120 ° of C constant temperature 20 minutes, obtains two polyureas.
Gained two polyureas are all squeezed in a upper still, stirred, be finally warmed up to 200 ° of C constant temperature 10 minutes.Then, turn still cooling; Treat that temperature is cooled to 90 ° of C, 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 naphthenate 37.9%; Two polyureas 2.5%; Lubricating base oil 54.5%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%.
Embodiment 3
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(20kg); Propyl carbinol (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); Stearic acid (1.9kg); Boric acid (2.32kg); Lauryl amine (1.31kg); MDI(0.89kg); 500SN(28kg).
By the method for example 1, prepare overbased compound calcium naphthenate base two polyurea greases, different is to use propyl carbinol, stearic acid, lauryl amine to replace also respective change of naphthenic acid, 12-oxystearic acid, stearylamine and each component quantity, 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 naphthenate 37.9%; Two polyureas 2.5%; Lubricating base oil 54.6%; Calcium stearate 2.3%; Lime borate 2.7%.
Embodiment 4
Feed composition: high base number calcium naphthenate (total basicnumber is 320mgKOH/g, 30kg); 150BS(25kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1.66kg); TDI(0.54kg); 500SN(23kg).
By the method for example 1, prepare compound calcium naphthenate base two polyurea greases of high base number, different is to use 320mgKOH/g high base number calcium naphthenate, Witco 1298 Soft Acid, tolylene diisocyanate (TDI) to replace also respective change of 400mgKOH/g high base number calcium naphthenate, naphthenic acid, MDI and each component quantity, 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 naphthenate 37.9%; Two polyureas 2.5%; Lubricating base oil 54.5%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%.
Embodiment 5
Feed composition: high base number calcium naphthenate (total basicnumber is 360mgKOH/g, 30kg); 150BS(15kg); Naphthenic 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(7kg).
By the method for example 1, prepare compound calcium naphthenate base two polyurea greases of high base number, different is to use the consumption of 360mgKOH/g high base number calcium naphthenate and base oil to change, thereby make each material rate that larger change occur, 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 naphthenate 53.8%; Two polyureas 3.6%; Lubricating base oil 35.4%; 12-oxystearic acid calcium 3.4%; Lime borate 3.8%.
Embodiment 6
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (4.5kg); MDI(2.1kg); 500SN(18.6kg).
By the method for example 1, prepare overbased compound calcium naphthenate base two polyurea greases, the amount of different is stearylamine, quadrol, MDI and base oil changes to some extent, 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 naphthenate 37.9%; Two polyureas 7.5%; Lubricating base oil 49.5%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%.
Embodiment 7
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); PAO 40(30kg); Naphthenic 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); PAO 10(9kg); Dithio Acidic phosphates zinc (2kg); Molybdenum dialkyldithiocarbamacompositions (1kg); Tungsten disulfide (2kg); Two selenizing tungsten (2kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased compound calcium naphthenate base two polyurea greases, different is that 10(100 ° of C kinematic viscosity of use full synthetic oil poly & Alpha ,-olefin oil PAO is 11mm
2/ s) and PAO 40(100 ° of C kinematic viscosity be 41mm
2/ s) replace respectively 500SN and 150BS, and before homogenizing, add additive dithio Acidic phosphates zinc, molybdenum dialkyldithiocarbamacompositions, tungsten disulfide, two selenizing tungsten, to right-di-iso-octyldiphenylamine (0.2kg), 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 naphthenate 38.7%; Two polyureas 2.6%; Lubricating base oil 45.2%; 12-oxystearic acid calcium 2.5%; Lime borate 2.7%; Dithio Acidic phosphates zinc 2.3%; Molybdenum dialkyldithiocarbamacompositions 1.2%; Tungsten disulfide 2.3%; Two selenizing tungsten 2.3%; To right-di-iso-octyldiphenylamine 0.2%.
Embodiment 8
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(30kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.94kg); Para-totuidine (0.38kg); MDI(0.88kg); 500SN(18kg).
By the method for example 1, prepare overbased compound calcium naphthenate base two polyurea greases, different is that monoamine kind has increased 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 naphthenate 37.8%; Two polyureas 2.5%; Lubricating base oil 54.4%; 12-oxystearic acid calcium 2.5%; Lime borate 2.8%.
Embodiment 9
Feed composition: high base number calcium naphthenate (total basicnumber is 360mgKOH/g, 30kg); 150BS(20kg); Naphthenic 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); Lauryl amine (0.58kg); MDI(0.78kg); 500SN(28kg); To p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare compound calcium naphthenate base two polyurea greases of high base number, different is that monoamine kind has increased lauryl amine, phosphoric acid and p-di-iso-octyldiphenylamine and base oil consumption are changed to some extent, 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 naphthenate 35.9%; Two 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 0.2%.
Feed composition: high base number calcium naphthenate (total basicnumber is 360mgKOH/g, 30kg); 150BS(30kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(3kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Acetic acid (2kg); Stearylamine (1.5kg); MDI(0.7kg); 500SN(18kg).
By the method for example 9, prepare compound calcium naphthenate base two polyurea greases of high base number, 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 naphthenate 36.8%; Two polyureas 2.5%; Lubricating base oil 52.9%; 12-oxystearic acid calcium 2.3%; Lime borate 2.6%; Lime acetate 2.9%.
Comparative example 1
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 30kg); 150BS(25kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); 500SN(25.2kg); To right-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 100 ° of C kinematic viscosity of 25kg of 320mgKOH/g are 31mm
2the HVI150BS lubricating base oil of/s, stirs, and heats to 80 ° of C, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature is controlled at 80 ° of C 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; Add 2.32kg boric acid and with 6 times of consoluet boric acid solution of hot water, stir, 80 ° of C constant temperature 30 minutes, material retrogradation; Under stirring, be warmed up to 110 ° of C, keep 60 minutes, dehydration; Finally be warmed up to 200 ° of C constant temperature 5 minutes, add 25.2kg lubricating base oil 500SN; Treat that temperature is cooled to 110 ° of C, add 0.2kg to stir after 10 minutes p-di-iso-octyldiphenylamine, 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 (total basicnumber is 320mgKOH/g, 30kg); 150BS(30kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); 500SN(18kg); To right-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare high base number calcium naphthenate base two polyurea greases, different is that the calcium sulfonate with high base number that high base number calcium naphthenate is 320mgKOH/g with total basicnumber replaces and do not contain diamines, 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 41.5%; Two polyureas 2.6%; Lubricating base oil 55.9%.
Each lubricating grease properties of sample data of table 1
Continued
Claims (24)
1. compound calcium naphthenate base two polyurea greases, take lubricating grease weight as benchmark, comprise following component:
1) non-newtonian fluid calcium naphthenate 10%-70%; 2) the calcium salt 1%-10% of higher fatty acid;
3) the calcium salt 1%-15% of small molecules mineral acid and/or lipid acid; 4) two polyureas 0.5%-30%;
5) lubricating base oil 10%-80%.
2. according to lubricating grease claimed in claim 1, wherein take lubricating grease weight as benchmark, comprise following component:
1) non-newtonian fluid calcium naphthenate 20%-60%; 2) the calcium salt 2%-6% of higher fatty acid;
3) the calcium salt 2%-10% of small molecules mineral acid and/or lipid acid; 4) two polyureas 1%-20%; 5) lubricating base oil 20%-70%.
3. according to lubricating grease claimed in claim 1, wherein said non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place.
4. according to lubricating grease claimed in claim 1, wherein said non-newtonian fluid calcium naphthenate total basicnumber is 250mgKOH/g-450mgKOH/g.
5. according to lubricating grease claimed in claim 1, said higher fatty acid is that carbon number is straight chain fatty acid or the hydroxy fatty acid of 8-20.
6. according to lubricating grease claimed in claim 1, said higher fatty acid is selected from one or more mixtures in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.
7. according to lubricating grease claimed in claim 1, the molecular weight of said small molecules mineral acid or lipid acid is less than or equal to 150.
8. according to lubricating grease claimed in claim 1, said small molecules mineral acid is selected from one or more the mixture in boric acid, phosphoric acid, sulfuric acid.
9. according to lubricating grease claimed in claim 1, said small molecules lipid acid is selected from one or more the mixture in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.
10. according to lubricating grease claimed in claim 1, wherein, said two polyureas have following structure:
Wherein, R
1, R
3alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene.
11. according to lubricating grease claimed in claim 10, wherein, and R
1, R
3the phenyl of phenyl or replacement, or the carbon number alkyl or cycloalkyl that is 8 ~ 24; RR
26 ~ 30 arylidene, alkylidene group or cycloalkylidene.
12. according to lubricating grease claimed in claim 10, wherein, and R
1, R
3the phenyl that phenyl or C1 ~ C3 alkyl or halogen replace, or carbon number be 10 ~ 18 alkyl or cycloalkyl, R
2at least one in methylene phenyl, phenylbenzene methylene radical, dicyclohexyl methylene radical, phenylenedimethylidyne and hexylidene.
The preparation method of described compound calcium naphthenate base two polyurea greases of one of 13. claims 1 ~ 12, comprising:
(1) in reactor A, newton's body calcium naphthenate, part base oil and transforming agent are mixed, heated, make material retrogradation;
(2) in aforesaid reaction vessel, add lime or calcium hydroxide, add respectively higher fatty acid and small molecules mineral acid and/or lipid acid, dehydration heats up;
(3) in the product of reactor A or in reactor B, add part base oil and monoamine and vulcabond to react, wherein vulcabond is 1:2 with the ratio of the amount of substance of monoamine;
(4) mixing of materials in reactor A is even, or mix after the material of reactor A and B is merged, be warmed up to 200 ° of C-220 ° of C constant temperature refinings, cooling, add surplus base oil, add necessary additive, obtain finished product.
14. according to the preparation method described in claim 13, in step (1), by newton's body calcium naphthenate, part base oil Hybrid Heating to 50 ° C-80 ° C, add successively required transforming agent to react, all transforming agents add rear intensification, 80 ° of C-90 ° of C constant temperature 60 minutes-90 minutes, make material retrogradation.
15. according to the preparation method described in claim 13, in step (2), the suspension liquid that adds lime or calcium hydroxide at 85 ° of C-100 ° of C, at 85 ° of C-100 ° of C, add higher fatty acid, stir 5 minutes-20 minutes, add small molecules mineral acid and/or lipid acid, stir 5 minutes-20 minutes, be warmed up to 105 ° of C-120 ° of C, dehydration.
16. according to the preparation method described in claim 13, in step (3), in the product of step (2) or in another reactor, adds part base oil and monoamine, stirs 2 minutes-8 minutes, then adds vulcabond, reacts 2 minutes-8 minutes.
17. according to the preparation method described in claim 13, in step (4), the product of step (2) and (3) is mixed to rear intensification, 100 ° of C-120 ° of C constant temperature 10 minutes-20 minutes, is finally warmed up to 200 ° of C-220 ° of C constant temperature 5 minutes-10 minutes; Be cooled to 150 ° of C-160 ° of C, add surplus lubricating base oil, treat that temperature is cooled to 100 ° of C-120 ° of C, add necessary additive, stir circulating filtration, homogenizing, degassed.
18. according to the preparation method described in claim 13, and described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthetic calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g.
19. according to the preparation method described in claim 13, 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, calcium carbonate, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate (ABS), C16-C62 naphthenic acid, water, the add-on of transforming agent is the 2%-30% of newton's body calcium naphthenate weight.
20. according to the preparation method described in claim 13, said transforming agent is selected from one or more in Witco 1298 Soft Acid, methyl alcohol, Virahol, butanols, C20-C40 naphthenic acid, acetic acid and water, and the add-on of transforming agent is the 6%-22% of newton's body calcium naphthenate weight.
21. according to the preparation method described in claim 13, and wherein, said monoamine structural formula is R
1-NH
2, or R
3-NH
2, R wherein
1or R
3be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl is 8 ~ 24, and aryl is the phenyl of phenyl or replacement.
22. according to the preparation method described in claim 12, 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 is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.
23. according to the preparation method described in claim 13, and wherein, said vulcabond structure is OCN-R
2-NCO, R
2that carbon number is 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
24. according to the preparation method described in claim 13, wherein, described vulcabond is selected from least one in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate or xylylene diisocyanate vulcabond.
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| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
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| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN102453599A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium-sulfonate-based tetrapolyurea lubricating grease and preparation method thereof |
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|---|---|---|---|---|
| CN108003964A (en) * | 2016-10-27 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of lubricating grease and preparation method thereof |
| CN108003964B (en) * | 2016-10-27 | 2021-04-06 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
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