CN103695076A - Composite calcium naphthenate tetraurea lubricating grease and preparation method thereof - Google Patents
Composite calcium naphthenate tetraurea lubricating grease and preparation method thereof Download PDFInfo
- Publication number
- CN103695076A CN103695076A CN201210365559.5A CN201210365559A CN103695076A CN 103695076 A CN103695076 A CN 103695076A CN 201210365559 A CN201210365559 A CN 201210365559A CN 103695076 A CN103695076 A CN 103695076A
- Authority
- CN
- China
- Prior art keywords
- acid
- calcium
- lubricating grease
- add
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Lubricants (AREA)
Abstract
The invention provides composite calcium naphthenate tetraurea lubricating grease and a preparation method thereof. The lubricating grease comprises the following components based on the weight of the lubricating grease: 1) 10-70% of non-Newtonian calcium naphthenate, 2) 1-10% of a calcium salt of a higher aliphatic acid, 3) a calcium salt of an aromatic acid, 4) 0.5-30% of tetraurea and 5) 10-80% of lube base oil. Calcium petroleum naphthenate or synthetic calcium naphthenate is adopted as a raw material of the lubricating grease. The lubricating grease also comprises a composite calcium densifier and the tetraurea compound. The lubricating grease has excellent extreme pressure anti-wear property and ultra-long lubricating lifetime, and has good adhesivity, water resistance, colloid stability, high dropping point, heat stability, corrosion resistance, salt fog resistance, and other performances.
Description
Technical field
The present invention relates to lubricant, definite a kind of compound calcium naphthenate base four 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 four 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 four polyurea compounds simultaneously.
The present invention also provides above-mentioned preparation of greases method.
Calcium naphthenate base four 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 1-10% of higher fatty acid, preferably 2-6%, most preferably 2.2-4.2%;
3) the calcium salt 1-15% of aromatic acid, preferably 2-12%, most preferably 3-10%;
4) four 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.
Said aromatic acid is the carboxylic acid that has at least 1 carboxyl to be directly connected with aromatic ring, and other substituting group can be the alkyl or aryl of hydrogen, alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno etc., and molecular weight is less than or equal to 550.The preferred binary aromatic acid of described aromatic acid, for example, can be selected from one or more in phthalic acid unsubstituted or that C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.Preferably phthalic acid, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, and one or more in methyl substituted biphenyl dicarboxylic acid, santowax dioctyl phthalate etc.
The calcium salt that can also contain small molecules mineral acid and/or small molecules lipid acid in lubricating grease of the present invention.The molecular weight of said small molecules mineral acid or small molecules lipid acid is less than or equal to 150.Wherein, small molecules mineral acid can be selected from one or more the mixture in boric acid, phosphoric acid, sulfuric acid etc., preferred boric acid and/or phosphoric acid; Small molecules lipid acid can be selected from one or more the mixture in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid etc., preferably acetic acid.
Said four polyureas have following structure:
R wherein
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8 ~ 24, preferably 10 ~ 18, and aryl can be the phenyl of phenyl or replacement, the phenyl that preferably phenyl or C1 ~ C3 alkyl or halogen replace.
R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2 ~ 12, preferably 2 ~ 8, and arylidene can be phenylene or biphenylene.
R wherein
3can be that carbon number is 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, at least one in preferable methyl phenylene, phenylbenzene methylene radical, dicyclohexyl methylene radical, a dimethyl phenylene and hexylidene.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 ° of C kinematic viscosities are 4-150mm
2/ s, preferably 10-60mm
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, anti-wear agent, rust-preventive agent etc.The preferred arylamine kind antioxidant of oxidation inhibitor wherein, accounts for the 0.1%-5% of lubricating grease gross weight, and preferably 0.2%-1%, can be pentanoic, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or their mixture, preferably di-iso-octyldiphenylamine.Anti-wear agent 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 four polyurea greases, comprising:
(1) in reactor A, newton's body calcium naphthenate, part base oil and transforming agent are mixed, heated, make material retrogradation become smectic;
(2) in aforesaid reaction vessel, add lime or calcium hydroxide, add respectively higher fatty acid and aromatic acid, dehydration heats up;
(3) in the product of reactor A or in reactor B, add part base oil and vulcabond, first add diamines to react, then add monoamine to react, wherein the mol ratio of vulcabond, diamines and monoamine is 2:1:2;
(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 200-220 ° of C constant temperature refining, 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), newton's body calcium naphthenate, part base oil Hybrid Heating are arrived to 50-90 ° of C, preferably constant temperature 10-30 minute, adds required transforming agent to react successively, preferably adds rear stirring about 10 minutes at every turn, react fully, all transforming agents add rear intensification, preferably, at 60-100 ° of C constant temperature 0.5-3 hour, make material retrogradation become smectic.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 one or more in 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 85-100 ° of C, at 85-100 ° of C, add higher fatty acid, stir 5-20 minute, add aromatic acid, can also add necessary small molecules mineral acid and/or small molecules lipid acid, stir 5-20 minute, be warmed up to 105-120 ° of C, preferably keep 30-60 minute, dehydration, cools to 90 ° of C-105 ° of C; Its Fatty Acids and aromatic acid addition sequence can exchange.
Said higher fatty acid is that carbon number is 8-20, preferably straight chain fatty acid or the hydroxy fatty acid of 10-16, for example one or more mixtures in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, preferably 12-oxystearic acid.
Said aromatic acid is the carboxylic acid that has at least 1 carboxyl to be directly connected with aromatic ring, and other substituting group can be the alkyl or aryl of hydrogen, alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno etc., and molecular weight is less than or equal to 550.The preferred binary aromatic acid of described aromatic acid, for example, can be selected from one or more in phthalic acid unsubstituted or that C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.Preferably phthalic acid, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, and one or more in methyl substituted biphenyl dicarboxylic acid, santowax dioctyl phthalate etc.
The molecular weight of said small molecules mineral acid or small molecules lipid acid is less than or equal to 150.Wherein, small molecules mineral acid can be selected from one or more the mixture in boric acid, phosphoric acid, sulfuric acid etc., preferred boric acid and/or phosphoric acid; Small molecules lipid acid can be selected from one or more the mixture in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid etc., preferably acetic acid.
The total amount of substance of the H+ OH-total amount of substance contained with calcium hydroxide of higher fatty acid and aromatic acid and small molecules mineral acid and/or small molecules lipid acid equate, the amount of calcium hydroxide also can excessive 1%-10%.
In step (3), in the product of step (2) or in another reactor, add part base oil and vulcabond, stir, add diamines, reaction 2-8 minute, adds monoamine, reaction 2-8 minute, the mol ratio of vulcabond, diamines and monoamine is 2:1:2, and monoamine, diamines and vulcabond can first be dissolved in part base oil.
Said vulcabond structure is OCN-R
3-NCO, R
3can be that carbon number is 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, preferable methyl phenylene, phenylbenzene methylene radical, dicyclohexyl methylene radical, a dimethyl phenylene and hexylidene etc.For example described vulcabond can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), 1, hexamethylene-diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), or at least one in xylylene diisocyanate (XDI) etc.
Said monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R wherein
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8 ~ 24, preferably 10 ~ 18, and aryl can be the phenyl of phenyl or replacement, the phenyl that preferably phenyl or C1 ~ C3 alkyl or halogen replace.Preferred monoamine can be the arylamine that is selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.
Said diamines can be aliphatic amide or arylamine, and structural formula is NH
2-R
2-NH
2, R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2 ~ 12, preferably 2 ~ 8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from the aromatic amine of Ursol D, O-Phenylene Diamine, 4,4 '-benzidine and/or be selected from quadrol, propylene diamine, 1, the straight-chain fatty amine of 6-hexanediamine.
In step (4), the product of step (2) and step (3) is mixed to rear intensification, preferably 100-120 ° of C constant temperature 10-20 minute, is finally warmed up to 200-220 ° of C constant temperature 5-10 minute; Be cooled to 150-160 ° of C, add surplus lubricating base oil, treat that temperature is cooled to 100-120 ° 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 2 preparations.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 four polyureas molecules-the stretching vibration absorption peak of NH-.
Fig. 2 is the infrared analysis spectrogram of four polyureas in the lubricating grease of embodiment 2 preparation.As can be seen from the figure, 3310 ~ 3323cm
-1the peak at place is in four polyureas molecules-the stretching vibration absorption peak of NH-, and 1630cm
-1the peak at place is in four polyureas molecules-vibration absorption peak of CO-.
Fig. 3 is the nuclear magnetic resonance spectroscopy spectrogram of four polyureas in the lubricating grease of embodiment 2 preparation.As can be seen from the figure, the peak of δ=155HZ left and right is in four polyureas molecules-chemical shift of CO-.
Fig. 4 is the Electrospray Ionization Mass Spectrometry spectrogram of four polyureas in the lubricating grease of embodiment 2 preparation.As can be seen from the figure, the mass-to-charge ratio of sample is 1100.4m/z, and the relative molecular mass of this and four polyurea compounds matches.
Embodiment
In embodiment, the method for calculation of each component concentration are as follows:
Non-newtonian fluid calcium naphthenate %=(overbased or high base number calcium naphthenate raw materials quality+transforming agent total mass)/lubricating grease total mass.Transforming agent all counts in the content of non-newtonian fluid calcium naphthenate.
The calcium salt of higher fatty acid and the calcium salt content of aromatic acid calculate with the higher fatty acid and the aromatic acid complete reaction that add.
In embodiment, overbased and high base number calcium naphthenate raw material, also can be according to the disclosed method preparation of CN101885677A (a kind of preparation method of highly basic calcium naphthenate) from Xinjiang Land Fine Petrochemical Co., Ltd.
In comparative example, calcium sulfonate with high base number raw material is purchased from Jinzhou Hui Fatianhe Chemical Co., Ltd..
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); Methyl alcohol (1kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg) stearylamine (1.08kg); Quadrol (0.12kg); MDI (1kg); 500SN (17kg).
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; Add 1kg methyl alcohol, stir 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 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 3.5kg terephthalic acid, stir, under stirring, be warmed up to 110 ° of C, keep 60 minutes, dehydration; Cool to 90 ° of C and add 1kg MDI rapid stirring 4 minutes, under rapid stirring, add 0.12kg quadrol, stir 4 minutes, add 1.08kg stearylamine to stir 4 minutes, the mol ratio of added MDI, quadrol and stearylamine is 2:1:2,120 ° 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 37.5%; Four polyureas 2.5%; Lubricating base oil 52.8%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 4.8%.
Embodiment 2
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 420mgKOH/g, 30kg); 150BS (30kg); Witco 1298 Soft Acid (2.8kg); Virahol (1kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.08kg); Quadrol (0.12kg); MDI (1kg); 500SN (17kg).
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 Witco 1298 Soft Acid, temperature is controlled at 50 ° of C left and right, stirs 10 minutes; Add 1kg Virahol, stir 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 becomes smectic; Add 1.8kgCa (OH)
2and with 4 times of water-reducible suspension liquids, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir, under stirring, be warmed up to 110 ° of C, keep 60 minutes, dehydration.
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 1kg MDI are warming up to 110 ° of C, add 0.12kg quadrol under rapid stirring, stir 4 minutes, add 1.08kg stearylamine to stir 4 minutes, the mol ratio of added MDI, quadrol and stearylamine is 2:1:2, and 120 ° of C constant temperature 20 minutes, obtains four polyureas.
Gained four 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.
By above-mentioned steps 2 same methods, prepare a small amount of four polyureas, with sherwood oil (60 ~ 90 ℃ of boiling points) washing, filtration is precipitated again, and gained precipitation obtains four polyurea compounds after drying.Its infrared spectrum, nuclear magnetic resonance spectroscopy spectrogram, Electrospray Ionization Mass Spectrometry spectrogram are shown in respectively Fig. 2, Fig. 3, Fig. 4.
The four polyureas molecular structural formulas that contain in component are:
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 37.5%; Four polyureas 2.5%; Lubricating base oil 52.8%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 4.8%.
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); Phthalic acid (3.5kg); Lauryl amine (0.88kg); Quadrol (0.14kg); MDI (1.18kg); 500SN (27kg).
By the method for example 1, prepare overbased compound calcium naphthenate base four polyurea greases, different is to use propyl carbinol, stearic acid, phthalic acid, lauryl amine to replace also respective change of naphthenic acid, 12-oxystearic acid, terephthalic 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 37.5%; Four polyureas 2.5%; Lubricating base oil 52.9%; Calcium stearate 2.3%; Calcium phthalate 4.8%.
Embodiment 4
Feed composition: high base number calcium naphthenate (total basicnumber is 320mgKOH/g, 30kg); 150BS (25kg); Witco 1298 Soft Acid (2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); M-phthalic acid (3.5kg); Stearylamine (1.25kg); Quadrol (0.14kg); TDI (0.81kg); 500SN (22kg).
By the method for example 1, prepare compound calcium naphthenate base four polyurea greases of high base number, different is to use 320mgKOH/g high base number calcium naphthenate, Witco 1298 Soft Acid, m-phthalic acid, tolylene diisocyanate (TDI) to replace also respective change of 400mgKOH/g high base number calcium naphthenate, naphthenic acid, terephthalic 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 37.5%; Four polyureas 2.5%; Lubricating base oil 52.8%; 12-oxystearic acid calcium 2.4%; M-phthalic acid calcium 4.8%.
Embodiment 5
Feed composition: high base number calcium naphthenate (total basicnumber is 360mgKOH/g, 30kg); 150BS (15kg); Naphthenic acid (2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); 2-methyl isophthalic acid, 4-phthalic acid (3.8kg); Stearylamine (1.08kg); Quadrol (0.12kg); MDI (1kg); 500SN (7kg).
By the method for example 1, prepare compound calcium naphthenate base four polyurea greases of high base number, different is to use 360mgKOH/g high base number calcium naphthenate, 2-methyl isophthalic acid, the consumption of 4-phthalic acid and base oil changes, 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 52.1%; Four polyureas 3.5%; Lubricating base oil 34.4%; 12-oxystearic acid calcium 3.3%; 2-methyl isophthalic acid, 4-phthalic acid calcium 6.7%.
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); 4,4 '-biphenyl dicarboxylic acid (5.1kg); Stearylamine (3.24kg); Quadrol (0.36kg); MDI (3kg); 500SN (18.6kg).
By the method for example 1, prepare overbased compound calcium naphthenate base four polyurea greases, different is to use 4,4 '-biphenyl dicarboxylic acid replaces terephthalic acid, and the amount of 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 36.4%; Four polyureas 7.2%; Lubricating base oil 47.6%; 12-oxystearic acid calcium 2.3%; 4,4 '-biphenyl dicarboxylic acid calcium 6.5%.
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); Terephthalic acid (3.5kg); Stearylamine (1.08kg); Quadrol (0.12kg); MDI (1kg); PAO 10 (9kg); Dithio Acidic phosphates zinc (2kg); Molybdenum dialkyldithiocarbamacompositions (1kg); Tungsten disulfide (2kg); Two selenizing tungsten (2kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased compound calcium naphthenate base four polyurea greases, different is that (100 ° of C kinematic viscosity are 10mm to use full synthetic oil poly & Alpha ,-olefin oil PAO 10
2/ s) and PAO 40 (100 ° of C kinematic viscosity are 40mm
2/ s) replace respectively 500SN and 150BS, and before homogenizing, add additive dithio Acidic phosphates zinc, molybdenum dialkyldithiocarbamacompositions, tungsten disulfide, two selenizing tungsten, right, right '-di-iso-octyldiphenylamine, 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%; Four polyureas 2.5%; Lubricating base oil 44.2%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 4.9%; Dithio Acidic phosphates zinc 2.3%; Molybdenum dialkyldithiocarbamacompositions 1.1%; Tungsten disulfide 2.3%; Two selenizing tungsten 2.3%; Right, right '-di-iso-octyldiphenylamine 0.2%.
Embodiment 8
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.08kg); Quadrol (0.12kg); MDI (1kg); 500SN (33kg).
By the method for example 1, prepare overbased compound calcium naphthenate base four polyurea greases, different is that right '-di-iso-octyldiphenylamine and base oil consumption change to some extent not containing oxidation inhibitor pair, 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 37.1%; Four polyureas 2.4%; Lubricating base oil 53.3%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 4.8%.
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); Terephthalic acid (7.6kg); Stearylamine (1.08kg); Quadrol (0.12kg); MDI (1kg); 500SN (28kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 9, prepare compound calcium naphthenate base four polyurea greases of high base number, different is has increased phosphoric acid and base oil consumption 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 34.2%; Four polyureas 2.2%; Lubricating base oil 49.2%; 12-oxystearic acid calcium 2.2%; Lime borate 2.4%; Terephthalic acid calcium 9.6%; Right, right '-di-iso-octyldiphenylamine 0.2%.
Embodiment 10
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(3kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Acetic acid (2kg); Stearylamine (1.08kg); Quadrol (0.12kg); MDI (1kg); 500SN (33kg).
By the method for example 9, prepare compound calcium naphthenate base four polyurea greases of high base number, different is has increased acetic acid and base oil consumption 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 36.0%; Four polyureas 2.4%; Lubricating base oil 51.8%; 12-oxystearic acid calcium 2.3%; Terephthalic acid calcium 4.7%; Lime acetate 2.8%.
Embodiment 11
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS (30kg); Naphthenic acid (2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Para-totuidine (0.61kg); Quadrol (0.17kg); MDI (1.42kg); 500SN (17kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased compound calcium naphthenate base four polyurea greases, different is to replace stearylamine with para-totuidine, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 37.4%; Four polyureas 2.5%; Lubricating base oil 52.7%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 4.8%; Right, right '-di-iso-octyldiphenylamine 0.2%.
Embodiment 12
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS (15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.03kg); 1,6-hexanediamine (0.22kg); MDI (0.95kg); 500SN (33kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased compound calcium naphthenate base four polyurea greases, different is with Witco 1298 Soft Acid, 1,6-hexanediamine replaces quadrol to replace naphthenic acid and quadrol and base oil consumption to change, 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 37.0%; Four polyureas 2.4%; Lubricating base oil 53.2%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 4.8%; Right, right '-di-iso-octyldiphenylamine 0.2%.
Comparative example 1
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); 500SN (20.2kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
A volume be 160L 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 30kg 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; 85 ° of C constant temperature 30 minutes, material retrogradation became smectic; 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.Be cooled to 160 ° of C, add the lubricating base oil 500SN that accounts for lubricating grease weight 20.2kg; Treat that temperature is cooled to 110 ° of C, add and account for lubricating grease weight 0.2kg couple, right '-di-iso-octyldiphenylamine stirred after 10 minutes, circulating filtration, homogenizing, the degassed finished product that obtains.Assay is in Table 1.
Comparative example 2
Feed composition: calcium sulfonate with high base number (320mgKOH/g, 30kg); 150BS (30kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI (0.7kg); 500SN (18kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare high base number composite calcium sulfonate base two polyurea greases, different is use the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g and do not contain diamines, and each performance data of lubricating grease finished product obtaining is in Table 1.
Each lubricating grease properties of sample data of table 1
Continued
Claims (26)
1. compound calcium naphthenate base four 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 aromatic acid; 4) four 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 aromatic acid; 4) four polyureas 1-20%; 5) lubricating base oil 20-70%.
3. according to lubricating grease claimed in claim 1, described non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm
-1-886cm
-1place occurs that crystal form calcium carbonate charateristic avsorption band, its total basicnumber are 250mgKOH/g-450mgKOH/g.
4. 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.
5. 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.
6. according to lubricating grease claimed in claim 1, described aromatic acid is the carboxylic acid that has at least 1 carboxyl to be directly connected with aromatic ring, and other substituting group can be the alkyl or aryl of hydrogen, alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, and molecular weight is less than 550.
7. according to lubricating grease claimed in claim 1, described aromatic acid is selected from one or more in phthalic acid unsubstituted or that C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.
8. according to lubricating grease claimed in claim 1, wherein also contain the calcium salt of small molecules mineral acid and/or small molecules lipid acid, described small molecules mineral acid and/or small molecules fatty acid molecule amount are less than or equal to 150.
9. 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, 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.
10. according to lubricating grease claimed in claim 1, wherein, said four polyureas have following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
11. according to lubricating grease claimed in claim 10, wherein, and R
1the phenyl of phenyl or replacement, or the carbon number alkyl or cycloalkyl that is 8 ~ 24; R
2that phenylene or biphenylene or carbon number are 2 ~ 12 alkylidene group; R
3that carbon number is 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
12. according to lubricating grease claimed in claim 10, wherein, and R
1the phenyl that phenyl or C1 ~ C3 alkyl or halogen replace, or carbon number be 10 ~ 18 alkyl or cycloalkyl, R
2phenylene or biphenylene, or the carbon number alkylidene group that is 2 ~ 8; R
3be selected from least one in methylphenylene, phenylbenzene methylene radical, dicyclohexyl methylene radical, a dimethyl phenylene and hexylidene.
The preparation method of described compound calcium naphthenate base four 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 become smectic;
(2) in aforesaid reaction vessel, add lime or calcium hydroxide, add respectively higher fatty acid and aromatic acid, dehydration heats up;
(3) in the product of reactor A or in reactor B, add part base oil and vulcabond, first add diamines to react, then add monoamine to react, wherein the mol ratio of vulcabond, diamines and monoamine is 2:1:2;
(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 200-220 ° of C constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
14. according to the preparation method described in claim 13, in step (1), newton's body calcium naphthenate, part base oil Hybrid Heating are arrived to 50-90 ° of C, add successively required transforming agent to react, all transforming agents add rear intensification, at 60-100 ° of C constant temperature 0.5-3 hour, making material retrogradation is smectic.
15. according to the preparation method described in claim 13, in step (2), the suspension liquid that adds lime or calcium hydroxide at 85-100 ° of C, at 85-100 ° of C, add higher fatty acid, stir 5-20 minute, add aromatic acid, and necessary small molecules mineral acid and/or small molecules lipid acid, stir 5-20 minute, be warmed up to 105-120 ° of C, dehydration.
16. according to the preparation method described in claim 13, in step (3), adds part base oil and vulcabond in the product of step (2) or in another reactor, stir 2-8 minute, under stirring, add diamines, reaction 2-8 minute, add monoamine, reaction 2-8 minute.
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, at 100-120 ° of C constant temperature 10-20 minute, is finally warmed up to 200-220 ° of C constant temperature 5-10 minute; Be cooled to 150-160 ° of C, add surplus lubricating base oil, treat that temperature is cooled to 100-120 ° 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 250-450mgKOH/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 calcium carbonate, boric acid, 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, and said transforming agent is selected from one or more in Witco 1298 Soft Acid, C16-C62 naphthenic acid, methyl alcohol, butanols, 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, R wherein
1be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl is 8 ~ 24, and aryl is the phenyl of phenyl or replacement.
22. according to the preparation method described in claim 13, 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 diamines structural formula is NH
2-R
2-NH
2, R wherein
2be alkylidene group or arylidene, the carbon number of alkylidene group is 2 ~ 12, and arylidene is phenylene or biphenylene.
24. according to the preparation method described in claim 13, and wherein, said diamines is selected from the aromatic amine of Ursol D, O-Phenylene Diamine, 4,4 '-benzidine, and/or is selected from quadrol, propylene diamine, 1, the straight-chain fatty amine of 6-hexanediamine.
25. according to the preparation method described in claim 13, and wherein, said vulcabond structure is OCN-R
3-NCO, R
3that carbon number is 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
26. according to the preparation method described in claim 13, and wherein, described vulcabond is selected from tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, or at least one in xylylene diisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210365559.5A CN103695076B (en) | 2012-09-27 | 2012-09-27 | A kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210365559.5A CN103695076B (en) | 2012-09-27 | 2012-09-27 | A kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103695076A true CN103695076A (en) | 2014-04-02 |
| CN103695076B CN103695076B (en) | 2016-08-24 |
Family
ID=50356746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210365559.5A Active CN103695076B (en) | 2012-09-27 | 2012-09-27 | A kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103695076B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293450A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based tetra-polyurea lubricating grease and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7171110B1 (en) * | 2001-11-30 | 2007-01-30 | Keen Personal Media, Inc. | System and a method for storing audio/video programs on a hard disk drive for presentation to a viewer |
| 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 |
-
2012
- 2012-09-27 CN CN201210365559.5A patent/CN103695076B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7171110B1 (en) * | 2001-11-30 | 2007-01-30 | Keen Personal Media, Inc. | System and a method for storing audio/video programs on a hard disk drive for presentation to a viewer |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 李玲等: "高碱性环烷酸钙的合成与性能研究", 《石油炼制与化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293450A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based tetra-polyurea lubricating grease and preparation method thereof |
| CN104293450B (en) * | 2013-07-17 | 2017-02-08 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based tetra-polyurea lubricating grease and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103695076B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102453599B (en) | Composite calcium-sulfonate-based tetrapolyurea lubricating grease and preparation method thereof | |
| CN102453600B (en) | Composite calcium sulfonate-based hexaurea grease | |
| CN102453598B (en) | Composite calcium sulfonate-based octaurea lubricating grease | |
| CN102417855B (en) | Calcium sulfonate tetra-polyurea lubricating grease and preparation method thereof | |
| CN102417856B (en) | Calcium-sulfonate-based hexapolyurea lubricating grease and preparation method thereof | |
| CN102417853A (en) | Calcium sulfonate octaurea lubricating grease and preparation method thereof | |
| CN103571570B (en) | A kind of Calcium naphthenate base four polyurea grease and preparation method thereof | |
| CN103695075B (en) | A kind of Composite calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN103571571B (en) | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103695074B (en) | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN103695076A (en) | Composite calcium naphthenate tetraurea lubricating grease and preparation method thereof | |
| CN103571588B (en) | A kind of Calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN103695138B (en) | A kind of Composite calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103627495B (en) | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN103571598B (en) | A kind of Calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN103627498B (en) | A kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof | |
| CN104449956B (en) | A kind of high base number composite calcium-base polyurea grease and preparation method thereof | |
| CN104450109B (en) | A kind of polyurea grease of high base number composite calcium-base four and preparation method thereof | |
| CN103627497B (en) | A kind of Composite calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103627470B (en) | A kind of Composite calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN104293452A (en) | Composite calcium naphthenate-based polyurea lubricating grease and preparation method thereof | |
| CN104450113B (en) | A kind of high base number composite calcium-base octa-polyurea lubricating grease and preparation method thereof | |
| CN104449958A (en) | Composite calcium sulfonate-calcium naphthenate-based urea octamer grease and preparation method thereof | |
| CN104450114A (en) | Composite calcium sulfonate-calcium naphthenate-based urea tetramer grease and preparation method thereof | |
| CN104449957A (en) | Composite calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |