CN103695074A - Composite calcium naphthenate diurea lubricating grease and preparation method thereof - Google Patents
Composite calcium naphthenate diurea lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention provides composite calcium naphthenate diurea 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) 1-15% of a calcium salt of an aromatic acid, 4) 0.5-30% of diurea, 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 diurea 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 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 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) 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.
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 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.
R2 wherein can 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 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 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, monoamine and vulcabond to react, wherein the mol ratio of vulcabond and monoamine is 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 minutes-20 minutes, be warmed up to 105 ° of C-120 ° of C, preferably keep 30 minutes-60 minutes, 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 OH that the total amount of substance of H+ of higher fatty acid and aromatic acid and small molecules mineral acid and/or small molecules lipid acid and calcium hydroxide are contained
-total amount of substance is equal, and 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 monoamine and vulcabond to react, wherein the mol ratio of vulcabond and monoamine is 1:2, 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, 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
2-NH
2, R wherein
1, R
2can 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 100-120 ° 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 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 the stretching vibration absorption peak of NH-in two polyureas molecules.
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..
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); Methyl alcohol (1kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.5kg); MDI (0.7kg); 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 0.7kg MDI rapid stirring 4 minutes, add 1.5kg stearylamine to stir 4 minutes, the mol ratio of added MDI and stearylamine is 1:2, 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 37.5%; Two polyureas 2.5%; Lubricating base oil 52.8%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 4.8%.
The two polyureas molecular structural formulas that contain in component are:
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 (1.5kg); MDI (0.7kg); 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.Sampling, its infrared spectrum is shown in Fig. 1.
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 the mol ratio of added MDI and stearylamine is 1:2, 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 37.5%; Two 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 (1.31kg); MDI (0.89kg); 500SN (27kg).
By the method for example 1, prepare overbased compound calcium naphthenate base two 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%; Two 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 (1.66kg); TDI (0.54kg); 500SN (22kg).
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, 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%; Two 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); Terephthalic acid (3.5kg); 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 52.1%; Two polyureas 3.5%; Lubricating base oil 34.4%; 12-oxystearic acid calcium 3.3%; Terephthalic 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 (4.5kg); MDI (2.1kg); 500SN (18.6kg).
By the method for example 1, prepare overbased compound calcium naphthenate base two polyurea greases, different is to use 4,4 '-biphenyl dicarboxylic acid replaces terephthalic acid, and the amount of stearylamine, 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%; Two 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 (1.5kg); MDI (0.7kg); 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 two 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%; Two 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); 2-methyl isophthalic acid, 4-phthalic acid (3.8kg); Stearylamine (0.94kg); Para-totuidine (0.38kg); MDI (0.88kg); 500SN (33kg).
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 do not contained oxidation inhibitor pair, right '-di-iso-octyldiphenylamine, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 37.1%; Two polyureas 2.4%; Lubricating base oil 53.3%; 12-oxystearic acid calcium 2.4%; 2-methyl isophthalic acid, 4-phthalic 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 (0.84kg); Lauryl amine (0.58kg); MDI (0.78kg); 500SN (28kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 9, prepare compound calcium naphthenate base two polyurea greases of high base number, monoamine kind that different is has increased lauryl amine, phosphoric acid and base oil consumption and has 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 34.2%; Two 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); Eight amine (1.5kg); MDI (0.7kg); 500SN (33kg).
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 36.0%; Two polyureas 2.4%; Lubricating base oil 51.8%; 12-oxystearic acid calcium 2.3%; Terephthalic acid calcium 4.7%; Lime acetate 2.8%.
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 (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 aromatic 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 aromatic acid; 4) two 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 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; R
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
2be 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 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 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 monoamine and vulcabond to react, wherein the mol ratio of vulcabond and monoamine is 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 other small molecules mineral acids 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), in the product of step (2) or in another reactor, add part base oil and monoamine, stir 2-8 minute, add again the vulcabond being dissolved in part base oil, 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), 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, 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 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 vulcabond structure is OCN-R
3-NCO, R
3that carbon number is 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
24. 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 in xylylene diisocyanate at least one.
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| CN102453598A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof |
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| 黎克芬等: "应用高碱值环烷酸钙研制DCB4015", 《润滑油》 * |
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| CN104293452B (en) * | 2013-07-17 | 2016-08-10 | 中国石油化工股份有限公司 | A kind of Composite calcium naphthenate base polyurea grease and preparation method thereof |
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