CN103695137A - Composite calcium naphthenate lubricating grease and preparation method thereof - Google Patents
Composite calcium naphthenate lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention provides composite calcium naphthenate 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, and 4) 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. The lubricating grease has excellent water-spraying resistance and water-spraying leaching resistance, and has excellent adhesivity, extreme pressure anti-wear property, colloid stability, high dropping point, heat stability, water resistance, corrosion resistance, salt fog resistance, and other performances.
Description
Technical field
The present invention relates to lubricant, the definite a kind of high base number complex loop alkanoic acid quicklime grease and preparation method thereof that says.
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.
Utilize the lubricating grease that calcium sulfonate with high base number is raw material production, because it has excellent high temperature performance, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion, since putting goods on the market, cause the extensive concern of domestic and international lubricating grease industry, 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 complex loop alkanoic acid quicklime grease, it is raw material that this lubricating grease has adopted high base number calcium naphthenate, contains composite calcium viscosifying agent simultaneously.
The present invention also provides above-mentioned preparation of greases method.
Calcium naphthenate base grease provided by the invention, take lubricating grease weight as benchmark, comprises 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%-18% of aromatic acid, preferably 2%-15%, most preferably 3%-12%;
4) 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, its structure is as shown in (I) formula, and its total basicnumber is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g, change into after non-newtonian fluid calcium naphthenate, its base number is constant.
Wherein, the alkyl chain that R is C3-C20, (CH
2)
nin also may comprise 1-4 five-ring or six-ring, n=7-36; M can be up to 45.
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.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 ° of C kinematic viscosities are 4mm
2/ s-60mm
2/ s, preferably 10mm
2/ s-30mm
2/ s.Synthetic oil can be poly & Alpha ,-olefin oil (PAO), ester class oil, alkyl-silicone oil, Fischer-Tropsch synthesis oil etc.
In lubricating grease of the present invention, can also contain various additives, as oxidation inhibitor, anti-wear agent, rust-preventive agent etc.The preferred arylamine kind antioxidant of oxidation inhibitor wherein, accounts for the 0.1%-5% of lubricating grease gross weight, and preferably 0.2%-1%, can be pentanoic, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or their mixture, preferably di-iso-octyldiphenylamine.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 complex loop alkanoic acid quicklime grease, comprising:
(1) newton's body calcium naphthenate, part base oil and transforming agent are mixed, heated, make material retrogradation;
(2) add lime or calcium hydroxide, add respectively higher fatty acid and aromatic acid, dehydration heats up;
(3) 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, 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, add successively required transforming agent to react, preferably add rear stirring about 10 minutes at every turn, react fully, preferably, 60 ° 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 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-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 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 etc., preferably one or more in Witco 1298 Soft Acid, methyl alcohol, Virahol, butanols, C20-C40 naphthenic acid, 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 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 H of higher fatty acid and aromatic acid and small molecules mineral acid and/or small molecules lipid acid
+the OH that total amount of substance 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), the product of step (2) is heated up, preferably at 100 ° C-120 ° C constant temperature 10-20 minute, be 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 has good extreme pressure anti-wear and overlength lubricating life, meanwhile, also has the performances such as good adhesivity, water resisting property, colloid stability, high dropping point, heat-resistant quality, non-corrosibility, resistance to salt(spray)fog.This product preparation process is simple, constant product quality.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of lubricating grease and the infrared spectrum of high base number calcium naphthenate raw material 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.In raw material, the absorption peak of unformed carbonic acid calcium is 863cm
-1, after one-tenth fat, its absorption peak is 874cm
-1.
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 naphthenic acid, acetic acid, Witco 1298 Soft Acid, methyl alcohol, butanols etc. all count in the content of non-newtonian fluid calcium naphthenate.
The content of the calcium salt of the calcium salt of higher fatty acid and small molecules mineral acid or lipid acid, calculates according to the amount of added higher fatty acid and small molecules mineral acid or lipid acid and calcium hydroxide complete reaction generation calcium salt.
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) purchased 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 (total acid value is 120mgKOH/g, acid content 70%, 2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); 500SN (17kg).
A volume be 110L 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 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 60 ° 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; 120 ° of C constant temperature 20 minutes, is warmed up to 200 ° of C constant temperature 5 minutes.Then, be cooled to 160 ° of C, adding 100 ° of C kinematic viscosity of 17kg is 11mm
2the HVI500SN lubricating base oil of/s; 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.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 38.4%; Lubricating base oil 54.2%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 5.0%.
Embodiment 2
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 420mgKOH/g, 30kg); 150BS (30kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Phthalic acid (3.5kg); 500SN (18kg).
By the method for example 1, prepare overbased complex loop alkanoic acid quicklime grease, the total basicnumber of the naphthenate with superhigh base number calcium that different is uses is 420mgKOH/g, and each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 3
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS (20kg); Butanols (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); Stearic acid (1.9kg); M-phthalic acid (3.5kg); 500SN (28kg).
By the method for example 1, prepare overbased complex loop alkanoic acid quicklime grease, different is to use butanols, stearic acid, m-phthalic acid to replace naphthenic acid, 12-oxystearic acid, terephthalic acid, the amount of base oil also changes to some extent, and each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 4
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 39kg); 150BS (20kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); 500SN (28kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare overbased complex loop alkanoic acid quicklime grease, different is to replace naphthenic acid with Witco 1298 Soft Acid, and the amount of base oil also 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 39.6%; Lubricating base oil 54.2%; 12-oxystearic acid calcium 2.0%; Terephthalic acid calcium 4.0%; Right, right '-di-iso-octyldiphenylamine 0.2%.
Embodiment 5
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); 500SN (7kg).
By the method for example 1, prepare overbased complex loop alkanoic acid quicklime grease, the amount of different is base oil changes to some extent, thereby makes each material rate that larger change occur, 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 54.0%; Lubricating base oil 35.6%; 12-oxystearic acid calcium 3.4%; Terephthalic acid calcium 7.0%.
Embodiment 6
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS (30kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); 500SN (17kg).
By the method for example 1, prepare overbased complex loop alkanoic acid quicklime grease, different is uses Witco 1298 Soft Acid to replace naphthenic acid and uses full synthetic oil poly & Alpha ,-olefin oil PAO 10 (100 ° of C kinematic viscosity are 11mm
2/ s) and PAO 40 (100 ° of C kinematic viscosity are 41mm
2/ s) replace respectively 500SN and 150BS, each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 7
Feed composition: high base number calcium naphthenate (total basicnumber is 320mgKOH/g, 30kg); 150BS (30kg); 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); 500SN (16.7kg).
By the method for example 1, prepare high base number complex loop alkanoic acid quicklime grease, the total basicnumber of the high base number calcium naphthenate that different is uses is 320mgKOH/g, and each performance data of lubricating grease finished product obtaining is in Table 1.
Embodiment 8
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(1.8kg); 12-oxystearic acid (2kg); 4,4'-biphenyl dicarboxylic acid (5.1kg); 500SN (20kg); Right, right '-di-iso-octyldiphenylamine (0.2kg); Dithio dialkyl amido formic acid molybdenum (4kg); Selenium Sulfide (4kg); Benzotriazole (0.4kg).
By the method for example 1, prepare high base number complex loop alkanoic acid quicklime grease, the total basicnumber of the high base number calcium naphthenate that different is uses is 360mgKOH/g, and adds certain additive, 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 33.4%; Lubricating base oil 50.0%; 12-oxystearic acid calcium 2.1%; 4,4'-biphenyl dicarboxylic acid calcium 5.9%; Right, right '-di-iso-octyldiphenylamine 0.2%; Dithio dialkyl amido formic acid molybdenum 4.0%; Selenium Sulfide 4.0%; Benzotriazole 0.4%.
Embodiment 9
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); 500SN (32kg).
By the method for example 1, prepare overbased complex loop alkanoic acid quicklime grease, different is not containing oxidation inhibitor pair, right '-di-iso-octyldiphenylamine, and the amount of base oil also 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 38.4%; Lubricating base oil 54.2%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 5.0%.
Embodiment 10
Feed composition: high base number calcium naphthenate (total basicnumber is 360mgKOH/g, 30kg); 150BS (30kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(3.3kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Terephthalic acid (3.5kg); 500SN (15kg); Right, 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 naphthenate with superhigh base number calcium and 100 ° of C kinematic viscosity of 30kg of 360mgKOH/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 60 ° of C, constant temperature 90 minutes, material retrogradation; Add 3.3kgCa (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, stir 10 minutes; Add 3.5kg terephthalic acid, stir, under stirring, be warmed up to 110 ° of C, keep 60 minutes, dehydration; 120 ° of C constant temperature 20 minutes, is warmed up to 200 ° of C constant temperature 5 minutes.Then, be cooled to 160 ° of C, adding 100 ° of C kinematic viscosity of 15kg is 11mm
2the HVI500SN lubricating base oil of/s; 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.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 38.2%; Lubricating base oil 51.5%; 12-oxystearic acid calcium 2.5%; Lime borate 2.7%; Terephthalic acid calcium 4.9%; Right, right '-di-iso-octyldiphenylamine (0.2kg) 0.2%.
Embodiment 11
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); Terephthalic acid (3.5kg); Acetic acid (2kg); 500SN (14kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 10, prepare high base number complex loop alkanoic acid quicklime grease, different is that boric acid changes acetic acid into, 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 38.5%; Lubricating base oil 50.8%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 5.0%; Lime acetate 3.1%; Right, right '-di-iso-octyldiphenylamine 0.2%.
Comparative example
Feed composition: calcium sulfonate with high base number (320mgKOH/g, 30kg); 150BS (20kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); 500SN (28kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare high base number composite calcium sulfonate base grease, different is that in reactant, newton's body calcium naphthenate replaces with calcium sulfonate with high base number, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that this example obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium sulphonate 38.5%; Lubricating base oil 55.4%; 12-oxystearic acid calcium 2.4%; Lime borate 3.7%.
Each lubricating grease properties of sample data of table 1
Continued
As seen from Table 1, adopt high base number naphthenic acid to be better than the prepared lubricating grease of employing calcium sulfonate with high base number as the performance of the prepared lubricating grease of raw material, especially aspect water resisting property and adhesion, having especially unique advantage, this is the result expecting useless.
Claims (16)
1. a complex loop alkanoic acid quicklime grease, take lubricating grease weight as benchmark, comprising:
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) 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) 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. the preparation method of the described complex loop alkanoic acid of one of claim 1 ~ 9 quicklime grease, comprising:
(1) newton's body calcium naphthenate, part base oil and transforming agent are mixed, heated, make material retrogradation;
(2) add lime or calcium hydroxide, add respectively higher fatty acid and aromatic acid, cooling after the dehydration that heats up;
(3) be warmed up to 200 ° of C-220 ° of C constant temperature refinings, cooling, add surplus base oil, add necessary additive, obtain finished product.
11. according to preparation method claimed in claim 10, in step (1), by newton's body calcium naphthenate, part base oil Hybrid Heating to 50 ° C-90 ° C, constant temperature 10 minutes-30 minutes, add successively required transforming agent to react, add rear stirring about 10 minutes at every turn, react fully, 60 ° of C-100 ° of C constant temperature 0.5 hour-3 hours, make material retrogradation.
12. according to preparation method claimed in claim 10, in step (2), the suspension liquid that adds lime or calcium hydroxide at 85 ° of C-100 ° of C, adds higher fatty acid at 85 ° of C-100 ° of C, stirs 5 minutes-20 minutes, add aromatic acid and 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, dehydration, cool to 90 ° of C-105 ° of C, the order of its Fatty Acids and small molecules acid can exchange.
13. according to preparation method claimed in claim 10, in step (3), the product of step (3) is heated up, and 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.
14. according to preparation method claimed in claim 10, 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.
15. according to preparation method claimed in claim 10, 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.
16. according to preparation method claimed in claim 10, 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.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN101935578A (en) * | 2010-10-11 | 2011-01-05 | 长沙众城石油化工有限责任公司 | Calcium sulfonate complex grease and preparation method thereof |
| CN102453600A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based hexaurea grease and preparation method thereof |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN101935578A (en) * | 2010-10-11 | 2011-01-05 | 长沙众城石油化工有限责任公司 | Calcium sulfonate complex grease and preparation method thereof |
| CN102453600A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based hexaurea 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》, vol. 42, no. 4, 30 April 2011 (2011-04-30), pages 62 - 66 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828478A (en) * | 2017-10-19 | 2018-03-23 | 中国石油化工股份有限公司 | A kind of Composite calcium naphthenate base lubricant composition and preparation method thereof |
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