CN103695137B - A kind of Composite calcium naphthenate base lubricating grease and preparation method thereof - Google Patents
A kind of Composite calcium naphthenate base lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of Composite calcium naphthenate base lubricating grease and preparation method thereof.With lubricating grease weight for benchmark, this lubricating grease comprises 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) lubricating base oil 10%-80%.Described lubricating grease have employed petroleum naphthenic acid calcium or synthesis calcium naphthenate is raw material, simultaneously containing composite calcium viscosifying agent.This lubricating grease has fabulous water resistant sprayability and water resistant drenches leachability, also has the performances such as excellent adhesivity, extreme pressure anti-wear, colloid stability, high dropping point, heat-resistant quality, non-corrosibility, resistance to salt(spray)fog simultaneously.
Description
Technical field
The present invention relates to lubricant, is specifically a kind of high base number Composite calcium naphthenate base lubricating grease and preparation method thereof.
Background technology
Overbased calcium alkyl-salicylate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffustivity, the purification agent of lubricating oil can be used as, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active naphthenic acid calcium.Mostly overbased calcium alkyl-salicylate is the acidic components extracted from the distillate that crude distillation obtains, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtain, about the Patents prepared has 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, but, 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 the requirement of people to environment protection is more and more higher, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment also received day by day to the concern of people.Find a kind of performance and the similar but large problem lubricating grease of the problems referred to above can being avoided to become people face at present of high base number composite calcium sulfonate.
Summary of the invention
The invention provides a kind of Composite calcium naphthenate base lubricating grease, it is raw material that this lubricating grease have employed overbased calcium alkyl-salicylate, simultaneously containing composite calcium viscosifying agent.
The present invention also provides above-mentioned preparation of greases method.
Calcium naphthenate base grease provided by the invention, with lubricating grease weight for benchmark, comprises following component:
1) non-newtonian fluid calcium naphthenate 10%-70%, preferred 20%-60%, most preferably 30%-55%;
2) the calcium salt 1%-10% of higher fatty acid, preferred 2%-6%, most preferably 2.2%-4.2%;
3) the calcium salt 1%-18% of aromatic acid, preferred 2%-15%, most preferably 3%-12%;
4) lubricating base oil 10%-80%, preferred 20%-70%, most preferably 30%-60%.
Described non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place, total basicnumber is 250mgKOH/g-450mgKOH/g, preferred 300mgKOH/g-400mgKOH/g.Described non-newtonian fluid calcium naphthenate is obtained by transforming agent conversion by newton's body calcium naphthenate.And containing unformed calcium carbonate in newton's body calcium naphthenate, 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 synthesis calcium naphthenate, its structure is as shown in (I) formula, and its total basicnumber is 250mgKOH/g-450mgKOH/g, preferred 300mgKOH/g-400mgKOH/g, after changing into non-newtonian fluid calcium naphthenate, its base number is constant.
Wherein, R is the alkyl chain of C3-C20, (CH
2)
nin also may comprise 1-4 five-ring or six-ring, n=7-36; M can up to 45.
Said higher fatty acid is carbon number is 8-20, the straight chain fatty acid of preferred 10-16 or hydroxy fatty acid, such as, one or more mixtures in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, preferred 12-oxystearic acid.
Said aromatic acid is the carboxylic acid having at least 1 carboxyl to be directly connected with aromatic ring, and other substituting group can be the alkyl or aryl etc. of hydrogen, alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, and molecular weight is less than or equal to 550.The preferred binary aromatic acid of described aromatic acid, such as, can be selected from one or more in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.Preferred 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 of small molecules mineral acid and/or small molecules lipid acid can also be contained 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 the mixture of one or more in boric acid, phosphoric acid, sulfuric acid etc., preferred boric acid and/or phosphoric acid; Small molecules lipid acid can be selected from the mixture of one or more in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid etc., preferred 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, preferred 10mm
2/ s-30mm
2/ s.Synthetic oil can be poly & Alpha ,-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Can also various additive be contained in lubricating grease of the present invention, as oxidation inhibitor, anti-wear agent, rust-preventive agent etc.Wherein the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.1%-5% of lubricating grease gross weight, preferred 0.2%-1%, can be pentanoic, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or their mixture, preferred di-iso-octyldiphenylamine.Anti-wear agent can be dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenumdisulphide, tetrafluoroethylene, thiophosphoric acid molybdenum, clorafin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, calcium carbonate and zinc oxide; Rust-preventive agent can be barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Described Composite calcium naphthenate base preparation of greases method, comprising:
(1) newton's body calcium naphthenate, part basis oil and transforming agent are mixed, heat, make material retrogradation;
(2) add lime or calcium hydroxide, add higher fatty acid and aromatic acid respectively, heat up dehydration;
(3) be warmed up to 200 ° of C-220 ° of C constant temperature refinings, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
Specifically, in step (1), by newton's body calcium naphthenate, part basis oil Hybrid Heating to 50 ° of C-90 ° of C, preferred constant temperature 10 minutes-30 minutes, add required transforming agent successively 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 synthesis calcium naphthenate, its total basicnumber 250mgKOH/g-450mgKOH/g, preferred 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., one or more in preferred 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, preferred 6%-22%.
In step (2), the suspension liquid of lime or calcium hydroxide is added at 85 ° of C-100 ° of C, add higher fatty acid at 85 ° of C-100 ° of C, stir 5 minutes-20 minutes, add aromatic acid, necessary small molecules mineral acid and/or small molecules lipid acid can also be added, 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 carbon number is 8-20, the straight chain fatty acid of preferred 10-16 or hydroxy fatty acid, such as, one or more mixtures in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, preferred 12-oxystearic acid.
Said aromatic acid is the carboxylic acid having at least 1 carboxyl to be directly connected with aromatic ring, and other substituting group can be the alkyl or aryl etc. of hydrogen, alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, and molecular weight is less than or equal to 550.The preferred binary aromatic acid of described aromatic acid, such as, can be selected from one or more in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.Preferred 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 the mixture of one or more in boric acid, phosphoric acid, sulfuric acid etc., preferred boric acid and/or phosphoric acid; Small molecules lipid acid can be selected from the mixture of one or more in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid etc., preferred acetic acid.
The H of higher fatty acid and aromatic acid and small molecules mineral acid and/or small molecules lipid acid
+total amount of substance and the OH contained by calcium hydroxide
-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, degassedly obtain finished product.
Lubricating grease of the present invention has good extreme pressure anti-wear and overlength lubricating life, meanwhile, also has the performances such as excellent 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 overbased calcium alkyl-salicylate 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 calcium carbonate 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 overbased calcium alkyl-salicylate 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 higher fatty acid and the calcium salt of small molecules mineral acid or lipid acid, the gauge generating calcium salt according to added higher fatty acid and small molecules mineral acid or lipid acid and calcium hydroxide complete reaction is calculated.
In embodiment, overbased and overbased calcium alkyl-salicylate raw material, also can 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 Huifa Tianhe 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, stir, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total basicnumber is 400mgKOH/g and 30kg 100 ° of C kinematic viscosity are 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 50 ° of C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at 50 ° of about C, stirs 10 minutes; Add the acetic acid of 0.56kg and the aqueous solution of acetic acid weight 4 times, stir 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, be warmed up to 110 ° of C under stirring, 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, the 100 ° of C kinematic viscosity adding 17kg are 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, after right '-di-iso-octyldiphenylamine stirs 10 minutes, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium 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).
Prepare overbased Composite calcium naphthenate base lubricating grease by the method for example 1, unlike the use of the total basicnumber of naphthenate with superhigh base number calcium be 420mgKOH/g, each performance data of lubricating grease finished product obtained 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).
Overbased Composite calcium naphthenate base lubricating grease is prepared by the method for example 1, naphthenic acid, 12-oxystearic acid, terephthalic acid is replaced unlike the use of butanols, stearic acid, m-phthalic acid, the amount of base oil also changes to some extent, and each performance data of lubricating grease finished product obtained 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).
Prepare overbased Composite calcium naphthenate base lubricating grease by the method for example 1, replace naphthenic acid unlike with Witco 1298 Soft Acid, the amount of base oil also changes to some extent, and each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium 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).
Prepare overbased Composite calcium naphthenate base lubricating grease by the method for example 1, the amount unlike base oil changes to some extent, thus makes each material rate that larger change occur, and each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium 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).
Prepare overbased Composite calcium naphthenate base lubricating grease by the method for example 1, replace naphthenic acid unlike the use of Witco 1298 Soft Acid and use 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 500SN and 150BS respectively, each performance data of lubricating grease finished product obtained is in table 1.
Embodiment 7
Feed composition: overbased calcium alkyl-salicylate (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).
Prepare high base number Composite calcium naphthenate base lubricating grease by the method for example 1, unlike the use of the total basicnumber of overbased calcium alkyl-salicylate be 320mgKOH/g, each performance data of lubricating grease finished product obtained is in table 1.
Embodiment 8
Feed composition: overbased calcium alkyl-salicylate (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).
Prepare high base number Composite calcium naphthenate base lubricating grease by the method for example 1, unlike the use of the total basicnumber of overbased calcium alkyl-salicylate be 360mgKOH/g, and add certain additive, each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium 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).
Prepare overbased Composite calcium naphthenate base lubricating grease by the method for example 1, unlike not containing oxidation inhibitor pair, right '-di-iso-octyldiphenylamine, the amount of base oil also changes to some extent, and each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 38.4%; Lubricating base oil 54.2%; 12-oxystearic acid calcium 2.4%; Terephthalic acid calcium 5.0%.
Embodiment 10
Feed composition: overbased calcium alkyl-salicylate (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, stir, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total basicnumber is 360mgKOH/g and 30kg 100 ° of C kinematic viscosity are 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 50 ° of C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at 50 ° of about C, stirs 10 minutes; Add the acetic acid of 0.56kg and the aqueous solution of acetic acid weight 4 times, stir 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, be warmed up to 110 ° of C under stirring, 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, the 100 ° of C kinematic viscosity adding 15kg are 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, after right '-di-iso-octyldiphenylamine stirs 10 minutes, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium 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: overbased calcium alkyl-salicylate (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).
Prepare high base number Composite calcium naphthenate base lubricating grease by the method for example 10, change acetic acid into unlike boric acid, each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium 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).
Prepare high base number composite calcium sulfonate base grease by the method for example 1, replace unlike newton's body calcium naphthenate calcium sulfonate with high base number in reactant, each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that this example obtains, with lubricating grease weight for 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%.
Table 1 each lubricating grease properties of sample data
Continued
As seen from Table 1, adopt high base number naphthenic acid to be better than as the performance of the lubricating grease prepared by raw material the lubricating grease adopted prepared by calcium sulfonate with high base number, especially in water resisting property and adhesion, have unique advantage especially, this is the result expected useless.
Claims (16)
1. a Composite calcium naphthenate base lubricating grease, with lubricating grease weight for 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 according to claim 1, wherein with lubricating grease weight for 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 according to claim 1, described non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place, its total basicnumber is 250mgKOH/g-450mgKOH/g.
4. according to lubricating grease according to claim 1, straight chain fatty acid or the hydroxy fatty acid of said higher fatty acid to be carbon number be 8-20.
5., according to lubricating grease according to 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 according to claim 1, described aromatic acid is the carboxylic acid having 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 according to claim 1, described aromatic acid is selected from one or more in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.
8., according to lubricating grease according to 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 according to claim 1, said small molecules mineral acid is selected from the mixture of one or more in boric acid, phosphoric acid, sulfuric acid, and said small molecules lipid acid is selected from the mixture of one or more in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.
10. one of claim 1 ~ 9 described Composite calcium naphthenate base preparation of greases method, comprising:
(1) newton's body calcium naphthenate, part basis oil and transforming agent are mixed, heat, make material retrogradation;
(2) add lime or calcium hydroxide, add higher fatty acid and aromatic acid respectively, cooling after the dehydration that heats up;
(3) be warmed up to 200 ° of C-220 ° of C constant temperature refinings, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
11. according to preparation method according to claim 10, in step (1), by newton's body calcium naphthenate, part basis oil Hybrid Heating to 50 ° of C-90 ° of C, constant temperature 10 minutes-30 minutes, add required transforming agent successively 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 according to claim 10, in step (2), add the suspension liquid of lime or calcium hydroxide at 85 ° of C-100 ° of C, add higher fatty acid at 85 ° of C-100 ° of C, stir 5 minutes-20 minutes, add small molecules mineral acid and/or the small molecules lipid acid of aromatic acid and necessity, 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 according to claim 10, in step (3), heats up to the product of step (3), 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 according to claim 10, and described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g.
15. according to preparation method according to 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 boric acid, calcium carbonate, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate (ABS), C16-C62 naphthenic acid, one or more in water, the add-on of transforming agent is the 2%-30% of newton's body calcium naphthenate weight.
16. according to preparation method according to 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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| 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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| 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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