CN103627495B - A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof - Google Patents
A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof Download PDFInfo
- Publication number
- CN103627495B CN103627495B CN201210311122.3A CN201210311122A CN103627495B CN 103627495 B CN103627495 B CN 103627495B CN 201210311122 A CN201210311122 A CN 201210311122A CN 103627495 B CN103627495 B CN 103627495B
- Authority
- CN
- China
- Prior art keywords
- acid
- calcium
- minutes
- lubricating grease
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Lubricants (AREA)
Abstract
The invention provides a kind of Composite calcium naphthenate base two polyurea 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 small molecules mineral acid and/or lipid acid; 4) two polyureas 0.5%-30%; 5) 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 and two polyurea compounds.This lubricating grease has excellent extreme pressure anti-wear and overlength lubricating life, also has the performances such as excellent adhesivity, water resisting property, colloid stability, high dropping point, heat-resistant quality, non-corrosibility simultaneously.
Description
Technical field
The present invention relates to lubricant, is specifically a kind of Composite calcium naphthenate base two polyurea 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.
What utilize calcium sulfonate with high base number to 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, 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 two polyurea grease, this lubricating grease have employed petroleum naphthenic acid calcium or synthesis calcium naphthenate is raw material, simultaneously containing composite calcium viscosifying agent and two polyurea compounds.
The present invention also provides above-mentioned preparation of greases method.
Calcium naphthenate base two polyurea 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 calcium 1%-10% of higher fatty acid, preferred 2%-6%, most preferably 2.2%-4.2%;
3) the calcium salt 1%-15% of small molecules mineral acid and/or lipid acid, preferred 2%-10%, most preferably 3%-8%;
4) two polyureas 0.5%-30%, preferred 1%-20%, most preferably 2%-10%;
5) 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, and its total basicnumber is 250mgKOH/g-450mgKOH/g, preferred 300mgKOH/g-400mgKOH/g, and after changing into non-newtonian fluid calcium naphthenate, its base number is constant.
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.
The molecular weight of said small molecules mineral acid and/or lipid acid is less than or equal to 150, said small molecules mineral acid is selected from 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.
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 the phenyl of phenyl or replacement, preferred phenyl or C1 ~ C3 alkyl or halogen substiuted.
R wherein
2can be carbon number be 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, at least one in preferred xylene, diphenylmethylene, dicyclohexylmethylene, phenylenedimethylidyne and hexylidene.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 ° of C kinematic viscosities are 4mm
2/ s-150mm
2/ s, preferred 10mm
2/ s-60mm
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, extreme pressure anti-wear additives, 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.Extreme pressure anti-wear additives 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.
The preparation method of described Composite calcium naphthenate base two polyurea grease, comprising:
(1) in reactor A, newton's body calcium naphthenate, part basis oil and transforming agent are mixed, heat, make material retrogradation;
(2) in aforesaid reaction vessel, add lime or calcium hydroxide, add higher fatty acid and small molecules acid respectively, heat up dehydration;
(3) in the product of reactor A or in reactor B, add part basis oil, monoamine and vulcabond to react, wherein vulcabond is 1:2 with the ratio of the amount of substance of monoamine;
(4) mixing of materials in reactor A is even, or mix after the material of reactor A and B is merged, be warmed up to 200 ° of C-220 ° of C constant temperature refinings, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
Specifically, preparation method of the present invention can complete in a reactor, also can use two reactors.
Specifically, in step (1), by newton's body calcium naphthenate, part basis oil Hybrid Heating to 50 ° of C-90 ° of C, preferred constant temperature 10 minutes-30 minutes, adds required transforming agent successively and reacts, and preferably adds rear stirring about 10 minutes at every turn, react fully, all transforming agents add rear intensification, preferably 85 ° of C-100 ° of C constant temperature 0.5 hour-3 hours, make material retrogradation.
Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, its total basicnumber 250-450mgKOH/g, preferred 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., preferred 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, preferred 6%-22%.
In step (2), the suspension liquid of lime or calcium hydroxide is added at 85 ° of C-100 ° of C, higher fatty acid is added at 85 ° of C-100 ° of C, stir 5 minutes-20 minutes, add small molecules mineral acid and/or lipid acid, stir 5 minutes-20 minutes, be warmed up to 105 ° of C-120 ° of C, preferred maintenance 30 minutes-60 minutes, dehydration;
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.
The molecular weight of said small molecules mineral acid and/or lipid acid is less than or equal to 150, said small molecules mineral acid is selected from 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.
The H of higher fatty acid and small molecules mineral acid and/or lipid acid
+total amount of substance and the OH contained by calcium hydroxide
-total amount of substance is equal, the OH contained by calcium hydroxide
-total amount of substance also can excessive 1-10%.
In step (3), in the product of step (2) or add part basis oil, monoamine and vulcabond in another reactor and react, wherein vulcabond is 1:2 with the ratio of the amount of substance of monoamine, and monoamine and vulcabond can first be dissolved in part basis oil.
Said vulcabond structure is OCN-R
2-NCO, R
2can be carbon number be 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, at least one in preferred xylene, diphenylmethylene, dicyclohexylmethylene, phenylenedimethylidyne and hexylidene.Such as described vulcabond can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), 1, hexamethylene-diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), or at least one in the vulcabond such as xylylene diisocyanate (XDI).
Said monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R
3-NH
2, R wherein
1, R
3can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8 ~ 24, preferably 10 ~ 18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1 ~ C3 alkyl or halogen substiuted.Preferred monoamine can be the arylamine being 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 rear intensification, preferably 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, degassedly obtain finished product.
Lubricating grease of the present invention compared with prior art, has excellent extreme pressure anti-wear and long 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 prepared by embodiment 1.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:
Overbased or the overbased calcium alkyl-salicylate raw materials quality+transforming agent total mass of non-newtonian fluid calcium naphthenate %=()/lubricating grease total mass.Transforming agent all counts in the content of non-newtonian fluid calcium naphthenate.
In embodiment, overbased and overbased calcium alkyl-salicylate raw material, also can according to the preparation method of a CN101885677A(highly basic calcium naphthenate from Xinjiang Land Fine Petrochemical Co., Ltd) disclosed method preparation.
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 (pure acid number 120mgKOH/g, acid content 70%, 2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); 500SN(18kg).
A volume be 160L and with heating, 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 80 ° of C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at 80 ° 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 85 ° of C, constant temperature 30 minutes, material retrogradation; Add 1.8kgCa (OH)
2and with 4 times of water-reducible suspension liquids, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 2.32kg boric acid and with the boric acid solution of 3 times of hot water dissolvings, stir, be warmed up to 110 ° of C under stirring, keep 60 minutes, dehydration; Cool to 90 ° of C and add 0.7kg MDI rapid stirring 4 minutes, add 1.5kg stearylamine and stir 4 minutes, added MDI is 1:2 with the ratio of the amount of substance of stearylamine, and 120 ° of C constant temperature 20 minutes, is finally warmed up to 200 ° of C constant temperature 5 minutes.Then, be cooled to 160 ° of C, adding the 100 ° of C kinematic viscosity accounting 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, 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 37.9%; Two polyureas 2.5%; Lubricating base oil 54.5%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%.
The two polyureas molecular structural formulas contained in component are:
Embodiment 2
Naphthenate with superhigh base number calcium (total basicnumber is 420mgKOH/g, 30kg); 150BS(30kg); Naphthenic acid (pure acid number 100mgKOH/g, acid content 60%, 2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); 500SN(18kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total basicnumber is 420mgKOH/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 95 ° of C, constant temperature 90 minutes, material retrogradation; Add 1.8kgCa (OH)
2and with 4 times of water-reducible suspension liquids, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 2.32kg boric acid and with 10 times of consoluet boric acid solution of hot water, stir, be warmed up to 110 ° of C under stirring, keep 60 minutes, dehydration.
Another volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle in 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, and stir 4 minutes, add 0.7kg MDI and stir 4 minutes, added MDI is 1:2 with the ratio of the amount of substance of stearylamine, and 120 ° of C constant temperature 20 minutes, obtains two polyureas.
Gained two polyureas is all squeezed in a upper still, stirs, be finally warmed up to 200 ° of C constant temperature 10 minutes.Then, still cooling is turned; Treat that temperature is cooled to 90 ° of C, 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 37.9%; Two polyureas 2.5%; Lubricating base oil 54.5%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%.
Embodiment 3
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(20kg); Propyl carbinol (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); Stearic acid (1.9kg); Boric acid (2.32kg); Lauryl amine (1.31kg); MDI(0.89kg); 500SN(28kg).
Overbased Composite calcium naphthenate base two polyurea grease is prepared by the method for example 1, replace naphthenic acid, 12-oxystearic acid, stearylamine and each component quantity also respective change unlike the use of propyl carbinol, stearic acid, lauryl amine, 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 37.9%; Two polyureas 2.5%; Lubricating base oil 54.6%; Calcium stearate 2.3%; Lime borate 2.7%.
Embodiment 4
Feed composition: overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 30kg); 150BS(25kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1.66kg); TDI(0.54kg); 500SN(23kg).
High base number Composite calcium naphthenate base two polyurea grease is prepared by the method for example 1, replace 400mgKOH/g overbased calcium alkyl-salicylate, naphthenic acid, MDI and each component quantity also respective change unlike the use of 320mgKOH/g overbased calcium alkyl-salicylate, Witco 1298 Soft Acid, tolylene diisocyanate (TDI), 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 37.9%; Two polyureas 2.5%; Lubricating base oil 54.5%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%.
Embodiment 5
Feed composition: overbased calcium alkyl-salicylate (total basicnumber is 360mgKOH/g, 30kg); 150BS(15kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); 500SN(7kg).
High base number Composite calcium naphthenate base two polyurea grease is prepared by the method for example 1, unlike the use of 360mgKOH/g overbased calcium alkyl-salicylate and the consumption of base oil change, thus making each material rate that larger change occur, 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 53.8%; Two polyureas 3.6%; Lubricating base oil 35.4%; 12-oxystearic acid calcium 3.4%; Lime borate 3.8%.
Embodiment 6
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (4.5kg); MDI(2.1kg); 500SN(18.6kg).
Prepare overbased Composite calcium naphthenate base two polyurea grease by the method for example 1, the amount unlike stearylamine, quadrol, MDI and base oil 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 37.9%; Two polyureas 7.5%; Lubricating base oil 49.5%; 12-oxystearic acid calcium 2.4%; Lime borate 2.7%.
Embodiment 7
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); PAO 40(30kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); PAO 10(9kg); Dithio Acidic phosphates zinc (2kg); Molybdenum dialkyldithiocarbamacompositions (1kg); Tungsten disulfide (2kg); Two tungsten selenide (2kg); To p-di-iso-octyldiphenylamine (0.2kg).
Preparing overbased Composite calcium naphthenate base two polyurea grease by the method for example 1, is 11mm unlike the use of full synthetic oil poly & Alpha ,-olefin oil PAO 10(100 ° of C kinematic viscosity
2/ s) and PAO 40(100 ° of C kinematic viscosity be 41mm
2/ s) replace 500SN and 150BS respectively, and before homogenizing, add additive dithio Acidic phosphates zinc, molybdenum dialkyldithiocarbamacompositions, tungsten disulfide, two tungsten selenide, to right-di-iso-octyldiphenylamine (0.2kg), 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 38.7%; Two polyureas 2.6%; Lubricating base oil 45.2%; 12-oxystearic acid calcium 2.5%; Lime borate 2.7%; Dithio Acidic phosphates zinc 2.3%; Molybdenum dialkyldithiocarbamacompositions 1.2%; Tungsten disulfide 2.3%; Two tungsten selenide 2.3%; To right-di-iso-octyldiphenylamine 0.2%.
Embodiment 8
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(30kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.94kg); Para-totuidine (0.38kg); MDI(0.88kg); 500SN(18kg).
Prepare overbased Composite calcium naphthenate base two polyurea grease by the method for example 1, add para-totuidine unlike monoamine kind, 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 37.8%; Two polyureas 2.5%; Lubricating base oil 54.4%; 12-oxystearic acid calcium 2.5%; Lime borate 2.8%.
Embodiment 9
Feed composition: overbased calcium alkyl-salicylate (total basicnumber is 360mgKOH/g, 30kg); 150BS(20kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Ca (OH)
2(5.2kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Phosphoric acid (3kg); Stearylamine (0.84kg); Lauryl amine (0.58kg); MDI(0.78kg); 500SN(28kg); To p-di-iso-octyldiphenylamine (0.2kg).
Prepare high base number Composite calcium naphthenate base two polyurea grease by the method for example 1, unlike monoamine kind add lauryl amine, phosphoric acid and to p-di-iso-octyldiphenylamine and base oil consumption change to some extent, 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 35.9%; Two polyureas 2.4%; Lubricating base oil 51.6%; 12-oxystearic acid calcium 2.3%; Lime borate 2.5%; Calcium phosphate 5.1%; To p-di-iso-octyldiphenylamine 0.2%.
Embodiment 10
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); Boric acid (2.32kg); Acetic acid (2kg); Stearylamine (1.5kg); MDI(0.7kg); 500SN(18kg).
Prepare high base number Composite calcium naphthenate base two polyurea grease by the method for example 9, unlike adding acetic 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 36.8%; Two polyureas 2.5%; Lubricating base oil 52.9%; 12-oxystearic acid calcium 2.3%; Lime borate 2.6%; Lime acetate 2.9%.
Comparative example 1
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 30kg); 150BS(25kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); 500SN(25.2kg); To right-di-iso-octyldiphenylamine (0.2kg).
A volume be 110L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add calcium sulfonate with high base number that 30kg total basicnumber is 320mgKOH/g and 25kg 100 ° of C kinematic viscosity are 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 80 ° of C, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature controls at 80 ° 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; Add 2.32kg boric acid and with 6 times of consoluet boric acid solution of hot water, stir, 80 ° of C constant temperature 30 minutes, material retrogradation; Be warmed up to 110 ° of C under stirring, keep 60 minutes, dehydration; Finally be warmed up to 200 ° of C constant temperature 5 minutes, add 25.2kg lubricating base oil 500SN; Treat that temperature is cooled to 110 ° of C, add after 0.2kg stirs 10 minutes to p-di-iso-octyldiphenylamine, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
Comparative example 2
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 30kg); 150BS(30kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); 500SN(18kg); To right-di-iso-octyldiphenylamine (0.2kg).
Prepare overbased calcium alkyl-salicylate base two polyurea grease by the method for example 1, the calcium sulfonate with high base number being 320mgKOH/g unlike overbased calcium alkyl-salicylate total basicnumber replaces and does not contain diamines, 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 sulphonate 41.5%; Two polyureas 2.6%; Lubricating base oil 55.9%.
Table 1 each lubricating grease properties of sample data
Continued
Claims (24)
1. Composite calcium naphthenate base two polyurea grease, with lubricating grease weight for benchmark, 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 small molecules mineral acid and/or lipid acid; 4) two polyureas 0.5%-30%; 5) lubricating base oil 10%-80%.
2. according to lubricating grease 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 small molecules mineral acid and/or lipid acid; 4) two polyureas 1%-20%; 5) lubricating base oil 20%-70%.
3., according to lubricating grease according to claim 1, wherein said non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place.
4., according to lubricating grease according to claim 1, wherein said non-newtonian fluid calcium naphthenate total basicnumber is 250mgKOH/g-450mgKOH/g.
5. 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.
6., 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.
7., according to lubricating grease according to claim 1, the molecular weight of said small molecules mineral acid or lipid acid is less than or equal to 150.
8., according to lubricating grease 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.
9., according to lubricating grease according to claim 1, 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. according to lubricating grease according to claim 1, wherein, said two polyureas have following structure:
Wherein, R
1, R
3alkyl, cycloalkyl or aryl, R
2to be carbon number be 6 ~ 30 alkylidene group, arylidene or cycloalkylidene.
11. according to lubricating grease according to claim 10, wherein, and R
1, R
3be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8 ~ 24; R
2the arylidene of 6 ~ 20, alkylidene group or cycloalkylidene.
12. according to lubricating grease according to claim 10, wherein, and R
1, R
3be the phenyl of phenyl or C1 ~ C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10 ~ 18, R
2it is at least one in xylene, diphenylmethylene, dicyclohexylmethylene, phenylenedimethylidyne and hexylidene.
The preparation method of one of 13. claims 1 ~ 12 described Composite calcium naphthenate base two polyurea grease, comprising:
(1) in reactor A, newton's body calcium naphthenate, part basis oil and transforming agent are mixed, heat, make material retrogradation;
(2) in aforesaid reaction vessel, add lime or calcium hydroxide, add higher fatty acid and small molecules mineral acid and/or lipid acid respectively, heat up dehydration;
(3) in the product of reactor A or in reactor B, add part basis oil and monoamine and vulcabond react, wherein vulcabond is 1:2 with the ratio of the amount of substance of monoamine;
(4) mixing of materials in reactor A is even, or mix after the material of reactor A and B is merged, be warmed up to 200 DEG C of-220 DEG C of constant temperature refinings, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
14. according to preparation method according to claim 13, in step (1), by newton's body calcium naphthenate, part basis oil Hybrid Heating to 50 DEG C-80 DEG C, add required transforming agent successively to react, all transforming agents add rear intensification, 80 DEG C of-90 DEG C of constant temperature 60 minutes-90 minutes, make material retrogradation.
15. according to preparation method according to claim 13, in step (2), the suspension liquid of lime or calcium hydroxide is added at 85 DEG C-100 DEG C, higher fatty acid is added at 85 DEG C-100 DEG C, stir 5 minutes-20 minutes, add small molecules mineral acid and/or lipid acid, stir 5 minutes-20 minutes, be warmed up to 105 DEG C-120 DEG C, dehydration.
16. according to preparation method according to claim 13, in step (3), add part basis oil and monoamine in the product of step (2) or in another reactor, stir 2 minutes-8 minutes, add vulcabond again, react 2 minutes-8 minutes.
17. according to preparation method according to claim 13, in step (4), the product of step (2) and (3) is mixed rear intensification, 100 DEG C of-120 DEG C of constant temperature 10 minutes-20 minutes, is finally warmed up to 200 DEG C of-220 DEG C of constant temperature 5 minutes-10 minutes; Be cooled to 150 DEG C-160 DEG C, add surplus lubricating base oil, treat that temperature is cooled to 100 DEG C-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
18. according to preparation method according to claim 13, 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.
19. according to preparation method according to 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 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.
20. according to preparation method according to claim 13, said transforming agent is selected from one or more in Witco 1298 Soft Acid, methyl alcohol, Virahol, butanols, C20-C40 naphthenic acid, acetic acid and water, and the add-on of transforming agent is the 6%-22% of newton's body calcium naphthenate weight.
21. according to preparation method according to 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 preparation method according to claim 13, and wherein, said monoamine is the arylamine being 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 preparation method according to claim 13, and wherein, said vulcabond structure is OCN-R
2-NCO, R
2to be carbon number be 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
24. according to preparation method according to claim 13, wherein, described vulcabond is selected from least one in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate or xylylene diisocyanate vulcabond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210311122.3A CN103627495B (en) | 2012-08-28 | 2012-08-28 | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210311122.3A CN103627495B (en) | 2012-08-28 | 2012-08-28 | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103627495A CN103627495A (en) | 2014-03-12 |
| CN103627495B true CN103627495B (en) | 2015-08-26 |
Family
ID=50208949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210311122.3A Active CN103627495B (en) | 2012-08-28 | 2012-08-28 | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103627495B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003964B (en) * | 2016-10-27 | 2021-04-06 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN102453599A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium-sulfonate-based tetrapolyurea lubricating grease and preparation method thereof |
-
2012
- 2012-08-28 CN CN201210311122.3A patent/CN103627495B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN102453599A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium-sulfonate-based tetrapolyurea lubricating grease and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高碱性环烷酸钙的合成与性能研究;李玲等;《石油炼制与化工》;20110430;第42卷(第4期);第62-66页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103627495A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102453600B (en) | Composite calcium sulfonate-based hexaurea grease | |
| CN102453599B (en) | Composite calcium-sulfonate-based tetrapolyurea lubricating grease and preparation method thereof | |
| CN102453598B (en) | Composite calcium sulfonate-based octaurea lubricating grease | |
| CN102417855B (en) | Calcium sulfonate tetra-polyurea lubricating grease and preparation method thereof | |
| CN103627496B (en) | A kind of Composite calcium naphthenate base lubricating grease and preparation method thereof | |
| CN102417853B (en) | Calcium sulfonate octaurea lubricating grease and preparation method thereof | |
| CN102417856B (en) | Calcium-sulfonate-based hexapolyurea lubricating grease and preparation method thereof | |
| CN103627495B (en) | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN103571570B (en) | A kind of Calcium naphthenate base four polyurea grease and preparation method thereof | |
| CN103571571B (en) | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103695075B (en) | A kind of Composite calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN103695074B (en) | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN103571598B (en) | A kind of Calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN103571588B (en) | A kind of Calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN103627498B (en) | A kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof | |
| CN103627497B (en) | A kind of Composite calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103627470B (en) | A kind of Composite calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN103695138B (en) | A kind of Composite calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103695137B (en) | A kind of Composite calcium naphthenate base lubricating grease and preparation method thereof | |
| CN104560318A (en) | Calcium naphthenate zirconium-based hexurea lubricating grease and preparation method thereof | |
| CN103695076A (en) | Composite calcium naphthenate tetraurea lubricating grease and preparation method thereof | |
| CN104449956A (en) | High base number composite calcium-based polyurea lubricating grease and preparation method thereof | |
| CN104560271A (en) | Calcium naphthenate zirconium-based polyurea lubricating grease and preparation method thereof | |
| CN104560274A (en) | Calcium sulfonate-calcium naphthenate zirconium-based polyurea lubricating grease and preparation method thereof | |
| CN104450110A (en) | Calcium sulfonate-calcium naphthenate-based polyurea grease and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |