CN103571571A - Calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof - Google Patents
Calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof Download PDFInfo
- Publication number
- CN103571571A CN103571571A CN201210266810.2A CN201210266810A CN103571571A CN 103571571 A CN103571571 A CN 103571571A CN 201210266810 A CN201210266810 A CN 201210266810A CN 103571571 A CN103571571 A CN 103571571A
- Authority
- CN
- China
- Prior art keywords
- add
- preparation
- lubricating grease
- calcium naphthenate
- vulcabond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Lubricants (AREA)
Abstract
The invention provides calcium naphthenate-based hexapolyurea lubricating grease and a preparation method thereof. On a basis of the lubricating grease weight, the lubricating grease comprises the following components: 1) 10-70% of non-newtonian calcium naphthenate; 2) 0.5-30% of hexapolyurea; 3) 10-80% of lubricating base oil. The calcium naphthenate-based hexapolyurea lubricating grease is obtained by converting newtonian calcium naphthenate, and reacting with diisocyanate, diamine, and monamine. The lubricating grease of the invention has excellent extreme-pressure abrasion resistance and long lubricating life, and also has excellent adhesiveness, water resistance, colloid stability, high dropping point, thermal stability, corrosion resistance, salt mist resistance, and the like.
Description
Technical field
The present invention relates to lubricant, definite a kind of calcium naphthenate base six polyurea greases and preparation method thereof that say.
Background technology
High base number calcium naphthenate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffustivity, the purification agent that can be used as lubricating oil, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development is mainly to make its high alkalization, exactly calcium carbonate is distributed to and in thinning oil, becomes a kind of colloidal dispersion system with having surface-active naphthenic acid calcium.The acidic components that extract the distillate mostly high base number calcium naphthenate is to obtain from crude distillation, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtain, the relevant Patents of preparing has CN 1465560 etc.
What to utilize calcium sulfonate with high base number be raw material production lubricating grease has excellent high temperature performance because of it, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion, since putting goods on the market, cause the extensive concern of domestic and international lubricating grease industry, yet, although high base number composite calcium sulfonate base grease has very excellent over-all properties, but the high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, simultaneously, along with people are more and more higher to the requirement of environment protection, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment is also received to people's concern day by day.Find a kind of performance and high base number composite calcium sulfonate similar but can avoid the lubricating grease of the problems referred to above to become the large problem that people face at present.
Summary of the invention
The invention provides a kind of calcium naphthenate base six polyurea greases, it is raw material that this lubricating grease has adopted petroleum naphthenic acid calcium or synthetic calcium naphthenate, contains six polyurea compounds that isocyanic ester and amine reaction produce simultaneously.
The present invention also provides above-mentioned preparation of greases method.
Naphthenate with superhigh base number calcium base provided by the invention six polyurea greases, take lubricating grease weight as benchmark, comprise following component:
1) non-newtonian fluid calcium naphthenate 10-70%, preferably 20-65%, most preferably 30-60%;
2) six polyureas 0.5-30%, preferably 1-20%, most preferably 2-10%;
3) lubricating base oil, 10-80%, preferably 20-70%, most preferably 30-60%.
Described non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm
-1-886cm
-1place occurs that crystal form calcium carbonate charateristic avsorption band, total basicnumber are 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Described non-newtonian fluid calcium naphthenate is to be transformed and obtained by transforming agent by newton's body calcium naphthenate.And in newton's body calcium naphthenate, contain unformed carbonic acid calcium, 860cm in infrared spectrum
-1-865cm
-1there is charateristic avsorption band in place.Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthetic calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, and preferably 300mgKOH/g-400mgKOH/g, changes into after non-newtonian fluid calcium naphthenate, and its base number is constant.
Described six polyureas have following structure:
R wherein
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8 ~ 24, preferably 10 ~ 18, and aryl can be the phenyl of phenyl or replacement, the phenyl that preferably phenyl or C1 ~ C3 alkyl or halogen replace.
R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2 ~ 12, preferably 2 ~ 8, and arylidene can be phenylene or biphenylene.
R wherein
3can be that carbon number is 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, preferably at least one in tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and hexylidene.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 ° of C kinematic viscosities are 4-150mm
2/ s, preferably 10-60mm
2/ s.Synthetic oil can be poly-a-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, extreme pressure anti-wear additives, 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.Extreme pressure anti-wear additives 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 calcium naphthenate base six polyurea greases, comprising:
(1) in reactor A, newton's body calcium naphthenate, part base oil and transforming agent are mixed, heated, treat material retrogradation, the dehydration that heats up, cooling;
(2) in the product of reactor A or in reactor B, add part base oil and monoamine, add vulcabond, add successively monoamine to react, add again diamines to react, add vulcabond to react, wherein the mol ratio of each added vulcabond, monoamine, diamines and vulcabond is 2:2:2:1 again;
(3) mixing of materials in reactor A is even, or mix after the material of reactor A and B is merged, be warmed up to 200-220 ° of C constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
Specifically, preparation method of the present invention can complete in a reactor, also can use two reactors.
In step (1), newton's body calcium naphthenate, part base oil Hybrid Heating are arrived to 50-80 ° of C, add successively required transforming agent to react, preferably add rear stirring about 10 minutes at every turn, react fully, all transforming agents add rear intensification, preferably, at 80-90 ° of C constant temperature 60-90 minute, when reaction system is by oily retrogradation, be warming up to 100-120 ℃, preferably 105-110 ℃ of dehydration is cooled to below 105 ℃ after water has taken off.
Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthetic calcium naphthenate, its total basicnumber 250-450mgKOH/g, preferably 300-400mgKOH/g.
Described transforming agent is selected from fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, cycloalkanes amine, cycloalkanol, the ether of C1-C5, and one or more in calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate (ABS), water etc., preferably Witco 1298 Soft Acid, C16-C62 naphthenic acid, methyl alcohol, butanols, acetic acid and water.The add-on of transforming agent is the 2-30% of newton's body calcium naphthenate weight, preferably 6-22%.
In step (2), in the product of step (1) or in another reactor, add successively part base oil and vulcabond, stir, add monoamine, reaction 2-8 minute, adds diamine reactant 2-8 minute, then adds vulcabond, reaction 2-8 minute, the mol ratio of each added vulcabond, monoamine, diamines and vulcabond is 2:2:2:1.
Said vulcabond structure is OCN-R
3-NCO, R
3can be that carbon number is 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, preferred tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene, hexylidene etc.For example described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl group diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), dicyclohexyl methyl vulcabond (HMDI), or at least one in an xylylene vulcabond (XDI) etc.
Said monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R wherein
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8 ~ 24, preferably 10 ~ 18, and aryl can be the phenyl of phenyl or replacement, the phenyl that preferably phenyl or C1 ~ C3 alkyl or halogen replace.Preferred monoamine can be the arylamine that is selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.
Said diamines can be aliphatic amide or arylamine, and structural formula is NH
2-R
2-NH
2, R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2 ~ 12, preferably 2 ~ 8, and arylidene can be phenylene or biphenylene.Preferred diamines can be to be selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine and/or be selected from quadrol, propylene diamine, 1, the straight-chain fatty amine of 6-hexanediamine.
In step (3), the product of step (1) and step (2) is mixed to rear intensification, preferably 100-120 ° of C constant temperature 10-20 minute, is finally warmed up to 200-220 ° of C constant temperature 5-10 minute; Be cooled to 150-160 ° of C, add surplus lubricating base oil, treat that temperature is cooled to 100-120 ° of C, add necessary additive, stir circulating filtration, homogenizing, the degassed finished product that obtains.
Lubricating grease of the present invention, has fabulous extreme pressure anti-wear and long lubricating life, meanwhile, also has the performances such as good adhesivity, water resisting property, colloid stability, high dropping point, heat-resistant quality, non-corrosibility, resistance to salt(spray)fog.This product preparation process is simple, constant product quality.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the lubricating grease of embodiment 1 preparation.As can be seen from the figure, at 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place.Meanwhile, at 3300cm
-1-3323cm
-1the peak at place is in six polyureas molecules-the stretching vibration absorption peak of NH-.
Fig. 2 is the infrared analysis spectrogram of six polyureas in the lubricating grease of embodiment 1 preparation.As can be seen from the figure, 3310 ~ 3323cm
-1the peak at place is in six polyureas molecules-the stretching vibration absorption peak of NH-, and 1630cm
-1the peak at place is in six polyureas molecules-vibration absorption peak of CO-.
Fig. 3 is the nuclear magnetic resonance spectroscopy spectrogram of six polyureas in the lubricating grease of embodiment 1 preparation.As can be seen from the figure, the peak of δ=155HZ left and right is in six polyureas molecules-chemical shift of CO-.
Fig. 4 is the Electrospray Ionization Mass Spectrometry spectrogram of six polyurea thickening agent in the lubricating grease of embodiment 1 preparation.As can be seen from the figure, the mass-to-charge ratio of sample is 1411.0m/z.The relative molecular mass of this and six polyureas matches.
Embodiment
In embodiment, the method for calculation of each component concentration are as follows:
Overbased or the high base number calcium naphthenate 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 high base number calcium naphthenate raw material is from Xinjiang Land Fine Petrochemical Co., Ltd, also can be according to the preparation method of a CN101885677A(highly basic calcium naphthenate) disclosed method preparation.
In comparative example, calcium sulfonate with high base number raw material is purchased from Jinzhou Hui Fatianhe Chemical Co., Ltd..
Feed composition: (total basicnumber is 400mgKOH/g to naphthenate with superhigh base number calcium, 30kg; 150BS(30kg); Naphthenic acid (total acid value is 120mgKOH/g, acid content 70%, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); 500SN(18kg).
Step 1: a volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in to add 30kg total basicnumber be that naphthenate with superhigh base number calcium and 100 ° of C kinematic viscosity of 30kg of 400mgKOH/g are 31mm
2the HVI150BS lubricating base oil of/s, stirs, and heats to 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; Add 2.32kg boric acid and with 6 times of consoluet boric acid solution of hot water, stir, 95 ° of C constant temperature 30 minutes, material retrogradation; Under stirring, be warmed up to 110 ° of C, keep 60 minutes, dehydration.
Step 2: another volume be 10L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in to add 10kg100 ° of C kinematic viscosity be 11mm
2the HVI500SN lubricating base oil of/s and 0.78kg MDI are preheating to 90 ° of C, under rapid stirring, add 0.84kg stearylamine, stir 4 minutes, under rapid stirring, add 0.19kg quadrol, stir 4 minutes, add 0.39kg MDI, the mol ratio of added MDI, stearylamine, quadrol and MDI is 2:2:2:1 successively, 120 ° of C constant temperature 20 minutes, obtains six polyureas.
Gained six polyureas are all squeezed in a upper still, stirred, be finally warmed up to 200 ° of C constant temperature 5 minutes.Then, be cooled to 160 ° of C, add 8kg lubricating base oil 500SN; Treat that temperature is cooled to 110 ° of C, circulating filtration, homogenizing, the degassed finished product that obtains.Assay is in Table 1.The six polyureas molecular structural formulas that contain in component are:
By above-mentioned steps 2 same methods, prepare a small amount of six polyureas, with sherwood oil (60 ~ 90 ℃ of boiling points) washing, filtration is precipitated again, and gained precipitation obtains six polyurea compounds after drying.Its infrared spectrum, nuclear magnetic resonance spectroscopy spectrogram, Electrospray Ionization Mass Spectrometry spectrogram are shown in respectively Fig. 2, Fig. 3, Fig. 4.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 41.5%; Six polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 2
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 420mgKOH/g, 30kg); 150BS(30kg); Naphthenic acid (total acid value is 120mgKOH/g, acid content 70%, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); 500SN(18kg).
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 the 30kg100 ° of C kinematic viscosity of 420mgKOH/g is 31mm
2the HVI150BS lubricating base oil of/s, stirs, and heats to 80 ° of C, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature is controlled at 80 ° of C left and right, stirs 10 minutes; The aqueous solution that adds 4 times of the acetic acid of 0.56kg and acetic acid weight, stirs 10 minutes; 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; Under stirring, be warmed up to 110 ° of C, keep 60 minutes, dehydration, cools to 90 ° of C; Adding by 5kg100 ° of C kinematic viscosity is 11mm
2the 0.78kg MDI that the HVI500SN lubricating base oil of/s dissolves, adds 0.84kg stearylamine under rapid stirring, stir 4 minutes, adds 0.19kg quadrol under rapid stirring, stirs 4 minutes, and adding by 5kg100 ° of C kinematic viscosity is 11mm
2the 0.39kg MDI that the HVI500SN lubricating base oil of/s dissolves, the mol ratio of added MDI, stearylamine, quadrol and MDI is 2:2:2:1 successively, 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, add 8kg lubricating base oil 500SN; Treat that temperature is cooled to 110 ° of C, circulating filtration, homogenizing, the degassed finished product that obtains.Assay is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 41.5%; Six polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 3
Feed composition: naphthenate with superhigh base number calcium (total basicnumber 400mgKOH/g, 30kg); 150BS(10kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Lauryl amine (0.66kg); Quadrol (0.21kg); MDI(1.33kg); 500SN(38kg).
By the method for example 1, prepare naphthenate with superhigh base number calcium base six polyurea greases, different is to use Witco 1298 Soft Acid, lauryl amine to replace naphthenic acid and stearylamine and each amounts of components to change 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 41.5%; Six polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 4
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(25kg); Propyl carbinol (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1kg); Quadrol (0.22kg); TDI(0.97kg); 500SN(23kg); Phenyl-a-naphthylamine (0.2kg).
By the method for example 1, prepare naphthenate with superhigh base number calcium base six polyurea greases, different is to use propyl carbinol, tolylene diisocyanate (TDI) to replace naphthenic acid and MDI, and oxidation inhibitor is phenyl-a-naphthylamine, 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%; Six polyureas 2.6%; Lubricating base oil 57.8%.
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); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); 500SN(7kg); To p-di-iso-octyldiphenylamine (0.4kg).
By the method for example 1, prepare naphthenate with superhigh base number calcium base six polyurea greases, the amount of different is 500SN is 7kg, thereby make each material rate that larger change occur, use is 0.4kg to p-di-iso-octyldiphenylamine in addition, 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 59.2%; Six polyureas 3.6%; Lubricating base oil 36.5%; To p-di-iso-octyldiphenylamine 0.7%.
Embodiment 6
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (2.52kg); Quadrol (0.56kg); MDI(3.51kg); 500SN(18kg).
By the method for example 1, prepare naphthenate with superhigh base number calcium base six polyurea greases, the consumption of different is stearylamine, quadrol, MDI and base oil changes to some extent, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 41.8%; Six polyureas 7.8%; Lubricating base oil 50.4%.
Embodiment 7
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); PAO40(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); PAO 10(23kg); Dithio Acidic phosphates zinc (2kg), molybdenum dialkyldithiocarbamacompositions (1kg), tungsten disulfide (2kg), two selenizing tungsten (2kg), to p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare naphthenate with superhigh base number calcium base six polyurea greases, different is that 10(100 ° of C kinematic viscosity of use full synthetic oil poly & Alpha ,-olefin oil PAO is 11mm
2/ s) and PAO 40(100 ° of C kinematic viscosity be 41mm
2/ s) replace respectively 500SN and 150BS, and before homogenizing, add additive dithio Acidic phosphates zinc, molybdenum dialkyldithiocarbamacompositions, tungsten disulfide, two selenizing tungsten, each performance data of lubricating grease finished product that p-di-iso-octyldiphenylamine (0.2kg) is obtained 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 38.3%; Six polyureas 2.4%; Lubricating base oil 51.6%; Dithio Acidic phosphates zinc 2.2%; Molybdenum dialkyldithiocarbamacompositions 1.1%; Tungsten disulfide 2.1%; Two selenizing tungsten 2.1%; To p-di-iso-octyldiphenylamine 0.2%.
Embodiment 8
Feed composition: high base number calcium naphthenate (total basicnumber is 320mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); 500SN(23kg).
By the method for example 1, prepare high base number calcium naphthenate base six polyurea greases, 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.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 41.5%; Six polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 9
Feed composition: high base number calcium naphthenate (total basicnumber is 360mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); 500SN(23kg).
By the method for example 1, prepare high base number calcium naphthenate base six polyurea greases, the total basicnumber of the high base number calcium naphthenate that different is uses is 360mgKOH/g, 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 41.5%; Six polyureas 2.6%; Lubricating base oil 55.9%.
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.78kg); 1,6-hexanediamine (0.40kg); MDI(1.26kg); 500SN(23kg).
By the method for example 1, prepare naphthenate with superhigh base number calcium base six polyurea greases, different is to use 1,6-hexanediamine to replace quadrol, 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 41.5%; Six polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 11
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.79kg); Ursol D (0.32kg); MDI(1.10kg); 500SN(23kg).
By the method for example 1, prepare naphthenate with superhigh base number calcium base six polyurea greases, different is to use Ursol D to replace quadrol, 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 41.5%; Six polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 12
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Propyl carbinol (1kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); 500SN(23kg).
By the method for example 1, prepare naphthenate with superhigh base number calcium base six polyurea greases, different is that transforming agent has increased propyl carbinol, and adds after adding naphthenic acid, and each performance data of lubricating grease finished product obtaining is in Table 1.
In the lubricating grease that the present embodiment obtains, take lubricating grease weight as benchmark, consist of: non-newtonian fluid calcium naphthenate 41.5%; Six polyureas 2.6%; Lubricating base oil 55.9%.
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 p-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 calcium sulfonate with high base number and the 25kg100 ° of C kinematic viscosity of 320mgKOH/g is 31mm
2the HVI150BS lubricating base oil of/s, stirs, and heats to 60 ° of C, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature is controlled at 65 ° 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; 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; Under stirring, be warmed up to 110 ° of C, keep 60 minutes, dehydration; Finally be warmed up to 200 ° of C constant temperature 5 minutes, add 25.2kg lubricating base oil 500SN; Treat that temperature is cooled to 110 ° of C, add to account for lubricating grease weight 0.2kg p-di-iso-octyldiphenylamine was stirred after 10 minutes circulating filtration, homogenizing, the degassed finished product that obtains.Assay is in Table 1.
Comparative example 2
Feed composition: calcium sulfonate with high base number (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 p-di-iso-octyldiphenylamine (0.2kg).
By the method for example 1, prepare high base number calcium naphthenate base two polyurea greases, different is that the calcium sulfonate with high base number that high base number calcium naphthenate is 320mgKOH/g with total basicnumber replaces and do not contain diamines, 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 sulphonate 41.5%; Two polyureas 2.6%; Lubricating base oil 55.9%.
Each lubricating grease properties of sample data of table 1
Continued
Claims (19)
1. calcium naphthenate base six polyurea greases, take lubricating grease weight as benchmark, comprise following component:
1) non-newtonian fluid calcium naphthenate 10-70%; 2) six polyureas 0.5-30%; 3) 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 20-65%; 2) six polyureas 1-20%; 3) lubricating base oil 20-70%.
3. according to lubricating grease claimed in claim 1, wherein said non-newtonian fluid calcium naphthenate is transformed and is obtained by newton's body calcium naphthenate, and its total basicnumber is 250-450mgKOH/g.
4. according to lubricating grease claimed in claim 1, wherein, said six polyureas have following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
5. according to lubricating grease claimed in claim 4, wherein, R
1the phenyl of phenyl or replacement, or the carbon number alkyl or cycloalkyl that is 8 ~ 24; R
2that phenylene or biphenylene or carbon number are 2 ~ 12 alkylidene group; R
3that carbon number is 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
6. according to lubricating grease claimed in claim 5, wherein, R
1the phenyl that phenyl or C1 ~ C3 alkyl or halogen replace, or carbon number be 10 ~ 18 alkyl or cycloalkyl, R
2phenylene or biphenylene, or the carbon number alkylidene group that is 2 ~ 8; R
3be selected from least one in tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and hexylidene.
7. the preparation method of described calcium naphthenate base six polyurea greases of one of claim 1 ~ 6, comprising:
(1) in reactor A, newton's body calcium naphthenate, part base oil and transforming agent are mixed, heated, treat material retrogradation, the dehydration that heats up, cooling;
(2) in the product of reactor A or in reactor B, add part base oil and vulcabond, add successively monoamine to react, add again diamines to react, add vulcabond to react, wherein the mol ratio of each added vulcabond, monoamine, diamines and vulcabond is 2:2:2:1 again;
(3) mixing of materials in reactor A is even, or mix after the material of reactor A and B is merged, be warmed up to 200-220 ° of C constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
8. according to preparation method claimed in claim 7, in step (1), newton's body calcium naphthenate, part base oil Hybrid Heating are arrived to 50-80 ° of C, add successively required transforming agent to react, all transforming agents add rear intensification, at 80-90 ° of C constant temperature 60-90 minute, when reaction system retrogradation, be warming up to 100-120 ℃ of dehydration, cooling after water has taken off.
9. according to preparation method claimed in claim 7, in step (2), in the product of step (1) or in another reactor, add successively part base oil and vulcabond, add monoamine, reaction 2-8 minute, add diamine reactant 2-8 minute, then add the vulcabond being dissolved in part base oil, reaction 2-8 minute.
10. according to preparation method claimed in claim 7, in step (3), the product of step (1) and step (2) is mixed to rear intensification, at 100-120 ° of C constant temperature 10-20 minute, be finally warmed up to 200-220 ° of C constant temperature 5-10 minute; Be cooled to 150-160 ° of C, add surplus lubricating base oil, treat that temperature is cooled to 100-120 ° of C, add necessary additive, stir circulating filtration, homogenizing, degassed.
11. according to preparation method claimed in claim 7, and described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthetic calcium naphthenate, and its total basicnumber is 250-450mgKOH/g.
12. according to preparation method claimed in claim 7, said transforming agent is selected from fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, cycloalkanes amine, cycloalkanol, the ether of C1-C5, and one or more in calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate (ABS), C16-C62 naphthenic acid, water, the add-on of transforming agent is the 2-30% of newton's body calcium naphthenate weight.
13. according to preparation method claimed in claim 7, and said transforming agent is selected from Witco 1298 Soft Acid, C16-C62 naphthenic acid, methyl alcohol, butanols, acetic acid, water, and the add-on of transforming agent is the 6-22% of newton's body calcium naphthenate weight.
14. according to preparation method claimed in claim 7, and wherein, said monoamine structural formula is R
1-NH
2, R wherein
1be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl is 8 ~ 24, and aryl is the phenyl of phenyl or replacement.
15. according to preparation method claimed in claim 7, and wherein, said monoamine is the arylamine that is selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide and/or para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.
16. according to preparation method claimed in claim 7, and wherein, said diamines structural formula is NH
2-R
2-NH
2, R wherein
2be alkylidene group or arylidene, the carbon number of alkylidene group is 2 ~ 12, and arylidene is phenylene or biphenylene.
17. according to preparation method claimed in claim 7, and wherein, said diamines is selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine, and/or be selected from quadrol, propylene diamine, 1, the straight-chain fatty amine of 6-hexanediamine.
18. according to preparation method claimed in claim 7, and wherein, said vulcabond structure is OCN-R
3-NCO, R
3that carbon number is 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
19. according to preparation method claimed in claim 7, and wherein, described vulcabond is selected from tolylene diisocyanate, methyldiphenyl group diisocyanate, hexamethylene vulcabond, dicyclohexyl methyl vulcabond, or at least one in an xylylene vulcabond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210266810.2A CN103571571B (en) | 2012-07-30 | 2012-07-30 | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210266810.2A CN103571571B (en) | 2012-07-30 | 2012-07-30 | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103571571A true CN103571571A (en) | 2014-02-12 |
| CN103571571B CN103571571B (en) | 2015-08-26 |
Family
ID=50044290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210266810.2A Active CN103571571B (en) | 2012-07-30 | 2012-07-30 | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103571571B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212612A (en) * | 2013-05-31 | 2014-12-17 | 中国石油化工股份有限公司 | Calcium naphthenate-based hexaurea lubricating grease and preparation method thereof |
| CN108003964A (en) * | 2016-10-27 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of lubricating grease and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657599A (en) * | 2004-02-18 | 2005-08-24 | 中国石油化工股份有限公司 | Polyurea grease composite |
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN102417856A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium-sulfonate-based hexapolyurea lubricating grease and preparation method thereof |
-
2012
- 2012-07-30 CN CN201210266810.2A patent/CN103571571B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657599A (en) * | 2004-02-18 | 2005-08-24 | 中国石油化工股份有限公司 | Polyurea grease composite |
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN102417856A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium-sulfonate-based hexapolyurea lubricating grease and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李玲等: "高碱性环烷酸钙的合成与性能研究", 《石油炼制与化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212612A (en) * | 2013-05-31 | 2014-12-17 | 中国石油化工股份有限公司 | Calcium naphthenate-based hexaurea lubricating grease and preparation method thereof |
| CN104212612B (en) * | 2013-05-31 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof |
| CN108003964A (en) * | 2016-10-27 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of lubricating grease and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103571571B (en) | 2015-08-26 |
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 | |
| CN102417855B (en) | Calcium sulfonate tetra-polyurea lubricating grease and preparation method thereof | |
| CN102453598B (en) | Composite calcium sulfonate-based octaurea lubricating grease | |
| CN102417853B (en) | Calcium sulfonate octaurea lubricating grease and preparation method thereof | |
| CN102417856B (en) | Calcium-sulfonate-based hexapolyurea lubricating grease and preparation method thereof | |
| CN103571571B (en) | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103571570B (en) | A kind of Calcium naphthenate base four polyurea grease and preparation method thereof | |
| CN103571588B (en) | A kind of Calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN103571598B (en) | A kind of Calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN103695075B (en) | A kind of Composite calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN103627495B (en) | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN103695074B (en) | A kind of Composite calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN104449956B (en) | A kind of high base number composite calcium-base polyurea grease and preparation method thereof | |
| CN103695138B (en) | A kind of Composite calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103695076A (en) | Composite calcium naphthenate tetraurea lubricating grease and preparation method thereof | |
| CN103627497B (en) | A kind of Composite calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN103627498B (en) | A kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof | |
| CN103627470B (en) | A kind of Composite calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN104212611A (en) | Calcium naphthenate-based polyurea lubricating grease and its preparation method | |
| CN104212535A (en) | Calcium naphthenate-based octaurea lubricating grease and its preparation method | |
| CN104293452A (en) | Composite calcium naphthenate-based polyurea lubricating grease and preparation method thereof | |
| CN104450109A (en) | High-base number composite calcium-based urea tetramer grease and preparation method thereof | |
| CN104449961A (en) | Calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof | |
| CN104450110A (en) | Calcium sulfonate-calcium naphthenate-based polyurea grease and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |