CN103571588B - A kind of Calcium naphthenate base eight polyurea grease and preparation method thereof - Google Patents

A kind of Calcium naphthenate base eight polyurea grease and preparation method thereof Download PDF

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CN103571588B
CN103571588B CN201210266228.6A CN201210266228A CN103571588B CN 103571588 B CN103571588 B CN 103571588B CN 201210266228 A CN201210266228 A CN 201210266228A CN 103571588 B CN103571588 B CN 103571588B
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calcium naphthenate
lubricating grease
lubricating
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CN103571588A (en
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何懿峰
孙洪伟
刘中其
段庆华
李玲
刘磊
姜靓
陈政
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention provides a kind of Calcium naphthenate base eight 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) eight polyureas 0.5-30%; 3) lubricating base oil, 10-80%.Described Calcium naphthenate base eight polyurea grease is transformed by newton's body calcium naphthenate, and carry out being obtained by reacting with vulcabond, diamines and monoamine.Lubricating grease of the present invention has excellent extreme pressure anti-wear and long lubricating life, 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 simultaneously.

Description

A kind of Calcium naphthenate base eight polyurea grease and preparation method thereof
Technical field
The present invention relates to lubricant, is specifically a kind of Calcium naphthenate base eight 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 Calcium naphthenate base eight polyurea grease, this lubricating grease have employed petroleum naphthenic acid calcium or synthesis calcium naphthenate is raw material, simultaneously containing eight polyurea compounds that isocyanic ester and amine reaction produce.
The present invention also provides above-mentioned preparation of greases method.
Naphthenate with superhigh base number calcium base eight polyurea grease provided by the invention, with lubricating grease weight for benchmark, comprises following component:
1) non-newtonian fluid calcium naphthenate 10-70%, preferred 20-65%, most preferably 30-60%;
2) eight polyureas 0.5-30%, preferred 1-20%, most preferably 2-10%;
3) 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 eight 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 the phenyl of phenyl or replacement, preferred phenyl or C1 ~ C3 alkyl or halogen substiuted.
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 carbon number be 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, at least one in preferred tolyl, methyldiphenyl base, dicyclohexylmethyl, an xylylene and hexylidene.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 DEG C of kinematic viscosities are 4-150mm 2/ s, preferred 10-60mm 2/ s.Synthetic oil can be poly-a-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 Calcium naphthenate base eight polyurea grease, comprising:
(1) in reactor A, newton's body calcium naphthenate, part basis oil and transforming agent are mixed, heated, treat material retrogradation, heat up dehydration, cooling;
(2) in the product of reactor A or in reactor B, add part basis oil and monoamine, add vulcabond, first add diamines to react, again add diamines to react, finally add monoamine again to react, the mol ratio of vulcabond, diamines, diamines and monoamine added by each time is 4:2:1:2;
(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 DEG C of constant temperature refining, 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 50-80 DEG C, add required transforming agent successively and react, preferably add rear stirring about 10 minutes at every turn, react fully, all transforming agents add rear intensification, preferably at 80-90 DEG C of constant temperature 60-90 minute, when reaction system is by oily retrogradation, be warming up to 100-120 DEG C, preferred 105-110 DEG C of dehydration, is cooled to less than 105 DEG C after water has taken off.
Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total basicnumber is 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), part basis oil and vulcabond is added in the product of step (1) or in another reactor, stir, add diamines, reaction 2-8 minute, again add diamine reactant 2-8 minute, add monoamine reaction 2-8 minute, the mol ratio of vulcabond, diamines, diamines and monoamine added by each time is 4:2:1:2.
Said vulcabond structure is OCN-R 3-NCO, R 3can be carbon number be 6 ~ 30, preferably 6 ~ 20 arylidene, alkylidene group or cycloalkylidene, preferred tolyl, methyldiphenyl base, dicyclohexylmethyl, an xylylene, hexylidene etc.Such as described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), dicyclohexylmethyl vulcabond (HMDI), or at least one in an xylylene diisocyanate (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 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.
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 selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
In step (3), the product of step (1) and step (2) is mixed rear intensification, preferred 100-120 DEG C of constant temperature 10-20 minute, is finally warmed up to 200-220 DEG C of constant temperature 5-10 minute; Be cooled to 150-160 DEG C, add surplus lubricating base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassedly obtain finished product.
Lubricating grease of the present invention, 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 eight polyureas molecules.
Fig. 2 is the infrared analysis spectrogram of eight polyureas in the lubricating grease of embodiment 1 preparation.As can be seen from the figure, 3310 ~ 3323cm -1the peak at place is the stretching vibration absorption peak of NH-in eight polyureas molecules, 1630cm -1the peak at place is the vibration absorption peak of-CO-in eight polyureas molecules.
Fig. 3 is the nuclear magnetic resonance spectroscopy spectrogram of eight polyureas in the lubricating grease of embodiment 1 preparation.As can be seen from the figure, the peak of about δ=155HZ is the chemical shift of-CO-in eight polyureas molecules.
Fig. 4 is the Electrospray Ionization Mass Spectrometry spectrogram of eight polyureas in the lubricating grease of embodiment 1 preparation.As can be seen from the figure, the mass-to-charge ratio of sample is 1721.4m/z, and the relative molecular mass of this and eight polyurea compounds matches.
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 (total acid value is 120mgKOH/g, acid content 70%, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); 500SN(18kg).
Step 1: 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 DEG C of kinematic viscosity are 31mm 2the HVI150BS lubricating base oil of/s, stirs, heats to 50 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG 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 DEG C of constant temperature 30 minutes, material retrogradation; Be warmed up to 110 DEG C under stirring, keep 60 minutes, dehydration.
Step 2: another volume be 10L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add 5kg100 DEG C of kinematic viscosity be 11mm 2hVI500SN lubricating base oil and the 1.28kg MDI of/s are preheating to 90 DEG C, 0.15kg quadrol is added under rapid stirring, stir 4 minutes, 0.08kg quadrol is again added under rapid stirring, stir 4 minutes, add 0.69kg stearylamine and stir 4 minutes, the mol ratio of added successively MDI, quadrol, quadrol and stearylamine is 4:2:1:2,120 DEG C of constant temperature 20 minutes, obtains eight polyureas.
Gained eight polyureas is all squeezed in a upper still, stirs, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, be cooled to 160 DEG C, add 13kg lubricating base oil 500SN; Treat that temperature is cooled to 110 DEG 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 41.5%; Eight polyureas 2.6%; Lubricating base oil 55.9%.
The eight polyureas molecular structural formulas contained in component are:
Prepare a small amount of eight polyureas again by above-mentioned steps 2 same method, with sherwood oil (boiling point 60 ~ 90 DEG C) washing, filtration is precipitated, and namely gained precipitation obtains eight polyurea compounds after drying.Its infrared spectrum, nuclear magnetic resonance spectroscopy spectrogram, Electrospray Ionization Mass Spectrometry spectrogram are shown in Fig. 2, Fig. 3, Fig. 4 respectively.
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 (0.69kg); Quadrol (0.23kg); MDI(1.28kg); 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 DEG C of kinematic viscosity are 31mm 2the HVI150BS lubricating base oil of/s, stirs, heats to 80 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 85 DEG 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, 95 DEG C of constant temperature 30 minutes, material retrogradation; Be warmed up to 110 DEG C under stirring, keep 60 minutes, dehydration; Cooling to 90 DEG C, to add by 18kg100 DEG C of kinematic viscosity be 11mm 2the 1.28kg MDI rapid stirring of the HVI500SN lubricating base oil dissolving of/s 4 minutes, 0.15kg quadrol is added under rapid stirring, stir 4 minutes, 0.08kg quadrol is again added under rapid stirring, stir 4 minutes, add 0.69kg stearylamine and stir 4 minutes, the mol ratio of added successively MDI, quadrol, quadrol and stearylamine is 4:2:1:2,120 DEG C of constant temperature 20 minutes, is finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, cool; Treat that temperature is cooled to 110 DEG 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 41.5%; Eight polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 3
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); 150BS(10kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Lauryl amine (0.52kg); Quadrol (0.26kg); MDI(1.42kg); 500SN(38kg).
Prepare naphthenate with superhigh base number calcium base eight polyurea grease by the method for example 1, unlike the use of Witco 1298 Soft Acid, lauryl amine replaces naphthenic acid and stearylamine and each amounts of components 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 41.5%; Eight 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 (0.84kg; Quadrol (0.28kg); TDI(1.08kg); 500SN(23kg).
Prepare naphthenate with superhigh base number calcium base eight polyurea grease by the method for example 1, replace naphthenic acid and MDI unlike the use of propyl carbinol, 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 39.6%; Eight 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 (0.69kg); Quadrol (0.23kg); MDI(1.28kg); 500SN(7kg); To right-di-iso-octyldiphenylamine (0.4kg).
Naphthenate with superhigh base number calcium base eight polyurea grease is prepared by the method for example 1, amount unlike 500SN is 7kg, thus make each material rate occur larger change, in addition be 0.4kg to right-di-iso-octyldiphenylamine, 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 59.2%; Eight polyureas 3.6%; Lubricating base oil 36.5%; To right-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 (2.07kg); Quadrol (0.69kg; MDI(3.84kg); 500SN(18.6kg).
Prepare naphthenate with superhigh base number calcium base eight polyurea grease by the method for example 1, the consumption 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 41.8%; Eight polyureas 7.8%; Lubricating base oil 50.4%.
Embodiment 7
Feed composition: naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 30kg); PAO 40(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg; Quadrol (0.23kg); MDI(1.28kg); PAO 10(23kg); Dithio Acidic phosphates zinc (2kg), molybdenum dialkyldithiocarbamacompositions (1kg), tungsten disulfide (2kg), two tungsten selenide (2kg), to right-di-iso-octyldiphenylamine (0.2kg).
Preparing naphthenate with superhigh base number calcium base eight polyurea grease by the method for example 1, is 11mm unlike the use of full synthetic oil poly & Alpha ,-olefin oil PAO 10(100 DEG C of kinematic viscosity 2/ s) and PAO 40(100 DEG 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, each performance data of lubricating grease finished product obtained right-di-iso-octyldiphenylamine (0.2kg) 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 38.3%; Eight polyureas 2.4%; Lubricating base oil 51.6%; Dithio Acidic phosphates zinc 2.2%; Molybdenum dialkyldithiocarbamacompositions 1.1%; Tungsten disulfide 2.1%; Two tungsten selenide 2.1%; To right-di-iso-octyldiphenylamine 0.2%.
Embodiment 8
Feed composition: overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); 500SN(23kg).
Prepare overbased calcium alkyl-salicylate base eight polyurea 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.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 41.5%; Eight polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 9
Feed composition: overbased calcium alkyl-salicylate (total basicnumber is 360mgKOH/g, 30kg); 150BS(25kg); Naphthenic acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); 500SN(23kg).
Prepare overbased calcium alkyl-salicylate base eight polyurea grease by the method for example 1, unlike the use of the total basicnumber of overbased calcium alkyl-salicylate be 360mgKOH/g, 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 41.5%; Eight polyureas 2.6%; Lubricating base oil 55.9%.
Embodiment 10
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 (0.34kg); MDI(1.08kg); 500SN(23kg).
Prepare naphthenate with superhigh base number calcium base eight polyurea grease by the method for example 1, replace quadrol unlike the use of 1,6-hexanediamine, 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 41.5%; Eight 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).
Prepare naphthenate with superhigh base number calcium base eight polyurea grease by the method for example 1, replace quadrol unlike the use of Ursol D, 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 41.5%; Eight 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 (0.69kg); Quadrol (0.23kg); MDI(1.28kg); 500SN(23kg).
Prepare naphthenate with superhigh base number calcium base eight polyurea grease by the method for example 1, add propyl carbinol, and add after adding naphthenic acid unlike transforming agent, each performance data of lubricating grease finished product simultaneously 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 41.5%; Eight 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 right-di-iso-octyldiphenylamine (0.2kg).
A volume be 110L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add the HVI150BS lubricating base oil that calcium sulfonate with high base number that 30kg total basicnumber is 320mgKOH/g and 25kg 100 DEG C of kinematic viscosity are 31mm2/s, stir, heat to 80 DEG C, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature controls at about 80 DEG 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 DEG C of constant temperature 30 minutes, material retrogradation; Be warmed up to 110 DEG C under stirring, keep 60 minutes, dehydration; Finally be warmed up to 200 DEG C of constant temperature 5 minutes, add 25.2kg lubricating base oil 500SN; Treat that temperature is cooled to 110 DEG C, add after 0.2kg stirs 10 minutes to right-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 calcium sulfonate with high base number 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

Claims (19)

1. Calcium naphthenate base eight polyurea grease, with lubricating grease weight for benchmark, comprises following component:
1) non-newtonian fluid calcium naphthenate 10-70%; 2) eight polyureas 0.5-30%; 3) 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 20-65%; 2) eight polyureas 1-20%; 3) lubricating base oil 20-70%.
3., according to lubricating grease according to claim 1, wherein said non-newtonian fluid calcium naphthenate is transformed by newton's body calcium naphthenate and obtains, and its total basicnumber is 250-450mgKOH/g.
4. according to lubricating grease according to claim 1, wherein, said eight 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 according to claim 4, wherein, R 1be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8 ~ 24; R 2be phenylene or biphenylene or carbon number be the alkylidene group of 2 ~ 12; R 3to be carbon number be 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
6. according to lubricating grease according to claim 4, wherein, R 1be the phenyl of phenyl or C1 ~ C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10 ~ 18, R 2be phenylene or biphenylene, or carbon number is the alkylidene group of 2 ~ 8; R 3be selected from least one in tolyl, methyldiphenyl base, dicyclohexylmethyl, an xylylene and hexylidene.
7. the preparation method of one of claim 1 ~ 6 described Calcium naphthenate base eight polyurea grease, comprising:
(1) in reactor A, newton's body calcium naphthenate, part basis oil and transforming agent are mixed, heated, treat material retrogradation, heat up dehydration, cooling;
(2) in the product of reactor A or in reactor B, add part basis oil and vulcabond, first add diamines to react, again add diamines to react, finally add monoamine again to react, the mol ratio of vulcabond, diamines, diamines and monoamine added by each time is 4:2:1:2;
(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 DEG C of constant temperature refining, 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.
8. according to preparation method according to claim 7, in step (1), by newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent successively to react, all transforming agents add rear intensification, at 80-90 DEG C of constant temperature 60-90 minute, when reaction system retrogradation, be warming up to 100-120 DEG C of dehydration, lower the temperature after water has taken off.
9., according to preparation method according to claim 7, in step (2), in the product of step (1) or in another reactor, add part basis oil and vulcabond, add diamines, reaction 2-8 minute, adds diamine reactant 2-8 minute again, adds monoamine reaction 2-8 minute.
10. according to preparation method according to claim 7, in step (3), the product of step (1) and step (2) is mixed rear intensification, at 100-120 DEG C of constant temperature 10-20 minute, be finally warmed up to 200-220 DEG C of constant temperature 5-10 minute; Be cooled to 150-160 DEG C, add surplus lubricating base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
11. according to preparation method according to claim 7, and described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total basicnumber is 250-450mgKOH/g.
12. according to preparation method according to 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 calcium carbonate, boric acid, 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.
13. according to preparation method according to 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 according to claim 7, and wherein, said monoamine structural formula is R 1-NH 2, R wherein 1be the phenyl of phenyl or C1 ~ C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10 ~ 18.
15. according to preparation method according to claim 7, 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.
16. according to preparation method according to claim 7, and wherein, said diamine structures 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 according to claim 7, and wherein, said diamines is selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine, and/or is selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
18. according to preparation method according to claim 7, and wherein, said vulcabond structure is OCN-R 3-NCO, R 3to be carbon number be 6 ~ 30 arylidene, alkylidene group or cycloalkylidene.
19. according to preparation method according to claim 7, and wherein, described vulcabond is selected from tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond, or at least one in an xylylene diisocyanate.
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