CN104450113A - High-base number composite calcium-based urea octamer grease and preparation method thereof - Google Patents
High-base number composite calcium-based urea octamer grease and preparation method thereof Download PDFInfo
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- CN104450113A CN104450113A CN201310418852.8A CN201310418852A CN104450113A CN 104450113 A CN104450113 A CN 104450113A CN 201310418852 A CN201310418852 A CN 201310418852A CN 104450113 A CN104450113 A CN 104450113A
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Abstract
The invention discloses high-base number composite calcium-based urea octamer grease. The high-base number composite calcium-based urea octamer grease comprises, by weight, 10-70% of non-Newtonian calcium sulfonate-calcium naphthenate, 1-20% of higher fatty acid calcium salt, 1-15% of micromolecular inorganic acid and/or lower fatty acid calcium salt, 0.5-30% of a polyurea compound and 10-80% of base oil, wherein the polyurea compound is a urea octamer compound. The invention also discloses a preparation method of the high-base number composite calcium-based urea octamer grease and the high-base number composite calcium-based urea octamer grease obtained by the preparation method. The high-base number composite calcium-based urea octamer grease has good corrosion resistance and high temperature resistance. Compared with the composite calcium sulfonate-based urea octamer grease, the high-base number composite calcium-based urea octamer grease has better mechanical stability, water resistance, adhesion resistance, salt mist resistance, colloid stability and extreme pressure antiwear property and a longer service life.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of high base number composite calcium-base eight polyurea grease and preparation method thereof.
Background technology
Calcium sulphonate is used as the history that the purification agent of lubricating oil and rust-preventive agent have decades, 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 alkyl benzene calcium sulfonate or alkyl carboxylic acid calcium.Calcium sulfonate with high base number can be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate according to mode of production difference.Calcium mahogany sulfonate is with oleum or SO
3sulfonation mineral lubricating oils produces by product mahogany acid during white oil, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtaining; Calcium alkylbenzenesulfonate is with oleum or SO
3the alkylbenzene of sulfonation synthesis, alkyl benzene sulphonate (ABS) warp and Ca (OH) of generation
2reaction, the contour alkalization technology of carbonating and obtaining.
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 CN1465560 etc.
Utilize calcium sulfonate with high base number for raw material production lubricating grease, because it has excellent high temperature performance, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion, since putting goods on the market, cause the extensive concern of domestic and international lubricating grease industry, but, although high base number composite calcium sulfonate base grease has very excellent over-all properties, but the high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, simultaneously, along with the requirement of people to environment protection is more and more higher, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment also received day by day to the concern of people.Find a kind of performance and high base number composite calcium sulfonate base grease is similar but the lubricating grease that can alleviate the problems referred to above becomes the large problem that people face at present.
Summary of the invention
The object of this invention is to provide a kind of performance and high base number composite calcium sulfonate base grease is similar, cost is low, and preparation technology is simple, the lubricating grease of environmental protection and preparation method thereof.
The present inventor finds under study for action, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The calcium salt of the higher fatty acid of 1-20 % by weight; The small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight, wherein, described polyurea compound is eight polyurea compounds.Performance and the high base number composite calcium sulfonate base grease of this lubricating grease are similar, and cost is low, and preparation technology is simple, environmental protection.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of high base number composite calcium-base eight polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The calcium salt of the higher fatty acid of 1-20 % by weight; The small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight, wherein, described polyurea compound is eight polyurea compounds.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The calcium salt of the higher fatty acid of 2-15 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid; Eight polyurea compounds of 1-20 % by weight; The base oil of 20-70 % by weight.
Second aspect, the invention provides the preparation method of high base number composite calcium-base eight polyurea grease as above, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, small molecules mineral acid and/or lower fatty acid, eight polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides a kind of preparation method of high base number composite calcium-base eight polyurea grease, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and base oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, small molecules mineral acid and/or lower fatty acid and react, heat up after reaction dehydration;
(3) in step (2) gained mixture, add base oil and vulcabond, then add diamines, diamines and monoamine successively and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
Fourth aspect, the invention provides high base number composite calcium-base eight polyurea grease obtained by method as above.
High base number composite calcium-base eight polyurea grease of the present invention, not only the same with Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, there is excellent non-corrosibility and high thermal resistance, but also there is the performance such as mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear being better than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 2.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of high base number composite calcium-base eight polyurea grease, this lubricating grease have employed calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate be raw material, simultaneously containing composite calcium viscosifying agent, isocyanic ester and amine reaction produce eight polyurea compounds.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of high base number composite calcium-base eight polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The calcium salt of the higher fatty acid of 1-20 % by weight; The small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight, wherein, described polyurea compound is eight polyurea compounds.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The calcium salt of the higher fatty acid of 2-15 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid; Eight polyurea compounds of 1-20 % by weight; The base oil of 20-70 % by weight.
Described non-newtonian fluid calcium sulphonate-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, is preferably 300mgKOH/g-400mgKOH/g.Described non-newtonian fluid calcium sulphonate-calcium naphthenate is obtained by transforming agent conversion by newton's body calcium sulphonate and newton's body calcium naphthenate.And containing unformed calcium carbonate in newton's body calcium sulphonate, newton's body calcium naphthenate, at infrared spectrum 860cm
-1-865cm
-1there is unformed calcium carbonate charateristic avsorption band in place.Described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.The base number of non-newtonian fluid calcium sulphonate-calcium naphthenate is the weight mean value of the base number of newton's body calcium sulphonate and the base number of newton's body calcium naphthenate.
In the present invention, higher fatty acid is carbon number is 8-20, the straight chain fatty acid of preferred 10-16 or hydroxy fatty acid, such as, at least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, is preferably 12-oxystearic acid.
In the present invention, the molecular weight of small molecules mineral acid or lower fatty acid is less than or equal to 150.Wherein, small molecules mineral acid can be selected from least one in boric acid, phosphoric acid, sulfuric acid etc., is preferably boric acid and/or phosphoric acid; Lower fatty acid can be selected from least one in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid etc., is preferably acetic acid.
In the present invention, described eight polyurea compounds preferably have following structure:
Wherein, R
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, preferred 2-8, and arylidene can be phenylene or biphenylene.
Wherein, R
3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, preferred 6-20, R
3be more preferably
in at least one.
Above-mentioned eight polyurea compounds can adopt the thinkable various method of those skilled in the art institute to obtain, and the method such as can recorded according to CN103060068A prepares.
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, is preferably 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, as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc. in lubricating grease of the present invention.Wherein, the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.01-5% of lubricating grease gross weight, preferred 0.1-2.5%, can be at least one in pentanoic, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of lubricating grease gross weight, preferred 0.8-8% can be at least one in 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 accounts for the 0.01-4.5% of lubricating grease gross weight, preferred 0.1-2%, can be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the preparation method of high base number composite calcium-base eight polyurea grease as above, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, small molecules mineral acid and/or lower fatty acid, eight polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
In the present invention, described above for the calcium salt of the calcium salt of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, small molecules mineral acid and/or lower fatty acid, eight polyurea compounds, base oil and additive, do not repeat them here.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are the total amount of base oil used, in the present invention, part basis oil is preferably 1:0.1-5 with the weight ratio of surplus base oil.
For non-newtonian fluid calcium sulphonate-calcium naphthenate, can be obtained by transforming agent conversion by newton's body calcium sulphonate and newton's body calcium naphthenate, such as, by newton's body calcium sulphonate, newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.
The third aspect, the invention provides a kind of preparation method of high base number composite calcium-base eight polyurea grease, comprising:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and base oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, small molecules mineral acid and/or lower fatty acid and react, heat up after reaction dehydration;
(3) in step (2) gained mixture, add base oil and vulcabond, then add diamines, diamines and monoamine successively and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
In step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent and react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute.
In the present invention, for the weight ratio of newton's body calcium sulphonate and newton's body calcium naphthenate without particular requirement, be preferably 1:0.25-4.The gross weight of newton's body calcium sulphonate and newton's body calcium naphthenate and the weight ratio of part basis oil are preferably 1:0.1-3.
Described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.
Described transforming agent is preferably selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water; More preferably at least one in the fatty alcohol of C1-C5, the lipid acid of C1-C5, the aliphatic ketone of C1-C5, the alkanoic of C1-C5, the aliphatic amide of C1-C5, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, the arylphosphonic acid of C6-C20, the diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate (ABS) and water is selected from; Further be preferably selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water.The add-on of transforming agent is preferably the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight, is more preferably the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
In the present invention, fatty alcohol comprises the fatty alcohol of straight chain, side chain and ring-type, and lipid acid, aliphatic ketone, alkanoic, aliphatic amide are in like manner.
In step (2), at 85-100 DEG C, add the suspension liquid of lime or calcium hydroxide, add higher fatty acid, stir 5-20 minute, add small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 100-120 DEG C, preferably keep 30-60 minute to realize dehydration.Wherein, the addition sequence of higher fatty acid and small molecules mineral acid and/or lower fatty acid can exchange.
In the present invention, higher fatty acid, small molecules mineral acid, lower fatty acid as previously mentioned, do not repeat them here.
In the present invention, the H of higher fatty acid and small molecules mineral acid and/or lower fatty acid
+oH contained by the suspension of total amount of substance and lime or calcium hydroxide
-total amount of substance is equal, OH
-amount also can excessive 1-10%.
In the present invention, in calcium hydroxide, the add-on of the suspension liquid of lime or calcium hydroxide is preferably the 1-15% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight; With H
+amount of substance meter, the mol ratio of higher fatty acid and small molecules mineral acid and/or lower fatty acid is preferably 1:1-10.
In the present invention, namely the suspension liquid of lime or calcium hydroxide refers to the suspension liquid that lime or calcium hydroxide are formed in water, and the solid content of suspension liquid is preferably 10-60 % by weight.
In step (3), in step (2) gained mixture, adding base oil and vulcabond, then add diamines, diamines and monoamine successively and react, is namely prepare eight polyurea compounds in step (2) gained mixture.
Prepare the method for eight polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, base oil and vulcabond can be added in step (2) gained mixture, add diamines, stir 2-8 minute, again add diamines, stir 2-8 minute, add monoamine again, stir 2-8 minute, the mol ratio of vulcabond, diamines, diamines and monoamine added by each time is 4:2:1:2.
In step of the present invention (3), the diamines added for twice can be the same or different, and in order to easy to operate, the diamines that preferably twice adds is identical.
Described vulcabond structure is OCN-R
3-NCO, R
3can be carbon number be 6-30, the arylidene of preferred 6-20, alkylidene group or cycloalkylidene, preferably
deng.Such as described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), at least one in dicyclohexylmethyl vulcabond (HMDI) and an xylylene diisocyanate (XDI) etc.
Described monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R
1 '-NH
2, R wherein
1, R
1 'can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 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.
Described 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, preferred 2-8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from Ursol D, O-Phenylene Diamine, 4, the aromatic amine of 4 '-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
In step (4), first at 100-120 DEG C of constant temperature 10-20 minute, be finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
In the present invention, in step (1), in the total amount of base oil used and step (3), in the total amount of base oil used and step (4), the weight ratio of the total amount of base oil used is preferably 1:0.1-5:0.1-5.
Fourth aspect, high base number composite calcium-base eight polyurea grease that the preparation method that present invention also offers is provided by third aspect present invention obtains.
Compared with high base number composite calcium-base eight polyurea grease obtained with the preparation method provided by second aspect, high base number composite calcium-base eight polyurea grease that the preparation method that the third aspect provides obtains has better mechanical stability, water resisting property and adhesivity, colloid stability, and has longer lubricating life.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following Examples and Comparative Examples:
Overbased or calcium sulfonate with high base number raw material weight+the overbased or overbased calcium alkyl-salicylate raw material weight+transforming agent gross weight of non-newtonian fluid calcium sulphonate-calcium naphthenate %=()/lubricating grease gross weight × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium sulphonate-calcium naphthenate.
Overbased and overbased calcium alkyl-salicylate raw material, also can according to method preparation disclosed in CN101885677A purchased from Xinjiang Land Fine Petrochemical Co., Ltd.
Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Naphthenic acid is purchased from Jinzhou Tie Chen petrochemical complex limited liability company.
Embodiment 1
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat 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 aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 100 DEG C, add the calcium hydroxide suspension liquid 9kg that solid content is 20 % by weight, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add the boric acid aqueous solution that 9.28kg concentration is 25 % by weight, stir 10 minutes, under stirring, be warmed up to 120 DEG C, keep 30 minutes, dehydration; Add the HVI500SN lubricating base oil of 2kg and 1.28kgMDI rapid stirring 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, MDI added successively, quadrol, quadrol are 4:2:1:2 with the ratio of the amount of substance of stearylamine, 120 DEG C of constant temperature 20 minutes, is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Service check the results are shown 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-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Embodiment 2
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat 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 aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 100 DEG C, add the calcium hydroxide suspension liquid 9kg that solid content is 20 % by weight, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add the boric acid aqueous solution that 9.28kg concentration is 25 % by weight, stir 10 minutes, under stirring, be warmed up to 120 DEG C, keep 30 minutes, dehydration.
Another volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add the HVI500SN lubricating base oil of 2kg and 1.28kg MDI rapid stirring 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, MDI added successively, quadrol, quadrol are 4:2:1:2 with the ratio of the amount of substance of stearylamine, 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 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Service check the results are shown in Table 1, and infrared spectrum is shown in Fig. 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
The eight polyureas molecular structural formulas contained in component are:
Embodiment 3
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 20kg); Propyl carbinol (2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); Stearic acid (1.9kg); Boric acid (2.32kg); Lauryl amine (0.52kg); Quadrol (0.26kg); MDI(1.42kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 28kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 320mgKOH/g and the HVI150BS lubricating base oil of 20kg, stir, heat to 80 DEG C, constant temperature 10 minutes; Add 2.8kg propyl carbinol, temperature controls at about 80 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 90 DEG C, constant temperature 60 minutes, material retrogradation; Add the calcium hydroxide suspension liquid 9kg that solid content is 20 % by weight, stir 10 minutes; Add 1.9kg stearic acid, stir 10 minutes; Add the boric acid aqueous solution that 9.28kg concentration is 25 % by weight, stir 10 minutes, under stirring, be warmed up to 120 DEG C, keep 30 minutes, dehydration; Add the HVI500SN lubricating base oil of 2kg and 1.28kg MDI rapid stirring 8 minutes, 0.17kg quadrol is added under rapid stirring, stir 8 minutes, 0.09kg quadrol is again added under rapid stirring, stir 8 minutes, add 0.52kg lauryl amine and stir 8 minutes, MDI added successively, quadrol, quadrol are 4:2:1:2 with the ratio of the amount of substance of stearylamine, 100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, remaining HVI500SN lubricating base oil is added; Treat that temperature is cooled to 120 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 sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.6 % by weight; Calcium stearate 2.3 % by weight; Lime borate 2.7 % by weight.
Embodiment 4
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.84kg); Quadrol (0.28kg); TDI(1.08kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; Replace naphthenic acid with Witco 1298 Soft Acid simultaneously; MDI is replaced with TDI; The consumption of each composition as above.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 sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Embodiment 5
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 1.8kg); Boric acid (1kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 7kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Transforming agent is naphthenic acid, boric acid and acetic acid, and its mesoboric acid adds after acetic acid; The consumption of each composition as above.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 sulphonate-calcium naphthenate 53.8 % by weight; Eight polyureas 3.6 % by weight; Lubricating base oil 35.4 % by weight; 12-oxystearic acid calcium 3.4 % by weight; Lime borate 3.8 % by weight.
Embodiment 6
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (2.07kg); Quadrol (0.69kg); MDI(3.84kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18.6kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, the consumption of each composition is as above.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 sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 7.5 % by weight; Lubricating base oil 49.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Embodiment 7
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); Full synthetic oil poly & Alpha ,-olefin oil PAO40(100 DEG C of kinematic viscosity is 41mm
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); Full synthetic oil poly & Alpha ,-olefin oil PAO10(100 DEG C of kinematic viscosity is 11mm
2/ s, 9kg); Dithio Acidic phosphates zinc (2kg); Molybdenum dialkyldithiocarbamacompositions (1kg); Tungsten disulfide (2kg); Two tungsten selenide (2kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Full synthetic oil poly & Alpha ,-olefin oil PAO40 and PAO10 is used to replace HVI150BS and HVI500SN respectively; And treat that temperature is cooled to 110 DEG C, add the dithio Acidic phosphates zinc of 2kg, stir 10 minutes, add the molybdenum dialkyldithiocarbamacompositions of 1kg, stir 10 minutes, add the tungsten disulfide of 2kg, stir 10 minutes, add two tungsten selenide of 2kg, stir 10 minutes, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.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 sulphonate-calcium naphthenate 38.7 % by weight; Eight polyureas 2.6 % by weight; Lubricating base oil 45.2 % by weight; 12-oxystearic acid calcium 2.5 % by weight; Lime borate 2.7 % by weight; Dithio Acidic phosphates zinc 2.3 % by weight; Molybdenum dialkyldithiocarbamacompositions 1.2 % by weight; Tungsten disulfide 2.3 % by weight; Two tungsten selenide 2.3 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 8
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 33kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; The consumption of each composition as above.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 sulphonate-calcium naphthenate 37.8 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.4 % by weight; 12-oxystearic acid calcium 2.5 % by weight; Lime borate 2.8 % by weight.
Embodiment 9
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 20kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (5.2kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Phosphoric acid (3kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 28kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Add after boric acid stirs 10 minutes, add phosphoric acid, stir 10 minutes, under stirring, be warmed up to 120 DEG C, keep 30 minutes, dehydration; And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.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 sulphonate-calcium naphthenate 35.9 % by weight; Eight polyureas 2.4 % by weight; Lubricating base oil 51.6 % by weight; 12-oxystearic acid calcium 2.3 % by weight; Lime borate 2.5 % by weight; Calcium phosphate 5.1 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 10
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 15kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (3kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Acetic acid (2kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 33kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, add after boric acid stirs 10 minutes, add acetic acid, stir 10 minutes, be then under agitation warmed up to 120 DEG C, keep 30 minutes, dehydration; The consumption of each composition as above.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 sulphonate-calcium naphthenate 36.8 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 52.9 % by weight; 12-oxystearic acid calcium 2.3 % by weight; Lime borate 2.6 % by weight; Lime acetate 2.9 % by weight.
Embodiment 11
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 15kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Para-totuidine (0.34kg); Quadrol (0.28kg); MDI(1.58kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Para-totuidine is used to replace stearylamine; The consumption of each composition as above.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 sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Embodiment 12
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 360mgKOH/g, 15kg); Overbased calcium alkyl-salicylate (total basicnumber is 360mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 15kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.63kg); 1,6-hexanediamine (0.4kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 33kg).
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 360mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 360mgKOH/g; Witco 1298 Soft Acid is used to replace naphthenic acid; 1,6-hexanediamine is used to replace quadrol; The consumption of each composition as above.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 sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Embodiment 13
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Stearylamine (0.69kg); Quadrol (0.23kg); MDI(1.28kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat 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 aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation.
Another volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add the HVI500SN lubricating base oil of 5kg, be warming up to 100 DEG C, add the calcium hydroxide suspension liquid 9kg that solid content is 20 % by weight, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add the boric acid aqueous solution that 9.28kg concentration is 25 % by weight, stir 10 minutes, obtain 12-oxystearic acid calcium and lime borate.
The 3rd volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add the HVI500SN lubricating base oil of 2kg and 1.28kg MDI rapid stirring 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, MDI added successively, quadrol, quadrol are 4:2:1:2 with the ratio of the amount of substance of stearylamine, 120 DEG C of constant temperature 20 minutes, obtains eight polyureas.
The 12-oxystearic acid calcium of gained and lime borate are all squeezed in first still, stirs, under stirring, be warmed up to 120 DEG C, keep 30 minutes, eight polyureas of the 3rd reactor gained are all squeezed in this still by dehydration, stir, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; 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 sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Embodiment 14
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with phenol, acetic acid is replaced with butyric acid.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 sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Embodiment 15
High base number composite calcium-base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
High base number composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with ketone, aqueous acetic acid is replaced with ether.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 sulphonate-calcium naphthenate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Comparative example 1
High base number composite calcium sulfonate base eight polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number calcium total basicnumber is that the overbased calcium sulphonate of 400mgKOH/g replaces, and each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate 37.9 % by weight; Eight polyureas 2.5 % by weight; Lubricating base oil 54.5 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Lime borate 2.7 % by weight.
Table 1 each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643; Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.
Table 1(continues) each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643; Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.
Embodiment 1 and comparative example 1 are compared and can find out, the prolongation Drawing cone in-degree of high base number composite calcium-base eight polyurea grease of the present invention and the difference of Drawing cone in-degree are less than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, water drenches number of dropouts much smaller than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, salt-fog test is better than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, water resistant spraying value is less than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, Stencil oil-dividing value is much smaller than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, tetra-ball machine test value is greater than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, the bearing lubrication life-span is greater than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, the mechanical stability of high base number composite calcium-base eight polyurea grease of the present invention is described, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear, lubricating life is all better than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, and high base number composite calcium-base eight polyurea grease of the present invention is the same with Composite calcium-sulfonate-batetrapolyurea eight polyurea grease has the performances such as excellent non-corrosibility and high thermal resistance.
Embodiment 1 is compared can find out with embodiment 2 and embodiment 13 respectively, high base number composite calcium-base eight polyurea grease prepared by original position, there is better mechanical stability, water resisting property and adhesivity, colloid stability, and there is longer lubricating life; Embodiment 1 is compared can find out with embodiment 14 and embodiment 15 respectively, transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, butanols, Virahol, boric acid, acetic acid and water, high base number composite calcium-base eight polyurea grease of preparation, has better mechanical stability, water resisting property and adhesivity, colloid stability.
As can be seen from Figure 1, the lubricating grease of embodiment 2 preparation is 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.
High base number composite calcium-base eight polyurea grease of the present invention, not only the same with Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, there is excellent non-corrosibility and high thermal resistance, but also there is the performance such as mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear being better than Composite calcium-sulfonate-batetrapolyurea eight polyurea grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (26)
1. high base number composite calcium-base eight polyurea grease, is characterized in that, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The calcium salt of the higher fatty acid of 1-20 % by weight; The small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight, wherein, described polyurea compound is eight polyurea compounds.
2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The calcium salt of the higher fatty acid of 2-15 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid; Eight polyurea compounds of 1-20 % by weight; The base oil of 20-70 % by weight.
3. lubricating grease according to claim 1 and 2, wherein, described non-newtonian fluid calcium sulphonate-calcium naphthenate is transformed by newton's body calcium sulphonate and newton's body calcium naphthenate and obtains, and the total basicnumber of described non-newtonian fluid calcium sulphonate-calcium naphthenate is 250-450mgKOH/g.
4. lubricating grease according to claim 1 and 2, wherein, straight chain fatty acid or the hydroxy fatty acid of described higher fatty acid to be carbon number be 8-20.
5. lubricating grease according to claim 4, wherein, described higher fatty acid is selected from least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.
6. lubricating grease according to claim 1 and 2, wherein, the molecular weight of small molecules mineral acid or lower fatty acid is less than or equal to 150.
7. lubricating grease according to claim 6, wherein, described small molecules mineral acid is selected from least one in boric acid, phosphoric acid, sulfuric acid, and described lower fatty acid is selected from least one in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.
8. lubricating grease according to claim 1 and 2, wherein, described eight polyurea compounds have following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
9. lubricating grease according to claim 8, 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
3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.
10. lubricating grease according to claim 9, 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
in at least one.
The preparation method of high base number composite calcium-base eight polyurea grease in 11. claim 1-10 described in any one, it is characterized in that, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, small molecules mineral acid and/or lower fatty acid, eight polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The preparation method of 12. 1 kinds of high base number composite calcium-base eight polyurea greases, it is characterized in that, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and base oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, small molecules mineral acid and/or lower fatty acid and react, heat up after reaction dehydration;
(3) in step (2) gained mixture, add base oil and vulcabond, then add diamines, diamines and monoamine successively and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
13. preparation methods according to claim 12, wherein, in step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute.
14. preparation methods according to claim 12, wherein, in step (2), at 85-100 DEG C, add the suspension liquid of lime or calcium hydroxide, add higher fatty acid, stir 5-20 minute, add small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 100-120 DEG C of dehydration.
15. preparation methods according to claim 12, wherein, in step (3), in step (2) gained mixture, add base oil and vulcabond, add diamines, stir 2-8 minute, again add diamines, stir 2-8 minute, then add monoamine, stir 2-8 minute, the mol ratio of vulcabond, diamines, diamines and monoamine added by each time is 4:2:1:2.
16. preparation methods according to claim 12, wherein, in step (4), first at 100-120 DEG C of constant temperature 10-20 minute, are finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
17. preparation methods according to claim 12, wherein, described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and the total basicnumber of described newton's body calcium sulphonate is 250-450mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and the total basicnumber of described newton's body calcium naphthenate is 250-450mgKOH/g.
18. preparation methods according to claim 12, wherein, described transforming agent is selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water, and the add-on of transforming agent is the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
19. preparation methods according to claim 18, wherein, described transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water, and the add-on of transforming agent is the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
20. preparation methods according to claim 12, wherein, the structural formula of described monoamine is R
1-NH
2, 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.
21. preparation methods according to claim 20, wherein, described 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.
22. preparation methods according to claim 12, wherein, the structural formula of described diamines is NH
2-R
2-NH
2, wherein, R
2the alkylidene group of to be carbon number be 2-8, or phenylene or biphenylene.
23. preparation methods according to claim 22, wherein, described diamines is selected from Ursol D, O-Phenylene Diamine, 4, the aromatic amine of 4 '-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
24. preparation methods according to claim 12, wherein, the structure of described vulcabond is OCN-R
3-NCO, R
3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.
25. preparation methods according to claim 24, wherein, described vulcabond is selected from least one in tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
26. high base number composite calcium-base eight polyurea greases obtained by the method in claim 12-25 described in any one.
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| CN102417853A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium sulfonate octaurea lubricating grease and preparation method thereof |
| CN102453598A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof |
| CN102453600A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Composite calcium sulfonate-based hexaurea grease and preparation method thereof |
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