CN104293452A - Composite calcium naphthenate-based polyurea lubricating grease and preparation method thereof - Google Patents
Composite calcium naphthenate-based polyurea lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention discloses composite calcium naphthenate-based polyurea lubricating grease which is characterized by including following components, on the basis of the weight of the lubricating grease, 20-60 wt% of non-Newtonian calcium naphthenate, 1-10 wt% of a calcium salt of a higher fatty acid, 0.5-25 wt% of a polyurea compound and 25-70 wt% of a basic oil. An infrared spectrogram of the non-Newtonian calcium naphthenate has a characteristic absorption peak of aragonite-type calcium carbonate. The invention also discloses a preparation method of the composite calcium naphthenate-based polyurea lubricating grease and the composite calcium naphthenate-based polyurea lubricating grease prepared through the same. The composite calcium naphthenate-based polyurea lubricating grease has excellent anti-corrosion property and anti-salt fog property, and has performances comprising a high-temperature-resistant performance, a water-resistant performance, an adhesive performance, a colloid stability and the like, which are better than those of a composite calcium sulfonate-based polyurea lubricating grease. The composite calcium naphthenate-based polyurea lubricating grease has a longer lubricating service life. The preparation method is simple, environmental-protective, low in cost and stable in product quality.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of Composite calcium naphthenate base 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 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 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 base grease.
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 naphthenate of 20-60 % by weight; The calcium salt of the higher fatty acid of 1-10 % by weight; The polyurea compound of 0.5-25 % by weight; The base oil of 25-70 % by weight, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the charateristic avsorption band of aragonite calcium carbonate; Described lubricating grease preferably also comprises the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 % by weight.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 Composite calcium naphthenate base polyurea grease, it is characterized in that, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium naphthenate of 20-60 % by weight; The calcium salt of the higher fatty acid of 1-10 % by weight; The polyurea compound of 0.5-25 % by weight; The base oil of 25-70 % by weight, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the charateristic avsorption band of aragonite calcium carbonate.
Preferably, with lubricating grease weight for benchmark, described lubricating grease also comprises the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 % by weight.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium naphthenate of 25-55 % by weight; The calcium salt of the higher fatty acid of 2-6 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 2-10 % by weight; 1.3-15 the polyurea compound of % by weight; The base oil of 35-60 % by weight.
Second aspect, the invention provides the preparation method of Composite calcium naphthenate base polyurea grease as above, it is characterized in that, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium naphthenate, higher fatty acid, the calcium salt of aromatic acid and/or small molecules mineral acid and/or lower fatty acid, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides a kind of preparation method of Composite calcium naphthenate base polyurea grease, it is characterized in that, the method comprises:
(1) by 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, aromatic acid and/or small molecules mineral acid and/or lower fatty acid reacts, heat up after reaction dehydration, then lowers the temperature;
(3) in step (2) gained mixture, add base oil and monoamine, or also add diamines, add vulcabond and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds base oil, adds necessary additive, obtains finished product.
Fourth aspect, the invention provides the Composite calcium naphthenate base polyurea grease obtained by method as above.
Composite calcium naphthenate base polyurea grease of the present invention, not only the same with Composite calcium-sulfonate-batetrapolyurea polyurea grease, there is excellent non-corrosibility and resistance to salt(spray)fog, but also there is the high thermal resistance, water resisting property and the performance such as adhesivity, colloid stability that are better than Composite calcium-sulfonate-batetrapolyurea 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 analysis spectrogram of the calcium carbonate in the overbased calcium alkyl-salicylate of embodiment 2.
Fig. 2 is the infrared analysis spectrogram of the calcium carbonate in the lubricating grease of embodiment 2 preparation.
Fig. 3 is the XRD crystal formation mensuration of the calcium carbonate in the lubricating grease of embodiment 2 preparation.
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 Composite calcium naphthenate base polyurea grease, this lubricating grease have employed petroleum naphthenic acid calcium or synthesis calcium naphthenate is raw material, simultaneously containing the polyurea compound that the reaction of composite calcium viscosifying agent, isocyanic ester and amine produces.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of Composite calcium naphthenate base polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium naphthenate of 20-60 % by weight; The calcium salt of the higher fatty acid of 1-10 % by weight; The polyurea compound of 0.5-25 % by weight; The base oil of 25-70 % by weight, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the charateristic avsorption band of aragonite calcium carbonate.
Preferably, with lubricating grease weight for benchmark, described lubricating grease also comprises the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 % by weight.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium naphthenate of 25-55 % by weight; The calcium salt of the higher fatty acid of 2-6 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 2-10 % by weight; 1.3-15 the polyurea compound of % by weight; The base oil of 35-60 % by weight.
The infrared absorption peak of the mainly carbonate that calcium carbonate occurs in infrared spectra, is divided into 4 regions: ν 1-1450cm
-1; ν 2-1080cm
-1; ν 3-870cm
-1with ν 4-710cm
-1.ν 1 bands of a spectrum are carbonate (CO
3 2-) antisymmetric stretching vibration absorption peak, ν 2 bands of a spectrum are carbonate symmetrical stretching vibration absorption peaks, and ν 3 bands of a spectrum are out-of-plane deformation vibration absorption peaks of carbonate, and ν 4 bands of a spectrum are in-plane bending vibration absorption peaks of carbonate.Generally speaking, the crystalline form of calcium carbonate can be distinguished by the difference of these absorption peaks.The characteristic absorbance of different crystal forms calcium carbonate is as follows: ν 3 bands of a spectrum of calcite type are 876cm
-1left and right, ν 4 bands of a spectrum are 712cm
-1left and right; ν 2 bands of a spectrum of aragonitic are 1082cm
-1left and right, ν 3 bands of a spectrum are 856cm
-1left and right, ν 4 bands of a spectrum are 712cm
-1and 700cm
-1(weak); Vaterite-type ν 3 bands of a spectrum are 876cm
-1left and right, ν 4 bands of a spectrum are 745cm
-1left and right; Amorphous ν 3 bands of a spectrum are 860cm
-1left and right.Environment residing for calcium carbonate is different, the peak position slightly difference of its infrared band.
Described non-newtonian fluid calcium naphthenate is at infrared spectrum 1082cm
-1left and right, 856cm
-1left and right, 712cm
-1left and right, 700cm
-1there is the charateristic avsorption band of aragonite calcium carbonate in place, total basicnumber is 250mgKOH/g-500mgKOH/g, preferred 300mgKOH/g-450mgKOH/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, at infrared spectrum 1076cm
-1left and right, 860cm
-1there is unformed calcium carbonate charateristic avsorption band at left and right place.Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-500mgKOH/g, preferred 300mgKOH/g-450mgKOH/g, and after changing into non-newtonian fluid calcium naphthenate, its base number is constant.
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, aromatic acid is the carboxylic acid having at least 1 carboxyl to be directly connected with aromatic ring, aromatic acid can be replace or unsubstituted aromatic acid, its substituting group can be at least one in alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno etc., and the molecular weight of aromatic acid is less than or equal to 550.Aromatic acid is preferably binary aromatic acid, such as, can be selected from least one in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.Be preferably phthalic acid, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, and at least one in methyl substituted biphenyl dicarboxylic acid, santowax dioctyl phthalate etc.
In the present invention, described polyurea compound is without particular requirement, and the polyurea compound can commonly used for this area can be such as at least one in dimerization carbamide compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds.Wherein the weight ratio of two polyurea compounds, four polyurea compounds, six polyurea compounds, eight polyurea compounds can be arbitrary proportion.More preferably described polyurea compound is two polyurea compounds.
In the present invention, described two polyurea compounds preferably have following structure:
Wherein, R
1, R
1 'can be the same or different, can be alkyl, cycloalkyl or aryl, and the carbon number of alkyl or cycloalkyl can be 8-24, and be preferably 10-18, aryl can be the phenyl of phenyl or replacement, is preferably the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R
3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R
3be more preferably
in at least one.
In the present invention, described four 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 phenyl or replacement, is preferably the phenyl of 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, and be preferably 2-8, 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, is preferably 6-20, R
3be more preferably
in at least one.
In the present invention, described six 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, and be preferably 2-8, 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, is preferably 6-20, R
3be more preferably
in at least one.
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, and be preferably 10-18, 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, and be preferably 2-8, 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, is preferably 6-20, R
3be more preferably
in at least one.
Above-mentioned polyurea compound can adopt the thinkable various method of those skilled in the art institute to obtain, and the method such as can recorded according to CN103060069A, CN103060070A, CN103060068A, CN103060067A 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, 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, 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 Composite calcium naphthenate base polyurea grease as above, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium naphthenate, higher fatty acid, the calcium salt of aromatic acid and/or small molecules mineral acid and/or lower fatty acid, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, 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 the calcium salt of non-newtonian fluid calcium naphthenate, higher fatty acid, aromatic acid, small molecules mineral acid and/or lower fatty acid, polyurea compound and base oil, 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 1:0.1-1 with the weight ratio of surplus base oil.
For non-newtonian fluid calcium naphthenate, can be obtained by transforming agent conversion by newton's body calcium naphthenate, such as, by 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, be greater than 90 DEG C and be less than or equal to 110 DEG C, preferred 95-110 DEG C, constant temperature 40-100 minute, be then warming up to 150-170 DEG C of dehydration.
The third aspect, the invention provides a kind of preparation method of Composite calcium naphthenate base polyurea grease, comprising:
(1) by 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, aromatic acid and/or small molecules mineral acid and/or lower fatty acid reacts, heat up after reaction dehydration, then lowers the temperature;
(3) in step (2) gained mixture, add base oil and monoamine, or also add diamines, add vulcabond and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds base oil, adds necessary additive, obtains finished product.
In step (1), by 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, be greater than 90 DEG C and be less than or equal to 110 DEG C, preferred 95-110 DEG C, constant temperature 40-100 minute.
The weight ratio of newton's body calcium naphthenate and base oil is preferably 1:0.1-1.
Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-500mgKOH/g, preferred 300mgKOH/g-450mgKOH/g.
Described transforming agent is selected from least one in water, fatty alcohol, aliphatic ether, lipid acid, naphthenic acid, alkanoic, aliphatic ketone, aliphatic amide, cycloalkanes amine, cycloalkanol, cycloalkanes ether, carbonic acid gas, aromatic alcohol, aromatic amine and alkyl benzene sulphonate (ABS), is preferably selected from least one in water, Virahol, methyl alcohol, ethanol, propyl alcohol, propyl carbinol, ketone, formaldehyde, glycol dimethyl ether, acetic acid, propionic acid, butyric acid, naphthenic acid, stearic acid, 12-oxystearic acid and Witco 1298 Soft Acid.Be more preferably A, B, C tri-class material, category-A material is ethanol, propyl alcohol, at least one in butanols and 12-oxystearic acid, category-B material is acetic acid, at least one in propionic acid and butyric acid, C class material is water, and feed postition is preferably category-A material to add prior to category-B material, namely first ethanol is added, propyl alcohol, at least one in butanols and 12-oxystearic acid, after mixing with newton's body calcium naphthenate, add acetic acid again, at least one in propionic acid and butyric acid, for the addition sequence of C class material water without particular requirement, can first add, can add later, also can add together with category-A material or category-B material.
The add-on of transforming agent is the 4-32% of newton's body calcium naphthenate weight, preferred 15-25%.When transforming agent is preferably A, B, C tri-class material, category-A material is at least one in ethanol, propyl alcohol, butanols and 12-oxystearic acid, category-B material is at least one in acetic acid, propionic acid and butyric acid, when C class material is water, the weight ratio of category-A material and category-B material and C class material is preferably 1:0.1-10:1-10, is more preferably 1:0.5-8:1-8.For the amount ratio between the concrete material selected in category-A material and category-B material and each material without particular requirement, as long as total amount can obtain better effect in above-mentioned scope.
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 aromatic acid and/or small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 150-170 DEG C, preferably keep 30-60 minute to realize dehydration, be then cooled to 100-120 DEG C.Wherein, the addition sequence of higher fatty acid and aromatic acid and/or small molecules mineral acid and/or lower fatty acid can exchange.
In the present invention, higher fatty acid, aromatic 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 aromatic acid and/or small molecules mineral acid and/or lower fatty acid
+total amount of substance and the OH contained by calcium hydroxide
-total amount of substance is equal, and the amount of calcium hydroxide also can excessive 1-10%.
In 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 naphthenate weight; With H
+amount of substance meter, the mol ratio of higher fatty acid and aromatic acid and/or 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), base oil and monoamine is added in step (2) gained mixture, or also add diamines, add vulcabond to react, namely be prepare polyurea compound in step (2) gained mixture, mixing polyureas can be prepared, also can prepare two independent polyurea compounds, four polyurea compounds, six polyurea compounds or eight polyurea compounds.
The method preparing mixing polyureas, without particular requirement, can adopt the thinkable various method of those skilled in the art, such as, can adopt the method for US Patent No. 3243372.
Prepare the method for two polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, can add base oil and monoamine in step (2) gained mixture, stir 2-8 minute, then add the vulcabond be dissolved in base oil, stir 2-8 minute, the mol ratio of vulcabond and monoamine is 1:2.
Prepare the method for four polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, can add base oil and vulcabond, stir, add diamines in step (2) gained mixture, stir 2-8 minute, add monoamine, stir 2-8 minute, the mol ratio of vulcabond, diamines and monoamine is 2:1:2.
Prepare the method for six 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, stir, add monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, then add vulcabond, stir 2-8 minute, the mol ratio of added successively vulcabond, monoamine, diamines and vulcabond is 2:2:2:1.
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, stir, add diamines, stir 2-8 minute, again add diamines, stir 2-8 minute, add monoamine, stir 2-8 minute, the mol ratio of added successively vulcabond, diamines, diamines and monoamine is 4:2:1:2.
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, be 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, 4,4-benzidines aromatic amine 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; Be cooled to 150-160 DEG C, 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 1:0.1-1:0.1-1.
Fourth aspect, the Composite calcium naphthenate base polyurea grease that the preparation method that present invention also offers is provided by third aspect present invention obtains.
Compared with the Composite calcium naphthenate base polyurea grease obtained with the preparation method provided by second aspect, the Composite calcium naphthenate base polyurea grease that the preparation method that the third aspect provides obtains has better high thermal resistance, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear.
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 the overbased calcium alkyl-salicylate raw materials quality+transforming agent total mass of non-newtonian fluid calcium naphthenate %=()/lubricating grease total mass × 100%.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 method preparation disclosed in CN101885677A from Xinjiang Land Fine Petrochemical Co., Ltd.
In comparative example, calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Embodiment 1
The Composite calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
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 320mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 80 DEG C, constant temperature 10 minutes; Add 1.8kg propyl carbinol, temperature controls at about 80 DEG C, stirs 10 minutes; Add 1.56kg butanic acid and 3.2kg water, stir 10 minutes; 95 DEG C of constant temperature 100 minutes, material retrogradation; Add the calcium hydroxide suspension liquid 10.8kg that solid content is 20 % by weight, stir 10 minutes, add the 12-oxystearic acid of 2.4kg, stir 10 minutes, add the terephthalic acid of 4.2kg, stir 10 minutes, under stirring, be warmed up to 160 DEG C, keep 45 minutes, dehydration, cools to 120 DEG C; Adding by 10kg100 DEG C of kinematic viscosity is 11mm
2the 10.7kg stearylamine that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, then adds the 5kg MDI with the dissolving of 5kg HVI500SN lubricating base oil, stirs 6 minutes, and 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 HVI500SN lubricating base oil 15kg; 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 28.6%; 12-oxystearic acid calcium 2.2%; Terephthalic acid calcium 4.4%; Two polyureas 13.4%; Lubricating base oil 51.4%.
Embodiment 2
The Composite calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium alkyl-salicylate that 33kg total basicnumber is 400mgKOH/g and 15kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 60 DEG C, constant temperature 10 minutes; Add 0.56kg ethanol, temperature controls at about 60 DEG C, stirs 10 minutes; Add 3.36kg propionic acid and 3.36kg water, stir 10 minutes; 100 DEG C of constant temperature 70 minutes, material retrogradation; Add the calcium hydroxide suspension liquid 5.2kg that solid content is 50 % by weight, stir 10 minutes, add the 12-oxystearic acid of 2kg, stir 10 minutes, add the boric acid of 2.6kg, stir 10 minutes, under stirring, be warmed up to 150 DEG C, keep 60 minutes, dehydration, cools to 110 DEG C; Adding by 5kg100 DEG C of kinematic viscosity is 11mm
2the 0.76kg amino dodecane that the HVI500SN lubricating base oil of/s dissolves, stirs 2 minutes, then adds the 0.34kg HDI with the dissolving of 5kgHVI500SN lubricating base oil, stirs 2 minutes, and 110 DEG C of constant temperature 15 minutes, is finally warmed up to 180 DEG C of constant temperature 20 minutes.Then, be cooled to 150 DEG C, add HVI500SN lubricating base oil 10kg; Treat that temperature is cooled to 100 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 47.1%; 12-oxystearic acid calcium 2.8%; Lime borate 3.4%; Two polyureas 1.4%; Lubricating base oil 45.3%.
Embodiment 3
The Composite calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
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 450mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 50 DEG C, constant temperature 10 minutes; Add 0.2kg n-propyl alcohol, 0.2kg propyl carbinol and 3.2kg water, temperature controls at about 50 DEG C, stirs 10 minutes; Add 2.96kg acetic acid, stir 10 minutes; 110 DEG C of constant temperature 40 minutes, material retrogradation; Cool to 85 DEG C, add the calcium hydroxide suspension liquid 7.8kg that solid content is 40 % by weight, stir 10 minutes, add the 12-oxystearic acid of 2kg, stir 10 minutes, add the phthalic acid of 3.5kg and the acetic acid of 2kg, stir 10 minutes, under stirring, be warmed up to 170 DEG C, keep 30 minutes, dehydration, cools to 100 DEG C; Adding by 3kg100 DEG C of kinematic viscosity is 11mm
2the 3.51kg para-totuidine that the HVI500SN lubricating base oil of/s dissolves, stirs 8 minutes, then adds the 3.09kg XDI with the dissolving of 3kg HVI500SN lubricating base oil, stirs 8 minutes, and 100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, be cooled to 155 DEG C, add HVI500SN lubricating base oil 6kg; 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 naphthenate 36.7%; 12-oxystearic acid calcium 2.3%; Calcium phthalate 4.7%; Lime acetate 2.9%; Two polyureas 7.3%; Lubricating base oil 46.1%.
Embodiment 4
The Composite calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
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 320mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 80 DEG C, constant temperature 10 minutes; Add 1.8kg propyl carbinol, temperature controls at about 80 DEG C, stirs 10 minutes; Add 1.56kg butanic acid and 3.2kg water, stir 10 minutes; 95 DEG C of constant temperature 100 minutes, material retrogradation.
Another volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle at 95 DEG C, add the calcium hydroxide suspension liquid 7.2kg that solid content is 30 % by weight, stir 10 minutes, add the 12-oxystearic acid of 2.4kg, stir 10 minutes, add the terephthalic acid of 4.2kg, stir 10 minutes, obtain 12-oxystearic acid calcium and terephthalic acid calcium.
The 3rd volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add by 10kg100 DEG C of kinematic viscosity be 11mm
2the 10.7kg stearylamine that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, then adds the 5kg MDI with the dissolving of 5kg HVI500SN lubricating base oil, stirs 6 minutes, and 120 DEG C of constant temperature 20 minutes, obtains two polyureas.
The 12-oxystearic acid calcium of gained and terephthalic acid calcium are all squeezed in first still, stir, 160 DEG C are warmed up under stirring, keep 45 minutes, dehydration, then cools to 120 DEG C, all squeezes in this still by two polyureas of the 3rd reactor gained, stir, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add HVI500SN lubricating base oil 15kg; 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 28.6%; 12-oxystearic acid calcium 2.2%; Terephthalic acid calcium 4.4%; Two polyureas 13.4%; Lubricating base oil 51.4%.
Embodiment 5
The Composite calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle A in add overbased calcium alkyl-salicylate that 30kg total basicnumber is 300mgKOH/g and 25kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 60 DEG C, constant temperature 10 minutes; Add 0.28kg ethanol and 0.28kg n-propyl alcohol, temperature controls at about 60 DEG C, stirs 10 minutes; Add 1.4kg acetic acid, 1.4kg butanic acid and 3.92kg water, stir 10 minutes; 110 DEG C of constant temperature 70 minutes, material retrogradation.
Volume be 10L and with heating, stir, circulation, cooling normal-pressure reaction kettle B at 90 DEG C, add the calcium hydroxide suspension liquid 22kg that solid content is 20 % by weight, stir 10 minutes, add the palmitinic acid of 2.4kg, stir 10 minutes, add the oxalic acid of the biphenyl dicarboxylic acid of 4.2kg, the phosphoric acid of 1kg and 2kg, stir 10 minutes, obtain calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and oxalic acid calcium.
Volume be 10L and with heating, stir, circulation, cooling normal-pressure reaction kettle C in add 5kg100 DEG C of kinematic viscosity be 11mm
2the HVI500SN lubricating base oil of/s and 1kg MDI rapidly pre-warming, to 90 DEG C, add 0.12kg quadrol under rapid stirring, stir 4 minutes, add 1.08kg stearylamine and stir 4 minutes, the mol ratio of added MDI, quadrol and stearylamine is 2:1:2, and 120 DEG C of constant temperature 20 minutes, obtains four polyureas.
Volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle D in add 10kg100 DEG C of kinematic viscosity be 11mm
2hVI500SN lubricating base oil and the 0.78kg MDI of/s are preheating to 90 DEG C, 0.84kg stearylamine is added under rapid stirring, stir 4 minutes, 0.19kg quadrol is added under rapid stirring, stir 4 minutes, add 0.39kg MDI, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.
Gained calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and oxalic acid calcium are all squeezed in reactor A, stir, 170 DEG C are warmed up under stirring, keep 30 minutes, dehydration, then cools to 110 DEG C, all squeezes in reactor A by gained four polyureas and six polyureas, stir, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, be cooled to 150 DEG C, add 8kg 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 34.2%; Calcium palmitate 2.6%; Biphenyl dicarboxylic acid calcium 5.0%; Calcium phosphate 1.6%; Oxalic acid calcium 2.9%; Four polyureas 2.2%; Six polyureas 2.2%; Lubricating base oil 49.2%.
Embodiment 6
The Composite calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle A in add naphthenate with superhigh base number calcium that 30kg total basicnumber is 420mgKOH/g and 10kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 50 DEG C, constant temperature 10 minutes; Add 0.56kg n-propyl alcohol and 2.8kg water, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg acetic acid, 1kg propionic acid and 0.8kg butanic acid, stir 10 minutes; 110 DEG C of constant temperature 40 minutes, material retrogradation.
Volume be 10L and with heating, stir, circulation, cooling normal-pressure reaction kettle B at 95 DEG C, add the calcium hydroxide suspension liquid 3.7kg that solid content is 60 % by weight, stir 10 minutes, add the lauric acid of 2.4kg, stir 10 minutes, add the butyric acid of 4.2kg, stir 10 minutes, obtain calcium laurate and Calcium Butyrate.
Volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle C in add 10kg100 DEG C of kinematic viscosity be 11mm
2hVI500SN lubricating base oil and the 1.17kg MDI of/s are preheating to 80 DEG C, the mixture of 0.84kg stearylamine, 0.19kg quadrol is added under rapid stirring, the mol ratio of added MDI, monoamine, diamines is 3:2:2, and 120 DEG C of constant temperature 20 minutes, obtains mixing polyureas.
Gained calcium laurate and Calcium Butyrate are all squeezed in reactor A, stirs, under stirring, be warmed up to 160 DEG C, keep 45 minutes, dehydration, then cools to 100 DEG C, gained mixing polyureas is all squeezed in reactor A, stirs, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, be cooled to 160 DEG C, add 8kg 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 46.8%; Calcium laurate 3.7%; Calcium Butyrate 7.1%; Polyurea compound 3.1%; Lubricating base oil 39.3%.
Embodiment 7
The Composite calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Composite calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, first add 1.56kg butanic acid, temperature controls at about 80 DEG C, stirs 10 minutes, then adds 1.8kg propyl carbinol and 3.2kg water, stirs 10 minutes.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 28.6%; 12-oxystearic acid calcium 2.2%; Terephthalic acid calcium 4.4%; Two polyureas 13.4%; Lubricating base oil 51.4%.
Embodiment 8
The Composite calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Composite calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, 1.8kg propyl carbinol is replaced with 3.2kg ketone, 1.56kg butanic acid and 3.2kg water are replaced with 3.36kg naphthenic 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 naphthenate 28.6%; 12-oxystearic acid calcium 2.2%; Terephthalic acid calcium 4.4%; Two polyureas 13.4%; Lubricating base oil 51.4%.
Comparative example 1
High base number composite calcium sulfonate base two polyurea grease is prepared by the method for embodiment 1, unlike, overbased calcium alkyl-salicylate total basicnumber is that the calcium sulfonate with high base number of 320mgKOH/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 28.6%; 12-oxystearic acid calcium 2.2%; Terephthalic acid calcium 4.4%; Two polyureas 13.4%; Lubricating base oil 51.4%.
Table 1 each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; Ball bearing lubricating life: ASTM D3336.
Embodiment 1 and comparative example 1 are compared and can find out, the dropping point of Composite calcium naphthenate base polyurea grease of the present invention is higher than Composite calcium-sulfonate-batetrapolyurea polyurea grease, water drenches number of dropouts much smaller than Composite calcium-sulfonate-batetrapolyurea polyurea grease, Stencil oil-dividing value is much smaller than Composite calcium-sulfonate-batetrapolyurea polyurea grease, the bearing lubrication life-span is much larger than Composite calcium-sulfonate-batetrapolyurea polyurea grease, the high thermal resistance of Composite calcium naphthenate base polyurea grease of the present invention is described, water resisting property and adhesivity, colloid stability, lubricating life is all better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and Composite calcium naphthenate base polyurea grease of the present invention is the same with Composite calcium-sulfonate-batetrapolyurea polyurea grease has the performances such as excellent non-corrosibility and resistance to salt(spray)fog.
Embodiment 1 and embodiment 4 are compared and can find out, Composite calcium naphthenate base polyurea grease prepared by original position, there is better water resisting property and adhesivity, colloid stability, and there is longer lubricating life; Embodiment 1 and embodiment 7 are compared and can be found out, in transforming agent, category-A material adds prior to category-B material, the Composite calcium naphthenate base polyurea grease of preparation, has better water resisting property and adhesivity, colloid stability, and has longer lubricating life; Embodiment 1 and embodiment 8 are compared and can find out, transforming agent is A, B, C tri-class material, category-A material is at least one in ethanol, propyl alcohol, butanols and 12-oxystearic acid, category-B material is at least one in acetic acid, propionic acid and butyric acid, C class material is water, the Composite calcium naphthenate base polyurea grease of preparation, has better water resisting property and adhesivity, colloid stability, and has longer lubricating life.
As can be seen from Figure 1, the ν of the calcium carbonate in the overbased calcium alkyl-salicylate of embodiment 2
2bands of a spectrum are at 1076-1077cm
-1left and right, ν
3bands of a spectrum are 860cm
-1left and right.Be illustrated as amorphous calcium carbonate.
As can be seen from Figure 2, containing 1082cm in the infrared spectrum of the calcium carbonate in the lubricating grease prepared of embodiment 2
-1left and right, 855cm
-1left and right, 700cm
-1left and right, 713cm
-1the absorption peaks such as left and right are the charateristic avsorption band of aragonite calcium carbonate, illustrate that the amorphous calcium carbonate in overbased calcium alkyl-salicylate transforms in order to aragonite calcium carbonate.
As can be seen from Figure 3, the XRD crystal formation of the calcium carbonate in lubricating grease prepared by embodiment 2 measures, intensity peak is had near angle 26 °, 27 °, 46 °, 33.5 °, 36 °, 38 °, 43 °, consistent with aragonite standard spectrogram, illustrate to there is aragonite calcium carbonate in sample after transforming.
Composite calcium naphthenate base polyurea grease of the present invention, not only the same with Composite calcium-sulfonate-batetrapolyurea polyurea grease, there is excellent non-corrosibility and resistance to salt(spray)fog, but also there is the high thermal resistance, water resisting property and the performance such as adhesivity, colloid stability that are better than Composite calcium-sulfonate-batetrapolyurea 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 (31)
1. a Composite calcium naphthenate base polyurea grease, is characterized in that, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium naphthenate of 20-60 % by weight; The calcium salt of the higher fatty acid of 1-10 % by weight; The polyurea compound of 0.5-25 % by weight; The base oil of 25-70 % by weight, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the charateristic avsorption band of aragonite calcium carbonate.
2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, described lubricating grease also comprises the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 % by weight.
3. lubricating grease according to claim 2, wherein, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium naphthenate of 25-55 % by weight; The calcium salt of the higher fatty acid of 2-6 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 2-10 % by weight; 1.3-15 the polyurea compound of % by weight; The base oil of 35-60 % by weight.
4. according to the lubricating grease in claim 1-3 described in any one, wherein, described non-newtonian fluid calcium naphthenate is transformed by newton's body calcium naphthenate and obtains, and its total basicnumber is 250-500mgKOH/g.
5. according to the lubricating grease in claim 1-3 described in any one, wherein, straight chain fatty acid or the hydroxy fatty acid of described higher fatty acid to be carbon number be 8-20.
6. lubricating grease according to claim 5, wherein, described higher fatty acid is selected from least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.
7. the lubricating grease according to Claims 2 or 3, wherein, the molecular weight of small molecules mineral acid or lower fatty acid is less than or equal to 150.
8. lubricating grease according to claim 7, 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.
9. the lubricating grease according to Claims 2 or 3, wherein, described aromatic acid is that replace or unsubstituted aromatic acid, and substituting group is at least one in the alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, and the molecular weight of described aromatic acid is less than or equal to 550.
10. according to lubricating grease according to claim 9, wherein, described aromatic acid is selected from least one in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.
11. according to the lubricating grease in claim 1-3 described in any one, and wherein, described polyurea compound is at least one in two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.
12. lubricating grease according to claim 11, wherein, described polyurea compound is two polyurea compounds, and this compound has following structure:
Wherein, R
1, R
1 'alkyl, cycloalkyl or aryl, R
3arylidene, alkylidene group or cycloalkylidene.
13. lubricating grease according to claim 12, wherein, R
1, R
1 'be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8-24; R
3the arylidene of 6-30, alkylidene group or cycloalkylidene.
14. lubricating grease according to claim 13, wherein, R
1, R
1 'be the alkyl of phenyl or C1-C3 or the phenyl of halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18, R
3be
with
in at least one.
The preparation method of the Composite calcium naphthenate base polyurea grease in 15. claim 1-14 described in any one, it is characterized in that, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium naphthenate, higher fatty acid, the calcium salt of aromatic acid and/or small molecules mineral acid and/or lower fatty acid, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
The preparation method of 16. 1 kinds of Composite calcium naphthenate base polyurea greases, is characterized in that, the method comprises:
(1) by 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, aromatic acid and/or small molecules mineral acid and/or lower fatty acid reacts, heat up after reaction dehydration, then lowers the temperature;
(3) in step (2) gained mixture, add base oil and monoamine, or also add diamines, add vulcabond and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds base oil, adds necessary additive, obtains finished product.
17. preparation methods according to claim 16, wherein, in step (1), by 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, be greater than 90 DEG C and be less than or equal to 110 DEG C of constant temperature 40-100 minute.
18. preparation methods according to claim 16, 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 aromatic acid and/or small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 150-170 DEG C of dehydration, be then cooled to 100-120 DEG C.
19. preparation methods according to claim 16, wherein, in step (3), in step (2) gained mixture, add base oil and monoamine, stir 2-8 minute, then add vulcabond, stir 2-8 minute, the mol ratio of vulcabond and monoamine is 1:2.
20. preparation methods according to claim 16, 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; Be cooled to 150-160 DEG C, add base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
21. preparation methods according to claim 16, wherein, described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250-500mgKOH/g.
22. preparation methods according to claim 16, wherein, described transforming agent is selected from least one in water, fatty alcohol, aliphatic ether, lipid acid, naphthenic acid, alkanoic, aliphatic ketone, aliphatic amide, cycloalkanes amine, cycloalkanol, cycloalkanes ether, carbonic acid gas, aromatic alcohol, aromatic amine and alkyl benzene sulphonate (ABS), and the add-on of transforming agent is the 4-32% of newton's body calcium naphthenate weight.
23. preparation methods according to claim 22, wherein, described transforming agent is A, B, C tri-class material, category-A material is at least one in ethanol, propyl alcohol, butanols and 12-oxystearic acid, category-B material is at least one in acetic acid, propionic acid and butyric acid, C class material is water, and the add-on of transforming agent is the 15-25% of newton's body calcium naphthenate weight.
24. preparation methods according to claim 23, wherein, category-A material adds prior to category-B material.
25. preparation methods according to claim 16, wherein, the structural formula of described monoamine is R
1-NH
2, R
1 '-NH
2, wherein, R
1, R
1 'be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18.
26. preparation methods according to claim 25, 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.
27. preparation methods according to claim 16, 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.
28. preparation methods according to claim 27, wherein, described diamines be selected from Ursol D, O-Phenylene Diamine, 4,4-benzidines aromatic amine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
29. preparation methods according to claim 16, 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.
30. preparation methods according to claim 29, wherein, described vulcabond is selected from least one in tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
The 31. Composite calcium naphthenate base polyurea greases obtained by the method in claim 16-30 described in any one.
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| WO2018192357A1 (en) * | 2017-04-19 | 2018-10-25 | 科聚亚(南京)化工有限公司 | Lubricating grease of polyurea/high base number calcium sulfonate composite |
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| CN102911761A (en) * | 2012-10-24 | 2013-02-06 | 中国石油化工股份有限公司 | High-temperature-resistant extreme pressure type lubricating grease composition and preparation method |
| CN103695074A (en) * | 2012-09-27 | 2014-04-02 | 中国石油化工股份有限公司 | Composite calcium naphthenate diurea lubricating grease and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103695074A (en) * | 2012-09-27 | 2014-04-02 | 中国石油化工股份有限公司 | Composite calcium naphthenate diurea lubricating grease and preparation method thereof |
| CN102911761A (en) * | 2012-10-24 | 2013-02-06 | 中国石油化工股份有限公司 | High-temperature-resistant extreme pressure type lubricating grease composition and preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018192357A1 (en) * | 2017-04-19 | 2018-10-25 | 科聚亚(南京)化工有限公司 | Lubricating grease of polyurea/high base number calcium sulfonate composite |
| CN108728202A (en) * | 2017-04-19 | 2018-11-02 | 科聚亚(南京)化工有限公司 | Polyureas/calcium sulfonate with high base number complex grease |
| US11225627B2 (en) | 2017-04-19 | 2022-01-18 | Lanxess Corporation | Lubricating grease of polyurea/high base number calcium sulfonate composite |
| CN108728202B (en) * | 2017-04-19 | 2022-12-20 | 朗盛公司 | Polyurea/high-base-number calcium sulfonate composite lubricating grease |
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| CN104293452B (en) | 2016-08-10 |
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