CN104560276A - Compound calcium sulfonate-calcium naphthenate zirconium-based lubricating grease and preparation method thereof - Google Patents
Compound calcium sulfonate-calcium naphthenate zirconium-based lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention discloses compound calcium sulfonate-calcium naphthenate zirconium-based lubricating grease. The lubricating grease comprises the following components in percentage by weight: 10-70 percent of non-newton calcium sulfonate-calcium naphthenate, 1-10 percent of zirconium salt of higher fatty acid, 1-15 percent of zirconium salt of aromatic acid and 10-80 percent of base oil, and optionally comprises 1-15 percent of zirconium salt of micromolecular inorganic acid and/or lower fatty acid, wherein the zirconium salt of higher fatty acid, the zirconium salt of aromatic acid and the zirconium salt of micromolecular inorganic acid and/or lower fatty acid are respectively prepared by reactions of higher fatty acid, aromatic acid, and micromolecular inorganic acid and/or lower fatty acid with a component A; and the component A is at least one of oxide of zirconium, hydroxide of zirconium and zirconium alkoxide. The invention further discloses a method for preparing the lubricating grease and the lubricating grease prepared by the method. The lubricating grease has excellent mechanical stability, excellent water resistance, excellent adhesion, salt mist resistance, colloid stability, extreme pressure antiwear property and the like.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of complex calcium sulfonate-calcium naphthenate zirconium base 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 sulfonate with high base number quicklime 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 sulfonate with high base number quicklime grease.
Zirconium belongs to IVB race as a kind of transition metal, is positioned at for the 5th cycle.Zirconium-containing compound has excellent lubrication, is often used as slip additive, as the oxide compound of zirconium is improved abradability as lubricant additive by CN101113382 and JP1973038444; WO2007143414 and US20060063682 describes zirconium tetrafluoride and can be used as one of wear reducing additive component becoming lubricant; US20060254823 finds that the lubricant containing 2 ethyl hexanoic acid zirconates shows good resistance to heavy loading and abrasion resistance; US20050043189 finds that fluozirconate is used in the lubricant as fluorine zirconic acid aluminium can be used as oxidation retarder; DE102004021812 finds the inorganic salt such as zirconium carbonate, sulfonic acid zirconium or zirconium phosphate to join inside lubricating grease and can improve abrasion resistance.
Summary of the invention
The object of this invention is to provide a kind of mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear all better, 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 zirconates of the higher fatty acid of 1-10 % by weight; The zirconates of the aromatic acid of 1-15 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the zirconates of lower fatty acid, wherein, the zirconates of described higher fatty acid is reacted by higher fatty acid and component A to form, the zirconates of described aromatic acid is reacted by aromatic acid and component A to form, the zirconates of described small molecules mineral acid and/or lower fatty acid is reacted by small molecules mineral acid and/or lower fatty acid and component A to form, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.This lubricating grease has good mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear, 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 complex calcium sulfonate-calcium naphthenate zirconium base grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The zirconates of the higher fatty acid of 1-10 % by weight; The zirconates of the aromatic acid of 1-15 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the zirconates of lower fatty acid, wherein, the zirconates of described higher fatty acid is reacted by higher fatty acid and component A to form, the zirconates of described aromatic acid is reacted by aromatic acid and component A to form, the zirconates of described small molecules mineral acid and/or lower fatty acid is reacted by small molecules mineral acid and/or lower fatty acid and component A to form, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-60 % by weight; The zirconates of the higher fatty acid of 2-6 % by weight; The zirconates of the aromatic acid of 2-10 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the zirconates of lower fatty acid.
Preferably, described component A is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, and in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10, is more preferably 1:0.5-5.
Second aspect, the invention provides the preparation method of complex calcium sulfonate as above-calcium naphthenate zirconium base grease, the method comprises: by non-newtonian fluid calcium sulphonate-calcium naphthenate, the zirconates of higher fatty acid, the zirconates of aromatic acid and part basis, oily and optionally small molecules mineral acid and/or lower fatty acid zirconates mixes, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides the preparation method of a kind of complex calcium sulfonate-calcium naphthenate zirconium base grease, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil and transforming agent mixing, heat up and treat material retrogradation;
(2) in step (1) products therefrom, component A is added, add higher fatty acid, aromatic acid and optionally small molecules mineral acid and/or lower fatty acid react, heat up after reaction dehydration, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide;
(3) step (2) reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds surplus base oil, add necessary additive, obtain finished product.
Fourth aspect, the invention provides the complex calcium sulfonate-calcium naphthenate zirconium base grease obtained by method as above.
Complex calcium sulfonate of the present invention-calcium naphthenate zirconium base grease, compares complex calcium sulfonate grease, has the performance such as better mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear.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.
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 complex calcium sulfonate-calcium naphthenate zirconium base grease, this lubricating grease have employed calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate are raw material, simultaneously containing compound zirconium viscosifying agent.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of complex calcium sulfonate-calcium naphthenate zirconium base grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The zirconates of the higher fatty acid of 1-10 % by weight; The zirconates of the aromatic acid of 1-15 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the zirconates of lower fatty acid, wherein, the zirconates of higher fatty acid is reacted by higher fatty acid and component A to form, the zirconates of aromatic acid is reacted by aromatic acid and component A to form, the zirconates of small molecules mineral acid and/or lower fatty acid is reacted by small molecules mineral acid and/or lower fatty acid and component A to form, and component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-60 % by weight; The zirconates of the higher fatty acid of 2-6 % by weight; The zirconates of the aromatic acid of 2-10 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the zirconates of lower fatty acid; More preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 30-55 % by weight; 2.2-4.5 the zirconates of the higher fatty acid of % by weight; The zirconates of the aromatic acid of 3-8 % by weight; The base oil of 30-60 % by weight; Optionally also comprise the small molecules mineral acid of 3-8 % by weight and/or the zirconates of lower fatty acid.
In the present invention, " optionally also comprise " and refer to comprise and also can not comprise, that is, the zirconates of small molecules mineral acid and/or lower fatty acid is selectable components, this component can be comprised in composite calcium naphthenate calcium zirconium base grease of the present invention, also can not comprise this component.
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.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.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; 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, 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, 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.
The present inventor surprisingly finds under study for action, when component A is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, namely when the raw material of zirconium is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, can further improve the mechanical stability of lubricating grease, water resisting property and adhesivity, colloid stability, therefore, component A is preferably the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is preferably 1:0.1-10, be more preferably 1:0.2-8, further be preferably 1:0.5-5, when the preferred molar ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, the mechanical stability of lubricating grease can be improved further, water resisting property and adhesivity, colloid stability.
In the present invention, oxide compound and/or the oxyhydroxide of zirconium are preferably selected from ZrO
2, ZrO (OH)
2, Zr (OH)
4and at least one in their hydrate.ZrO (OH)
2hydrate can be the wet hydrogen zirconium white of brand-new, it can pass through ZrOX
28H
2o(X is F, Cl, Br or I) or ZrO (NO
3)
22H
2o etc. obtain with alkali reaction, and wherein, alkali can be NaOH, KOH, strong aqua etc., preferred ZrOCl
28H
2o and NaOH reacts.
In the present invention, the general formula of zirconium alkoxide can be Zr (OR
1)
4, R
1can be the alkyl of C1-C10, be preferably the alkyl of C2-C6; More preferably, zirconium alkoxide is selected from least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and Pentyl alcohol zirconium.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 DEG C of kinematic viscosities are 4-60mm
2/ s, preferred 10-30mm
2/ s.Synthetic oil can be poly & Alpha ,-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Can also various additive be contained, 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 complex calcium sulfonate as above-calcium naphthenate zirconium base grease, the method comprises: by non-newtonian fluid calcium sulphonate-calcium naphthenate, the zirconates of higher fatty acid, the zirconates of aromatic acid and part basis, oily and optionally small molecules mineral acid and/or lower fatty acid zirconates mixes, 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 zirconates of the zirconates of the zirconates of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, aromatic acid, small molecules mineral acid and/or lower fatty acid, 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, 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 60-90 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 the preparation method of a kind of complex calcium sulfonate-calcium naphthenate zirconium base grease, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil and transforming agent mixing, heat up and treat material retrogradation;
(2) in step (1) products therefrom, component A is added, add higher fatty acid, aromatic acid and optionally small molecules mineral acid and/or lower fatty acid react, heat up after reaction dehydration, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide;
(3) step (2) reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds surplus base oil, add necessary additive, obtain finished product.
In step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, preferred constant temperature 10-30 minute, add required transforming agent to react, 8-12 minute is stirred after preferably adding often kind of transforming agent, after all transforming agents add, at 60-90 DEG C of constant temperature 60-90 minute.
In step of the present invention (1), 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.
In the present invention, 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; 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.
As previously mentioned, the present inventor surprisingly finds under study for action, in step (2), when component A is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, namely when the raw material of zirconium is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, can further improve the mechanical stability of obtained lubricating grease, water resisting property and adhesivity, colloid stability, therefore, preferably, in step (2), at 85-100 DEG C, add component A, add higher fatty acid, stir 5-20 minute, add aromatic acid, and optionally small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 100-120 DEG C, preferred maintenance 30-60 minute, dehydration, described component A is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is preferably 1:0.1-10, be more preferably 1:0.2-8, further be preferably 1:0.5-5.Wherein, the addition sequence of higher fatty acid and aromatic acid, small molecules mineral acid and/or lower fatty acid can exchange.
In the present invention, " optionally small molecules mineral acid and/or lower fatty acid " refers in step (2) can comprise small molecules mineral acid and/or lower fatty acid, also small molecules mineral acid and/or lower fatty acid can not be comprised, that is, small molecules mineral acid and/or lower fatty acid are optional raw materials.
In the present invention, higher fatty acid, aromatic acid, small molecules mineral acid, lower fatty acid, the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide as previously mentioned, do not repeat them here.
In the present invention, the H of higher fatty acid and aromatic acid and optionally small molecules mineral acid and/or lower fatty acid
+total amount of substance equals all and the oxide compound of zirconium, the oxyhydroxide of zirconium and the H needed for zirconium alkoxide
+mole number, but the oxyhydroxide of the oxide compound of zirconium, zirconium and zirconium alkoxide are relative to higher fatty acid and aromatic acid and optionally small molecules mineral acid and/or lower fatty acid can excessive 1-10%.
In the present invention, the add-on of the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide 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 aromatic acid and optionally small molecules mineral acid and/or lower fatty acid is preferably 1:1-10.
In step (3), be warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add surplus 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), part basis oil used is preferably 1:0.1-5 with the weight ratio of surplus base oil in step (3).
Fourth aspect, the complex calcium sulfonate that the preparation method that present invention also offers is provided by third aspect present invention obtains-calcium naphthenate zirconium base grease.
Compared with the complex calcium sulfonate obtained with the preparation method provided by second aspect-calcium naphthenate zirconium base grease, the complex calcium sulfonate that the preparation method that the third aspect provides obtains-calcium naphthenate zirconium base grease has better mechanical stability, water resisting property and adhesivity, colloid stability.
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.
The content of the zirconates of the zirconates of higher fatty acid, the zirconates of aromatic acid and small molecules mineral acid and/or lower fatty acid, the gauge generating zirconates according to added higher fatty acid, aromatic acid and the oxide compound of small molecules mineral acid and/or lower fatty acid and zirconium, the oxyhydroxide of zirconium and zirconium alkoxide complete reaction is calculated.
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
Complex calcium sulfonate-calcium naphthenate zirconium base 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); Zr (OH)
4(3.9kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 17kg).
A volume be 110L 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 30 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 60 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 100 DEG C, add the Zr (OH) that solid content is 20 % by weight
4suspension liquid 19.5kg, stirs 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir, be warmed up to 110 DEG C under stirring, keep 45 minutes, dehydration; Be warmed up to 200 DEG C of constant temperature 10 minutes.Then, the HVI500SN lubricating base oil of 17kg is added; 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 37.7 % by weight; Lubricating base oil 53.2 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.5 % by weight.
Embodiment 2
Complex calcium sulfonate-calcium naphthenate zirconium base grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 420mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 420mgKOH/g, 24kg); (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); Ethanol zirconium (5.5kg); Zr (OH)
4(0.65kg); 12-oxystearic acid (2kg); Phthalic acid (3.5kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 17kg).
A volume be 110L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 6kg total basicnumber is 420mgKOH/g, 24kg total basicnumber is the naphthenate with superhigh base number calcium of 420mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 65 DEG C, constant temperature 20 minutes; Add 2.8kg naphthenic acid, temperature controls at about 65 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 75 DEG C, constant temperature 75 minutes, material retrogradation; Be warmed up to 85 DEG C, successively add the Zr (OH) that 5.5kg ethanol zirconium and solid content are 20 % by weight
4suspension liquid 3.25kg, in zirconium, Zr (OH)
4be 1:5 with the mol ratio of ethanol zirconium, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg phthalic acid, stir, be warmed up to 100 DEG C under stirring, keep 60 minutes, dehydration; Be warmed up to 230 DEG C of constant temperature 5 minutes.Then, the HVI500SN lubricating base oil of 17kg 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 37.7 % by weight; Lubricating base oil 53.2 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.5 % by weight.
Embodiment 3
Complex calcium sulfonate-calcium naphthenate zirconium base 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); Butanols (2.8kg); Acetic acid (0.56kg); Zirconium-n-butylate (3.13kg); Zr (OH)
4(2.6kg); Stearic acid (1.9kg); M-phthalic acid (3.5kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 28kg).
A volume be 110L 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 overbased calcium alkyl-salicylate of 320mgKOH/g and the HVI150BS lubricating base oil of 20kg, stir, heat to 80 DEG C, constant temperature 10 minutes; Add 2.8kg butanols, 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; Successively add the Zr (OH) that 3.13kg zirconium-n-butylate and solid content are 20 % by weight
4suspension liquid 13kg, in zirconium, Zr (OH)
4be 1:0.5 with the mol ratio of zirconium-n-butylate, stir 10 minutes; Add 1.9kg stearic acid, stir 10 minutes; Add 3.5kg m-phthalic acid, stir, be warmed up to 120 DEG C under stirring, keep 30 minutes, dehydration; Be warmed up to 180 DEG C of constant temperature 20 minutes.Then, the HVI500SN lubricating base oil of 28kg is added; 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 sulphonate-calcium naphthenate 37.8 % by weight; Lubricating base oil 53.2 % by weight; Zirconyl stearate 2.5 % by weight; Terephthalic acid oxygen zirconium 6.5 % by weight.
Embodiment 4
Complex calcium sulfonate-calcium naphthenate zirconium base grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 33kg); 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); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Zirconium-n-propylate (4.0kg); Zr (OH)
4(2.0kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 28kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
Complex calcium sulfonate-calcium naphthenate zirconium base 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; Naphthenic acid is replaced with Witco 1298 Soft Acid; Add Zr (OH)
4time also add zirconium-n-propylate, in zirconium, Zr (OH)
4be 1:1 with the mol ratio of zirconium-n-propylate; And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir after 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 43.7 % by weight; Lubricating base oil 49.5 % by weight; 12-oxystearic acid oxygen zirconium 2.2 % by weight; Terephthalic acid oxygen zirconium 4.4 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 5
Complex calcium sulfonate-calcium naphthenate zirconium base 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, 2.8kg); Acetic acid (0.56kg); Zr (OH)
4(3.9kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 7kg).
Complex calcium sulfonate-calcium naphthenate zirconium base 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; 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 52.6 % by weight; Lubricating base oil 34.7 % by weight; 12-oxystearic acid oxygen zirconium 3.7 % by weight; Terephthalic acid oxygen zirconium 9.0 % by weight.
Embodiment 6
Complex calcium sulfonate-calcium naphthenate zirconium base 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); Poly alpha olefine synthetic oil PAO40(100 DEG C kinematic viscosity is 40mm
2/ s, 30kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Zr (OH)
4(3.9kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Poly alpha olefine synthetic oil PAO10(100 DEG C kinematic viscosity is 11mm
2/ s, 17kg).
Complex calcium sulfonate-calcium naphthenate zirconium base grease is prepared according to the method for embodiment 1, unlike, use Witco 1298 Soft Acid to replace naphthenic acid; Poly alpha olefine synthetic oil PAO40(100 DEG C of kinematic viscosity is used to be 40mm
2/ s) and poly alpha olefine synthetic oil PAO10(100 DEG C kinematic viscosity be 11mm
2/ s) replace HVI150BS(100 DEG C of kinematic viscosity to be 31mm respectively
2/ s) and HVI500SN(100 DEG C of kinematic viscosity be 11mm
2/ s); 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 37.7 % by weight; Lubricating base oil 53.2 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.5 % by weight.
Embodiment 7
Complex calcium sulfonate-calcium naphthenate zirconium base 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); (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); Zr (OH)
4(3.9kg); 12-oxystearic acid (2kg); 2-methyl isophthalic acid, 4-phthalic acid (3.8kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 16.7kg).
Complex calcium sulfonate-calcium naphthenate zirconium base 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; Use 2-methyl isophthalic acid, 4-phthalic acid replaces terephthalic 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 37.7 % by weight; Lubricating base oil 52.8 % by weight; 12-oxystearic acid oxygen zirconium 2.7 % by weight; 2-methyl isophthalic acid, 4-phthalic acid oxygen zirconium 6.8 % by weight.
Embodiment 8
Complex calcium sulfonate-calcium naphthenate zirconium base 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, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Zr (OH)
4(3.9kg); 12-oxystearic acid (2kg); 4,4'-biphenyl dicarboxylic acid (5.1kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 20kg); Right, right '-di-iso-octyldiphenylamine (0.2kg); Dithio dialkyl amido formic acid molybdenum (4kg); Selenium Sulfide (4kg); Benzotriazole (0.4kg).
Complex calcium sulfonate-calcium naphthenate zirconium base 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; Terephthalic acid is replaced with 4,4'-biphenyl dicarboxylic acid; And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stirs 10 minutes, adds the dithio dialkyl amido formic acid molybdenum of 4kg, stir 10 minutes, add the Selenium Sulfide of 4kg, stir 10 minutes, add the benzotriazole of 0.4kg, 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 32.9 % by weight; Lubricating base oil 49.2 % by weight; 12-oxystearic acid oxygen zirconium 2.3 % by weight; 4,4'-biphenyl dicarboxylic acid oxygen zirconium 7.2 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight; Dithio dialkyl amido formic acid molybdenum 3.9 % by weight; Selenium Sulfide 3.9 % by weight; Benzotriazole 0.4 % by weight.
Embodiment 9
Complex calcium sulfonate-calcium naphthenate zirconium base 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, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Zr (OH)
4(3.9kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 32kg).
Complex calcium sulfonate-calcium naphthenate zirconium base 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; 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 37.7 % by weight; Lubricating base oil 53.2 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.5 % by weight.
Embodiment 10
Complex calcium sulfonate-calcium naphthenate zirconium base 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, 30kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Zr (OH)
4(7.1kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Terephthalic acid (3.5kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 15kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
Complex calcium sulfonate-calcium naphthenate zirconium base grease is prepared according to the method for embodiment 1, unlike, use Witco 1298 Soft Acid to replace naphthenic acid; After adding 12-oxystearic acid, also add boric acid, and then add terephthalic acid; And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir after 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 37.0 % by weight; Lubricating base oil 49.9 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Lime borate 4.0 % by weight; Terephthalic acid oxygen zirconium 6.3 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 11
Complex calcium sulfonate-calcium naphthenate zirconium base 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); Zr (OH)
4(6.5kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Acetic acid (2kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 14kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
Complex calcium sulfonate-calcium naphthenate zirconium base 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; Also acetic acid is added after adding terephthalic acid, and then the dehydration that heats up; And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir after 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 37.1 % by weight; Lubricating base oil 48.9 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 4.8 % by weight; Zirconyl acetate 6.4 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 12
Complex calcium sulfonate-calcium naphthenate zirconium base 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); Zr (OH)
4(3.9kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 17kg).
A volume be 110L 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 30 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 60 DEG C, constant temperature 90 minutes, material retrogradation.
Another volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add 7kg HVI500SN lubricating base oil, at 100 DEG C, add the Zr (OH) that solid content is 20 % by weight
4suspension liquid 19.5kg, stirs 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir 10 minutes, obtain 12-oxystearic acid oxygen zirconium and terephthalic acid oxygen zirconium.
Gained 12-oxystearic acid oxygen zirconium and terephthalic acid oxygen zirconium are all squeezed in a upper still, stirs, under stirring, be warmed up to 110 DEG C, keep 45 minutes, dehydration; Be warmed up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oil is added; 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 37.7 % by weight; Lubricating base oil 53.2 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.5 % by weight.
Embodiment 13
Complex calcium sulfonate-calcium naphthenate zirconium base grease that the present embodiment is prepared for illustration of the present invention.
Complex calcium sulfonate-calcium naphthenate zirconium base 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 37.7 % by weight; Lubricating base oil 53.2 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.5 % by weight.
Embodiment 14
Complex calcium sulfonate-calcium naphthenate zirconium base grease that the present embodiment is prepared for illustration of the present invention.
Complex calcium sulfonate-calcium naphthenate zirconium base grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with methyl propyl ketone, aqueous acetic acid is replaced with butyl 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 37.7 % by weight; Lubricating base oil 53.2 % by weight; 12-oxystearic acid oxygen zirconium 2.6 % by weight; Terephthalic acid oxygen zirconium 6.5 % by weight.
Embodiment 15
Complex calcium sulfonate-calcium naphthenate zirconium base grease that the present embodiment is prepared for illustration of the present invention.
Complex calcium sulfonate-calcium naphthenate zirconium base grease is prepared according to the method for embodiment 4, unlike, at Zr (OH)
4when constant with the total mole number of zirconium-n-propylate, adjustment Zr (OH)
4be 1:0.1 with the mol ratio of zirconium-n-propylate.Each physicochemical property of gained fat 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 43.7 % by weight; Lubricating base oil 49.5 % by weight; 12-oxystearic acid oxygen zirconium 2.2 % by weight; Terephthalic acid oxygen zirconium 4.4 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 16
Complex calcium sulfonate-calcium naphthenate zirconium base grease that the present embodiment is prepared for illustration of the present invention.
Complex calcium sulfonate-calcium naphthenate zirconium base grease is prepared according to the method for embodiment 4, unlike, at Zr (OH)
4when constant with the total mole number of zirconium-n-propylate, adjustment Zr (OH)
4be 1:10 with the mol ratio of zirconium-n-propylate.Each physicochemical property of gained fat 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 43.7 % by weight; Lubricating base oil 49.5 % by weight; 12-oxystearic acid oxygen zirconium 2.2 % by weight; Terephthalic acid oxygen zirconium 4.4 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 17
Complex calcium sulfonate-calcium naphthenate zirconium base grease that the present embodiment is prepared for illustration of the present invention.
Complex calcium sulfonate-calcium naphthenate zirconium base grease is prepared according to the method for embodiment 4, unlike, zirconium-n-propylate is replaced with equimolar Zr (OH)
4.Each physicochemical property of gained fat 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 43.7 % by weight; Lubricating base oil 49.5 % by weight; 12-oxystearic acid oxygen zirconium 2.2 % by weight; Terephthalic acid oxygen zirconium 4.4 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 18
Complex calcium sulfonate-calcium naphthenate zirconium base grease that the present embodiment is prepared for illustration of the present invention.
Complex calcium sulfonate-calcium naphthenate zirconium base grease is prepared according to the method for embodiment 4, unlike, by Zr (OH)
4replace with equimolar zirconium-n-propylate.Each physicochemical property of gained fat 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 43.7 % by weight; Lubricating base oil 49.5 % by weight; 12-oxystearic acid oxygen zirconium 2.2 % by weight; Terephthalic acid oxygen zirconium 4.4 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Comparative example 1
Complex calcium sulfonate grease is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number calcium is replaced with overbased calcium sulphonate, Zr used (OH) that total basicnumber is 400mgKOH/g
4with Ca (OH)
2replace, adjust consumption simultaneously and make each component content consistent with embodiment 1.Each physicochemical property of gained fat 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 37.7 % by weight; Lubricating base oil 53.2 % by weight; 12-oxystearic acid calcium 2.6 % by weight; Terephthalic acid calcium 6.5 % by weight.
Comparative example 2
Calcium sulfonate grease is prepared according to the method for embodiment 5, unlike, overbased calcium alkyl-salicylate is replaced with the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, Zr used (OH)
4with Ca (OH)
2replace, adjust consumption simultaneously and make each component content consistent with embodiment 5.Each physicochemical property of gained fat 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 52.6 % by weight; Lubricating base oil 34.7 % by weight; 12-oxystearic acid calcium 3.7 % by weight; Terephthalic acid calcium 9.0 % by weight.
Embodiment 1 and comparative example 1 are compared, embodiment 5 and comparative example 2 are compared, can find out, complex calcium sulfonate of the present invention-prolongation Drawing cone the in-degree of calcium naphthenate zirconium base grease and the difference of Drawing cone in-degree are less than complex calcium sulfonate grease, water drenches number of dropouts and is less than complex calcium sulfonate grease, salt-fog test is better than complex calcium sulfonate grease, water resistant spraying value is less than complex calcium sulfonate grease, Stencil oil-dividing value is less than complex calcium sulfonate grease, tetra-ball machine test value is greater than complex calcium sulfonate grease, the mechanical stability of complex calcium sulfonate of the present invention-calcium naphthenate zirconium base grease is described, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear is all better than complex calcium sulfonate grease.
Embodiment 1 and embodiment 12 are compared and can find out, complex calcium sulfonate-calcium naphthenate zirconium base grease prepared by original position, there is better mechanical stability, water resisting property and adhesivity, colloid stability; Embodiment 1 is compared can find out with embodiment 13 and embodiment 14 respectively, transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water, complex calcium sulfonate-calcium naphthenate zirconium the base grease of preparation, has better mechanical stability, water resisting property and adhesivity, colloid stability; Embodiment 4 is compared can find out with embodiment 15 and embodiment 16 respectively, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5, complex calcium sulfonate-calcium naphthenate zirconium the base grease of preparation, has better mechanical stability, water resisting property and adhesivity, colloid stability; Embodiment 4 is compared can find out with embodiment 17 and embodiment 18 respectively, the raw material of zirconium is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, complex calcium sulfonate-calcium naphthenate zirconium the base grease of preparation, has better mechanical stability, water resisting property and adhesivity, colloid stability.
Table 1 each lubricating grease properties of sample data
Each indication test method: outward appearance: range estimation; 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.
Table 1 (Continued) each lubricating grease properties of sample data
Each indication test method: outward appearance: range estimation; 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.
Complex calcium sulfonate of the present invention-calcium naphthenate zirconium base grease, compares complex calcium sulfonate grease, has the performance such as better mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
More than describe the preferred embodiment of the present invention in detail; 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 (25)
1. complex calcium sulfonate-calcium naphthenate zirconium base 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 zirconates of the higher fatty acid of 1-10 % by weight; The zirconates of the aromatic acid of 1-15 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the zirconates of lower fatty acid, wherein, the zirconates of described higher fatty acid is reacted by higher fatty acid and component A to form, the zirconates of described aromatic acid is reacted by aromatic acid and component A to form, the zirconates of described small molecules mineral acid and/or lower fatty acid is reacted by small molecules mineral acid and/or lower fatty acid and component A to form, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.
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 20-60 % by weight; The zirconates of the higher fatty acid of 2-6 % by weight; The zirconates of the aromatic acid of 2-10 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the zirconates of lower fatty acid.
3. lubricating grease according to claim 1 and 2, wherein, 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.
4. lubricating grease according to claim 3, 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.
5. 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.
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. lubricating grease according to claim 1 and 2, 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.
8. according to lubricating grease according to claim 7, 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.
9. lubricating grease according to claim 1 and 2, wherein, the molecular weight of small molecules mineral acid and lower fatty acid is less than or equal to 150.
10. lubricating grease according to claim 9, 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.
11. lubricating grease according to claim 1 and 2, wherein, described component A is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, and in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10.
12. lubricating grease according to claim 11, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5.
13. lubricating grease according to claim 1 and 2, wherein, oxide compound and/or the oxyhydroxide of zirconium are selected from ZrO
2, ZrO (OH)
2, Zr (OH)
4and at least one in their hydrate.
14. lubricating grease according to claim 1 and 2, wherein, the general formula of described zirconium alkoxide is Zr (OR
1)
4, R
1for the alkyl of C1-C10.
15. lubricating grease according to claim 14, wherein, described zirconium alkoxide is selected from least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and Pentyl alcohol zirconium.
The preparation method of the complex calcium sulfonate in 16. claim 1-15 described in any one-calcium naphthenate zirconium base grease, it is characterized in that, the method comprises: by non-newtonian fluid calcium sulphonate-calcium naphthenate, the zirconates of higher fatty acid, the zirconates of aromatic acid and part basis, oily and optionally small molecules mineral acid and/or lower fatty acid zirconates mixes, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The preparation method of 17. 1 kinds of complex calcium sulfonate-calcium naphthenate zirconium base greases, it is characterized in that, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil and transforming agent mixing, heat up and treat material retrogradation;
(2) in step (1) products therefrom, component A is added, add higher fatty acid, aromatic acid and optionally small molecules mineral acid and/or lower fatty acid react, heat up after reaction dehydration, and described component A is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide;
(3) step (2) reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds surplus base oil, add necessary additive, obtain finished product.
18. methods according to claim 17, wherein, in step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 60-90 DEG C of constant temperature 60-90 minute.
19. methods according to claim 17, wherein, in step (2), at 85-100 DEG C, add component A, add higher fatty acid, stir 5-20 minute, add aromatic acid and optionally small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 100-120 DEG C of dehydration, described component A is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10.
20. methods according to claim 19, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5.
21. methods according to claim 17, wherein, in step (3), are warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
22. methods according to claim 17, 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.
23. methods according to claim 17, 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.
24. methods according to claim 23, 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.
25. complex calcium sulfonate-calcium naphthenate zirconium the base greases obtained by the method in claim 17-24 described in any one.
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| CN112795422A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
| CN112795421A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Calcium-based lubricating grease and preparation method thereof |
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| 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 |
| 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 |
| CN103060067A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
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| 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 |
| CN103060067A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112795422A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
| CN112795421A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Calcium-based lubricating grease and preparation method thereof |
| CN112795422B (en) * | 2019-10-28 | 2023-04-07 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
| CN112795421B (en) * | 2019-10-28 | 2023-04-07 | 中国石油化工股份有限公司 | Calcium-based lubricating grease and preparation method thereof |
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