CN104450110A - Calcium sulfonate-calcium naphthenate-based polyurea grease and preparation method thereof - Google Patents
Calcium sulfonate-calcium naphthenate-based polyurea grease and preparation method thereof Download PDFInfo
- Publication number
- CN104450110A CN104450110A CN201310418626.XA CN201310418626A CN104450110A CN 104450110 A CN104450110 A CN 104450110A CN 201310418626 A CN201310418626 A CN 201310418626A CN 104450110 A CN104450110 A CN 104450110A
- Authority
- CN
- China
- Prior art keywords
- calcium
- add
- naphthenate
- weight
- sulphonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses calcium sulfonate-calcium naphthenate-based polyurea grease. The calcium sulfonate-calcium naphthenate-based polyurea grease comprises, by weight, 10-70% of non-Newtonian calcium sulfonate-calcium naphthenate, 0.5-30% of a polyurea compound and 10-80% of base oil. The invention also discloses a preparation method of the calcium sulfonate-calcium naphthenate-based polyurea grease and the calcium sulfonate-calcium naphthenate-based polyurea grease obtained by the preparation method. The calcium sulfonate-calcium naphthenate-based polyurea grease has excellent corrosion resistance and high temperature resistance. Compared with the calcium sulfonate-based polyurea grease, the calcium sulfonate-calcium naphthenate-based polyurea grease has better mechanical stability, water resistance, adhesion resistance, salt mist resistance, extreme pressure antiwear property and colloid stability and a longer service life. The preparation method has simple processes, environmental friendliness, a low cost and stable product quality.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of calcium sulphonate-Calcium naphthenate base polyurea grease and preparation method thereof.
Background technology
Calcium sulphonate is used as the history that the purification agent of lubricating oil and rust-preventive agent have decades, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active alkyl benzene calcium sulfonate or alkyl carboxylic acid calcium.Calcium sulfonate with high base number can be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate according to mode of production difference.Calcium mahogany sulfonate is with oleum or SO
3sulfonation mineral lubricating oils produces by product mahogany acid during white oil, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtaining; Calcium alkylbenzenesulfonate is with oleum or SO
3the alkylbenzene of sulfonation synthesis, alkyl benzene sulphonate (ABS) warp and Ca (OH) of generation
2reaction, the contour alkalization technology of carbonating and obtaining.
Overbased calcium alkyl-salicylate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffustivity, the purification agent of lubricating oil can be used as, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active naphthenic acid calcium.Mostly overbased calcium alkyl-salicylate is the acidic components extracted from the distillate that crude distillation obtains, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtain, about the Patents prepared has CN1465560 etc.
Utilize calcium sulfonate with high base number for raw material production lubricating grease, because it has excellent high temperature performance, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion, since putting goods on the market, cause the extensive concern of domestic and international lubricating grease industry, but, although 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 sulfonate with high base number quicklime grease is similar but the lubricating grease that can alleviate the problems referred to above becomes the large problem that people face at present.
Summary of the invention
The object of this invention is to provide a kind of performance and sulfonate with high base number quicklime grease is similar, cost is low, and preparation technology is simple, the lubricating grease of environmental protection and preparation method thereof.
The present inventor finds under study for action, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight.Performance and the sulfonate with high base number quicklime 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 calcium sulphonate-Calcium naphthenate base polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight.
Second aspect, the invention provides the preparation method of calcium sulphonate as above-Calcium naphthenate base polyurea grease, the method comprises: non-newtonian fluid calcium sulphonate-calcium naphthenate, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides the preparation method of a kind of calcium sulphonate-Calcium naphthenate base polyurea grease, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, heat up dehydration further;
(2) in step (1) products therefrom, add part basis oil and monoamine, or also add diamines, add vulcabond and react;
(3) be warmed up to 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
Fourth aspect, the invention provides the calcium sulphonate-Calcium naphthenate base polyurea grease obtained by method as above.
Calcium sulphonate of the present invention-Calcium naphthenate base polyurea grease, not only the same with calcium sulphonate base polyurea grease, there is excellent non-corrosibility and high thermal resistance, but also there is the performance such as mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear being better than calcium sulphonate base polyurea grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 2.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of calcium sulphonate-Calcium naphthenate base polyurea grease, this lubricating grease have employed calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate be raw material, simultaneously containing isocyanic ester and amine reaction produce polyurea compound.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of calcium sulphonate-Calcium naphthenate base polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight.
Described non-newtonian fluid calcium sulphonate-calcium naphthenate is at infrared spectrum 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place, total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.Described non-newtonian fluid calcium sulphonate-calcium naphthenate is obtained by transforming agent conversion by newton's body calcium sulphonate and newton's body calcium naphthenate.And containing unformed calcium carbonate in newton's body calcium sulphonate, newton's body calcium naphthenate, at infrared spectrum 860cm
-1-865cm
-1there is unformed calcium carbonate charateristic avsorption band in place.Described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.The base number of non-newtonian fluid calcium sulphonate-calcium naphthenate is the weight mean value of the base number of newton's body calcium sulphonate and the base number of newton's body calcium naphthenate.
In the present invention, 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
with-(CH
2)
6-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
with-(CH
2)
6-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
with-(CH
2)
6-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
with-(CH
2)
6-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, is preferably 10-60mm
2/ s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Can also various additive be contained, as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc. in lubricating grease of the present invention.Wherein, the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.01-5% of lubricating grease gross weight, preferred 0.1-2.5%, can be at least one in pentanoic, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of lubricating grease gross weight, preferred 0.8-8% can be at least one in dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenumdisulphide, tetrafluoroethylene, thiophosphoric acid molybdenum, clorafin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, calcium carbonate and zinc oxide; Rust-preventive agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferred 0.1-2%, can be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the preparation method of calcium sulphonate as above-Calcium naphthenate base polyurea grease, the method comprises: non-newtonian fluid calcium sulphonate-calcium naphthenate, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
In the present invention, described above for non-newtonian fluid calcium sulphonate-calcium naphthenate, 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 1:0.1-5 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 80-100 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.
The third aspect, the invention provides the preparation method of a kind of calcium sulphonate-Calcium naphthenate base polyurea grease, comprising:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, heat up dehydration further;
(2) in step (1) products therefrom, add part basis oil and monoamine, or also add diamines, add vulcabond and react;
(3) be warmed up to 180-230 DEG C of constant temperature refining, add 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, add required transforming agent and react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.
In the present invention, for the weight ratio of newton's body calcium sulphonate and newton's body calcium naphthenate without particular requirement, be preferably 1:0.25-4.The gross weight of newton's body calcium sulphonate and newton's body calcium naphthenate and the weight ratio of part basis oil are preferably 1:0.1-3.
Described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.
Described transforming agent is preferably selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water; More preferably at least one in the fatty alcohol of C1-C5, the lipid acid of C1-C5, the aliphatic ketone of C1-C5, the alkanoic of C1-C5, the aliphatic amide of C1-C5, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, the arylphosphonic acid of C6-C20, the diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate (ABS) and water is selected from; Further be preferably selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water.The add-on of transforming agent is preferably the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight, is more preferably the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
In the present invention, fatty alcohol comprises the fatty alcohol of straight chain, side chain and ring-type, and lipid acid, aliphatic ketone, alkanoic, aliphatic amide are in like manner.
In step (2), part basis oil and monoamine is added in step (1) products therefrom, or also add diamines, add vulcabond to react, namely be prepare polyurea compound in step (1) products therefrom, 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 (1) products therefrom, 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 (1) products therefrom, 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 (1) products therefrom, 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 (1) products therefrom, 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
-(CH
2)
6-etc.Such as, described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), at least one in dicyclohexylmethyl vulcabond (HMDI) and an xylylene diisocyanate (XDI) etc.
Described monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R
1 '-NH
2, R wherein
1, R
1 'can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.Preferred monoamine can be the arylamine being selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.
Described diamines can be aliphatic amide or arylamine, and structural formula is NH
2-R
2-NH
2, R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, preferred 2-8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from Ursol D, O-Phenylene Diamine, 4, the aromatic amine of 4 '-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
In step (3), first at 100-120 DEG C of constant temperature 10-20 minute, be finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add 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), in base oil used and step (2), in base oil used and step (3), the weight ratio of base oil used is preferably 1:0.1-5:0.1-5.
Fourth aspect, the calcium sulphonate that the preparation method that present invention also offers is provided by third aspect present invention obtains-Calcium naphthenate base polyurea grease.
Compared with the calcium sulphonate obtained with the preparation method provided by second aspect-Calcium naphthenate base polyurea grease, the calcium sulphonate that the preparation method that the third aspect provides obtains-Calcium naphthenate base polyurea grease has better mechanical stability, water resisting property and adhesivity.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following Examples and Comparative Examples:
Overbased or calcium sulfonate with high base number raw material weight+the overbased or overbased calcium alkyl-salicylate raw material weight+transforming agent gross weight of non-newtonian fluid calcium sulphonate-calcium naphthenate %=()/lubricating grease gross weight × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium sulphonate-calcium naphthenate.
Overbased and overbased calcium alkyl-salicylate raw material, also can according to method preparation disclosed in CN101885677A purchased from Xinjiang Land Fine Petrochemical Co., Ltd.
Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Naphthenic acid is purchased from Jinzhou Tie Chen petrochemical complex limited liability company.
Embodiment 1
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Add the boric acid aqueous solution that 16.24kg concentration is 14.3 % by weight, stir 10 minutes, be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 120 DEG C under stirring, keep 30 minutes, dehydration; Add HVI500SN lubricating base oil and the 1.5kg stearylamine of 2kg, stir 4 minutes, the 0.7kg MDI dissolved with 2kg HVI500SN lubricating base oil is added under stirring, stir 4 minutes, added MDI and the mol ratio of stearylamine are 1:2,120 DEG C of constant temperature 20 minutes, is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.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 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 2
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Add the boric acid aqueous solution that 16.24kg concentration is 14.3 % by weight, stir 10 minutes, be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 120 DEG C under stirring, keep 30 minutes, dehydration.
Another volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add HVI500SN lubricating base oil and the 1.5kg stearylamine of 2kg, be warming up to 120 DEG C, stir 4 minutes, the 0.7kg MDI dissolved with 2kg HVI500SN lubricating base oil is added under stirring, stir 4 minutes, added MDI and the mol ratio of stearylamine are 1:2, and 120 DEG C of constant temperature 20 minutes, obtains two polyureas.
Gained two polyureas is all squeezed in a upper still, stirs, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.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 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
The two polyureas molecular structural formulas contained in component are:
Embodiment 3
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 10kg); Witco 1298 Soft Acid (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Lauryl amine (1.31kg); MDI(0.89kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 38kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 320mgKOH/g and the HVI150BS lubricating base oil of 10kg, stir, heat to 80 DEG C, constant temperature 10 minutes; Add 2.8kg Witco 1298 Soft Acid, temperature controls at about 80 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Add the boric acid aqueous solution that 16.24kg concentration is 14.3 % by weight, stir 10 minutes, be warmed up to 90 DEG C, constant temperature 60 minutes, material retrogradation; Be warmed up to 100 DEG C under stirring, keep 60 minutes, dehydration; Add HVI500SN lubricating base oil and the 1.31kg lauryl amine of 2kg, stir 8 minutes, the 0.89kg MDI dissolved with 2kg HVI500SN lubricating base oil is added under stirring, stir 8 minutes, added MDI and the mol ratio of lauryl amine are 1:2,100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, remaining HVI500SN lubricating base oil is added; Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 4
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Propyl carbinol (2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.66kg); TDI(0.54kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; Replace naphthenic acid with propyl carbinol simultaneously; MDI is replaced with TDI; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 39.6 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 57.8 % by weight.
Embodiment 5
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 7kg); Right, right '-di-iso-octyldiphenylamine (0.4kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; And treat that temperature is cooled to 110 DEG C, add the right of 0.4kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 59.2 % by weight; Two polyureas 3.6 % by weight; Lubricating base oil 36.5 % by weight; Right, right '-di-iso-octyldiphenylamine 0.7 % by weight.
Embodiment 6
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (4.5kg); MDI(2.1kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 18kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, the consumption of each composition is as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.8 % by weight; Two polyureas 7.8 % by weight; Lubricating base oil 50.4 % by weight.
Embodiment 7
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); Full synthetic oil poly & Alpha ,-olefin oil PAO40(100 DEG C of kinematic viscosity is 41mm
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); Full synthetic oil poly & Alpha ,-olefin oil PAO10(100 DEG C of kinematic viscosity is 11mm
2/ s, 23kg); Dithio Acidic phosphates zinc (2kg), molybdenum dialkyldithiocarbamacompositions (1kg), tungsten disulfide (2kg), two tungsten selenide (2kg), right, right '-di-iso-octyldiphenylamine (0.2kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Full synthetic oil poly & Alpha ,-olefin oil PAO40 and PAO10 is used to replace HVI150BS and HVI500SN respectively; And treat that temperature is cooled to 110 DEG C, add the dithio Acidic phosphates zinc of 2kg, stir 10 minutes, add the molybdenum dialkyldithiocarbamacompositions of 1kg, stir 10 minutes, add the tungsten disulfide of 2kg, stir 10 minutes, add two tungsten selenide of 2kg, stir 10 minutes, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 38.3 % by weight; Two polyureas 2.4 % by weight; Lubricating base oil 51.6 % by weight; Dithio Acidic phosphates zinc 2.2 % by weight; Molybdenum dialkyldithiocarbamacompositions 1.1 % by weight; Tungsten disulfide 2.1 % by weight; Two tungsten selenide 2.1 % by weight; To p-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 8
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 9
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; 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 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 10
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 15kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.94kg); Para-totuidine (0.38kg); MDI(0.88kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, after adding stearylamine, also add para-totuidine, and then add MDI; 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 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 11
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 15kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (0.84kg); Lauryl amine (0.58kg); MDI(0.78kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; After adding stearylamine, also add lauryl amine, and then add MDI; 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 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 12
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 360mgKOH/g, 15kg); Overbased calcium alkyl-salicylate (total basicnumber is 360mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil
2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Propyl carbinol (1kg); Acetic acid (0.56kg); Boric acid (2.32kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil
2/ s, 23kg).
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 360mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 360mgKOH/g; Transforming agent adds propyl carbinol, adds after adding naphthenic 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 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 13
Calcium sulphonate-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 calcium sulfonate with high base number that 10kg total basicnumber is 350mgKOH/g, (100 DEG C of kinematic viscosity are 31mm to the HVI150BS lubricating base oil of naphthenate with superhigh base number calcium that 20kg total basicnumber is 400mgKOH/g and 25kg
2/ s, lower same), stir, heat to 60 DEG C, constant temperature 10 minutes; Add 3kg naphthenic acid, temperature controls at about 60 DEG C, stirs 10 minutes; Add the 12.5kg butanols aqueous solution that concentration is 20%, stir 10 minutes; 87 DEG C of constant temperature 70 minutes, material retrogradation; Be warmed up to 120 DEG C under stirring, keep 30 minutes, dehydration.
Volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle B in add the HVI500SN lubricating base oil of 5kg (100 DEG C of kinematic viscosity be 11mm
2/ s, lower with) 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 2:1:2,120 DEG C of constant temperature 20 minutes, obtains four polyureas.
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 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 four polyureas and six polyureas are all squeezed in reactor A, stirs, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, be cooled to 150 DEG C, add 8kg HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 40.4 % by weight; Four polyureas 2.5 % by weight; Six polyureas 2.5 % by weight; Lubricating base oil 54.6 % by weight.
Embodiment 14
Calcium sulphonate-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 sulphonate that 20kg total basicnumber is 400mgKOH/g, 10kg total basicnumber is the naphthenate with superhigh base number calcium of 420mgKOH/g and the HVI150BS lubricating base oil of 10kg, stir, heat to 50 DEG C, constant temperature 10 minutes; Add 2kg Witco 1298 Soft Acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2kg concentration is 20 % by weight, stir 10 minutes; 83 DEG C of constant temperature 80 minutes, material retrogradation; Be warmed up to 110 DEG C under stirring, keep 45 minutes, dehydration.
Volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add the HVI500SN lubricating base oil of 10kg and 1.17kg MDI is 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 3:2:2,120 DEG C of constant temperature 20 minutes, obtains mixing polyureas.
Gained polyurea compound is all squeezed in a upper still, stir, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, the HVI500SN lubricating base oil of 8kg 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 52.5 % by weight; Polyurea compound 3.5 % by weight; Lubricating base oil 44.0 % by weight.
Embodiment 15
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with phenol, acetic acid is replaced with butyric acid, boric acid is replaced with acetone.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 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Embodiment 16
Calcium sulphonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium sulphonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with ketone, aqueous acetic acid is replaced with ether, boric acid aqueous solution is replaced with ethamine.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 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Comparative example 1
Calcium sulfonate with high base number base two polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number calcium total basicnumber is that the overbased calcium sulphonate of 400mgKOH/g replaces, and each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate 41.5 % by weight; Two polyureas 2.6 % by weight; Lubricating base oil 55.9 % by weight.
Table 1 each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643; Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.
Table 1(continues) each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643; Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.
Embodiment 1 and comparative example 1 are compared and can find out, the prolongation Drawing cone in-degree of calcium sulphonate of the present invention-Calcium naphthenate base polyurea grease and the difference of Drawing cone in-degree are less than calcium sulphonate base polyurea grease, water drenches number of dropouts much smaller than calcium sulphonate base polyurea grease, salt-fog test is better than calcium sulphonate base polyurea grease, water resistant spraying value is less than calcium sulphonate base polyurea grease, Stencil oil-dividing value is much smaller than calcium sulphonate base polyurea grease, tetra-ball machine test value is greater than calcium sulphonate base polyurea grease, the bearing lubrication life-span is greater than calcium sulphonate base polyurea grease, the mechanical stability of calcium sulphonate of the present invention-Calcium naphthenate base polyurea grease is described, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear, lubricating life is all better than calcium sulphonate base polyurea grease, and calcium sulphonate of the present invention-Calcium naphthenate base polyurea grease is the same with calcium sulphonate base polyurea grease has the performances such as excellent non-corrosibility and high thermal resistance.
Embodiment 1 and embodiment 2 are compared and can find out, calcium sulphonate-Calcium naphthenate base polyurea grease prepared by original position, there is better mechanical stability, water resisting property and adhesivity; Embodiment 1 is compared can find out with embodiment 15 and embodiment 16 respectively, transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, butanols, Virahol, boric acid, acetic acid and water, calcium sulphonate-Calcium naphthenate base the polyurea grease of preparation, has better mechanical stability, water resisting property and adhesivity and colloid stability.
As can be seen from Figure 1, the lubricating grease of embodiment 2 preparation is at 873cm
-1-886cm
-1there is crystal form calcium carbonate charateristic avsorption band in place.Meanwhile, at 3300cm
-1-3323cm
-1the peak at place is the stretching vibration absorption peak of-NH-in two polyureas molecules.
Calcium sulphonate of the present invention-Calcium naphthenate base polyurea grease, not only the same with calcium sulphonate base polyurea grease, there is excellent non-corrosibility and high thermal resistance, but also there is the performance such as mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear being better than calcium sulphonate base 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 (22)
1. calcium sulphonate-Calcium naphthenate base polyurea grease, is characterized in that, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight.
2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight.
3. lubricating grease according to claim 1 and 2, wherein, described non-newtonian fluid calcium sulphonate-calcium naphthenate is transformed by newton's body calcium sulphonate and newton's body calcium naphthenate and obtains, and the total basicnumber of described non-newtonian fluid calcium sulphonate-calcium naphthenate is 250-450mgKOH/g.
4. lubricating grease according to claim 1 and 2, wherein, described polyurea compound is at least one in two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.
5. lubricating grease according to claim 4, 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.
6. lubricating grease according to claim 5, 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.
7. lubricating grease according to claim 6, 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-(CH
2)
6-at least one.
8. the preparation method of the calcium sulphonate in claim 1-7 described in any one-Calcium naphthenate base polyurea grease, it is characterized in that, the method comprises: non-newtonian fluid calcium sulphonate-calcium naphthenate, polyurea compound and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
9. a preparation method for calcium sulphonate-Calcium naphthenate base polyurea grease, it is characterized in that, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, heat up dehydration further;
(2) in step (1) products therefrom, add part basis oil and monoamine, or also add diamines, add vulcabond and react;
(3) be warmed up to 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
10. preparation method according to claim 9, 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 80-100 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.
11. preparation methods according to claim 9, wherein, in step (2), in the product of step (1), add part basis oil and monoamine, stir 2-8 minute, then add vulcabond, stir 2-8 minute, the mol ratio of vulcabond and monoamine is 1:2.
12. preparation methods according to claim 9, wherein, in step (3), first at 100-120 DEG C of constant temperature 10-20 minute, are finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
13. preparation methods according to claim 9, 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.
14. preparation methods according to claim 9, 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.
15. preparation methods according to claim 14, 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.
16. preparation methods according to claim 9, 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.
17. preparation methods according to claim 16, 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.
18. preparation methods according to claim 9, 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.
19. preparation methods according to claim 18, wherein, described diamines is selected from Ursol D, O-Phenylene Diamine, 4, the aromatic amine of 4 '-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
20. preparation methods according to claim 9, 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.
21. preparation methods according to claim 20, wherein, described vulcabond is selected from least one in tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
22. calcium sulphonate-Calcium naphthenate base the polyurea greases obtained by the method in claim 9-21 described in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310418626.XA CN104450110B (en) | 2013-09-13 | 2013-09-13 | A kind of sulfoacid calcium Calcium naphthenate base polyurea grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310418626.XA CN104450110B (en) | 2013-09-13 | 2013-09-13 | A kind of sulfoacid calcium Calcium naphthenate base polyurea grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104450110A true CN104450110A (en) | 2015-03-25 |
| CN104450110B CN104450110B (en) | 2018-01-05 |
Family
ID=52896869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310418626.XA Active CN104450110B (en) | 2013-09-13 | 2013-09-13 | A kind of sulfoacid calcium Calcium naphthenate base polyurea grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104450110B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003301190A (en) * | 2002-02-06 | 2003-10-21 | Nsk Ltd | Grease composition and rotary apparatus |
| CN101935578A (en) * | 2010-10-11 | 2011-01-05 | 长沙众城石油化工有限责任公司 | Calcium sulfonate complex grease and preparation method thereof |
| CN102417853A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium sulfonate octaurea lubricating grease and preparation method thereof |
| CN102417856A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium-sulfonate-based hexapolyurea lubricating grease and preparation method thereof |
| CN102417855A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium sulfonate tetra-polyurea 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 |
-
2013
- 2013-09-13 CN CN201310418626.XA patent/CN104450110B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003301190A (en) * | 2002-02-06 | 2003-10-21 | Nsk Ltd | Grease composition and rotary apparatus |
| CN102417853A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium sulfonate octaurea lubricating grease and preparation method thereof |
| CN102417856A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium-sulfonate-based hexapolyurea lubricating grease and preparation method thereof |
| CN102417855A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium sulfonate tetra-polyurea lubricating grease and preparation method thereof |
| CN101935578A (en) * | 2010-10-11 | 2011-01-05 | 长沙众城石油化工有限责任公司 | Calcium sulfonate complex 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104450110B (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104449959A (en) | High-base number composite calcium-based grease and preparation method thereof | |
| CN103571570B (en) | A kind of Calcium naphthenate base four polyurea grease and preparation method thereof | |
| CN104560318A (en) | Calcium naphthenate zirconium-based hexurea lubricating grease and preparation method thereof | |
| CN104449956A (en) | High base number composite calcium-based polyurea lubricating grease and preparation method thereof | |
| CN104450109A (en) | High-base number composite calcium-based urea tetramer grease and preparation method thereof | |
| CN104450110A (en) | Calcium sulfonate-calcium naphthenate-based polyurea grease and preparation method thereof | |
| CN103571588B (en) | A kind of Calcium naphthenate base eight polyurea grease and preparation method thereof | |
| CN103571571A (en) | Calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof | |
| CN104560320A (en) | Compound calcium naphthenatezirconium-based polyurea lubricating grease and preparation method thereof | |
| CN104560317A (en) | Compound calcium sulfonate-calcium naphthenate zirconium-based polyurea lubricating grease and preparation method thereof | |
| CN103571598B (en) | A kind of Calcium naphthenate base two polyurea grease and preparation method thereof | |
| CN104449961A (en) | Calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof | |
| CN104450115A (en) | Calcium sulfonate-calcium naphthenate-based urea tetramer grease and preparation method thereof | |
| CN104450116A (en) | Calcium sulfonate-calcium naphthenate-based urea octamer grease and preparation method thereof | |
| CN104450112A (en) | High-base number composite calcium-based urea hexamer grease and preparation method thereof | |
| CN104450113A (en) | High-base number composite calcium-based urea octamer grease and preparation method thereof | |
| CN104560273A (en) | Compound calcium sulfonate-calcium naphthenate zirconium-based octaurea lubricating grease and preparation method thereof | |
| CN104212611A (en) | Calcium naphthenate-based polyurea lubricating grease and its preparation method | |
| CN104449960A (en) | Composite calcium sulfonate-calcium naphthenate-based polyurea grease and preparation method thereof | |
| CN104212535A (en) | Calcium naphthenate-based octaurea lubricating grease and its preparation method | |
| CN104449957A (en) | Composite calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof | |
| CN104560316B (en) | A kind of polyurea grease of sulfoacid calcium calcium naphthenate zirconium base four and preparation method thereof | |
| CN104449958A (en) | Composite calcium sulfonate-calcium naphthenate-based urea octamer grease and preparation method thereof | |
| CN104293452A (en) | Composite calcium naphthenate-based polyurea lubricating grease and preparation method thereof | |
| CN104450114A (en) | Composite calcium sulfonate-calcium naphthenate-based urea tetramer grease and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |