CN103060069B - Lubricating grease and preparation method thereof - Google Patents
Lubricating grease and preparation method thereof Download PDFInfo
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- CN103060069B CN103060069B CN201110319576.0A CN201110319576A CN103060069B CN 103060069 B CN103060069 B CN 103060069B CN 201110319576 A CN201110319576 A CN 201110319576A CN 103060069 B CN103060069 B CN 103060069B
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Abstract
The invention relates to a lubricating grease, comprising 40-95 wt% of a lubricating base oil, 1-59 wt% of a composite zirconium based densifier and 1-59 wt% of bipolyurea; and the composite zirconium based densifier is a compound zirconium soap generated from reaction of higher aliphatic acid, aromatic acid, water and zirconium alkoxide. The invention also relates to a preparation method of the lubricating grease. The method comprises the following steps: subjecting the zirconium alkoxide, higher aliphatic acid and aromatic acid to a first contact reaction in lubricating base oil at 60-120 DEG C; then subjecting the mixture obtained from the first contact reaction and water to a second contact reaction at 85-100 DEG C, and heating the products obtained from the second contact reaction for dehydration; and introducing the bipolyurea into the obtained reaction products. The lubricating grease provided by the invention has high drop point, excellent colloidal stability, and excellent extreme pressure wear resistance and ball bearing lubrication life.
Description
Technical field
The present invention relates to a kind of lubricating grease, and this preparation of greases method.
Background technology
Zirconium belongs to IVB family as a kind of transition metal, is positioned at for the 5th cycle.Zirconium-containing compound has good lubrication, is often used as slip additive, as CN101113382A and JP1973038444 disclose the oxide compound of zirconium as lubricant additive to improve abradability; WO2007143414 and US20060063682 disclose and can adopt zirconium tetrafluoride as wear reducing additive, to become one of component of lubricant; US20060254823 discloses the lubricant that contains 2 ethyl hexanoic acid zirconates, and this lubricant shows good resistance to heavy loading and abrasion resistance; US20050043189 discloses fluozirconate and has been used in lubricant as fluorine zirconic acid aluminium can be used as oxidation retarder; DE102004021812 discloses the inorganic salt such as zirconium carbonate, sulfonic acid zirconium or zirconium phosphate has been joined in lubricating grease to improve abrasion resistance.
The patent of preparing zirconium base grease using zirconates as viscosifying agent has US4189387, wherein, viscosifying agent is only containing a kind of zirconates, the Hypophosporous Acid, 50 or the monocarboxylic acid that by alkyl, are replaced react and make with zirconium hydroxide, products obtained therefrom extreme pressure property is better, but dropping point is not high enough, and the viscosifying agent of the relatively good product of effect contains fluorine element, the difficult acquisition of raw material.
Summary of the invention
The object of this invention is to provide a kind of new lubricating grease and preparation method thereof, this lubricating grease has good extreme pressure anti-wear and longer lubricating life.
The invention provides a kind of lubricating grease, wherein, the lubricating base oil that this lubricating grease contains 40-95 % by weight, the compound zirconium base viscosifying agent of 1-59 % by weight and two polyureas of 1-59 % by weight, described compound zirconium base viscosifying agent is by higher fatty acid, aromatic acid and water, to be reacted the compound zirconium soap generating with zirconium alkoxide.
The present invention also provides a kind of preparation of greases method, and the method comprises: in reactor A, at 60-120 ℃, zirconium alkoxide, higher fatty acid and aromatic acid are carried out in lubricating base oil to the first contact reacts; Then, at 85-100 ℃, the mixture obtaining and water are carried out to the second contact reacts after described the first contact reacts, and by the product obtaining after described the second contact reacts dehydration that heats up; Then carry out following step (1) or (2):
(1) product of reactor A is mixed with vulcabond, then gained mixture is reacted with monoamine, and the mixture obtaining is warming up to 200-220 ℃ refines;
(2) vulcabond being dissolved in lubricating base oil is reacted with monoamine in reactor B, product merging that then will reaction gained mixture and reactor A, and the mixture obtaining is warming up to 200-220 ℃ refines;
Wherein, the mol ratio of vulcabond and monoamine is 1: (1.5-2.5).
Lubricating grease according to the present invention has higher dropping point, shows good colloid stability, but also has good extreme pressure and antiwear behavior and ball bearing lubricating life.
Accompanying drawing explanation
Fig. 1 is the infrared analysis spectrogram of two polyureas in the lubricating grease prepared of embodiment 1;
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of two polyureas in the lubricating grease prepared of embodiment 1;
Fig. 3 is the Electrospray Ionization Mass Spectrometry spectrogram of two polyureas in the lubricating grease prepared of embodiment 1.
Embodiment
The invention provides a kind of lubricating grease, wherein, the lubricating base oil that this lubricating grease contains 40-95 % by weight, the compound zirconium base viscosifying agent of 1-59 % by weight and two polyureas of 1-59 % by weight, described compound zirconium base viscosifying agent is by higher fatty acid, aromatic acid and water, to be reacted the compound zirconium soap generating with zirconium alkoxide.
Under preferable case, take the gross weight of described lubricating grease as benchmark, the content of described lubricating base oil is 50-90 % by weight, and the content of described compound zirconium base viscosifying agent is 2-45 % by weight, and the content of described two polyureas is 1-28 % by weight.
Lubricating grease according to the present invention, described lubricating base oil can be the conventional various lubricating base oils that use in this area, for example, can be that 100 ℃ of viscosity are 2-150mm
2/ s (is preferably 2-150mm
2/ s, more preferably 8-50mm
2/ lubricating base oil s).Concrete, described lubricating base oil can be for example at least one in mineral oil, vegetables oil and synthetic oil.Described synthetic oil can be poly-a-olefin oil (PAO), ester class oil, alkyl-silicone oil, Fischer-Tropsch synthesis oil etc.
Lubricating grease according to the present invention, generates in the process of described compound zirconium base viscosifying agent in reaction, and the mol ratio of the consumption of water and the consumption of described zirconium alkoxide can be 1-20: 1, be preferably 1.9-10: 1; The mol ratio of total consumption of the consumption of described zirconium alkoxide and described higher fatty acid and described aromatic acid is 1: 1-1.5, is preferably 1: 1.01-1.35; The mol ratio of the consumption of described higher fatty acid and described aromatic acid is 1: 0.5-7, is preferably 1: 1-4.
Lubricating grease according to the present invention, the general formula of described zirconium alkoxide can be Zr (OR
1)
4, wherein, R
1can be the alkyl of C1-C10, be preferably the alkyl of C2-C6.Concrete, described zirconium alkoxide can be for example ethanol zirconium (R
1for ethyl), zirconium-n-propylate (R
1for n-propyl), zirconium-n-butylate (R
1for normal-butyl), zirconium tert-butoxide (R
1for the tertiary butyl), Pentyl alcohol zirconium (R
1for n-pentyl) and zirconium tert-butoxide (R
1for tert-pentyl) at least one.
Lubricating grease according to the present invention, described higher fatty acid is preferably the straight chain fatty acid of C8-C24 or the hydroxy fatty acid of C8-C24.Concrete, described higher fatty acid for example can be for being selected from least one in lauric acid, oleic acid, palmitinic acid, stearic acid, 12-oxystearic acid and eicosyl carboxylic acid.
Lubricating grease according to the present invention, the structural formula of described aromatic acid is preferably suc as formula shown in (I),
Wherein, R
2, R
3, R
4, R
5and R
6be thiazolinyl, the alkynyl of C2-C5 of carboxyl substituted or the aryl of the C6-C12 of carboxyl substituted of the C2-C5 of alkyl, the carboxyl substituted of the C1-C5 of fluorinated aryl, the carboxyl substituted of fluoro-alkyl, the C6-C12 of aryl, the C1-C5 of alkynyl, the C6-C12 of thiazolinyl, the C2-C5 of alkyl, the C2-C5 of hydrogen, carboxyl, C1-C5 independently of one another.
In the first preferred implementation, in formula (I), R
2, R
3and R
4in one be carboxyl, R
2, R
3and R
4in two other and R
5and R
6be the alkyl of hydrogen, C1-C5, the thiazolinyl of C2-C5, the alkynyl of C2-C5, aryl, the fluoro-alkyl of C1-C5 or the fluorinated aryl of C6-C12 of C6-C12 independently of one another.More preferably, R
2, R
3and R
4in one be carboxyl, R
2, R
3and R
4in two other and R
5and R
6be the alkyl of hydrogen, C1-C5 or the aryl of C6-C12 independently of one another.
In the second preferred implementation, in formula (I), R
2, R
3and R
4in thiazolinyl, the alkynyl of C2-C5 of carboxyl substituted or the aryl of the C6-C12 of carboxyl substituted of C2-C5 of alkyl, carboxyl substituted of the C1-C5 that is carboxyl substituted, R
2, R
3and R
4in two other and R
5and R
6be the alkyl of hydrogen, C1-C5, the thiazolinyl of C2-C5, the alkynyl of C2-C5, aryl, the fluoro-alkyl of C1-C5 or the fluorinated aryl of C6-C12 of C6-C12 independently of one another.More preferably, R
2, R
3and R
4in alkyl of C1-C5 that is carboxyl substituted or the aryl of the C6-C12 of carboxyl substituted, R
2, R
3and R
4in two other and R
5and R
6be the alkyl of hydrogen, C1-C5 or the aryl of C6-C12 independently of one another.
In the third preferred implementation, in formula (I), R
2, R
3, R
4, R
5and R
6be the alkyl of hydrogen, C1-C5, the thiazolinyl of C2-C5, the alkynyl of C2-C5, aryl, the fluoro-alkyl of C1-C5 or the fluorinated aryl of C6-C12 of C6-C12 independently of one another.More preferably, R
2, R
3, R
4, R
5and R
6be the alkyl of hydrogen, C1-C5 or the aryl of C6-C12 independently of one another.
Still more preferably, described aromatic acid is at least one in phenylformic acid, phthalic acid, m-phthalic acid, terephthalic acid and biphenyl dicarboxylic acid (as 4,4 '-biphenyl dicarboxylic acid).
Lubricating grease according to the present invention, described two polyureas are preferably the compound shown in formula (II),
Wherein, each R
1independently selected from alkyl, cycloalkyl or aryl, R
3be selected from alkylidene group, cycloalkylidene or arylidene.
More preferably, in formula (II), each R
1independently selected from the alkyl of C8-C24, cycloalkyl or the C6-C10 aryl of C8-C24, R
3be selected from alkylidene group, the cycloalkylidene of C6-C30 or the arylidene of C6-C30 of C6-C30.
Further preferably, in formula (II), each R
1the phenyl that the phenyl replacing independently selected from the alkyl of the cycloalkyl of the alkyl of C10-C18, C10-C18, phenyl, C1-C3 or halogen replace, R
3be selected from xylylene or hexylidene between methylene phenyl, methylenediphenyl, sub-dicyclohexyl methyl, Asia.
Still more preferably, in formula (II), each R
1independently selected from dodecyl, tetradecyl, hexadecyl, octadecyl, phenyl, tolyl or chlorophenyl, R
3be selected from xylylene or hexylidene between methylene phenyl, methylenediphenyl, sub-dicyclohexyl methyl, Asia.
Lubricating grease according to the present invention, described lubricating grease can also contain conventional other the various additives that use in this area, as oxidation inhibitor, anti-wear agent, rust-preventive agent etc.Described oxidation inhibitor is preferably arylamine kind antioxidant, can account for the 0.1-5 % by weight of described lubricating grease total amount, preferably 0.2-1 % by weight, described arylamine kind antioxidant can be for example pentanoic, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or their mixture, is preferably di-iso-octyldiphenylamine.
The present invention also provides a kind of preparation of greases method, and the method comprises: in reactor A, at 60-120 ℃, zirconium alkoxide, higher fatty acid and aromatic acid are carried out in lubricating base oil to the first contact reacts; Then, at 85-100 ℃, the mixture obtaining and water are carried out to the second contact reacts after described the first contact reacts, and by the product obtaining after described the second contact reacts dehydration that heats up; Then carry out following step (1) or (2):
(1) product of reactor A is mixed with vulcabond, then gained mixture is reacted with monoamine, and the mixture obtaining is warming up to 200-220 ℃ refines;
(2) vulcabond being dissolved in lubricating base oil is reacted with monoamine in reactor B, product merging that then will reaction gained mixture and reactor A, and the mixture obtaining is warming up to 200-220 ℃ refines;
Wherein, the mol ratio of vulcabond and monoamine is 1: (1.5-2.5).
In the preferred case, with respect to the described lubricating base oil of 100 weight parts, the consumption of described zirconium alkoxide is 10-100 weight part, the mol ratio of the consumption of water and the consumption of described zirconium alkoxide is 1-20: 1, the mol ratio of total consumption of the consumption of described zirconium alkoxide and described higher fatty acid and described aromatic acid is 1: 1-1.5, the mol ratio of the consumption of described higher fatty acid and the consumption of described aromatic acid is 1: 0.5-7.
More preferably, with respect to the described lubricating base oil of 100 weight parts, the consumption of described zirconium alkoxide is 20-60 weight part, the mol ratio of the consumption of water and the consumption of described zirconium alkoxide is 1.9-10: 1, the mol ratio of total consumption of the consumption of described zirconium alkoxide and described higher fatty acid and described aromatic acid is 1: 1.01-1.35, the mol ratio of the consumption of described higher fatty acid and described aromatic acid is 1: 1-4.
Method according to the present invention, described zirconium alkoxide, described higher fatty acid and described aromatic acid all with above describe identical.
Method according to the present invention, can produce the alkyl alcohol and water of C1-C10 in described the first contact reacts and described the second contact reacts process, these alcohol and waters can high temperature (more than 100 ℃) under vapor away.
Method according to the present invention, in described the first catalytic process of enforcement, can, by described zirconium alkoxide, described higher fatty acid and the direct hybrid reaction of described aromatic acid, also described zirconium alkoxide, described higher fatty acid and described aromatic acid can be carried out to stepwise reaction.
By described zirconium alkoxide, described higher fatty acid and the direct hybrid reaction of described aromatic acid in the situation that, described the first catalytic condition optimization comprises: temperature of reaction is 90-120 ℃, and the reaction times is 20-100 minute.
In the situation that described zirconium alkoxide, described higher fatty acid and described aromatic acid are carried out to stepwise reaction, described the first catalytic operating process can comprise the following steps:
(a), at 60-100 ℃, under the existence of described lubricating base oil, described zirconium alkoxide is mixed and contacts 5-60 minute with described higher fatty acid;
(b), at 100-120 ℃, under the existing of described lubricating base oil, the mixture that step (a) is obtained mixes and contacts 10-60 minute with described aromatic acid.
Method according to the present invention, described the second catalytic condition optimization comprises: temperature of reaction is 90-100 ℃; Reaction times is 15-60 minute.
In a kind of preferred implementation, described the first contact reacts and described the second catalytic operating process comprise: zirconium alkoxide is mixed with lubricating base oil, be warming up to 60-100 ℃, add described higher fatty acid, and react 5-60 minute at this temperature; Then, add described aromatic acid, be warming up to 100-120 ℃, and react 10-60 minute at this temperature; Afterwards, add water, at 85-100 ℃, react 5-60 minute, then, be warming up to 105-220 ℃ and dewater.
Method according to the present invention, in step (1) and step (2), the mol ratio of vulcabond and monoamine is preferably 1: (1.9-2.1), most preferably be 1: 2.
Method according to the present invention, in step (1) and step (2), the reaction conditions of described reaction preferably includes: temperature of reaction is 80-140 ℃, and the reaction times is 1-20 minute.
In the present invention, the general formula of described monoamine can be R
1nH
2, wherein, R
1can be the alkyl of C8-C24, cycloalkyl or the C6-C10 aryl of C8-C24.Under preferable case, described monoamine is at least one in aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, amino dodecane, tetradecy lamine, cetylamine and stearylamine.
In the present invention, described vulcabond can be for being dissolved in the vulcabond of the various routines in described lubricating base oil, and its general formula can be OCN-R
3-NCO, wherein, R
3can be alkylidene group, the cycloalkylidene of C6-C30 or the arylidene of C6-C30 of C6-C30.Under preferable case, described vulcabond is at least one in tolylene diisocyanate, methyldiphenyl group diisocyanate, hexamethylene vulcabond, dicyclohexyl methyl vulcabond and an xylylene vulcabond.
Method according to the present invention, in step (1), can directly mix the product of described reactor A with vulcabond, also can first vulcabond be dissolved in lubricating base oil, then mixes with the product of described reactor A.
Method according to the present invention, the object of the refining process in step (1) and step (2) is that each composition in lubricating grease is fully mixed, to form good soap structure in follow-up process of cooling, thereby obtain the lubricating grease of high comprehensive performance.The time of described refining can be 1-20 minute, is preferably 5-10 minute.In one, more preferably in embodiment, after completing described refining process, the mixture obtaining after refining is cooled to 155-165 ℃, optionally in mixture, adds lubricating base oil afterwards.
Method according to the present invention, the lubricating base oil using in the lubricating base oil using in described the first contact reacts and the second contact reacts process, step (1) and step (2) and complete the lubricating base oil that selectivity adds after described refining process each other can be identical or different.And the consumption of the lubricating base oil in described the first contact reacts and the second contact reacts process can account for the 10-90 % by weight of total consumption of the lubricating base oil in whole described preparation of greases process; The consumption of the lubricating base oil in step (1) and step (2) can account for the 10-90 % by weight of total consumption of the lubricating base oil in whole described preparation of greases process; The amount of the lubricating base oil that selectivity adds after completing described refining process can account for the 0-80 % by weight of total consumption of the lubricating base oil in whole described preparation of greases process.
In one embodiment, described preparation of greases method can also comprise in described lubricating grease introduces the conventional additive using in other this areas, as oxidation inhibitor, anti-wear agent, rust-preventive agent etc.Described oxidation inhibitor is preferably arylamine kind antioxidant, for example, can be pentanoic, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or their mixture, is preferably di-iso-octyldiphenylamine.Introduce other additives in described lubricating grease in the situation that, described additive preferably adds after completing described refining process.
Method according to the present invention, the in the situation that of enforcement according to step (1) after completing described the first contact reacts and described the second contact reacts, described preparation of greases method of the present invention can be implemented in a reactor (being reactor A); The in the situation that of enforcement according to step (2) after completing described the first contact reacts and described the second contact reacts, described preparation of greases method of the present invention need to be implemented in two reactors (being reactor A and reactor B).
The invention will be further described by the following examples.
The separation method of two polyureas: first, by sherwood oil for lubricating grease (boiling point 60-90 ℃) washing, filtration is precipitated, soaks precipitation 5-10 minute and stirs with the dilute acetic acid solution of 5 % by weight, filters, and filter residue water cleans, then uses the NaHCO of 1 % by weight
3solution soaking, filter, by filter residue water clean to filtrate pH value be 7 o'clock, the precipitation obtaining is dried, obtain two polyureas.
Embodiment 1
The present embodiment is used for illustrating described lubricating grease of the present invention and preparation method thereof.
Feed composition: zirconium iso-propoxide Virahol complex compound (9.33kg); 12-oxystearic acid (4.80kg); Phthalic acid (2.60kg); Stearylamine (1.5kg); 4,4 '-diphenylmethanediisocyanate (MDI, 0.7kg); HVI500SN base oil (40kg).
A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add the HVI500SN base oil of 9.33kg zirconium iso-propoxide Virahol complex compound (purchased from Sigma-Aldrich company) and 9kg (100 ℃ of kinematic viscosity be 11mm
2/ s, purchased from Exxon Mobil chemical company), stir, heat to 80 ℃, add the 12-oxystearic acid (purchased from prestige Ninghua, Tongliao City work limited liability company) of 4.80kg, isothermal reaction 20 minutes; Add 2.60kg phthalic acid, be warming up to 105 ℃, react 30 minutes, add the HVI500SN base oil of 6kg, be cooled to 95 ℃, add 1kg water, isothermal reaction 20 minutes; Under stirring, be warmed up to 110 ℃ and dewater, after finished off water, constant temperature is stand-by;
Another volume be 5L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add the HVI500SN base oil of 5kg, be preheating to 90 ℃ and add the MDI rapid stirring 4 minutes of 1kg, under agitation add 1.5kg stearylamine, and continue to stir 4 minutes, the MDI adding and the mol ratio of stearylamine are 1: 2,120 ℃ of constant temperature 20 minutes, gained material is squeezed in a upper reactor, stir, be finally warmed up to 200 ℃, constant temperature refining 5 minutes.
Then, be cooled to 160 ℃, add the HVI500SN base oil of 20kg; Treat that temperature is cooled to 110 ℃, circulating filtration, homogenizing, the degassed lubricating grease that obtains.According to material, feed intake to calculate and learn, the composition of this lubricating grease is as two polyureas 4.2 % by weight, lubricating base oil 76.7 % by weight, compound zirconium base viscosifying agent 19.1 % by weight.
From described lubricating grease, isolate two polyureas, and isolated two polyureas are carried out respectively to infrared analysis, nuclear magnetic resonance spectroscopy and Electrospray Ionization Mass Spectrometry, obtain spectrogram as shown in Figure 1-Figure 3.As can be seen from the figure, 3310cm
-1～3323cm
-1the peak at place is in two polyureas molecules-the stretching vibration absorption peak of NH-, and 1630cm
-1the peak at place is in two polyureas molecules-vibration absorption peak of CO-; The peak of as can be seen from the figure, δ=155HZ left and right is in two polyureas molecules-chemical shift of CO-; As can be seen from the figure, the mass-to-charge ratio of sample is 788.7m/z, and the relative molecular mass of this and two polyureas matches.Therefore, by the spectral data of Fig. 1-Fig. 3, can be determined, the molecular structural formula of two polyureas in this lubricating grease is as follows.
Comparative example 1
By the HVI500SN base oil of 280kg (100 ℃ of viscosity 11mm
2/ s, purchased from Exxon Mobil chemical company), the 12-oxystearic acid of 90kg adds in normal-pressure reaction kettle, stirs, and is warmed up to after 90 ℃, adds the Zr (OH) of 27kg
4, being warming up to 105 ℃, draining saponification 2 hours, is then warming up to 205 ℃, adds the HVI500SN base oil of 180kg, treats that temperature is cooled to 110 ℃, circulating filtration, homogenizing, the degassed lubricating grease that obtains.According to material, feed intake to calculate and learn, the composition of this lubricating grease is as lubricating base oil 80.9 % by weight, compound zirconium base viscosifying agent 19.1 % by weight.
Comparative example 2
By the HVI500SN oil of 260kg (100 ℃ of viscosity 11mm
2/ s, purchased from Exxon Mobil chemical company), 12-oxystearic acid and the 15kg sebacic acid of 45kg add in normal-pressure reaction kettle, stirs, and is warmed up to after 90 ℃, adds 50kg to be dissolved with the LiOHH of 12.3kg
2the aqueous solution of O, is warming up to 105 ℃, and draining saponification 2 hours, is then warming up to 205 ℃, adds the HVI500SN base oil of 180kg, treats that temperature is cooled to 110 ℃, circulating filtration, homogenizing, the degassed lubricating grease that obtains.According to material, feed intake to calculate and learn, the composition of this lubricating grease is as lubricating base oil 87.6 % by weight, compound lithium base viscosifying agent 12.4 % by weight.
Embodiment 2
The present embodiment is used for illustrating described lubricating grease of the present invention and preparation method thereof.
Feed composition: ethanol zirconium (6.72kg); Stearic acid (4.55kg); Terephthalic acid (2.66kg); Stearylamine (1.5kg); MDI (0.7kg); Poly alpha olefine synthetic oil PAO 10 (110kg).
A volume be 150L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add the poly alpha olefine synthetic oil PAO10 of 6.72kg ethanol zirconium (purchased from Sigma-Aldrich company) and 20kg (100 ℃ of kinematic viscosity be 10mm
2/ s, purchased from Exxon Mobil chemical company), stir, heat to 80 ℃, add the stearic acid of 4.55kg, isothermal reaction 60 minutes; Add 2.66kg terephthalic acid, be warming up to 105 ℃ of reactions 30 minutes, add the poly alpha olefine synthetic oil PAO 10 of 20kg, be cooled to 95 ℃, add 1kg water, isothermal reaction 20 minutes; Under stirring, being warmed up to 110 ℃ dewaters, after finished off water, add the MDI of 0.7kg, and continue to stir 4 minutes, then under agitation add the stearylamine of 1.5kg, and continue to stir 4 minutes, the MDI adding and the mol ratio of stearylamine are 1: 2,120 ℃ of constant temperature 20 minutes, is finally warmed up to 200 ℃, constant temperature refining 5 minutes.Then, be cooled to 160 ℃, add the poly alpha olefine synthetic oil PAO 10 of 70kg; Treat that temperature is cooled to 110 ℃, circulating filtration, homogenizing, the degassed lubricating grease that obtains.According to material, feed intake to calculate and learn, the composition of this lubricating grease is as two polyureas 1.8 % by weight; Lubricating base oil 90.2 % by weight; Compound zirconium base viscosifying agent 8 % by weight.
Embodiment 3
The present embodiment is used for illustrating described lubricating grease of the present invention and preparation method thereof.
Feed composition: zirconium tert-butoxide (22.15kg, purchased from Sigma-Aldrich company); 12-oxystearic acid (4.8kg); M-phthalic acid (8kg); Amino dodecane (1.31kg); MDI (0.89kg); Poly alpha olefine synthetic oil PAO 6 (50kg).
According to the method for embodiment 1, prepare lubricating grease, difference is, replaces zirconium iso-propoxide by zirconium tert-butoxide, replace stearylamine with amino dodecane, replace phthalic acid with m-phthalic acid, replace HVI500SN base oil to replace with poly alpha olefine synthetic oil PAO 6, their consumption is as implied above.
According to material, feed intake to calculate and learn, so the composition of the lubricating grease of preparation is as two polyureas 3.1 % by weight; Lubricating base oil 70.5 % by weight; Compound zirconium base viscosifying agent 26.4 % by weight.
Embodiment 4
The present embodiment is used for illustrating described lubricating grease of the present invention and preparation method thereof.
Feed composition: ethanol zirconium (0.99kg, purchased from Sigma-Aldrich company); 12-oxystearic acid (0.3kg); 4,4 '-biphenyl dicarboxylic acid (0.7kg); Para-totuidine (1.17kg); Stearylamine (2.93kg); Tolylene diisocyanate (TDI, 1.90kg); HVI500SN base oil (16kg); Right, p-di-iso-octyldiphenylamine (0.1kg).
According to the method for embodiment 1, prepare lubricating grease, difference is, with ethanol zirconium replacement zirconium iso-propoxide, with 4,4 '-biphenyl dicarboxylic acid replaces phthalic acid, with the mixture replacement stearylamine of para-totuidine and stearylamine, with 1,6-hexanediamine replacement quadrol, replace MDI with TDI, and it is right to add after refining, p-di-iso-octyldiphenylamine, the consumption of various materials is as implied above.
According to material, feed intake to calculate and learn, so the composition of the lubricating grease of preparation is as two polyureas 25.5 % by weight; Lubricating base oil 68.1 % by weight; Compound zirconium base viscosifying agent 6 % by weight; Right, p-di-iso-octyldiphenylamine 0.4 % by weight.
Test case
(1) according to the method for GB/T 269-1991, detect the Drawing cone in-degree of various lubricating grease;
(2) according to the method for GB/T 3498-2008, detect the dropping point of various lubricating grease;
(3) according to the method for SH/T 0324-1992, detect the Stencil oil-dividing of various lubricating grease;
(4) according to the method for the method of SH/T 0202-1992 and SH/T 0204-1992, respectively various lubricating grease is carried out to tetra-ball machine test, detect respectively P
b, P
dand D
40 60;
(5) according to the method for ASTMD 3336-2005, detect the ball bearing lubricating life of various lubricating grease;
Above-mentioned detected result is as shown in table 1 below.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Lubricating grease color | Tawny | Canescence | Canescence | Tawny | Grey | Light brown |
| Dropping point, ℃ | 326 | 321 | 331 | 330 | 90 | 262 |
| Drawing cone in-degree, 0.1mm | 231 | 285 | 212 | 221 | 264 | 263 |
| Stencil oil-dividing (100 ℃, 24h), % by weight | 2.58 | 4.22 | 2.44 | 3.07 | 2.90 | 3.33 |
| PB，N | 696 | 490 | 981 | 392 | 785 | 392 |
| PD，N | 4905 | 1962 | 7848 | 1569 | 1098 | 1568 |
| D 40 60，mm | 0.55 | 0.59 | 0.43 | 0.68 | 1.22 | 0.72 |
| Ball bearing lubricating life (160 ℃), h | 220 | 160 | 400 | 300 | 40 | 60 |
As can be seen from Table 1, lubricating grease according to the present invention, has good colloid stability, extreme pressure and antiwear behavior and ball bearing lubricating life.
Claims (17)
1. a lubricating grease, it is characterized in that, the lubricating base oil that this lubricating grease contains 40-95 % by weight, the compound zirconium base viscosifying agent of 1-59 % by weight and two polyureas of 1-59 % by weight, described compound zirconium base viscosifying agent is by higher fatty acid, aromatic acid and water, to be reacted the compound zirconium soap generating with zirconium alkoxide, wherein, 100 of described lubricating base oil ℃ of viscosity are 2-150mm
2/ s; In reaction, generate in the process of described compound zirconium base viscosifying agent, the mol ratio of the consumption of water and the consumption of described zirconium alkoxide is 1-20:1, the mol ratio of total consumption of the consumption of described zirconium alkoxide and described higher fatty acid and described aromatic acid is 1:1-1.5, and the mol ratio of the consumption of described higher fatty acid and described aromatic acid is 1:0.5-7; Described higher fatty acid is the straight chain fatty acid of C8-C24 or the hydroxy fatty acid of C8-C24; The structural formula of described aromatic acid as shown in the formula (I),
Formula (I)
Wherein, R
2, R
3, R
4, R
5and R
6be thiazolinyl, the alkynyl of C2-C5 of carboxyl substituted or the aryl of the C6-C12 of carboxyl substituted of the C2-C5 of alkyl, the carboxyl substituted of the C1-C5 of fluorinated aryl, the carboxyl substituted of fluoro-alkyl, the C6-C12 of aryl, the C1-C5 of alkynyl, the C6-C12 of thiazolinyl, the C2-C5 of alkyl, the C2-C5 of hydrogen, carboxyl, C1-C5 independently of one another.
2. lubricating grease according to claim 1, wherein, take the gross weight of described lubricating grease as benchmark, the content of described lubricating base oil is 50-90 % by weight, and the content of described compound zirconium base viscosifying agent is 2-45 % by weight, and the content of described two polyureas is 1-28 % by weight.
3. lubricating grease according to claim 1 and 2, wherein, 100 ℃ of viscosity of described lubricating base oil are 8-50mm
2/ s.
4. lubricating grease according to claim 1 and 2, wherein, described lubricating base oil is at least one in mineral oil, vegetables oil and synthetic oil.
5. lubricating grease according to claim 1, wherein, the general formula of described zirconium alkoxide is Zr (OR
1)
4, R
1for the alkyl of C1-C10.
6. lubricating grease according to claim 5, wherein, described zirconium alkoxide is at least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide, Pentyl alcohol zirconium and zirconium tert-butoxide.
7. lubricating grease according to claim 1, wherein, described higher fatty acid is selected from least one in lauric acid, oleic acid, palmitinic acid, stearic acid, 12-oxystearic acid and eicosyl carboxylic acid.
8. lubricating grease according to claim 1, wherein, described aromatic acid is at least one in phenylformic acid, phthalic acid, m-phthalic acid, terephthalic acid and biphenyl dicarboxylic acid.
9. lubricating grease according to claim 1, wherein, described two polyureas are the compound shown in formula (II),
Formula (II)
Wherein, each R
1independently selected from alkyl, cycloalkyl or aryl, R
3be selected from alkylidene group, cycloalkylidene or arylidene.
10. lubricating grease according to claim 9, wherein, each R
1independently selected from the alkyl of C8-C24, cycloalkyl or the C6-C10 aryl of C8-C24, R
3be selected from alkylidene group, the cycloalkylidene of C6-C30 or the arylidene of C6-C30 of C6-C30.
11. lubricating grease according to claim 10, wherein, each R
1the phenyl that the phenyl replacing independently selected from the alkyl of the cycloalkyl of the alkyl of C10-C18, C10-C18, phenyl, C1-C3 or halogen replace, R
3be selected from xylylene or hexylidene between methylene phenyl, methylenediphenyl, sub-dicyclohexyl methyl, Asia.
12. 1 kinds of preparation of greases methods, the method comprises: in reactor A, at 60-120 ℃, zirconium alkoxide, higher fatty acid and aromatic acid are carried out in lubricating base oil to the first contact reacts; Then, at 85-100 ℃, the mixture obtaining and water are carried out to the second contact reacts after described the first contact reacts, and by the product obtaining after described the second contact reacts dehydration that heats up; Then carry out following step (1) or (2):
(1) product of reactor A is mixed with vulcabond, then gained mixture is reacted with monoamine, and the mixture obtaining is warming up to 200-220 ℃ refines;
(2) vulcabond being dissolved in lubricating base oil is reacted with monoamine in reactor B, product merging that then will reaction gained mixture and reactor A, and the mixture obtaining is warming up to 200-220 ℃ refines;
Wherein, the mol ratio of vulcabond and monoamine is 1:(1.5-2.5); With respect to the described lubricating base oil of 100 weight parts, the consumption of described zirconium alkoxide is 10-100 weight part, the mol ratio of the consumption of water and the consumption of described zirconium alkoxide is 1-20:1, the mol ratio of total consumption of the consumption of described zirconium alkoxide and described higher fatty acid and described aromatic acid is 1:1-1.5, and the mol ratio of the consumption of described higher fatty acid and the consumption of described aromatic acid is 1:0.5-7; In step (1) and step (2), the reaction conditions of described reaction comprises: temperature of reaction is 80-140 ℃, and the reaction times is 1-20 minute.
13. methods according to claim 12, wherein, with respect to the described lubricating base oil of 100 weight parts, the consumption of described zirconium alkoxide is 20-60 weight part, the mol ratio of the consumption of water and the consumption of described zirconium alkoxide is 1.9-10:1, the mol ratio of total consumption of the consumption of described zirconium alkoxide and described higher fatty acid and described aromatic acid is 1:1.01-1.35, and the mol ratio of the consumption of described higher fatty acid and described aromatic acid is 1:1-4.
14. methods according to claim 12, wherein, the general formula of described monoamine is R
1nH
2, wherein, R
1for the alkyl of C8-C24, cycloalkyl or the C6-C10 aryl of C8-C24.
15. methods according to claim 14, wherein, described monoamine is at least one in aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, amino dodecane, tetradecy lamine, cetylamine and stearylamine.
16. methods according to claim 12, wherein, the general formula of described vulcabond is OCN-R
3-NCO, wherein, R
3for alkylidene group, the cycloalkylidene of C6-C30 or the arylidene of C6-C30 of C6-C30.
17. methods according to claim 16, wherein, described vulcabond is at least one in tolylene diisocyanate, methyldiphenyl group diisocyanate, hexamethylene vulcabond, dicyclohexyl methyl vulcabond and an xylylene vulcabond.
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| CN106147926B (en) * | 2015-04-28 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of composite polyurea lubricating grease and preparation method thereof |
| CN111100731B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
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|---|---|---|---|---|
| US4189387A (en) * | 1978-08-31 | 1980-02-19 | King James P | Lubricant compositions based on zirconium polymers |
| CN1493673A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Preparation method of polyurea-composite calcium lubricating grease |
| CN1600843A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for fabricating polyurea lithium based lubricating grease |
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2011
- 2011-10-20 CN CN201110319576.0A patent/CN103060069B/en active Active
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|---|---|---|---|---|
| US4189387A (en) * | 1978-08-31 | 1980-02-19 | King James P | Lubricant compositions based on zirconium polymers |
| CN1493673A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Preparation method of polyurea-composite calcium lubricating grease |
| CN1600843A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for fabricating polyurea lithium based lubricating grease |
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| Title |
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| EPU聚脲-醋酸钙复合润滑脂的研究及应用;宗明;《石油商技》;20040831;第22卷(第4期);第12-14页 * |
| 宗明.EPU聚脲-醋酸钙复合润滑脂的研究及应用.《石油商技》.2004,第22卷(第4期),第12-14页. |
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