CN103060070B - Lubricating grease and preparation method thereof - Google Patents

Lubricating grease and preparation method thereof Download PDF

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CN103060070B
CN103060070B CN201110319922.5A CN201110319922A CN103060070B CN 103060070 B CN103060070 B CN 103060070B CN 201110319922 A CN201110319922 A CN 201110319922A CN 103060070 B CN103060070 B CN 103060070B
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acid
zirconium
consumption
lubricating grease
lubricating
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CN103060070A (en
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何懿峰
孙洪伟
刘磊
段庆华
刘中其
姜靓
陈政
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention relates to lubricating grease, comprising 40-95 wt% of lubricating base oil, 1-59 wt% of a compound zirconium-based thickening agent and 1-59 wt% of a tetrapolyurea, wherein the compound zirconium-based thickening agent is a compound zirconium sceps formed by reacting a higher aliphatic acid, an aromatic acid and water with zirconium alkoxide. The invention also relates to a preparation method of the lubricating grease. The method comprises the steps of performing a first contact reaction on the zirconium alkoxide, the higher aliphatic acid and the aromatic acid in the lubricating base oil at a temperature of 60-120 DEG C; then performing a second reaction on the obtained mixture from the first contact reaction with water at a temperature of 85-100 DEG C; and heating the obtained product from the second reaction for dehydration; and then introducing the tetrapolyurea in the obtained reaction product. The lubricating grease has relatively high boiling point, presents excellent colloid stability and has good extreme pressure antiwear property and ball bearing lubrication life.

Description

A kind of lubricating grease and preparation method thereof
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 that the zirconates of usining is prepared zirconium base grease 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 compound zirconium base viscosifying agent of the lubricating base oil that this lubricating grease contains 40-95 % by weight, 1-59 % by weight and four 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 diamines and monoamine successively, and the mixture obtaining is warming up to 200-220 ℃ refines;
(2) vulcabond being dissolved in lubricating base oil is reacted with diamines and monoamine successively 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;
The mol ratio of the vulcabond wherein, adding successively, diamines and monoamine is (1.5-2.5): 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 four polyureas in the lubricating grease of embodiment 1 preparation;
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of four polyureas in the lubricating grease of embodiment 1 preparation;
Fig. 3 is the Electrospray Ionization Mass Spectrometry spectrogram of four polyureas in the lubricating grease of embodiment 1 preparation.
Embodiment
The invention provides a kind of lubricating grease, wherein, the compound zirconium base viscosifying agent of the lubricating base oil that this lubricating grease contains 40-95 % by weight, 1-59 % by weight and four 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, the gross weight of described lubricating grease of take is benchmark, and 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 four polyureas is 1-28 % by weight.
Lubricating grease according to the present invention, described lubricating base oil can for the conventional various lubricating base oils that use in this area, for example, can be 2-150mm for 100 ℃ of viscosity 2/ s (is preferably 2-150mm 2/ s, more preferably 8-50mm 2/ s) lubricating base oil.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),
Formula (I)
Wherein, R 2, R 3, R 4, R 5and R 6be the alkyl of hydrogen, carboxyl, C1-C5 independently of one another, the alkynyl of the thiazolinyl of C2-C5, C2-C5, the fluoro-alkyl of the aryl of C6-C12, C1-C5, the alkyl of the C1-C5 of the fluorinated aryl of C6-C12, carboxyl substituted, the thiazolinyl of the C2-C5 of carboxyl substituted, the aryl of the alkynyl of the C2-C5 of carboxyl substituted or the C6-C12 of carboxyl substituted.
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 independently of one another, the alkynyl of the thiazolinyl of C2-C5, C2-C5, the fluoro-alkyl of the aryl of C6-C12, C1-C5 or the fluorinated aryl of C6-C12.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 alkyl of C1-C5 that is carboxyl substituted, the thiazolinyl of the C2-C5 of carboxyl substituted, the aryl of the alkynyl of the C2-C5 of carboxyl substituted or 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 independently of one another, the alkynyl of the thiazolinyl of C2-C5, C2-C5, the fluoro-alkyl of the aryl of C6-C12, C1-C5 or the fluorinated aryl of C6-C12.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 independently of one another, the alkynyl of the thiazolinyl of C2-C5, C2-C5, the fluoro-alkyl of the aryl of C6-C12, C1-C5 or the fluorinated aryl of C6-C12.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 four polyureas are preferably the compound shown in formula (II),
Formula (II)
Wherein, each R 1independently selected from alkyl, cycloalkyl or aryl, R 2be selected from alkylidene group or arylidene, each R 3independently selected from alkylidene group, cycloalkylidene or arylidene.
More preferably, in formula (II), each R 1independently selected from the alkyl of C8-C24, the cycloalkyl of C8-C24 or C6-C10 aryl, R 2be selected from the alkylidene group of C2-C12 or the arylidene of C6-C14, each R 3arylidene independently selected from the alkylidene group of C6-C30, the cycloalkylidene of C6-C30 or C6-C30.
Further preferably, in formula (II), each R 1independently selected from the alkyl of C10-C18, the phenyl that the phenyl that the alkyl of the cycloalkyl of C10-C18, phenyl, C1-C3 replaces or halogen replace, R 2be selected from alkylidene group, phenylene or the biphenylene of C2-C8, each R 3independently 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 2be selected from ethylidene, propylidene, butylidene, pentylidene, hexylidene, phenylene or biphenylene, each R 3independently 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, preferred 0.2-1 % by weight, described arylamine kind antioxidant for example can, for pentanoic, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or their mixture, be 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 diamines and monoamine successively, and the mixture obtaining is warming up to 200-220 ℃ refines;
(2) vulcabond being dissolved in lubricating base oil is reacted with diamines and monoamine successively 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;
The mol ratio of the vulcabond wherein, adding successively, diamines and monoamine is (1.5-2.5): 1: (1.5-2.5).
In the preferred case, described lubricating base oil with respect to 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, described lubricating base oil with respect to 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 describe above 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 implementing described the first catalytic process, 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 the vulcabond adding successively, diamines and monoamine is preferably (1.9-2.1): 1: (1.9-2.1), most preferably be 2: 1: 2.
Method according to the present invention, in step (1) and step (2), the reaction conditions of every secondary response preferably includes respectively: 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 for the alkyl of C8-C24, the cycloalkyl of C8-C24 or C6-C10 aryl.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, the general formula of described diamines can be NH 2-R 2-NH 2, R 2for the alkylidene group of C2-C12 or the arylidene of C6-C14.Under preferable case, described diamines is quadrol, propylene diamine, 1,6-hexanediamine, Ursol D, O-Phenylene Diamine and 4, at least one in 4 '-benzidine.
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 3it can be the arylidene of the alkylidene group of C6-C30, the cycloalkylidene of C6-C30 or 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, and to form good soap structure in follow-up process of cooling, thereby obtains the lubricating grease of high comprehensive performance.The time of described refining can be 1-20 minute, is preferably 5-10 minute.In a kind of more preferably embodiment, after completing described refining process, the mixture obtaining after refining is cooled to 155-165 ℃, optionally in mixture, add 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, for pentanoic, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or their mixture, be 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 four 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, filters, by filter residue water clean to filtrate pH value be 7 o'clock, the precipitation obtaining is dried, obtain four 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 (1.08kg); Quadrol (0.12kg); 4,4 '-diphenylmethanediisocyanate (MDI, 1kg); 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 0.12kg quadrol, stir 4 minutes, under agitation add 1.08kg stearylamine, and continue to stir 4 minutes, the mol ratio of the MDI adding successively, quadrol and stearylamine is 2: 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 four 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 four polyureas, and isolated four 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 four polyureas molecules-the stretching vibration absorption peak of NH-, and 1630cm -1the peak at place is in four polyureas molecules-vibration absorption peak of CO-; As can be seen from the figure, the peak of δ=155HZ left and right is in four polyureas molecules-chemical shift of CO-; As can be seen from the figure, the mass-to-charge ratio of sample is 1100.4m/z, and the relative molecular mass of this and four polyureas matches.Therefore, by the spectral data of Fig. 1-Fig. 3, can be determined, the molecular structural formula of four 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 HVI500SN oil (100 ℃ of viscosity 11mm of 260kg 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 (1.08kg); Quadrol (0.12kg); MDI (1kg); 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, be warmed up to 110 ℃ and dewater, after finished off water, add the MDI of 1kg, and continue to stir 4 minutes, then under agitation add 0.12kg quadrol, and continue to stir 4 minutes.The stearylamine that under agitation adds 1.08kg, and continue stirring 4 minutes, the mol ratio of the MDI adding successively, quadrol and stearylamine is 2: 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 four 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 (0.88kg); Quadrol (0.14kg); MDI (1.18kg); Poly alpha olefine synthetic oil PAO 6 (50kg).
According to the method for embodiment 1, prepare lubricating grease, difference is to replace zirconium iso-propoxide by zirconium tert-butoxide, with amino dodecane, replace stearylamine, with m-phthalic acid, replace phthalic acid, with poly alpha olefine synthetic oil PAO 6, replace HVI500SN base oil to replace, 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 four 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 (1.9kg); 1,6-hexanediamine (1kg); Tolylene diisocyanate (TDI, 3.1kg); 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, to replace zirconium iso-propoxide, with 4,4 '-biphenyl dicarboxylic acid replaces phthalic acid, with para-totuidine, replace stearylamine, with 1,6-hexanediamine, replace quadrol, with TDI, replace MDI, 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 four polyureas 25.9 % by weight; Lubricating base oil 67.8 % by weight; Compound zirconium base viscosifying agent 5.9 % 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, ℃ ＞330 320 ＞330 ＞330 90 262
Drawing cone in-degree, 0.1mm 235 291 213 225 264 264
Stencil oil-dividing (100 ℃, 24h), % by weight 2.55 4.81 3.66 2.78 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 0.61 0.43 0.68 1.22 0.72
Ball bearing lubricating life (160 ℃), h 260 160 440 400 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 (21)

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 four polyureas of 1-59 % by weight, described compound zirconium base viscosifying agent is by higher fatty acid, aromatic acid and water react the compound zirconium soap generating with zirconium alkoxide, wherein, 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, 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 the alkyl of hydrogen, carboxyl, C1-C5 independently of one another, the alkynyl of the thiazolinyl of C2-C5, C2-C5, the fluoro-alkyl of the aryl of C6-C12, C1-C5, the alkyl of the C1-C5 of the fluorinated aryl of C6-C12, carboxyl substituted, the thiazolinyl of the C2-C5 of carboxyl substituted, the aryl of the alkynyl of the C2-C5 of carboxyl substituted or the C6-C12 of carboxyl substituted.
2. lubricating grease according to claim 1, wherein, the gross weight of described lubricating grease of take is benchmark, and 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 four 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 2-150mm 2/ s.
4. lubricating grease according to claim 3, wherein, 100 ℃ of viscosity of described lubricating base oil are 8-50mm 2/ s.
5. lubricating grease according to claim 3, wherein, described lubricating base oil is at least one in mineral oil, vegetables oil and synthetic oil.
6. lubricating grease according to claim 1, wherein, the general formula of described zirconium alkoxide is Zr (OR 1) 4, R 1alkyl for C1-C10.
7. lubricating grease according to claim 6, wherein, described zirconium alkoxide is at least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, Pentyl alcohol zirconium and zirconium tert-butoxide.
8. 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.
9. 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.
10. lubricating grease according to claim 1, wherein, described four polyureas are the compound shown in formula (II),
formula (II)
Wherein, each R 1independently selected from alkyl, cycloalkyl or aryl, R 2be selected from alkylidene group or arylidene, each R 3independently selected from alkylidene group, cycloalkylidene or arylidene.
11. lubricating grease according to claim 10, wherein, each R 1independently selected from the alkyl of C8-C24, the cycloalkyl of C8-C24 or C6-C10 aryl, R 2be selected from the alkylidene group of C2-C12 or the arylidene of C6-C14, each R 3arylidene independently selected from the alkylidene group of C6-C30, the cycloalkylidene of C6-C30 or C6-C30.
12. lubricating grease according to claim 10, wherein, each R 1independently selected from the alkyl of C10-C18, the phenyl that the phenyl that the alkyl of the cycloalkyl of C10-C18, phenyl, C1-C3 replaces or halogen replace, R 2be selected from alkylidene group, phenylene or the biphenylene of C2-C8, each R 3independently selected from xylylene or hexylidene between methylene phenyl, methylenediphenyl, sub-dicyclohexyl methyl, Asia.
13. 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 diamines and monoamine successively, and the mixture obtaining is warming up to 200-220 ℃ refines;
(2) vulcabond being dissolved in lubricating base oil is reacted with diamines and monoamine successively 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;
The mol ratio of the vulcabond wherein, adding successively, diamines and monoamine is (1.5-2.5): 1:(1.5-2.5); Described lubricating base oil with respect to 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.
14. methods according to claim 13, wherein, described lubricating base oil with respect to 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.
15. methods according to claim 13, wherein, the general formula of described monoamine is R 1nH 2, wherein, R 1for the alkyl of C8-C24, the cycloalkyl of C8-C24 or C6-C10 aryl.
16. methods according to claim 15, 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.
17. methods according to claim 13, wherein, the general formula of described diamines is NH 2-R 2-NH 2, R 2for the alkylidene group of C2-C12 or the arylidene of C6-C14.
18. methods according to claim 17, wherein, described diamines is quadrol, propylene diamine, 1,6-hexanediamine, Ursol D, O-Phenylene Diamine and 4, at least one in 4 '-benzidine.
19. methods according to claim 13, wherein, the general formula of described vulcabond is OCN-R 3-NCO, wherein, R 3arylidene for the alkylidene group of C6-C30, the cycloalkylidene of C6-C30 or C6-C30.
20. methods according to claim 19, wherein, described vulcabond is at least one in tolylene diisocyanate, methyldiphenyl group diisocyanate, hexamethylene vulcabond, dicyclohexyl methyl vulcabond and an xylylene vulcabond.
21. methods according to claim 13, wherein, in step (1) and step (2), the reaction conditions of every secondary response comprises respectively: temperature of reaction is 80-140 ℃, the reaction times is 1-20 minute.
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CN104513687B (en) * 2013-09-30 2017-06-30 中国石油化工股份有限公司 A kind of polyurea grease of calcium zirconium base four and preparation method thereof
CN104560324B (en) * 2013-10-29 2017-11-03 中国石油化工股份有限公司 A kind of polyurea grease of composite calcium naphthenate calcium zirconium base four and preparation method thereof
CN104560322B (en) * 2013-10-29 2017-11-03 中国石油化工股份有限公司 A kind of polyurea grease of calcium naphthenate zirconium base four and preparation method thereof
CN104560270B (en) * 2013-10-29 2017-11-03 中国石油化工股份有限公司 A kind of polyurea grease of complex calcium sulfonate calcium naphthenate zirconium base four and preparation method thereof
CN104560316B (en) * 2013-10-29 2017-11-03 中国石油化工股份有限公司 A kind of polyurea grease of sulfoacid calcium calcium naphthenate zirconium base four and preparation method thereof
CN104560268B (en) * 2013-10-29 2017-11-03 中国石油化工股份有限公司 A kind of composite calcium naphthenate calcium zirconium base lubricating grease and preparation method thereof
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
CN109825358A (en) * 2019-03-25 2019-05-31 常熟理工学院 A kind of four polyurea grease of compound lithium base and preparation method thereof

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