CN103289786B - Composite calcium-base octa-polyurea lubricating grease and preparation method thereof - Google Patents
Composite calcium-base octa-polyurea lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite calcium-base octa-polyurea lubricating grease which contains lubricating base oil, octa-polyurea and composite calcium soap, wherein the composite calcium soap is a mixture of higher fatty acid calcium and aromatic acid calcium. The invention also relates to a preparation method of the composite calcium-base octa-polyurea lubricating grease, which comprises the following steps: (1) in the presence of the lubricating base oil, carrying out contact reaction on diisocyanate, diamine and monoamine in a mol ratio of (3.9-4.1):(2.9-3.1):2, and heating the reaction mixture for refinement; (2) in the presence of the lubricating base oil, carrying out contact reaction on the calcium hydroxide, higher fatty acid and aromatic acid, and heating to dehydrate the reaction mixture; and (3) mixing the product obtained in the step (1) with the product obtained in the step (2). The composite calcium-base octa-polyurea lubricating grease provided by the invention has excellent comprehensive properties.
Description
Technical field
The present invention relates to a kind of composite calcium-base eight polyurea grease, and this preparation of greases method.
Background technology
Polyurea grease (abbreviation polyurea grease) is the lubricating grease prepared by the organic compound multiviscosisty base oil containing urea groups in molecule.Because polyurea thickening agent is different from metal soap base viscosifying agent, not metal ion, to avoid in soap base viscosifying agent metal ion to the catalysed oxidn of grease base oil, therefore polyurea grease has good oxidation stability and thermostability, makes polyurea grease be more suitable for the lubrication of hot conditions.
At present, the report of article and patent mainly concentrates on preparation and the synthesis aspect of two polyurea greases, and two polyurea grease shear stabilities are poor, works 100,000 times and work 60 cone penetration differences all more than 80 units.Little to the report of eight polyurea greases.The salient features such as dropping point, extreme pressure property, colloid stability, oxidation stability of eight polyurea greases increases than existing two polyurea greases.Therefore there is more excellent PERFORMANCE OF GREASES, and can be widely used.But, because the shear stability of eight polyurea greases is not good, thus limit its application under the working condition of high temperature, high speed and heavy loading.
Complex calcium lubricating grease is the high dropping point grease developed the earliest, a kind of heatproof, withstand voltage, broad-spectrum excellent lubricating grease, there is good mechanical stability, colloid stability and anti-water drenching energy, but sclerosis problem is its widely used lethal factor of restriction, improve the main contents that sclerosis problem is complex calcium lubricating grease research always.
In order to solve the sclerosis problem that complex calcium lubricating grease exists, those skilled in the art attempt to introduce polyurea grease in complex calcium lubricating grease, such as, US5084193 discloses lubricating grease containing polyureas and calcium complex soap and preparation method thereof, the method comprises: first prepare polyurea grease and prepare composite calcium-base fat again, but after preparing polyurea grease, reactor temperature can up to 89-90 DEG C, follow-uply there will be phenomenon of seriously volatilizing when adding short chain acids again, and the over-all properties of the complex calcium lubricating grease prepared according to the method is not good, remains to be further improved.CN1364859A and CN1657599A individually discloses calcium base polyurea grease, but the polyureas that they use is all two polyureas, and their shear stability does not still improve.
Summary of the invention
The object of the invention is the above-mentioned defect existed to overcome existing lubricating grease, providing a kind of new composite calcium-base eight polyurea grease and preparation method thereof.
The invention provides a kind of composite calcium-base eight polyurea grease, wherein, this lubricating grease contains lubricating base oil, eight polyureas and calcium complex soap, and described calcium complex soap is the mixture of higher fatty acid calcium and aromatic acid calcium.
Present invention also offers a kind of preparation method of composite calcium-base eight polyurea grease, the method comprises the following steps:
(1) under the existence of lubricating base oil, by vulcabond, diamines and monoamine contact reacts, heat up the mixture obtained after reaction refining, and wherein, the mol ratio of vulcabond, diamines and monoamine is (3.9-4.1): (2.9-3.1): 2;
(2) under the existence of lubricating base oil, by calcium hydroxide and higher fatty acid and aromatic acid contact reacts, the mixture obtained is carried out intensifications dewater after reaction;
(3) the product mixing that product step (1) obtained and step (2) obtain.
Composite calcium-base eight polyurea grease according to the present invention has excellent over-all properties.Concrete, in described composite calcium-base eight polyurea grease of the present invention, by introducing eight polyureas, overcome the problem of the sclerosis that traditional complex calcium lubricating grease exists; By introducing the mixture of higher fatty acid calcium and aromatic acid calcium, overcome the defect that the over-all properties of traditional polyurea grease existence is bad.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the infrared analysis spectrogram of eight polyureas in the lubricating grease of embodiment 1 preparation;
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of eight polyureas in the lubricating grease of embodiment 1 preparation;
Fig. 3 is the Electrospray Ionization Mass Spectrometry spectrogram of eight polyureas in the lubricating grease of embodiment 1 preparation.
Embodiment
The invention provides a kind of composite calcium-base eight polyurea grease, this lubricating grease contains lubricating base oil, eight polyureas and calcium complex soap, and described calcium complex soap is the mixture of higher fatty acid calcium and aromatic acid calcium.
Main improvements of the present invention are, the mixture of higher fatty acid calcium and aromatic acid calcium is used to replace conventional calcium complex soap, as the composite calcium-base viscosifying agent of lubricating grease, to overcome the not good defect of over-all properties that conventional complex calcium lubricating grease exists, and the respective kind of described lubricating base oil, described eight polyureas and described calcium complex soap and content range all can be same or similar with the composite calcium-base polyurea grease of routine.
Under preferable case, relative to the described lubricating base oil of 100 weight parts, the content of described eight polyureas is 0.5-22 weight part, is more preferably 3-15 weight part; The content of described calcium complex soap is 2.2-36 weight part, is more preferably 5-25 weight part.
In described calcium complex soap, the ratio of described higher fatty acid calcium and described aromatic acid calcium can change in very wide scope.Under preferable case, in order to improve the over-all properties of described lubricating grease further, the mol ratio of described higher fatty acid calcium and described aromatic acid calcium is 1: 0.1-10, is more preferably 1: 0.2-5.
Described calcium complex soap can obtain according to the method for routine, such as, described calcium complex soap can be prepared by calcium hydroxide and higher fatty acid and aromatic acid being reacted, and also namely described calcium complex soap can be the saponification reaction product of calcium hydroxide and higher fatty acid and aromatic acid.Preferably, the mol ratio of the consumption of described higher fatty acid and described aromatic acid is 1: 0.1-10, is more preferably 1: 0.2-5.More preferably, the ratio of the integral molar quantity of the integral molar quantity of calcium hydroxide and the carboxyl in described higher fatty acid and the carboxyl in aromatic acid is 0.4-0.6: 1, is more preferably 0.5-0.55: 1, most preferably is 0.5: 1.
In the preferred case, in order to improve the over-all properties of described composite calcium-base eight polyurea grease further, particularly mechanical stability, colloid stability and anti-water drenching energy, the aromatic acid calcium in described calcium complex soap is preferably the mixture of unitary aromatic acid calcium and binary aromatic acid calcium.Further preferably, in the mixture of unitary aromatic acid calcium and binary aromatic acid calcium, the mol ratio of described unitary aromatic acid calcium and described binary aromatic acid calcium is 0.1-2: 1, is more preferably 0.2-0.8: 1.Under this preferable case, described calcium complex soap can be prepared by calcium hydroxide and higher fatty acid, unitary aromatic acid and binary aromatic acid being reacted, and also namely described calcium complex soap can be the saponification reaction product of calcium hydroxide and higher fatty acid, unitary aromatic acid and binary aromatic acid.
Described higher fatty acid can this area routine use higher fatty acid, can be such as the straight chain fatty acid of C12-C24 or the hydroxy fatty acid of C12-C24.Preferably, described higher fatty acid is be selected from least one in lauric acid, oleic acid, palmitinic acid, stearic acid, 12-oxystearic acid and eicosyl carboxylic acid.
The structural formula of described unitary aromatic acid preferably such as formula shown in (I),
Wherein, R
2, R
3, R
4, R
5and R
6be the fluorinated aryl of hydrogen, the alkyl of C1-C5, the thiazolinyl of C2-C5, the alkynyl of C2-C5, the aryl of C6-C12, the fluoro-alkyl of C1-C5 or C6-C12 independently of one another.
Under preferable case, R
2, R
3, R
4, R
5and R
6be the alkyl of hydrogen or C1-C5 independently of one another.
More preferably, R
2, R
3, R
4, R
5and R
6be the alkyl of hydrogen or C1-C2 independently of one another.
Most preferably, described unitary aromatic acid is at least one in phenylformic acid, p-methylbenzoic acid, o-toluic acid and m-methyl benzoic acid.
The structural formula of described binary aromatic acid preferably such as formula shown in (II),
Wherein, R
7, R
8, R
9, R
10and R
11in one be carboxyl, the alkyl of C1-C5 of carboxyl substituted or the aryl of the C6-C12 of carboxyl substituted, R
7, R
8, R
9, R
10and R
11in other four be the fluorinated aryl of hydrogen, the alkyl of C1-C5, the thiazolinyl of C2-C5, the alkynyl of C2-C5, the aryl of C6-C12, the fluoro-alkyl of C1-C5 or C6-C12 independently of one another.
Under preferable case, R
7, R
8, R
9, R
10and R
11in one be the phenyl of carboxyl, carboxymethyl or carboxyl substituted, R
7, R
8, R
9, R
10and R
11in other four be the alkyl of hydrogen or C1-C2 independently of one another.
Still more preferably, described binary aromatic acid is at least one in phthalic acid, m-phthalic acid, terephthalic acid and biphenyl dicarboxylic acid (as 4,4 '-biphenyl dicarboxylic acid).
Most preferably, described binary aromatic acid is terephthalic acid and/or 4,4 '-biphenyl dicarboxylic acid.
Described eight polyureas can various eight polyureas that use of this area routine, such as can for such as formula the compound shown in (III),
Wherein, each R
1independently selected from alkyl, cycloalkyl or aryl, each R
2independently selected from alkylidene group or arylidene, each R
3independently selected from alkylidene group, cycloalkylidene or arylidene.
More preferably, in formula (III), each R
1independently selected from the alkyl of C8-C24, the cycloalkyl of C8-C24 or C6-C10 aryl, each R
2independently selected from the alkylidene group of C2-C12 or the arylidene of C6-C14, each R
3independently selected from the arylidene of the alkylidene group of C6-C30, the cycloalkylidene of C6-C30 or C6-C30.In the present invention, the alkyl of described C8-C24 can be substituted or unsubstituted alkyl, and substituting group can be halogen, such as Cl, Br usually; The cycloalkyl of described C8-C24 can be substituted or unsubstituted cycloalkyl, and substituting group can be halogen, such as Cl, Br usually; Described C6-C10 aryl can be substituted or unsubstituted aryl, and substituting group can be the alkyl of halogen (such as Cl, Br), C1-C5 usually.
Further preferably, in formula (III), each R
1the phenyl that the phenyl replaced independently selected from the alkyl of the cycloalkyl of the alkyl of C10-C18, C10-C18, phenyl, C1-C3 or halogen (such as Cl, Br) replace, each R
2independently selected from the alkylidene group of C2-C8, phenylene or biphenylene, each R
3independently selected from xylylene or hexylidene between xylene, methylenediphenyl, sub-dicyclohexylmethyl, Asia.
Still more preferably, in formula (III), each R
1independently selected from dodecyl, tetradecyl, hexadecyl, octadecyl, phenyl, tolyl or chlorophenyl, each R
2independently selected from ethylidene, propylidene, butylidene, pentylidene, hexylidene, phenylene or biphenylene, each R
3independently selected from xylylene or hexylidene between xylene, methylenediphenyl, sub-dicyclohexylmethyl, Asia.
Described lubricating base oil can be the various lubricating base oils that this area routine uses, such as, can be 100 DEG C of viscosity be 2-150mm
2/ s (is preferably 2-100mm
2/ s, is more preferably 8-50mm
2/ s) lubricating base oil.Concrete, described lubricating base oil can be such as at least one in mineral oil, vegetables oil and synthetic oil.Described synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Other various additives that composite calcium-base eight polyurea grease according to the present invention can also use containing this area routine, described additive can be such as at least one in extreme pressure anti-wear additives, oxidation inhibitor and rust-preventive agent.Relative to the described lubricating base oil of 100 weight parts, described additive level can be 0.1-15 weight part, is preferably 0.5-10 weight part.
Described extreme pressure anti-wear additives can be such as at least one in dithio Acidic phosphates zinc, dithio dialkyl amido zinc formate, 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.
Described oxidation inhibitor is preferably arylamine kind antioxidant, and described arylamine kind antioxidant can be such as at least one in the amino p-cresol of pentanoic, di-iso-octyldiphenylamine, phenyl-a-naphthylamine, 2,6 ditertiary butyl p cresol and 2,6-di-t-butyl-alpha, alpha-dimethyl.
Described rust-preventive agent can be such as at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Present invention also offers a kind of preparation method of composite calcium-base eight polyurea grease, the method comprises the following steps:
(1) under the existence of lubricating base oil, by vulcabond, diamines and monoamine contact reacts, heat up the mixture obtained after reaction refining, and wherein, the mol ratio of vulcabond, diamines and monoamine is (3.9-4.1): (2.9-3.1): 2;
(2) under the existence of lubricating base oil, by calcium hydroxide and higher fatty acid and aromatic acid contact reacts, the mixture obtained is carried out intensifications dewater after reaction;
(3) the product mixing that product step (1) obtained and step (2) obtain.
Method according to the present invention, implement in the reactor that step (1) is different with step (2) each leisure, by preparing eight polyurea greases and complex calcium lubricating grease respectively, then both eight polyurea greases and complex calcium lubricating grease are mixed, heat remaining in the preparation process of eight polyureas can not be had an impact to the preparation process of calcium complex soap, thus avoid in the preparation process of conventional composite calcium-base polyurea grease the problem easily causing the strong volatilization of small molecules acid.
Step (1) can the preparation method of eight polyurea greases conveniently be implemented.
In step (1), there is no particular limitation for the catalytic condition of vulcabond, diamines and monoamine, and such as, described catalytic condition can comprise: temperature of reaction is 60-120 DEG C, and the reaction times is 5-60 minute.
In step (1), the condition of described refining can comprise: temperature is 200-220 DEG C, and the time is 1-30 minute.
Under preferable case, the mol ratio of vulcabond, diamines and monoamine is 4: 3: 2.
The general formula of described monoamine can be R
1nH
2, wherein, R
1can be the alkyl of C8-C24, the cycloalkyl of C8-C24 or C6-C10 aryl.The alkyl of described C8-C24 can be substituted or unsubstituted alkyl, and substituting group can be halogen, such as Cl, Br usually; The cycloalkyl of described C8-C24 can be substituted or unsubstituted cycloalkyl, and substituting group can be halogen, such as Cl, Br usually; Described C6-C10 aryl can be substituted or unsubstituted aryl, and substituting group can be the alkyl of halogen (such as Cl, Br), C1-C5 usually.Under preferable case, R
1the phenyl that the phenyl replaced for the alkyl of the cycloalkyl of the alkyl of C10-C18, C10-C18, phenyl, C1-C3 or halogen (such as Cl, Br) replace.Preferred, described monoamine is at least one in aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, amino dodecane, tetradecy lamine, cetylamine and stearylamine.
The general formula of described diamines can be NH
2-R
2-NH
2, wherein, R
2for the alkylidene group of C2-C12 or the arylidene of C6-C14, be preferably the alkylidene group of C2-C8, phenylene or biphenylene.Preferred, described diamines is quadrol, propylene diamine, 1,6-hexanediamine, Ursol D, O-Phenylene Diamine and 4, at least one in 4 '-benzidine.
Described vulcabond can 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 the arylidene of the alkylidene group of C6-C30, the cycloalkylidene of C6-C30 or C6-C30, be preferably xylylene or hexylidene between xylene, methylenediphenyl, sub-dicyclohexylmethyl, Asia.Preferred, described vulcabond is at least one in tolylene diisocyanate, methylenediphenyl diisocyanates, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
In a preferred embodiment, the specific operation process of step (1) comprising:
(1-1) lubricating base oil mixed with vulcabond and be heated to 50-60 DEG C, then adding a part of diamines, be warming up to 75-90 DEG C, reaction 20-30 minute, and then adding another part diamines, and continuing reaction 20-30 minute;
(1-2) monoamine is mixed with lubricating base oil, be heated to 50-60 DEG C, then add in the mixture that step (1-1) obtains, mix rear continuation and keep reaction 20-30 minute;
(1-3) mixture that step (1-2) obtains is warming up to 200-220 DEG C of refining 5-10 minute, is then cooled to 150-160 DEG C, then optionally adds lubricating base oil and carry out chilling, to be cooled to 100-120 DEG C, then grind.
Above-mentioned preferred embodiment in, in step (1-1), the amount of diamines that first time adds can account for the 50-80 % by mole of the total consumption of diamines, and the amount of the diamines that second time adds can account for the 20-50 % by mole of the total consumption of diamines.Most preferably, the amount of the diamines that first time adds accounts for 2/3 of the total mole dosage of diamines, and the amount that second time adds accounts for 1/3 of the total mole dosage of diamines.
In above-mentioned preferred implementation, the amount of the lubricating base oil used separately in step (1-1) and step (1-2) can account for the 20-60 % by weight of the lubricating base oil gross weight used in step (1), is preferably 25-50 % by weight; The amount of the lubricating base oil used in step (1-3) can account for the 0-40 % by weight of the lubricating base oil gross weight used in step (1), is preferably 10-35 % by weight.And the lubricating base oil used separately in step (1-1), step (1-2) and step (1-3) can be identical or different.
Method according to the present invention, in step (2), described aromatic acid is preferably the mixture of unitary aromatic acid and binary aromatic acid.More preferably, the mol ratio of described unitary aromatic acid and described binary aromatic acid is 0.1-2: 1, more preferably 0.2-0.8: 1.
In step (2), calcium hydroxide can comprise with higher fatty acid and the catalytic condition of aromatic acid: temperature of reaction is 40-90 DEG C, and the reaction times is 20-120 minute.
Under preferable case, the mol ratio of the consumption of described higher fatty acid and described aromatic acid is 1: 0.1-10, is more preferably 1: 0.2-5.
Under preferable case, the ratio of the integral molar quantity of the integral molar quantity of calcium hydroxide and the carboxyl in described higher fatty acid and the carboxyl in aromatic acid can be 0.4-0.6: 1, is preferably 0.5-0.55: 1, most preferably is 0.5: 1.
Described higher fatty acid, described unitary aromatic acid and described binary aromatic acid all with describe above identical.
In a preferred embodiment, the specific operation process of step (2) can comprise:
(2-1a) by the aqueous solution of lubricating base oil and calcium hydroxide, add aromatic acid (mixture as unitary aromatic acid and binary aromatic acid), reaction 10-15 minute, be warming up to 80-90 DEG C, add higher fatty acid, be uniformly mixed 20-30 minute, be warming up to 105-110 DEG C and dewater, be then warming up to 200-220 DEG C and insulation refining 1-30 minute;
(2-2a) mixture obtained in step (2-1a) is mixed with lubricating base oil, obtain the lubricating grease that temperature is 100-120 DEG C, and by this lubricating grease three-roll grinder grinding 1-3 time.
Wherein, the amount of the lubricating base oil used in step (2-1a) can account for the 50-80 % by weight of the lubricating base oil gross weight used in step (2); The amount of the lubricating base oil used in step (2-2a) can account for the 20-50 % by weight of the lubricating base oil gross weight used in step (2).
In another kind of preferred implementation, the specific operation process of step (2) can comprise:
(2-1b) lubricating base oil and higher fatty acid and aromatic acid (mixture as unitary aromatic acid and binary aromatic acid) are mixed, be warming up to 80-90 DEG C, add calcium hydroxide aqueous solution, be uniformly mixed 40-60 minute, be warming up to 105-110 DEG C to dewater, be then warming up to 200-220 DEG C and insulation refining 1-30 minute;
(2-2b) mixture obtained in step (2-1a) is mixed with lubricating base oil, obtain the lubricating grease that temperature is 100-120 DEG C, and by this lubricating grease three-roll grinder grinding 1-3 time.
Wherein, the amount of the lubricating base oil used in step (2-1b) can account for the 50-80 % by weight of the lubricating base oil gross weight used in step (2); The amount of the lubricating base oil used in step (2-2b) can account for the 20-50 % by weight of the lubricating base oil gross weight used in step (2).
Method according to the present invention, relative to total consumption of the described lubricating base oil of 100 weight parts, total consumption of vulcabond, diamines and monoamine in step (2) can be 0.5-22 weight part, is preferably 3-15 weight part; Total consumption of calcium hydroxide, higher fatty acid and aromatic acid in step (2) is 2.2-36 weight part, is preferably 5-25 weight part.And the consumption of lubricating base oil can account for the 30-70 % by weight of total consumption of lubricating base oil in whole preparation process in step (1); In step (2), the consumption of lubricating base oil can account for the 30-70 % by weight of total consumption of grease base oil in whole preparation process.In addition, step (3) also can add a certain amount of lubricating base oil, to adjust the correlated performance of the lubricating grease of final preparation, in step (3), the add-on of lubricating base oil can account for the 0-30 % by weight of total consumption of grease base oil in whole preparation process.Described lubricating base oil is identical with above-described.
The preparation method of composite calcium-base eight polyurea grease according to the present invention can also be included at least one step in step (1)-step (3) other the various additives adding this area routine and use, and described additive can be such as at least one in extreme pressure anti-wear additives, oxidation inhibitor and rust-preventive agent.Relative to total consumption of the described lubricating base oil of 100 weight parts, total consumption of described extreme pressure anti-wear additives, oxidation inhibitor and rust-preventive agent can be 0.1-15 % by weight, is preferably 0.5-10 weight part.Described extreme pressure anti-wear additives, oxidation inhibitor and rust-preventive agent are all identical with above-described separately.
The invention will be further described by the following examples.
The separation method of eight polyureas: first by lubricating grease sherwood oil (boiling point 60-90 DEG C) washing, filtration is precipitated, and the dilute acetic acid solution precipitated with 5 % by weight is soaked 5-10 minute and stirred, filters, filter residue use water cleans, then uses the NaHCO of 1 % by weight
3solution soaking, filters, and when being 7 by the cleaning of filter residue water to filtrate pH value, the precipitation obtained being carried out drying, obtains eight polyureas.
Embodiment 1
The present embodiment is for illustration of described composite calcium-base eight polyurea grease provided by the invention and preparation method thereof.
(1) eight polyurea greases are prepared
Feed composition: (100 DEG C of viscosity are 11mm to HVI500SN base oil
2/ s, purchased from Exxon Mobil chemical company): 435g; Stearylamine (purchased from ACROS company): 20.39g; Quadrol: 6.81g; 4,4 '-diphenylmethanediisocyanate (purchased from ACROS company, MDI): 37.80g;
First by the HVI500SN base oil of 150g and 37.8g MDI Hybrid Heating to 50 DEG C, then add the quadrol of 4.54g, and be warming up to 80 DEG C, after reacting 30 minutes, then add the quadrol of 2.27g, and continue reaction 30 minutes, obtain mixture A1; 150g HVI500SN base oil is mixed with 20.39g stearylamine, be heated to 60 DEG C, and add in mixture A1, be warming up to 80 DEG C of reactions 30 minutes, be then warming up to 210 DEG C and keep 10 minutes, naturally cool to 150 DEG C afterwards, add 115g HVI500SN base oil, be cooled to 110 DEG C, and grind 2 times with three-roll grinder, obtain eight polyurea greases.
(2) complex calcium lubricating grease is prepared
Feed composition: (purchased from Exxon Mobil chemical company, 100 DEG C of viscosity are 11mm to HVI500SN base oil
2/ s): 427g; Terephthalic acid: 29.05g; Phenylformic acid: 10.68g; Ca (OH)
2: 19.11g; 12-oxystearic acid (purchased from prestige Ninghua, Tongliao City work limited liability company): 23.7g;
In 280g HVI500SN base oil, add the lime milk solution containing 19.11g calcium hydroxide, add 29.05g terephthalic acid and 10.68g phenylformic acid, react 10 minutes, be warming up to 80 DEG C, add 23.7g 12-oxystearic acid, be uniformly mixed 30 minutes, be warming up to 105 DEG C, after finished off water, be warming up to 210 DEG C, keep 10 minutes, add 147g HVI500SN base oil, be cooled to 120 DEG C, then grind 2 times with three-roll grinder, obtain complex calcium lubricating grease.
(3) composite calcium-base eight polyurea grease is prepared
Eight polyurea greases obtained above getting and each 200g mixing of complex calcium lubricating grease, 400g altogether, and add 3g tungsten disulfide, 5g Selenium Sulfide, 5g fluorographite, 3g di-iso-octyldiphenylamine and 5g zinc naphthenate, after using mixing machine to mix 5 minutes, carry out circulating filtration, homogenizing, degassed successively, obtain composite calcium-base eight polyurea grease.
Can calculate according to material and learn, the composition of the lubricating grease of so preparation as: lubricating base oil accounts for 81.9 % by weight, and eight polyureas account for 6.2 % by weight, and calcium complex soap accounts for 6.9 % by weight, and other additives account for 5.0 % by weight.
From described composite calcium-base eight polyurea grease, isolate eight polyureas, and isolated eight polyureas are carried out infrared analysis, nuclear magnetic resonance spectroscopy and Electrospray Ionization Mass Spectrometry respectively, obtain spectrogram as shown in Figure 1-Figure 3.As can be seen from Figure 1,3310cm
-1~ 3323cm
-1the peak at place is the stretching vibration absorption peak of-NH-in eight polyureas molecules, 1630cm
-1the peak at place is the vibration absorption peak of-CO-in eight polyureas molecules; As can be seen from Figure 2, the peak of about δ=155HZ is the chemical shift of-CO-in eight polyureas molecules; As can be seen from Figure 3, the mass-to-charge ratio of sample is 1721.4m/z, and the relative molecular mass of this and eight polyureas matches.Therefore, can be determined by the spectral data of Fig. 1-Fig. 3, the molecular structural formula of eight polyureas in this composite calcium-base eight polyurea grease is as follows.
Comparative example 1
Composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, difference is, prepare in the process of complex calcium lubricating grease in step (2), replace terephthalic acid and benzoic mixture with the acetic acid of 26.3g, thus obtained composite calcium-base eight polyurea grease.
Comparative example 2
Prepare composite calcium-base polyurea grease according to the method for embodiment 1, difference is, in the process preparing polyurea grease, do not add quadrol, thus obtained composite calcium-base two polyurea grease.
Embodiment 2
The present embodiment is for illustration of described composite calcium-base eight polyurea grease provided by the invention and preparation method thereof.
Composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, difference is, prepare in the process of complex calcium lubricating grease in step (2), replace terephthalic acid with the phenylformic acid of 2 times of molar weights, thus obtained composite calcium-base eight polyurea grease.
Embodiment 3
The present embodiment is for illustration of described composite calcium-base eight polyurea grease provided by the invention and preparation method thereof.
Composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, difference is, prepare in the process of complex calcium lubricating grease in step (2), replace terephthalic acid with the m-phthalic acid of same molar, thus obtained composite calcium-base eight polyurea grease.
Embodiment 4
The present embodiment is for illustration of described composite calcium-base eight polyurea grease provided by the invention and preparation method thereof.
Composite calcium-base eight polyurea grease is prepared according to the method for embodiment 1, difference is, other additives are not added in step (3), as tungsten disulfide, Selenium Sulfide, fluorographite, di-iso-octyldiphenylamine and zinc naphthenate, thus obtained composite calcium-base eight polyurea grease.
Embodiment 5
The present embodiment is for illustration of described composite calcium-base eight polyurea grease provided by the invention and preparation method thereof.
(1) eight polyurea greases are prepared
Feed composition: (purchased from China National Offshore Oil Corporation (CNOOC), 100 DEG C of viscosity are 12mm to naphthene base crude oil
2/s): 469.5g; Amino dodecane (purchased from ACROS company): 8.0g; 1,6-hexanediamine (purchased from ACROS company): 7.5g; Tolylene diisocyanate (purchased from ACROS company, TDI): 15.0g;
First by the naphthene base crude oil of 150g and 15.0g TDI Hybrid Heating to 50 DEG C, then add 1, the 6-hexanediamine of 5.0g, and be warming up to 80 DEG C, after reacting 30 minutes, then add 1, the 6-hexanediamine of 2.5g, and continue reaction 30 minutes, obtain mixture B1; 150g naphthene base crude oil is mixed with 8.0g amino dodecane, be heated to 60 DEG C, and add in mixture B1, be warming up to 80 DEG C of reactions 30 minutes, be then warming up to 210 DEG C and keep 10 minutes, naturally cool to 150 DEG C afterwards, add 169.5g naphthene base crude oil, be cooled to 110 DEG C, and grind 2 times with three-roll grinder, obtain eight polyurea greases.
(2) complex calcium lubricating grease is prepared
Feed composition: (purchased from China National Offshore Oil Corporation (CNOOC), 100 DEG C of viscosity are 12mm to naphthene base crude oil
2/ s): 341g; 4,4 '-biphenyl dicarboxylic acid: 96.80g; P-methylbenzoic acid: 12.24g; Ca (OH)
2: 36.63g; Eicosyl carboxylic acid (purchased from ACROS company): 31.25g;
In 241g naphthene base crude oil, add the lime milk solution containing 36.63g calcium hydroxide, add 96.80g4,4 '-biphenyl dicarboxylic acid and 12.24g p-methylbenzoic acid, react 10 minutes, be warming up to 80 DEG C, add 31.25g eicosyl carboxylic acid, be uniformly mixed 30 minutes, be warming up to 105 DEG C, after finished off water, be warming up to 210 DEG C, keep 10 minutes, add 100g naphthene base crude oil, be cooled to 120 DEG C, then grind 2 times with three-roll grinder, obtain complex calcium lubricating grease.
(3) composite calcium-base eight polyurea grease is prepared
Eight polyurea greases obtained above getting and each 200g mixing of complex calcium lubricating grease, 400g altogether, and add 1g tungsten disulfide, 1g Selenium Sulfide, 1g calcium carbonate, 1g di-iso-octyldiphenylamine and 1g barium mahogany sulfonate, after using mixing machine to mix 5 minutes, carry out circulating filtration, homogenizing, degassed successively, obtain composite calcium-base eight polyurea grease.
Can calculate according to material and learn, the composition of the lubricating grease of so preparation as: lubricating base oil accounts for 80.1 % by weight, and eight polyureas account for 3.0 % by weight, and calcium complex soap accounts for 15.7 % by weight, and other additives account for 1.2 % by weight.
Embodiment 6
The present embodiment is for illustration of described composite calcium-base eight polyurea grease provided by the invention and preparation method thereof.
(1) eight polyurea greases are prepared
Feed composition: (purchased from Exxon Mobil chemical company, 100 DEG C of kinematic viscosity are 10mm to poly alpha olefine synthetic oil PAO 10
2/ s): 355.5g; Para-totuidine (purchased from ACROS company): 21.50g; 4,4 '-benzidine (purchased from ACROS company): 55.47g; Hexamethylene diisocyanate (purchased from ACROS company, HMDI): 67.53g;
First by the poly alpha olefine synthetic oil PAO 10 of 100g with 67.53g HMDI Hybrid Heating to 50 DEG C, then add 4 of 36.98g, 4 '-benzidine, and be warming up to 80 DEG C, after reacting 30 minutes, then add 4 of 18.49g, 4 '-benzidine, and continue reaction 30 minutes, obtain mixture C 1; 100g poly alpha olefine synthetic oil PAO 10 is mixed with 21.50g para-totuidine, be heated to 60 DEG C, and add in mixture C 1, be warming up to 80 DEG C of reactions 30 minutes, be then warming up to 210 DEG C and keep 10 minutes, naturally cool to 150 DEG C afterwards, add 155.5g poly alpha olefine synthetic oil PAO 10, be cooled to 110 DEG C, and grind 2 times with three-roll grinder, obtain eight polyurea greases.
(2) complex calcium lubricating grease is prepared
Feed composition: (purchased from Exxon Mobil chemical company, 100 DEG C of kinematic viscosity are 10mm to poly alpha olefine synthetic oil PAO 10
2/ s): 463g; 4,4 '-biphenyl dicarboxylic acid: 4.11g; M-methyl benzoic acid: 1.77g; Ca (OH)
2: 6.92g; Lauric acid (purchased from ACROS company): 28g;
In 280g poly alpha olefine synthetic oil PAO 10, add the lime milk solution containing 6.92g calcium hydroxide, add 4.11g 4,4 '-biphenyl dicarboxylic acid and 1.77g m-methyl benzoic acid, react 10 minutes, be warming up to 80 DEG C, add 28g lauric acid, be uniformly mixed 30 minutes, be warming up to 105 DEG C, after finished off water, be warming up to 210 DEG C, keep 10 minutes, add 183g poly alpha olefine synthetic oil PAO 10, be cooled to 120 DEG C, then grind 2 times with three-roll grinder, obtain complex calcium lubricating grease.
(3) composite calcium-base eight polyurea grease is prepared
Eight polyurea greases obtained above getting and each 200g mixing of complex calcium lubricating grease, 400g altogether, and add 1g tungsten disulfide, 1g Selenium Sulfide, 1g calcium carbonate, 1g di-iso-octyldiphenylamine and 1g barium mahogany sulfonate, after using mixing machine to mix 5 minutes, carry out circulating filtration, homogenizing, degassed successively, obtain composite calcium-base eight polyurea grease.
Can calculate according to material and learn, the composition of the lubricating grease of so preparation as: lubricating base oil accounts for 80.8 % by weight, and eight polyureas account for 14.3 % by weight, and calcium complex soap accounts for 3.7 % by weight, and other additives account for 1.2 % by weight.
Test case
(1) dropping point of various different lubricating grease is detected according to the method for GB/T 3498-2008;
(2) detect the Drawing cone in-degree of various different lubricating grease according to the method for GB/T 269-1991 and extend Drawing cone in-degree;
(3) the copper corrosion performance of various different lubricating grease is detected according to the method for GB/T 7326-1987;
(4) Stencil oil-dividing of various different lubricating grease is detected according to the method for SH/T 0324-1992;
(5) the water pouring number of dropouts of various different lubricating grease is detected according to the method for SH/T 0109-2004;
(6) P of various different lubricating grease is detected according to the method for SH/T 0202-1992
b, P
dand wear scar diameter;
(7) respectively hardening test is carried out to various different lubricating grease according to the method for SH/T 0370-1995, to detect their resistance hardening energy;
Above-mentioned detected result is as shown in table 1 below.
Table 1
As can be seen from the data of table 1, composite calcium-base eight polyurea grease according to the present invention overcomes the problem of the sclerosis that conventional complex calcium lubricating grease exists, and properties is all better, shows excellent over-all properties.Particularly, the Drawing cone in-degree difference of described composite calcium-base eight polyurea grease of the present invention, front and back cone penetration difference of hardening, Stencil oil-dividing and water pouring number of dropouts are all obviously less, thus show excellent mechanical stability, colloid stability and anti-water drenching energy.
Claims (33)
1. composite calcium-base eight polyurea grease, is characterized in that, this lubricating grease contains lubricating base oil, eight polyureas and calcium complex soap, and described calcium complex soap is the mixture of higher fatty acid calcium and aromatic acid calcium; Described aromatic acid calcium is the mixture of unitary aromatic acid calcium and binary aromatic acid calcium; The mol ratio of described unitary aromatic acid calcium and described binary aromatic acid calcium is 0.1-2:1; Relative to the described lubricating base oil of 100 weight parts, the content of described eight polyureas is 0.5-22 weight part, and the content of described calcium complex soap is 2.2-36 weight part; Described calcium complex soap is the saponification reaction product of calcium hydroxide and higher fatty acid, unitary aromatic acid and binary aromatic acid;
The structural formula of described binary aromatic acid such as formula shown in (II),
Wherein, R
7, R
8, R
9, R
10and R
11in one be carboxyl, the alkyl of C1-C5 of carboxyl substituted or the aryl of the C6-C12 of carboxyl substituted, R
7, R
8, R
9, R
10and R
11in other four be the fluorinated aryl of hydrogen, the alkyl of C1-C5, the thiazolinyl of C2-C5, the alkynyl of C2-C5, the aryl of C6-C12, the fluoro-alkyl of C1-C5 or C6-C12 independently of one another.
2. lubricating grease according to claim 1, wherein, in described calcium complex soap, the mol ratio of higher fatty acid calcium and aromatic acid calcium is 1:0.1-10.
3. lubricating grease according to claim 2, wherein, in described calcium complex soap, the mol ratio of higher fatty acid calcium and aromatic acid calcium is 1:0.2-5.
4. lubricating grease according to claim 1, wherein, the mol ratio of described unitary aromatic acid calcium and described binary aromatic acid calcium is 0.2-0.8:1.
5. lubricating grease according to claim 1, wherein, the structural formula of described unitary aromatic acid such as formula shown in (I),
Wherein, R
2, R
3, R
4, R
5and R
6be the fluorinated aryl of hydrogen, the alkyl of C1-C5, the thiazolinyl of C2-C5, the alkynyl of C2-C5, the aryl of C6-C12, the fluoro-alkyl of C1-C5 or C6-C12 independently of one another.
6. lubricating grease according to claim 5, wherein, in formula (I), R
2, R
3, R
4, R
5and R
6be the alkyl of hydrogen or C1-C2 independently of one another.
7. lubricating grease according to claim 6, wherein, described unitary aromatic acid is at least one in phenylformic acid, p-methylbenzoic acid, o-toluic acid and m-methyl benzoic acid.
8. lubricating grease according to claim 1, wherein, in formula (II), R
7, R
8, R
9, R
10and R
11in one be the phenyl of carboxyl, carboxymethyl or carboxyl substituted, R
7, R
8, R
9, R
10and R
11in other four be the alkyl of hydrogen or C1-C2 independently of one another.
9. lubricating grease according to claim 8, wherein, described binary aromatic acid is at least one in phthalic acid, m-phthalic acid, terephthalic acid and biphenyl dicarboxylic acid.
10. lubricating grease according to claim 1, wherein, described higher fatty acid is the straight chain fatty acid of C12-C24 or the hydroxy fatty acid of C12-C24.
11. lubricating grease according to claim 10, wherein, described higher fatty acid is be selected from least one in lauric acid, oleic acid, palmitinic acid, stearic acid, 12-oxystearic acid and eicosyl carboxylic acid.
12. according to the lubricating grease in claim 1-3 described in any one, and wherein, described eight polyureas are the compound shown in formula (III),
Wherein, each R
1independently selected from alkyl, cycloalkyl or aryl, each R
2independently selected from alkylidene group or arylidene, each R
3independently selected from alkylidene group, cycloalkylidene or arylidene.
13. lubricating grease according to claim 12, wherein, each R
1independently selected from the alkyl of C8-C24, the cycloalkyl of C8-C24 or C6-C10 aryl, each R
2independently selected from the alkylidene group of C2-C12 or the arylidene of C6-C14, each R
3independently selected from the arylidene of the alkylidene group of C6-C30, the cycloalkylidene of C6-C30 or C6-C30.
14. lubricating grease according to claim 13, wherein, each R
1the phenyl replaced independently selected from the alkyl of the cycloalkyl of the alkyl of C10-C18, C10-C18, phenyl, C1-C3 or the phenyl of halogen substiuted, each R
2independently selected from the alkylidene group of C2-C8, phenylene or biphenylene, each R
3independently selected from xylylene or hexylidene between xylene, methylenediphenyl, sub-dicyclohexylmethyl, Asia.
15. according to the lubricating grease in claim 1-3 described in any one, and wherein, described lubricating base oil is at least one in mineral oil, vegetables oil and synthetic oil.
16. according to the lubricating grease in claim 1-3 described in any one, and wherein, described lubricating grease is also containing at least one in extreme pressure anti-wear additives, oxidation inhibitor and rust-preventive agent.
17. lubricating grease according to claim 16, wherein, relative to the described lubricating base oil of 100 weight parts, the total content of described extreme pressure anti-wear additives, oxidation inhibitor and rust-preventive agent is 0.1-15 weight part.
18. lubricating grease according to claim 16, wherein, described extreme pressure anti-wear additives is at least one in dithio Acidic phosphates zinc, dithio dialkyl amido zinc formate, 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; Described oxidation inhibitor is at least one in the amino p-cresol of pentanoic, di-iso-octyldiphenylamine, phenyl-a-naphthylamine, 2,6 ditertiary butyl p cresol and 2,6-di-t-butyl-alpha, alpha-dimethyl; Described rust-preventive agent is at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
The preparation method of 19. 1 kinds of composite calcium-base eight polyurea greases, the method comprises the following steps:
(1) under the existence of lubricating base oil, by vulcabond, diamines and monoamine contact reacts, heat up the mixture obtained after reaction refining, and wherein, the mol ratio of vulcabond, diamines and monoamine is (3.9-4.1): (2.9-3.1): 2;
(2) under the existence of lubricating base oil, by calcium hydroxide and higher fatty acid and aromatic acid contact reacts, the mixture obtained is carried out intensifications dewater after reaction;
(3) the product mixing that product step (1) obtained and step (2) obtain;
In step (2), described aromatic acid is the mixture of unitary aromatic acid and binary aromatic acid; The mol ratio of described unitary aromatic acid and described binary aromatic acid is 0.1-2:1;
Wherein, the specific operation process of step (1) comprising:
(1-1) lubricating base oil mixed with vulcabond and be heated to 50-60 DEG C, then adding a part of diamines, be warming up to 75-90 DEG C, reaction 20-30 minute, and then adding another part diamines, and continuing reaction 20-30 minute;
(1-2) monoamine is mixed with lubricating base oil, be heated to 50-60 DEG C, then add in the mixture that step (1-1) obtains, mix rear continuation and keep reaction 20-30 minute;
(1-3) mixture that step (1-2) obtains is warming up to 200-220 DEG C of refining 5-10 minute, is then cooled to 150-160 DEG C, then optionally adds lubricating base oil and carry out chilling, to be cooled to 100-120 DEG C, then grind.
20. methods according to claim 19, wherein, in step (1), the mol ratio of vulcabond, diamines and monoamine is 4:3:2.
21. methods according to claim 19 or 20, 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.
22. methods according to claim 21, 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.
23. methods according to claim 19 or 20, wherein, the general formula of described diamines is NH
2-R
2-NH
2, wherein, R
2for the alkylidene group of C2-C12 or the arylidene of C6-C14.
24. methods according to claim 23, wherein, described diamines is quadrol, propylene diamine, 1,6-hexanediamine, Ursol D, O-Phenylene Diamine and 4, at least one in 4 '-benzidine.
25. methods according to claim 19 or 20, wherein, the general formula of described vulcabond is OCN-R
3-NCO, wherein, R
3for the arylidene of the alkylidene group of C6-C30, the cycloalkylidene of C6-C30 or C6-C30.
26. methods according to claim 25, wherein, described vulcabond is at least one in tolylene diisocyanate, methylenediphenyl diisocyanates, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
27. methods according to claim 19, wherein, in step (2), the mol ratio of described unitary aromatic acid and described binary aromatic acid is 0.2-0.8:1.
28. according to the method in claim 19 or 27 described in any one, and wherein, in step (2), described catalytic condition comprises: temperature of reaction is 40-90 DEG C, and the reaction times is 20-120 minute.
29. according to the method in claim 19 or 27 described in any one, wherein, relative to total consumption of the described lubricating base oil of 100 weight parts, total consumption of vulcabond, diamines and monoamine in step (1) is 0.5-22 weight part, and total consumption of calcium hydroxide, higher fatty acid and aromatic acid in step (2) is 2.2-36 weight part.
30. according to the method in claim 19 or 27 described in any one, and wherein, in step (2), the mol ratio of described higher fatty acid and described aromatic acid is 1:0.1-10.
31. methods according to claim 30, wherein, the mol ratio of described higher fatty acid and described aromatic acid is 1:0.2-5.
32. according to the method in claim 19 or 27 described in any one, and wherein, described method is also included at least one step in step (1)-step (3) at least one added in extreme pressure anti-wear additives, oxidation inhibitor and rust-preventive agent.
33. methods according to claim 32, wherein, relative to total consumption of the described lubricating base oil of 100 weight parts, total consumption of described extreme pressure anti-wear additives, oxidation inhibitor and rust-preventive agent is 0.1-15 weight part.
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| CN1657599A (en) * | 2004-02-18 | 2005-08-24 | 中国石油化工股份有限公司 | Polyurea grease composite |
| CN101278036A (en) * | 2005-09-29 | 2008-10-01 | 出光兴产株式会社 | lubricating composition |
| CN101880583A (en) * | 2010-07-02 | 2010-11-10 | 邹鸣 | Solid-liquid phase composite lubricating grease and preparation method thereof |
| CN102134523A (en) * | 2010-01-21 | 2011-07-27 | Nok克鲁勃株式会社 | Grease composition |
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| US3243372A (en) * | 1961-01-24 | 1966-03-29 | Chevron Res | Greases thickened with polyurea |
| CN1657599A (en) * | 2004-02-18 | 2005-08-24 | 中国石油化工股份有限公司 | Polyurea grease composite |
| CN101278036A (en) * | 2005-09-29 | 2008-10-01 | 出光兴产株式会社 | lubricating composition |
| CN102134523A (en) * | 2010-01-21 | 2011-07-27 | Nok克鲁勃株式会社 | Grease composition |
| CN101880583A (en) * | 2010-07-02 | 2010-11-10 | 邹鸣 | Solid-liquid phase composite lubricating grease and preparation method thereof |
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