CN105586115B - Excellent compound lithium base grease of a kind of Wear vesistance and preparation method thereof - Google Patents
Excellent compound lithium base grease of a kind of Wear vesistance and preparation method thereof Download PDFInfo
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- CN105586115B CN105586115B CN201410571998.0A CN201410571998A CN105586115B CN 105586115 B CN105586115 B CN 105586115B CN 201410571998 A CN201410571998 A CN 201410571998A CN 105586115 B CN105586115 B CN 105586115B
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Abstract
The invention discloses the compound lithium base greases that a kind of Wear vesistance is excellent, and on the basis of the weight of lubricant composition, the lubricant composition includes following components：The additive of the lubricating base oil of 65 95 weight %, the lithium base thickening agent of 5 35 weight % and 0.1 15 weight %, the additive contain the compound of structure shown in formula (I).The present invention also provides the preparation methods of the excellent compound lithium base grease of Wear vesistance.The compound lithium base grease of the present invention, due to containing multipurpose additive, drastically increase the anti-attrition ability and oxidation resistance of lubricating grease, the other performance of lithium base grease is influenced simultaneously little, still there is splendid heat-resisting quantity, colloid stability, bearing capacity and water proofing property so that the lubricant composition can be competent in the harsh working condition such as high temperature, high speed, high load capacity, more water.
Description
Technical field
The present invention relates to lubricating grease fields, and in particular, to a kind of excellent lithium of Wear vesistance containing special additive
Base grease composition and preparation method thereof.
Background technology
Lithium base grease is that the 1940s is with fastest developing speed so far, and current output is maximum, application field it is most wide one
Kind multipurpose grease.National Lubricating Grease association is using a national lithium base grease proportion as its grease industry of measurement
The mark of technical merit.Lithium base grease has good colloid stability, mechanical stability, service life is long, scope is wide etc.
Advantage is a kind of preferable multipurpose, long-life lubricating grease, but there is also some defects for lithium base grease：Such as inoxidizability
Energy is poor, abrasion resistance is poor, water repelling property is also poor.
The conventional production methods of lithium base grease are using 12- hydroxy stearic acids or stearic acid and hydroxide in base oil
Lithium reacts, and heating saponification obtains final product, such as US3980572.
In order to improve the performance of lithium base grease, formula and process aspect have all carried out different degrees of improvement.Such as
A kind of color is more shallow, the better lithium base of antioxygenic property lubricates by being prepared for the improvement of preparation process by CN101126045A
Fat；CN1718702A selects high viscosity mineral oil to be prepared for a kind of high extreme pressure lithium base lubricating grease；CN101880581A is improved instead
Temperature is answered, greatly improves product service life and water-resistance.US3681242、US3929651、US3711407、
CN1052890, CN1052891, CN1055384, CN101705141A report the composition and preparation method of lithium base grease, adopt
It is combined with 12- hydroxy lithium stearates and binary acid or boric acid, two component of salicylic lithium salts, also has and answered using three components
It closes；CN101921650 makes it be formed with soap molecule and acts synergistically, and then improve by adding in surfactant into formula
The arrangement mode of soap molecule and cure the ability of base oil so as to improve the dropping point of lubricating grease；CN101993769A provides one
The preparation method of the lithium base grease of kind simple process, reduces production cost；CN101200670 provides a kind of comprehensive performance
The preparation method of preferable lithium base grease, especially to being damaged bearing with repair function；CN10148137 is using relatively low
The lithium base grease of high dropping point has been made in refining temperature, reduces the oil ageing in preparation process, improves lubricating grease
Oxidation stability.
Recently as the development of modern industry, the industrial departments such as bearing, automobile, printing and dyeing, mine, metallurgy, aerospace are to profit
The quality of consistent lubricant proposes increasingly harsher requirement, and many lubricant housings are all disposably to fill fat, in the process of running no longer
Supplement is replaced, so higher to the abrasion resistance requirement of fat.
The content of the invention
The purpose of the invention is to meet the high request to the abrasion resistance of lubricating grease, it is excellent to provide a kind of Wear vesistance
Compound lithium base grease and preparation method thereof.
The present inventor has found that the additive in lubricant composition contains structure shown in formula (I) under study for action
Multipurpose additive：
It can make lubricant composition that there are the performances such as excellent anti-attrition is anti-oxidant.
Therefore, to achieve these goals, on the one hand, the present invention provides the lithium base greases that a kind of Wear vesistance is excellent
Composition, on the basis of the weight of lubricant composition, the lubricant composition includes following components：65-95 weight %'s
The additive of lubricating base oil, the lithium base thickening agent of 5-35 weight % and 0.1-15 weight %, the additive contain formula (I) institute
Show the compound of structure：
Preferably, on the basis of the weight of lubricant composition, the lubricant composition includes following components：70-90
The additive of the lubricating base oil of weight %, the lithium base thickening agent of 8-30 weight % and 0.5-10 weight %.
Preferably, on the basis of the weight of lubricant composition, the content of the compound of structure shown in formula (I) is 0.1-10
Weight %, more preferably 1-5 weight %.
On the other hand, the present invention provides a kind of preparation method of the excellent compound lithium base grease of Wear vesistance, institutes
The method of stating includes：
(1) by partial lubrication base oil, higher fatty acids and optional small molecule acid Hybrid Heating, it is warming up to 80-105
DEG C, lithium source is added in, carries out saponification；
(2) 180-220 DEG C is warming up to be refined；
(3) remaining lubricating base oil is added in, 100-120 DEG C is cooled to, then adds in additive；
(4) ground 2-4 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, by advanced
The dosage of lithium base thickening agent prepared by aliphatic acid, optional small molecule acid and lithium source is 5-35 weight %, and the dosage of additive is
0.1-15 weight %, the additive contain the compound of structure shown in formula (I)：
Preferably, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 70-90 weight %, by height
The dosage of lithium base thickening agent prepared by grade aliphatic acid, optional small molecule acid and lithium source is 8-30 weight %, the dosage of additive
For 0.5-10 weight %.
Preferably, on the basis of the weight of lubricant composition, the dosage of the compound of structure shown in formula (I) is 0.1-10
Weight %, more preferably 1-5 weight %.
The compound lithium base grease of the present invention, due to containing multipurpose additive, drastically increases the anti-attrition of lubricating grease
Ability and oxidation resistance, while the other performance of lithium base grease is influenced less, still with splendid heat-resisting quantity, colloid
Stability, bearing capacity and water proofing property so that it is severe that the lubricant composition can be competent in high temperature, high speed, high load capacity, more water etc.
Carve working condition.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the reaction equation of (a) the step of preparing multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing multipurpose additive.
Fig. 3 is the hydrogen spectrum spectrogram of multipurpose additive prepared by preparation example.
Fig. 4 is the carbon spectrum spectrogram of multipurpose additive prepared by preparation example.
Fig. 5 is the mass spectrogram of multipurpose additive prepared by preparation example.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides the compound lithium base grease that a kind of Wear vesistance is excellent, using the weight of lubricant composition as
Benchmark, lubricant composition include following components：The lubricating base oil of 65-95 weight %, the lithium base thickening agent of 5-35 weight %
With the additive of 0.1-15 weight %, additive contains the compound of structure shown in formula (I)：
In the present invention, what multipurpose additive referred to is the compound of structure shown in formula (I).
In the present invention, it is preferable that on the basis of the weight of lubricant composition, the lubricant composition is included with the following group
Point：The additive of the lubricating base oil of 70-90 weight %, the lithium base thickening agent of 8-30 weight % and 0.5-10 weight %.
In the present invention, on the basis of the weight of lubricant composition, the content of the compound of structure is preferably shown in formula (I)
0.1-10 weight %, more preferably 1-5 weight %.
It is contemplated that the compound of structure shown in formula (I) is contained and reality by the additive in compound lithium base grease
Existing goal of the invention, even if compound lithium base grease has the performances such as excellent anti-attrition is anti-oxidant.Therefore, for lithium base grease
In each conventional constituents selection, do not limit specifically.
In the present invention, lubricating base oil can be lubricating base oil commonly used in the art, such as can be mineral oil,
At least one of vegetable oil and synthetic oil.100 DEG C of kinematic viscosity of lubricating base oil are preferably 4-60mm2/ s, more preferably 6-
32mm2/s.For the specific species of mineral oil, vegetable oil and synthetic oil, also there is no particular limitation, and it is normal that this field may be employed
Mineral oil, vegetable oil and synthetic oil, for example, mineral oil can select paraffinic base, cycloalkyl series, vegetable oil can be castor
At least one of sesame oil, rapeseed oil, peanut oil and soybean oil etc., synthetic oil can be poly-a-olefin oil (PAO), Esters oil, fluorine
At least one of oil and silicone oil etc..
In the present invention, lithium base thickening agent can be lithium base thickening agent commonly used in the art, for example, can be that acid is anti-with lithium source
It should generate, acid includes higher fatty acids and optional small molecule acid.
In the present invention, " optional ", which refers to have, not to be had." optional small molecule acid " refers to that small molecule acid is
A kind of optional component can include the component, can not also include the component, i.e. lithium base thickening agent of the invention can be by
Higher fatty acids is generated with lithium source reaction, can also be generated by higher fatty acids and small molecule acid with lithium source reaction.
Wherein, higher fatty acids can be the aliphatic acid of C12-C25, be preferably lauric acid, palmitic acid, stearic acid and 12-
At least one of hydroxy stearic acid, more preferably stearic acid and/or 12- hydroxy stearic acids.
Wherein, small molecule acid can be C2-C11 carboxylic acid, be preferably acetic acid, propionic acid, ethanedioic acid, adipic acid, azelaic acid,
In at least one of decanedioic acid and terephthalic acid (TPA), more preferably decanedioic acid, azelaic acid, adipic acid and terephthalic acid (TPA) extremely
Few one kind.
Wherein, lithium source is preferably lithium hydroxide.It will be understood by those skilled in the art that in actual use, generally
Add in lithium hydroxide aqueous solution, for lithium hydroxide aqueous solution concentration without particular/special requirement, such as can be 5-30 weight %.
Above-mentioned lithium base thickening agent may be employed the thinkable various methods of those skilled in the art institute and obtain.
In the present invention, since the multipurpose additive of structure shown in formula (I) and other additives have preferable compatibility, because
This, according to the use needs of lubricating grease, additive of the invention can also contain other antioxidant, extreme pressure anti-wear additives and antirust
At least one of agent.
In the present invention, for other antioxidant, extreme pressure anti-wear additives, antirust agent species and content without particular/special requirement, can
With using the species and content of this field routine.For example, antioxidant can be arylamine kind antioxidant, be preferably diphenylamines, phenyl-
At least one of alpha-naphthylamine and di-iso-octyldiphenylamine, more preferably di-iso-octyldiphenylamine, the content of antioxidant can account for
The 0.01-5 weight % of lubricant composition total weight, preferably 0.1-2.5 weight %；Extreme pressure anti-wear additives can be two thio dioxanes
Base trbasic zinc phosphate, two thio dialkyl amido formic acid molybdenums, two thio dialkyl amido lead formates, molybdenum disulfide, polytetrafluoroethylene (PTFE), two
At least one of butyl antimony dithiocarbamate, tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and zinc oxide, pole
The content of pressure antiwear additive can account for the 0.5-12 weight % of lubricant composition total weight, be preferably 0.5-5 weight %；Antirust agent
Can be barium mahogany sulfonate, mahogany acid lithium, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid at least
One kind, the content of antirust agent can account for the 0.01-4.5 weight % of lubricant composition total weight, be preferably 0.1-2 weight %.
In the present invention, the preparation method of the compound of structure preferably includes shown in formula (I)：
(a) aniline, sulfur chloride and 4- chloroanilines are reacted, generate the intermediate M shown in formula (II),
(b) the intermediate M and dimercapto -1,3,4- thiadiazoles that step (a) obtains is carried out nucleophilic in alkaline conditions to take
Generation reaction, generates the multipurpose additive shown in formula (I),
In step (a) of the present invention, the concrete mode that aniline, sulfur chloride and 4- chloroanilines react is preferably included：
(i) under an inert atmosphere, in the first solvent, aniline is fully reacted with sulfur chloride at -20-0 DEG C；
(ii) 4- chloroanilines are added in the reaction system of step (i), reacts 1-3h at 15-30 DEG C.
In the present invention, inert atmosphere can be the inert atmosphere of this field routine, such as can be by gases such as nitrogen, argon gas
It provides.
In step (i) of the present invention, the first solvent is preferably selected from dichloromethane, tetrahydrofuran, toluene, dimethylbenzene and dioxy six
At least one of ring, more preferably dichloromethane and/or tetrahydrofuran, are still more preferably dichloromethane.
In the present invention in step (i), fully reacted and refer to that the reaction was complete, i.e., reaction raw materials are reacted completely.
Method commonly used in the art may be employed to be monitored reaction, to confirm that the reaction was complete, such as thin layer chromatography may be employed
(TLC) or the methods of gas-chromatography, is monitored.
In step (ii) of the present invention, 1-3h is reacted at 15-30 DEG C, preferably after step (i) fully reaction, by reactant
The temperature of system is gradually increased to 15-30 DEG C, adds 4- chloroanilines and carries out reaction 1-3h.It, can be further under the preferable case
Improve reaction yield.
In step (ii) of the present invention, the feed postition of 4- chloroanilines is preferably to add in by several times, such as can divide 3-4 times and add
Enter.Under the preferable case, reaction yield can be further improved.When being added in for gradation, each addition can be identical,
Can not also be same, in order to easy to operate, preferably each addition is identical.
In step (ii) of the present invention, react 1-3h, stop reaction mode can be those skilled in the art it is contemplated that
Various modes, be quenched for example, quencher can be added in, quencher can be quencher commonly used in the art, such as can
Think saturated salt solution.
In the present invention, the dosage of aniline, sulfur chloride and 4- chloroanilines is substantially equimolar amounts, but aniline and sulfur chloride can
With appropriate excessive.The molar ratio of aniline, sulfur chloride and 4- chloroanilines is preferably 0.9-1.5：0.9-1.5：0.8-1.2.
It will be understood by those skilled in the art that in step (a) of the present invention, purer intermediate M, goes back in order to obtain
It needing to post-process the system after reaction, the mode of post processing can include washing, drying, solvent is removed under reduced pressure, for example,
By the reaction system after being quenched respectively with distilled water and saturated common salt water washing, then anhydrous calcium chloride is added at 15-30 DEG C
Or the drier such as anhydrous slufuric acid lithium, keep 10-60min.After being filtered to remove drier, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain intermediate M.
In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4- chloroanilines are reacted is as shown in Figure 1, figure
In 1, the first solvent is not construed as limiting the scope of the present invention using dichloromethane, purpose by way of example only.
In step (b) of the present invention, the condition of nucleophilic substitution preferably includes：Under an inert atmosphere, in the second solvent,
Dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed into 10-30min at 15-30 DEG C, then add in intermediate
M is fully reacted.I.e. alkaline condition is provided by alkaline reagent.
" inert atmosphere ", " fully being reacted " are as previously mentioned, details are not described herein.
In the present invention, intermediate M is preferably slowly added to, such as can be added in by several times, can generally divide 3-4 addition.
Under the preferable case, reaction yield can be further improved.When being added in for gradation, each addition can be identical, also may be used
With difference, in order to easy to operate, preferably each addition is identical.
In the present invention, the second solvent is preferably selected from dichloromethane, tetrahydrofuran, toluene, dimethylbenzene, N, N- dimethyl formyls
At least one of amine, more preferably dichloromethane and/or n,N-Dimethylformamide, are still more preferably N, N- dimethyl
Formamide.
In the present invention, alkaline reagent is preferably selected from least one of inorganic bases such as potassium carbonate, lithium carbonate, lithium methoxide.
In the present invention, catalyst is preferably potassium sulfate.
In step (b) of the present invention, the dosage of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate M is substantially etc.
Mole, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Dimercapto -1,3,4- thiadiazoles, alkalescence examination
The molar ratio of agent and intermediate M are preferably 0.9-3.0：0.9-5.0：0.8-1.5.
In step (b) of the present invention, the dosage of catalyst can be catalytic amount, with mole of dimercapto-1,3,4-thiadiazole
On the basis of number, the dosage of catalyst is preferably 5-100 moles of %, more preferably 10-50 moles of %.
In step (b) of the present invention, reaction equation such as Fig. 2 that dimercapto-1,3,4-thiadiazole and intermediate M are reacted
Shown, in Fig. 2, alkaline reagent does not form the scope of the present invention and limits using potassium carbonate, purpose by way of example only
System.
It will be understood by those skilled in the art that purer final product, i.e. multiple-effect of the invention add in order to obtain
Add agent, the method for the invention for preparing multipurpose additive, which preferably further includes, post-processes the system after reaction, the side of post processing
Formula can include washing, drying, solvent is removed under reduced pressure, for example, the system after abundant reaction to be poured into the acetic acid of 1-10 times of volume
In ethyl ester (or dichloromethane), respectively with distilled water and saturated common salt water washing, then anhydrous calcium chloride is added at 15-30 DEG C
Or the drier such as anhydrous slufuric acid lithium, keep 10-60min.After being filtered to remove drier, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain final product.
Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention preferably carries out under stiring, for
Mixing speed can be the mixing speed of this field routine, for example, mixing speed can be 100-800rpm without particular/special requirement.
In the present invention, for the first solvent and the second solvent amount without particular/special requirement, can be the solvent of this field routine
Dosage, this is known to those skilled in the art, and details are not described herein.
As described above, it is contemplated that structure shown in formula (I) is contained by the additive in compound lithium base grease
Compound and realize goal of the invention, even if lubricant composition has the performances such as excellent anti-attrition is anti-oxidant.Therefore, for lithium base
Without particular/special requirement method commonly used in the art may be employed, for example, second aspect, the present invention in preparation of greases method
A kind of preparation method of the excellent compound lithium base grease of Wear vesistance is additionally provided, this method includes：
(1) by partial lubrication base oil, higher fatty acids and optional small molecule acid Hybrid Heating, it is warming up to 80-105
DEG C, lithium source is added in, carries out saponification；
(2) 180-220 DEG C is warming up to be refined；
(3) remaining lubricating base oil is added in, 100-120 DEG C is cooled to, then adds in additive；
(4) ground 2-4 times by three-roller；
Wherein, on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 65-95 weight %, by advanced
The dosage of lithium base thickening agent prepared by aliphatic acid, optional small molecule acid and lithium source is 5-35 weight %, and the dosage of additive is
0.1-15 weight %, additive contain the compound of structure shown in formula (I)：
In the method for the present invention, it is preferable that on the basis of the weight of lubricant composition, the dosage of lubricating base oil is 70-
90 weight %, the dosage of the lithium base thickening agent prepared by higher fatty acids, optional small molecule acid and lithium source is 8-30 weight %,
The dosage of additive is 0.5-10 weight %.
In the method for the present invention, the molar ratio of the total amount and lithium source of higher fatty acids and optional small molecule acid is preferably chemistry
Ratio is measured, lithium source can also excess 1-10 weight %.The molar ratio of higher fatty acids and optional small molecule acid is preferably 1:
0.1-1.It will be understood by those skilled in the art that according to by higher fatty acids, optional small molecule acid and lithium source preparation
The dosage of lithium base thickening agent counter can release the dosage of higher fatty acids, small molecule acid and lithium source, this is those skilled in the art
Known, details are not described herein.
In the present invention, can also not have as previously mentioned, " optional " refers to have." optional small molecule acid " refers to small
Molecule acid is a kind of optional component, can include the component, can not also include the component；" higher fatty acids with it is optional
The molar ratio of small molecule acid is 1:0.1-1 " is to refer to when containing small molecule acid, the molar ratio of higher fatty acids and small molecule acid
Preferably 1:0.1-1.In short, it will be understood by those skilled in the art that the lithium base thickening agent of the present invention can be by advanced fat
Fat acid is generated with lithium source reaction, can also be generated by higher fatty acids and small molecule acid with lithium source reaction.
In the method for the present invention, on the basis of the weight of lubricant composition, the dosage of the compound of structure is excellent shown in formula (I)
Elect 0.1-10 weight % as, more preferably 1-5 weight %.
It will be understood by those skilled in the art that in the method for the present invention, the dosage of lubricating base oil is partial lubrication base
The sum of the dosage of plinth oil and the dosage of remaining lubricating base oil.Partial lubrication base oil and the weight ratio of remaining lubricating base oil are excellent
Elect 50-75 as:25-50.
In the method for the present invention step (1), 80-95 DEG C is preferably warming up to, the saponification time is preferably 0.2-1.5h, more excellent
Elect 0.5-1h as.
In the method for the present invention step (2), 190-210 DEG C is preferably warming up to, the time of refining is preferably 5-15min.
Each step of the method for the present invention preferably carries out under stiring, can be this field for mixing speed without particular/special requirement
Conventional mixing speed, for example, mixing speed can be 20-400rpm.
Lubricating base oil, higher fatty acids, small molecule acid, lithium source, additive are as previously mentioned, details are not described herein.
Embodiment
The present invention is further illustrated for following embodiment, but is not intended to limit the present invention.
In the following Examples and Comparative Examples：
The monitoring method that the reaction was complete：Thin-layer chromatography chromatography (TLC) fluorescence developing method.
Gross production rate=final product mole/aniline moles × 100%
The physico-chemical analysis method of product：Constituent content is measured by inductively coupled plasma ion emission spectroscopy method.
Structure characterization methods：Nuclear magnetic resonance method (1H hydrogen is composed,13C carbon is composed), high resolution mass spectrum.
Preparation example
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 300rpm), adds in 150ml
Dichloromethane, then add in 0.2mol sulfur chloride, after being fully cooled in ice-water bath, add in the aniline of 0.2mol.Monitoring
Ice-water bath is removed to after the reaction was complete, 25 DEG C is placed at room temperature, after reaction system is gradually increased to 25 DEG C, is added three times 4- chlorine
Aniline is reacted, and each addition is identical, adds in 4- chloroanilines 0.15mol altogether.30ml saturations are added in after when sustained response 2 is small
Reaction is quenched in saline solution, and then reaction system is transferred in separatory funnel, respectively with 50ml distilled water and 50ml saturated salt solutions
Washing, and add in 10g anhydrous slufuric acids lithium dry 20min at 25 DEG C.Filtrate after filtering is evaporated off molten under 40 DEG C, 0.05MPa
Agent obtains intermediate M1.
Nitrogen protection is filled in the 500ml flasks with electromagnetic agitation sub (mixing speed 400rpm), adds in 150ml
DMF (n,N-Dimethylformamide), then add in 0.2mol dimercapto-1,3,4-thiadiazoles and 0.2mol potassium carbonate,
The potassium sulfate of 0.05mol stirs 20 minutes at 25 DEG C, is added three times above-mentioned intermediate M1, and each addition is identical, adds in altogether
Intermediate M10.12mol.Then reaction system is added in 250ml ethyl acetate, and is transferred to separatory funnel by monitoring to the reaction was complete
In, respectively with 100ml distilled water (twice) and 50ml saturated common salt water washings, and add in 15g anhydrous slufuric acids lithium and done at 25 DEG C
Dry 20min.Solvent is evaporated off under 40 DEG C, 0.03MPa in filtrate after filtering, obtains final product S1.It is 76% to calculate gross production rate.
The physico-chemical analysis data of product are as follows：Sulfur content, 41.3%；Nitrogen content, 13.9%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 3, Fig. 4 and
Fig. 5.
Physico-chemical analysis data, Fig. 3, Fig. 4 and Fig. 5 from above-mentioned preparation example can be seen that S1 with the knot shown in formula (I)
Structure.
Embodiment 1
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 540kg 150BS base oils, (100 DEG C of viscosity are 31mm2/ s, similarly hereinafter) and 62.75kg12- hydroxy stearic acids
In addition fat kettle, the agitating and heating under 180rpm is warming up to 95 DEG C, and adding in 27.03kg lithium hydroxide aqueous solutions, (concentration is
16.7 weight %), carry out saponification 0.5h；
(2) 190 DEG C are warming up to, refines 8min；
(3) 180kg 150BS base oils are added in, stirring is cooled to 120 DEG C, adds in 16kg S1, is stirred under 180rpm equal
It is even；
(4) 2 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：8 weight of 12- hydroxy lithium stearates
Measure %；90 weight % of lubricating base oil；S12 weight %.
Embodiment 2
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 153.5kg 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) and the addition of 102.83kg stearic acid
In fat kettle processed, agitating and heating, is warming up to 85 DEG C at 200 rpm, and adding in 101.47kg lithium hydroxide aqueous solutions, (concentration is 30 weights
Measure %), carry out saponification 1h；
(2) 210 DEG C are warming up to, refines 5min；
(3) 100kg 500SN base oils are added in, stirring is cooled to 105 DEG C, adds in 3.6kg S1, stirs at 200 rpm
Uniformly；
(4) 3 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：29 weight % of lithium stearate；Profit
70 weight % of sliding base oil；S11 weight %.
Embodiment 3
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 170kg PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and the addition of 88.14kg stearic acid
In fat kettle processed, agitating and heating, is warming up to 80 DEG C at 300 rpm, and adding in 41.3kg lithium hydroxide aqueous solutions, (concentration is 30 weights
Measure %), carry out saponification 0.8h；
(2) 195 DEG C are warming up to, refines 15min；
(3) 167.5kg PAO6 synthetic hydrocarbon oils are added in, stirring is cooled to 100 DEG C, adds in 22.5kg S1, at 300 rpm
It stirs evenly；
(4) 4 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：20 weight % of lithium stearate；Profit
75 weight % of sliding base oil；S15 weight %.
Embodiment 4
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by the miscella of 400kg 500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter) and 94.12kg
12- hydroxy stearic acids are added in fat kettle processed, the agitating and heating under 230rpm, are warming up to 90 DEG C, add in 67.66kg lithium hydroxide water
Solution (concentration is 20 weight %), carries out saponification 0.6h；
(2) 200 DEG C are warming up to, refines 10min；
(3) miscella of 125kg 500SN and 150BS are added in, stirring is cooled to 120 DEG C, adds in 19.2kg S1,
It is stirred evenly under 230rpm；
(4) 2 times are ground into fat by three-roller.Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：15 weight of 12- hydroxy lithium stearates
Measure %；82 weight % of lubricating base oil；S13 weight %.
Comparative example 1
Method according to embodiment 4 prepares lithium base grease, unlike, it is added without S1.Properties of product are as shown in table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：12- hydroxy lithium stearates 15.5
Weight %, 84.5 weight % of lubricating base oil.
Embodiment 5
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 540kg 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter), 37.95kg 12- hydroxy stearic acids
It is added in 23.77kg azelaic acids in fat kettle processed, the agitating and heating under 180rpm, is warming up to 85 DEG C, add in 163.76kg hydroxides
Lithium aqueous solution (concentration is 10 weight %), carries out saponification 0.5h；
(2) 200 DEG C are warming up to, refines 5min；
(3) 180kg 500SN base oils are added in, stirring is cooled to 120 DEG C, adds in 16kg S1, is stirred under 180rpm equal
It is even；
(4) 2 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：4.8 weight of 12- hydroxy lithium stearates
Measure %；3.2 weight % of azelaic acid lithium；90 weight % of lubricating base oil；S12 weight %.
Embodiment 6
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 95kg 150BS base oils, (100 DEG C of viscosity are 30mm2/ s, similarly hereinafter), 66.99kg stearic acid and 7.82kg
Terephthalic acid (TPA) is added in fat kettle processed, at 200 rpm agitating and heating, is warming up to 80 DEG C, and it is water-soluble to add in 84.26kg lithium hydroxides
Liquid (concentration is 16.9 weight %), carries out saponification 1h；
(2) 190 DEG C are warming up to, refines 15min；
(3) 90kg 150BS base oils are added in, stirring is cooled to 110 DEG C, adds in 2.7kg S1, and stirring is equal at 200 rpm
It is even；
(4) 3 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：25.8 weight % of lithium stearate；
3.2 weight % of terephthalic acid (TPA) lithium；70 weight % of lubricating base oil；S11 weight %.
Embodiment 7
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by 260.5kg PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter), 74.29kg stearic acid and
28.59kg adipic acids are added in fat kettle processed, at 300 rpm agitating and heating, are warming up to 95 DEG C, add in 94.12kg lithium hydroxide water
Solution (concentration is 30 weight %), carries out saponification 0.8h；
(2) 195 DEG C are warming up to, refines 8min；
(3) 240kg PAO6 synthetic hydrocarbon oils are added in, stirring is cooled to 100 DEG C, adds in 26.7kg S1, stirs at 300 rpm
It mixes uniformly；
(4) 4 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：14.2 weight % of lithium stearate；
5.8 weight % of lithium adipate；75 weight % of lubricating base oil；S15 weight %.
Embodiment 8
The present embodiment is used to illustrate compound lithium base grease of the present invention and preparation method thereof.
(1) by the miscella of 456kg 500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter), the 12- of 87.8kg
Hydroxy stearic acid and 29.34kg decanedioic acid are added in fat kettle processed, and the agitating and heating under 230rpm is warming up to 90 DEG C, adds in
100.33kg lithium hydroxide aqueous solutions (concentration is 25 weight %), carry out saponification 0.6h；
(2) 210 DEG C are warming up to, refines 10min；
(3) miscella of 200kg500SN and 150BS is added in, stirring is cooled to 115 DEG C, 24kg S1 is added in, in 230rpm
Under stir evenly；
(4) 2 times are ground into fat by three-roller.Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：12- hydroxy lithium stearates 11.1
Weight %；3.9 weight % of decanedioic acid lithium；82 weight % of lubricating base oil；S13 weight %.
Comparative example 2
Method according to embodiment 8 prepares lithium base grease, unlike, it is added without S1.Properties of product are as shown in table 2.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, form and be：12- hydroxy lithium stearates 11.5
Weight %；4 weight % of decanedioic acid lithium；84.5 weight % of lubricating base oil.
Table 1
Each indication test method：Dropping point：GB/T 3498；Work cone penetration：GB/T 269；Oxidation stability：SH/T
0325；Stencil oil-dividing：SH/T 0324；Tetra-ball machine test PB, PD：SH/T 0202；Copper corrosion：GB/T 7326；Anticorrosion
Property：GB/T 5018；Water drenches number of dropouts：SH/T 0109；Coefficient of friction：SH/T 0847.
Table 2
Each indication test method：Dropping point：GB/T 3498；Work cone penetration：GB/T 269；Oxidation onset temperature：ASTM
D5483；Stencil oil-dividing：SH/T 0324；Copper corrosion：GB/T 7326；Anticorrosive property：GB/T 5018；Water drenches number of dropouts：SH/
T 0109；Tetra-ball machine test PB, PD：SH/T 0202；Coefficient of friction：SH/T 0847.
It will be understood by those skilled in the art that dropping point is higher, the heat-resisting quantity of lubricating grease is better；Work cone penetration is got over
Small, the thickening performance of grease thickener is better；Oxidation stability is smaller, and the antioxygenic property of lubricating grease is better；Oxidation starting
Temperature is higher, and the oxidation resistance of lubricating grease is better；Stencil oil-dividing value is smaller, and the colloid stability of lubricating grease is better；PB, PD value
Bigger, the bearing capacity of lubricating grease is better；Water leaching number of dropouts is smaller, and the water resistance of lubricating grease is better；Coefficient of friction is smaller, profit
The antifriction performance of consistent lubricant is better.
By embodiment 4 compared with comparative example 1, by embodiment 8 compared with comparative example 2, it can be seen that the present invention
Lubricating grease have better heat-resisting quantity, inoxidizability, colloid stability, bearing capacity, water proofing property and antifriction performance.
The compound lithium base grease of the present invention, due to containing multipurpose additive, drastically increases the anti-attrition of lubricating grease
Ability and oxidation resistance, while the other performance of lithium base grease is influenced less, still with splendid heat-resisting quantity, colloid
Stability, bearing capacity and water proofing property so that it is severe that the lubricant composition can be competent in high temperature, high speed, high load capacity, more water etc.
Carve working condition.
The preferred embodiment of the present invention is described in detail above in association with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that the specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (23)
1. a kind of excellent compound lithium base grease of Wear vesistance, on the basis of the weight of lubricant composition, the lubrication
Oil/fat composition includes following components：The lubricating base oil of 65-95 weight %, the lithium base thickening agent of 5-35 weight % and 0.1-15 weights
Measure the additive of %, which is characterized in that the additive contains the compound of structure shown in formula (I)：
2. lubricant composition according to claim 1, wherein, on the basis of the weight of lubricant composition, the profit
Grease composition includes following components：The lubricating base oil of 70-90 weight %, the lithium base thickening agent and 0.5-10 of 8-30 weight %
The additive of weight %.
3. lubricant composition according to claim 1 or 2, wherein, on the basis of the weight of lubricant composition, formula
(I) content of the compound of structure shown in is 0.1-10 weight %.
4. lubricant composition according to claim 3, wherein, on the basis of the weight of lubricant composition, formula (I) institute
The content for showing the compound of structure is 1-5 weight %.
5. lubricant composition according to claim 1 or 2, wherein, the lubricating base oil is mineral oil, vegetable oil and
At least one of synthetic oil.
6. lubricant composition according to claim 1 or 2, wherein, the lithium base thickening agent is given birth to for acid and lithium source reaction
Into the acid includes higher fatty acids and optional small molecule acid.
7. lubricant composition according to claim 6, wherein, the higher fatty acids is the aliphatic acid of C12-C25, institute
State the carboxylic acid that small molecule acid is C2-C11.
8. lubricant composition according to claim 7, wherein, the higher fatty acids is lauric acid, palmitic acid, tristearin
At least one of acid and 12- hydroxy stearic acids, the small molecule acid is acetic acid, propionic acid, ethanedioic acid, adipic acid, azelaic acid, the last of the ten Heavenly stems
At least one of diacid and terephthalic acid (TPA).
9. lubricant composition according to claim 6, wherein, the lithium source is lithium hydroxide.
10. lubricant composition according to claim 1 or 2, wherein, the additive also containing other antioxidant,
At least one of extreme pressure anti-wear additives and antirust agent.
11. lubricant composition according to claim 10, wherein, the antioxidant is arylamine kind antioxidant.
12. lubricant composition according to claim 11, wherein, the antioxidant is diphenylamines, phenyl-α-naphthylamine and
At least one of di-iso-octyldiphenylamine.
13. lubricant composition according to claim 10, wherein, the extreme pressure anti-wear additives are two thio Acidic phosphates
Zinc, two thio dialkyl amido formic acid molybdenums, two thio dialkyl amido lead formates, molybdenum disulfide, polytetrafluoroethylene (PTFE), dibutyl two
At least one of thiocarbamic acid antimony, tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and zinc oxide.
14. lubricant composition according to claim 10, wherein, the antirust agent is barium mahogany sulfonate, mahogany acid
At least one of sodium, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
15. the preparation method of lubricant composition described in claim 1, the described method includes：
(1) by partial lubrication base oil, higher fatty acids and optional small molecule acid Hybrid Heating, 80-105 DEG C is warming up to, is added
Enter lithium source, carry out saponification；
(2) 180-220 DEG C is warming up to be refined；
(3) remaining lubricating base oil is added in, 100-120 DEG C is cooled to, then adds in additive；
(4) ground 2-4 times by three-roller.
16. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, lubricating base oil
Dosage is 70-90 weight %, and the dosage of the lithium base thickening agent prepared by higher fatty acids, optional small molecule acid and lithium source is 8-
30 weight %, the dosage of additive is 0.5-10 weight %.
17. the method according to claim 15 or 16, wherein, on the basis of the weight of lubricant composition, shown in formula (I)
The dosage of the compound of structure is 0.1-10 weight %.
18. the method according to claim 11, wherein, on the basis of the weight of lubricant composition, structure shown in formula (I)
Compound dosage be 1-5 weight %.
19. the method according to claim 15 or 16, wherein, the partial lubrication base oil and the remaining lubrication base
The weight ratio of oil is 50-75:25-50.
20. the method according to claim 15 or 16, wherein, the molar ratio of higher fatty acids and optional small molecule acid is
1:0.1-1。
21. the method according to claim 15 or 16, wherein, in step (1), 80-95 DEG C is warming up to, the saponification time
For 0.2-1.5h.
22. according to the method for claim 21, wherein, the saponification time is 0.5-1h
23. the method according to claim 15 or 16, wherein, in step (2), 190-210 DEG C is warming up to, the refining
Time is 5-15min.
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| CN107502423B (en) * | 2017-08-01 | 2020-02-14 | 太原理工大学 | Lithium-based lubricating grease with layered potassium magnesium phosphate as additive and preparation method thereof |
| CN107502422B (en) * | 2017-08-01 | 2020-02-14 | 太原理工大学 | Layered potassium calcium phosphate composite lithium-based lubricating grease composition and preparation method thereof |
| CN111909757A (en) * | 2020-09-03 | 2020-11-10 | 无锡市润尔石化有限公司 | Novel environment-friendly lubricating grease and preparation method thereof |
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