CN105586134B - Excellent calcium base grease composition of a kind of Wear vesistance and preparation method thereof - Google Patents
Excellent calcium base grease composition of a kind of Wear vesistance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the calcium base grease compositions 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 calcium 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 calcium base grease composition of Wear vesistance.The calcium base grease composition of the present invention, due to containing multipurpose additive, greatly improve the anti-attrition ability and oxidation resistance of lubricating grease, the other performance of calcium-base grease is influenced simultaneously little, still there is splendid heat-resisting quantity, colloid stability and bearing capacity 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 calcium of Wear vesistance containing special additive
Base grease composition and preparation method thereof.
Background technology
China produces calcium-base grease since the 1940s, and due to its production technology and equipment is simple, raw material is easy
, low cost product is deep to be welcome by the producer and user.Calcium-base grease has good water-resistance, is not easy to emulsify,
There is preferable adhesiveness to metal surface, colloid stability is also preferable, not condensate oil in storage process, but since it contains centainly
The constitution water of amount, when temperature in use is more than 100 DEG C, the easy evaporation loss of water causes the structure of calcium-base grease to be destroyed, and
Lubricating action is lost, thus calcium-base grease is generally only used on friction part of the operating temperature no more than 60 DEG C.
Complex calcium lubricating grease is a kind of earliest complex-soap base grease of development, it is with aliphatic acid calcium soap and low molecular acid calcium
Calcium complex soap made of salt is thickened grease product made of moderately viscous mineral lubricating oil or synthetic lubricant fluid, has higher
Temperature tolerance, consistency change very little under high temperature；There is good water-resistance simultaneously, mechanical stability, colloid stability and preferably
Extreme pressure property, use temperature range is wider, is a kind of widely used brand-name grease.But since complex calcium lubricating grease exists
There are problems that hardening during storage and use, greatly limit it and promote and apply.
In recent years for improve complex calcium lubricating grease performance, have formula and manufacturing process on make improvements as
CN1888036 and CN101935573A；Have through the selection to small molecule acid and long chain organic acid type and the adjustment of ratio and
Some small molecules sour (boric acid) and other adminiclies (titanium dioxide) is selected to improve the hardening problem of complex calcium lubricating grease, but
Production time is too long and hardening improves limitation；Also have its performance is improved by introducing polyurea grease, such as
CN1493673, US5084193 and US4902435 mix complex calcium lubricating grease, but raw materials for production with polyureas base grease
With the process is more complicated.
Anhydrous calcium-base grease is free of water, and dropping point is higher than 140 DEG C, and maximum operation (service) temperature is higher by 50 than common calcium-base grease
DEG C or more, it is short-term up to 120 DEG C；Water-resistance and mechanical stability are better than mixing calcium-base grease；With complex calcium lubricating grease phase
Compare, anhydrous calcium-base grease does not store hardening and the problem of by thermmohardening, and production technology is fairly simple, manufactures cost
Less than complex calcium lubricating grease.Anhydrous calcium-base grease function admirable has good oxidation stability, water resistance, colloid peace
Qualitative, wear resistence, low temperature flow, rust-preventing characteristic and mechanical 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 the abrasion resistance requirement to fat is higher.
Invention content
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
Calcium base grease composition 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 calcium-base grease 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 calcium 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 calcium 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 calcium base grease composition of Wear vesistance, institutes
The method of stating includes：
(1) partial lubrication base oil, higher fatty acids, optional middle molecule acid and small molecule acid, calcium hydroxide are mixed
Heating carries out saponification；
(2) heating is refined；
(3) remaining lubricating base oil is added in, 100-130 DEG C is cooled to, then adds in additive；
(4) it is 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 calcium base thickening agent prepared by aliphatic acid, optional middle molecule acid and small molecule acid, calcium hydroxide is 5-35 weight %, is added
The dosage for adding agent is 0.1-15 weight %, and the additive contains 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 calcium base thickening agent prepared by grade aliphatic acid, optional middle molecule acid and small molecule acid, calcium hydroxide is 8-30 weight %,
The dosage of additive is 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 calcium base grease composition of the present invention, due to containing multipurpose additive, greatly improves the anti-attrition of lubricating grease
Ability and oxidation resistance, while the other performance of calcium-base grease is influenced less, still with splendid heat-resisting quantity, colloid
Stability and bearing capacity so that the lubricant composition can be competent in the harsh operating mode such as high temperature, high speed, high load capacity, more water
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 understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides the calcium base grease composition 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 calcium 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 calcium 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 %.
The present invention is directed to contain the compound of structure shown in formula (I) by the additive in calcium base grease composition and reality
Existing goal of the invention, even if calcium base grease composition has the performances such as excellent anti-attrition is anti-oxidant.Therefore, for calcium-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 5-
32mm2/s.For the specific type of mineral oil, vegetable oil and synthetic oil, also there is no particular limitation, and it is normal that this field may be used
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, calcium base thickening agent can be calcium base thickening agent commonly used in the art, for example, can be acid and hydroxide
Calcium reaction generation, acid include higher fatty acids, optional middle molecule acid and small molecule acid.
In the present invention, " optional ", which refers to have, not to be had." optional middle molecule acid and small molecule acid " refers to
Middle molecule acid and small molecule acid are optional components, can include both components, can not also include both components,
That is, the calcium base thickening agent of the present invention can be generated by higher fatty acids and calcium hydroxide reaction, can also by higher fatty acids, in
Molecule acid and small molecule acid are generated with calcium hydroxide reaction.
Wherein, higher fatty acids can be the aliphatic acid of C12-C25, 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, middle molecule acid is preferably the carboxylic acid of C6-C10, more preferably octanoic acid, benzoic acid, terephthalic acid (TPA), azelaic acid
At least one of with decanedioic acid.
Wherein, small molecule acid is preferably acetic acid.
Above-mentioned calcium base thickening agent may be used 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 type and content without particular/special requirement, can
With using the type and content of this field routine.For example, antioxidant can be arylamine kind antioxidant, 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 %, preferably 0.5-5 weight % of lubricant composition total weight；Antirust agent
Can be barium mahogany sulfonate, calcium mahogany sulfonate, 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, 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 under alkaline condition 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 used to be monitored reaction, to confirm that the reaction was complete, such as thin layer chromatography may be used
(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,
It can also be different, 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 be 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 dead plaster, 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, calcium carbonate, calcium 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, alkalinity 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 that the present invention prepares multipurpose additive, which preferably further includes, post-processes the system after reaction, the side of post processing
Formula can include washing, drying, solvent be 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 dead plaster, 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, the present invention is directed to contain structure shown in formula (I) by the additive in calcium base grease composition
Compound and realize goal of the invention, even if lubricant composition has the performances such as excellent anti-attrition is anti-oxidant.Therefore, for calcium base
Without particular/special requirement method commonly used in the art may be used, for example, second aspect, the present invention in preparation of greases method
A kind of preparation method of the excellent calcium base grease composition of Wear vesistance is additionally provided, this method includes：
(1) partial lubrication base oil, higher fatty acids, optional middle molecule acid and small molecule acid, calcium hydroxide are mixed
Heating carries out saponification；
(2) heating is refined；
(3) remaining lubricating base oil is added in, 100-130 DEG C is cooled to, then adds in additive；
(4) it is 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 calcium base thickening agent prepared by aliphatic acid, optional middle molecule acid and small molecule acid, calcium hydroxide is 5-35 weight %, is added
The dosage for adding agent is 0.1-15 weight %, and additive contains 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 calcium base thickening agent prepared by higher fatty acids, optional middle molecule acid and small molecule acid, calcium hydroxide
For 8-30 weight %, the dosage of additive is 0.5-10 weight %.
In the method for the present invention, higher fatty acids and optional middle molecule acid and the total amount of small molecule acid and rubbing for calcium hydroxide
, than being preferably stoichiometric ratio, calcium hydroxide can also excess 1-10 weight % for you.Optional middle molecule acid and higher fatty acids
Molar ratio be preferably 1:The total amount of 0.37-3.4, higher fatty acids and optional middle molecule acid is rubbed with optional small molecule acid
You are than preferably 1:0.9-4.It will be understood by those skilled in the art that according to by higher fatty acids, optional middle molecule acid
The dosage of the calcium base thickening agent prepared with small molecule acid and calcium hydroxide, counter can release higher fatty acids, middle molecule acid, small point
The dosage of sub- acid and calcium hydroxide, this is known to those skilled in the art, and details are not described herein.
In the present invention, can also not have as previously mentioned, " optional " refers to have." optional middle molecule acid and small molecule
Acid " refer to that middle molecule acid and small molecule acid are optional components, can include both components, can not also including this two
Kind component." molar ratio of the total amount and calcium hydroxide of higher fatty acids and optional middle molecule acid and small molecule acid is counted for chemistry
Amount ratio " refers to that when not containing middle molecule acid and small molecule acid the molar ratio of higher fatty acids and calcium hydroxide is counted for chemistry
Ratio is measured, when containing middle molecule acid and during small molecule acid, higher fatty acids and the total amount and hydroxide of middle molecule acid and small molecule acid
The molar ratio of calcium is stoichiometric ratio." optional middle molecule acid and the molar ratio of higher fatty acids is 1:0.37-3.4, advanced fat
The total amount of fat acid and optional middle molecule acid and the molar ratio of optional small molecule acid are 1:0.9-4 " refers to divide in containing
When sub- acid and small molecule acid, the molar ratio of middle molecule acid and higher fatty acids is 1:0.37-3.4, higher fatty acids and middle molecule
The total amount of acid is 1 with the molar ratio of small molecule acid:0.9-4.In short, it will be understood by those skilled in the art that the present invention
Calcium base thickening agent can be generated by higher fatty acids and calcium hydroxide reaction, can also be sour and small by higher fatty acids, middle molecule
Molecule acid is generated with calcium hydroxide 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)
It is selected as 0.1-10 weight %, 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
It is selected as 50-75:25-50.
In the method for the present invention step (1), when not containing middle molecule acid and small molecule acid, step (1) preferably includes：By portion
Point lubricating base oil and higher fatty acids Hybrid Heating, are warming up to 80-105 DEG C, more preferable 80-95 DEG C, add in calcium hydroxide into
Row saponification, saponification time are 0.2-1.5h, more preferably 0.5-1h；When containing middle molecule acid and during small molecule acid,
Step (1) preferably includes：Partial lubrication base oil and calcium hydroxide are mixed, at 15-50 DEG C, small molecule acid is added in and carries out the
One saponification then heats to 80-100 DEG C, adds in higher fatty acids and carries out the second saponification, molecule acid in then adding in
Carry out third saponification, the first saponification, the second saponification, third saponification time be 10-60min, more
Preferably 20-40min.
In the method for the present invention step (2), when not containing middle molecule acid and small molecule acid, in step (2), preferably it is warming up to
140-160 DEG C is refined, and the time of refining is preferably 5-15min；When containing middle molecule acid and during small molecule acid, step (2)
In, 180-220 DEG C is preferably warming up to, more preferable 190-210 DEG C is refined, and 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, middle molecule acid, small molecule acid, calcium hydroxide, additive are as previously mentioned, herein
It repeats no more.
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.Sustained response adds in 30ml saturations after 2 hours
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 dead plasters 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 be 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 dead plasters 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 calcium base grease composition of the present invention and preparation method thereof.
(1) by 54kg 150BS base oils, (100 DEG C of viscosity are 30mm2/ s, similarly hereinafter) and the addition of 6kg 12- hydroxy stearic acids
In fat kettle processed, the agitating and heating under 180rpm is warming up to 85 DEG C, adds in the mixture of 0.76kg calcium hydroxides and 4kg water, carries out
Saponification 0.5h；
(2) 140 DEG C are warming up to, refines 15min；
(3) 18kg 150BS base oils are added in, stirring is cooled to 120 DEG C, adds in 1.6kg 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 stearic acid calciums
Measure %；90 weight % of lubricating base oil；S12 weight %.
Embodiment 2
The present embodiment is used to illustrate calcium base grease composition of the present invention and preparation method thereof.
(1) by 25kg 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) and 13.6kg stearic acid addition fat processed
In kettle, agitating and heating, is warming up to 80 DEG C at 200 rpm, adds in the mixture of 1.83kg calcium hydroxides and 2kg water, carries out saponification
React 1h；
(2) 145 DEG C are warming up to, refines 8min；
(3) 10kg 500SN base oils are added in, stirring is cooled to 105 DEG C, adds in 0.5kg 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 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：29 weight % of calcium stearate；Profit
70 weight % of sliding base oil；S11 weight %.
Embodiment 3
The present embodiment is used to illustrate calcium base grease composition of the present invention and preparation method thereof.
(1) by 22kg PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and 10.9kg stearic acid addition system
In fat kettle, agitating and heating, is warming up to 95 DEG C at 300 rpm, adds in the mixture of 1.5kg calcium hydroxides and 4kg water, carries out soap
Change reaction 0.8h；
(2) 160 DEG C are warming up to, refines 5min；
(3) 21.5kg PAO6 synthetic hydrocarbon oils are added in, stirring is cooled to 130 DEG C, adds in 2.9kg 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 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, form and be：20 weight % of calcium stearate；Profit
75 weight % of sliding base oil；S15 weight %.
Embodiment 4
The present embodiment is used to illustrate calcium base grease composition of the present invention and preparation method thereof.
(1) by the miscella of 40kg 500SN and 150BS, (100 DEG C of viscosity are 16mm2/ s, similarly hereinafter) and 11.3kg 12- hydroxyls
Base stearic acid is added in fat kettle processed, the agitating and heating under 230rpm, is warming up to 90 DEG C, adds in 1.45kg calcium hydroxides and 2.8kg
The mixture of water carries out saponification 0.6h；
(2) 150 DEG C are warming up to, refines 10min；
(3) miscella of 25.6kg 500SN and 150BS are added in, stirring is cooled to 100 DEG C, adds in 2.4kg 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 stearic acid calciums
Measure %；82 weight % of lubricating base oil；S13 weight %.
Comparative example 1
Method according to embodiment 4 prepares calcium-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 stearic acid calciums 15.5
Weight %, 84.5 weight % of lubricating base oil.
Embodiment 5
The present embodiment is used to illustrate calcium base grease composition of the present invention and preparation method thereof.
(1) by 64.1kg 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) and the suspension of the calcium hydroxide containing 2kg
Liquid (calcium hydroxide content is 8 weight %) is added in fat kettle processed, is stirred under 180rpm, 1.6kg vinegar is added at 25 DEG C
Acid reacts 20min, then heats to 80 DEG C, adds in the 12- hydroxy stearic acids of 2.3kg, reacts 30min, then adds in 2.7kg
Octanoic acid reacts 40min；
(2) 190 DEG C are warming up to, refines 15min；
(3) 21.4kg 500SN base oils are added in, stirring is cooled to 120 DEG C, adds in 1.9kg S1, is stirred under 180rpm
Uniformly；
(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 stearic acid calciums 2.55
Weight %；3.25 weight % of calcium octoate；2.2 weight % of calcium acetate, 90 weight % of lubricating base oil；S12 weight %.
Embodiment 6
The present embodiment is used to illustrate calcium base grease composition of the present invention and preparation method thereof.
(1) by 13kg 150BS base oils, (100 DEG C of viscosity are 30mm2/ s, similarly hereinafter) and the suspension of the calcium hydroxide containing 3.9kg
Liquid (calcium hydroxide content is 10 weight %) is added in fat kettle processed, is stirred at 200 rpm, 4.5kg vinegar is added at 15 DEG C
Acid reacts 40min, then heats to 100 DEG C, adds in the 12- hydroxy stearic acids of 2.8kg, reacts 20min, then adds in 1.5kg
Terephthalic acid (TPA) reacts 30min；
(2) 210 DEG C are warming up to, refines 5min；
(3) 130kg 150BS base oils are added in, stirring is cooled to 100 DEG C, adds in 0.4kg S1, stirs at 200 rpm
Uniformly；
(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：12- hydroxy stearic acid calciums 7.95
Weight %；5.33 weight % of terephthalic acid (TPA) calcium；15.72 weight % of calcium acetate；70 weight % of lubricating base oil；S11 weight %.
Embodiment 7
The present embodiment is used to illustrate calcium base grease composition of the present invention and preparation method thereof.
(1) by 10kg PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, similarly hereinafter) and the calcium hydroxide containing 1.1kg it is outstanding
Supernatant liquid (calcium hydroxide content is 12 weight %) is added in fat kettle processed, is stirred, is added at 35 DEG C at 300 rpm
0.73kg acetic acid reacts 25min, then heats to 90 DEG C, adds in the stearic acid of 2.9kg, reacts 40min, then adds in 0.6kg
Decanedioic acid reacts 20min；
(2) 195 DEG C are warming up to, refines 10min；
(3) 8kg PAO6 synthetic hydrocarbon oils are added in, stirring is cooled to 110 DEG C, adds in 1.2kg S1, and stirring is equal at 300 rpm
It is even；
(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：12.99 weight % of calcium stearate；
3.03 weight % of decanedioic acid calcium；3.98 weight % of calcium acetate；75 weight % of lubricating base oil；S15 weight %.
Embodiment 8
The present embodiment is used to illustrate calcium base grease composition of the present invention and preparation method thereof.
(1) by the miscella of 37.8kg 500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, similarly hereinafter) and hydrogen containing 2.9kg
The suspension (calcium hydroxide content is 16 weight %) of calcium oxide is added in fat kettle processed, is stirred under 230rpm, at 50 DEG C
Lower addition 3kg acetic acid, reacts 30min, then heats to 95 DEG C, add in the stearic acid of 4.75kg, react 25min, then add in
1.2kg octanoic acids, react 35min；
(2) 205 DEG C are warming up to, refines 8min；
(3) miscella of 19kg 500SN and 150BS are added in, stirring is cooled to 130 DEG C, 2.1kgS1 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：7.32 weight % of calcium stearate；
1.97 weight % of calcium octoate；5.71 weight % of calcium acetate；82 weight % of lubricating base oil；S13 weight %.
Comparative example 2
Method according to embodiment 8 prepares calcium-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：7.55 weight % of calcium stearate；
2.03 weight % of calcium octoate；5.89 weight % of calcium acetate；84.53 weight % of lubricating base oil.
Table 1
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；Friction coefficient：SH/T
0847。
Table 2
Each indication test method：Dropping point：GB/T 3498；Work cone penetration：GB/T 269；Surface hardened layer value：GB/T
269；Oxidation onset temperature：ASTM D5483；Stencil oil-dividing：SH/T 0324；Tetra-ball machine test PB, PD：SH/T 0202；Friction
Coefficient：SH/T 0847；Copper corrosion：GB/T 7326；Anticorrosive property：GB/T 5018.
It will be understood by those skilled in the art that dropping point is higher, the high temperature resistance of lubricating grease is better；Work cone penetration
Smaller, the thickening performance of grease thickener is better；Surface hardened layer value is smaller, and the resistance hardening of lubricating grease can be better；It aoxidizes
Beginning 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 is bigger, and the bearing capacity of lubricating grease is better；Friction coefficient is smaller, and the antifriction performance of lubricating grease is better.
Embodiment 4 and comparative example 1 are compared, embodiment 8 and comparative example 2 are compared, it can be seen that the present invention
Lubricating grease have better heat-resisting quantity, inoxidizability, colloid stability, bearing capacity and antifriction performance.
The calcium base grease composition of the present invention, due to containing multipurpose additive, greatly improves the anti-attrition of lubricating grease
Ability and oxidation resistance, while the other performance of calcium-base grease is influenced less, still with splendid heat-resisting quantity, colloid
Stability and bearing capacity so that the lubricant composition can be competent in the harsh operating mode such as high temperature, high speed, high load capacity, more water
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 of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that 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 (25)
1. a kind of excellent calcium base grease composition 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 calcium 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 calcium 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 calcium base thickening agent is anti-with calcium hydroxide for acid
It should generate, the acid includes higher fatty acids, optional middle molecule acid and 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 middle molecule acid is C6-C10；The small molecule acid is acetic acid.
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 middle molecule acid are octanoic acid, benzoic acid, terephthalic acid (TPA), azelaic acid and the last of the ten Heavenly stems
At least one of diacid.
9. lubricant composition according to claim 1 or 2, wherein, the additive is also containing other antioxidant, pole
Press at least one of antiwear additive and antirust agent.
10. lubricant composition according to claim 9, wherein, the antioxidant is arylamine kind antioxidant.
11. lubricant composition according to claim 10, wherein, the antioxidant is diphenylamines, phenyl-α-naphthylamine and
At least one of di-iso-octyldiphenylamine.
12. lubricant composition according to claim 9, 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.
13. lubricant composition according to claim 9, wherein, the antirust agent is barium mahogany sulfonate, mahogany acid
At least one of sodium, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
14. the preparation method of lubricant composition described in claim 1, the method includes：
(1) by partial lubrication base oil, higher fatty acids, optional middle molecule acid and small molecule acid, calcium hydroxide Hybrid Heating,
Carry out saponification；
(2) heating is refined；
(3) remaining lubricating base oil is added in, 100-130 DEG C is cooled to, then adds in additive；
(4) it is ground 2-4 times by three-roller.
15. 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 calcium base prepared by higher fatty acids, optional middle molecule acid and small molecule acid, calcium hydroxide is thick
The dosage of agent is 8-30 weight %, and the dosage of additive is 0.5-10 weight %.
16. the method according to claims 14 or 15, 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 %.
17. 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 %.
18. the method according to claims 14 or 15, wherein, the partial lubrication base oil and the remaining lubrication base
The weight ratio of oil is 50-75:25-50.
19. the method according to claims 14 or 15, wherein, the molar ratio of optional middle molecule acid and higher fatty acids is
1:The total amount of 0.37-3.4, higher fatty acids and optional middle molecule acid is 1 with the molar ratio of optional small molecule acid:0.9-4.
20. the method according to claims 14 or 15, wherein,
When not containing middle molecule acid and small molecule acid, step (1) includes：Partial lubrication base oil and higher fatty acids are mixed
Heating is warming up to 80-105 DEG C, adds in calcium hydroxide and carries out saponification, the saponification time is 0.2-1.5h；
When containing middle molecule acid and during small molecule acid, step (1) includes：Partial lubrication base oil and calcium hydroxide are mixed,
It at 15-50 DEG C, adds in small molecule acid and carries out the first saponification, then heat to 80-100 DEG C, add in higher fatty acids and carry out
Second saponification, molecule acid carries out third saponification, the first saponification, the second saponification, third in then adding in
The time of saponification is 10-60min.
21. according to the method for claim 20, wherein, when not containing middle molecule acid and small molecule acid, step (1) is wrapped
It includes：By partial lubrication base oil and higher fatty acids Hybrid Heating, it is warming up to 80-95 DEG C.
22. it according to the method for claim 20, wherein, when not containing middle molecule acid and small molecule acid, is wrapped in step (1)
It includes：It adds in calcium hydroxide and carries out saponification, the saponification time is 0.5-1h.
23. according to the method for claim 20, wherein, when containing middle molecule acid and during small molecule acid, step (1) includes：
First saponification, the second saponification, third saponification time be 20-40min.
24. the method according to claims 14 or 15, wherein,
When not containing middle molecule acid and small molecule acid, in step (2), it is warming up to 140-160 DEG C and is refined, the time of refining
For 5-15min；
When containing middle molecule acid and during small molecule acid, in step (2), being warming up to 180-220 DEG C and refined, the time of refining is
5-15min。
25. the method according to claim 11, wherein,
When containing middle molecule acid and during small molecule acid, in step (2), being warming up to 190-210 DEG C and refined, the time of refining is
5-15min。
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| CN107254346B (en) * | 2017-06-14 | 2020-04-21 | 太原理工大学 | Calcium zirconium phosphate-based lubricating grease and preparation method thereof |
| CN107523383B (en) * | 2017-08-01 | 2020-01-31 | 太原理工大学 | Environment-friendly layered calcium potassium phosphate grease and preparation method thereof |
| CN107502418B (en) * | 2017-08-01 | 2020-01-31 | 太原理工大学 | Environment-friendly layered potassium magnesium calcium phosphate grease and preparation method thereof |
| CN112522017B (en) * | 2019-09-17 | 2023-03-31 | 中国石油化工股份有限公司 | Composite barium-based lubricating grease and preparation method thereof |
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