CN109942510A - Thiazole derivative grafted olefin and its preparation method and application - Google Patents
Thiazole derivative grafted olefin and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to lubricate oil/grease technical field, a kind of thiazole derivative grafted olefin and its preparation method and application is specifically disclosed.The thiazole derivative grafted olefin has structural formula shown in specification formula (I)~(IV).Heterocyclic compound of the thiazole derivative grafted olefin containing S, N provided by the invention, with form compact and stable structure, bearing capacity and greasy property are good, can form adsorbed film and chemical reaction film in metal surface, can effectively improve the anticorrosive of lubricating oil, antifriction, wear-resistant and extreme pressure property.It is a kind of environmental-friendly Ashless type multifunctional material simultaneously as being free of P and heavy metal element, polymerization reaction can occurs with alhpa olefin and generate thiazole derivative grafting polyalphaolefin base and be used for lubricating oil or lubricating grease.
Description
Technical field
The invention belongs to lubricate oil/grease technical field, and in particular to a kind of thiazole derivative grafted olefin and its preparation
Methods and applications.
Background technique
Lubricating oil is a kind of multifunctional lubricant for protecting mechanical facility, it is widely used in numerous areas.
Generally, lubricating oil is made of base oil and additive, and base oil is the theme of lubricating oil, determine the viscosity of lubricating oil, density,
The most basic physical property and service performance such as flash-point, condensation point, pour point, but if base oil is used alone, can exist anti-
Deficiency in terms of the greasy properties such as burn into is anti-oxidant, antiwear and antifriction, resistance to extreme pressure, it is therefore desirable to various additives be added, to adapt to
The demand of various operating conditions.
The drawback that most tradition EP agents presence keep the reduction of oil product antioxygenic property, copper corrosion serious, common two
Alkyl zinc dithiophosphate (ZDDP) contains more S, P, is unable to satisfy increasingly harsh environmental requirement.And thiazole derivative
It is a kind of additive with excellent properties, it is not only without phosphorus ashless but also multi-party with anticorrosive, extreme-pressure anti-wear, antioxygen etc.
Face performance, thus be usually added in base oil as additive.But since it is heterocycle compound, it is most of
It is almost insoluble in conventional base oil, even if being modified to it to improve the compatibility with base oil, it is added as additive
In base oil also can exist disperse it is unstable, be easy to the problems such as settling.
Summary of the invention
Oil after, extreme pressure and antiwear behavior difference poor for current base oil antiseptic property and thereto addition thiazoles additive
The problems such as dissolubility is poor, dispersion is unstable, the present invention provide a kind of thiazole derivative grafted olefin and preparation method thereof.
Further, the present invention provides a kind of base oil and the base comprising above-mentioned thiazole derivative grafted olefin structure
The preparation method of plinth oil.
Further, the present invention also provides a kind of lubricating oil or lubricating grease comprising the base oil.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of thiazole derivative grafted olefin, the thiazole derivative grafted olefin have shown in formula (I)~(IV)
Structural formula:
Wherein, R1Selected from carbon atom number be 1~30 alkyl, any one of alkyl thiol；R2Selected from NH or S, a >=0；
R3Selected from carbon atom number be 1~30 alkyl, any one of alkyl thiol, m=1 or 2 or 3, n >=0.
Correspondingly, the preparation method of thiazole derivative grafted olefin as described above, comprising the following steps:
Carbon enoic acid and acylating agent are subjected to mixed processing, are warming up to 40~90 DEG C, constant temperature reflux is then evaporated under reduced pressure, obtains
To carbene acyl chlorides；
The carbene acyl chlorides, thiazole derivative and reaction medium X are subjected to mixing treatment, are warming up to 40~90 DEG C, instead
1~5h is answered, being made has structural formula thiazole derivative grafted olefin as shown in formula (I)~(II)；
Alternatively, thiazole derivative, carboxylic acid A and reaction medium Y are carried out mixing treatment, 50~100 DEG C are warming up to, reaction
1~2h is down to room temperature after filtering and obtaining filtrate, and the pH for adjusting filtrate is 1~2, obtains the precipitating of precipitation, and recrystallized
Processing, obtains thiazoles mercaptan acid；
The thiazoles mercaptan acid and carbene alcohol are subjected to mixing treatment, are warming up to 130~180 DEG C, 6~12h is reacted, obtains
There must be structural formula thiazole derivative grafted olefin as shown in formula (III)~(IV).
Correspondingly, a kind of base oil, the base oil are that thiazole derivative is grafted alhpa olefin base oil；The thiazoles
Derivative is selected from least one thiazole derivative grafted olefin shown in formula (I)~(IV).
And the preparation method of the base oil the following steps are included: make formula (I)~(IV) institute under the effect of the catalyst
Polymerization reaction occurs for any thiazole derivative grafted olefin and alhpa olefin shown, obtains base oil.
Further, a kind of lubricating oil contains base oil as described above in the lubricating oil.
A kind of lubricating grease contains base oil as described above in the lubricating grease.
The invention has the benefit that
Compared with the existing technology, thiazole derivative grafted olefin provided by the invention, due to the mercapto of thiazole derivative
Base or amino and olefin(e) compound are grafted or are grafted by sulfydryl reactive grafting active group and olefin(e) compound, therefore
With the function that high polymeric occurs with alhpa olefin, so that the polymerizate comprising thiazole derivative structure has well
Corrosion resistance, extreme pressure and antiwear behavior.
The preparation of thiazole derivative grafted olefin of the invention has simple process, does not need complicated equipment, can grasp
The features such as strong feature of the property made, and thiazole derivative grafted olefin yield height, purity is high, by-product is few.
Base oil of the invention since it contains thiazole derivative structure, thus there is good anticorrosive, extreme pressure to resist
Characteristic is ground, while also having the characteristics that good oil-soluble, stably dispersing, not easily settled, therefore when as lubricating oil not
It needs that such additive is added thereto again, the cost of lubricating grease can be effectively reduced.
Lubricating oil or lubricating grease rouge provided by the invention, due to containing in base oil therein, oil-soluble is good, dispersion is steady
Fixed, not easily settled and corrosion resistance, extreme-pressure anti-wear, the good thiazole derivative structure of inoxidizability, are prepared by it
Lubricating oil or lubricating grease equally have preferable anticorrosive and extreme pressure and antiwear behavior, so as to reduce excessive corrosion inhibitor
With the addition of extreme pressure anti-wear additives.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The present invention provides a kind of thiazole derivative grafted olefin, the thiazole derivative grafted olefin has formula
(I) structural formula shown in~(IV):
Wherein, R1Selected from carbon atom number be 1~30 alkyl, any one of alkyl thiol；R2Selected from NH or S, a >=0；
R3Selected from carbon atom number be 1~30 alkyl, any one of alkyl thiol, m=1 or 2 or 3, n >=0.
Wherein, the specific structure of the thiazole derivative grafted olefin of formula (I) is preferred:
The specific structure of the thiazole derivative grafted olefin of formula (II) is preferred:
The specific structure of the derivative grafted olefin of the thiazoles of formula (III) is preferred:
The specific structure of the thiazole derivative grafted olefin of formula (IV) is preferred:
The thiazole derivative grafted olefin that foregoing invention provides, due to the sulfydryl or amino and alkene of thiazole derivative
Compound grafting is grafted by sulfydryl reactive grafting active group and olefin(e) compound, therefore is had and sent out with alhpa olefin
With alhpa olefin high polymeric can occur for the function of raw high polymeric under the action of catalyst, to assign polymerizate with good
Corrosion resistance well, extreme pressure anti-wear.Additionally, due to heterocyclic compound of the thiazole derivative grafted olefin containing S, N of the invention
Object, with form compact and stable structure, bearing capacity and greasy property are all preferable, can form adsorbed film and change in metal surface
Reaction film is learned, the anticorrosive of lubricating oil, antifriction, wear-resistant and extreme pressure property are effectively improved.Meanwhile P and heavy metal element are free of, it is
A kind of environmental-friendly Ashless type multifunctional material.
Further, the present invention also provides the preparation methods of thiazole derivative grafted olefin as described above.
The preparation method of the thiazole derivative grafted olefin as shown in formula (I)~(II) the following steps are included:
Carbon enoic acid and acylating agent are subjected to mixed processing, are warming up to 40~90 DEG C, constant temperature reflux is then evaporated under reduced pressure, obtains
To carbene acyl chlorides；
The carbene acyl chlorides, thiazole derivative and reaction medium X are subjected to mixing treatment, are warming up to 40~90 DEG C, instead
1~5h is answered, being made has structural formula thiazole derivative grafted olefin as shown in formula (I)~(II).
For another example thiazole derivative grafted olefin shown in formula (III)~(IV) preparation method the following steps are included:
Thiazole derivative, carboxylic acid A and reaction medium Y are subjected to mixing treatment, are warming up to 50~100 DEG C, reaction 1~
2h is down to room temperature after filtering and obtaining filtrate, and the pH for adjusting filtrate is 1~2, obtains the precipitating of precipitation, and carry out at recrystallization
Reason, obtains thiazoles mercaptan acid；
The thiazoles mercaptan acid and carbene alcohol are subjected to mixing treatment, are warming up to 130~180 DEG C, 6~12h is reacted, obtains
There must be structural formula thiazole derivative grafted olefin as shown in formula (III)~(IV).
In the preparation method of thiazole derivative grafted olefin shown in above-mentioned formula (I)~(II), acylating agent is selected from oxalyl
At least one of chlorine, thionyl chloride, chlorobenzoyl chloride；The reaction medium X is selected from acetone, N,N-dimethylformamide, tetrahydro
At least one of furans, this few class reaction medium have preferable point to thiazole derivative and carbene acyl chlorides mixed system
It dissipates, compatibility performance；The carbon diluted acid isA >=0, double bond can polymerize with alkene,
It reacts to form grafting thiazole with sulfydryl or amino after carboxyl is acylated.
In the preparation method of thiazole derivative grafted olefin shown in above-mentioned formula (I)~(II), the feed ratio of each raw material
Example is preferably as follows: according to molar ratio and acylating agent by chlorine mole in terms of, the carbon diluted acid: acylating agent=1:(0.5~2)；It is described
Carbene acyl chlorides: thiazole derivative=(0.5~2): 1.
It is further preferred that according to molar ratio and acylating agent by chlorine mole in terms of, the carbon diluted acid: acylating agent=1:(0.8
~1.1)；The carbene acyl chlorides: thiazole derivative=(0.7~1.2): 1.Acylating agent is slightly excessive, is conducive to improve yield, when
When acylating agent is chlorobenzoyl chloride, slightly excessive chlorobenzoyl chloride is conducive to inhibit thermal polymerization, reduces the generation of side reaction, but excessively too
Yield will mostly be reduced.
Specifically, the reaction equation of thiazole derivative grafted olefin shown in formula (I)~(II) is as follows:
Wherein, a >=0, R1Selected from carbon atom number be 1~30 alkyl, any one of alkyl thiol, R2For NH or S.
In the preparation method of thiazole derivative grafted olefin shown in above-mentioned formula (III)~(IV), the carboxylic acid A is selected from
Any one of monoxone, chloropropionic acid, acrylic acid, butenoic acid, wherein sulfydryl is sent out under the action of reaction medium Y with carboxylic acid containing chlorine
With carboxylic acid containing double bonds addition reaction occurs for raw substitution reaction.
The reaction medium Y is selected from any one of sodium hydroxide solution, potassium hydroxide solution, sulfuric acid, and sodium hydroxide is molten
Liquid, potassium hydroxide solution mass concentration be 1%~10%, the mass concentration of sulfuric acid is not less than 70%.Wherein, reaction medium Y
Catalytic action is played in the reaction system, when carboxylic acid A is monoxone or chloropropionic acid, using alkali as catalytic condition, sulfydryl occurs and replaces
Halogen reaction；When carboxylic acid A is acrylic acid or butenoic acid, using acid as catalytic condition, the addition reaction of double bond occurs, to make thiophene
Zole derivatives carboxyl grafting group.
In the preparation method of thiazole derivative grafted olefin shown in above-mentioned formula (III)~(IV), each raw material feeds intake
Ratio is preferably as follows: according to molar ratio, the thiazole derivative: carboxylic acid A: reaction medium Y=(0.5~3): 1:(1~3)；
The thiazoles mercaptan acid: carbene alcohol=(0.5~2): 1.When carboxylic acid A is monoxone or chloropropionic acid, reaction medium Y is then alkali soluble
Liquid, carboxylic acid A excessively make thiazole fully reacting, and reaction medium Y, which is excessively conducive to reaction, to carry out；When carboxylic acid A is acrylic acid
Or when butenoic acid, reaction medium Y is then the concentrated sulfuric acid, and reaction medium Y can also be suitably excessive at this time.Thiazole: A: reaction is situated between
The theoretical proportions of matter Y are (1~2): 1:1, and reaction medium Y is appropriate excessive preferable, is (0.5~2): 1:(1 it is advantageous to ratio
~2), deviation ratio is too big so that yield is reduced, and side reaction occurs.
It is further preferred that according to molar ratio, the thiazole derivative: carboxylic acid A: reaction medium Y=(0.8~2): 1:
(1~2)；The thiazoles mercaptan acid: carbene alcohol=(0.7~1.2): 1.
In the preparation method of thiazole derivative grafted olefin shown in above-mentioned formula (III)~(IV), the pH value tune of filtrate
Section can be using concentrated hydrochloric acid etc..
In the preparation method of thiazole derivative grafted olefin shown in above-mentioned formula (III)~(IV), the acquisition of sediment,
Including being filtered, being washed to the precipitating of precipitation, dried.The precipitating of acquisition is recrystallized using dehydrated alcohol, is thus obtained
Obtain the higher thiazoles mercaptan acid of purity.
Specifically, the reaction equation of thiazole derivative grafted olefin shown in formula (III)~(IV) is as follows:
For thiazole derivative grafted olefin shown in formula (III), reaction equation is as follows:
Wherein, m=b+1, b=1 or 2；
Wherein, m
=c, c=1 or 2, R3Selected from carbon atom number be 1~30 alkyl, any one of alkyl thiol, n >=0；
For thiazole derivative grafted olefin shown in formula (IV), reaction equation is as follows:
Wherein, m=b+1, b=1 or 2；
Wherein, m=c, c=1 or 2；
n≥0。
Thiazole derivative used includes but is not limited to thiophene in the preparation method of thiazole derivative grafted olefin of the present invention
Diazole and its derivative, phenyl thiazole and its derivative.
The thiazole derivative grafted olefin of the preparation method of thiazole derivative grafted olefin of the invention, acquisition has
The features such as yield is high, with high purity, by-product is few, and its preparation process is simple, does not need complicated equipment, has operability
By force, it is suitable for industrialization large-scale production.
On the basis of above-mentioned thiazole derivative grafted olefin, formula (I)~(IV) institute is utilized the present invention also provides a kind of
Show that the thiazole derivative grafted olefin of structural formula synthesizes a kind of base oil.
Specifically, the preparation method of the base oil includes the following steps:
Under the action of catalyst, it polymerize thiazole derivative grafted olefin shown in formula (I)~(IV) with alhpa olefin
Reaction obtains thiazole derivative and is grafted polyalphaolefin base.
Preferably, catalyst is selected from BF3、AlCl3, any one of Ziegler-Natta.And alhpa olefin is selected from C8~C12
Alhpa olefin, preferably 1- octene, 1- decene, 1- dodecylene.
Base oil of the invention can make due to directly polymerizeing thiazole derivative grafted olefin with alhpa olefin
Thiazole derivative grafted olefin becomes a part of base oil, thoroughly solves that dispersion is uneven, dispersion is unstable, it is heavy to be easy
The problem of drop, and can also make base oil that there is good corrosion resistance, extreme pressure anti-wear etc., thus the base oil can be straight
It connects and is used as lubricating oil, without such additive is added into lubricating oil again.
Because of this, containing the preparation side of above-mentioned base oil in the lubricating grease the present invention also provides a kind of lubricating grease
The base oil that method obtains.It specifically can be that routinely lubricating grease preparation process is made by above-mentioned lubricating oil, i.e., by above-mentioned basis
Oil and thickening agent, antioxidant etc. are mixed with, and lubricating grease is obtained.Thickening agent is lithium soap thickening agent common in lubricating grease
Or powder thickening agent, not reinflated herein to repeat, thus obtained lubricating grease can show good corrosion resistance and wear-resistant
Damage, resistance to extreme pressure energy, it is possible to reduce the addition of excessive corrosion inhibitor and extreme pressure anti-wear additives.
Technical solution in order to better illustrate the present invention, the skill illustrated the present invention below by way of multiple embodiments
Art scheme.
Embodiment 1
A kind of thiazole derivative grafted olefin, base oil and preparation method thereof.The thiazole derivative grafted olefin is
2-[4-morpholinodithio base-sulfydryl acrylate；Base oil is that thiazole derivative is grafted polyalphaolefin base.
Wherein, 2-[4-morpholinodithio base-sulfydryl acrylate preparation method the following steps are included:
(1) 1.05mol acrylic acid is added drop-wise in 1mol thionyl chloride, adds 5 ‰ hydroquinone polymerization inhibitor, stirred
Uniformly, 50 DEG C are warming up to, acryloyl chloride, yield 83% is made in constant temperature reflux, vacuum distillation；
(2) acryloyl chloride obtained is uniformly mixed in acetone with 2-mercaptobenzothiazole, is reacted under conditions of 50 DEG C
2-[4-morpholinodithio base-sulfydryl acrylate is made in 1.5h.
Above-mentioned thiazole derivative grafting polyalphaolefin base the preparation method is as follows:
The aforementioned 2-[4-morpholinodithio base-sulfydryl acrylate being prepared and 1- decene are added in polymerization reaction system,
In AlCl3Catalytic condition it is lower 60 DEG C polymerization be prepared thiazole derivative grafting polyalphaolefin base.
Embodiment 2
A kind of thiazole derivative grafted olefin, base oil and preparation method thereof.The thiazole derivative grafted olefin is
Thiadiazoles sulfydryl decylate；Base oil is that thiazole derivative is grafted polyalphaolefin base.
Wherein, thiadiazoles sulfydryl decylate preparation method the following steps are included:
(1) 0.8mol decylenic acid is added drop-wise in 1mol chlorobenzoyl chloride, adds 5 ‰ hydroquinone polymerization inhibitor, stirred
Uniformly, 70 DEG C are warming up to, decene acyl chlorides, yield 71% is made in constant temperature reflux, vacuum distillation；
(2) decene acyl chlorides obtained is uniformly mixed in tetrahydrofuran with 2- methyl-5-sulfydryl-1,3,4-thiadiazole,
3h is reacted under the conditions of 70 DEG C, thiadiazoles sulfydryl decylate is made.
Above-mentioned thiazole derivative grafting polyalphaolefin base the preparation method is as follows:
The aforementioned thiadiazoles sulfydryl decylate being prepared and 1- decene are added in polymerization reaction system, in BF3Urge
Thiazole derivative grafting polyalphaolefin base is prepared in 25 DEG C of polymerizations under the conditions of change.
Embodiment 3
A kind of thiazole derivative grafted olefin, base oil and preparation method thereof.The thiazole derivative grafted olefin is
Thiadiazoles sulphur acetic acid ubidecarenone；Base oil is that thiazole derivative is grafted polyalphaolefin base.
Wherein, thiadiazoles sulphur acetic acid ubidecarenone preparation method the following steps are included:
(1) by 0.1mol2- methyl-5-sulfydryl-1,3,4-thiadiazole, the hydrogen of 0.11mol monoxone and 0.22mol2wt%
Aqueous solution of sodium oxide is stirred to react 3h at 85 DEG C, filters, is cooled to room temperature, and is acidified to pH=1.5 with hydrochloric acid, precipitating is precipitated, take out
Filter is washed, dry, obtains thiadiazoles sulphur acetic acid, yield 81%.
(2) after mixing by thiadiazoles sulphur acetic acid obtained and 0.2mol decenol, temperature is controlled at 160 DEG C, is reacted
6h is cooled to room temperature, and obtains thiadiazoles sulphur acetic acid ubidecarenone.
Above-mentioned thiazole derivative grafting polyalphaolefin base the preparation method is as follows:
By it is aforementioned be prepared thiadiazoles sulphur acetic acid ubidecarenone and 1- decene are added into polymerization reaction system,
Thiazole derivative grafting polyalphaolefin base is prepared in the lower 80 DEG C of polymerizations of the catalytic condition of Ziegler-Natta.
Embodiment 4
A kind of thiazole derivative grafted olefin, base oil and preparation method thereof.The thiazole derivative grafted olefin is
Benzothiazole sulphur propionic acid butene esters；Base oil is that thiazole derivative is grafted polyalphaolefin base.
Wherein, benzothiazole sulphur propionic acid butene esters preparation method the following steps are included:
(1) by 0.2mol2- mercaptobenzothiazoler, the potassium hydroxide aqueous solution of 0.25mol chloropropionic acid and 0.5mol2wt%
It is uniformly mixed, is stirred to react 1.5h at 95 DEG C, filter, be cooled to room temperature, be acidified to pH=1 with hydrochloric acid, precipitating is precipitated, filter,
Washing, it is dry, obtain benzothiazole sulphur propionic acid, yield 75%.
(2) after mixing by benzothiazole sulphur propionic acid obtained and 0.2mol butenol, temperature is controlled at 150 DEG C, instead
7h is answered, is cooled to room temperature, benzothiazole sulphur propionic acid butene esters are obtained.
Above-mentioned thiazole derivative grafting polyalphaolefin base the preparation method is as follows:
The aforementioned benzothiazole sulphur propionic acid butene esters being prepared are added in the polymerization reaction system of 1- octene,
AlCl3Catalytic condition it is lower 60 DEG C polymerization be prepared thiazole derivative grafting polyalphaolefin base.
Embodiment 5
A kind of thiazole derivative grafted olefin, base oil and preparation method thereof.The thiazole derivative grafted olefin is
Thiadiazoles sulphur butyric acid octene ester；Base oil is that thiazole derivative is grafted polyalphaolefin base.
Wherein, thiadiazoles sulphur butyric acid octene ester preparation method the following steps are included:
(1) by 0.2mol2- methyl -5- sulfydryl -1,3,4- thiadiazoles, the sulphur of 0.11mol butenoic acid and 0.12mol70%
Acid is uniformly mixed, and is stirred to react 1h at 80 DEG C, is filtered, is cooled to room temperature, and is acidified to pH=1 with hydrochloric acid, be precipitated precipitating, filtering,
Washing, drying, obtain thiadiazoles sulphur butyric acid, yield 72%.
(2) after mixing by thiadiazoles sulphur butyric acid obtained and 0.1mol matsutake alcohol, temperature is controlled at 170 DEG C, is reacted
10h is cooled to room temperature, and obtains thiadiazoles sulphur butyric acid octene ester.
Above-mentioned thiazole derivative grafting polyalphaolefin base the preparation method is as follows:
The aforementioned thiadiazoles sulphur butyric acid octene ester being prepared is added in the polymerization reaction system of 1- octene,
Thiazole derivative grafting polyalphaolefin base is prepared in the lower 80 DEG C of polymerizations of the catalytic condition of Ziegler-Natta.
Embodiment 6
A kind of thiazole derivative grafted olefin, base oil and preparation method thereof.The thiazole derivative grafted olefin is
Benzothiazole sulphur propylene carbonate；Base oil is that thiazole derivative is grafted polyalphaolefin base.
Wherein, benzothiazole sulphur propylene carbonate preparation method the following steps are included:
(1) sulfuric acid of 0.2mol2- mercaptobenzothiazoler, 0.16mol acrylic acid and 0.18mol70% is uniformly mixed,
70 DEG C are stirred to react 2h, filter, are cooled to room temperature, and are acidified to pH=1.5 with hydrochloric acid, and precipitating is precipitated, filtering, washes, is dry, obtains
To benzothiazole sulphur propionic acid, yield 78%.
(2) after mixing by benzothiazole sulphur propionic acid obtained and 0.15mol propenyl, temperature is controlled at 145 DEG C, instead
7h is answered, is cooled to room temperature, benzothiazole sulphur propylene carbonate is obtained.
Above-mentioned thiazole derivative grafting polyalphaolefin base the preparation method is as follows:
The aforementioned benzothiazole sulphur propylene carbonate being prepared is added in the polymerization reaction system of 1- dodecylene,
Thiazole derivative grafting polyalphaolefin base is prepared in the lower 80 DEG C of polymerizations of the catalytic condition of Ziegler-Natta.
Comparative example 1
A kind of lubricating oil, for common polyalphaolefin base Mobil PAO10.
Comparative example 2.
A kind of lubricating oil is made of 99% PAO10 base oil and 1% dimercaptothiodiazole dimer.
Comparative example 3
A kind of lubricating oil, by 99% PAO10 base oil and 1% molybdenum dialkyl-dithiophosphate.
For the oil property for verifying the base oil of Examples 1 to 6 and the lubricating oil of comparative example 1~3, it is carried out accordingly
Performance detection.
According to GB/T3142-82 standard, in each base oil maximum nonseizure load PB and sintering load PD carry out
Measurement.Experiment is using Jinan unexpectedly at tetra- ball frictional testing machine of the MRS-10 of measuring technology Co., Ltd.Experiment carries out at room temperature,
Revolving speed is 1450r/min, and experimental period 10s, the results are shown in Table 1.
On the Jinan unexpectedly omnipotent friction wear testing machine of NMW-1 at measuring technology production, according to NB/SH/T0189-
2017 standards carry out long mill, experiment condition are as follows: load 40kgf, revolving speed 1200r/min, 75 DEG C of experimental temperature, and experimental period
60min.The results are shown in Table 1 for wear scar diameter (WSD).
Copper corruption experiment is carried out according to the standard method of GB/T5096-2017, experiment condition is 100 DEG C of constant temperature 3h, test knot
Fruit is listed in Table 1 below.
Table 1
As shown in Table 1, existing base oil is in the case where being added without additive, oil product no corrosion, but extreme pressure is anti-
It grinds poor.Some thiazoles additives are directly added into base oil, then additive cannot be dissolved in oil, be precipitated.It is added
After the extreme pressure anti-wear additives molybdenum dialkyl-dithiophosphate of low-phosphorous environment-friendly, extreme pressure and antiwear behavior is improved, but due to the additive pair
Copper sheet has corrosion, so that copper corruption is deteriorated；At this time, it is also necessary to efficient corrosion inhibitor be added to make up the corrosion caused by it
Property, but the addition of excessive additive, on the one hand increase cost, on the other hand each additive has volatility, increases the row of VOC
It puts, is unfavorable for environmental requirement.In actual application, many traditional extreme pressure anti-wear additives can all have the case where corrosion metal,
And then it also requires that additional corrosion inhibitor is added.And since Examples 1 to 6 is to be grafted to prepare by thiazole derivative
Polyalphaolefin base does not need that excessive additive is added, while just there is preferable corrosion resistance, extreme-pressure anti-wear
Performance also gets a promotion, thus the base oil that Examples 1 to 6 obtains can be used directly as lubricating oil.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.
Claims (10)
1. a kind of thiazole derivative grafted olefin, which is characterized in that the thiazole derivative grafted olefin have formula (I)~
(IV) structural formula shown in:
Wherein, R1Selected from carbon atom number be 1~30 alkyl, any one of alkyl thiol；R2Selected from NH or S, a >=0；R3Choosing
From carbon atom number be 1~30 alkyl, any one of alkyl thiol, m=1 or 2 or 3, n >=0.
2. a kind of preparation method of thiazole derivative grafted olefin, which comprises the following steps:
Carbon enoic acid and acylating agent are subjected to mixed processing, are warming up to 40~90 DEG C, constant temperature reflux is then evaporated under reduced pressure, obtains carbon
Alkene acyl chlorides；
The carbene acyl chlorides, thiazole derivative and reaction medium X are subjected to mixing treatment, are warming up to 40~90 DEG C, reaction 1~
5h, being made has structural formula thiazole derivative grafted olefin as shown in formula (I)~(II)；
Alternatively, thiazole derivative, carboxylic acid A and reaction medium Y are carried out mixing treatment, it is warming up to 50~100 DEG C, reaction 1~
2h obtains filtrate through filtering, and filtrate temperature is down to room temperature, and the pH for adjusting filtrate is 1~2, obtains the precipitating of precipitation, and carry out weight
Crystallization treatment obtains thiazoles mercaptan acid；
The thiazoles mercaptan acid and carbene alcohol are subjected to mixing treatment, are warming up to 130~180 DEG C, 6~12h is reacted, is had
There is structural formula thiazole derivative grafted olefin as shown in formula (III)~(IV)；
Wherein,
Wherein, R1Selected from carbon atom number be 1~30 alkyl, any one of alkyl thiol；R2Selected from NH or S, a >=0；R3Choosing
From carbon atom number be 1~30 alkyl, any one of alkyl thiol, m=1 or 2 or 3, n >=0.
3. the preparation method of thiazole derivative grafted olefin as claimed in claim 2, which is characterized in that the acylating agent choosing
From at least one of oxalyl chloride, thionyl chloride, chlorobenzoyl chloride；The reaction medium X is selected from acetone, N, N- dimethyl formyl
At least one of amine, tetrahydrofuran；The carbon diluted acid is
4. the preparation method of thiazole derivative grafted olefin as claimed in claim 2 or claim 3, which is characterized in that according to mole
Than and acylating agent by chlorine mole in terms of, the carbon diluted acid: acylating agent=1:(0.5~2)；The carbene acyl chlorides: thiazoles is derivative
Object=(0.5~2): 1.
5. the preparation method of thiazole derivative grafted olefin as claimed in claim 2, which is characterized in that the reaction medium
Y is selected from any one of sodium hydroxide solution, potassium hydroxide solution, sulfuric acid；The carboxylic acid A is selected from monoxone, chloropropionic acid, propylene
Any one of acid, butenoic acid.
6. the preparation method of the thiazole derivative grafted olefin as described in claim 2 or 5, which is characterized in that according to mole
Than the thiazole derivative: carboxylic acid A: reaction medium Y=(0.5~3): 1:(1~3)；The thiazoles mercaptan acid: carbene
Alcohol=(0.5~2): 1.
7. a kind of base oil, which is characterized in that the base oil is that thiazole derivative is grafted alhpa olefin base oil；The thiazole
Analog derivative at least one thiazole derivative grafted olefin shown in formula (I)~(IV) in claim 1.
8. the preparation method of base oil as claimed in claim 7, which comprises the following steps:
Under the effect of the catalyst occur any thiazole derivative grafted olefin and alhpa olefin as described in claim 1 poly-
Reaction is closed, base oil is obtained.
9. a kind of lubricating oil, which is characterized in that contain base oil as claimed in claim 7 in the lubricating oil.
10. a kind of lubricating grease, which is characterized in that contain base oil as claimed in claim 7 in the lubricating grease.
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