CN109942510B - Thiazole derivative grafted olefin and preparation method and application thereof - Google Patents
Thiazole derivative grafted olefin and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lubricating oil/grease, and particularly discloses thiazole derivative grafted olefin as well as a preparation method and application thereof. The thiazole derivative grafted olefin has structural formulas shown in the formulas (I) to (IV) in the specification. The thiazole derivative grafted olefin S, N-containing heterocyclic compound provided by the invention has a compact and stable structure, good bearing capacity and lubricating performance, can form an adsorption film and a chemical reaction film on the surface of metal, and can effectively improve the corrosion resistance, friction reduction, wear resistance and extreme pressure performance of lubricating oil. Meanwhile, the material does not contain P and heavy metal elements, is an environment-friendly ashless multifunctional material, and can generate polymerization reaction with alpha olefin to generate thiazole derivative grafted poly-alpha olefin base oil which is used for lubricating oil or lubricating grease.
Description
Technical Field
The invention belongs to the technical field of lubricating oil/grease, and particularly relates to thiazole derivative grafted olefin as well as a preparation method and application thereof.
Background
Lubricating oil is a multifunctional lubricant for protecting mechanical facilities, and is widely used in various fields. Generally, a lubricating oil consists of a base oil and additives, wherein the base oil is the subject of the lubricating oil and determines the most basic physical properties and use performances of the lubricating oil, such as viscosity, density, flash point, condensation point, pour point and the like, but if the base oil is used alone, the lubricating properties of corrosion resistance, oxidation resistance, wear resistance, friction reduction, extreme pressure resistance and the like are insufficient, so that various additives are required to be added to meet the requirements of various working conditions.
Most of the traditional extreme pressure additives have the disadvantages of reduced oxidation resistance of oil products and serious copper corrosion, and the commonly used Zinc Dialkyl Dithiophosphate (ZDDP) contains more S, P and cannot meet increasingly severe environmental protection requirements. The thiazole derivative is an additive with excellent performance, not only has no phosphorus and ash, but also has various performances of corrosion resistance, extreme pressure wear resistance, oxidation resistance and the like, so that the thiazole derivative is often used as an additive to be added into base oil. However, since it is a heterocyclic compound, most of them are hardly soluble in conventional base oils, and even if they are modified to improve compatibility with base oils, they have problems of unstable dispersion, easy sedimentation, and the like when added as additives to base oils.
Disclosure of Invention
Aiming at the problems of poor corrosion resistance and extreme pressure wear resistance of the conventional base oil, poor oil solubility, unstable dispersion and the like after thiazole additives are added into the base oil, the invention provides thiazole derivative grafted olefin and a preparation method thereof.
Further, the invention provides a base oil containing the thiazole derivative grafted olefin structure and a preparation method of the base oil.
Further, the invention also provides lubricating oil or lubricating grease containing the base oil.
In order to achieve the above object, the technical solution of the present invention is as follows:
a thiazole derivative-grafted olefin having the structural formula shown in formulas (I) to (IV):
wherein R is1Any one selected from alkyl and alkyl sulfydryl with 1-30 carbon atoms; r2Selected from NH or S, a is more than or equal to 0; r3Is selected from alkyl and alkyl sulfydryl with 1-30 carbon atoms, m is 1 or 2 or 3, and n is not less than 0.
Accordingly, the preparation method of thiazole derivative grafted olefin comprises the following steps:
mixing the carbon olefine acid and the acylating agent, heating to 40-90 ℃, refluxing at constant temperature, and then distilling under reduced pressure to obtain the carbon olefine acid chloride;
mixing the carbenoyl chloride, the thiazole derivative and a reaction medium X, heating to 40-90 ℃, and reacting for 1-5 h to prepare thiazole derivative grafted olefin with a structural formula shown in formulas (I) - (II);
or mixing the thiazole derivative, the carboxylic acid A and the reaction medium Y, heating to 50-100 ℃, reacting for 1-2 h, filtering to obtain filtrate, cooling to room temperature, adjusting the pH of the filtrate to 1-2, obtaining precipitated precipitate, and performing recrystallization to obtain thiazole mercaptoacid;
mixing the thiazole mercapto acid and the carbene alcohol, heating to 130-180 ℃, and reacting for 6-12 h to obtain the thiazole derivative grafted olefin with the structural formulas (III) - (IV).
Accordingly, a base oil which is a thiazole derivative-grafted alpha olefin base oil; the thiazole derivative is selected from at least one thiazole derivative grafted olefin shown in formulas (I) to (IV).
And, the preparation method of the base oil comprises the following steps: any thiazole derivative grafted olefin shown in formulas (I) to (IV) and alpha olefin are subjected to polymerization reaction under the action of a catalyst to obtain the base oil.
Further, a lubricating oil, which contains the base oil as described above.
A grease which contains the base oil.
The invention has the beneficial effects that:
compared with the prior art, the thiazole derivative grafted olefin provided by the invention has the function of high polymerization with alpha olefin because the mercapto or amino of the thiazole derivative is grafted with the olefin compound or active groups are grafted through the mercapto reaction so as to be grafted with the olefin compound, so that a polymerization product containing the thiazole derivative structure has good corrosion resistance and extreme pressure wear resistance.
The preparation method of the thiazole derivative grafted olefin has the characteristics of simple process, no need of complex equipment and strong operability, and the thiazole derivative grafted olefin has the characteristics of high yield, high purity, few byproducts and the like.
The base oil has good corrosion resistance and extreme pressure wear resistance due to the structure of thiazole derivatives, and has the characteristics of good oil solubility, stable dispersion, difficult sedimentation and the like, so that the base oil does not need to be added with the additives when being used as lubricating oil, and the cost of the lubricating grease can be effectively reduced.
Because the base oil of the lubricating oil or the lubricating grease provided by the invention contains the thiazole derivative structure with good oil solubility, stable dispersion, difficult sedimentation, good corrosion resistance, extreme pressure wear resistance and oxidation resistance, the lubricating oil or the lubricating grease prepared by the lubricating oil or the lubricating grease also has good corrosion resistance and extreme pressure wear resistance, thereby reducing the addition of excessive corrosion resistance agents and extreme pressure wear resistance agents.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides thiazole derivative grafted olefin which has a structural formula shown in formulas (I) to (IV):
wherein R is1Any one selected from alkyl and alkyl sulfydryl with 1-30 carbon atoms; r2Selected from NH or S, a is more than or equal to 0; r3Is selected from alkyl and alkyl sulfydryl with 1-30 carbon atoms, m is 1 or 2 or 3, and n is not less than 0.
Among them, the specific structure of the thiazole derivative-grafted olefin of the formula (I) is preferably:
the specific structure of the thiazole derivative-grafted olefin of the formula (II) is preferably as follows:
the specific structure of the thiazole-derived branched olefin of formula (III) is preferred:
the specific structure of the thiazole derivative-grafted olefin of the formula (IV) is preferably as follows:
the thiazole derivative grafted olefin provided by the invention has the function of high polymerization with alpha olefin because the mercapto or amino of the thiazole derivative is grafted with the olefin compound or active groups are grafted through the mercapto reaction so as to be grafted with the olefin compound, and can be highly polymerized with the alpha olefin under the action of a catalyst, so that a polymerization product has good corrosion resistance and extreme pressure abrasion resistance. In addition, because the thiazole derivative grafted olefin heterocyclic compound containing S, N has a compact and stable structure and good bearing capacity and lubricating performance, an adsorption film and a chemical reaction film can be formed on the surface of metal, and the corrosion resistance, friction reduction, wear resistance and extreme pressure performance of the lubricating oil are effectively improved. Meanwhile, the material does not contain P and heavy metal elements, and is an environment-friendly ash-free multifunctional material.
Further, the invention also provides a preparation method of the thiazole derivative grafted olefin.
The preparation method of thiazole derivative grafted olefin shown in formulas (I) to (II) comprises the following steps:
mixing the carbon olefine acid and the acylating agent, heating to 40-90 ℃, refluxing at constant temperature, and then distilling under reduced pressure to obtain the carbon olefine acid chloride;
and mixing the carbenoyl chloride, the thiazole derivative and a reaction medium X, heating to 40-90 ℃, and reacting for 1-5 hours to obtain the thiazole derivative grafted olefin with the structural formulas (I) - (II).
The preparation method of the thiazole derivative grafted olefin shown in formulas (III) to (IV) comprises the following steps:
mixing thiazole derivatives, carboxylic acid A and a reaction medium Y, heating to 50-100 ℃, reacting for 1-2 h, obtaining filtrate through suction filtration, cooling to room temperature, adjusting the pH of the filtrate to 1-2, obtaining precipitated precipitate, and performing recrystallization treatment to obtain thiazole mercapto acid;
mixing the thiazole mercapto acid and the carbene alcohol, heating to 130-180 ℃, and reacting for 6-12 h to obtain the thiazole derivative grafted olefin with the structural formulas (III) - (IV).
In the preparation method of the thiazole derivative grafted olefin shown in the formulas (I) to (II), the acylating agent is selected from at least one of oxalyl chloride, thionyl chloride and benzoyl chloride; the reaction medium X is selected from at least one of acetone, N-dimethylformamide and tetrahydrofuran, and the reaction media have good dispersion and compatibility on a thiazole derivative and carbenoyl chloride mixed system; the carbonic acid is
a is more than or equal to 0, double bonds can be polymerized with olefin, and carboxyl groups react with sulfydryl or amino groups after acylation to form the grafted thiazole derivative.
In the above process for producing olefin grafted with thiazole derivatives represented by the formulae (I) to (II), the feed ratio of each raw material is preferably as follows: the molar ratio of the carbonic acid to the acylating agent is calculated by the mol of chlorine: (0.5-2) an acylating agent; the carbenoyl chloride: thiazole derivatives (0.5-2) and 1.
Further preferably, the molar ratio of the carbonic acid: (0.8-1.1) of an acylating agent; the carbenoyl chloride: thiazole derivatives (0.7-1.2): 1. When the acylating agent is benzoyl chloride, the yield is improved, and when the acylating agent is benzoyl chloride, the yield is reduced because the benzoyl chloride is slightly excessive and thermal polymerization is inhibited, and side reactions are reduced.
Specifically, the reaction equation of olefin grafting of thiazole derivatives represented by the formulas (I) to (II) is as follows:
wherein a is not less than 0, R1Selected from alkyl and alkyl sulfydryl with 1-30 carbon atoms, R2Is NH or S.
In the preparation method of the thiazole derivative grafted olefin shown in the formulas (III) to (IV), the carboxylic acid A is selected from one of chloroacetic acid, chloropropionic acid, acrylic acid and crotonic acid, wherein, the mercapto group is subjected to substitution reaction with chlorocarboxylic acid under the action of a reaction medium Y and is subjected to addition reaction with carboxylic acid containing double bonds.
The reaction medium Y is selected from any one of sodium hydroxide solution, potassium hydroxide solution and sulfuric acid, the mass concentration of the sodium hydroxide solution and the potassium hydroxide solution is 1-10%, and the mass concentration of the sulfuric acid is not less than 70%. Wherein, the reaction medium Y plays a catalytic role in a reaction system, and when the carboxylic acid A is chloroacetic acid or chloropropionic acid, the mercapto-substituted halogen reaction is carried out under the catalysis of alkali; when the carboxylic acid A is acrylic acid or crotonic acid, the addition reaction of double bonds occurs under the catalysis of acid, so that the thiazole derivative is grafted with a carboxyl group.
In the above-mentioned method for preparing olefin grafted with thiazole derivatives represented by the formulae (III) to (IV), the ratio of the raw materials is preferably as follows: the thiazole derivatives have the following molar ratio: carboxylic acid A: reaction medium Y ═ (0.5-3) 1 (1-3); the thiazole mercapto acid: and (0.5-2) 1 for carbaenol. When the carboxylic acid A is chloroacetic acid or chloropropionic acid, the reaction medium Y is an alkali solution, the thiazole derivative is completely reacted due to the excessive amount of the carboxylic acid A, and the excessive amount of the reaction medium Y is favorable for the reaction; when the carboxylic acid A is acrylic acid or crotonic acid, the reaction medium Y is concentrated sulfuric acid, in which case the reaction medium Y may also be present in a suitable excess. Thiazole derivatives: a: the theoretical proportion of the reaction medium Y is (1-2): 1: 1, and the reaction medium Y is preferably in excess, so that the preferable ratio is (0.5 to 2):1: (1-2), too large deviation ratio lowers the yield and causes side reaction.
Further preferably, the thiazole derivative: carboxylic acid A: reaction medium Y ═ (0.8-2) 1 (1-2); the thiazole mercapto acid: and (0.7-1.2) 1 for carbaenol.
In the method for preparing the thiazole derivative-grafted olefin represented by the formulae (III) to (IV), concentrated hydrochloric acid or the like can be used for adjusting the pH value of the filtrate.
In the preparation method of the thiazole derivative grafted olefin shown in the formulas (III) to (IV), the acquisition of the precipitate comprises the steps of carrying out suction filtration, washing, drying and the like on the precipitated precipitate. And recrystallizing the obtained precipitate by adopting absolute ethyl alcohol, thereby obtaining the thiazole mercaptoacid with higher purity.
Specifically, the reaction equation of olefin grafting of thiazole derivatives represented by the formulas (III) to (IV) is as follows:
for the thiazole derivative grafted olefin shown in the formula (III), the reaction formula is as follows:
for the thiazole derivative grafted olefin shown in the formula (IV), the reaction formula is as follows:
thiazole derivatives used in the preparation method of olefin grafted by thiazole derivatives of the invention include but are not limited to thiadiazole and derivatives thereof, phenylthiazole and derivatives thereof.
The thiazole derivative grafted olefin prepared by the preparation method has the characteristics of high yield, high purity, few byproducts and the like, and the preparation method is simple in preparation process, free of complex equipment, strong in operability and suitable for industrial large-scale production.
On the basis of the thiazole derivative grafted olefin, the invention also provides a base oil synthesized by using the thiazole derivative grafted olefin with the structural formulas shown in formulas (I) to (IV).
Specifically, the preparation method of the base oil comprises the following steps:
and (2) carrying out polymerization reaction on thiazole derivative grafted olefin shown in formulas (I) to (IV) and alpha olefin under the action of a catalyst to obtain the thiazole derivative grafted poly-alpha olefin base oil.
Preferably, the catalyst is selected from BF3、AlCl3And Ziegler-Natta. The alpha olefin is selected from C8-C12 alpha olefins, preferably 1-octene, 1-decene, 1-dodecene.
The base oil of the invention can lead the thiazole derivative grafted olefin to become a part of the base oil because the thiazole derivative grafted olefin is directly polymerized with the alpha olefin, thus thoroughly solving the problems of uneven dispersion, unstable dispersion and easy sedimentation, and leading the base oil to have good corrosion resistance, extreme pressure abrasion resistance and the like, therefore, the base oil can be directly used as lubricating oil without adding the additives into the lubricating oil.
Also for this reason, the present invention provides a grease comprising the base oil obtained by the above-mentioned method for preparing a base oil. The lubricating grease can be prepared from the lubricating oil according to a conventional lubricating grease preparation process, namely, the base oil is mixed with a thickening agent, an antioxidant and the like to prepare the lubricating grease. The thickening agent is a common lithium soap thickening agent or powder thickening agent in the lubricating grease, and details are not repeated, so that the obtained lubricating grease can show good corrosion resistance, abrasion resistance and extreme pressure resistance, and excessive addition of an anti-corrosion agent and an extreme pressure anti-wear agent can be reduced.
In order to better explain the technical solution of the present invention, the technical solution of the present invention is exemplified by a plurality of examples below.
Example 1
Thiazole derivative grafted olefin, base oil and preparation methods thereof. The thiazole derivative grafted olefin is 2-benzothiazolyl-mercapto acrylate; the base oil is thiazole derivative grafted poly-alpha olefin base oil.
The preparation method of the 2-benzothiazolyl-mercaptoacrylate comprises the following steps:
(1) dripping 1.05mol of acrylic acid into 1mol of thionyl chloride, adding 5 per mill of hydroquinone polymerization inhibitor, stirring uniformly, heating to 50 ℃, refluxing at constant temperature, and distilling under reduced pressure to obtain acryloyl chloride with the yield of 83%;
(2) and uniformly mixing the prepared acryloyl chloride and 2-mercaptobenzothiazole in acetone, and reacting for 1.5h at the temperature of 50 ℃ to prepare the 2-benzothiazolyl-mercaptoacrylate.
The preparation method of the thiazole derivative grafted poly-alpha-olefin base oil comprises the following steps:
adding the 2-benzothiazolyl-mercaptoacrylic ester and 1-decene into a polymerization reaction system in AlCl3The thiazole derivative graft poly-alpha-olefin base oil is prepared by polymerization at 60 ℃ under the catalytic condition.
Example 2
Thiazole derivative grafted olefin, base oil and preparation methods thereof. The thiazole derivative grafted olefin is thiadiazole mercapto decanoate; the base oil is thiazole derivative grafted poly-alpha olefin base oil.
The preparation method of the thiadiazole mercapto decanoate comprises the following steps:
(1) dripping 0.8mol of decenoic acid into 1mol of benzoyl chloride, adding 5 per mill of hydroquinone polymerization inhibitor, uniformly stirring, heating to 70 ℃, refluxing at constant temperature, and distilling under reduced pressure to obtain decenoic acyl chloride with the yield of 71%;
(2) uniformly mixing the prepared decenyl chloride and 2-methyl-5-mercapto-1, 3, 4-thiadiazole in tetrahydrofuran, and reacting for 3h at 70 ℃ to prepare thiadiazole mercapto decanoate.
The preparation method of the thiazole derivative grafted poly-alpha-olefin base oil comprises the following steps:
adding the prepared thiadiazole mercapto decanoate and 1-decene into a polymerization reaction system, and reacting at BF3The thiazole derivative grafted poly-alpha-olefin base oil is prepared by polymerization at 25 ℃ under the catalytic condition.
Example 3
Thiazole derivative grafted olefin, base oil and preparation methods thereof. The thiazole derivative grafted olefin is thiadiazole sulfoacetic acid decenyl ester; the base oil is thiazole derivative grafted poly-alpha olefin base oil.
The preparation method of the thiadiazole thioglycollic acid decenyl ester comprises the following steps:
(1) 0.1mol of 2-methyl-5-mercapto-1, 3, 4-thiadiazole, 0.11mol of chloroacetic acid and 0.22mol of 2 wt% sodium hydroxide aqueous solution are stirred at 85 ℃ for reaction for 3h, suction filtration is carried out, cooling is carried out to room temperature, hydrochloric acid is used for acidification until the pH value is 1.5, precipitate is separated out, suction filtration is carried out, water washing and drying are carried out, and the thiadiazole thioacetic acid is obtained with the yield of 81%.
(2) And uniformly mixing the prepared thiadiazole thioacetic acid with 0.2mol of decenol, controlling the temperature at 160 ℃, reacting for 6h, and cooling to room temperature to obtain the thiadiazole thioacetic decenyl ester.
The preparation method of the thiazole derivative grafted poly-alpha-olefin base oil comprises the following steps:
adding the prepared decylene thiadiazolthioacetate and 1-decene into a polymerization reaction system, and polymerizing at 80 ℃ under the catalysis of Ziegler-Natta to prepare the thiazole derivative grafted polyalphaolefin base oil.
Example 4
Thiazole derivative grafted olefin, base oil and preparation methods thereof. The thiazole derivative grafted olefin is benzothiazole thiopropionic acid butenyl ester; the base oil is thiazole derivative grafted poly-alpha olefin base oil.
The preparation method of the benzothiazole thiopropionic butenyl ester comprises the following steps:
(1) uniformly mixing 2-mercaptobenzothiazole, 0.25mol chloropropionic acid and 0.5mol potassium hydroxide aqueous solution with the concentration of 2 wt%, stirring and reacting at 95 ℃ for 1.5h, performing suction filtration, cooling to room temperature, acidifying to pH 1 with hydrochloric acid, separating out a precipitate, performing suction filtration, washing with water, and drying to obtain the benzothiazole thiopropionic acid with the yield of 75%.
(2) And uniformly mixing the prepared benzothiazole thiopropionic acid with 0.2mol of butenol, controlling the temperature at 150 ℃, reacting for 7h, and cooling to room temperature to obtain the benzothiazole thiopropionic acid butenolide.
The preparation method of the thiazole derivative grafted poly-alpha-olefin base oil comprises the following steps:
the preparation of the aboveAdding the obtained benzothiazole thiopropionic butenyl ester into a polymerization reaction system of 1-octene3The thiazole derivative graft poly-alpha-olefin base oil is prepared by polymerization at 60 ℃ under the catalytic condition.
Example 5
Thiazole derivative grafted olefin, base oil and preparation methods thereof. The thiazole derivative grafted olefin is thiadiazole thiobutyric octenyl ester; the base oil is thiazole derivative grafted poly-alpha olefin base oil.
The preparation method of the thiadiazole thiobutyric octenyl ester comprises the following steps:
(1) evenly mixing 2-methyl-5-mercapto-1, 3, 4-thiadiazole, 0.11mol of crotonic acid and 0.12mol of 70% of sulfuric acid, stirring and reacting at 80 ℃ for 1h, performing suction filtration, cooling to room temperature, acidifying to pH 1 with hydrochloric acid, separating out a precipitate, filtering, washing with water, and drying to obtain thiadiazole thiobutyric acid with the yield of 72%.
(2) And (3) uniformly mixing the prepared thiadiazole thiobutyric acid with 0.1mol of octenol, controlling the temperature at 170 ℃, reacting for 10 hours, and cooling to room temperature to obtain the thiadiazole thiobutyric acid octenyl ester.
The preparation method of the thiazole derivative grafted poly-alpha-olefin base oil comprises the following steps:
adding the prepared thiadiazole thiobutyric acid octenyl ester into a polymerization reaction system of 1-octene, and polymerizing at 80 ℃ under the catalysis of Ziegler-Natta to prepare the thiazole derivative grafted poly-alpha-olefin base oil.
Example 6
Thiazole derivative grafted olefin, base oil and preparation methods thereof. The thiazole derivative grafted olefin is benzothiazole thiopropionic allyl ester; the base oil is thiazole derivative grafted poly-alpha olefin base oil.
The preparation method of the benzothiazole allyl thiopropionate comprises the following steps:
(1) evenly mixing 2-mercaptobenzothiazole, 0.16mol acrylic acid and 0.18mol sulfuric acid 70%, stirring at 70 ℃ for reaction for 2h, carrying out suction filtration, cooling to room temperature, acidifying with hydrochloric acid to pH 1.5, separating out precipitate, filtering, washing with water, and drying to obtain the benzothiazole thiopropionic acid with the yield of 78%.
(2) And (3) uniformly mixing the prepared benzothiazole thiopropionic acid with 0.15mol of allyl alcohol, controlling the temperature at 145 ℃, reacting for 7h, and cooling to room temperature to obtain the benzothiazole thiopropionic acid allyl ester.
The preparation method of the thiazole derivative grafted poly-alpha-olefin base oil comprises the following steps:
adding the prepared benzothiazole thiopropionic allyl ester into a polymerization reaction system of 1-dodecene, and polymerizing at 80 ℃ under the catalysis of Ziegler-Natta to prepare the thiazole derivative grafted poly-alpha olefin base oil.
Comparative example 1
A lubricating oil which is a conventional polyalphaolefin base oil, mobil PAO 10.
Comparative example 2.
A lubricating oil is composed of 99% of PAO10 base oil and 1% of dimercaptothiadiazole dimer.
Comparative example 3
A lubricating oil consisting of 99% PAO10 base stock and 1% molybdenum dialkyl dithiophosphate.
In order to verify the oil properties of the base oils of examples 1 to 6 and the lubricating oils of comparative examples 1 to 3, corresponding property tests were performed.
The maximum seizure-free load PB and the maximum sintering load PD in each base oil were measured in accordance with GB/T3142-82. MRS-10 four-ball friction tester available from Jinan Competition testing technology, Inc. was used for the experiments. The experiment was carried out at room temperature at 1450r/min for 10s, and the results are given in Table 1.
On an NMW-1 universal friction wear testing machine produced by a Jinan Competition testing technology, long grinding is carried out according to NB/SH/T0189-2017 standard, and the experimental conditions are as follows: the load is 40kgf, the rotating speed is 1200r/min, the experiment temperature is 75 ℃, and the experiment time is 60 min. The results for the Wear Scar Diameter (WSD) are listed in table 1.
The copper corrosion test is carried out according to the standard method of GB/T5096-2017, the test condition is that the temperature is kept constant at 100 ℃ for 3 hours, and the test result is listed in Table 1.
TABLE 1
As can be seen from Table 1, the oil product of the conventional base oil has no corrosiveness under the condition of no addition of additives, but has poor extreme pressure antiwear performance. If some thiazole additives are directly added into base oil, the additives cannot be dissolved in the oil, and precipitation occurs. After the low-phosphorus environment-friendly extreme pressure antiwear agent, namely molybdenum dialkyl dithiophosphate, is added, the extreme pressure antiwear performance is improved, but the additive corrodes a copper sheet, so that the copper corrosion is deteriorated; at this time, a high-efficiency corrosion inhibitor is required to be added to compensate for the corrosivity caused by the corrosion inhibitor, but the addition of too many additives increases the cost on one hand, and each additive has volatility, increases the emission of VOC, and is not beneficial to the environmental protection requirement on the other hand. In the practical application process, corrosion metal exists in many traditional extreme pressure antiwear agents, and further, an additional corrosion inhibitor needs to be added. In examples 1 to 6, the polyalphaolefin base oil prepared by grafting the thiazole derivative has better corrosion resistance without adding excessive additives, and the extreme pressure wear resistance is improved, so that the base oil obtained in examples 1 to 6 can be directly used as lubricating oil.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A base oil, characterized in that the base oil is a thiazole derivative-grafted alpha olefin base oil; the thiazole derivative is selected from at least one thiazole derivative grafted olefin shown in formulas (I) to (IV) below;
wherein R is1Any one selected from alkyl and alkyl sulfydryl with 1-30 carbon atoms; r2Selected from NH or S, a is more than or equal to 0; r3Is selected from alkyl and alkyl sulfydryl with 1-30 carbon atoms, m is 1 or 2 or 3, and n is not less than 0.
2. The method of making the base oil of claim 1, comprising the steps of:
any thiazole derivative grafted olefin shown in formulas (I) to (IV) and alpha olefin are subjected to polymerization reaction under the action of a catalyst to obtain the base oil.
3. The method of claim 2, wherein the thiazole derivative-grafted olefin is prepared by the method comprising the steps of:
mixing the carbon olefine acid and the acylating agent, heating to 40-90 ℃, refluxing at constant temperature, and then distilling under reduced pressure to obtain the carbon olefine acid chloride;
mixing the carbenoyl chloride, the thiazole derivative and a reaction medium X, heating to 40-90 ℃, and reacting for 1-5 h to prepare thiazole derivative grafted olefin with a structural formula shown in formulas (I) - (II);
or mixing the thiazole derivative, the carboxylic acid A and the reaction medium Y, heating to 50-100 ℃, reacting for 1-2 h, performing suction filtration to obtain a filtrate, cooling the temperature of the filtrate to room temperature, adjusting the pH of the filtrate to 1-2, obtaining a precipitated precipitate, and performing recrystallization to obtain thiazole mercaptoacid;
mixing the thiazole mercapto acid and the carbene alcohol, heating to 130-180 ℃, and reacting for 6-12 h to obtain the thiazole derivative grafted olefin with the structural formulas (III) - (IV).
4. The process according to claim 3, wherein the acylating agent is at least one compound selected from the group consisting of oxalyl chloride, thionyl chloride and benzoyl chloride; what is needed isThe reaction medium X is at least one selected from acetone, N-dimethylformamide and tetrahydrofuran; the carbene acid is
a≥0。
5. The process according to claim 3 or 4, wherein the ratio of the carbene acid: (0.5-2) an acylating agent; the carbenoyl chloride: thiazole derivatives (0.5-2) and 1.
6. The method of claim 3, wherein 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 any one of chloroacetic acid, chloropropionic acid, acrylic acid and crotonic acid.
7. The preparation method according to claim 3 or 6, wherein the thiazole derivative: carboxylic acid A: reaction medium Y ═ (0.5-3) 1 (1-3); the thiazole mercapto acid: and (0.5-2) 1 for carbaenol.
8. A lubricating oil comprising the base oil according to claim 1.
9. A grease comprising the base oil according to claim 1.
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| WO1998039399A1 (en) * | 1997-03-06 | 1998-09-11 | Uniroyal Chemical Company, Inc. | Ashless friction modifier with viscosity index improving credit and lubricating oil composition containing same |
| US7442673B2 (en) * | 2003-08-15 | 2008-10-28 | Crompton Corporation | Reaction products of mercaptobenzothiazoles, mercaptothiazolines, and mercaptobenzimidazoles with epoxides as lubricant additives |
| CN101787322A (en) * | 2010-03-18 | 2010-07-28 | 上海交通大学 | Extreme pressure antiwear agent containing ester-based thiadiazole derivative and preparation method thereof |
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