CN116589443A - Dynamic disulfide bond-based compound, lubricant, and preparation method and application thereof - Google Patents
Dynamic disulfide bond-based compound, lubricant, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lubricating materials, and provides a compound based on dynamic disulfide bonds, a lubricant, a preparation method and application thereof. The compound based on dynamic disulfide bonds can realize high-efficiency capture of various base oils through ring-opening polymerization of disulfide bonds and coordination of aluminum-carboxyl, so that the compound can be used as a gel factor or thickener for preparing gel lubricants or lubricating grease. The invention adopts the compound based on dynamic disulfide bond and base oil to prepare the lubricant, and the obtained lubricant not only has excellent tribological property and mechanical strength, but also has good heat stability, shear thinning and creep recovery characteristics and the like; meanwhile, the lubricant provided by the invention has excellent self-adaptability to mechanical force, can effectively avoid creeping leakage of the lubricant, and has wide application prospect in the lubrication field.
Description
Technical Field
The invention relates to the technical field of lubricating materials, in particular to a compound based on dynamic disulfide bonds, a lubricant, a preparation method and application thereof.
Background
The lubricating material with excellent synthesis performance has important significance for prolonging the service life of equipment and avoiding the sudden failure of the equipment caused by material abrasion.
The supermolecule gel lubricant has excellent thixotropic property, can quickly change into liquid phase when thixotropic or heated by external force, can quickly form gel state when static or cooled, and has great potential application value in the aspects of mechanical sealing, lubrication and the like. Supermolecular gel lubricants also exhibit some self-adaptation: the noncovalent bond is broken under the action of shearing force, and the lubricant is converted into a sol state; when the shear force is removed, the self-assembly is carried out again, and the initial gel state is restored.
However, current supramolecular gel lubricants are typically non-covalently crosslinked physical gels, with relatively small bond energies and relatively slow "break" and "bind" speeds, and thus the resulting lubricants have low mechanical strength and relatively weak adaptability to mechanical forces.
Disclosure of Invention
In view of this, the present invention provides a dynamic disulfide bond-based compound, and a lubricant, and a preparation method and application thereof. The compound based on dynamic disulfide bonds can be used as a gel factor or a thickener for preparing gel lubricant or lubricating grease, and the obtained gel lubricant and lubricating grease have high mechanical strength, good mechanical adaptability and excellent tribological performance.
In order to achieve the above object, the present invention provides the following technical solutions:
a dynamic disulfide bond-based compound having a structure represented by any one of formulas I to VI:
in formula II, formula III and formula VI, n is independently 2 to 7.
The invention also provides a preparation method of the dynamic disulfide bond-based compound, which comprises the following steps:
when the dynamic disulfide bond-based compound has a structure shown in formula I, the preparation method comprises the following steps: mixing lipoic acid, aluminum isopropoxide and chloroform for reaction to obtain a compound based on dynamic disulfide bonds, which has a structure shown in a formula I; the molar ratio of the lipoic acid to the aluminum isopropoxide is 3-3.1:1;
when the dynamic disulfide bond-based compound has a structure represented by formula II or formula III, the preparation method comprises the following steps: mixing long-chain fatty acid, lipoic acid, aluminum isopropoxide and chloroform for reaction to obtain a compound with a structure shown in a formula II or a formula III and based on dynamic disulfide bonds; when the dynamic disulfide bond-based compound has a structure shown in a formula II, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 2-2.05:1-1.05:1; when the dynamic disulfide bond-based compound has a structure shown in a formula III, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:2-2.05:1;
when the dynamic disulfide bond-based compound has a structure represented by formula IV or formula V, the preparation method comprises the steps of: mixing lipoic acid, aluminum isopropoxide and chloroform for reaction, mixing the obtained reaction solution with water for continuous reaction, and obtaining a dynamic disulfide bond-based compound with a structure shown in a formula IV or a formula V; when the dynamic disulfide bond-based compound has a structure shown in a formula IV, the molar ratio of the lipoic acid to the aluminum isopropoxide is 2-2.1:1; when the dynamic disulfide bond-based compound has a structure shown in a formula V, the molar ratio of the lipoic acid to the aluminum isopropoxide is 1-1.05:1;
when the dynamic disulfide bond-based compound has a structure represented by formula VI, the preparation method comprises the steps of: mixing long-chain fatty acid, lipoic acid, aluminum isopropoxide and chloroform for reaction, mixing the obtained reaction liquid with water, and continuing the reaction to obtain a compound with a structure shown in a formula VI and based on dynamic disulfide bonds; the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:1.
Preferably, the long chain fatty acid is caprylic acid, capric acid, lauric acid, n-tetradecanoic acid, n-hexadecanoic acid or stearic acid.
Preferably, when preparing the compound based on dynamic disulfide bond with the structure shown in the formula IV, the water is used in an amount of 15-30% of the aluminum isopropoxide; when preparing a compound based on dynamic disulfide bonds with a structure shown in a formula V, the water is used in an amount of 25-40% of the mass of the aluminum isopropoxide; in the preparation of the dynamic disulfide bond-based compound having the structure shown in formula VI, the water is used in an amount of 15 to 30% by mass of the aluminum isopropoxide.
The invention also provides application of the dynamic disulfide bond-based compound disclosed by the scheme or the dynamic disulfide bond-based compound prepared by the preparation method disclosed by the scheme as a gelator or thickener in a lubricant.
The invention also provides a lubricant comprising the dynamic disulfide bond-based compound and base oil according to the scheme; the lubricant is gel lubricant or lubricating grease.
Preferably, the mass fraction of the dynamic disulfide bond-based compound in the lubricant is 1 to 15%.
Preferably, the base oil is one or more of white oil, ester oil, poly alpha-olefin, 500SN, a51, MVI300, 150BS, and polyethylene glycol.
The invention also provides a preparation method of the lubricant according to the scheme, when the lubricant is a gel lubricant, the preparation method comprises the following steps: heating, mixing and cooling the dynamic disulfide bond-based compound and base oil to obtain the gel lubricant;
when the lubricant is a grease and the dynamic disulfide bond based compound has a structure represented by formula I, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with lipoic acid solution for reaction, cooling the obtained product feed liquid, and grinding to obtain the lubricating grease; the molar ratio of the lipoic acid to the aluminum isopropoxide is 3-3.1:1;
when the lubricant is a grease and the dynamic disulfide bond-based compound has a structure represented by formula II or formula III, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with long-chain fatty acid and lipoic acid solution for reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product feed liquid to obtain the lubricating grease; when the dynamic disulfide bond-based compound has a structure shown in a formula II, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 2.05:1-1.05:1; when the dynamic disulfide bond-based compound has a structure shown in a formula III, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:2-2.05:1;
when the lubricant is grease and the dynamic disulfide bond-based compound has a structure represented by formula IV or formula V, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with lipoic acid solution for reaction, mixing the obtained reaction liquid with water for continuous reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product liquid to obtain the lubricating grease; when the dynamic disulfide bond-based compound has a structure shown in a formula IV, the molar ratio of the lipoic acid to the aluminum isopropoxide is 2-2.1:1; when the dynamic disulfide bond-based compound has a structure shown in a formula V, the molar ratio of the lipoic acid to the aluminum isopropoxide is 1-1.05:1;
when the lubricant is a grease and the dynamic disulfide bond based compound has a structure represented by formula VI, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with long-chain fatty acid and lipoic acid solution for reaction, mixing the obtained reaction liquid with water for continuous reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product liquid to obtain the lubricating grease; the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:1.
The invention also provides application of the lubricant disclosed by the scheme or the lubricant prepared by the preparation method disclosed by the scheme in the field of lubrication of mechanical parts.
The invention provides a compound based on dynamic disulfide bonds, which has a structure shown in any one of formulas I to VI. The compound based on dynamic disulfide bonds can realize high-efficiency capture of various base oils through ring-opening polymerization of disulfide bonds and coordination of aluminum-carboxyl, so that the compound can be used as a gel factor or thickener for preparing gel lubricants or lubricating grease.
The present invention also provides a lubricant comprising a dynamic disulfide bond-based compound and a base oil, which can be classified into a gel lubricant and a grease according to the preparation method. The invention adopts the compound based on dynamic disulfide bond and base oil to prepare the lubricant, and the obtained lubricant not only has excellent tribological property and mechanical strength, but also has good heat stability, shear thinning and creep recovery characteristics and the like. Based on shear thinning and creep recovery characteristics, the lubricant provided by the invention has excellent self-adaptability to mechanical force, can effectively avoid creeping leakage of the lubricant, and has wide application prospect in the lubrication field.
Drawings
FIG. 1 shows the gel lubricant A when the stress is gradually increased and then decreased 1 Modulus trend of (a);
FIG. 2 shows the gel lubricant A with alternating stress levels 1 Modulus change trend of (c).
FIG. 3 is a gel lubricant A 1 Is a thermal weight loss curve of (2).
Detailed Description
The invention provides a compound based on dynamic disulfide bonds, which has a structure shown in any one of formulas I to VI:
in formula II, formula III and formula VI, n is independently 2 to 7.
In the present invention, the n is preferably 2, 3, 4, 5, 6 or 7.
The invention also provides a preparation method of the dynamic disulfide bond-based compound, which adopts different preparation methods according to different structural formulas, and is respectively described in detail below.
In the present invention, when the dynamic disulfide bond-based compound has a structure represented by formula I, the preparation method comprises the steps of:
mixing lipoic acid, aluminum isopropoxide and chloroform for reaction to obtain a compound based on dynamic disulfide bonds, which has a structure shown in a formula I; the molar ratio of the lipoic acid to the aluminum isopropoxide is 3-3.1:1.
In the present invention, the temperature of the reaction is preferably 50 to 60 ℃, more preferably 52 to 55 ℃, and the time of the reaction is preferably 6 hours; in the specific embodiment of the invention, sulfur Xin Suanrong is preferably added into chloroform, then aluminum isopropoxide solution is added into the obtained lipoic acid solution, and then the reaction is carried out under the conditions of stirring and heating; after the reaction is finished, the invention preferably carries out vacuum solvent removal on the obtained product liquid to obtain the dynamic disulfide bond-based compound with the structure shown in the formula I.
In the present invention, when the dynamic disulfide bond-based compound has a structure represented by formula II or formula III, the preparation method comprises the steps of:
mixing long-chain fatty acid, lipoic acid, aluminum isopropoxide and chloroform for reaction to obtain a compound with a structure shown in a formula II or a formula III and based on dynamic disulfide bonds; when the dynamic disulfide bond-based compound has a structure shown in a formula II, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 2-2.05:1-1.05:1, preferably 2:1:1; when the dynamic disulfide bond-based compound has a structure shown in formula III, the molar ratio of the long-chain fatty acid, lipoic acid and aluminum isopropoxide is 1-1.05:2-2.05:1, preferably 1:2:1.
In the present invention, when preparing the dynamic disulfide bond based compound having the structure shown in formula II or formula III, the specific operation steps, operation conditions and post-treatment method are the same as those when preparing the dynamic disulfide bond based compound having the structure shown in formula I, and only long chain fatty acid is added; in the embodiment of the present invention, it is preferable to dissolve the long-chain fatty acid and lipoic acid in chloroform and then add aluminum isopropoxide in chloroform solution to the resulting mixed solution for reaction.
In the present invention, when the dynamic disulfide bond-based compound has a structure represented by formula IV or formula V, the preparation method comprises the steps of:
mixing lipoic acid, aluminum isopropoxide and chloroform for reaction (marked as a first reaction), mixing the obtained reaction liquid with water for continuous reaction (marked as a second reaction), and obtaining a compound based on dynamic disulfide bonds, which has a structure shown in a formula IV or a formula V; when the dynamic disulfide bond-based compound has a structure shown in formula IV, the molar ratio of the lipoic acid to the aluminum isopropoxide is 2-2.1:1, more preferably 2:1; when the dynamic disulfide bond-based compound has a structure represented by formula V, the molar ratio of lipoic acid to aluminum isopropoxide is 1 to 1.05:1, preferably 1:1.
In the present invention, the temperature of the first reaction is preferably 50 to 60 ℃, more preferably 52 to 55 ℃, and the time of the first reaction is preferably 6 hours; the time of the second reaction is preferably 50 to 60 ℃, more preferably 52 to 55 ℃, and the time of the second reaction is preferably 1h. In the present invention, in preparing the dynamic disulfide bond-based compound having the structure represented by formula IV, the amount of the water is preferably 15 to 30% by mass, more preferably 20 to 25% by mass, of the aluminum isopropoxide; in preparing the dynamic disulfide bond-based compound having the structure represented by formula V, the amount of water is preferably 25 to 40% by mass, more preferably 30 to 35% by mass, of the aluminum isopropoxide. In the specific embodiment of the invention, lipoic acid is preferably dissolved in chloroform, then aluminum isopropoxide chloroform solution is added, the first reaction is carried out under the conditions of stirring and heating, water is directly added into the obtained reaction liquid after the first reaction is finished, and the second reaction is carried out under the conditions of heating and stirring; after the second reaction is completed, the obtained product feed liquid is preferably subjected to vacuum solvent removal to obtain the dynamic disulfide bond-based compound with the structure shown in the formula IV or the formula V.
In the present invention, when the dynamic disulfide bond-based compound has a structure represented by formula VI, the preparation method comprises the steps of: mixing long-chain fatty acid, lipoic acid, aluminum isopropoxide and chloroform for reaction, mixing the obtained reaction liquid with water, and continuing the reaction to obtain a compound with a structure shown in a formula VI and based on dynamic disulfide bonds; the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:1, and is preferably 1:1:1.
In the invention, when the compound based on dynamic disulfide bond with the structure shown in the formula VI is prepared, the specific operation steps, operation conditions and post-treatment method are the same as those when the compound based on dynamic disulfide bond with the structure shown in the formula I is prepared, only long-chain fatty acid is added, and the dosage of water is changed; in the specific embodiment of the invention, the long-chain fatty acid and the lipoic acid are preferably dissolved in the chloroform, then the chloroform solution of the aluminum isopropoxide is added, the first reaction is carried out under the conditions of stirring and heating, after the first reaction is finished, water is directly added into the obtained reaction liquid, and the second reaction is carried out under the conditions of heating and stirring. In the present invention, in preparing the dynamic disulfide bond-based compound having the structure of formula VI, the amount of water is preferably 15 to 30% by mass, more preferably 20 to 25% by mass, of the aluminum isopropoxide.
In the present invention, the long-chain fatty acid is preferably caprylic acid, capric acid, lauric acid, n-tetradecanoic acid, n-hexadecanoic acid or stearic acid, preferably stearic acid; and will not be described in detail later.
The invention also provides application of the dynamic disulfide bond-based compound according to the scheme or the dynamic disulfide bond-based compound prepared by the preparation method according to the scheme as a gelator or thickener in a lubricant; in the present invention, the lubricant includes a gel lubricant or grease, and the dynamic disulfide-based compound functions as a gelator when the dynamic disulfide-based compound is used to prepare the gel lubricant, and functions as a thickener when the dynamic disulfide-based compound is used to prepare the grease.
The invention also provides a lubricant comprising the dynamic disulfide bond-based compound and base oil according to the scheme; the lubricant is gel lubricant or lubricating grease.
In the present invention, the mass fraction of the dynamic disulfide bond-based compound in the lubricant is preferably 1 to 15%, more preferably 3 to 12%, and the balance is base oil.
In the present invention, the base oil is preferably one or more of white oil, ester oil, poly-alpha-olefin, 500SN, a51, MVI300, 150BS, and polyethylene glycol (PEG); the PEG is preferably PEG200 and/or PEG400.
The invention also provides a preparation method of the lubricant, which is divided into gel lubricant and lubricating grease, and the preparation method is respectively described below.
In the present invention, when the lubricant is a gel lubricant, the preparation method includes the steps of: the dynamic disulfide bond based compound and base oil are heat mixed (denoted as first heat mixed) and then cooled to obtain the gel lubricant.
In the invention, the temperature of the first heating and mixing is preferably 145-165 ℃, more preferably 150-160 ℃, and the heat preservation time of the first heating and mixing is preferably 15-25 min, more preferably 18-22 min; the first heated mixing is preferably performed under stirring conditions; and naturally cooling the obtained mixed feed liquid to room temperature after heating and mixing are finished.
In the present invention, when the lubricant is grease, it is prepared by directly synthesizing the thickener in situ in the base oil, as will be described in detail below.
In the present invention, when the lubricant is grease and the dynamic disulfide bond-based compound has a structure represented by formula I, the preparation method comprises the steps of:
heating and mixing aluminum isopropoxide and base oil (denoted as second heating and mixing), mixing the mixture and lipoic acid solution for reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product feed liquid to obtain the lubricating grease; the molar ratio of the lipoic acid to the aluminum isopropoxide is 3-3.1:1, preferably 3:1.
In the present invention, the temperature of the second heating and mixing is preferably 120 to 130 ℃, and the second heating and mixing is preferably performed under stirring, and the time of the second heating and mixing is not particularly limited, and the aluminum isopropoxide can be completely dissolved.
After aluminum isopropoxide is completely dissolved, the lipoic acid solution is preferably added into the system for reaction; the solvent of the lipoic acid solution is preferably dichloromethane or trichloromethane, more preferably dichloromethane; the reaction temperature is preferably 75-85 ℃, and the reaction time is preferably 5-15 min; the temperature of the heat preservation is preferably 130-150 ℃, more preferably 135-145 ℃, and the time of the heat preservation is preferably 5-10 min, more preferably 6-8 min; the cooling is preferably natural cooling to room temperature; the grinding is preferably performed by three-roll grinding, and the number of grinding is preferably 3.
In the present invention, when the lubricant is grease and the dynamic disulfide bond-based compound has a structure represented by formula II or formula III, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with long-chain fatty acid and lipoic acid solution for reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product feed liquid to obtain the lubricating grease; when the dynamic disulfide bond-based compound has a structure shown in a formula II, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 2-2.05:1-1.05:1, preferably 2:1:1; when the dynamic disulfide bond-based compound has a structure shown in formula III, the molar ratio of the long-chain fatty acid, lipoic acid and aluminum isopropoxide is 1-1.05:2-2.05:1, preferably 1:2:1.
In the invention, when the dynamic disulfide bond-based compound has a structure shown in a formula II or a formula III, the preparation method of the lubricating grease is basically the same as that when the dynamic disulfide bond-based compound has a structure shown in a formula I, only long-chain fatty acid is added, and other operating conditions are unchanged; in the specific embodiment of the invention, preferably after aluminum isopropoxide is completely dissolved in base oil, long-chain fatty acid is added into the system, the reaction is carried out for 5 to 15 minutes (preferably 10 minutes) at 120 to 130 ℃, then the temperature of the reaction system is reduced to 85 to 90 ℃, lipoic acid solution is added for 5 to 15 minutes (preferably 10 minutes), and heat preservation, cooling and grinding are carried out after the reaction is finished.
In the present invention, when the lubricant is grease and the dynamic disulfide bond-based compound has a structure represented by formula IV or formula V, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with lipoic acid solution for reaction, mixing the obtained reaction liquid with water for continuous reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product liquid to obtain the lubricating grease; when the dynamic disulfide bond-based compound has a structure shown in a formula IV, the molar ratio of the lipoic acid to the aluminum isopropoxide is 2-2.1:1, preferably 2:1; when the dynamic disulfide bond-based compound has a structure represented by formula V, the molar ratio of lipoic acid to aluminum isopropoxide is 1 to 1.05:1, preferably 1:1.
In the invention, when the dynamic disulfide bond-based compound has a structure shown in a formula IV or a formula V, the preparation method of the lubricating grease is the same as that when the dynamic disulfide bond-based compound has a structure shown in a formula I, only the steps of mixing the obtained reaction liquid with water and continuing the reaction are added, meanwhile, the heat preservation time is prolonged, and other conditions are unchanged; in the invention, the temperature for continuous reaction after adding water is preferably 75-85 ℃, and the reaction time is preferably 5-15 min; the heat preservation time is preferably 10-15 min, the heat preservation temperature is the same as that of the scheme, and the heat preservation is not repeated here, and excessive water is removed through heat preservation; the amount of water used is the same as that used in the preparation of the dynamic disulfide bond compound having the structure represented by formula IV or formula V, and will not be described in detail herein.
In the present invention, when the lubricant is grease and the dynamic disulfide bond-based compound has a structure represented by formula VI, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with long-chain fatty acid and lipoic acid solution for reaction, mixing the obtained reaction liquid with water for continuous reaction, cooling the obtained product liquid, and grinding to obtain the lubricating grease; the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:1, and more preferably 1:1:1.
In the invention, when the dynamic disulfide bond-based compound has a structure shown in a formula VI, the preparation method of the lubricating grease is basically the same as that when the dynamic disulfide bond-based compound has a structure shown in a formula IV or a formula V, only long-chain fatty acid is added, and other operation conditions are unchanged; in the specific embodiment of the invention, preferably, after aluminum isopropoxide is completely dissolved in base oil, long-chain fatty acid is added into the system to react for 5-15 min at 120-130 ℃, then the temperature of the reaction system is reduced to 85-90 ℃, lipoic acid solution is added to react, the obtained reaction solution and water are mixed and continue to react after the reaction is finished, and then the obtained product feed liquid is subjected to heat preservation, cooling and grinding.
The invention also provides application of the lubricant disclosed by the scheme or the lubricant prepared by the preparation method disclosed by the scheme in the field of lubrication of mechanical parts. The invention has no special requirements on the types of the mechanical parts, and the mechanical parts common in the field can be used, such as wind power bearings; the invention is not particularly limited to the particular method of application described, as it is known to those skilled in the art.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Lipoic acid (0.01 mol) and stearic acid (0.02 mol) are dissolved in chloroform (50 mL), a solution of aluminum isopropoxide (0.01 mol) in chloroform (50 mL) is added to the solution, the mixture is heated to 55 ℃ under stirring, and after the reaction is completed, the solvent is removed in vacuo to obtain a gel factor (having a structure shown in formula II).
Heating 0.5g of gel factor and 9.5g of base oil PAO10 to 160 ℃, stirring and mixing for 20min to obtain an oil solution, and cooling to room temperature to obtain a gel lubricant, which is marked as A 1 。
Example 2
The gel factor preparation method is the same as in example 1.
Heating 0.5g gel factor and 9.5g base oil 500SN to 160deg.C, stirring and mixing for 20min to obtain SG 21 The oil solution was cooled to room temperature to give a gel lubricant, designated A 2 。
Example 3
Lipoic acid (0.01 mol) and stearic acid (0.01 mol) were dissolved in chloroform (50 mL), to which was added aluminum isopropoxide (0.01 mol) in chloroform (50 mL), and the mixture was heated to 55℃with stirring, and reacted for 6 hours. Then, 0.4g of water was added to the mixed solution, and the heating and stirring were continued for 1 hour. After the reaction, the solvent was removed in vacuo to give the gelator (having the structure shown in formula VI).
Heating 0.5g gel factor and 9.5g base oil 500SN to 160deg.C, stirring and mixing for 20min to obtain SG 21 The oil solution is cooled to room temperature to obtain the supermolecule gel lubricant, which is marked as A 3 。
Example 4
Lipoic acid (0.03 mol) was dissolved in chloroform (50 mL), and to the solution was added an aluminum isopropoxide (0.01 mol) solution of chloroform (50 mL), and the mixture was heated to 55℃with stirring, and reacted for 6 hours. After the reaction, the solvent was removed in vacuo to give the gelator (having the structure shown in formula I).
0.5g of gel factor and 9.5g of base oil PEG400 were heated to 160℃,stirring and mixing for 20min to obtain oil solution, and cooling to room temperature to obtain supramolecular gel lubricant, denoted as A 4 。
Example 5
Lipoic acid (0.02 mol) and stearic acid (0.01 mol) were dissolved in chloroform (50 mL), to which was added an aluminum isopropoxide (0.01 mol) solution of chloroform (50 mL), and the mixture was heated to 55℃with stirring, and reacted for 6 hours. After the reaction, the solvent was removed in vacuo to give the gelator (having the structure shown in formula III).
Heating 0.5g of gel factor and 9.5g of base oil PEG400 to 160 ℃, stirring and mixing for 20min to obtain an oil solution, and cooling to room temperature to obtain a gel lubricant, which is marked as A 5 。
Example 6
Aluminum isopropoxide (0.01 mol) and 60g of base oil PAO10 were added to a 250mL beaker and heated to 125℃with stirring. After complete dissolution of the aluminum isopropoxide, stearic acid (0.02 mol) was added to the beaker, and after 10min of reaction, the heating temperature was reduced to 80 ℃. Lipoic acid (0.01 mol) was dissolved in methylene chloride (20 mL), and the lipoic acid solution was added to a beaker and reacted for 10min. Raising the temperature to 140 ℃, and preserving the heat for 8min. Then, cooling to room temperature, grinding three times by a three-roll mill to obtain grease, denoted as B 1 。
Example 7
Aluminum isopropoxide (0.01 mol) and 60g of base oil 500SN were added to a 250mL beaker and heated to 125 ℃ with stirring. After complete dissolution of the aluminum isopropoxide, stearic acid (0.02 mol) was added to the beaker, and after 10min of reaction, the heating temperature was reduced to 80 ℃. Lipoic acid (0.01 mol) was dissolved in methylene chloride (20 mL), and the lipoic acid solution was added to a beaker and reacted for 10min. Raising the temperature to 140 ℃, and preserving the heat for 8min. Then, cooling to room temperature, grinding three times by a three-roll mill to obtain grease, denoted as B 2 。
Example 8
Aluminum isopropoxide (0.01 mol) and 60g of base oil PEG400 were added to a 250mL beaker and heated to 125℃with stirring. Lipoic acid (0.02 mol) was dissolved in methylene chloride (20 mL), and after aluminum isopropoxide was completely dissolved in a beaker, the heating temperature was lowered to 80 ℃, and the lipoic acid solution was added to the beaker.After 10min of reaction, 0.4g of water was added, and the reaction was continued for 10min. After the reaction was completed, the temperature was raised to 140℃to remove excess water, and the temperature was maintained for 12 minutes. Then, cooling to room temperature, grinding three times by a three-roll mill to obtain grease, denoted as B 3 。
Example 9
Aluminum isopropoxide (0.01 mol) and 60g of base oil PEG400 were added to a 250mL beaker and heated to 125℃with stirring. Lipoic acid (0.01 mol) was dissolved in methylene chloride (20 mL), and after aluminum isopropoxide was completely dissolved in a beaker, the heating temperature was lowered to 80 ℃, and lipoic acid solution was added to the beaker. After 10min of reaction, 0.7g of water was added, and the reaction was continued for 10min. After the reaction was completed, the temperature was raised to 140℃to remove excess water, and the temperature was maintained for 12 minutes. Then, cooling to room temperature, grinding three times by a three-roll mill to obtain grease, denoted as B 4 。
Performance test:
1. coefficient of friction test
The frictional wear properties of each gel lubricant and grease were evaluated using an SRV-IV microvibration frictional wear tester manufactured by Optimol grease company, germany, and compared with PAO10, 500SN, PEG400. The friction pair of the SRV-IV micro-vibration friction wear testing machine is a bearing steel ball and a bearing steel disc, and the testing conditions are as follows: the temperature is 25 ℃, the frequency is 25Hz, the amplitude is 1mm, the load is 300N, and the experiment time is 30min.
TABLE 1 average coefficient of friction of base oils and greases obtained from gel lubricants and examples 1 to 9
As can be seen from the results in table 1, the gel lubricants and greases prepared according to the present invention exhibit excellent lubricating properties as compared to the pure base oil, with a significant reduction in the average coefficient of friction.
2. Drop point and cone penetration test of grease
The drop point and penetration test results of the greases prepared in examples 6 to 9 are shown in Table 2, the drop point test method is GB/T3498, and the working penetration test method is GB/T3498-2008.
TABLE 3 penetration and drop Point of greases B1 to B4
| Sample numbering | B 1 | B 2 | B 3 | B 4 |
| Drop point (DEG C) | 141 | 139 | 161 | 155 |
| Work cone penetration (0.1 mm) | 225 | 219 | 308 | 313 |
According to the data in Table 2, the lubricating grease provided by the invention has higher high-temperature resistance and higher consistency, and can meet the use requirements.
3. Mechanical adaptivity test
Evaluation of gel lubricant A prepared in example 1 using a HAAKE MARS RS6000 rheometer 1 Mechanical adaptation of (c).
The gel lubricant A1 was tested for modulus change upon stress sweep, wherein the stress gradually increased from 1Pa to high shear stress (3000 Pa) and gradually decreased to 1Pa, shear frequency: 5Hz; test temperature: 20 ℃; the test results are shown in FIG. 1. As can be seen from FIG. 1, the gel lubricant A after the shear stress is greater than the crossover point 1 G' below G ", to transition to a sol state. Subsequently, in the course of the gradual decrease of the shear stress from high stress to 0.1Pa, both G 'and G' gradually increase, and the intersection point occurs again. This illustrates gel lubricant A 1 After being converted into a sol state under high shear stress, the gel state is gradually restored along with the reduction of the shear stress.
FIG. 2 is a gel lubricant A 1 Modulus change at high and low shear stress alternation (shear frequency: 5Hz; temperature: 20 ℃). As can be seen in fig. 3, the gel lubricant a 1 G 'is higher than G "under low shear stress conditions and G' is lower than G" under high shear stress conditions. This illustrates gel lubricant A 1 Upon experiencing high shear stress, the gel structure is broken down to a sol state; and gradually self-assembled to recover to gel state under low shear stress.
The change trend of the modulus along with the stress shows that the gel lubricant disclosed by the invention is structurally destroyed under high shear stress to be converted into sol, can be self-assembled again under low shear stress, and can be recovered to a gel state in a short time, so that the high self-adaptability of the gel lubricant to the shear force is proved. At the same time, the higher storage modulus demonstrates its high mechanical strength.
4. Thermal stability test
Fig. 3 shows the thermal weight loss curve of the gel lubricant A1 obtained by the test using STA449F3, the thermal decomposition initiation temperature of which is 200 ℃ or higher, which is similar to that of the base oil PAO10, and the excellent thermal stability thereof is confirmed.
In addition, for lubricant A 2 、A 3 、A 4 、A 5 、B 1 、B 2 、B 3 、B 4 The same mechanical adaptation test and thermal stability test were performed, and the results show that the obtained lubricants have excellent mechanical adaptation and thermal stability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A dynamic disulfide bond-based compound having a structure represented by any one of formulas I to VI:
in formula II, formula III and formula VI, n is independently 2 to 7.
2. A process for the preparation of a dynamic disulfide bond based compound as claimed in claim 1, comprising the steps of:
when the dynamic disulfide bond-based compound has a structure shown in formula I, the preparation method comprises the following steps: mixing lipoic acid, aluminum isopropoxide and chloroform for reaction to obtain a compound based on dynamic disulfide bonds, which has a structure shown in a formula I; the molar ratio of the lipoic acid to the aluminum isopropoxide is 3-3.1:1;
when the dynamic disulfide bond-based compound has a structure represented by formula II or formula III, the preparation method comprises the following steps: mixing long-chain fatty acid, lipoic acid, aluminum isopropoxide and chloroform for reaction to obtain a compound with a structure shown in a formula II or a formula III and based on dynamic disulfide bonds; when the dynamic disulfide bond-based compound has a structure shown in a formula II, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 2-2.05:1-1.05:1; when the dynamic disulfide bond-based compound has a structure shown in a formula III, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:2-2.05:1;
when the dynamic disulfide bond-based compound has a structure represented by formula IV or formula V, the preparation method comprises the steps of: mixing lipoic acid, aluminum isopropoxide and chloroform for reaction, mixing the obtained reaction solution with water for continuous reaction, and obtaining a dynamic disulfide bond-based compound with a structure shown in a formula IV or a formula V; when the dynamic disulfide bond-based compound has a structure shown in a formula IV, the molar ratio of the lipoic acid to the aluminum isopropoxide is 2-2.1:1; when the dynamic disulfide bond-based compound has a structure shown in a formula V, the molar ratio of the lipoic acid to the aluminum isopropoxide is 1-1.05:1;
when the dynamic disulfide bond-based compound has a structure represented by formula VI, the preparation method comprises the steps of: mixing long-chain fatty acid, lipoic acid, aluminum isopropoxide and chloroform for reaction, mixing the obtained reaction liquid with water, and continuing the reaction to obtain a compound with a structure shown in a formula VI and based on dynamic disulfide bonds; the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:1.
3. The method of claim 2, wherein the long chain fatty acid is caprylic acid, capric acid, lauric acid, n-tetradecanoic acid, n-hexadecanoic acid, or stearic acid.
4. A method according to claim 2 or 3, wherein the amount of water used in the preparation of the dynamic disulfide bond-based compound having the structure represented by formula IV is 15 to 30% of the mass of the aluminum isopropoxide; when preparing a compound based on dynamic disulfide bonds with a structure shown in a formula V, the water is used in an amount of 25-40% of the mass of the aluminum isopropoxide; in the preparation of the dynamic disulfide bond-based compound having the structure shown in formula VI, the water is used in an amount of 15 to 30% by mass of the aluminum isopropoxide.
5. Use of a dynamic disulfide bond based compound according to claim 1 or a dynamic disulfide bond based compound prepared by the preparation method according to any one of claims 2 to 4 as a gelator or thickener in lubricants.
6. A lubricant comprising the dynamic disulfide bond-based compound of claim 1 and a base oil; the lubricant is gel lubricant or lubricating grease.
7. The lubricant according to claim 6, wherein the mass fraction of the dynamic disulfide bond based compound in the lubricant is 1 to 15%.
8. The lubricant of claim 6, wherein the base oil is one or more of white oil, ester oil, poly-alpha-olefin, 500SN, a51, MVI300, 150BS, and polyethylene glycol.
9. The method for producing a lubricant according to any one of claims 6 to 8, wherein when the lubricant is a gel lubricant, the method comprises the steps of: heating, mixing and cooling the dynamic disulfide bond-based compound and base oil to obtain the gel lubricant;
when the lubricant is a grease and the dynamic disulfide bond based compound has a structure represented by formula I, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with lipoic acid solution for reaction, cooling the obtained product feed liquid, and grinding to obtain the lubricating grease; the molar ratio of the lipoic acid to the aluminum isopropoxide is 3-3.1:1;
when the lubricant is a grease and the dynamic disulfide bond-based compound has a structure represented by formula II or formula III, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with long-chain fatty acid and lipoic acid solution for reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product feed liquid to obtain the lubricating grease; when the dynamic disulfide bond-based compound has a structure shown in a formula II, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 2.05:1-1.05:1; when the dynamic disulfide bond-based compound has a structure shown in a formula III, the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:2-2.05:1;
when the lubricant is grease and the dynamic disulfide bond-based compound has a structure represented by formula IV or formula V, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with lipoic acid solution for reaction, mixing the obtained reaction liquid with water for continuous reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product liquid to obtain the lubricating grease; when the dynamic disulfide bond-based compound has a structure shown in a formula IV, the molar ratio of the lipoic acid to the aluminum isopropoxide is 2-2.1:1; when the dynamic disulfide bond-based compound has a structure shown in a formula V, the molar ratio of the lipoic acid to the aluminum isopropoxide is 1-1.05:1;
when the lubricant is a grease and the dynamic disulfide bond based compound has a structure represented by formula VI, the preparation method comprises the steps of: heating and mixing aluminum isopropoxide and base oil, mixing the mixture with long-chain fatty acid and lipoic acid solution for reaction, mixing the obtained reaction liquid with water for continuous reaction, and sequentially carrying out heat preservation, cooling and grinding on the obtained product liquid to obtain the lubricating grease; the molar ratio of the long-chain fatty acid to the lipoic acid to the aluminum isopropoxide is 1-1.05:1.
10. Use of a lubricant according to any one of claims 6 to 8 or a lubricant prepared by a method according to claim 9 in the lubrication field of mechanical parts.
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