CN113461626A - Preparation method of benzotriazole derivative and metal passivator - Google Patents
Preparation method of benzotriazole derivative and metal passivator Download PDFInfo
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- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/22—Organic compounds containing nitrogen
- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
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- C10L2230/085—Metal deactivators
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; Insulating oil or insulators
Abstract
The embodiment of the invention relates to the technical field of metal passivators, and particularly relates to a preparation method of benzotriazole derivatives and a metal passivator. According to the preparation method of the benzotriazole derivative and the metal passivator provided by the embodiment of the invention, alkyl benzotriazole, paraformaldehyde, fatty amine and an organic solvent are used as raw materials, and the benzotriazole derivative is synthesized through a Mannich reaction. The method does not need high temperature condition, and has high operation safety; acid or alkali catalysis is not needed, and the reaction process is simple and mild; the non-aqueous solvent is used, the by-products are less, and the yield of the benzotriazole derivatives is high; the post-treatment of the reaction is simple, and three wastes are not generated. The benzotriazole derivative and the metal passivator provided by the embodiment of the invention have the advantages of excellent oil solubility, environmental protection and low toxicity, and can efficiently inhibit the oxidation of oil products and the generation of acidic substances so as to reduce the damage to metal equipment.
Description
Technical Field
The embodiment of the invention relates to the technical field of metal passivators, and particularly relates to a preparation method of benzotriazole derivatives and a metal passivator.
Background
The metal ions contained in the oil products (such as fuel oil, insulating oil and lubricating oil) can play a role in catalyzing free radical chain reaction in the oil product oxidation process, accelerate the oxidation speed of the oil products, generate acid, oil sludge, precipitate and the like. Among them, acid corrodes metal parts, and sludge and precipitates thicken oil, resulting in the sticking of piston rings and the clogging of oil passages. Technicians generally adopt a mode of adding a metal deactivator in an oil product to inhibit the catalytic action of metal ions on the oxidation of the oil product.
Currently, the types of metal deactivators are mainly benzotriazoles and thiadiazoles. Compared with the thiadiazole metal passivator, the benzotriazole metal passivator has the film forming effect, can react with copper ions, can effectively mask the oxidation catalysis effect of the copper ions on oil products, and has better oxidation resistance.
In the process of implementing the invention, the inventor finds that in the prior art, the preparation process of the benzotriazole metal passivator is relatively complex, the inhibition effect of the prepared benzotriazole metal passivator on oil oxidation is not ideal, and the increasingly severe requirements of equipment on oil are difficult to meet.
Disclosure of Invention
In order to simplify the preparation process of the benzotriazole metal passivator and improve the passivation effect of the benzotriazole metal passivator, the embodiment of the invention provides a preparation method of the benzotriazole metal passivator and a metal passivator, and the benzotriazole derivative with good inhibition effect on oil oxidation can be prepared by using a non-aqueous solvent under the conditions of no need of acid-base catalysis and protective gas.
In order to solve the above technical problem, an embodiment of the present invention provides the following technical solutions:
in a first aspect, an embodiment of the present invention provides a preparation method of benzotriazole derivatives, where the method includes:
adding alkyl benzotriazole, fatty amine, paraformaldehyde and an organic solvent into a reaction kettle and uniformly mixing;
and heating and stirring the mixture of the alkyl benzotriazole, the fatty amine, the paraformaldehyde and the organic solvent to carry out a Mannich reaction on the alkyl benzotriazole, the fatty amine and the paraformaldehyde to generate a benzotriazole derivative.
Optionally, the alkyl benzotriazole is at least one of 1-methyl benzotriazole, 4-methyl benzotriazole and 5-methyl benzotriazole.
Optionally, the fatty amine is a secondary amine with a carbon chain length of C8-C20.
Optionally, the heating and stirring a mixture of the alkylbenzotriazole, the fatty amine, the paraformaldehyde, and the organic solvent includes:
heating the mixture of the alkylbenzotriazole, the fatty amine, the paraformaldehyde and the organic solvent to 50-80 ℃.
Optionally, the reaction time of the alkylbenzotriazole, the fatty amine and the paraformaldehyde is 6-10 h.
Optionally, the mass ratio of the organic solvent to the alkylbenzotriazole is 1: (0.1-0.6).
Optionally, the molar ratio of the alkylbenzotriazole to the paraformaldehyde to the fatty amine is (1.0-1.3): (1.0-1.35): (0.95-1.3).
In a second aspect, an embodiment of the present invention provides a metal passivator, where the metal passivator includes, by mass:
70-80 parts of a phenolic antioxidant, 1-10 parts of an organic solvent and 1-20 parts of the benzotriazole derivative in the first aspect;
optionally, the phenolic antioxidant comprises at least one of 2, 6-di-tert-butyl-p-cresol, 2-tert-butyl-5-pentadecylphenol and 4, 4' -methylenebis (2, 6-di-tert-butylphenol).
Optionally, the addition amount of the metal passivator in the oil product is 200-500 ppm.
The beneficial effects of the embodiment of the invention are as follows: different from the situation of the prior art, the embodiment of the invention provides a preparation method of benzotriazole derivatives and a metal passivator. The method does not need high temperature condition, and has high operation safety; acid or alkali catalysis is not needed, and the reaction process is simple and mild; the non-aqueous solvent is used, the by-products are less, and the yield of the benzotriazole derivatives is high; the post-treatment of the reaction is simple, and three wastes are not generated. The product of the invention has excellent oil solubility, environmental protection and low toxicity, and can efficiently inhibit the oxidation of oil products and the generation of acidic substances so as to reduce the damage to metal equipment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be briefly described below. It is obvious that the drawings described below are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a flow chart of the preparation of benzotriazole derivatives according to one embodiment of the present invention;
FIG. 2 is an infrared spectrum of benzotriazole derivatives provided by an embodiment of the present invention;
FIG. 3 is a graph showing the appearance and appearance of a copper coupon in an oil sample corresponding to benzotriazole derivatives according to an embodiment of the present invention;
FIG. 4 is an oil appearance diagram and a comparison chart of copper sheet corrosion tests corresponding to benzotriazole derivatives provided by one embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and 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.
It should be noted that, if not conflicted, the various features of the embodiments of the invention may be combined with each other within the scope of protection of the invention. Additionally, while functional block divisions are performed in the device diagrams, with logical sequences shown in the flowcharts, in some cases, the steps shown or described may be performed in a different order than the block divisions in the device diagrams, or the flowcharts.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The benzotriazole metal passivator mainly comprises benzotriazole, but the addition amount of the benzotriazole is large (0.05-0.1%), the benzotriazole is almost insoluble in oil, and the benzotriazole metal passivator does not have oxidation resistance per se, so that the increasingly severe requirements of equipment on oil products are difficult to meet. And the existing preparation process of the metal passivator of the benzotriazole derivative is relatively complex.
In the related art, the method for preparing the benzotriazole fatty amine derivative comprises the following steps: the method comprises the steps of taking sodium benzotriazole, fatty amine and formaldehyde as raw materials, reacting at 70-100 ℃ by taking acid as a catalyst and water as a medium, washing with water, drying, and purifying by using methanol to obtain a final product. In the method, the benzotriazole sodium needs to be prepared by multi-step reaction, so that the production cost is increased; the method takes acid as a catalyst, and is difficult to completely remove from the product, so that the product performance is influenced; in addition, the method takes water as a medium for reaction, and needs to be washed with water and distilled for removing the solvent for many times in the post-treatment process, so that a large amount of industrial wastewater can be generated in the production of the benzotriazole aliphatic amine derivative, and thus, the method is not economical and environment-friendly and has low production efficiency.
In the related technology, methylbenzotriazole, formaldehyde and diisooctylamine are used as raw materials, the methylbenzotriazole is dissolved by ethanol under the protection of nitrogen at the temperature of 80-120 ℃, then a formaldehyde water solution is dropwise added, the reaction lasts for 8-20 hours, and the final product (namely, the benzotriazole derivative) is obtained through high-temperature reduced pressure distillation. The method needs to complete the reaction for a long time under the conditions of higher temperature and nitrogen protection, and has low production efficiency. The formaldehyde used in the method is a formaldehyde aqueous solution, and the storage and transportation difficulty is relatively high; the reaction in the method needs to be carried out at a higher temperature, and the product needs to be purified by high-temperature reduced pressure distillation in the post-treatment process, so that the energy consumption of the whole production process is high, and the production cost of the product is increased.
In order to simplify the process flow for preparing the benzotriazole derivative, the embodiment of the invention provides a preparation method of the benzotriazole derivative, which can prepare the benzotriazole derivative by taking alkyl benzotriazole, paraformaldehyde and fatty amine as raw materials under the condition of no need of protective gas and acid-base catalyst. The method has the advantages of high operation safety, simple and mild reaction process, less by-products, high yield, simple post-treatment and no generation of three wastes. To facilitate the reader's understanding of the invention, reference will now be made to specific examples.
The embodiment of the invention provides a preparation method of benzotriazole derivatives, and fig. 1 schematically shows a process for preparing the benzotriazole derivatives, and as shown in fig. 1, the method comprises the following steps:
s11, adding alkyl benzotriazole, fatty amine, paraformaldehyde and an organic solvent into a reaction kettle, and uniformly mixing;
in the embodiment of the invention, the alkylbenzotriazole and the fatty amine can be any suitable type, and can be set by a person skilled in the art according to actual conditions; for example, the alkylbenzotriazole may be at least one of tolyltriazole, 5-methyl-1H-benzotriazole, and the like.
The alkyl benzotriazole is methyl benzotriazole, and the fatty amine is diisooctylamine. The raw materials for preparing the benzotriazole derivatives comprise methylbenzotriazole, diisooctylamine and paraformaldehyde. The organic solvent is monohydric aliphatic alcohol with carbon content of 2-4. The methylbenzotriazole is in the form of white particles or powder, is insoluble in water, is soluble in organic solvents such as alcohol, benzene, toluene and chloroform, and can also be dissolved in dilute alkali solution. Paraformaldehyde (PF) is an industrially important linear oxymethylene polymer of the formula HO (CH)2O)nH (wherein n is a positive integer). Paraformaldehyde is white or colorless crystalline powder or granular or flaky solid, and is divided into low-polymerization-degree paraformaldehyde and solid paraformaldehyde. Paraformaldehyde generally refers to a low degree of polymerization solid formaldehyde product, the degree of polymerization n of which is 8 to 10 for polyoxymethylene glycol. Because the effective component of the paraformaldehyde is higher than that of industrial formaldehyde, the paraformaldehyde is solid particles, is beneficial to chemical synthesis in chemical industry, pharmacy and other industrial fields and has wide application particularly in the aspect of synthesis requiring anhydrous formaldehyde as a raw material. Formaldehyde is polymerized by hydrogen bonding and participates in chemical reactions after depolymerization. At room temperature, firstly introducing an organic solvent into a reaction vessel, then dissolving alkyl benzotriazole into the organic solvent, then adding aliphatic amine and paraformaldehyde into the organic solvent, and uniformly mixing the compounds in the reaction vessel by a stirring mode. In order to enable the benzotriazole derivative to have a good passivation effect on metal, the molar ratio of alkyl benzotriazole, paraformaldehyde and fatty amine is (1.0-1.3): (1.0-1.35): (0.95-1.3). The amount of organic solvent and methylbenzotriazoleThe mass ratio of the azole is 1: (0.1-0.6).
S12, heating and stirring the mixture of the alkyl benzotriazole, the fatty amine, the paraformaldehyde and the organic solvent to enable the alkyl benzotriazole, the fatty amine and the paraformaldehyde to carry out a Mannich reaction to generate a benzotriazole derivative.
In this embodiment, a mixture of the methylbenzotriazole, the diisooctylamine, the paraformaldehyde, and the organic solvent is heated to 50 ℃ to 80 ℃, and reacts for 6 to 10 hours under a stirring condition to generate the benzotriazole derivative. The synthesized benzotriazole derivative is N, N-di (2-ethylhexyl) -methyl-1H-benzotriazole-1-methylamine. The action mechanism of the metal passivator provided by the embodiment of the invention is film-forming, namely, a chemical film is generated on the surface of metal, so that the metal or the metal is prevented from being changed into ions to enter oil, and the catalytic action of the metal passivator on the oil is weakened.
The paraformaldehyde in the embodiment of the invention can be depolymerized to generate formaldehyde, so that the methylbenzotriazole, the diisooctylamine and the formaldehyde are subjected to Mannich reaction to generate N, N-bis (2-ethylhexyl) -methyl-1H-benzotriazol-1-methylamine. The IR spectrum of N, N-bis (2-ethylhexyl) -methyl-1H-benzotriazole-1-methylamine is shown in FIG. 2.
The reaction equation for the mannich reaction in the examples of the present invention is as follows:
optionally, in some embodiments, the method further includes the following steps:
s13, desolventizing and concentrating the product of the Mannich reaction.
And (3) distilling the product of the Mannich reaction under reduced pressure to remove the solvent and the byproduct water to obtain concentrated N, N-bis (2-ethylhexyl) -methyl-1H-benzotriazole-1-methylamine. When the addition amount of the N, N-di (2-ethylhexyl) -methyl-1H-benzotriazole-1-methylamine in an oil product is 0.01-0.03 wt%, a good metal passivation effect can be achieved.
The embodiment of the invention also provides a metal passivator, which comprises 70-80 parts of phenolic antioxidant, 1-10 parts of organic solvent and 1-20 parts of benzotriazole derivative provided by the embodiment. The benzotriazole derivative and the phenol antioxidant provided by the embodiment have a synergistic effect, the passivation effect of the benzotriazole derivative and the phenol antioxidant is better than that of any component when the benzotriazole derivative and the phenol antioxidant are used independently, and the antioxidant effect of the phenol antioxidant is better improved. The phenolic antioxidant may specifically be at least one of 2, 6-di-tert-butyl-p-cresol, 2-tert-butyl-5-pentadecylphenol and 4, 4' -methylenebis (2, 6-di-tert-butylphenol). In order to achieve a better passivation effect, the addition amount of the metal passivator in the oil product is 200-500 ppm. When the addition amount of the metal passivator is less than 200ppm, the passivation effect of the metal passivator cannot meet the requirement, and when the addition amount of the metal passivator reaches 500ppm, the passivation effect of the metal passivator approaches saturation, so that when the content of the metal passivator is more than 500ppm, the waste of the metal passivator is caused.
Example 1
90.61g of methylbenzotriazole and 151.02g of ethanol are added into a 500mL four-neck flask, and 22.44g of paraformaldehyde and 164.18g of diisooctylamine are added after the methylbenzotriazole is completely dissolved. Then a thermometer, a condenser tube and a mechanical stirrer are arranged. Starting a stirrer, heating at 60 ℃ for reaction for 7 hours, and stopping the reaction; and (3) cooling the reaction product to room temperature, and distilling the reaction product to 70 ℃ under reduced pressure by using a rotary evaporation device or a reduced pressure distillation device under the condition that the vacuum degree is 0.08-0.1 MPa to obtain yellow liquid, namely the benzotriazole derivative synthesized by the method.
Example 2
79.95g of 5-methyl-1H-benzotriazole and 133.25g of ethanol are added into a 500mL four-neck flask, 19.80g of paraformaldehyde and 144.87g of diisooctylamine are added after the raw materials are dissolved, and a thermometer, a condenser tube and a mechanical stirrer are arranged. Starting a stirrer, heating at 60 ℃ for reaction for 7 hours, and stopping the reaction; and (3) cooling the reaction product to room temperature, and distilling the reaction product to 70 ℃ under reduced pressure by using a rotary evaporation device or a reduced pressure distillation device under the condition that the vacuum degree is 0.08-0.1 MPa to obtain a light yellow liquid, namely the benzotriazole derivative synthesized by the method.
Example 3
159.60g of 5-methyl-1H-benzotriazole and 266.00g of ethanol are added into a 1000mL four-neck flask, 43.24g of paraformaldehyde and 318.80g of diisooctylamine are added after the raw materials are dissolved, and a thermometer, a condenser tube and a mechanical stirrer are arranged. Starting a stirrer, heating at 70 ℃ for reaction for 7 hours, and stopping the reaction; and (3) cooling the reaction product to room temperature, and distilling the reaction product to 70 ℃ under reduced pressure by using a rotary evaporation device or a reduced pressure distillation device under the condition that the vacuum degree is 0.08-0.1 MPa to obtain a light yellow liquid, namely the benzotriazole derivative synthesized by the method.
Example 4
173.10g of 5-methyl-1H-benzotriazole and 247.28g of ethanol are added into a 1000mL four-neck flask, after the raw materials are dissolved, 30.03g of paraformaldehyde and 229.39g of diisooctylamine are added, and a thermometer, a condenser tube and a mechanical stirrer are arranged. Starting a stirrer, heating at 70 ℃ for reaction for 8h, and stopping the reaction; and (3) cooling the reaction product to room temperature, and distilling the reaction product to 70 ℃ under reduced pressure by using a rotary evaporation device or a reduced pressure distillation device under the condition that the vacuum degree is 0.08-0.1 MPa to obtain a light yellow liquid, namely the benzotriazole derivative synthesized by the method.
Example 5
133.15g of 5-methyl-1H-benzotriazole and 190.21g of ethanol are added into a 1000mL four-neck flask, after the raw materials are dissolved, 40.54g of paraformaldehyde and 313.90g of diisooctylamine are added, and a thermometer, a condenser tube and a mechanical stirrer are arranged. Starting a stirrer, heating at 70 ℃ for reaction for 8h, and stopping the reaction; and (3) cooling the reaction product to room temperature, and distilling the reaction product to 70 ℃ under reduced pressure by using a rotary evaporation device or a reduced pressure distillation device under the condition that the vacuum degree is 0.08-0.1 MPa to obtain a light yellow liquid, namely the benzotriazole derivative synthesized by the method.
Example 6
The metal passivator comprises the benzotriazole derivative synthesized in the example 1 and 2, 6-di-tert-butyl-p-cresol, wherein the addition amounts of the benzotriazole derivative and the 2, 6-di-tert-butyl-p-cresol in the oil product are respectively 0.01 wt% and 0.1 wt%.
Example 7
The metal passivator comprises the benzotriazole derivative synthesized in the example 1 and 2-tert-butyl-5-pentadecylphenol, wherein the addition amounts of the benzotriazole derivative and the 2-tert-butyl-5-pentadecylphenol in the oil product are respectively 0.02 wt% and 0.1 wt%.
Example 8
The metal passivator comprises benzotriazole derivatives synthesized in example 1 and 4, 4' -methylenebis (2, 6-di-tert-butylphenol), wherein the addition amounts of the benzotriazole derivatives and 2, 6-di-tert-butyl-p-cresol in the oil product are respectively 0.03 wt% and 0.1 wt%.
Comparative example 1
The metal passivator comprises 2, 6-di-tert-butyl-p-cresol, and does not comprise benzotriazole derivatives. The addition amount of 2, 6-di-tert-butyl-p-cresol in the oil product is 0.2 wt%.
Comparative example 2
The metal passivator comprises 2, 6-di-tert-butyl-p-cresol, and does not comprise benzotriazole derivatives. The addition amount of 2, 6-di-tert-butyl-p-cresol in the oil product is 0.1 wt%.
Comparative example 3
The metal passivator comprises benzotriazole derivatives, excluding phenolic antioxidants. The addition amount of the benzotriazole derivative in the oil product is 0.3 wt%.
Comparative example 4
The metal passivator comprises benzotriazole derivatives, excluding phenolic antioxidants. The addition amount of the benzotriazole derivative in the oil product is 0.01 wt%.
The test method is as follows:
(1) performance testing of benzotriazole derivatives of examples 1 to 5: and (3) carrying out appearance visual inspection, infrared analysis, high-performance liquid phase analysis, gas phase analysis, nuclear magnetic analysis, copper sheet corrosion test (GB/T5096-.
(2) Performance testing of the metal passivators in examples 6-8 and comparative examples 1-4: adding a metal deactivator to the hydraulic oil. And performing a hydrolysis stability test, a rotary oxygen bomb test and a PDSC test by using the prepared hydraulic oil.
The test results were as follows:
example 1: the product is a yellow transparent liquid; the content of methylbenzotriazole is 0.66 wt%; the content of diisooctylamine is 0.51 wt%; the corrosion grade of the copper sheet is 1 b; the oil solubility is good; the density was 0.9504g/cm3(20 ℃ C.); kinematic viscosity of 80mm2S (40 ℃ C.); the base number is 150.3 mgKOH/g; the hydrolytic stability (namely the weight loss of the copper sheet) measured in the anti-wear hydraulic oil is 0.12mg/cm2。
As can be seen from Table 1, compared with the same products sold in the market (a comparative test is carried out on benzotriazole and thiadiazole derivatives T561), the products synthesized by the method of the invention are more stable and stable. Has good hydrolytic stability, longer oxidation induction period and excellent wear resistance. The test results are shown in table 1.
Table one: the properties of different types of metal deactivators.
Copper sheets a, B and C in fig. 3 are the appearance of copper test pieces in oil samples without metal passivator, with T561 and with benzotriazole derivatives synthesized in example 1. Wherein, the surface of the copper sheet A is the roughest, and the corrosion phenomenon is the most serious; the copper sheet C has the smoothest surface, the minimum color change and the least obvious corrosion phenomenon, so the metal passivation effect of the benzotriazole derivative synthesized in the example 1 is the best.
In fig. 4, a test tube a, a test tube b, and a test tube c are oil samples obtained after performing corrosion experiments on copper test pieces in the oil samples to which the metal passivator is not added, the T561 is added, and the benzotriazole derivative synthesized in example 1 is added, wherein colors of liquids in the test tube a, the test tube b, and the test tube c are sequentially lightened. The color of the oil sample in the test tube c to which the benzotriazole derivative synthesized in example 1 was added was the lightest, and thus the metal passivation effect of the benzotriazole derivative synthesized in example 1 was the best.
Example 2: the product is a light yellow transparent liquid; the content of 5-methyl-1H-benzotriazole is 0.76 wt%; the content of diisooctylamine is 0.91 wt%; the corrosion grade of the copper sheet is 1 b; the oil solubility is good; the density was 0.9496g/cm3(measured at 20 ℃); kinematic viscosity of 80mm2(ii)/s (measured at 40 ℃); the base number is 148.7mg KOH/g; the weight loss of the copper sheet is 0.13mg/cm2。
Example 3: the product is a light yellow transparent liquid; the content of 5-methyl-1H-benzotriazole is 0.47 wt%; the content of diisooctylamine is 1.21 wt%; the corrosion grade of the copper sheet is 1 b; the oil solubility is good; the density was 0.9502g/cm3(measured at 20 ℃); kinematic viscosity (measured at 40 ℃)80mm2S; a base number of 153.2 mgKOH/g; hydrolytic stability (measured in anti-wear hydraulic oil), weight loss of copper sheet 0.18mg/cm2。
Example 4: the product is a light yellow transparent liquid; the content of 5-methyl-1H-benzotriazole is 2.17 wt%; the content of diisooctylamine is 0.89 wt%; copper sheet corrosion grade 1 b; the oil solubility is good; the density was 0.9418g/cm3(measured at 20 ℃); kinematic viscosity of 80mm2(ii)/s (measured at 40 ℃); base number 122.2mg KOH/g; the weight loss of the copper sheet is 0.39mg/cm2。
Example 5: the product is a light yellow transparent liquid; the content of 5-methyl-1H-benzotriazole is 0.59 percent by weight; 2.61 wt% of diisooctylamine; copper sheet corrosion grade 1 b; the oil solubility is good; density 0.9588g/cm3(measured at 20 ℃); kinematic viscosity of 80mm2(ii)/s (measured at 40 ℃); the base number is 163.1 mgKOH/g; the weight loss of the copper sheet is 0.22mg/cm2。
Example 6:
table two, the different examples and comparative examples provide the performance of the metal passivators.
As can be seen from the comparison of the data of comparative examples 1 to 4 and examples 6 to 8 in the table II, the inhibition effect of the benzotriazole derivatives and the phenolic antioxidants used in combination on the oxidation of the oil products is better than the inhibition effect of any single component on the oil products. For example: the phenolic antioxidant was added in an amount of 0.1 wt% in each of comparative example 2 and example 6, but the metal deactivator in example 6 was more effective in inhibiting oil oxidation than in comparative example 2. The addition amount of the benzotriazole derivatives in comparative example 4 and example 6 is 0.01 wt%, but the inhibition effect of the metal passivator on oil oxidation in example 6 is better than that in comparative example 2. The addition amount of the metal passivator in comparative example 3 is 0.3 wt%, and the use amount of the metal passivator in example 6 is 0.11 wt%, and it can be known from the experimental results of comparative example 3 and example 6 that the benzotriazole derivative and the phenolic antioxidant which are used together can obtain better inhibition effect on oil products under the condition of less use amount.
According to the embodiment of the invention, the inhibition effect of the metal passivator on oil oxidation is greatly improved through the synergistic effect of the benzotriazole derivative and the phenol antioxidant. Even under the condition of low addition of the metal passivator (such as 0.01 wt% of benzotriazole derivative and 0.1 wt% of phenolic antioxidant), excellent antioxidant effect can be obtained.
The method adopts Mannich reaction, does not need high temperature condition and has high operation safety. Acid or alkali catalysis is not needed, and the reaction process is simple and mild. The non-aqueous solvent is used, the by-product is less, and the yield is high. Simple post-treatment and no generation of three wastes. The product has excellent oil solubility, environmental protection and low toxicity. The lubricating oil additive has good compatibility with other oil additives, can be used as a fuel oil additive, a lubricating oil additive and an insulating oil additive, can effectively inhibit the damage of nonferrous metals in oil products to mechanical equipment, and has the effects of oxidation resistance, wear resistance and the like. Meanwhile, the addition amount is small (0.01-0.03 percent) and is only one fifth to one third of the dosage of benzotriazole. Compared with the currently commonly used metal passivator, the effect of the metal passivator provided by the compounding scheme is improved by 20-50%, and the performance of the compounded oil product exceeds the level of foreign complexing agents and foreign similar oil products.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the benzotriazole derivative is characterized by comprising the following steps:
adding alkyl benzotriazole, fatty amine, paraformaldehyde and an organic solvent into a reaction kettle and uniformly mixing;
and heating and stirring the mixture of the alkyl benzotriazole, the fatty amine, the paraformaldehyde and the organic solvent to carry out a Mannich reaction on the alkyl benzotriazole, the fatty amine and the paraformaldehyde to generate a benzotriazole derivative.
2. The preparation method of the benzotriazole derivatives of claim 1, wherein the alkyl benzotriazole is at least one of 1-methyl benzotriazole, 4-methyl benzotriazole and 5-methyl benzotriazole.
3. The preparation method of benzotriazole derivatives of claim 1, wherein the fatty amine is a secondary amine with a carbon chain length of C8-C20.
4. The method for preparing benzotriazole derivatives according to claim 1, wherein the heating and stirring of the mixture of alkylbenzotriazole, fatty amine, paraformaldehyde and organic solvent comprises:
heating the mixture of the alkylbenzotriazole, the fatty amine, the paraformaldehyde and the organic solvent to 50-80 ℃.
5. The preparation method of benzotriazole derivatives of claim 1, wherein the reaction time of the alkyl benzotriazole, the fatty amine and the paraformaldehyde is 6-10 h.
6. The preparation method of benzotriazole derivatives according to claim 1, wherein the mass ratio of the organic solvent to the alkyl benzotriazole is 1: (0.1-0.6).
7. The preparation method of benzotriazole derivatives according to any one of claims 1-6, wherein the molar ratio of alkyl benzotriazole, paraformaldehyde and fatty amine is (1.0-1.3): (1.0-1.35): (0.95-1.3).
8. The metal passivator is characterized by comprising the following components in parts by mass:
70-80 parts of phenolic antioxidant, 1-10 parts of organic solvent and 1-20 parts of benzotriazole derivative as claimed in any one of claims 1-7.
9. A phenolic antioxidant according to claim 8, characterised in that the phenolic antioxidant comprises at least one of 2, 6-di-tert-butyl-p-cresol, 2-tert-butyl-5-pentadecylphenol and 4, 4' -methylenebis (2, 6-di-tert-butylphenol).
10. The metal deactivator according to claim 8 or 9, wherein the metal deactivator is added in an amount of 200-500 ppm in the oil product.
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