CN111303061B - Arylamine compound and preparation method and application thereof - Google Patents
Arylamine compound and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
- C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10M133/40—Six-membered ring containing nitrogen and carbon only
- C10M133/42—Triazines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
- C10M2215/222—Triazines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
Abstract
The invention relates to an arylamine compound, a preparation method and application thereof. The arylamine compound has a structure shown in formula III, wherein R1Selected from H and alkyl with 1-30 carbon atoms; r2、R3Independently selected from one of the following structures:
R4、R5、R6、R7、R8each independently selected from alkyl groups having 1 to 18 carbon atoms. The arylamine compound disclosed by the invention has excellent oxidation resistance and good lubricating property.
Description
Technical Field
The invention relates to the field of chemical multifunctional additives, in particular to arylamine compounds, and a preparation method and application thereof.
Background
The lubricating oil is a liquid lubricant which is used on various automobile transmissions, mechanical equipment and precision instruments to reduce friction and protect machines and workpieces, is mainly used for reducing friction between surfaces of moving parts, and has the functions of cooling, sealing, corrosion prevention, rust prevention, insulation, power transmission, impurity cleaning and the like on the mechanical equipment. Lubricating oils are generally composed of two parts, a base oil and additives. The base oil is the main component of the lubricating oil, and determines the basic properties of the lubricating oil, and the additive can make up and improve the deficiency in the performance of the base oil and endow certain new performance.
During the use process of the lubricating oil, a series of chemical changes such as oxidation, polymerization, decomposition and the like can occur under the catalytic action of oxygen in the air, byproducts (sulfur-containing compounds, nitrogen-containing compounds and the like) generated by fuel combustion, high temperature and some metals and the like, so that a series of consequences such as corrosion, oil product viscosity change, paint film and oil sludge generation and the like can be generated. The oxidation is the main reason of the deterioration of the lubricating oil, the service life of the lubricating oil is greatly shortened, the service life of the lubricating oil is shortened, the discharge amount of waste oil is increased, and the energy conservation and emission reduction are not facilitated. Thus, there is a high call in the industry for antioxidants to improve the oxidation stability of lubricating oils.
The most common classes of antioxidants are sterically hindered phenols and alkylated diphenylamines, such as 2, 6-di-tert-butyl-p-cresol, isooctyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, butyl-octylated diphenylamine, dioctyldiphenylamine. Generally, amine antioxidants are superior to phenolic antioxidants in terms of high temperature resistance and enhanced oxidative induction.
However, the conventional amine antioxidants still need to be further improved in the aspects of high temperature resistance and oxidation induction period improvement, for example, the thermogravimetric loss of butyl-octylated diphenylamine is large, and dioctyl diphenylamine and dinonyl diphenylamine have poor effects in the aspect of oxidation induction period improvement.
Therefore, it is necessary to conduct an intensive research on amine antioxidants to prepare a multifunctional additive capable of meeting the increasingly stringent requirements of energy conservation and emission reduction.
Disclosure of Invention
Under the background, the invention provides the arylamine compound and the preparation method thereof, and the obtained arylamine compound not only has excellent oxidation resistance, but also has good lubricating property.
The specific technical scheme is as follows:
an arylamine compound has a structure shown in a formula III;
wherein R is1Selected from H and alkyl with 1-30 carbon atoms;
R2、R3independently selected from one of the following structures:
R4、R5、R6、R7、R8each independently selected from alkyl groups having 1 to 18 carbon atoms.
In some preferred embodiments, the R is1Selected from H and isooctyl.
In some preferred embodiments, the R is2、R3Independently selected from one of the following structures:
in some preferred embodiments, the R is4、R5、R6、R7Each independently selected from butyl or octyl.
The invention also provides a preparation method of the arylamine compound.
The specific technical scheme is as follows:
a preparation method of arylamine compounds comprises the following steps:
reacting the compound with the structure shown in the formula I with cyanuric chloride to prepare a compound with the structure shown in the formula II;
reacting the compound with the structure of the formula II with an active reactant to prepare a compound with the structure of the formula III;
the active reactant is selected from one or more of alcohol, sodium alkoxide, organic amine and dialkyl dithiocarbamate;
wherein R is1Selected from H and alkyl with 1-30 carbon atoms;
R2、R3independently selected from one of the following structures:
R4、R5、R6、R7、R8each independently selected from alkyl groups having 1 to 18 carbon atoms.
In some preferred embodiments, the reactive reactant is selected from one or more of dibutyl dithiocarbamate, di-n-octyl dithiocarbamate, dibutylamine and di-n-octylamine.
In some preferred embodiments, the compound having the structure of formula I, cyanuric chloride and an alkaline agent are mixed in a solvent and reacted at 0-15 ℃ for 3min-30 min.
In some preferred embodiments, the molar ratio of the compound having the structure of formula I to cyanuric chloride is (0.8-1.2): 1.
in some preferred embodiments, the molar ratio of the alkaline agent to cyanuric chloride is (0.4-2): 1.
in some preferred embodiments, the compound having the structure of formula II and the reactive reactant are mixed in a solvent and reacted at 30-90 ℃ for 3-12 h.
In some preferred embodiments, the molar ratio of the compound having the structure of formula II to the active reactant is 1: (2-2.2).
The invention also provides an antioxidant lubricating multifunctional additive.
The specific technical scheme is as follows:
the antioxidant lubricating multifunctional additive is prepared with the aromatic amine compound or the aromatic amine compound prepared through the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the arylamine compound has longer oxidation stability and longer oxidation induction period, has excellent oxidation resistance and good lubricating property, and can be used as an oxidation-resistant lubricating multifunctional additive.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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.
In the present invention, when any variable (e.g. R)1、R2Etc.) occur more than one time in any constituent, then the definition of each occurrence is independent of the definition of each other occurrence. Also, combinations of substituents and variables are permissible only if such combinations result in stable compounds.
In the present invention, "substituted" in the expression "substituted or unsubstituted" means that a hydrogen atom in a substituent is substituted by a substituent, and "unsubstituted" means that a hydrogen atom in a group is not substituted by a substituent.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms.
During the use process of the lubricating oil, a series of chemical changes such as oxidation, polymerization, decomposition and the like can occur under the catalytic action of oxygen in the air, byproducts (sulfur-containing compounds, nitrogen-containing compounds and the like) generated by fuel combustion, high temperature and some metals and the like, so that a series of consequences such as corrosion, oil product viscosity change, paint film and oil sludge generation and the like can be generated. The oxidation is the main reason of the deterioration of the lubricating oil, the service life of the lubricating oil is greatly shortened, the service life of the lubricating oil is shortened, the discharge amount of waste oil is increased, and the energy conservation and emission reduction are not facilitated. Thus, there is a high call in the industry for antioxidants to improve the oxidation stability of lubricating oils.
The most common classes of antioxidants are sterically hindered phenols and alkylated diphenylamines, such as 2, 6-di-tert-butyl-p-cresol, isooctyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, butyl-octylated diphenylamine, dioctyldiphenylamine. Generally, amine antioxidants are superior to phenolic antioxidants in terms of high temperature resistance and enhanced oxidative induction.
However, the conventional amine antioxidants still need to be further improved in the aspects of high temperature resistance and oxidation induction period improvement, for example, the thermogravimetric loss of butyl-octylated diphenylamine is large, and dioctyl diphenylamine and dinonyl diphenylamine have poor effects in the aspect of oxidation induction period improvement.
Therefore, it is necessary to conduct an intensive research on amine antioxidants to prepare a multifunctional additive capable of meeting the increasingly stringent requirements of energy conservation and emission reduction.
The inventor obtains an arylamine compound with a structure shown in a formula III through long-term experience accumulation and a large number of creative experiments in the field;
wherein R is1Selected from H and alkyl with 1-30 carbon atoms;
R2、R3independently selected from one of the following structures:
R4、R5、R6、R7、R8each independently selected from alkyl groups having 1 to 18 carbon atoms.
The amine compound has longer oxidation stability and longer oxidation induction period, has excellent oxidation resistance and good lubricating property, and can be used as an oxidation-resistant lubricating multifunctional additive.
In some preferred embodiments, the R is1Selected from H and isooctyl.
In some preferred embodiments, the R is2、R3Independently selected from one of the following structures:
in some preferred embodiments, the R is4、R5、R6、R7Each independently selected from butyl or octyl.
In some preferred embodiments, the R is8Is selected from isooctyl or alkyl with 12-13 carbon atoms.
A preparation method of arylamine compounds comprises the following steps:
reacting the compound with the structure shown in the formula I with cyanuric chloride to prepare a compound with the structure shown in the formula II;
reacting the compound with the structure of the formula II with an active reactant to prepare a compound with the structure of the formula III;
the active reactant is selected from one or more of alcohol, sodium alkoxide, organic amine and dialkyl dithiocarbamate;
wherein R is1Selected from H and alkyl with 1-30 carbon atoms;
R2、R3independently selected from one of the following structures:
R4、R5、R6、R7、R8each independently selected from alkyl groups having 1 to 18 carbon atoms.
Wherein, the compound with the structure of formula I can be directly purchased through commercial sources.
Reacting a compound with a structure shown in a formula I with cyanuric chloride to prepare a compound with a structure shown in a formula II, wherein the synthetic route of the step is as follows:
the compound with the structure shown in the formula I, cyanuric chloride and an alkaline agent can be mixed in a solvent and reacted for 3min to 30min at the temperature of 0 ℃ to 15 ℃. Preferably, the reaction time is 15 min.
Preferably, the molar ratio of the compound having the structure of formula I to cyanuric chloride is (0.8-1.2): 1. it will be appreciated that the molar ratio of the compound having the structure of formula I to cyanuric chloride may be 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2: 1. More preferably, the molar ratio of the compound having the structure of formula I to cyanuric chloride is 1: 1.
it is understood that the compound having the structure of formula I can be dissolved in a solvent and then reacted with cyanuric chloride under the action of an alkaline agent.
Preferably, the solvent is selected from one or more of petroleum ether, cyclohexane, n-hexane, n-heptane, carbon tetrachloride, chloroform, dichloromethane, ethanol, ethyl acetate and tetrahydrofuran.
Preferably, the alkaline agent is one or more selected from sodium carbonate, potassium carbonate and triethylamine.
Preferably, the molar ratio of the alkaline agent to cyanuric chloride is (0.4-2): 1. it will be appreciated that the molar ratio of the alkaline agent to cyanuric chloride may be 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2: 1. More preferably, the molar ratio of the alkaline agent to cyanuric chloride is 0.8: 1.
after the compound with the structure of the formula II is obtained, the compound is reacted with an active reactant to prepare the compound with the structure of the formula III.
In some preferred embodiments, the reactive reactant is selected from one or more of dibutyl dithiocarbamate, di-n-octyl dithiocarbamate, dibutylamine and di-n-octylamine.
Preferably, the molar ratio of the compound having the structure of formula II to the active reactant is 1: (2-2.2). It will be appreciated that the molar ratio of the compound having the structure of formula II to the active reactant may be 1:2, 1:2.1, 1: 2.2. More preferably, the molar ratio of the compound having the structure of formula II to the active reactant may be 1:2.
In some preferred embodiments, when two reactive reactants are present, for example dibutyl dithiocarbamate and dibutyl amine, the compound having the structure of formula II, dibutyl dithiocarbamate and dibutyl amine can be weighed out in a 1:1:1 molar ratio. In this case, the compound having the structure of formula II may be reacted with one of the reactive reactants before the reaction product is reacted with the other reactive reactant.
Preferably, the compound with the structure of the formula II and the active reactant are mixed in a solvent and reacted for 3h to 12h at 30 ℃ to 90 ℃. More preferably, the reaction is carried out at 65-75 ℃ for 4-10 h.
Preferably, the solvent is selected from one or more of petroleum ether, cyclohexane, n-hexane, n-heptane, carbon tetrachloride, chloroform, dichloromethane, ethanol, ethyl acetate and tetrahydrofuran.
Generally speaking, dialkyl dithiocarbamic acid derivatives are useful as extreme pressure antiwear agents that react with s-triazine to produce a variety of compounds. However, most of the currently researched synthetic routes are designed for improving the extreme pressure antiwear performance. When the active reactant contains dibutyl dithiocarbamate or di-n-octyl dithiocarbamate, dialkyl dithiocarbamate can be regarded as an auxiliary antioxidant, and reacts with the compound containing amino and having the structure of formula II, so that the compound can be matched with the amine main antioxidant to play a good antioxidant synergistic effect, and meanwhile, the prepared compound of formula III also has good lubricity.
In addition, the inventor of the present application finds that when the active reactant contains dibutylamine or di-n-octylamine, dibutylamine or di-n-octylamine can be also used as a secondary antioxidant, and can react with the compound with the structure of formula II containing amine groups, and can also be used together with the amine-based primary antioxidant to exert a good antioxidant synergistic effect, and meanwhile, the prepared compound with the structure of formula III also has good lubricity. It will be appreciated that the compound having the structure of formula II may be reacted with dibutylamine or di-n-octylamine under the action of an alkaline agent.
Preferably, the alkaline agent is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and triethylamine.
The following is further illustrated with reference to specific examples:
example 1
The embodiment provides an arylamine compound and a preparation method thereof, and the preparation method comprises the following steps:
14.7g (79.6mmol) of p-aminodiphenylamine is weighed and placed in a 500mL three-necked flask, 250mL of tetrahydrofuran is added for dissolution, the reaction temperature is controlled to be 0 ℃ in ice bath, and 14.7g (79.6mmol) of cyanuric chloride and 6.75g (63.7mmol) of Na are added into the reaction flask2CO3After the addition of the raw materials, N2And (4) protecting, slowly stirring, reacting for 15 minutes at 0 ℃, and filtering to obtain a solution containing the compound with the structure shown in the formula II.
Adding 36.2g of sodium dibutyldithiocarbamate (the compound with the structure of the formula II and the sodium dibutyldithiocarbamate are in a molar ratio of 1: 2) into the solution containing the compound with the structure of the formula II, taking tetrahydrofuran as a solvent, heating to 70 ℃, stirring and refluxing for 5 hours, filtering, evaporating the solvent, washing with water, and drying to obtain a final product 1a, wherein the structural formula of the final product is shown as the formula III.
Nuclear magnetic resonance characterization of the final product 1 a: 1H NMR (500MHz, CDCl3) δ 8.74(s,0H), 7.68-7.62 (m,1H), 7.24-7.17 (m,1H), 7.09-7.01 (m,2H),6.88(tt, J ═ 7.0,1.3Hz,0H),6.57(s,0H),3.56(t, J ═ 6.3Hz,4H), 1.68-1.64 (m,1H),1.62(d, J ═ 0.8Hz,1H),1.34(H, J ═ 7.2Hz,4H),0.94(t, J ═ 7.4Hz,6H).
Elemental analysis results: c, 59.26; h, 7.15; n, 14.28; s, 19.37.
Example 2
This example provides an arylamine compound and a preparation method thereof, which are substantially the same as those in example 1, except that p-aminodiphenylamine as a raw material is changed to 4- (2-octylamino) diphenylamine, and sodium dibutyldithiocarbamate is changed to sodium di-n-octyldithiocarbamate, and specifically includes the following steps:
79.6mmol of 4- (2-octylamino) diphenylamine is weighed and placed in a 500mL three-neck flask, 250mL of tetrahydrofuran is added for dissolution, the reaction temperature is controlled to be 0 ℃ in ice bath, 14.7g (79.6mmol) of cyanuric chloride and 6.75g (63.7mmol) of Na are added into the reaction flask2CO3After the addition of the raw materials, N2And (4) protecting, slowly stirring, reacting for 10 minutes at 5 ℃, and filtering to obtain a solution containing the compound with the structure shown in the formula II.
In the solution containing the compound having the structure represented by the formula II, the compound having the structure represented by the formula II and sodium di-n-octyldithiocarbamate are 1:2, adding sodium di-n-octyl dithiocarbamate, taking tetrahydrofuran as a solvent, heating to 70 ℃, stirring and refluxing for 5 hours, filtering, evaporating the solvent, washing with water, and drying to obtain a final product 1b, wherein the structural formula is shown as a formula III.
Example 3
This example provides an arylamine compound and a preparation method thereof, the preparation method is basically the same as that in example 1, except that the raw material sodium dibutyldithiocarbamate is changed into dibutylamine, and sodium carbonate is added at the same time, specifically including the following steps:
14.7g (79.6mmol) of p-aminodiphenylamine is weighed and placed in a 500mL three-necked flask, 250mL of tetrahydrofuran is added for dissolution, the reaction temperature is controlled to be 0 ℃ in ice bath, and 14.7g (79.6mmol) of cyanuric chloride and 6.75g (63.7mmol) of Na are added into the reaction flask2CO3After the addition of the raw materials, N2And (4) protecting, slowly stirring, reacting for 15 minutes at 0 ℃, and filtering to obtain a solution containing the compound with the structure shown in the formula II.
In the solution containing the compound having the structure represented by formula II, dibutylamine and sodium carbonate are 1: 2: 2, adding dibutylamine and sodium carbonate, taking ethanol as a solvent, heating to 70 ℃, stirring and refluxing for 10 hours, filtering, evaporating the solvent, washing with water, and drying to obtain a final product 2a, wherein the structural formula is shown as a formula III.
Nuclear magnetic resonance characterization of the final product 2 a: 1H NMR (500MHz, CDCl3) δ 7.68-7.62 (m,1H), 7.24-7.17 (m,1H), 7.09-7.01 (m,1H),3.55(t, J ═ 8.2Hz,2H),1.68(tt, J ═ 8.2,6.8Hz,2H),1.37(p, J ═ 7.1Hz,2H),0.95(t, J ═ 7.4Hz,3H).
Elemental analysis results: c, 72.08; h, 9.66; n,18.31.
Example 4
This example provides an arylamine compound and a preparation method thereof, the preparation method is basically the same as that in example 3, except that p-aminodiphenylamine as a raw material is changed to 4- (2-octylamino) diphenylamine, and dibutylamine is changed to di-n-octylamine, and the preparation method specifically includes the following steps:
79.6mmol of 4- (2-octylamino) diphenylamine is weighed and placed in a 500mL three-neck flask, 250mL of tetrahydrofuran is added for dissolution, the reaction temperature is controlled to be 0 ℃ in ice bath, 14.7g (79.6mmol) of cyanuric chloride and 6.75g (63.7mmol) of Na are added into the reaction flask2CO3After the addition of the raw materials, N2And (4) protecting, slowly stirring, reacting for 10 minutes at 5 ℃, and filtering to obtain a solution containing the compound with the structure shown in the formula II.
In the solution containing the compound having the structure represented by formula II, di-n-octylamine, and sodium carbonate are 1: 2: 2, adding di-n-octylamine and sodium carbonate, taking ethanol as a solvent, heating to 70 ℃, stirring and refluxing for 10 hours, filtering, evaporating the solvent, washing with water, and drying to obtain a final product 2b, wherein the structural formula is shown as a formula III.
Example 5
This example provides an arylamine compound and a preparation method thereof, the preparation method is substantially the same as that in example 1, except that the active reactants are sodium dibutyldithiocarbamate and dibutylamine, and sodium carbonate is added at the same time, specifically including the following steps:
14.7g (79.6mmol) of p-aminodiphenylamine is weighed and placed in a 500mL three-necked flask, 250mL of tetrahydrofuran is added for dissolution, the reaction temperature is controlled to be 0 ℃ in ice bath, and 14.7g (79.6mmol) of cyanuric chloride and 6.75g (63.7mmol) of Na are added into the reaction flask2CO3After the addition of the raw materials, N2Protecting, slowly stirring, reacting at 0 deg.C for 15min, and filteringFiltering to obtain a solution containing the compound with the structure shown in the formula II.
In the solution containing the compound having the structure represented by formula II, dibutylamine and sodium carbonate are 1:1:1, adding dibutylamine and sodium carbonate, mixing, heating to 70 ℃ by taking tetrahydrofuran as a solvent, stirring and refluxing for 4 hours, then adding sodium dibutyldithiocarbamate with the molar quantity equal to that of the compound with the structure of the formula II, heating to 70 ℃, stirring and refluxing for 4 hours, filtering, evaporating the solvent, washing with water, and drying to obtain a final product 3a, wherein the structural formula of the final product is shown as the formula III.
Nuclear magnetic resonance characterization of the final product 3 a: 1H NMR (500MHz, CDCl3) δ 7.68-7.62 (m,0H), 7.24-7.17 (m,1H), 7.09-7.01 (m,1H), 3.59-3.51 (m,2H), 1.73-1.59 (m,2H),1.36(dq, J ═ 20.6,7.2Hz,2H),0.94(q, J ═ 7.4Hz,3H).
Elemental analysis results: c, 65.13; h, 7.65; n, 18.89; s,11.23.
Example 6
This example provides an arylamine compound and a preparation method thereof, which are substantially the same as those in example 5, except that p-aminodiphenylamine as a raw material is changed to 4- (2-octylamino) diphenylamine, dibutylamine is changed to di-n-octylamine, and sodium dibutyldithiocarbamate is changed to di-n-octylsodium dithiocarbamate, and the preparation method specifically includes the following steps:
79.6mmol of 4- (2-octylamino) diphenylamine is weighed and placed in a 500mL three-neck flask, 250mL of tetrahydrofuran is added for dissolution, the reaction temperature is controlled to be 0 ℃ in ice bath, 14.7g (79.6mmol) of cyanuric chloride and 6.75g (63.7mmol) of Na are added into the reaction flask2CO3After the addition of the raw materials, N2Protecting, slowly stirring, reacting at 5 deg.C for 10 min, and filtering to obtain a filtrate containing a compound represented by formula IIA solution of a compound of structure (la).
In the solution containing the compound having the structure represented by formula II, di-n-octylamine, and sodium carbonate are 1:1:1, adding di-n-octylamine and sodium carbonate, mixing, heating to 70 ℃ by taking tetrahydrofuran as a solvent, stirring and refluxing for 4 hours, then adding di-n-octyldithiocarbamic acid sodium salt with the molar quantity equal to that of the compound with the structure of the formula II, heating to 70 ℃, stirring and refluxing for 4 hours, filtering, evaporating the solvent, washing with water, and drying to obtain a final product 3b, wherein the structural formula of the final product is shown as the formula III.
Comparative example
The most commonly used antioxidant on the market, dioctylated diphenylamine, was used as a comparative example.
The following tests were carried out for examples 1 to 6 and comparative example
Determination of oxidation stability of lubricating oils-rotating oxygen bomb method (RPVOT): adopting SH/T0193-.
Lubricating oil oxidation induction period determination-Pressure Differential Scanning Calorimetry (PDSC): adopting SH/T0719-2002 standard test method, the test temperature is 210 deg.C, and the pressure is 3.5 MPa.
The standard test method of an SH/T0189 four-ball friction wear testing machine is adopted to evaluate the wear resistance of the alloy, and the standard test method of a GB/T12583 four-ball friction wear testing machine is adopted to evaluate the extreme pressure performance of the alloy.
The final products of examples 1 to 6 and comparative example were added to a commercial No. 46 ashless hydraulic oil at 0.5% by mass, stirred uniformly, and then tested. The test results are shown in Table 1.
TABLE 1
Pb loading was 981N, 1020N, 1069N, 1118N, 1167N, 1236N, 1294N.
As can be seen from Table 1, the end products 1a, 1b, 2a, 2b, 3a, 3b prepared in examples 1-6 have excellent antioxidant and lubricating properties.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. An arylamine compound is characterized by having a structure shown in a formula III;
wherein R is1Selected from H and alkyl with 1-30 carbon atoms;
R2、R3independently selected from one of the following structures:
R4、R5、R6、R7、R8are respectively provided withIndependently selected from alkyl groups having 1 to 18 carbon atoms.
2. An arylamine compound according to claim 1 wherein R is1Selected from H and isooctyl.
3. An arylamine compound according to claim 1 wherein R is2、R3Independently selected from one of the following structures:
4. an arylamine compound according to claim 3 wherein R is4、R5、R6、R7Each independently selected from butyl or octyl.
5. The preparation method of the arylamine compound is characterized by comprising the following steps of:
reacting the compound with the structure shown in the formula I with cyanuric chloride to prepare a compound with the structure shown in the formula II;
reacting the compound with the structure of the formula II with an active reactant to prepare a compound with the structure of the formula III;
the active reactant is selected from one or more of alcohol, sodium alkoxide, organic amine and dialkyl dithiocarbamate;
wherein R is1Selected from H and alkyl with 1-30 carbon atoms;
R2、R3independently selected from one of the following structures:
R4、R5、R6、R7、R8each independently selected from alkyl groups having 1 to 18 carbon atoms.
6. A process for the preparation of an aromatic amine compound according to claim 5 wherein the reactive reactant is selected from one or more of dibutyl dithiocarbamate, di-n-octyl dithiocarbamate, dibutylamine and di-n-octylamine.
7. A process for the preparation of an aromatic amine compound according to claim 5 or 6, wherein the compound having the structure of formula I, cyanuric chloride and an alkaline agent are mixed in a solvent and reacted at 0-15 ℃ for 3-30 min.
8. A process for the preparation of an aromatic amine compound according to claim 7, wherein the molar ratio of the compound having the structure of formula I to cyanuric chloride is (0.8-1.2): 1.
9. a process for the preparation of an aromatic amine compound according to claim 7 wherein the molar ratio of the basic agent to cyanuric chloride is (0.4-2): 1.
10. a process for the preparation of an aromatic amine compound according to claim 5 or 6, wherein the compound having the structure of formula II is mixed with the active reactant in a solvent and reacted at 30-90 ℃ for 3-12 h.
11. A process for the preparation of an aromatic amine compound according to claim 10 wherein the molar ratio of the compound having the structure of formula II to active reactants is 1: (2-2.2).
12. An antioxidant lubricating multifunctional additive, which is characterized in that the raw materials comprise the arylamine compound as claimed in any one of claims 1 to 4 or the arylamine compound prepared by the preparation method as claimed in any one of claims 5 to 11.
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