CN108069874A - New schiff base type amine antioxidants, its preparation method and application - Google Patents

New schiff base type amine antioxidants, its preparation method and application Download PDF

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Publication number
CN108069874A
CN108069874A CN201710546324.9A CN201710546324A CN108069874A CN 108069874 A CN108069874 A CN 108069874A CN 201710546324 A CN201710546324 A CN 201710546324A CN 108069874 A CN108069874 A CN 108069874A
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oil
amine antioxidants
schiff bases
aldehyde
alkyl
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俞莎莎
冯建湘
蔡涛
曾红玲
刘升高
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/45—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms doubly-bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/20—[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom
    • 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
    • C10M133/22—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones
    • 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
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses a kind of new schiff base type amine antioxidants, its preparation method and applications.The schiff bases amine antioxidants include the compound with structure shown in lower formula (I) or (II)：R in formula1, R2, R3, R4, R5, R6, R7, R8, R9, R10At least alkyl of the linear chain or branch chain selected from H, C1~C20 or alkyl or aryl containing benzene ring substitution group or containing O, S, N, P and/or Si, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10Represent identical group or different groups, X at least selected from S, O, NH orWherein m is 0 or 1.The schiff base type amine antioxidants of the present invention have excellent thermal stability and good antioxygenic property, and preparation process is simple, it, can be in lubricating oil, liquid fuel, thermoplastic polymer, resin or oligomer or natural or synthetic plastics or the multiple fields extensive use such as rubber or elastomer suitable for large-scale production.

Description

New schiff base type amine antioxidants, its preparation method and application
Technical field
The present invention relates to a kind of antioxidant, more particularly to a kind of new schiff base type amine antioxidants, its preparation side Method and application.
Background technology
Lubricating oil is made of mostly base oil and additive.Lube oil additive is the Specialty Chemical object added in base oil Matter, so that lubricating oil obtains certain new characteristic or improves some existing characteristics in lubricating oil.For example, automobile engine oil (i.e. vapour Car engine lubricating oil) during long-term storage and use, inevitably contacted with air, so in air Oxygen, which is had an effect, there is oxidative phenomena, and particularly the hydrocarbon compound under high temperature and metal catalytic effect in lubricating oil can turn Various oxidation products are melted into, including acidic materials, deposit, greasy filth etc., this can seriously affect the normal work of engine, directly Influence the normal operation of equipment.Therefore, in order to improve the quality of lubricating oil, in lubricating oil harmonic process, it is necessary to Xiang Ji A certain amount of high performance antioxidation agent is added in plinth oil, can just slow down the oxidation of oil product, is prolonged the service life and the drain period.With The development in social progress and epoch, the requirement to lube oil additive is also higher and higher.The power of engine is increasing, It is required that oil product has good applied at elevated temperature performance；The extension of oil draining period, it is desirable that oil product has better oxidation stability；Environmental protection will Ask increasingly harsher, it is desirable that use the relatively low additive of phosphorus, sulfur content.Therefore high temperature, multiple-effect and energy conservation and environmental protection become lubrication The developing direction of oily antioxidant.
At present, schiff bases are good and environmental-friendly obtained people as lube oil additive due to synthesizing simple, performance Extensive concern, especially its schiff bases phenolic compound formed with phenol can significantly improve oil product as a kind of antioxidant Antioxygenic property.But the comprehensive performance showed when such schiff bases antioxidant is as lubricating oil, fuel oil additive need Further promoted.
The content of the invention
It is steady with excellent heat it is a primary object of the present invention to provide a kind of new schiff base type amine antioxidants Qualitative and good antioxygenic property.
Another object of the present invention is to provide a kind of method for preparing the schiff base type amine antioxidants.
Another object of the present invention is to provide the application of the schiff base type amine antioxidants.
For achieving the above object, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of new schiff bases amine antioxidants, and it includes with lower formula (I) or (II) institute Show the compound of structure：
R in formula1, R2, R3, R4, R5, R6, R7, R8, R9, R10It is at least selected from the alkyl of the linear chain or branch chain of H, C1~C20 or contains Benzene ring substitution group or alkyl or aryl containing O, S, N, P and/or Si, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10Represent phase With group or different groups, X at least selected from-S- ,-O- ,-NH- orWherein m is 0 or 1.
Further, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10Any one of or both shown in the lower formula (III) Structure：
R in formula11, R12At least selected from H, C1~C20 linear chain or branch chain alkyl containing benzene ring substitution group or containing O, S, N, the alkyl or aryl of P and/or Si, R11、R12Represent identical group or different groups.
Further, R11、R12Either or both be selected from structure shown in lower formula (IV) or formula (V)：
R in formula13, R14, R15, R16At least the alkyl of the linear chain or branch chain selected from H, C1~C20 or containing benzene ring substitution group or contain There are the alkyl or aryl of O, S, N, P and/or Si, R13、R14、R15、R16Represent identical group or different groups, n or m choosings From any integer in 1-40.
The embodiment of the present invention additionally provides a kind of method for preparing the schiff base type amine antioxidants, including：Make aldehyde and/ Or ketone in liquid-phase reaction system and has with diphenylamines and/or diphenylamine derivatives and/or phenothiazine and/or phenothiazine derivative It is reacted under the conditions of catalyst is existing, obtains the schiff bases amine antioxidants.
The embodiment of the present invention additionally provides the purposes of the new schiff bases amine antioxidants, such as is easily being dropped by oxidation The purposes in the organic material field of solution.
For example, the purposes includes：At least using the schiff bases amine antioxidants as antioxidant in lubricating oil, combustion It is applied in oil, plastics or rubber.
Further, the purposes includes：By the schiff bases amine antioxidants single dose either with other additives Compounding is added in easily by the organic host materials of oxidative degradation, improves the inoxidizability of substance.
Compared with prior art, the present invention at least has the following advantages that：
(1) present invention is introduced into a molecule simultaneously by the way that schiff bases and diphenylamines and/or its derivative are acted on group Form new Schiff alkalamides (compound) antioxidant, which has superior heat-stability and good In addition antioxygenic property introduces sulphur in some molecules, it is enable to have anti-extreme pressure concurrently.
(2) in the preparation method of schiff bases amine antioxidants provided by the invention, substituted using aldehyde compound and amino Diphenylamines and/or its derivative can obtain product, operating process is simply easy in the presence of a catalyst as reaction raw materials Row, the reaction time is shorter, and reaction temperature is moderate, and post processing is easy.
(3) schiff bases amine antioxidants provided by the invention are suitable for easily being dropped by oxidation in the case of usual air or oxygen In the organic host materials of solution, in such application, the schiff bases amine antioxidants of antioxidant amounting can for example be lubricated with matrix Oil, liquid fuel, thermoplastic polymer, resin or oligomer or natural or synthetic plastics or rubber or elastomer are mixed.
(4) schiff bases amine antioxidants provided by the invention are suitable for being used in combination with other types of additive and add in extremely Easily in the organic host materials of oxidative degradation, having been given play in the case of usual air or oxygen more excellent includes antioxidant Various performances inside.
More detailed explanation will hereafter be made to technical scheme.It is understood, however, that in model of the present invention It, can between above-mentioned each technical characteristic of the invention and each technical characteristic specifically described in below (eg embodiment) in enclosing It is combined with each other, so as to form new or preferred technical solution.As space is limited, not repeated them here.
Description of the drawings
Fig. 1 is a kind of schiff bases amine antioxidants in the embodiment of the present invention 11H NMR spectras (DMSO-d6, 400MHz)；
Fig. 2 is a kind of schiff bases amine antioxidants in the embodiment of the present invention 113C NMR spectras (DMSO-d6, 100MHz)；
Fig. 3 is a kind of schiff bases amine antioxidants in the embodiment of the present invention 21H NMR spectras (CDCl3, 400MHz)；
Fig. 4 is a kind of schiff bases amine antioxidants in the embodiment of the present invention 213C NMR spectras (CDCl3, 100MHz)；
Fig. 5 is a kind of schiff bases amine antioxidants in the embodiment of the present invention 51H NMR spectras (CDCl3, 400MHz)；
Fig. 6 is a kind of schiff bases amine antioxidants in the embodiment of the present invention 513C NMR spectras (CDCl3, 100MHz).
Fig. 7 is a kind of schiff bases amine antioxidants in the embodiment of the present invention 61H NMR spectras (DMSO-d6, 400MHz)；
Fig. 8 is a kind of schiff bases amine antioxidants in the embodiment of the present invention 613C NMR spectras (DMSO-d6, 100MHz)；
Fig. 9 is schiff bases amine antioxidants of the present invention and phenols (BHT), the TGA comparison diagrams of amine antioxidants (DPA).
Specific embodiment
As previously mentioned, inventor is able to propose skill of the invention by in-depth study and a large amount of practices for a long time Art scheme, it is as detailed below.
A kind of schiff bases amine antioxidants that the one side of the embodiment of the present invention provides, which include, has lower formula (I) or (II) The compound of shown structure：
R in formula1, R2, R3, R4, R5, R6, R7, R8, R9, R10It is at least selected from the alkyl of the linear chain or branch chain of H, C1~C20 or contains Benzene ring substitution group or alkyl or aryl containing O, S, N, P and/or Si, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10Represent phase Same group or different groups, X are at least selected from-S- ,-O- ,-NH-,Wherein m is 0 or 1.
Wherein, the schiff base type amine antioxidants refer to there is schiff bases and diphenylamines in same antioxygen agent molecule The complex type antioxidant of double-unit, therefore claim schiff base type amine antioxidants.
Preferably, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10Any one of or both be selected from structure shown in lower formula (III)：
R in formula11, R12At least selected from H, C1~C20 linear chain or branch chain alkyl containing benzene ring substitution group or containing O, S, N, the alkyl or aryl of P and/or Si.
Further, R11, R12Represent identical group or different groups.
It is further preferred that R11Or R12Either or both be selected from structure shown in lower formula (IV) or formula (V)：
R in formula13, R14, R15, R16At least the alkyl of the linear chain or branch chain selected from H, C1~C20 or containing benzene ring substitution group or contain There are the alkyl or aryl of O, S, N, P and/or Si.R13, R14, R15, R16Represent identical group or different groups.N or m Any integer in 1-40.
Further, some non-limiting embodiments of the schiff base type amine antioxidants represented by structure above Reference can be made to following any structure formula：
Some preferred embodiments of the present invention are combined using diphenylamines and/or its derivative as substrate and by it with schiff bases, A series of new schiff base type amine antioxidants are developed, thermal stability is good, and volatility is low, can be used as antioxidant in high temperature Lower use.Such schiff base type amine antioxidants single dose shows extraordinary inoxidizability in lubricating oil simultaneously, surmounts The antioxygenic property of diphenylamines, and can also reach extraordinary antioxygenic property when with other additive compounds, it can conduct It is the antioxidant for lubricant oil of a kind of high-temperature efficient energy-saving environment-friendly type.
A kind of method for preparing the schiff bases amine antioxidants that the other side of the embodiment of the present invention provides includes： Make aldehyde and/or ketone with diphenylamines and/or diphenylamine derivatives and/or phenothiazine and/or phenothiazine derivative in liquid phase reactor body It is reacted in system and under the conditions of having existing for catalyst, obtains the schiff bases amine antioxidants.
In some more preferred embodiment, the preparation method includes：Take aldehydes or ketones, diphenylamines and/or two Anil and/or phenothiazine and/or phenothiazine derivative react in the presence of having catalyst in liquid phase reaction medium, obtain Obtain the schiff bases amine antioxidants.
For example, in one more specific embodiment, the preparation method can include：Reactant A and reactant B are being urged Agent C is reacted there are formula, in optional liquid phase reaction medium D, is suitable for so as to be formed, is especially suited as antioxidant Reaction product, i.e., foregoing schiff bases amine antioxidants.
It is, for example, possible to use component forms the product of the present invention as reactant below：
Reactant A：Aldehydes or ketones include alkyl aldehydes or ketones and/or fragrant aldehydes or ketones；Preferably, the reactant A is selected from Aldehyde non-exclusively can include formaldehyde, acetaldehyde, positive propionic aldehyde, n-butanal isobutylaldehyde etc. selected from all kinds of alkyl aldehydes, and without being limited thereto； Or aromatic aldehyde includes benzaldehyde, 1- naphthaldehydes, 9- formaldehydes, p-tolyl aldehyde etc., and it is without being limited thereto；Or phenolic aldehyde includes 2- hydroxyls Benzaldehyde, 3- hydroxy benzaldehydes, 4- hydroxy benzaldehydes etc., it is more preferred to big steric hindrance phenolic aldehyde, 3,5- di-t-butyl -2- hydroxyls Benzaldehyde, 3,5- dimethyl-Benzaldehyde,2-hydroxy, 3,5- ditertbutyl-4-hydroxy Benzaldehydes, 3,5- dimethyl -4- hydroxyls Benzaldehyde etc., and it is without being limited thereto；Or sulfydryl substitution phenolic aldehyde includes 2- hydroxyls -3- ((normal-butyl sulfydryl) methyl) benzaldehyde, 2- hydroxyls Base -5- ((n-octyl sulfydryl) methyl) benzaldehyde etc., it is more preferred to big steric hindrance sulfydryl substitution phenolic aldehyde, 3- tertiary butyls -5- ((n-octyl sulfydryl) methyl)-Benzaldehyde,2-hydroxy, 3- tertiary butyls -5- ((phenethyl sulfydryl) methyl)-Benzaldehyde,2-hydroxy, 3- ((n-octyl sulfydryl) methyl) -5- tertiary butyls-Benzaldehyde,2-hydroxy, 3- ((phenethyl sulfydryl) methyl) -5- tertiary butyl -2- hydroxyls Benzaldehyde etc., and it is without being limited thereto.
Reactant B：The diphenylamines and/or diphenylamine derivatives and/or phenothiazine and/or phenothiazine of amino substitution derive Object, can be unrestricted including 2- amino-diphenylamines, 2- amino -4- methyl-diphenylamines, 2, and 2 '-diamino-diphenylamine, 2- amino - 4 '-methyl-diphenylamine, 3- amino-diphenylamines, 4- amino-diphenylamines, 4,4 '-diamino-diphenylamine, 2- amino phenthazine, 3- Amino phenthazine, 4- amino phenthazine, 5- amino phenthazine etc., it is more preferred to 2- amino-diphenylamines, 2,2 '-diamino Diphenylamines, 4- amino-diphenylamines, 4,4 '-diamino-diphenylamine.
Catalyst C：In some embodiments, preferably from acidic catalyst, non-limiting example includes Bronsted acid for example Sulfuric acid, hydrochloric acid, nitric acid, trifluoromethanesulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, formic acid, acetic acid etc.；Or lewis acid includes trifluoro Change borate ether, alchlor, ferric trichloride, zinc dichloride etc., and it is without being limited thereto.
It is further preferred that the dosage of the catalyst is：Reactant A:The molar ratio of catalyst C is preferably 1:0.01- 1:5, especially preferably 1:0.1-1:3,
Liquid phase reaction medium D：The liquid phase reaction medium is inert organic solvents, and the organic solvent that can be used is unrestricted Example includes for example one or more isomeric hexane bodies, one or more heptane isomers, one or more octane isomers, one Kind or a variety of decane, the mixture of one or more for example above-mentioned alkanes solvents；Hexamethylene, hexahydrotoluene；Dichloromethane, bromine Chloromethanes, 1,2- dichloroethanes, glycol dibromide, chloroform, chlorobenzene；A kind of and a variety of aromatic compounds such as benzene, toluene, neighbour Dimethylbenzene, meta-xylene, one or more chlorinations and/or bromination solvent mixture as escribed above；A kind of alkanol such as methanol, Ethyl alcohol, isopropanol, normal propyl alcohol, n-butanol, sec-butyl alcohol, isobutanol, 2-Ethylhexyl Alcohol, octanol and other liquid or eutectic homotype Isomery alkanol or its mixture；One or more ethers such as dialkyl ethers, tetrahydrofuran, dioxane or its mixture, two Methylformamide, dimethyl sulfoxide (DMSO) etc., and it is not limited to this.
It is further preferred that the molar ratio of the reactant A and reactant B can be 1:0.1-1:10, especially preferably 1:0.5-1:5。
In some embodiments, the reaction temperature that the preparation method uses is 0 DEG C -200 DEG C, and further preferably 50 ℃-150℃。
In some embodiments, the reaction time that the preparation method uses is more preferably 1h- for 0.5h-10h 5h。
Some post-processing operations are also needed after reaction described, these postprocessing working procedures may be employed known to industry Mode is implemented.
The purposes of the schiff bases amine antioxidants is additionally provided in some embodiments, for example, it is anti-as what is had excellent performance Oxygen agent product lubricating oil, fuel oil, plastics or rubber when there are when air or oxygen easily by the organic material field of oxidative degradation Application.
Wherein, not only there is hindered phenol anti-oxidants and alkylation for schiff bases amine antioxidants described in one type The excellent properties of diphenylamine antioxidant, and sulphur is introduced in some molecules, make it have anti-extreme pressure energy.
Correspondingly, when as lubricating oil, fuel oil when additive in compositions, one or more Schiffs of the invention Alkalamides antioxidant can with part of dilution or be dissolved in base oil or process oil or can with other be commonly used in various profits The component mixing of lubrication prescription.The example for the base oil that can be used includes I, II and Group III mineral oil, poly alpha olefin, synthetic ester, gas Body is to the oil and biological base oil of liquid source.In addition, usually by one or more reaction products of the present invention and diluent, solvent or Carrier fluid or/and one or more other are suitble to additives combination, can be formed to I. C. engine oil, railway and marine lubricants, Natural gas engine machine oil, steam turbine oil, gas turbine oil, aviation turbine oil, corrosion and oxygenated oil, hydraulic oil, compressor liquid, Oily, manually and automatically transmission fluid, gear oil, lubricating grease etc. compositions of additives is quenched in rail oil.
In some embodiments, finished lube contains the schiff bases amine antioxidants of antioxygen dosage, it is preferred that institute It is 0.01-10wt% that schiff bases amine antioxidants, which are stated, as the addition concentration range of antioxidant, and further preferably scope is 0.01-5wt%.
The schiff bases amine antioxidants of the present invention can be used as the commercially available antioxidant used at present in lubricating oil preparation All or part of substitute.Particularly, schiff bases amine antioxidants of the invention can be with typically finding in lubricating oil Other additives are used in combination, and this combination actually can provide synergistic effect to lubricating oil, to improve required performance, such as Improve the performances such as the controlling, is wear-resisting of deposit, friction, anti-oxidant.The agent that is typically added used in lubricating oil and fuel is Dispersant, detersive, antirust agent, antioxidant, anti-wear agent, antifoaming agent, frictional index modifier, demulsifier, viscosity index (VI) are improved Agent and pour point depressor, such as the description as described in additive composition for lubricant oil in United States Patent (USP) US 5498809A, the disclosure of which Full text is described herein by reference reference.
In some embodiments, the dispersant that can be used in combination with the schiff bases amine antioxidants of the present invention wraps without limitation Include polyisobutenyl succinimide, polyisobutylene succinic acid ester, Mannich Base ashless dispersants and/or its analog, metal and Ashless alkyl phenate, metal and ashless alkylsulfonate, metal and ashless alkyl monosulfide phenates, metal and ashless water Benzasalicin derivative and/or its analog.
In some embodiments, schiff bases amine antioxidants of the invention are except can be in lubricating oil, fuel oil, plastics or rubber It is outer as antioxidant exclusive use in glue, but also can be with the antioxidant compounding use of different structure.It can be uncommon with the present invention Husband's alkalamides antioxidant be used in combination antioxidant without limitation include alkylated diphenylamine, N- alkylated diphenylamines, phenyl-α- Naphthylamines, alkylation phenyl-α-naphthylamine, hindered phenol, dimethyl quinoline, trimethyldihydroquinoline and its derivative, alkvlated hvdroquinones, Alkylidene bisphenols, Hydroxylated thiodiphenyl ethers, thiopropionate, metal dithiocarbamate, 1,3,4- dimercaptos thiophene two Azoles and its derivative, oil-soluble copper compounds and the like.
In some embodiments, the anti-wear additive that can be used in combination with the schiff bases amine antioxidants of the present invention is unrestricted Ground includes organic boric acid ester, organophosphorus ester, organic phosphite, sulfur-containing organic compound, olefine sulfide, sulfide aliphatic acid and spreads out Biology, chlorinated paraffin, zinc dialkyl dithiophosphate, zinc diaryl dithiophosphates, phosphoric acid vulcanization hydrocarbon and/or its is similar Object.
In some embodiments, the antifoaming agent that can be used in combination with the schiff bases amine antioxidants of the present invention wraps without limitation Include poly- alcoxyl alkane and its analog.
In some embodiments, the antirust agent that can be used in combination with the schiff bases amine antioxidants of the present invention wraps without limitation Include polyoxyalkylene polyol, benzotriazole analog derivative and its analog.
In some embodiments, the pour point depressor that can be used in combination with the schiff bases amine antioxidants of the present invention is non-limiting Including poly- subunit acrylate and its analog.
To make the present invention it is more readily appreciated that being done further to technical scheme below in conjunction with several embodiments Illustrate explanation, it is noted that these embodiments are only to the exemplary illustrated of the present invention, wherein used various reactions It is more typical example to participate in object and process conditions, but by the verification of inventor's a large number of experiments, it is listed in above Other types of reaction partner and other process conditions be also applicable, and also equal attainable cost invents claimed skill Art effect.
Benzaldehyde 5g-7.5g, 4-ADPA 12g-15g and sulfuric acid 0.1g-1g are dissolved in about 100mL tetra- by embodiment 1 It in hydrogen furans, is added in the heavy wall glass bomb with magneton, is reacted under conditions of reaction temperature is 50 DEG C -110 DEG C 3h-8h after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target Product,1H NMR spectras,13C NMR spectras can refer to Fig. 1-Fig. 2 respectively.1H NMR(400MHz,DMSO-d6)δ6.85(t,J =6.8Hz, 1H), 7.11-7.15 (m, 4H), 7.24-7.30 (m, 4H), 7.49 (s, 3H), 7.92 (s, 2H), 8.33 (s, 1H), 8.66(s,1H).13C NMR(100MHz,DMSO-d6)δ116.87,117.04,119.83,122.41,128.25,128.73, 129.21,130.80,136.51,142.21,142.95,143.23,156.79.IR(film):745,824,1315,1450, 1508,1588,1623,3413. the present embodiment product yields are average more than 70%, and preferred product yield is more than 95%, production Product purity is more than 98%.
P-tolyl aldehyde 6g-9g, 4-ADPA 14g-17g and hydrochloric acid 0.1g-2g are dissolved in about by embodiment 2 It in 100mL chloroforms, is added in the heavy wall glass bomb with magneton, in the condition that reaction temperature is 60 DEG C -100 DEG C Lower reaction 6h-10h after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain To target product,1H NMR spectras,13C NMR spectras can refer to Fig. 3-Fig. 4 respectively.1H NMR(400MHz,CDCl3)δ2.38 (s, 3H), 5.76 (s, 1H), 6.89-6.93 (m, 1H), 7.05 (d, J=8Hz, 4H), 7.18-7.27 (m, 6H), 7.77 (d, J =7.6Hz, 2H), 8.44 (s, 1H)13C NMR(100MHz,CDCl3)δ21.54,117.54,118.48,120.83, 122.14,128.52,129.30,129.42,133.87,141.33,143.13,145.18,157.89.IR(film):686, 738,826,1333,1348,1498,1530,1587,1603,1623,2920,3034,339 8. the present embodiment product yields are put down More than 50%, preferred product yield is more than 75%, and product purity is more than 98%.
Embodiment 3 is by p-t-Butylbenzaldehyde 1g-1.5g, 2- aminodiphenylamine 3g-4g and p-methyl benzenesulfonic acid 0.5g-3g It is dissolved in about 20mL dichloromethane, is added in the heavy wall glass bomb with magneton, be 30 DEG C -60 DEG C in reaction temperature Under the conditions of react 5h-10h, after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization is It can obtain target product.The present embodiment product yield is average more than 60%, and preferably greater than 80%, product purity is more than 98%.
Embodiment 4 is by 4-methoxybenzaldehyde 7.8g-10g, 4- amino-2-methyl diphenylamines 10g-15g and fluoroform sulphur Sour 0.5g-1g is dissolved in about 20mL methanol, is added in the heavy wall glass bomb with magneton, reaction temperature for 60 DEG C- 5-10h is reacted under conditions of 80 DEG C, after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, again Crystallization can obtain target product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 80%, production Product purity is more than 98%.
Benzaldehyde 7.8g-10g, 4,4 '-diamino-diphenylamine 10g-15g and formic acid 3g-6g are dissolved in about by embodiment 5 In 100mL methanol, it is added in the heavy wall glass bomb with magneton, it is anti-under conditions of reaction temperature is 60 DEG C -80 DEG C 5h-9h is answered, after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain mesh Product is marked,1H NMR spectras,13C NMR spectras can refer to Fig. 5-Fig. 6 respectively.1H NMR(400MHz,CDCl3)δ5.84(s, 1H),7.10-7.13(m,4H),7.24-7.26(m,4H),7.46-7.47(m,6H),7.89-7.91(m,4H),8.52(s, 1H).13C NMR(100MHz,CDCl3)δ118.35,122.30,128.57,128.72,130.99,136.46,141.58, 145.02,157.93.IR(film):689,719,753,835,1102,1188,1319,1515,1624,2850,2920, 3351,3414. the present embodiment product yields are average more than 60%, and preferably greater than 90%, product purity is more than 98%.
Embodiment 6 is by 3,5- di-t-butyls-Benzaldehyde,2-hydroxy 9.4g-12g, 4-ADPA 9g-14g and sulfuric acid 3g-6g is dissolved in about 80mL chloroforms, is added in the heavy wall glass bomb with magneton, reaction temperature for 60 DEG C- 5h-9h is reacted under conditions of 80 DEG C, after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, again Crystallization can obtain target product,1H NMR spectras,13C NMR spectras can refer to Fig. 7-Fig. 8 respectively.1H NMR(400MHz, DMSO-d6)δ1.30(s,9H),1.42(s,9H),6.85-6.89(m,1H),7.11-7.15(m,4H),7.25-7.29(m, 2H), 7.35 (d, J=2.4Hz, 1H), 7.38-7.40 (m, 2H), 7.45 (d, J=2.4Hz, 1H), 8.39 (s, 1H), 8.95 (s,1H),14.21(s,1H).13C NMR(100MHz,DMSO-d6)δ29.27,31.28,33.88,34.58,116.75, 117.29,118.53,120.17,122.39,126.48,127.00,129.23,135.61,139.10,139.94,142.86, 157.28,160.92,161.00.IR(film):690,716,746,773,804,833,864,874,1169,1195,1242, 1273,1323,1360,1434,1473,1490,1517,1600,1615,2157,2960,3 406. the present embodiment product yields Averagely more than 80%, preferred product yield is more than 90%, and product purity is more than 98%.
Embodiment 7 by 3,5- dimethyl -4- hydroxy benzaldehydes 8.2g-10.5g, 4,4 '-diamino-diphenylamine 9g-14g and Hydrochloric acid 2g-4g is dissolved in about 80mL methanol, is added in the heavy wall glass bomb with magneton, reaction temperature for 60 DEG C- 4h-7h is reacted under conditions of 80 DEG C, after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, again Crystallization can obtain target product.The present embodiment product yield is average more than 60%, and preferably greater than 80%, product purity is big In 98%.
Embodiment 8 is by 3- tertiary butyls -5- ((n-octyl sulfydryl) methyl)-Benzaldehyde,2-hydroxy 12g-14.8g, 2- amino two Aniline 10g-13.8g and acetic acid 2g-4g is dissolved in about 80mL methanol, is added in the heavy wall glass bomb with magneton, Reaction temperature be 60 DEG C -80 DEG C under conditions of react 4h-7h, after reaction, by reaction mixture be cooled to room temperature using Solvent is removed under reduced pressure, recrystallization can obtain target product.The present embodiment product yield is average more than 60%, preferred to produce Product yield is more than 80%, and product purity is more than 98%.
Embodiment 9 is by 3- ((phenethyl sulfydryl) methyl) -5- tertiary butyls-Benzaldehyde,2-hydroxy 11g-15.5g, 4- amino two Aniline 7g-9g and alchlor 1g-3g is dissolved in about 80mL ethyl alcohol, is added in the heavy wall glass bomb with magneton, Reaction temperature be 60 DEG C -80 DEG C under conditions of react 3h-5h, after reaction, by reaction mixture be cooled to room temperature using Solvent is removed under reduced pressure, recrystallization can obtain target product.The present embodiment product yield is average more than 70%, preferred to produce Product yield is more than 90%, and product purity is more than 98%.
10 2- chlorine of embodiment is by phenylacetaldehyde 7g-14g, 4- amino -3 '-ethyoxyl-diphenylamines 9g-12g and ferric trichloride 1g-3g is dissolved in about 50mL ethyl alcohol, is added in the heavy wall glass bomb with magneton, is 80 DEG C -100 DEG C in reaction temperature Under conditions of react 4h-5h, after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, is recrystallized It can obtain target product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 80%, product Purity is more than 98%.
Embodiment 11 is by 3- ((phenethyl sulfydryl) methyl) -5- tertiary butyl -2- hydroxy acetophenone 11g-14g, 3- amino fens Thiazine 9g-12g and hydrochloric acid 0.5g-1g is dissolved in about 50mL tetrahydrofurans, is added in the heavy wall glass bomb with magneton, 1h-2h is reacted under conditions of reaction temperature is 60 DEG C -80 DEG C, after reaction, reaction mixture is cooled to room temperature and is passed through again It crosses and solvent is removed under reduced pressure, recrystallization can obtain target product.The present embodiment product yield is average more than 80%, preferably Product yield is more than 90%, and product purity is more than 98%.
Butyl ketone 5g-6g, 4-ADPA 9g-15g and acetic acid 0.5g-1g are dissolved in about 50mL dichloromethanes by embodiment 12 It in alkane, is added in the heavy wall glass bomb with magneton, reacts 1h-2h under conditions of reaction temperature is 40 DEG C -60 DEG C, After reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target product.. The present embodiment product yield is average more than 50%, and preferred product yield is more than 70%, and product purity is more than 95%.
Benzophenone 10-15g, 4-ADPA 9-15g and stannous chloride 1-2g are dissolved in about 50mL tri- by embodiment 13 It in chloromethanes, is added in the heavy wall glass bomb with magneton, is reacted under conditions of reaction temperature is 60 DEG C -80 DEG C 2h-3h after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target Product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 70%, and product purity is more than 95%.
1- naphthaldehydes 5g-8g, 2- aminodiphenylamine 9g-15g and ferric trichloride 1g-2g are dissolved in about 50mL tetra- by embodiment 14 It in hydrogen furans, is added in the heavy wall glass bomb with magneton, is reacted under conditions of reaction temperature is 50 DEG C -70 DEG C 2h-3h after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target Product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 80%, and product purity is more than 95%.
N-butanal 10g-16g, 4-ADPA 5g-8g and alchlor 1g-2g are dissolved in about 50mL tetra- by embodiment 15 It in hydrogen furans, is added in the heavy wall glass bomb with magneton, is reacted under conditions of reaction temperature is 150 DEG C -170 DEG C 1h-3h after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target Product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 80%, and product purity is more than 95%.
Isobutylaldehyde 10g-16g, 4-ADPA 5g-8g and alchlor 1g-2g are dissolved in about 50mL tetra- by embodiment 16 It in hydrogen furans, is added in the heavy wall glass bomb with magneton, is reacted under conditions of reaction temperature is 150 DEG C -170 DEG C 1h-3h after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target Product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 70%, and product purity is more than 90%.
Benzaldehyde 5g-8g, 4- amino -3 '-methoxyl group phenthazine 6g-10g and stannous chloride 1g-2g are dissolved in by embodiment 17 In about 50mL tetrahydrofurans, it is added in the heavy wall glass bomb with magneton, it is anti-under conditions of reaction temperature is 200 DEG C 1h-3h is answered, after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain mesh Mark product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 70%, and product purity is more than 95%.
2- butanone 7g-9g, 4- amino phenthazine 6g-10g and stannous chloride 1g-2g are dissolved in about 50mL tetrahydrochysenes by embodiment 18 It in furans, is added in the heavy wall glass bomb with magneton, reacts 1h-3h under conditions of reaction temperature is 200 DEG C, instead After answering, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target product.Originally Embodiment product yield is average more than 60%, and preferred product yield is more than 70%, and product purity is more than 95%.
1- acetonaphthone 7g-9g, 2- amino phenthazine 6g-10g and stannous chloride 1g-2g are dissolved in about 50mL tetra- by embodiment 18 It in hydrogen furans, is added in the heavy wall glass bomb with magneton, reacts 1h-3h under conditions of reaction temperature is 150 DEG C, After reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target product.. The present embodiment product yield is average more than 60%, and preferred product yield is more than 70%, and product purity is more than 95%.
Acetophenone 4g-6g, 4,4 '-diaminophenothiazine 6g-10g and alchlor 1g-2g are dissolved in about 50 by embodiment 19 It in mL tetrahydrofurans, is added in the heavy wall glass bomb with magneton, is reacted under conditions of reaction temperature is 0 DEG C 0.5h-3h after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain mesh Mark product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 80%, and product purity is more than 95%.
N-octaldehyde 3g-5g, 4,4 '-diaminophenothiazine 6g-10g and stannous chloride 1g-2g are dissolved in about 50 by embodiment 20 It in mL tetrahydrofurans, is added in the heavy wall glass bomb with magneton, is reacted under conditions of reaction temperature is 150 DEG C 1h-3h after reaction, reaction mixture is cooled to room temperature using solvent is removed under reduced pressure, recrystallization can obtain target Product.The present embodiment product yield is average more than 60%, and preferred product yield is more than 70%, and product purity is more than 95%.
The application performance that schiff bases amine antioxidants product is obtained to previous embodiment is tested as follows, including：
Thermal stability analysis
While antioxidant plays antioxidant effect in lubricating oil, hot environment, high warm are inevitably touched Stability is the important indicator of anti-oxidant performance.It, will be in hot environment if antioxidant does not possess good thermal stability Volatilization is even decomposed, and reduces its effective content in lubricating oil, this inevitably results in the decline of antioxygen efficiency.
Thermal weight loss temperature (TG) is the index for evaluating thermal stability under antioxidant high temperature, and the height of thermal weight loss temperature is straight Connect the use environment for being related to antioxidant.In the present invention using TA companies of the U.S. Q500 types thermogravimetric analyzer to antioxidant BHT, 1 product of diphenylamines (DPA) and embodiment, the thermal stability of 6 product of 2 product of embodiment, 5 product of embodiment and embodiment are surveyed Examination.Experiment condition is：Heating temperature range is to be raised to 600 DEG C, 10 DEG C/min of heating rate from room temperature, and test gas is N2Gas Atmosphere, N2Flow velocity is 100 mL/min.The result is shown in Fig. 9 and tables 1.From the results, it was seen that the schiff bases amine antioxidants of the present invention Thermal stability than traditional BHT and diphenylamine antioxidant is greatly improved, and can meet to oil product operating environment requirements Higher aeroengine oil, the demand of top-grade lubricating oil belong to that molecular weight is big, the good novel antioxidant of thermostabilization.
The thermal weight loss temperature comparisons of 1 antioxidant of table
Temperature BHT DPA Embodiment 1 Embodiment 2 Embodiment 5 Embodiment 6
T0.5%/℃ 69.97 78.45 181.62 193.12 259.43 215.95
T1%/℃ 74.13 85.03 192.04 203.19 269.34 225.12
T5%/℃ 87.75 107.73 219.54 230.36 299.59 252.30
T10%/℃ 96.67 118.65 233.38 244.03 314.93 266.46
T50%/℃ 125.45 152.48 277.27 282.19 364.76 307.61
T90%/℃ 140.91 167.71 295.51 304.36 392.31 332.93
T99.5%/℃ 145.91 172.24 300.06 340.89 - 373.48
Antioxidation Behavior
Antioxygen property is the evaluation most important index of antioxidant, directly affects the service life of lubricating oil.Pressurization differential is swept The oxidation induction period that calorimetry (PDSC) measures is retouched, can be used for characterizing oil ageing stability.The present invention uses The HPDSC827C test equipments of METTLER companies.Using testing standard：SH/T 0719-2002, using test pressure 3.5MPa, 180 DEG C of test temperature.Example weight：3.0 ± 0.2mg uses the oxygen of purity >=99.5%, oxygen flow： 100ml/min.Base oil selects synthetic oil PAO.Antioxidant is added in the ratio of 5 μm of ol/g base oils.To embodiment 1, implement Example 2, the antioxygenic property of 9 product of embodiment 5, embodiment 6 and embodiment are tested.Test result is shown in Table 2.
2 schiff bases amine antioxidants of table and phenolic antioxidant, the antioxygenic property comparison of amine antioxidants
Test sample Oxidation induction period (OIT/min)
PAO 2.8
BHT 14.3
DPA 13.9
Embodiment 1 23.6
Embodiment 2 29.1
Embodiment 5 34.8
Embodiment 6 26.5
Embodiment 9 50.4
The oxidation induction period of oil product is measured using PDSC, induction period is longer, and antioxygen property is better.From Table 2, it can be seen that The schiff bases amine antioxidants of the present invention have excellent high-temperature oxidation resistance.Likewise, using similar approach to remaining reality It applies example and other schiff bases amine amine antioxidants contained by the present invention is tested, can also find that it has good behaviour so that Oil ageing induction period improves about 7-17 times.According to the literature, the addition of 3000ppm schiff bases phenolic antioxidants is added in The inoxidizability of lubricating oil is only made to improve about 17%, it can be seen that the inoxidizability of schiff bases amine antioxidants of the invention is remote It is much better than schiff bases phenolic antioxidant.
Compound Antioxidation Behavior 1
The present invention uses the HPDSC827C test equipments of METTLER companies.Using testing standard：SH/T 0719-2002, Using test pressure 3.5MPa, 180 DEG C of test temperature.Example weight：3.0 ± 0.2mg, using the oxygen of purity >=99.5%, Oxygen flow：100ml/min.Base oil selects synthetic oil PAO.Antioxidant is added in the ratio of 5 μm of ol/g base oils.To implementing Antioxygenic property after example 1 is compounded with other antioxidant is tested.Test result is shown in Table 3.
Antioxygenic property after 3 embodiment 1 of table and other additive compounds
Test sample Oxidation induction period (OIT/min)
PAO 2.8
BHT 14.3
N-octyl thioether 2.8
Benzyl sulfide 3.4
Phenol thioether 10.2
Embodiment 1 23.6
Embodiment 1+BHT 32
Embodiment 1+ n-octyl thioethers 71.1
Embodiment 1+ benzyl sulfides 34.7
Embodiment 1+ phenol thioethers 48.7
From table 3 it is observed that the schiff bases amine antioxidants of the present invention are excellent with having after other antioxidant compounding High-temperature oxidation resistance.Likewise, using similar approach to other schiff bases amine amines contained by remaining embodiment and the present invention Antioxidant is tested, and can also find that it has good behaviour.
Compound Antioxidation Behavior 2
The present invention uses the HPDSC827C test equipments of METTLER companies.Using testing standard：SH/T 0719-2002, Using test pressure 3.5MPa, test temperature is as shown in table 3.Example weight：3.0 ± 0.2mg uses the oxygen of purity >=99.5% Gas, oxygen flow：100ml/min.Base oil selects synthetic oil PAO.Antioxidant is added in the ratio of 5 μm of ol/g base oils.It is right Antioxygenic property after embodiment 6 is compounded with other additive compounds is tested.Test result is shown in Table 4.
Antioxygenic property after 4 embodiment 6 of table and other additive compounds
As can be seen from Table 4, schiff bases amine antioxidants of the invention after other different performance additive compounds with having There is excellent high-temperature oxidation resistance.Likewise, using similar approach to other Schiffs contained by remaining embodiment and the present invention Alkali amine amine antioxidants are tested, and can also find that it has good behaviour.
Technical scheme is described in detail in embodiment described above, it should be understood that the above is only For specific embodiments of the present invention, it is not intended to limit the invention, all any modifications made in the spirit of the present invention, Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of new schiff bases amine antioxidants, it is characterised in that include the chemical combination with structure shown in lower formula (I) or (II) Object：
R in formula1, R2, R3, R4, R5, R6, R7, R8, R9, R10At least it is selected from the alkyl of the linear chain or branch chain of H, C1~C20 or containing phenyl ring Substituent group or alkyl or aryl containing O, S, N, P and/or Si, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10Represent identical Group or different groups, X at least selected from-S- ,-O- ,-NH- orWherein m is 0 or 1.
2. new schiff bases amine antioxidants according to claim 1, it is characterised in that：R1, R2, R3, R4, R5, R6, R7, R8, R9, R10Any one of or both be selected from structure shown in lower formula (III)：
R in formula11, R12At least the alkyl of the linear chain or branch chain selected from H, C1~C20 or containing benzene ring substitution group or contain O, S, N, P And/or the alkyl or aryl of Si, R11、R12Represent identical group or different groups.
3. new schiff bases amine antioxidants according to claim 2, it is characterised in that：R11、R12Either or both Selected from structure shown in lower formula (IV) or formula (V)：
R in formula13, R14, R15, R16At least selected from H, C1~C20 linear chain or branch chain alkyl containing benzene ring substitution group or containing O, S, the alkyl or aryl of N, P and/or Si, R13、R14、R15、R16Represent identical group or different groups, n or m are selected from 1- Any integer in 40.
4. new schiff bases amine antioxidants according to claim 1, which is characterized in that the Schiff alkalamides antioxygen Agent has following any structural formula：
5. the preparation method of a kind of new schiff bases amine antioxidants, it is characterised in that including：Make aldehyde and/or ketone and diphenylamines And/or diphenylamine derivatives and/or phenothiazine and/or phenothiazine derivative in liquid-phase reaction system and have existing for catalyst Under the conditions of reacted, obtain the schiff bases amine antioxidants.
6. preparation method according to claim 5, it is characterised in that including：Aldehydes or ketones, diphenylamines and/or diphenylamines is taken to spread out Biology and/or phenothiazine and/or phenothiazine derivative react in the presence of having catalyst in liquid phase reaction medium, described in acquisition Schiff bases amine antioxidants.
7. according to the preparation method any one of claim 5-6, it is characterised in that：
The aldehyde and/or ketone include alkyl aldehydes and/or alkyl ketone and/or aromatic aldehyde and/or aromatic ketone；Preferably, the alkyl Aldehyde includes any one of formaldehyde, acetaldehyde, positive propionic aldehyde, n-butanal, isobutylaldehyde or two or more combinations；Preferably, the virtue Fragrant aldehyde includes any one of benzaldehyde, 1- naphthaldehydes, 9- formaldehydes, p-tolyl aldehyde or two or more combinations；It is preferred that , the aldehyde includes phenolic aldehyde；It is further preferred that the phenolic aldehyde includes Benzaldehyde,2-hydroxy, 3- hydroxy benzaldehydes, 4- hydroxy benzenes Any one of formaldehyde or two or more combinations；Still more preferably, the phenolic aldehyde is big steric hindrance phenolic aldehyde；It is further excellent Choosing, the big steric hindrance phenolic aldehyde includes 3,5- di-t-butyls-Benzaldehyde,2-hydroxy, 3,5- dimethyl-Benzaldehyde,2-hydroxy, 3,5- Any one of ditertbutyl-4-hydroxy Benzaldehyde, 3,5- dimethyl -4- hydroxy benzaldehydes or two or more combinations；It is preferred that , the aldehyde includes sulfydryl and substitutes phenolic aldehyde；It is further preferred that the sulfydryl substitution phenolic aldehyde includes 2- hydroxyls -3- ((positive fourths Base sulfydryl) methyl) benzaldehyde, any one of 2- hydroxyls -5- ((n-octyl sulfydryl) methyl) benzaldehyde or two or more groups It closes；Still more preferably, the big steric hindrance sulfydryl substitution phenolic aldehyde includes 3- tertiary butyls -5- ((n-octyl sulfydryl) methyl) -2- Hydroxy benzaldehyde, 3- tertiary butyls -5- ((phenethyl sulfydryl) methyl)-Benzaldehyde,2-hydroxy, 3- ((n-octyl sulfydryl) methyl) -5- Any one of tertiary butyl-Benzaldehyde,2-hydroxy, 3- ((phenethyl sulfydryl) methyl) -5- tertiary butyls-Benzaldehyde,2-hydroxy or two Kind or more combination；
And/or the diphenylamine derivatives includes the diphenylamines of amino substitution；Preferably, the diphenylamine derivatives includes 2- Amino-diphenylamines, 2- amino -4- methyl-diphenylamines, 2,2 '-diamino-diphenylamine, 2- amino -4 '-methyl-diphenylamine, 3- ammonia Base-diphenylamines, 4- amino-diphenylamines, 4, any one of 4 '-diamino-diphenylamine or two or more combinations；It is more highly preferred to , the diphenylamine derivatives include 2- amino-diphenylamines, 2,2 '-diamino-diphenylamine, 4- amino-diphenylamines, 4,4 '-two Any one of aminodiphenylamine or two or more combinations；
And/or the phenothiazine derivative includes 2- amino phenthazine, 3- amino phenthazine, 4- amino phenthazine, 5- amino fens Any one of thiazine or two or more combinations；
And/or the catalyst includes acidic catalyst；Preferably, the acidic catalyst includes Bronsted acid；Further preferably , the Bronsted acid is included in sulfuric acid, hydrochloric acid, nitric acid, trifluoromethanesulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, formic acid, acetic acid Any one or more combinations；Preferably, the acidic catalyst includes lewis acid；It is further preferred that the road Lewis acid includes any one of boron trifluoride ether, alchlor, ferric trichloride, zinc dichloride or two or more combinations；
And/or the liquid phase reaction medium includes inert organic solvents；Preferably, the inert organic solvents include alkane, ring Any one or any one derivative in alkane, alkanol, ether, aromatic compound；Preferably, the alkane includes hexane Combination more than any one of isomers, heptane isomers, octane isomer and decane isomers or both；Preferably, institute Stating cycloalkanes includes hexamethylene and/or hexahydrotoluene；Preferably, the aromatic compound include benzene, toluene, ortho-xylene, Combination more than any one of dimethylbenzene or both；Preferably, the inert organic solvents include chlorinated solvent and/or bromination Solvent；It is further preferred that the chlorinated solvent and/or bromination solvent include dichloromethane, bromochloromethane, 1,2-, bis- chloroethenes Combination more than any one of alkane, glycol dibromide, chloroform, chlorobenzene or both；Preferably, the alkanol includes first Any one of alcohol, ethyl alcohol, isopropanol, normal propyl alcohol, n-butanol, sec-butyl alcohol, isobutanol, 2-Ethylhexyl Alcohol and octanol or both with On combination；Preferably, the ether includes dialkyl ethers, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide (DMSO) Any one of or both more than combination；
And/or the aldehyde and/or the molar ratio of ketone and catalyst are 1:0.01-1:5, it is preferably 1:0.1-1:3；
And/or the aldehyde and/or ketone and diphenylamines and/or diphenylamine derivatives and/or phenothiazine and/or phenothiazine derivative Molar ratio be 1:0.1-1:10, it is preferably 1:0.5-1:5；
And/or the reaction temperature that the preparation method uses is 0 DEG C -200 DEG C, is more preferably 50 DEG C -150 DEG C；
And/or the reaction time that the preparation method uses for 0.5h-10h, further preferably 1h-5h；
And/or the preparation method further includes：It is described after reaction, carry out post-processing operation.
8. new schiff bases amine antioxidants any one of claim 1-4 are easily being led by the organic material of oxidative degradation The purposes in domain；Preferably, the purposes includes：At least using the schiff bases amine antioxidants as antioxidant in lubrication It is applied in oil, fuel oil, plastics or rubber.
9. include the composition of the new schiff bases amine antioxidants any one of claim 1-4；
Preferably, the composition is also comprising base oil or process oil, and the schiff bases amine antioxidants are at least partly Dilute or be dissolved in base oil or process oil；It is further preferred that the base oil include I, II or Group III mineral oil, poly- α- Alkene, synthetic ester, the oil of gas to liquid source or biological base oil；
The composition further includes any one or two or more combinations in diluent, solvent or carrier fluid；
It is further preferred that the lubricant oil composite includes I. C. engine oil, railway and marine lubricants, natural gas engine Oil, steam turbine oil, gas turbine oil, aviation turbine oil, corrosion and oxygenated oil, hydraulic oil, rail oil, are quenched compressor liquid Oil, manual transmission liquid, automatic transmission fluid, gear oil or lubricating grease；
It is further preferred that applied to the additive in the composition further include dispersant, detersive, antirust agent, antioxidant, Any one of anti-wear agent, antifoaming agent, frictional index modifier, demulsifier, viscosity index improver or pour point depressor or two Kind or more combination；
Still more preferably, the dispersant includes polyisobutenyl succinimide, polyisobutylene succinic acid ester, Mannich base Ashless dispersant and/or its analog, metal and ashless alkyl phenate, metal and ashless alkylsulfonate, metal and nothing The alkyl monosulfide phenates of ash, metal and any one of ashless salicin derivatives and/or its analog or two or more Combination；
Still more preferably, the antioxidant includes alkylated diphenylamine, N- alkylated diphenylamines, phenyl-α-naphthylamine, alkyl It is double to change phenyl-α-naphthylamine, hindered phenol, dimethyl quinoline, trimethyldihydroquinoline and its derivative, alkvlated hvdroquinones, alkylidene Phenol, Hydroxylated thiodiphenyl ethers, thiopropionate, metal dithiocarbamate, 1,3,4- dimercaptothiodiazoles and its spread out Biology or any one of oil-soluble copper compounds and/or its analog or two or more combinations；
Still more preferably, the anti-wear additive includes organic boric acid ester, organophosphorus ester, organic phosphite, organic Sulfur-containing compound, olefine sulfide, sulfurized fatty acid derivative, chlorinated paraffin, zinc dialkyl dithiophosphate, two sulphur of diaryl Any one of hydrocarbon and/or its analog for vulcanizing for trbasic zinc phosphate or phosphoric acid or two or more combinations；
Still more preferably, the antifoaming agent includes poly- alcoxyl alkane and/or its analog；
Still more preferably, the antirust agent includes polyoxyalkylene polyol, benzotriazole analog derivative and/or its is similar Any one of object or two or more combinations；
Still more preferably, the pour point inhibition includes poly- subunit acrylate and/or its analog.
10. composition according to claim 9, it is characterised in that：The composition is lubricant oil composite, and described Addition concentration of the schiff bases amine antioxidants in lubricant oil composite is 0.01-10wt%, especially preferably 0.01-5wt%.
CN201710546324.9A 2016-11-11 2017-07-06 New schiff base type amine antioxidants, its preparation method and application Pending CN108069874A (en)

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CN111233699A (en) * 2018-11-28 2020-06-05 中国科学院宁波材料技术与工程研究所 Cardanol Schiff base antioxidant and preparation method and application thereof
CN111233699B (en) * 2018-11-28 2023-10-27 中国科学院宁波材料技术与工程研究所 Cardanol Schiff base antioxidant and preparation method and application thereof
CN111952650A (en) * 2020-08-13 2020-11-17 上海元城汽车技术有限公司 Proton exchange membrane, preparation method thereof and fuel cell
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CN112759532B (en) * 2021-01-11 2023-06-06 中国人民解放军空军军医大学 Reagent for visual rapid and sensitive detection of bacillus anthracis and detection method thereof
CN115449410A (en) * 2022-09-29 2022-12-09 浙江大学 Antioxidant for improving oxidizing property of fuel and application thereof
CN116284642A (en) * 2023-05-18 2023-06-23 平原倍斯特化工有限公司 Yellowing-resistant isocyanate composition and preparation method thereof
CN118006026A (en) * 2024-04-10 2024-05-10 安徽和盛新材料科技有限公司 Anti-aging polyethylene color master batch and preparation method thereof

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