CN114105895A - Novel p-phenylenediamine compound, preparation method and application thereof - Google Patents
Novel p-phenylenediamine compound, 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
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a novel p-phenylenediamine compound, a preparation method and application thereof. The compound has a structure shown in the formula I, wherein R1Is a straight chain or branched chain alkyl of C4-C16, R2Is C3-C10 straight chain or branched chain alkyl, C3-C10 naphthenic base, phenyl or C3-C10 alkyl substituted phenyl. The compound can provide better heat-resistant oxygen fatigue aging resistance and long-acting protective performance than the conventional anti-aging agent, and stronger discoloration resistance. The compound can be used as an additive for plastics, elastomers, lubricating oil and the like, and can delay the degradation tendency caused by oxygen, ozone, repeated mechanical action and the like in the using process.
Description
Technical Field
The invention belongs to the field of anti-aging agents, and particularly relates to a novel p-phenylenediamine compound, and a preparation method and application thereof.
Background
Currently, p-phenylenediamine compounds, including dialkyl p-phenylenediamine, alkyl aryl p-phenylenediamine, and diaryl p-phenylenediamine, are commonly used as age resistors for rubber articles, particularly tires, and the most widely used age resistor is 6PPD (N- (1, 3-dimethylbutyl) -N ' -phenyl p-phenylenediamine), and others are IPPD (N-isopropyl-N ' -phenyl p-phenylenediamine), 77PD (N, N ' -bis (1, 4-dimethylpentyl) p-phenylenediamine), DTPD (diphenyl p-phenylenediamine, a mixture of di (tolyl) p-phenylenediamine and phenyl tolyl p-phenylenediamine), and the like.
The widely used rubber antioxidant 6PPD has smaller molecular weight, and the antioxidant rapidly migrates to the surface in the use process of rubber products or tires, thereby causing the pollution and the discoloration of the surfaces of the tires; the anti-aging agent DTPD is diaryl p-phenylenediamine which is regarded as a long-acting after-effect anti-aging agent, has relatively long anti-aging performance, but has poor compatibility with rubber and causes blooming due to large using amount. In recent years, users have more and more high attention on the aging resistance and surface discoloration of tires, and therefore, a compound which has a longer-acting aging protection effect and is discoloration resistant compared with the existing product is urgently needed in the field.
Disclosure of Invention
The compound has the structure shown in the formula I, contains a p-phenylenediamine structure which is good at removing free radicals, contains two long-chain alkyl groups to enhance the compatibility with rubber, has a physical shielding effect, and has a delaying effect on the oxidation and bending fatigue deterioration of unsaturated rubber. The invention discovers that the compound can provide better heat-resistant oxygen fatigue aging and long-acting protective performance than the conventional anti-aging agent, and stronger discoloration resistance. The compound can be used as an additive for plastics, elastomers, lubricating oil and the like, and can delay the degradation tendency caused by oxygen, ozone, repeated mechanical action and the like in the using process.
In particular, the present invention provides compounds of formula I:
wherein R is1Is a straight chain or branched chain alkyl of C4-C16, R2Is C3-C10 straight chain or branched chain alkyl, C3-C10 naphthenic base, phenyl or C3-C10 alkyl substituted phenyl.
In one or more embodiments, in the compounds of formula I, R1Is n-butyl, tert-butyl, n-hexyl, isohexyl, tert-octyl, n-dodecyl, n-tetradecyl or n-hexadecyl.
In one or more embodiments, in the compounds of formula I, R1Is a straight chain or branched chain alkyl of C4-C12.
In one or more embodiments, in the compounds of formula I, R1Is tert-butyl, tert-octyl or n-dodecyl.
In one or more embodiments, in the compounds of formula I, R2Is a branched alkyl of C3-C10.
In one or more embodiments, in the compounds of formula I, R2Is isopropyl, 1, 3-dimethylbutyl, 1, 4-dimethylpentyl, cyclohexyl or phenyl.
In one or more embodiments, in the compounds of formula I, R2Is a branched alkyl group of C3-C7, a naphthenic group of C3-C7 or a phenyl group.
In one or more embodiments, in the compounds of formula I, R2Is isopropyl, 1, 3-dimethylbutyl, 1, 4-dimethylpentyl or phenyl.
In one or more embodiments, the compound of formula I is selected from:
the present invention also provides a process for the preparation of a compound of formula I according to any one of the embodiments of the present invention, comprising:
(1) reacting cyanuric chloride with a compound A of the formula to produce an intermediate M of the formula:
(2) reacting intermediate M with R1NH2Reacting to obtain the compound shown in the formula I:
wherein R is1And R2As defined in any one of the embodiments of the invention.
In one or more embodiments, the method has one or more of the following features:
the amount of the compound A added in the step (1) is 100 to 120 percent of the amount of the cyanuric chloride added in the step (1);
the step (1) is carried out in the presence of alkali liquor; and
the reaction temperature in the step (1) is-5-10 ℃.
In one or more embodiments, the alkali solution is selected from one or more of sodium carbonate solution, sodium hydroxide solution, potassium carbonate solution, potassium hydroxide solution, triethylamine, triisopropylamine, N-isopropyldiethylamine, N-diisopropylethylamine, and the like, and preferably from one or more of sodium carbonate solution, sodium hydroxide solution, potassium carbonate solution, and potassium hydroxide solution.
In one or more embodiments, compound a is selected from N-phenyl-p-phenylenediamine, N-isopropyl-p-phenylenediamine, N-cyclohexyl-p-phenylenediamine, N- (1, 3-dimethyl) butyl-p-phenylenediamine, and N- (1, 4-dimethyl) pentyl-p-phenylenediamine.
In one or more embodiments, the method has one or more of the following features:
r added in the step (2)1NH2The amount of the substance (b) is 400 to 480 percent of the amount of the substance of the intermediate M added in the step (2); and
the reaction temperature in the step (2) is 60-150 ℃.
In one or more embodiments, R1NH2Is n-butylamine, tert-butylamine, n-hexylamine, isohexylamine, tert-octylamine, dodecylamine, tetradecylamine or hexadecylamine.
The invention also provides a rubber composition containing a compound of formula I according to any one of the embodiments of the invention.
The present invention also provides a rubber article comprising the rubber composition according to any of the embodiments of the present invention; preferably, the rubber article is a tire.
The invention also provides the use of a compound of formula I according to any of the embodiments of the invention for improving the antioxidant properties and/or the discoloration resistance of a rubber or rubber article; preferably, the rubber article is a tire.
Drawings
FIG. 1 is a graph showing the tensile product retention before and after aging of the vulcanized rubber sheets of test examples 1 to 4.
FIG. 2 is a graph showing the retention of tear strength before and after aging of the vulcanized rubber sheets of test examples 1 to 4.
Fig. 3 is a schematic diagram of a Lab color model for color difference evaluation.
Detailed Description
To make the features and effects of the present invention obvious to those skilled in the art, the terms and words used in the specification and claims are generally described and defined below. 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 theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as numbers, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
As used herein, alkyl refers to a straight or branched chain monovalent saturated hydrocarbon group, typically containing 1 to 16 carbon atoms (C1-C16 alkyl), for example, 3 to 16 carbon atoms (C3-C16 alkyl). Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1, 4-dimethylpentyl, tert-octyl, n-dodecyl, n-tetradecyl, or n-hexadecyl.
As used herein, cycloalkyl refers to a monovalent saturated hydrocarbon ring, typically containing 3 to 10 carbon atoms (C3-C10 cycloalkyl), such as 3 to 8 carbon atoms (C3-C8 cycloalkyl). Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl. Herein, cycloalkyl groups may be optionally substituted with alkyl groups, and the number of alkyl substituents on the cycloalkyl groups may be 1 or 2.
The invention finds that the compound with the structure shown in the following formula I contains a p-phenylenediamine structure which is good at clearing free radicals, also contains two long-chain alkyl groups to enhance the compatibility with rubber, has a physical shielding effect mainly caused by the long-chain alkyl groups, has a delaying effect on the oxidation and bending fatigue deterioration of unsaturated rubber, and can provide better heat-oxygen fatigue aging resistance and long-acting protection performance and stronger discoloration resistance than a conventional anti-aging agent:
wherein R is1Is a straight chain or branched chain alkyl of C4-C16, R2Is C3-C10 straight chain or branched chain alkyl, C3-C10 naphthenic base, phenyl or C3-C10 alkyl substituted phenyl.
In certain embodiments, in the compounds of formula I, R1Is n-butyl, tert-butyl, n-hexyl, isohexyl, tert-octyl, n-dodecyl, n-tetradecyl or n-hexadecyl.
In certain embodiments, in the compounds of formula I, R1Straight or branched chain alkyl groups of C4 to C12, including, but not limited to, t-butyl, t-octyl, or n-dodecyl, for example. In some embodiments, in the compounds of formula I, R1Is a branched alkyl group of C4-C8, such as tert-butyl or tert-octyl.
In certain embodiments, in the compounds of formula I, R2Is a branched alkyl of C3-C10.
In certain embodiments, in the compounds of formula I, R2Is isopropyl, 1, 3-dimethylbutyl, 1, 4-dimethylpentyl, cyclohexyl or phenyl.
In certain embodiments, in the compounds of formula I, R2Is a branched alkyl group of C3-C7, a naphthenic group of C3-C7 or a phenyl group. In certain embodiments, in the compounds of formula I, R2Examples of branched alkyl or phenyl groups having C3-C7 include, but are not limited to, isopropyl, 1, 3-dimethylbutyl, 1, 4-dimethylpentyl, or phenyl. In some embodiments, in the compounds of formula I, R2A branched alkyl group of C3 to C7, such as isopropyl, 1, 3-dimethylbutyl or 1, 4-dimethylpentyl. In some embodiments, in the compounds of formula I, R2Is isopropyl. In some embodiments, in the compounds of formula I, R2Is 1, 3-dimethylbutyl or 1, 4-dimethylpentyl.
It has been found in the present invention that, in general, in the compounds of the formula I, R1、R2The longer the chain, the better the flexibility, the higher the tear strength retention. Thus, in some preferred embodiments, in the compounds of formula I, R1A linear or branched alkyl group of C8 to C12, such as t-octyl or n-dodecyl; and/or, R2Branched alkyl of C6 to C7, for example 1, 3-dimethylbutyl or 1, 4-dimethylpentyl.
In certain embodiments, the compound of formula I is selected from:
in some embodiments, the compound of formula I is selected from:
the process of the present invention for preparing a compound of formula I, comprising:
(1) cyanuric chloride is reacted with a compound A of the formula to produce an intermediate M of the formula, wherein R2Is a straight chain or branched chain alkyl of C3-C10, a cycloalkyl of C3-C10, a phenyl or a phenyl substituted by C3-C10 alkyl:
(2) reacting intermediate M with R1NH2Reacting to obtain the compound of formula I, wherein R1Is a straight chain or branched chain alkyl of C4-C16:
among them, preferred R in the compound A2And R1NH2Preferred of (1) R1May be as described in any of the embodiments herein.
In the step (1), cyanuric chloride (TCT) and a compound A (N-R) are used2P-phenylenediamines, such as N-alkyl-p-phenylenediamines or N-aryl-p-phenylenediamines). In step (1), compound A is preferably used in excess. The compound a is preferably added in an excess of not more than 20% with respect to the TCT added, i.e. the amount of substance of compound a added is preferably 100% to 120% of the amount of substance of TCT added. In some embodiments, compound a is added in an excess of 10-20% relative to the amount of TCT added, i.e., the amount of material of compound a added is 110-120% of the amount of material of TCT added. It is understood that, herein, an excess of a certain raw material X with respect to another raw material Y by a certain percentage value means a percentage value of the amount of the substance of the added raw material X which is beyond the amount of the substance of the raw material X theoretically required for just completely reacting with the added raw material Y (or the substance of the raw material Y produced in the reaction).
In some embodiments, compound a used in step (1) is selected from N-phenyl-p-phenylenediamine, N-isopropyl-p-phenylenediamine, N-cyclohexyl-p-phenylenediamine, N- (1, 3-dimethyl) butyl-p-phenylenediamine, or N- (1, 4-dimethyl) pentyl-p-phenylenediamine.
In the step (1), alkali liquor is used as an acid binding agent to neutralize HCl generated in the reaction, namely the reaction in the step (1) is carried out in the presence of alkali liquor. The alkali solution suitable for the present invention is not particularly limited, and may be, for example, one or more of sodium carbonate solution, sodium hydroxide solution, potassium carbonate solution, potassium hydroxide solution, triethylamine, triisopropylamine, N-isopropyldiethylamine, N-diisopropylethylamine, and the like. It is understood that sodium carbonate solution, sodium hydroxide solution, potassium carbonate solution, and potassium hydroxide solution refer to aqueous solutions of sodium carbonate, sodium hydroxide, potassium carbonate, and potassium hydroxide, respectively, herein. In some embodiments, the alkali solution is one or more selected from the group consisting of a sodium carbonate solution, a sodium hydroxide solution, a potassium carbonate solution, and a potassium hydroxide solution. In step (1), an excess of lye may be added, for example, the lye may be present in an excess of less than 20% or less than 10% relative to the TCT. In the present invention, when an aqueous solution of an inorganic base (e.g., sodium carbonate solution, sodium hydroxide solution, potassium carbonate solution, and potassium hydroxide solution) is used as the alkali solution, the concentration of the alkali solution is usually 20 to 50% by weight.
In the present invention, the reactions of step (1) and step (2) are carried out in a nonpolar solvent. It is to be understood that, herein, non-polar solvents include non-polar solvents and less polar solvents. The non-polar solvent suitable for use in the present invention may be selected from one or more of toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane and trimethylcyclohexane. In some embodiments, the present invention uses toluene, xylene, or mixtures thereof as a solvent.
The reaction temperature in the step (1) is controlled to be-5-10 ℃. Preferably, in step (1), compound A is added first, followed by addition of the lye. Preferably, the compound A is added at-5 to 0 ℃. Preferably, adding alkali liquor at 0-10 ℃ and continuing the reaction. Preferably, compound a and lye are added slowly. Preferably, the addition rate of compound A and the lye is not more than 0.015 mol/min, such as between 0.01 mol/min and 0.015 mol/min, based on the amount of substance of the base in compound A or the lye, such as about 30 minutes for the addition of compound A and the lye, respectively, when 0.3 to 0.4mol of compound A and lye are used. In a preferred embodiment, in the step (1), the compound A is slowly added into a mixture of TCT and a solvent at a temperature of-5-0 ℃, after the compound A is added, the temperature of a reaction system is raised to 0-10 ℃, then alkali liquor is slowly added, and the reaction is continued. The compound A may be dissolved in a solvent and then added to a mixture of TCT and a solvent, as required. In the step (1), after the alkali liquor is added, the reaction is preferably continued for 2 to 3 hours. After the reaction is completed, conventional purification may be performed, and for example, phase separation, water washing, and drying may be performed to obtain a solution of the intermediate M.
In step (2), the intermediate M is further reacted with an alkyl primary amine (R)1NH2) Reacting to prepare the compound I. Step (2) use of excess R1NH2As an acid-binding agent. Added R relative to added intermediate M1NH2Preferably, the excess does not exceed 120%, i.e. R is added1NH2The amount of substance(s) of (c) is preferably not more than 480% of the amount of substance(s) of the added intermediate M. In some embodiments, R is added relative to intermediate M added1NH2Excess of 100-120%, i.e. added R1NH2The amount of the substance (b) is 400 to 480% of the amount of the substance of the intermediate M to be added.
In some embodiments, R used in step (2)1NH2Selected from n-butylamine, tert-butylamine, n-hexylamine, isohexylamine, tert-octylamine, dodecylamine (n-dodecylprimary amine), tetradecylamine (n-tetradecylprimamine) or hexadecylamine (n-hexadecylprimary amine).
The reaction temperature in the step (2) is preferably 60-150 ℃. Whether the reaction is complete can be judged by sampling to detect whether the intermediate M still exists. The reaction time of the step (2) is usually 3 to 6 hours. The reaction of step (2) is preferably carried out in a closed vessel, for example, in an autoclave. After the reaction of step (2) is completed, conventional purification such as neutralization with an alkaline solution, washing with water, and distillation of the organic phase to recover the solvent and excess R1NH2To obtain the target compound (the compound of the formula I).
The compound of the formula I can provide better heat-oxygen fatigue aging resistance and long-acting protective performance and stronger discoloration resistance for the rubber composition than a conventional anti-aging agent. Accordingly, the present invention also provides a rubber composition comprising one or more of the compounds of formula I as described herein.
The raw materials of the rubber composition generally include a diene elastomer, a reinforcing filler, an antioxidant and a crosslinking agent. The amounts of diene elastomer, reinforcing filler, antioxidant and crosslinking agent used in the rubber composition of the present invention may be those conventionally used in the art. The amount of the compound of the formula I to be used in the rubber composition may be about 0.1 to 5 parts by mass, for example, about 0.5 to 5 parts by mass, 2 to 3 parts by mass, or 2.5 parts by mass, based on 100 parts by mass of the diene elastomer. Herein, the rubber composition includes unvulcanized rubber and vulcanized rubber. The unvulcanized rubber is vulcanized (cured) to obtain a vulcanized rubber.
Diene elastomer means an elastomer whose monomers comprise dienes (e.g. butadiene, isoprene). The diene elastomer suitable for use in the present invention may be various diene elastomers known in the art, including, but not limited to, one or more selected from Natural Rubber (NR), Butadiene Rubber (BR), isoprene rubber, styrene-butadiene rubber (SBR), Chloroprene Rubber (CR), nitrile-butadiene rubber (NBR), isoprene/butadiene copolymer, isoprene/styrene copolymer, and isoprene/butadiene/styrene copolymer. In certain embodiments, the rubber composition of the present invention wherein the diene elastomer is comprised of natural rubber (e.g., SCR5) and butadiene rubber (e.g., BR 9000); the mass ratio of the natural rubber and the butadiene rubber is not particularly limited, and is, for example, 1: 9 to 9: 1. 2: 8 to 8: 2. 3: 7 to 7: 3. 4: 6 to 6: 4. or 1: about 1.
The reinforcing filler may be a reinforcing filler conventionally used for rubbers, including but not limited to one or more selected from carbon black, titanium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, clay and talc. In some embodiments, the reinforcing filler in the rubber composition of the present invention is carbon black. The reinforcing filler may be used in an amount of 40 to 60 parts by mass per 100 parts by mass of the diene elastomer.
The cross-linking agent may be sulphur. The amount of the crosslinking agent to be used may be 1 to 3 parts by mass per 100 parts by mass of the diene elastomer.
The rubber composition of the present invention may optionally contain other anti-aging agents known in the art (e.g., 6PPD, IPPD, 77PD, DTPD, etc.) in addition to the compound of formula I of the present invention. When the rubber composition of the present invention comprises the compound of the formula I of the present invention and other antioxidant, the total amount of the compound of the formula I and other antioxidant used in the rubber composition is usually 0.1 to 5 parts by mass, for example, 0.5 to 5 parts by mass, 2 to 3 parts by mass, etc., based on 100 parts by mass of the diene elastomer; the amount ratio between the compound of formula I and the other antioxidant can be determined according to performance requirements.
The raw materials for the rubber composition may also include other ingredients commonly used in rubber, including but not limited to adjuvants and accelerators, and the like. The amounts of auxiliaries and accelerators may be those conventionally used in the art.
The auxiliary may include a softener used for improving processability. The softener may be a petroleum type softener such as aromatic oil, processed oil, lubricating oil, paraffin, liquid paraffin, petroleum pitch, vaseline, etc., or a fatty oil type softener such as castor oil, linseed oil, rapeseed oil, coconut oil, wax (e.g., beeswax, carnauba wax, and lanolin), tall oil, linoleic acid, palmitic acid, stearic acid, and lauric acid, etc. The auxiliary agent can also comprise an active agent, such as zinc oxide, and can play a role in accelerating vulcanization speed, improving rubber thermal conductivity, wear resistance, tearing resistance and the like. In general, the auxiliary is used in a total amount of 5 to 20 parts by mass per 100 parts by mass of the diene elastomer, and for example, 2 to 8 parts by mass of an aromatic oil, 2 to 8 parts by mass of zinc oxide and 1 to 4 parts by mass of stearic acid may be used.
The accelerator is usually a vulcanization accelerator, and may be at least one of sulfonamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde amine, imidazoline and xanthate vulcanization accelerators. For example, the accelerator may be accelerator NS (N-tert-butyl-2-benzothiazolesulfenamide). Generally, the accelerator is used in an amount of 0.5 to 1.5 parts by mass per 100 parts by mass of the diene elastomer.
In addition, plasticizers such as DMP (dimethyl phthalate), DEP (diethyl phthalate), DBP (dibutyl phthalate), DHP (diheptyl phthalate), DOP (dioctyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BBP (butylbenzyl phthalate), DWP (dilauryl phthalate), DCHP (dicyclohexyl phthalate), and the like may also be used in the rubber composition, if necessary. The amount of plasticizer used is that amount conventionally used in the art.
The unvulcanized rubber of the present invention can be prepared by a conventional rubber mixing method, for example, by a two-stage mixing method: mixing the mixture in a first-stage internal mixer, mixing the diene elastomer, the reinforcing filler, the auxiliary agent and the anti-aging agent, and discharging rubber at the temperature of more than 110 ℃; mixing the rubber obtained in the first stage with a cross-linking agent and an accelerant by a two-stage open mill. Generally, the diene elastomer is added into a thermo-mechanical mixer (such as an internal mixer), after a certain time of kneading, the reinforcing filler, the auxiliary agent and the anti-aging agent are added, and the kneading is continued until the mixture is uniform, the reinforcing filler, the auxiliary agent and the anti-aging agent can be added in batches, and the temperature during the kneading is controlled between 110 ℃ and 190 ℃, preferably between 150 ℃ and 160 ℃; then, the mixture is cooled to 100 ℃ or lower, the crosslinking agent and the accelerator are added, and kneading is carried out again while controlling the temperature to 110 ℃ or lower, for example, about 70 ℃ during kneading, to obtain an unvulcanized rubber.
The unvulcanized rubber of the present invention can be vulcanized by a conventional vulcanization method to obtain a vulcanized rubber; the vulcanization temperature is usually from 130 ℃ to 200 ℃, for example around 145 ℃; the vulcanization time depends on the vulcanization temperature, the vulcanization system and the vulcanization kinetics and is usually from 15 to 60 minutes, for example around 30 minutes. The unvulcanized rubber obtained by kneading may be subjected to conventional tableting prior to vulcanization.
The compound I and the rubber composition are used for rubber products, particularly rubber tires, and can endow the rubber products or the rubber tires with better heat-oxygen fatigue aging resistance, long-term protection performance and stronger discoloration resistance compared with the conventional anti-aging agent. Accordingly, the present invention also provides a rubber article comprising the rubber composition described herein. The rubber product can be a tire, a rubber shoe, a sealing strip, a sound insulation board, a vibration-proof cushion and the like. In certain embodiments, the rubber article is a tire, such as a tread, belt, and sidewall of a tire. The belt of the tire may contain, in addition to the rubber composition of the present invention, reinforcing materials conventionally used in the art. The invention also provides the use of the compounds of formula I according to the invention for improving the antioxidant properties and/or the discoloration resistance of rubbers.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise indicated, conventional in the art. The starting compounds in the preparation examples are all commercially available.
Example 1: 2- (4-isopropylamino) aniline-4, 6-di-tert-butylamine-1, 3, 5-triazine (Compound I-1)
(1) Adding 60g of cyanuric chloride (TCT) (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 43g of toluene solution of 4-isopropylaminoaniline (0.32mol of 4-isopropylaminoaniline is dissolved in 100mL of toluene in a cooling environment at-5 ℃), after dripping, heating the reaction system to 10 ℃, slowly dripping NaOH aqueous solution (13g is dissolved in 40mL of water and is dripped in 30 min), continuously stirring for 2 hours after reaction, demixing the reaction system after finishing, removing a water phase, washing an organic phase for three times, then adding 6g of anhydrous sodium sulfate, drying and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L high-pressure autoclave, adding 92.2g (1.28mol) of tert-butylamine, heating to 70 ℃ in a sealed manner for reaction for 4h, sampling liquid phase for detection, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-1).
1H-NMR(300MHz,CDCl3)δ7.19-7.17(m,2H),6.57(s,1H),6.47(d,J＝6Hz,2H),4.93(s,2H),3.58-3.46(m,1H),1.34(s,18H),1.12(d,J＝6Hz,6H).
Example 2: 2- (4-anilino) aniline-4, 6-di-tert-butylamine-1, 3, 5-triazine (Compound I-2)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 64.4g of a toluene solution of 4-anilinoaniline under a cooling environment at the temperature of-5 ℃ (0.35mol of 4-anilinoaniline is dissolved in 120mL of toluene, and dripping is finished within about 30 min), heating a reaction system to 10 ℃ after dripping is finished, slowly dripping NaOH aqueous solution (13g is dissolved in 40mL of water and dripping is finished within 30 min), continuously stirring for 3 hours after reaction, standing for layering after the reaction is finished, removing a water phase, washing an organic phase for three times by water, adding 6g of anhydrous sodium sulfate, drying, and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L high-pressure autoclave, adding 92.2g (1.28mol) of tert-butylamine, heating to 70 ℃ in a sealed manner for reaction for 4h, sampling liquid phase for detection, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-2).
1H-NMR(300MHz,CDCl3)δ7.45-7.38(m,2H),7.33-7.23(m,2H),7.14-6.99(m,6H),6.97-6.86(m,1H),5.70-5.64(m,2H),1.46(s,18H).
Example 3: 2- (4- (1, 3-dimethyl) butylamino) aniline-4, 6-di-tert-butylamine-1, 3, 5-triazine (Compound I-3)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 67.2g of toluene solution of 4- (1, 3-dimethyl) butylamino-aniline (0.35mol of 4- (1, 3-dimethyl) butylamino-aniline dissolved in 80mL of toluene in a cooling environment at-5 ℃ (finishing dripping within about 30 min), heating the reaction system to 10 ℃ after finishing dripping, slowly dripping NaOH aqueous solution (13g of NaOH dissolved in 40mL of water, finishing dripping within 30 min), continuously stirring for 2 hours after reaction, standing for layering after finishing, separating a water phase, washing an organic phase for three times, adding 4g of anhydrous sodium sulfate, drying, and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L high-pressure autoclave, adding 92.2g (1.28mol) of tert-butylamine, heating to 70 ℃ in a sealed manner for reaction for 4h, sampling liquid phase for detection, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-3).
1H-NMR(300MHz,CDCl3)δ7.19-7.15(m,2H),6.77(s,1H),6.46(d,J＝6Hz,2H),4.82(s,2H),3.42-3.36(m,1H),1.71-1.63(m,1H),1.32(s,18H),1.18-1.12(m,2H),1.06(d,J＝6Hz,3H),0.87-0.82(m,6H).
Example 4: 2- (4- (1, 4-dimethyl) pentylamino) aniline-4, 6-di-tert-butylamine-1, 3, 5-triazine (Compound I-4)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 72.1g of toluene solution of 4- (1, 4-dimethyl) pentylamino-aniline (0.35mol of 4- (1, 4-dimethyl) pentylamino-aniline dissolved in 80mL of toluene and dripping completed within about 30 min) in a cooling environment at-5 ℃, heating the reaction system to 10 ℃ after dripping, slowly dripping NaOH aqueous solution (13g of NaOH dissolved in 40mL of water and dripping completed within 30 min), continuously stirring for 2 hours after reaction, standing for layering after finishing, separating a water phase, washing an organic phase for three times, adding 8g of anhydrous sodium sulfate, drying and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L high-pressure autoclave, adding 92.2g (1.28mol) of tert-butylamine, heating to 70 ℃ in a sealed manner for reaction for 4h, sampling liquid phase for detection, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-4).
1H-NMR(300MHz,CDCl3)δ7.19-7.16(m,2H),6.55(s,1H),6.45(d,J＝6Hz,2H),4.88(s,2H),3.33-3.29(m,1H),1.54-1.42(m,3H),1.35(s,18H),1.23-1.14(m,2H),1.08(d,J＝6Hz,3H),0.83-0.80(m,6H).
Example 5: 2- (4-isopropylamino) aniline-4, 6-di-tert-octylamine-1, 3, 5-triazine (compound I-5)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 43g of toluene solution of 4-isopropylaminoaniline (0.32mol of 4-isopropylaminoaniline is dissolved in 100mL of toluene and the dripping is finished within about 30 min) in a cooling environment at the temperature of-5 ℃, heating the reaction system to 10 ℃ after the dripping is finished, slowly dripping NaOH aqueous solution (13g of NaOH aqueous solution is dissolved in 40mL of water and the dripping is finished within 30 min), continuously stirring for 2 hours after the reaction, layering the reaction system after the reaction is finished, removing a water phase, washing the organic phase for three times, adding 6g of anhydrous sodium sulfate, drying and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L four-mouth bottle, adding 192g (1.28mol) of tert-octylamine, heating to 90-100 ℃, reacting for 4 hours, sampling, detecting by a liquid phase, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-5).
1H-NMR(300MHz,CDCl3)δ7.30-7.27(m,2H),6.56(d,J＝6Hz,2H),4.98(s,2H),3.77-3.71(m,2H),2.20(s,1H),1.90(s,4H),1.49(s,12H),1.28-1.21(m,6H),1.04(s,18H).
Example 6: 2- (4-anilino) aniline-4, 6-di-tert-octylamine-1, 3, 5-triazine (Compound I-6)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 64.4g of a toluene solution of 4-anilinoaniline under a cooling environment at the temperature of-5 ℃ (0.35mol of 4-anilinoaniline is dissolved in 120mL of toluene, and dripping is finished within about 30 min), heating a reaction system to 10 ℃ after dripping is finished, slowly dripping NaOH aqueous solution (13g is dissolved in 40mL of water and dripping is finished within 30 min), continuously stirring for 2 hours after reaction, standing for layering after the reaction is finished, removing a water phase, washing an organic phase for three times by water, adding 6g of anhydrous sodium sulfate, drying, and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L four-neck flask, adding 192g (1.28mol) of tert-octylamine, heating to 110-120 ℃ for reaction for 4 hours, sampling, detecting by a liquid phase, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-6).
1H-HMR(300MHz，CDCl3)δ7.44-7.36(m,2H),7.34-7.21(m,3H),7.12-6.99(m,4H),6.97-6.88(m,1H),5.68-5.66(m,2H)1.51(s,12H),1.07-1.05(m,4H),1.03(s,18H).
Example 7: 2- (4- (1, 3-dimethyl) butylamino) aniline-4, 6-di-tert-octylamine-1, 3, 5-triazine (Compound I-7)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 67.2g of toluene solution of 4- (1, 3-dimethyl) butylamino-aniline (0.35mol of 4- (1, 3-dimethyl) butylamino-aniline dissolved in 80mL of toluene in a cooling environment at-5 ℃ (finishing dripping within about 30 min), heating the reaction system to 10 ℃ after finishing dripping, slowly dripping NaOH aqueous solution (13g of NaOH dissolved in 40mL of water, finishing dripping within 30 min), continuously stirring for 2 hours after reaction, standing for layering after finishing, separating a water phase, washing an organic phase for three times, adding 6g of anhydrous sodium sulfate, drying, and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L four-neck flask, adding 192g (1.28mol) of tert-octylamine, heating to 100-110 ℃, reacting for 4 hours, sampling, detecting by a liquid phase, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-7).
1H-NMR(300MHz,CDCl3)δ7.20-7.15(m,2H),6.45(d,J＝6Hz,2H),4.84(s,2H),3.34-3.26(m,1H),1.80(s,3H),1.51-1.43(m,1H),1.38(s,12H),1.23-1.15(m,2H),1.09(d,J＝6Hz,4H),0.92(s,18H)0.82-0.81(m,6H).
Example 8: 2- (4- (1, 4-dimethyl) pentylamino) aniline-4, 6-di-tert-octylamine-1, 3, 5-triazine (Compound I-8)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 72.1g of toluene solution of 4- (1, 4-dimethyl) pentylamino-aniline (0.35mol of 4- (1, 4-dimethyl) pentylamine is dissolved in 80mL of toluene in a cooling environment at-5 ℃, finishing dripping after about 30 min), heating the reaction system to 10 ℃ after finishing dripping, slowly dripping NaOH aqueous solution (13g is dissolved in 40mL of water, finishing dripping in 30 min), continuously stirring for 2 hours after reaction, standing for layering after finishing, separating a water phase, washing an organic phase for three times, adding 6g of anhydrous sodium sulfate, drying, and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L four-neck flask, adding 192g (1.28mol) of tert-octylamine, heating to 100-110 ℃, reacting for 4 hours, sampling, detecting by a liquid phase, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-8).
1H-NMR(300MHz,CDCl3)δ7.20(s,2H),7.15(s,1H),6.46(d,J＝6Hz,2H),4.90(s,2H),3.45-3.40(m,1H),1.80(s,4H),1.73-1.63(m,2H),1.38(s,12H),1.20-1.14(m,2H),1.07(d,J＝6Hz,4H),0.92(s,18H)0.88-0.84(m,6H).
Example 9: 2- (4-isopropylamino) aniline-4, 6-didodecylamine) -1,3, 5-triazine (Compound I-9)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 43g of toluene solution of 4-isopropylaminoaniline (0.32mol of 4-isopropylaminoaniline is dissolved in 100mL of toluene and the dripping is finished within about 30 min) in a cooling environment at the temperature of-5 ℃, heating the reaction system to 10 ℃ after the dripping is finished, slowly dripping NaOH aqueous solution (13g of NaOH aqueous solution is dissolved in 40mL of water and the dripping is finished within 30 min), continuously stirring for 2 hours after the reaction, layering the reaction system after the reaction is finished, removing a water phase, washing the organic phase for three times, adding 6g of anhydrous sodium sulfate, drying and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L reaction kettle, adding 235.5g (1.28mol) of dodecylamine, heating to 120-130 ℃ for reaction for 4 hours, sampling, detecting by a liquid phase, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-9).
1H-NMR(300MHz,DMSO-d6)δ8.43-8.17(m,1H),7.39(d,J＝18Hz,2H),6.53(d,J＝18Hz,2H),4.90(s,1H),3.46(s,1H),3.19(s,4H),1.51(s,4H),1.25(s,40H),1.11(d,J＝6Hz,6H),0.87-0.84(m,6H).
Example 10: 2- (4-anilino) aniline-4, 6-didodecylamine) -1,3, 5-triazine (Compound I-10)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 64.4g of a toluene solution of 4-anilinoaniline (0.35mol of 4-anilinoaniline is dissolved in 120mL of toluene and the dripping is finished within about 30 min) in a cooling environment at the temperature of-5 ℃, heating the reaction system to 10 ℃ after the dripping is finished, slowly dripping NaOH aqueous solution (13g of the NaOH aqueous solution is dissolved in 40mL of water and the dripping is finished within 30 min), continuously stirring for 2 hours after the reaction, layering the reaction system after the reaction is finished, removing a water phase, washing the organic phase for three times, adding 6g of anhydrous sodium sulfate, drying and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L reaction kettle, adding 235.5g (1.28mol) of dodecylamine, heating to 130-140 ℃ for reaction for 4 hours, sampling, detecting by a liquid phase, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-10).
1H-HMR(300MHz，CDCl3)δ7.52-7.50(m,2H),7.32-7.22(m,2H),7.1-6.97(m,4H),6.92-6.85(m,1H),5.67-5.67(m,2H),5.04-5.08(m,2H),3.39(s,4H),1.28(s,36H),0.95-0.86(m,10H).
Example 11: 2- (4- (1, 3-dimethyl) butylamino) aniline-4, 6-didodecylamine) -1,3, 5-triazine (Compound I-11)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 67.2g of toluene solution of 4- (1, 3-dimethyl) butylamino-aniline (0.35mol of 4- (1, 3-dimethyl) butylamino-aniline dissolved in 80mL of toluene in a cooling environment at-5 ℃ (finishing dripping within about 30 min), heating the reaction system to 10 ℃ after finishing dripping, slowly dripping NaOH aqueous solution (13g of NaOH dissolved in 40mL of water, finishing dripping within 30 min), continuously stirring for 2 hours after reaction, layering the reaction system after finishing, removing a water phase, washing an organic phase for three times, adding 6g of anhydrous sodium sulfate, drying and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L reaction kettle, adding 235.5g (1.28mol) of dodecylamine, heating to 130-140 ℃ for reaction for 4 hours, sampling, detecting by a liquid phase, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-11).
1H-NMR(300MHz,DMSO-d6)δ8.44-8.12(m,1H),7.38(d,J＝18Hz,2H),6.50(d,J＝18Hz,2H),4.86(s,1H),3.38(s,1H),3.19(s,4H),1.75-1.72(m,1H),1.49(s,6H),1.25(s,40H),1.05(d,J＝6Hz,3H),0.90(d,J＝6Hz,3H)0.87-0.84(m,10H).
Example 12: 2- (4- (1, 4-dimethyl) pentylamino) aniline-4, 6-bis (dodecylamine) -1,3, 5-triazine (Compound I-12)
(1) Adding 60g of TCT (0.32mol) and 400mL of xylene into a 1L three-neck flask, slowly dripping 72.1g of toluene solution of 4- (1, 4-dimethyl) pentylamino-aniline (0.35mol of 4- (1, 4-dimethyl) pentylamino-aniline dissolved in 80mL of toluene and dripping completed within about 30 min) in a cooling environment at-5 ℃, heating the reaction system to 10 ℃ after dripping, slowly dripping NaOH aqueous solution (13g of NaOH dissolved in 40mL of water and dripping completed within 30 min), continuously stirring for 2 hours after reaction, demixing the reaction system after finishing, separating a water phase, washing an organic phase for three times, adding 6g of anhydrous sodium sulfate, drying and filtering to obtain an intermediate solution;
(2) adding the intermediate solution into a 1L reaction kettle, adding 235.5g (1.28mol) of dodecylamine, heating to 140-150 ℃ for reaction for 4 hours, sampling, detecting by a liquid phase, and cooling when the intermediate cannot be detected; adding NaOH solution (26g is dissolved in 80g of water), stirring until the solid is dissolved, standing for layering, separating out the water phase, washing the organic phase with water for three times, distilling under reduced pressure to evaporate out light components, and cooling and solidifying residual liquid to obtain the target product (the compound I-12).
1H-NMR(300MHz,DMSO-d6)δ8.43-8.10(m,1H),7.40(d,J＝18Hz,2H),6.56(s,2H),6.43(d,J＝18Hz,2H),4.88(s,1H),3.46(s,1H),3.19(s,4H),1.48(s,6H),1.27-1.23(m,44H),1.07(d,J＝6Hz,3H),0.93(d,J＝6Hz,1H),0.87-0.84(m,10H).
Test example:
the mixed sizes of test examples 1-4 were prepared according to the formulations shown in table 1 for application performance testing, comprising the following steps:
1. adding natural rubber SCR5 and synthetic rubber BR into an internal mixer, kneading for a period of time, adding carbon black N550, aromatic oil, zinc oxide, stearic acid and an anti-aging agent (6PPD, compound I-1, compound I-4 or compound I-7), and continuing kneading until the mixture is uniformly mixed; the temperature during kneading is controlled between 150 ℃ and 160 ℃;
2. cooling the whole mixture to below 100 ℃, then adding the crosslinking system (sulphur S and accelerator NS), kneading the whole mixture; controlling the temperature during kneading to not more than 110 ℃;
3. the resulting rubber composition was rolled into a sheet shape (thickness: 2 to 3mm), and vulcanized at a vulcanization temperature of 145 ℃ for 30 minutes.
The sources of the ingredients in table 1 are as follows:
SCR 5: xishuangbanna Mizhongji rubber Limited natural rubber SCR 5;
BR: synthetic rubber BR9000 of Nanjing Yangzi petrochemical rubber Co., Ltd;
n550: carbon black N550 by Cabot corporation;
aromatic oil: general reagents of Shanghai Tantake Technique, Inc.;
stearic acid: stearic Acid (AR), a common reagent of shanghai tatatake technologies ltd;
zinc oxide: zinc oxide (AR), a general agent used by shanghai tatatake technologies gmbh;
and NS: vulcanization accelerator NS of saint ao chemical science and technology ltd;
s: sublimed sulfur (AR) by the chemical agents of the national drug group;
6 PPD: antioxidant SIRANTOX 6PPD of Saint chemical science and technology Limited;
compound I-1: the compound synthesized in example 1;
compound I-4: the compound synthesized in example 4;
compound I-7: example 7 synthetic compound.
Table 1: formulation of rubber composition (unit: parts by mass)
| Formulation of | Test example 1 | Test example 2 | Test example 3 | Test example 4 |
| SCR5 | 50.0 | 50.0 | 50.0 | 50.0 |
| BR | 50.0 | 50.0 | 50.0 | 50.0 |
| N550 | 50.0 | 50.0 | 50.0 | 50.0 |
| Aromatic oil | 5.0 | 5.0 | 5.0 | 5.0 |
| Zinc oxide | 5.0 | 5.0 | 5.0 | 5.0 |
| Stearic acid | 2.0 | 2.0 | 2.0 | 2.0 |
| 6PPD | 2.5 | |||
| Compound I-1 | 2.5 | |||
| Compound I-4 | 2.5 | |||
| Compound I-7 | 2.5 | |||
| NS | 0.8 | 0.8 | 0.8 | 0.8 |
| S | 1.5 | 1.5 | 1.5 | 1.5 |
| Total up to | 166.8 | 166.8 | 166.8 | 166.8 |
The vulcanized rubber sheets of test examples 1 to 4 were evaluated for oxidation resistance and discoloration resistance according to the following methods.
(1) And (3) evaluating the oxidation resistance:
aging the vulcanized rubber sheet in a hot air aging oven at 100 ℃ for 24h and 48h, measuring the tensile strength and the elongation at break before and after aging according to GB/T528-1992 'determination of tensile properties of vulcanized rubber and thermoplastic rubber', and calculating the retention rate of a tensile product (the product of the tensile strength and the elongation at break); according to GB/T529-1999 tear strength determination of vulcanized rubber or thermoplastic rubber, tear strength before and after aging is determined, tear strength retention rate is calculated, and higher retention rate indicates better stability and stronger oxidation resistance. The test results are shown in fig. 1 and 2.
As can be seen from the test results of FIG. 1 and FIG. 2, the tensile product retention after aging for 24h is slightly different, the tensile product retention of test example 2 containing compound I-1 is the highest, and the tensile product retention of other test examples is almost the same; test example 4 containing compound I-7 after 48h aging exhibited the highest tensile product retention; the retention of tear strength after aging for 48h was highest for test example 3 containing compound I-4, which is higher than the other test examples. In a whole view, the antioxidant performance of the novel antioxidant is superior to that of the traditional antioxidant 6 PPD.
(2) Weather aging discoloration performance evaluation:
after the vulcanized film was aged for three weeks in a natural weather environment, the color difference between the film and a blank sample to which no antioxidant was added was measured by a color difference meter CS-10/200/210/220 according to ASTM D1729 (standard method for evaluating color difference of opaque articles), and the evaluation is shown in table 2 and fig. 3, in which L denotes black and white, + denotes white, -denotes black; a represents red and green, + represents red-green; b represents yellow-blue, + represents partial yellow, -represents partial blue; Δ E denotes the total color difference. The test results are shown in table 3.
According to the measured data and the evaluation standard, the total color difference delta E between the test example 1 containing the antioxidant 6PPD and a blank sample is the largest and reaches 11.08, the color difference is very large, and the discoloration resistance is poor; and the absolute value of the total color difference delta E of the three test cases containing the compounds I-1, I-4 and I-7 and a blank sample is very small, is in the range of 0-0.5, belongs to a tiny and acceptable degree, and has strong discoloration resistance. Experimental results show that the novel anti-aging agent has better discoloration resistance than the traditional anti-aging agent 6 PPD.
Table 2: color difference judgment standard
| Δ E range | Chromatic aberration (tolerance) |
| 0～0.25 | Very small or none; ideal match |
| 0.25～0.5 | Micro; acceptableMatching |
| 0.5～1.0 | Small to medium; acceptable in some applications |
| 1.0～2.0 | Medium; acceptable in certain applications |
| 2.0～4.0 | A difference exists; acceptable in certain applications |
| 4.0 or more | Is very large; are unacceptable in most applications |
Table 3: color difference test results
Claims (10)
1. A compound of the formula I:
wherein R is1Is a straight chain or branched chain alkyl of C4-C16, R2Is C3-C10 straight chain or branched chain alkyl, C3-C10 naphthenic base, phenyl or C3-C10 alkyl substituted phenyl.
2. A compound of formula I according to claim 1, wherein R is1Is n-butyl, tert-butyl, n-hexyl, isohexyl, tert-octyl, n-dodecyl, n-tetradecyl or n-hexadecyl.
3. A compound of formula I according to claim 1, wherein R is2Is isopropyl, 1, 3-dimethylbutyl, 1, 4-dimethylpentyl, cyclohexyl or phenyl.
4. A compound of formula I according to claim 1, wherein R is1Is a linear or branched alkyl group of C4-C12, and/or R2Is a branched alkyl group of C3-C7, a naphthenic group of C3-C7 or a phenyl group.
5. The compound of formula I according to claim 1, selected from the group consisting of:
6. a process for the preparation of a compound of formula I according to any one of claims 1 to 5, characterized in that it comprises:
(1) in the presence of alkali liquor, cyanuric chloride is reacted with a compound A shown in the following formula to prepare an intermediate M shown in the following formula:
(2) reacting intermediate M with R1NH2Reacting to obtain the compound shown in the formula I:
wherein R is1And R2The process as claimed in any of claims 1 to 4The term is defined.
7. The method of claim 6, wherein the method has one or more of the following features:
in the reaction system in the step (1), the amount of the substance of the compound A is 100-120% of that of the cyanuric chloride;
the reaction temperature in the step (1) is-5-10 ℃;
in the reaction system of the step (2), R1NH2The amount of the substance (b) is 400 to 480 percent of the amount of the substance of the intermediate M; and
the reaction temperature in the step (2) is 60-150 ℃.
8. A rubber composition, characterized in that it contains a compound of formula I according to any one of claims 1 to 5.
9. A rubber article comprising the rubber composition of claim 8; preferably, the rubber article is a tire.
10. Use of a compound of formula I according to any one of claims 1 to 5 for improving the antioxidant properties and/or the discoloration resistance of a rubber or rubber article; preferably, the rubber article is a tire.
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010886349.5A Pending CN114105895A (en) | 2020-08-28 | 2020-08-28 | Novel p-phenylenediamine compound, preparation method and application thereof |
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| Country | Link |
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| CN (1) | CN114105895A (en) |
| WO (1) | WO2022041528A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115536913B (en) * | 2022-10-12 | 2024-04-16 | 科迈特新材料有限公司 | Heat-resistant and aging-resistant modifier for rubber and preparation method thereof |
| CN115739047A (en) * | 2022-11-18 | 2023-03-07 | 电子科技大学长三角研究院(湖州) | Preparation method and application of nitrogen-rich adsorbent for removing perfluoro and polyfluoroalkyl substances (PFAS) from water |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3334046A (en) * | 1965-07-20 | 1967-08-01 | Geigy Chem Corp | Compositions stabilized with substituted 1, 3, 5-triazines |
| BE793389A (en) * | 1971-12-27 | 1973-06-27 | Degussa | PHENYLENEDIAMINE-S-TRIAZINE COMPOUNDS AND THEIR USE |
| US3928344A (en) * | 1971-12-27 | 1975-12-23 | Degussa | Phenylenediamine-s-triazines |
| DE2360853A1 (en) * | 1973-12-06 | 1975-06-12 | Degussa | Heat- and light-stabilising thermoplastics - with amino- and ether gp-contg. 1,3,5-triazines also contg 4-phenylamino-phenylamine gp |
| JPS51142059A (en) * | 1975-05-23 | 1976-12-07 | Asahi Chem Ind Co Ltd | A stabilized polyurethane elastomer composition |
| IL87542A (en) * | 1987-08-28 | 1993-01-31 | Uniroyal Chem Co Inc | Arylenediamino substituted triazine derivatives, processes for the preparation thereof and compositions containing the same |
-
2020
- 2020-08-28 CN CN202010886349.5A patent/CN114105895A/en active Pending
- 2020-11-27 WO PCT/CN2020/132058 patent/WO2022041528A1/en active Application Filing
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| WO2022041528A1 (en) | 2022-03-03 |
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