Compound having anti-aging and anti-discoloration effects and method for producing same

Abstract

The present invention provides a compound having anti-aging and anti-discoloration effects and a method for preparing the same. The compound has the structure of formula (I) below, where R, R1, and R2 are as defined herein. Compared with existing antioxidant products, the compound of the present invention has longer-lasting anti-aging and anti-discoloration properties and can be used as an antioxidant for rubber products, particularly rubber tires, to prevent aging and deterioration of rubber products or rubber tires caused by light, heat, oxygen, fatigue, etc. during use. TIFF2023501170000038.tif62170

Description

[Technical field]

[0001] The present invention belongs to the field of rubber auxiliary agents, and specifically relates to a compound having anti-aging and anti-discoloration effects and a preparation method thereof. [Background technology]

[0002] At present, p-phenylenediamine compounds are generally used as antioxidants in rubber products, especially tire products, but derivatives such as dialkyl p-phenylenediamine, alkylaryl p-phenylenediamine and diaryl p-phenylenediamine are widely used, including N-(1,3-dimethylbutyl)-N'-phenyl p-phenylenediamine (simply referred to as 6PPD or 4020), N-isopropyl-N'-phenyl p-phenylenediamine (simply referred to as IPPD), N,N'-bis(1,4-dimethylpentyl) p-phenylenediamine (simply referred to as 77PD), diphenyl p-phenylenediamine mixture (simply referred to as antioxidant 3100 or DTPD), etc.

[0003] Existing antioxidant products have a relatively remarkable effect on anti-aging in fields such as tires, but the antioxidant in the rubber product or tire will rapidly migrate to the surface of the rubber product or tire due to its own discoloration during use, further discoloring and damaging the surface of the rubber product or tire; at the same time, due to the rapid migration of the antioxidant to the surface of rubber products such as tires, the content of the antioxidant in the product will be rapidly reduced, and its sustained protective performance will be relatively poor.

[0004] In recent years, with the demand for green and sustainable economic development, users are also paying more attention to issues such as tire aging resistance and surface discoloration, etc. Therefore, it is more urgent to develop an antioxidant with longer-term anti-aging performance and anti-discoloration performance than existing antioxidant products. Summary of the Invention [Problem to be solved by the invention]

[0005] Based on the above problems existing in the prior art, the present invention provides a series of compounds with anti-aging and anti-discoloration effects and their preparation method. The compounds of the present invention have longer-term anti-aging and anti-discoloration performance, and can be used as anti-aging agents for rubber products, especially rubber tires, to prevent the aging and deterioration of rubber products or rubber tires caused by light, heat, oxygen, fatigue, etc. during use. [Means for solving the problem]

[0006] Specifically, the present invention provides a compound represented by formula (I):

[0007] [ka]

[0008] where R is C3-C16 alkyl, C3-C16 alkyl substituted with C3-C10 cycloalkyl, C3-C10 cycloalkyl, or C3-C10 cycloalkyl substituted with C3-C16 alkyl;

[0009] R1 and R2 may be the same or different and are each independently selected from C3-C10 alkyl, C3-C10 cycloalkyl, or C3-C10 alkyl substituted with C6-C14 aryl, C3-C10 cycloalkyl, C3-C10 cycloalkyl substituted with C3-C10 alkyl, C6-C14 aryl, and C6-C14 aryl substituted with C3-C10 alkyl.

[0010] In one or more embodiments, R is a C3-C10 alkyl or a C3-C10 cycloalkyl, preferably a C3-C10 branched alkyl or a C3-C10 cycloalkyl, more preferably isopropyl, tert-butyl, tert-octyl, or cyclohexyl.

[0011] In one or more embodiments, R1 and R2 may be the same or different and are each independently a C3-C10 alkyl or phenyl, preferably each independently a C3-C10 branched alkyl or phenyl, more preferably each independently isopropyl, 1,4-dimethylpentyl, or phenyl.

[0012] In one or more embodiments, the compound is selected from the following:

[0013] [ka]

[0014] [ka]

[0015] [ka]

[0016] [ka]

[0017] The present invention further provides a method of making a compound according to any one of the embodiments of the present invention, the method comprising:

[0018] (1) Cyanuric chloride is reacted with NHR to produce intermediate A represented by the following formula:

[0019] [ka]

[0020] (2) reacting intermediate A with N-R1-p-phenylenediamine to produce intermediate B represented by the following formula:

[0021] [ka]

[0022] (3) reacting intermediate B with N-R2-p-phenylenediamine to produce a compound of formula (I):

[0023] [ka]

[0024] wherein R, R1 and R2 in the compounds of formula A, formula B and formula (I) are as defined in any one of the embodiments of the present invention.

[0025] In one or more embodiments, in the reaction of step (1), an alkaline solid powder is added, and the reaction temperature is 0 to 35° C.;

[0026] In one or more embodiments, in the reaction of step (2), an alkaline solution is added, and the reaction temperature is 50 to 100° C.;

[0027] In one or more embodiments, the reaction temperature in step (3) is 80 to 180°C.

[0028] In one or more embodiments, R1 and R2 are the same, and the above steps (2) and (3) are combined into step (2'): intermediate A is reacted with N-R1-p-phenylenediamine to produce the compound of formula (I).

[0029] In one or more embodiments, an alkaline solution is added to the reaction in step (2'), and the reaction is first carried out at 50-100°C and then at 80-180°C.

[0030] The present invention further provides a rubber composition comprising the compound according to any one of the embodiments of the present invention.

[0031] The present invention further relates to a rubber product produced by using the rubber composition according to any one of the embodiments of the present invention as a rubber component; preferably, the rubber product is a tire.

[0032] The present invention further relates to the use of the compound according to any one of the embodiments of the present invention in improving the anti-aging and / or anti-discoloration performance of rubber or a rubber product; preferably, the rubber product is a tire. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] In order for those skilled in the art to understand the features and advantages of the present invention, only the following general explanations and definitions of the terms and terms referred to in the specification and claims are provided. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art of the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0034] The theories or mechanisms described and disclosed herein, whether true or false, should not limit the scope of the invention in any way; that is, the invention can be practiced without being limited by any particular theory or mechanism.

[0035] All features (e.g., values, amounts, contents, concentrations, etc.) defined herein as numerical or percentage ranges are for brevity and convenience only, and the description of a numerical or percentage range is therefore deemed to specifically disclose and include all the possible subranges and individual numerical values ​​(including integers and fractions) within that range.

[0036] In this specification, in order to simplify the description, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, unless there is a contradiction in the combination of these technical features, various technical features in each embodiment or example can be arbitrarily combined, and all possible combinations should be considered to be within the scope of the description.

[0037] As used herein, alkyl refers to a linear or branched monovalent saturated hydrocarbon group generally containing 1 to 16 carbon atoms (C1-C16 alkyl), preferably 3 to 16 carbon atoms (C3-C16 alkyl).

[0038] Examples of alkyl include, but are not limited to, methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, tert-butyl, 1,4-dimethylpentyl, and tert-octyl. As used herein, alkyl may be optionally substituted with aryl or cycloalkyl, and generally the number of substituents is one. Examples of substituted alkyl include, but are not limited to, cyclohexylmethyl, phenylmethyl, and phenylethyl. As used herein, alkylene refers to a linear or branched divalent saturated hydrocarbon group, generally containing 1 to 16 carbon atoms (C1-C16 alkylene), and preferably containing 3 to 16 carbon atoms (C3-C16 alkylene). Examples of alkylene include, but are not limited to, methylene, ethylene, and 1,3-propylene.

[0039] As used herein, cycloalkyl refers to a monovalent saturated hydrocarbon ring containing 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl. As used herein, cycloalkyl may be optionally substituted with alkyl. The number of substituents may be one or two. Examples of substituted cycloalkyl include, but are not limited to, methylcyclohexyl.

[0040] As used herein, cycloalkylene refers to a divalent saturated hydrocarbon ring containing 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. Examples of cycloalkylene include, but are not limited to, 1,2-cyclopentanediyl and 1,2-cyclohexanediyl.

[0041] As used herein, aryl refers to a monovalent group remaining after removing one hydrogen atom from the aromatic core carbon of an aromatic hydrocarbon molecule. The number of ring carbon atoms of an aryl is usually 6 to 14. Exemplary aryls include phenyl and naphthyl. An aryl may be optionally substituted with alkyl, cycloalkyl, and / or aryl. The number of substituents may be one or two. Exemplary substituted aryls include, but are not limited to, 2-methylphenyl, 4-cyclohexylphenyl, 4-(2-methylcyclohexyl)phenyl, and 4-biphenyl.

[0042] The present invention has found that a compound having the structure shown in formula (I) can provide better weather resistance, durability and color fastness than conventional anti-aging agents, and the specific structure is as follows:

[0043] [ka]

[0044] where R is C3-C16 alkyl, C3-C16 alkyl substituted with C3-C10 cycloalkyl, C3-C10 cycloalkyl, or C3-C10 cycloalkyl substituted with C3-C16 alkyl;

[0045] R1 and R2 may be the same or different and are each independently selected from C3-C10 alkyl, C3-C10 cycloalkyl, or C3-C10 alkyl substituted with C6-C14 aryl, C3-C10 cycloalkyl, C3-C10 cycloalkyl substituted with C3-C10 alkyl, C6-C14 aryl, and C6-C14 aryl substituted with C3-C10 alkyl.

[0046] Preferred R is C3-C10 alkyl or C3-C10 cycloalkyl. In one embodiment, R is C3-C10 alkyl, preferably C3-C10 branched alkyl or C3-C10 cycloalkyl, such as isopropyl, tert-butyl, tert-octyl, or cyclohexyl.

[0047] Preferably, R1 and R2 are each independently C3-C10 alkyl or phenyl. In a preferred embodiment, R1 and R2 are each independently C3-C10 branched alkyl or phenyl. In one embodiment, R1 and R2 are each independently isopropyl, 1,4-dimethylpentyl, or phenyl.

[0048] In certain embodiments, R is tert-butyl or tert-octyl, and R1 and R2 are each independently 1,4-dimethylpentyl or phenyl.

[0049] The compounds of the present invention having the structure shown in formula (I) can be prepared in three steps.

[0050] In the first step, intermediate A is produced using cyanuric chloride (TCT) and NHR as reactants; where R is C3-C16 alkyl, C3-C16 alkyl substituted with C3-C10 cycloalkyl, C3-C10 cycloalkyl, or C3-C10 cycloalkyl substituted with C3-C16 alkyl;

[0051] [ka]

[0052] The second step is to further react intermediate A with N-R1-p-phenylenediamine to produce intermediate B; where R1 is C3-C10 alkyl, C3-C10 cycloalkyl, or C3-C10 alkyl substituted with C6-C14 aryl, C3-C10 cycloalkyl, C3-C10 cycloalkyl substituted with C3-C10 alkyl, C6-C14 aryl, or C6-C14 aryl substituted with C3-C10 alkyl;

[0053] [ka]

[0054] The third step is to further react intermediate B with N-R2-p-phenylenediamine to produce the target product compound of formula (I); where R2 is C3-C10 alkyl, C3-C10 cycloalkyl, or C3-C10 alkyl substituted with C6-C14 aryl, C3-C10 cycloalkyl, C3-C10 cycloalkyl substituted with C3-C10 alkyl, C6-C14 aryl, or C6-C14 aryl substituted with C3-C10 alkyl;

[0055] [ka]

[0056] However, preferred R, R1 and R2 of intermediate A, intermediate B and compound of formula (I) are as described in any one of the embodiments of this specification.

[0057] In the first step, an excess of NHR can be used to improve the conversion of cyanuric chloride. Relative to cyanuric chloride, NHR may have an excess of generally 10% or less. In certain embodiments, the excess of NHR is 8% or less, or 5% or less. In this specification, unless otherwise specified, an excess of a particular substance means that the amount of that substance added is greater than the amount of cyanuric chloride added. In this specification, the excess percentage is expressed based on the amount of substance, for example, when 1 mol of cyanuric chloride is used, an excess of NHR of 10% or less means that 1 mol to 1.1 mol of NHR can be used.

[0058] The first step reaction generally uses an alkaline solid powder as an acid acceptor to neutralize the HCl generated during the reaction process. The alkaline solid powder suitable for the present invention is not particularly limited, and may be, for example, one or more of sodium carbonate, magnesium carbonate, calcium carbonate, calcium oxide, magnesium oxide, magnesium hydroxide, etc. In general, an excess of alkaline solid powder may be added to the first step reaction to better neutralize HCl. The excess value of alkaline solid powder relative to cyanuric chloride is not particularly limited, and may be, for example, an excess of 80% or less.

[0059] The reaction temperature of the first step is generally controlled at 0 to 35°C. The reaction of the first step is generally carried out in a non-polar solvent, for example, toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane, trimethylcyclohexane, etc. The reaction time of the first step can be determined by detecting the progress of the reaction. In this specification, the method of detecting the progress of the reaction may be a method known in the art, for example, gas chromatography (GC) or high performance liquid chromatography (HPLC) to detect whether cyanuric acid chloride has completely reacted. After the reaction, the solid is filtered off to obtain a solution of intermediate A.

[0060] In the second step, an excess of N-R1-p-phenylenediamine can be used to improve the conversion of intermediate A. Relative to cyanuric chloride, N-R1-p-phenylenediamine may generally have an excess of up to 20%. In one embodiment, N-R1-p-phenylenediamine has an excess of up to 10%.

[0061] In the reaction of the second step, generally, an alkaline solution is used as an acid acceptor. In the second step, generally, an excess of an alkaline solution is added, for example, the alkali in the alkaline solution may have an excess of 20% or less or 10% or less relative to cyanuric chloride. The alkaline solution suitable for the present invention is not particularly limited, and may be, for example, one or more of sodium hydroxide solution, potassium hydroxide solution, triethylamine, triisopropylamine, N-isopropyldiethylamine, N,N-diisopropylethylamine, etc. In the present invention, when the alkaline solution is an aqueous solution of inorganic alkali (such as sodium hydroxide solution, potassium hydroxide solution), its concentration is not particularly limited, and is generally 10wt% to 50wt%, and may be, for example, 25wt%.

[0062] The reaction temperature of the second step is generally controlled at 50-100°C. The reaction of the second step is generally carried out in a non-polar solvent, such as toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane, trimethylcyclohexane, etc. The time of the reaction of the second step can be determined by detecting the progress of the reaction, and detecting whether the content of N-R1-p-phenylenediamine continues to decrease by GC or HPLC. After the reaction, the solution of intermediate B is obtained by purification (for example, settling, separating the aqueous phase, or washing with water).

[0063] In the third step, an excess of N-R2-p-phenylenediamine can be used to improve the conversion of intermediate B. Relative to cyanuric chloride, N-R2-p-phenylenediamine may generally have an excess of up to 20%. In one embodiment, N-R2-p-phenylenediamine has an excess of up to 10%.

[0064] The reaction temperature of the third step is generally controlled at 80-180°C. The reaction of the third step is generally carried out in a non-polar solvent, for example, toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane, trimethylcyclohexane, etc. The time of the reaction of the third step can be determined by detecting the progress of the reaction, and detecting whether the content of N-R2-p-phenylenediamine continues to decrease by GC or HPLC. After the reaction is completed, an alkaline solution (such as sodium hydroxide, potassium hydroxide solution, etc.) is added to neutralize and remove HCl. After neutralization, the compound of formula (I) is obtained by purification (for example, separating the aqueous phase, washing the organic phase with water, distilling the organic matter from the solvent to obtain a crude product, and recrystallizing and purifying the crude product, and drying).

[0065] When R1 and R2 of the compound of formula (I) are the same, the second and third steps of the above preparation method may be combined, i.e., intermediate A is reacted with N-R1-p-phenylenediamine to prepare the compound of formula (I).

[0066] In an embodiment in which the second step and the third step are combined (hereinafter referred to as a combined reaction), the amount of N-R1-p-phenylenediamine added in the combined reaction is the sum of the amount of N-R1-p-phenylenediamine added in the second step reaction and the amount of N-R2-p-phenylenediamine added in the third step reaction. The combined reaction is generally carried out in a stepwise temperature control manner, that is, the reaction is first carried out at 50 to 100°C, and then at 80 to 180°C. The timing of switching the reaction temperature can be determined by detecting the progress of the reaction. For example, when it is detected by GC or HPLC that the content of N-R1-p-phenylenediamine has decreased to half the amount added, the temperature is switched from 50 to 100°C to 80 to 180°C. The merging reaction is generally carried out in a non-polar solvent, for example, toluene, xylene, trimethylbenzene, chlorobenzene, methylcyclohexane, dichlorobenzene, trichlorobenzene, dimethylcyclohexane, trimethylcyclohexane, etc. The total time of the merging reaction can be determined by detecting the progress of the reaction, for example, by detecting whether the content of N-R1-p-phenylenediamine continues to decrease by GC or HPLC. The merging reaction is carried out with an alkali solution (for example, one or more of sodium hydroxide solution, potassium hydroxide solution, triethylamine, triisopropylamine, N-isopropyldiethylamine, N,N-diisopropylethylamine, etc.) as an acid acceptor. After the reaction is completed, the compound of formula (I) is obtained by neutralizing with the addition of an alkali solution, removing HCl, and purifying (for example, separating the aqueous phase, washing the organic phase with water, distilling the organic matter from the solvent to obtain a crude product, recrystallizing and purifying the crude product, and drying).

[0067] The compounds of the present invention can provide better anti-aging and anti-discoloration performance to rubber compositions.Therefore, the present invention further provides a rubber composition comprising one or more of the compounds of formula I described herein.Generally, the rubber composition further comprises a diene elastomer, a reinforcing filler and a crosslinking agent.

[0068] Diene elastomer refers to an elastomer whose monomer comprises a diene (e.g., butadiene, isoprene). Diene elastomers suitable for the present invention include, but are not limited to, various diene elastomers known in the art, such as natural rubber (NR), butadiene rubber (BR), isoprene rubber, styrene butadiene rubber (SBR), neoprene rubber (CR), nitrile butadiene rubber (NBR), isoprene / butadiene copolymer, isoprene / styrene copolymer, isoprene / butadiene / styrene copolymer, etc. In one embodiment, in the rubber composition of the present invention, the diene elastomer is composed of natural rubber (e.g., SCR5) and cis-butadiene rubber (e.g., BR9000); the weight ratio of natural rubber and cis-butadiene rubber may be 1:9 to 9:1, for example, 2:8 to 8:2, 3:7 to 7:3, 4:6 to 6:4, or 1:1.

[0069] Typically, the amount of the compound of formula I used in the rubber composition is 0.1 to 5 parts by mass, for example, 1 to 5 parts by mass, 1.5 to 3.5 parts by mass, or 2 to 3 parts by mass, based on 100 parts by mass of the diene elastomer.

[0070] The rubber composition may also contain other commonly used ingredients such as, but not limited to, reinforcing fillers, auxiliaries, crosslinking agents, accelerators, etc. In the present invention, the amounts of reinforcing fillers, auxiliaries, crosslinking agents and accelerators used may be those amounts commonly used in the art.

[0071] The reinforcing filler may be carbon black, titanium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, etc. Generally, 40 to 60 parts by weight of reinforcing filler is used per 100 parts by weight of diene elastomer.

[0072] The auxiliary is, for example, a softener used to improve processability. The softener may be a petroleum-based softener such as aromatic oil, processing oil, lubricating oil, paraffin, liquid paraffin, petroleum bitumen, petrolatum, or a fatty oil-based softener such as castor oil, linseed oil, rapeseed oil, coconut oil, wax (such as beeswax, carnauba wax, lanolin, etc.), tall oil, linoleic acid, palmitic acid, stearic acid, lauric acid, etc. The auxiliary may also be an activator such as zinc oxide, which can accelerate the vulcanization rate and improve the thermal conductivity, wear resistance, tear resistance, etc. of the rubber. Usually, 5 to 20 parts by weight of the auxiliary is used per 100 parts by weight of the diene elastomer, for example, 2 to 8 parts by weight of aromatic oil, 2 to 8 parts by weight of zinc oxide, and 1 to 4 parts by weight of stearic acid are used.

[0073] The crosslinking agent may be sulfur. Generally, 1 to 3 parts by weight of crosslinking agent is used per 100 parts by weight of diene elastomer.

[0074] The accelerator is typically a vulcanization accelerator and may be at least one of sulfonamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldamine, aldehydeamine, imidazoline, and xanthate vulcanization accelerators. For example, the accelerator may be accelerator NS (N-tert-butyl-2-benzothiazole sulfenamide). Typically, 0.5 to 1.5 parts by weight of the accelerator are used per 100 parts by weight of the diene elastomer.

[0075] Furthermore, if necessary, a plasticizer such as DMP (dimethyl phthalate), DEP (diethyl phthalate), DBP (dibutyl phthalate), DHP (diheptyl phthalate), DOP (dioctyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BBP (butyl benzyl phthalate), DWP (dilauryl phthalate), DCHP (dicyclohexyl phthalate), etc. may be used in the rubber composition. The amount of the plasticizer used is the amount normally used in this field.

[0076] The rubber product of the present invention can be prepared by a conventional method, for example, by a two-stage mixing method, in which the diene elastomer, reinforcing filler, auxiliary agent, and antioxidant are mixed in an internal mixer in the first stage, and the discharge temperature is above 110°C;

[0077] Usually, first, a diene elastomer is added to a thermomechanical mixer (such as an internal mixer), and after a certain period of kneading, a reinforcing filler, an auxiliary agent, and an antioxidant are added, and kneading is continued until uniform; the reinforcing filler, the auxiliary agent, and the antioxidant are added in batches, and the temperature during kneading is controlled to 110°C to 190°C, preferably 150°C to 160°C; then, the mixture is cooled to below 100°C, a crosslinking agent and an accelerator are added and mixed again, and while kneading, the temperature is controlled to 110°C or less (such as 70°C), and finally, vulcanization is performed to obtain a vulcanized rubber. Optionally, the resulting rubber composition is tableted before vulcanization. The vulcanized rubber composition is vulcanized by a conventional method to obtain a vulcanized rubber; the vulcanization (curing) temperature is usually 130°C to 200°C, for example 145°C; the vulcanization time varies depending on the vulcanization temperature, vulcanization system, and vulcanization speed, and is usually 15 to 60 minutes, for example 30 minutes.

[0078] When the compound of the present invention is used in a rubber product, particularly a rubber tire, it can provide the rubber product or rubber tire with better anti-aging properties; and compared with existing anti-aging products, the rubber product or rubber tire containing the compound of the present invention has less surface contamination and discoloration, and has excellent discoloration resistance. Therefore, the present invention further provides a rubber product obtained by adopting the rubber composition described in the present invention as a rubber component and manufacturing it. The rubber product may be a tire, a rubber shoe, a weather strip, an insulation board, a shock pad, etc. In a specific embodiment, the rubber product is a tire, for example, a tire tread, a belt layer, and a sidewall. In addition to the rubber composition described herein as the belt layer of the tire, the rubber product may include a reinforcing material conventionally used in the art. The present invention further provides the application of the rubber composition described herein in improving the anti-aging performance and / or anti-discoloration performance of rubber or rubber products. EXAMPLES

[0079] The present invention will be described below with reference to specific examples. It should be understood that these examples are merely illustrative and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are conventional methods, reagents and materials in the art unless otherwise specified. The raw material compounds in the preparation examples can be purchased from commercial sources.

[0080] Preparation Example 1: Preparation of 2-isopropylamine-4,6-di(4-aminophenylaniline)-1,3,5-triazine (Compound I-1)

[0081] (1) Synthesis of intermediate A1 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g toluene, add 74.2g sodium carbonate solid powder, add 39.6g isopropylamine toluene solution (0.67mol isopropylamine+80g toluene) dropwise for 1.5h under vigorous stirring condition at 10℃, react for 1.5h after completion, take a sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out the solid, and obtain a colorless transparent solution of intermediate A1.

[0082] (2) Synthesis of intermediate B11 142.6g N-phenyl-p-phenylenediamine (0.77mol) was weighed and dissolved in 180g toluene. The temperature was raised to 65℃, and while vigorously stirring, the toluene solution of intermediate A1 obtained in step (1) was dropped. At the same time, 112.6g sodium hydroxide solution (25wt%) was dropped for 1-2h. The mixture was kept warm for 1h, and a sample was taken for GC detection. When the content of N-phenyl-p-phenylenediamine did not decrease, the reaction was stopped, the mixture was left to stand, and the aqueous phase was separated to obtain a toluene solution containing intermediate B11.

[0083] (3) Synthesis of Compound I-1 132.5g N-phenyl-p-phenylenediamine (0.72mol) was added to the toluene solution of intermediate B11 obtained in step (2), and the temperature was raised to 80°C, and the reaction was carried out. Detection was performed by GC. When the content of N-phenyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g of sodium hydroxide solution (25wt%) was added for neutralization, the aqueous phase was separated, and the organic phase was washed with water, and then the toluene was distilled to obtain a crude product. After that, it was recrystallized with petroleum ether and dried to obtain 289.2g (yield 90%) of 2-isopropylamine-4,6-di(4-aminophenylaniline)-1,3,5-triazine (compound I-1).

[0084] [ka]

[0085] Characteristics of compound I-1: blue solid. 1 H-HMR(400MHz, DMSO-D6, δ ppm):8.71(s, 2H), 7.93(s, 2H), 7.64(br, 4H), 7.17(t, 4H), 6.99(q, 8H), 6.73(t, 2H), 6.31(s, 1H), 3.4(s, 1H), 1.41(s, 6H).

[0086] Preparation Example 2: Preparation of 2-isopropylamine-4,6-di(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (Compound I-2)

[0087] (1) Synthesis of intermediate A1 Weigh out 118.1g cyanuric acid chloride (0.64mol) and dissolve it in 360g xylene. Add 71.2g ultrafine calcium carbonate solid powder. Under vigorous stirring at 10℃, add 38.4g isopropylamine xylene solution (0.65mol isopropylamine+80g xylene) dropwise for 1.5h. After the dropwise addition is completed, react for 1.5h. Take a sample for GC detection. When cyanuric acid chloride can no longer be detected, the reaction is terminated and the solid is filtered off to obtain a colorless transparent solution of intermediate A1.

[0088] (2) Synthesis of intermediate B12 152.4g N-1,4-dimethylpentyl-p-phenylenediamine (0.74mol) was weighed, dissolved in 180g xylene, heated to 70℃, and stirred vigorously while dropping the xylene solution of intermediate A1 obtained in step (1). At the same time, 157.6g potassium hydroxide solution (25wt%) was dropped for 1-2h, kept warm for 1h, and a sample was taken for GC detection. When the content of N-1,4-dimethylpentyl-p-phenylenediamine did not decrease, the reaction was stopped, the mixture was left to stand, and the aqueous phase was separated to obtain a xylene solution containing intermediate B12.

[0089] (3) Synthesis of Compound I-2 152.5g N-1,4-dimethylpentyl-p-phenylenediamine (0.74mol) was added to the xylene solution of intermediate B12 obtained in step (2), and the temperature was raised to 110°C, and the reaction was carried out. Detection was performed by GC. When the content of N-1,4-dimethylpentyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g of sodium hydroxide solution (25wt%) was added for neutralization, and the organic phase was washed with water, and then xylene was distilled to obtain a crude product. Then, the product was recrystallized with petroleum ether and dried to obtain 283g (yield 81%) of 2-isopropylamine-4,6-di(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (compound I-2).

[0090] [ka]

[0091] Characteristics of compound I-2: Purple-brown solid. 1 H-HMR(400MHz, DMSO-D6, δ ppm):8.39(s, 2H), 7.32(d, 4H), 6.48(d, 4H), 6.09(S, 1H), 4.92(t, 3H), 3.31-3.21(m, 2H), 1.56-1.43(m, 4H), 1.42-1.13(m, 12H), 1.06(d, 6H), 0.85(q, 12H).

[0092] Preparation Example 3: Preparation of 2-tert-butylamine-4,6-di(4-aminophenylaniline)-1,3,5-triazine (Compound I-3)

[0093] (1) Synthesis of intermediate A2 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g trimethylbenzene, add 71.2g ultrafine magnesium carbonate solid powder, add 49.1g tert-butylamine trimethylbenzene solution (0.67mol tert-butylamine + 80g toluene) dropwise for 1.5h under vigorous stirring at 15℃, react for 1.5h after completion of dropwise addition, take a sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out the solid, and obtain a colorless transparent solution of intermediate A2.

[0094] (2) Synthesis of intermediate B21 Weigh out 131.5g N-phenyl-p-phenylenediamine (0.71mol) and dissolve it in 180g trimethylbenzene. Heat the mixture to 65℃, and add dropwise the trimethylbenzene solution of intermediate A2 obtained in step (1) while stirring vigorously. At the same time, add dropwise 71.1g triethylamine for 1-2 hours, keep warm for 1 hour, and take a sample for GC detection. When the content of N-phenyl-p-phenylenediamine stops decreasing, stop the reaction and wash with water to obtain a trimethylbenzene solution containing intermediate B21.

[0095] (3) Synthesis of Compound I-3 In the trimethylbenzene solution of intermediate B21 obtained in step (2), 123.3g N-phenyl-p-phenylenediamine (0.67mol) was added, the temperature was raised to 105℃, the reaction was carried out, and detection was carried out by GC. When the content of N-phenyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, 71.1g triethylamine was added for neutralization and washed with water, and then trimethylbenzene was distilled to obtain a crude product. Then, the product was recrystallized with petroleum ether and dried to obtain 280g (yield 85%) of 2-tert-butylamine-4,6-di(4-aminophenylaniline)-1,3,5-triazine (compound I-3).

[0096] [ka]

[0097] Characteristics of compound I-3: dark blue solid. 1 H-NMR (400MHz, DMSO-D6, δ PPm):8.71(s, 2H), 7.93(s, 2H), 7.64(br, 4H), 7.17(t, 4H), 6.99(q, 8H), 6.73(t, 2H), 6.31(s, 1H), 1.41(s, 9H).

[0098] Preparation Example 4: Preparation of 2-tert-butylamine-4,6-di(4-isopropylamineaniline)-1,3,5-triazine (compound I-4)

[0099] (1) Synthesis of intermediate A2 Weigh out 118.1g cyanuric acid chloride (0.64mol) and dissolve it in 360g chlorobenzene. Add 64g calcium oxide solid powder. Under vigorous stirring at 15℃, add 49.1g tert-butylamine toluene solution (0.67mol tert-butylamine + 80g chlorobenzene) dropwise for 1.5h. After the dropwise addition is completed, react for 1.5h. Take a sample for GC detection. When cyanuric acid chloride can no longer be detected, the reaction is terminated and the solid is filtered off to obtain a colorless transparent solution of intermediate A2.

[0100] (2) Synthesis of intermediate B22 Weigh out 105g N-isopropyl-p-phenylenediamine (0.7mol) and dissolve it in 180g chlorobenzene. Heat the mixture to 60℃, and add the chlorobenzene solution of intermediate A2 obtained in step (1) dropwise while stirring vigorously. At the same time, add 100.5g triisopropylamine dropwise for 1-2 hours. Keep the mixture warm for 1 hour, and take a sample for GC detection. When the content of N-isopropyl-p-phenylenediamine stops decreasing, stop the reaction and wash with water to obtain a chlorobenzene solution containing intermediate B22.

[0101] (3) Synthesis of compound I-4 In the chlorobenzene solution of intermediate B22 obtained in step (2), 114g N-isopropyl-p-phenylenediamine (0.76mol) was added, the temperature was raised to 80℃, the reaction was carried out, and detection was performed by GC. When the content of N-isopropyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g sodium hydroxide solution (25wt%) was added for neutralization, the organic phase was washed with water, and then chlorobenzene was distilled to obtain a crude product. Then, the product was recrystallized with petroleum ether and dried to obtain 258g (yield 90%) of 2-tert-butylamine-4,6-di(4-isopropylamineaniline)-1,3,5-triazine (compound I-4).

[0102] [ka]

[0103] Characteristics of compound I-4: purple-brown solid. 1 H-HMR(400MHz, DMSO- D6, δ ppm):8.29(s, 2H), 7.33(d, 4H), 6.44(d, 4H), 6.02(S, 1H), 4.92(d, 2H), 3.4(d, 2H), 1.42-1.13(m, 9H), 0.85(q, 12H).

[0104] Example 5: 2-tert-butylamine-4,6-di(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (Compound I-5)

[0105] (1) Synthesis of intermediate A2 Weigh out 118.1g cyanuric acid chloride (0.64mol) and dissolve it in 360g dichlorobenzene. Add 38.4g ultrafine magnesium oxide solid powder. Under vigorous stirring at 20℃, add 51.3g tert-butylamine dichlorobenzene solution (0.7mol tert-butylamine+80g dichlorobenzene) dropwise for 1.5h. After the dropwise addition is completed, react for 1.5h. Take a sample for GC detection. When cyanuric acid chloride can no longer be detected, the reaction is terminated and the solid is filtered off to obtain a colorless transparent solution of intermediate A2.

[0106] (2) Synthesis of intermediate B23 144.2g N-1,4-dimethylpentyl-p-phenylenediamine (0.7mol) was weighed, dissolved in 180g dichlorobenzene, heated to 70℃, and stirred vigorously while dropping the dichlorobenzene solution of intermediate A2 obtained in step (1). At the same time, 157.6g potassium hydroxide solution (25wt%) was dropped for 1-2h, kept warm for 1h, and a sample was taken for GC detection. When the content of N-1,4-dimethylpentyl-p-phenylenediamine did not decrease, the reaction was stopped, and the aqueous phase was separated to obtain a dichlorobenzene solution containing intermediate B23.

[0107] (3) Synthesis of Compound I-5 148.4g N-1,4-dimethylpentyl-p-phenylenediamine (0.72mol) was added to the dichlorobenzene solution of intermediate B23 obtained in step (2), and the temperature was raised to 150℃, and the reaction was carried out. Detection was performed by GC. When the content of N-1,4-dimethylpentyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g sodium hydroxide solution (25wt%) was added for neutralization to obtain a crude product. Then, the product was recrystallized with petroleum ether and dried to obtain 286.7g (yield 80%) of 2-tert-butylamine-4,6-di(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (compound I-5).

[0108] [ka]

[0109] Characteristics of compound I-5: deep purple solid. 1 H-NMR(400MHz, DMSO-D6, δ ppm):8.29(s, 2H), 7.33(d, 4H), 6.44(d, 4H), 6.02(S, 1H), 4.92(d, 2H), 3.31-3.21(m, 2H), 1.56-1.43(m, 4H), 1.42-1.13(m, 15H), 1.06(d, 6H), 0.85(q, 12H).

[0110] Preparation Example 6: 2-tert-butylamine-4-(4-aminophenylaniline)-6-(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (Compound I-6)

[0111] (1) Synthesis of intermediate A2 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g methylcyclohexane, add 71.2g ultrafine magnesium hydroxide solid powder, add 49.1g tert-butylamine in methylcyclohexane (0.67mol tert-butylamine + 80g methylcyclohexane) dropwise for 1.5h under vigorous stirring at 20℃, react for 1.5h after completion of dropwise addition, take a sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out the solid, and obtain a colorless transparent solution of intermediate A2.

[0112] (2) Synthesis of intermediate B21 Weigh out 124.0g N-phenyl-p-phenylenediamine (0.67mol) and dissolve it in 180g methylcyclohexane. Heat the mixture to 50℃, and add the methylcyclohexane solution of intermediate A2 obtained in step (1) dropwise while stirring vigorously. At the same time, add 157.6g potassium hydroxide solution (25wt%) dropwise for 1-2h. Keep the mixture warm for 1h, and take a sample for GC detection. When the content of N-phenyl-p-phenylenediamine stops decreasing, stop the reaction and wash with water to obtain a methylcyclohexane solution containing intermediate B21.

[0113] (3) Synthesis of Compound I-6 131.9g N-1,4-dimethylpentyl-p-phenylenediamine (0.64mol) was added to the methylcyclohexane solution of intermediate B21 obtained in step (2), and the temperature was raised to 160°C, and the reaction was carried out. Detection was performed by GC. When the content of N-1,4-dimethylpentyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g sodium hydroxide (25wt%) was added for neutralization, and the mixture was washed with water. Then, the methylcyclohexane was distilled to obtain a crude product. Then, the product was recrystallized with petroleum ether and dried to obtain 261.7g (yield 76%) of 2-tert-butylamine-4-(4-aminophenylaniline)-6-(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (compound I-6).

[0114] [ka]

[0115] Characteristics of compound I-6: deep purple solid. 1H-NMR(400MHz, DMSO-D6, δPPm):8.56(d, 2H), 7.90(s, 1H), 7.68(d, 2H), 7.39(d, 2H), 7.21(t, 2H), 7.02(t, 4H), 6.79(t, 1H), 6.52(d, 2H), 6.22(s, 1H), 5.0(d, 1H), 3.37(m, 1H), 1.6-1.45(m, 2H), 1.43(s, 9H), 1.31-1.18(m, 3H), 1.11(d, 3H), 0.89(q, 6H).

[0116] Example 7: 2-tert-octylamine-4,6-di(4-aminophenylaniline)-1,3,5-triazine (compound I-7)

[0117] (1) Synthesis of intermediate A3 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g trichlorobenzene, add 71.2g sodium carbonate solid powder, add 86.5g tert-octylamine trichlorobenzene solution (0.67mol tert-octylamine + 80g trichlorobenzene) dropwise for 1.5h under vigorous stirring condition at 30℃, react for 1.5h after dropping, take sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out solid, obtain colorless transparent solution of intermediate A3.

[0118] (2) Synthesis of intermediate B31 129.6g N-phenyl-p-phenylenediamine (0.7mol) was weighed and dissolved in 180g trichlorobenzene. The temperature was raised to 70℃, and the trichlorobenzene solution of intermediate A3 obtained in step (1) was dropped into the solution while vigorously stirring. At the same time, 157.6g potassium hydroxide (25wt%) was dropped into the solution for 1-2h, and the solution was kept warm for 1h. A sample was taken for GC detection. When the content of N-phenyl-p-phenylenediamine did not decrease, the reaction was stopped and the solution was left to stand. The aqueous phase was separated to obtain a trichlorobenzene solution containing intermediate B31.

[0119] (3) Synthesis of compound I-7 The trichlorobenzene solution of intermediate B31 obtained in step (2) was added with 136.2g N-phenyl-p-phenylenediamine (0.74mol), heated to 105℃, reacted, and detected by GC. When the content of N-phenyl-p-phenylenediamine did not decrease, cooled to stop the reaction, added 112.6g sodium hydroxide solution (25wt%) for neutralization, separated the aqueous phase, and distilled trichlorobenzene in the organic phase to obtain a crude product. Then, recrystallized with petroleum ether and dried to obtain 322.1g (yield 88%) 2-tert-octylamine-4,6-di(4-aminophenylaniline)-1,3,5-triazine (compound I-7).

[0120] [ka]

[0121] Characteristics of compound I-7: Blue-brown solid. 1 H-NMR(400MHz, DMSO-D6, δ ppm):8.6(d, 2H), 7.95(s, 2H), 7.63(s, 4H), 7.16(t, 4H), 6.99(q, 8H), 6.72(t, 2H), 6.17(br, 1H), 1.9(s, 2H), 1.42(s, 6H), 0.96(s, 9H).

[0122] Example 8: 2-tert-octylamine-4,6-di(4-isopropylamineaniline)-1,3,5-triazine (compound I-8)

[0123] (1) Synthesis of intermediate A3 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g dimethylcyclohexane, add 71.2g ultrafine sodium carbonate solid powder, add 86.5g tert-octylamine dimethylcyclohexane solution (0.67mol tert-octylamine + 80g dimethylcyclohexane) dropwise for 1.5h under vigorous stirring at 30℃, react for 1.5h after completion of dropwise addition, take a sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out the solid, and obtain a colorless transparent solution of intermediate A3.

[0124] (2) Synthesis of intermediate B32 105g N-isopropyl-p-phenylenediamine (0.7mol) was weighed and dissolved in 180g dimethylcyclohexane. The temperature was raised to 65℃, and while vigorously stirring, the dimethylcyclohexane solution of intermediate A3 obtained in step (1) was dropped. At the same time, 112.6g sodium hydroxide solution (25wt%) was dropped for 1-2h. The mixture was kept warm for 1h, and a sample was taken for GC detection. When the content of N-phenyl-p-phenylenediamine did not decrease, the reaction was stopped, the mixture was left to stand, and the aqueous phase was separated to obtain a dimethylcyclohexane solution containing intermediate B32.

[0125] (3) Synthesis of compound I-8 108g N-isopropyl-p-phenylenediamine (0.72mol) was added to the dimethylcyclohexane solution of intermediate B32 obtained in step (2), and the temperature was raised to 90°C, and the reaction was carried out. Detection was performed by GC. When the content of N-isopropyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g sodium hydroxide solution (25wt%) was added for neutralization, and the organic phase was washed with water, and then dimethylcyclohexane was distilled to obtain a crude product. Then, the product was recrystallized with petroleum ether and dried to obtain 293.5g (yield 91%) of 2-tert-octylamine-4,6-di(4-isopropylamineaniline)-1,3,5-triazine (compound I-8).

[0126] [ka]

[0127] Characteristics of compound I-8: Purple-brown solid. 1 H-HMR(400MHz, DMSO-D6, δ ppm):8.29(s, 2H), 7.33(d, 4H), 6.44(d, 4H), 6.02(S, 1H), 4.92(d, 2H), 3.4(d, 2H), 1.9(s, 2H), 1.42-1.13(m, 18H), 0.96(s, 9H).

[0128] Example 9: 2-tert-octylamine-4-(4-aminophenylaniline)-6-(4-isopropylamineaniline)-1,3,5-triazine (Compound I-9)

[0129] (1) Synthesis of intermediate A3 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g trimethylcyclohexane, add 71.2g sodium carbonate solid powder, add 86.5g tert-octylamine trimethylcyclohexane solution (0.67mol tert-octylamine + 80g trimethylcyclohexane) dropwise for 1.5h under vigorous stirring at 35℃, react for 1.5h after completion of dropwise addition, take a sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out the solid, and obtain a colorless transparent solution of intermediate A3.

[0130] (2) Synthesis of intermediate B31 129.6g N-phenyl-p-phenylenediamine (0.7mol) was weighed and dissolved in 180g trimethylcyclohexane. The temperature was raised to 70℃, and while vigorously stirring, the trimethylcyclohexane solution of intermediate A3 obtained in step (1) was dropped. At the same time, 157.6g potassium hydroxide (25wt%) was dropped for 1-2h, and the mixture was kept warm for 1h. A sample was taken for GC detection. When the content of N-phenyl-p-phenylenediamine did not decrease, the reaction was stopped, the mixture was left to stand, and the aqueous phase was separated to obtain a trimethylcyclohexane solution containing intermediate B31.

[0131] (3) Synthesis of compound I-9 The trimethylcyclohexa solution of intermediate B31 obtained in step (2) was added with 105g N-isopropyl-p-phenylenediamine (0.7mol), heated to 100℃, reacted, and detected by GC. When the content of N-isopropyl-p-phenylenediamine did not decrease, cooled to stop the reaction, added 112.6g sodium hydroxide solution (25wt%) for neutralization, washed the organic phase with water, and then distilled trimethylcyclohexane to obtain a crude product. Then, recrystallized with petroleum ether and dried to obtain 296.7g (yield 85%) 2-tert-octylamine-4-(4-aminophenylaniline)-6-(4-isopropylamineaniline)-1,3,5-triazine (compound I-9).

[0132] [ka]

[0133] Characteristics of compound I-9: Purple-brown solid. 1H-HMR(400MHz, DMSO-D6, δ ppm):8.47(q, 2H), 7.93(s, 1H), 7.6(s, 2H), 7.38(s, 2H), 7.17(t, 2H), 6.9(t, 4H), 6.77(t, 1H), 6.45(d, 2H), 6.14(d, 1H), 4.95(d, 1H), 3.29(m, 1H), 1.50(m, 2H), 1.41-1.31(m, 12H), 0.95(s, 9H).

[0134] Example 10: 2-tert-octylamine-4-(4-aminophenylaniline)-6-(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (Compound I-10)

[0135] (1) Synthesis of intermediate A3 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g xylene, add 71.2g sodium carbonate solid powder, add 86.5g tert-octylamine xylene solution (0.67mol tert-octylamine + 80g xylene) dropwise for 1.5h under vigorous stirring at 35℃, react for 1.5h after completion of dropwise addition, take a sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out the solid, and obtain a colorless transparent solution of intermediate A3.

[0136] (2) Synthesis of intermediate B31 129.6g N-phenyl-p-phenylenediamine (0.7mol) was weighed and dissolved in 180g xylene. The temperature was raised to 80℃, and while vigorously stirring, the xylene solution of intermediate A3 obtained in step (1) was dropped. At the same time, 157.6g potassium hydroxide (25wt%) was dropped for 1-2h, and the mixture was kept warm for 1h. A sample was taken for HPLC detection. If intermediate A3 was not detected, the reaction was stopped and the sample was washed with water to obtain a xylene solution containing intermediate B31.

[0137] (3) Synthesis of compound I-10 131.9g N-1,4-dimethylpentyl-p-phenylenediamine (0.64mol) was added to the xylene solution of intermediate B31 obtained in step (2), and the temperature was raised to 110°C, and the reaction was carried out. Detection was performed by GC. When the content of N-1,4-dimethylpentyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g of sodium hydroxide solution (25wt%) was added for neutralization, and the mixture was washed with water, and the xylene was distilled to obtain a crude product. Then, the mixture was recrystallized with petroleum ether and dried to obtain 288.9g (yield 76%) of 2-tert-octylamine-4-(4-aminophenylaniline)-6-(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (compound I-10).

[0138] [ka]

[0139] Characteristics of compound I-10: deep purple solid. 1 H-NMR(400MHz, DMSO-D6, δ ppm): 8.49(q, 2H), 7.91(s, 1H), 7.64(s, 2H), 7.34(s, 2H), 7.17(t, 2H), 6.98(t, 4H), 6.73(t, 1H), 6.48(d, 2H), 6.04(d, 1H), 4.95(d, 1H), 3.29(m, 1H), 1.89(s, 1H), 1.50(m, 2H), 1.40(s, 6H), 1.31-1.18(m, 4H), 1.07(d, 3H), 0.95(s, 9H), 0.86(q, 6H).

[0140] Example 11: 2-tert-octylamine-4-(4-isopropylamineaniline)-6-(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (Compound I-11)

[0141] (1) Synthesis of intermediate A3 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g xylene, add 71.2g sodium carbonate solid powder, add 86.5g tert-octylamine xylene solution (0.67mol tert-octylamine + 80g xylene) dropwise for 1.5h under vigorous stirring at 35℃, react for 1.5h after completion of dropwise addition, take a sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out the solid, and obtain a colorless transparent solution of intermediate A3.

[0142] (2) Synthesis of intermediate B32 105g N-isopropyl-p-phenylenediamine (0.7mol) was weighed and dissolved in 180g xylene. The temperature was raised to 65℃, and while vigorously stirring, the xylene solution of intermediate A3 obtained in step (1) was dropped. At the same time, 112.6g sodium hydroxide solution (25wt%) was dropped for 1-2h. The mixture was kept warm for 1h, and a sample was taken for GC detection. If intermediate A3 was not detected, the reaction was stopped and the mixture was left to stand, and the aqueous phase was separated to obtain a xylene solution containing intermediate B32.

[0143] (3) Synthesis of Compound I-11 144.2g N-1,4-dimethylpentyl-p-phenylenediamine (0.7mol) was added to the xylene solution of intermediate B33 obtained in step (2), and the temperature was raised to 120 ° C., and the reaction was carried out, and detection was performed by GC. When the content of N-1,4-dimethylpentyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g of sodium hydroxide solution (25wt%) was added for neutralization, and the organic phase was washed with water, and xylene was distilled to obtain a crude product. Then, it was recrystallized with petroleum ether and dried to obtain 286.7g (yield 80%) 2-tert-octylamine-4-(4-isopropylamineaniline)-6-(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (compound I-11).

[0144] [ka]

[0145] Characteristics of compound I-11: Purple-brown viscous solid. 1 H-HMR(400MHz, DMSO-D6, δ ppm):8.32(d, 2H), 7.39(s, 4H), 6.49(d, 4H), 6.04(br, 1H), 4.99(t, 3H), 3.21-3.32(m, 2H), 1.36-1.15(m, 15H), 1.08-1.13(d, 6H), 1.02(s, 9H), 0.91(q, 6H).

[0146] Example 12: 2-tert-octylamine-4,6-di(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (Compound I-12)

[0147] (1) Synthesis of intermediate A3 Weigh out 118.1g cyanuric acid chloride (0.64mol), dissolve in 360g xylene, add 71.2g sodium carbonate solid powder, add 86.5g tert-octylamine xylene solution (0.67mol tert-octylamine + 80g xylene) dropwise for 1.5h under vigorous stirring at 25℃, react for 1.5h after completion of dropwise addition, take a sample for GC detection, when cyanuric acid chloride can no longer be detected, end the reaction, filter out the solid, and obtain a colorless transparent solution of intermediate A3.

[0148] (2) Synthesis of intermediate B33 144.2g N-1,4-dimethylpentyl-p-phenylenediamine (0.7mol) was weighed and dissolved in 180g xylene. The temperature was raised to 90℃, and while vigorously stirring, the xylene solution of intermediate A3 obtained in step (1) was dropped. At the same time, 112.6g sodium hydroxide solution (25wt%) was dropped for 1-2h. The mixture was kept warm for 1h, and a sample was taken for GC detection. If intermediate A3 was not detected, the reaction was stopped and the mixture was left to stand, and the aqueous phase was separated to obtain a xylene solution containing intermediate B33.

[0149] (3) Synthesis of compound I-12 152.4g N-1,4-dimethylpentyl-p-phenylenediamine (0.74mol) was added to the xylene solution of intermediate B33 obtained in step (2), and the temperature was raised to 180°C, and the reaction was carried out. Detection was performed by GC. When the content of N-1,4-dimethylpentyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g of sodium hydroxide solution (25wt%) was added for neutralization, and the organic phase was washed with water, and xylene was distilled to obtain a crude product. Then, the product was recrystallized with petroleum ether and dried to obtain 295.6g (yield 75%) of 2-tert-octylamine-4,6-di(4-(1,4-dimethylpentylamino)aniline)-1,3,5-triazine (compound I-12).

[0150] [ka]

[0151] Properties of compound I-12: Deep purple viscous liquid. 1 H-NMR(400MHz, DMSO-D6, δ ppm):8.30(d, 2H), 7.38(s, 4H), 6.51(d, 4H), 5.94(br, 1H), 4.99(d, 2H), 3.21-3.32(m, 2H), 1.91(s, 2H), 1.58-1.44(m, 4H), 1.38(s, 6H), 1.36-1.15(m, 6H), 1.08-1.13(d, 6H), 0.99(s, 9H), 0.91(q, 12H).

[0152] Example 13: 2-Cyclohexylamine-4,6-di(4-aminophenylaniline)-1,3,5-triazine (Compound I-13)

[0153] (1) Synthesis of intermediate A4 Weigh out 118.1g cyanuric acid chloride (0.64mol) and dissolve it in 360g toluene. Add 71.2g sodium carbonate solid powder. Under vigorous stirring at 25℃, add 66.4g cyclohexylamine toluene solution (0.67mol cyclohexylamine+80g toluene) dropwise for 1.5h. After the dropwise addition is completed, react for 1.5h. Take a sample for GC detection. When cyanuric acid chloride can no longer be detected, the reaction is terminated and the solid is filtered off to obtain a colorless transparent solution of intermediate A4.

[0154] (2) Synthesis of intermediate B43 128.8g N-phenyl-p-phenylenediamine (0.7mol) was weighed and dissolved in 180g toluene. The temperature was raised to 100℃, and while vigorously stirring, the toluene solution of intermediate A4 obtained in step (1) was dropped. At the same time, 112.6g sodium hydroxide solution (25wt%) was dropped for 1-2h. The mixture was kept warm for 1h, and a sample was taken for GC detection. If intermediate A4 was not detected, the reaction was stopped and the mixture was left to stand, and the aqueous phase was separated to obtain a toluene solution containing intermediate B43.

[0155] (3) Synthesis of compound I-13 132.5g N-phenyl-p-phenylenediamine (0.72mol) was added to the toluene solution of intermediate B43 obtained in step (2), and the temperature was raised to 140°C, and the reaction was carried out. Detection was performed by GC. When the content of N-phenyl-p-phenylenediamine did not decrease, the reaction was stopped by cooling, and 112.6g of sodium hydroxide solution (25wt%) was added for neutralization, and the organic phase was washed with water, and then toluene was distilled to obtain a crude product. Then, the product was recrystallized with petroleum ether and dried to obtain 277.5g (yield 80%) of 2-cyclohexylamine-4,6-di(4-aminophenylaniline)-1,3-5-triazine (compound I-13).

[0156] [ka]

[0157] Characteristics of compound I-13: Dark brown solid. 1 H-NMR (400MHz, DMSO-D6, δ ppm):8.63(s, 2H),7.82(s, 2H),7.64(br, 4H),7.19(t, 4H),6.89(q, 8H),6.65(t, 2H),6.21(s, 1H),3.2-3.4(m, 5H), 2.41(br, 6H).

[0158] Test Example: The rubber compositions of Test Examples 1 to 6 were prepared according to the formulations shown in Table 1, and specifically included the following steps. 1. Add natural rubber SCR5 and synthetic rubber BR to the internal mixer and knead for a certain period of time, then add carbon black N550, aromatic oil, zinc oxide, stearic acid, antioxidant (6PPD, compound I-5, compound I-3, compound I-6, compound I-10 or compound I-12) and continue kneading until uniform; the temperature during kneading was controlled between 150℃ and 160℃. 2. The whole mixture was cooled to below 100°C, then the crosslinking system (sulfur S and accelerator NS) was added and the whole mixture was kneaded, controlling the temperature during kneading so that it did not exceed 110°C. 3. The obtained rubber composition is rolled into a plate (thickness 2 to 3 mm) and then vulcanized at a vulcanization temperature of 145° C. for 30 minutes.

[0159] The ingredients in Table 1 come from the following sources: SCR5: Xishuangbanna Sinochemical Rubber Co., Ltd. Natural rubber SCR5; BR: Nanjing Yangzi Petrochemical Rubber Co., Ltd. Synthetic rubber BR9000; N550: CABOT Company Carbon Black N550; Aroma oil: Shanghai Titan Technology Co., Ltd. General reagents; Stearic acid: Shanghai Titan Technology Co., Ltd. General reagent Stearic acid (AR); Zinc oxide: Shanghai Titan Technology Co., Ltd. General Reagent Zinc oxide (AR); NS: Sennics Company vulcanization accelerator NS; S: Sinopharm Group Chemical Reagents Company Sublimable Sulfur (AR); 6PPD: Sennics Company Anti-aging agent SIRANTOX 6PPD; Compound I-5: the compound synthesized in Example 5; Compound I-3: the compound synthesized in Example 3; Compound I-6: the compound synthesized in Example 6; Compound I-10: the compound synthesized in Example 10; Compound I-12: The compound synthesized in Example 12.

[0160] [Table 1]

[0161] The ozone resistance and discoloration resistance of the vulcanized rubber sheets of Test Examples 1 to 6 were evaluated by the following methods. The results are shown in Table 3.

[0162] (1) Evaluation method for ozone resistance Test sheets of various rubber compositions were subjected to an ozone degradation test under the conditions of a temperature of 40°C, an ozone concentration of 50 μm, and an elongation of 20%. After 39 hours, the test sheets were examined for their degradation state. The evaluation of ozone resistance is based on the density of cracks formed and is judged as follows: 0: No cracks 1: A small number of cracks (crack density <10 / cm) 2: Many cracks (10 cracks / cm ≤ crack density < 40 cracks / cm) 3: Many cracks (crack density ≧40 / cm)

[0163] (2) Evaluation method for discoloration resistance The vulcanized rubber sheet is placed in a Ziploc bag, the rubber sheet is placed against the bag, and the bag is exposed to outdoor conditions for two weeks, after which the color change of the bag is observed. The evaluation criteria for the color fastness grade are shown in Table 2.

[0164] [Table 2]

[0165] [Table 3]

[0166] From Tables 1 and 2, it can be seen that the ozone resistance of the rubber material containing the compound of the present invention is equal to or higher than that of the rubber composition containing a conventional antioxidant, and discoloration of the rubber material containing the compound of the present invention is clearly suppressed.

Claims

1. A compound represented by the following formula (I): 【Chemistry 1】 provided that R is C3 to C16 alkyl, C3 to C16 alkyl substituted with C3 to C10 cycloalkyl, C3 to C10 cycloalkyl, or C3 to C10 cycloalkyl substituted with C3 to C16 alkyl; R 1 and R 2 may be the same or different and are each independently selected from C3 to C10 alkyl, C3 to C10 cycloalkyl or C3 to C10 alkyl substituted with C6 to C14 aryl, C3 to C10 cycloalkyl, C3 to C10 cycloalkyl substituted with C3 to C10 alkyl, C6 to C14 aryl and C6 to C14 aryl substituted with C3 to C10 alkyl.

2. 2. The compound according to claim 1, wherein R is C3-C10 alkyl or C3-C10 cycloalkyl.

3. The compound according to claim 2, wherein R is a C3-C10 branched alkyl or a C3-C10 cycloalkyl.

4. The compound according to claim 3, wherein R is isopropyl, tert-butyl, tert-octyl or cyclohexyl.

5. R 1 and R 2 may be the same or different and are each independently a C3 to C10 alkyl or phenyl.

6. The compound according to claim 5, wherein R 1 and R 2 may be the same or different and each independently represents a C3 to C10 branched alkyl or phenyl.

7. The compound according to claim 6, wherein R 1 and R 2 may be the same or different and are each independently isopropyl, 1,4-dimethylpentyl, or phenyl.

8. 2. The compound according to claim 1, characterized in that the compound is selected from the following: 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】

9. A method for preparing a compound according to any one of claims 1 to 8, comprising: (1) Cyanuric chloride is reacted with NH 2 and reacting with R to produce intermediate A represented by the following formula: 【Chemistry 6】 (2) Intermediate A is reacted with N-R 1 - reacting with p-phenylenediamine to produce intermediate B represented by the following formula: 【Chemistry 7】 (3) Intermediate B is reacted with N-R 2 - reacting with p-phenylenediamine to produce a compound of formula (I): 【Chemistry 8】 However, intermediate A, intermediate B and R and R of the compound of formula (I) 1 and R 2 is as defined in any one of claims 1 to 8.

10. 10. The method according to claim 9, characterized in that it has one or more of the following features: (A) adding an alkaline solid powder to the reaction of step (1), the reaction temperature is 0-35°C; (B) adding an alkaline solution to the reaction in step (2), the reaction temperature is 50-100° C.; and (C) The reaction temperature in step (3) is 80 to 180° C.

11. R 1 and R 2 10. The method according to claim 9, further comprising the steps of: (2') Intermediate A is reacted with N-R 1 -p-phenylenediamine to produce the compound of formula (I).

12. The method of claim 11, wherein an alkaline solid powder is added to the reaction in step (1), and the reaction temperature is 0 to 35°C.

13. The method according to claim 11, wherein an alkaline solution is added to the reaction in step (2'), and the reaction is first carried out at 50 to 100°C and then at 80 to 180°C.

14. A rubber composition comprising the compound according to any one of claims 1 to 8.

15. A rubber product produced by using the rubber composition according to claim 14 as a rubber component.

16. The rubber product described in claim 15, wherein the rubber product is a tire.

17. Use of a compound according to any one of claims 1 to 8 for improving the anti-aging and / or anti-discoloration properties of rubber or rubber products.

18. The method of claim 17, wherein the rubber product is a tire.

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