CN114671777A - Preparation method of amide antioxidant - Google Patents

Preparation method of amide antioxidant Download PDF

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CN114671777A
CN114671777A CN202210271353.XA CN202210271353A CN114671777A CN 114671777 A CN114671777 A CN 114671777A CN 202210271353 A CN202210271353 A CN 202210271353A CN 114671777 A CN114671777 A CN 114671777A
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catalyst
supported
formula
independently selected
reaction
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CN114671777B (en
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段盛元
刘国安
崔丽娟
张永坤
王铁宏
汪远航
刘磊
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Rianlon Zhuhai New Material Co ltd
Rianlon Corp
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Rianlon Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C241/04—Preparation of hydrazides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

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Abstract

The invention relates to a preparation method of an amide antioxidant, which comprises the following steps: the hindered phenol carboxylic ester shown in formula I and organic amine are subjected to ammonolysis (amination) reaction under the action of a supported alkaline catalyst to prepare the amide antioxidant, wherein the organic amine has a formula II or a formulaIII is shown in the specification;

Description

Preparation method of amide antioxidant
Technical Field
The invention relates to the field of chemical synthesis, in particular to a preparation method of an amide antioxidant.
Background
Amide antioxidants are commonly used in plastic rubber products such as wires, cables, etc. that come into contact with metals, particularly copper. The simultaneous existence of the amide group and the hindered phenol enables the compound to have the effect of a hindered phenol antioxidant and the capability of metal passivation. Meanwhile, the amide antioxidant has proper melting point and excellent compatibility, so that the amide antioxidant can be uniformly dispersed in the base material. The sales volume of the products in the market is in a rapid growth trend year by year, has a strong development prospect and is popular with wire and cable customers.
Currently, the common amide antioxidants have the brands 1019, 1098, 1024, 697 and the like. The compound is mainly synthesized by the following three processes:
1) The hindered phenol carboxylic ester and the organic amine are directly reacted to form an amido bond, the process needs higher reaction temperature, and for the amide antioxidant, the higher reaction temperature can cause product dealkylation to influence reaction selectivity and product yield.
2) Hindered phenol carboxylic ester and acyl chloride reagent form acyl chloride compound, then further form amido bond with organic amine, acyl chloride reagent includes thionyl chloride, phosphorus trichloride or phosphorus oxychloride etc. uses it to increase the safety risk in the production process, and thionyl chloride, phosphorus trichloride etc. acyl chloride reagent all belong to the dangerous reagent of high toxicity, acyl chloride reaction process is comparatively violent at the same time, if the dropping speed is too fast, the temperature control system is invalid, throw material proportion mistake and probably lead to spraying material even explosion.
3) Hindered phenol carboxylic ester and organic amine are subjected to ammonolysis (amination) reaction under the action of a catalyst, and common catalysts mainly comprise: the catalyst comprises a basic catalyst, an acidic (Lewis acid) catalyst and an organic tin catalyst, wherein the basic catalyst increases the attack capability of organic amine by capturing the proton of the organic amine in the reaction process so that the organic amine is easier to react with the carbenium ion of an ester group; in the reaction process of the acidic catalyst, metal cations of Lewis acid can form nucleophilic ion groups firstly, and then react with carbenium ions to reduce the attack difficulty of the carbenium ions, so that organic amine can react with the carbenium ions more easily; the organic tin catalyst is similar to an acid catalyst, and reduces the attack difficulty of the carbocation. The process has high requirements on the types of catalysts, and the use of different catalysts has certain limitations, for example, protonic acid of an acid catalyst can react with organic amine to cause the reduction of the nucleophilicity of the organic amine; the organotin catalysts have certain toxicity, particularly the trihydrocarbon stannide (R3SnX) has the highest toxicity to human bodies, and the European Union has issued the specification documents of 89/677/EEC, 1999/51/EC, 2002/62/EC and the like to limit the use of the organotin compounds; the alkaline catalyst has excellent catalytic potential, but the conventional alkaline catalyst needs to be subjected to post-treatment such as washing, pickling and the like after the reaction is finished, the washing and pickling process can cause material loss, and the product yield is low.
Based on the above, there is a need to develop a safe preparation process of amide antioxidants, which is easy to control the reaction process and can ensure the purity and yield of the product.
Disclosure of Invention
The invention aims to provide a process for synthesizing an amide antioxidant by adopting supported alkaline catalysis, which can reduce the reaction difficulty and avoid violent and difficult control of the reaction, can be recycled and reused by a simple filtering method, and is beneficial to reduction of production unit consumption and improvement of product purity and yield.
The preparation method of the amide antioxidant comprises the following steps:
the hindered phenol carboxylate in the formula I and organic amine are subjected to ammonolysis (amination) reaction under the action of a supported basic catalyst to prepare an amide antioxidant, wherein the organic amine has a structure shown in a formula II or a formula III;
Figure BDA0003553380080000021
in the formula I, R1 and R2 are respectively and independently selected from H, CH3 and t-Bu; r3 is C1-C20 alkylene, R4 is C1-C20 alkyl;
in the formula II, R5、R6Each independently selected from H or C1-C20Alkyl groups of (a);
in the formula III, R5、R6Each independently selected from H or C1-C20Alkyl groups of (a); r7Is C0-C20An alkylene group of (a).
Further, in the formula I, R1 and R2 are respectively and independently selected from t-Bu; r3 is a C1-C4 alkylene group, R4 is methyl or ethyl; more preferably, R3 is C2 alkylene;
In the formula II, R5、R6Each independently selected from H or C1-C4Alkyl groups of (a);
in the formula III, R5、R6Each independently selected from H or C1-C4Alkyl groups of (a); r7Is C0-C6An alkylene group of (a).
Further, the active component of the alkaline supported catalyst is one or more of hydroxide, carbonate, nitrate and fluoride of alkali metals; preferably, the active ingredient is selected from one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium nitrate, sodium nitrate, potassium fluoride and sodium fluoride;
the carrier of the alkaline supported catalyst is selected from one or more of alumina, molecular sieve, zirconia, zinc oxide, silica, carbon black, montmorillonite and activated carbon.
Further, the average particle size of the supported alkaline catalyst is controlled to be 5-50 μm; preferably, the average particle size of the alkaline supported catalyst is 10-45 μm; more preferably, the average particle size of the alkaline supported catalyst is 30-40 μm.
Further, the supported catalyst is prepared by loading active ingredients on a carrier through an impregnation microwave method.
Further, the preparation method of the alkaline supported catalyst comprises the following steps: s1. dissolving the active ingredient in an aqueous solution; s2, adding a carrier, controlling the temperature to be between 50 and 90 ℃, and reacting for 12 to 24 hours; s3. and drying the water by evaporation at a high temperature, and radiating the dried water in a microwave generator for 10-60 min.
Further, the concentration of the active ingredients is 10-30 wt%; the mass ratio of the carrier to the active ingredients is 1: (2-30), preferably 1 (2-10).
Furthermore, the working frequency of the microwave generator is 915 MHz-2450 MHz.
Further, the supported basic catalyst is added in an amount of 0.5 to 1% by weight based on the hindered phenol-based carboxylate.
Further, the temperature of the aminolysis (amination) reaction is between 50 and 150 ℃.
The invention achieves the following positive effects: the supported alkaline catalyst is used for catalyzing the hindered phenol carboxylic ester to react with the organic amine, the process reduces the reaction temperature, avoids the increase of impurities caused by dealkylation, has safe whole process route and high product yield, and simultaneously, the catalyst participating in the reaction can be completely removed by a simple filtering method and can be reused for many times, thereby avoiding the problems of catalyst treatment process, hazardous waste discharge and the like, saving the production time and improving the production yield. The production cost is lower, and the production process is mild and safe.
Detailed Description
The present invention will be described in detail with reference to the following embodiments, but it should be understood that the scope of the present invention is not limited by these embodiments and the principle of the present invention, but is defined by the claims.
In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable.
The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.
Technical and scientific terms used herein are to be defined only in accordance with their definitions, and are to be understood as having ordinary meanings in the art without any definitions.
The invention provides a preparation method of an amide antioxidant, which comprises the following steps:
the hindered phenol carboxylate in the formula I and organic amine are subjected to ammonolysis (amination) reaction under the action of a supported basic catalyst to prepare an amide antioxidant, wherein the organic amine has a structure shown in a formula II or a formula III;
Figure BDA0003553380080000051
in the formula I, R1、R2Each independently selected from H, CH3And t-Bu; r is3Is C1-C20Alkylene of (A), R4Is C1-C20Alkyl groups of (a);
in the formula II, R5、R6Each independently selected from H or C1-C20Alkyl groups of (a);
in the formula III, R5、R6Each independently selected from H or C1-C20Alkyl groups of (a); r7Is C0-C20An alkylene group of (a).
The preparation method adopts the supported alkaline catalyst to prepare the amide antioxidant, can reduce the reaction temperature, avoids the increase of impurities caused by dealkylation, has safe whole process route and high product yield, can directly filter and recover the catalyst after the reaction is finished, and does not influence the product yield and purity after repeated use.
Preferably, in formula I, R1、R2Each independently selected from t-Bu; r3Is C1-C4Alkylene of (A), R4Is methyl or ethyl; more preferably, R3Is C2An alkylene group of (a);
in the formula II, R5、R6Each independently selected from H or C1-C4Alkyl groups of (a); in the formula III, R5、R6Each independently selected from H or C 1-C4Alkyl groups of (a); r is7Is C0-C6An alkylene group of (a).
As used herein, alkylene refers to a free divalent radical of an alkane formed by the loss of two hydrogen atoms from the same or different two carbons, e.g., C2Alkylene of (a) is-CH2-CH2-。C0The alkylene group of (a) means H. The organic amine shown in formula II or formula III in the present invention includes, but is not limited to, one or a mixture of several of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, dibutylamine, diisobutylamine, pentylamine, isoamylamine, ethylenediamine, propylenediamine, 1, 3 propylenediamine, and hexamethylenediamine.
In order to meet the requirement of catalyzing the catalytic efficiency of the amide antioxidants and reduce the reaction temperature, the active component of the alkaline supported catalyst is one or more of hydroxides, carbonates, nitrates and fluorides of alkali metals; preferably, the active ingredient is selected from one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium nitrate, sodium nitrate, potassium fluoride, sodium fluoride. The support of the basic supported catalyst includes, but is not limited to: alumina, molecular sieve, zirconia, zinc oxide, silicon dioxide, carbon black, montmorillonite and activated carbon.
The requirement of the ammonolysis (amination) reaction on the average particle size of the catalyst needs to be controlled within the range of 5-50 mu m, and the catalyst is a heterogeneous catalyst and cannot be compatible with raw materials and uniformly distributed in the reaction process, so the particle size influences the reaction speed, the consistency of the solution and the filtration requirement, and the excessive particle size can cause the slow reaction speed; the solution with too small particle size is viscous, and the catalyst is not easy to filter. The average particle size of the supported alkaline catalyst is controlled to be 5-50 mu m, so that the catalytic efficiency can be improved, and the operation is convenient. Preferably, the average particle size of the alkaline supported catalyst is 10-45 μm; more preferably, the average particle size of the alkaline supported catalyst is 30-40 μm.
In order to obtain a high-efficiency catalyst in the above particle size range, the supported catalyst is prepared by supporting an active ingredient on a carrier by an impregnation microwave method. The preparation method of the alkaline supported catalyst comprises the following steps: s1. dissolving the active ingredient in an aqueous solution; s2, adding a carrier, controlling the temperature to be between 50 and 90 ℃, and reacting for 12 to 24 hours; s3. and drying the water by evaporation at a high temperature, and radiating the dried water in a microwave generator for 10-60 min.
The invention adopts an immersion microwave method to prepare the alkaline supported catalyst, firstly the active ingredients react at a certain temperature to generate an alkaline active center, and then the alkaline active center is firmly fixed on a carrier by microwave heating. The preparation method of the catalyst has high efficiency and better dispersion effect of the active ingredients.
In the preparation method of the supported catalyst, the concentration of the active component is 10-30 wt%; for example, 15 wt%, 20 wt%, 25 wt%, 30 wt%; the mass ratio of the carrier to the active ingredients is 1: (2-30), e.g., 1: 5; 1: 8; 1: 10; 1: 15; 1: 20; 1: 25; preferably 1 (2-10);
in the preparation method of the supported catalyst, in order to ensure the loading rate and the particle size of the alkaline supported catalyst, the working frequency of the microwave generator is as follows: 915MHz to 2450MHz, for example, 1000MHz, 1200MHz, 1500MHz, 1800MHz, 2000 MHz. Wherein, too low frequency can not lead the alkaline active center and the carrier to be firmly combined, and too high frequency can lead the carrier to generate melting agglomeration and increase the particle size.
The addition amount of the supported basic catalyst is 0.5-1% of the weight of the hindered phenol carboxylic ester.
The temperature of the aminolysis (amination) reaction of the invention is 50-150 ℃.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Preparation of the catalyst
Example A
The preparation method of the NaOH loaded molecular sieve comprises the following steps:
dissolving 40g of NaOH in 200g of water, adding 4g of molecular sieve, controlling the temperature at 80 ℃, reacting for 12h, raising the temperature to evaporate water, placing in a microwave generator, and radiating for 30min at the working frequency of 2450MHz of the microwave generator. The average grain diameter is 38.85 μm by the detection of a laser grain size distribution instrument.
Example B
The preparation method of the KOH loaded alumina comprises the following steps:
dissolving 40g of KOH in 200g of water, adding 8g of alumina, controlling the temperature at 80 ℃, reacting for 24h, raising the temperature to evaporate water, placing in a microwave generator, radiating for 60min at the working frequency of 915MHz of the microwave generator. The average grain diameter is 30.11 μm by the detection of a laser grain size distribution instrument.
Comparative example A
Preparation method (chemical impregnation) of NaOH loaded molecular sieve:
40g of KOH is dissolved in 200g of water, 4g of molecular sieve is added, the temperature is controlled at 80 ℃, the reaction is carried out for 12 hours, then the temperature is raised, the water is evaporated, and the average particle size is 37.12 mu m by the detection of a laser particle size distribution instrument.
Comparative example B
The preparation method of the NaOH loaded molecular sieve (muffle furnace heating method) comprises the following steps:
dissolving 40g of KOH in 200g of water, adding 4g of molecular sieve, controlling the temperature to be 80 ℃, reacting for 12h, raising the temperature to evaporate water, placing in a muffle furnace, controlling the temperature to be 800 ℃, roasting for 12h, taking out and grinding. The average grain diameter is 80.52 μm by the detection of a laser grain size distribution instrument.
Preparation of amide antioxidant
Example 1
160g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 20g of propylenediamine and 0.5g of NaOH supported molecular sieve catalyst (prepared in example A) are put into a 200ml four-neck flask, stirred, mixed uniformly, heated to 100 ℃ for reaction for 10 hours, cooled after the reaction is finished, washed, decolored, cooled, crystallized and filtered to obtain the antioxidant 1019.
The above procedure was repeated (without catalyst make-up) after the NaOH supported molecular sieve catalyst was recovered by filtration, with the results shown in table 1:
TABLE 1 Recycling of NaOH-loaded molecular sieve catalyst
Figure BDA0003553380080000081
Figure BDA0003553380080000091
Note: the recovered catalyst was used with a part of the material stuck and washed with a solvent, and the same operation was carried out in all the examples.
Example 2
160g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 20g of propylenediamine and 1g of a catalyst (prepared in example B) of KOH-supported alumina are put into a 200ml four-neck flask, stirred, mixed uniformly, heated to 100 ℃ for reaction for 10 hours, cooled after the reaction is finished, washed, decolored, cooled, crystallized and filtered to obtain the antioxidant 1019.
The KOH supported alumina catalyst was recovered by filtration and the above procedure was repeated (without catalyst make-up), with the results shown in table 2:
TABLE 2 recycle of KOH-supported alumina catalyst
Figure BDA0003553380080000092
Example 3
32g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 6g of hexamethylenediamine and 0.1g of NaOH supported molecular sieve catalyst (prepared in example A) are put into a 100ml four-neck flask, stirred and mixed uniformly, heated to 100 ℃ for reaction for 10 hours, cooled after the reaction is finished, washed, cooled and crystallized, and filtered to obtain the antioxidant 1098.
The above procedure was repeated (without catalyst make-up) after the NaOH supported molecular sieve catalyst was recovered by filtration, with the results shown in table 3:
TABLE 3 recycle of NaOH-supported molecular sieve catalyst
Figure BDA0003553380080000101
Example 4
32g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 6g of hexamethylenediamine and 0.2g of KOH-supported alumina catalyst (prepared in example B) are put into a 100ml four-neck flask, stirred and mixed uniformly, heated to 100 ℃ for reaction for 10 hours, cooled after the reaction is finished, washed, cooled and crystallized, and filtered to obtain the antioxidant 1098.
The KOH supported alumina was filtered and recovered and the above procedure was repeated (without catalyst replacement) and the results are shown in table 4:
TABLE 4 recycle of KOH-supported alumina catalyst
Figure BDA0003553380080000102
Figure BDA0003553380080000111
Example 5
145g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 12g of hydrazine hydrate and 0.5g of NaOH supported molecular sieve catalyst (prepared in example A) are put into a 200ml four-mouth bottle, stirred and mixed uniformly, heated to 120 ℃ for reaction for 10 hours, cooled after the reaction is finished, washed, cooled and crystallized, and filtered to obtain the antioxidant 1024.
The above procedure was repeated (without catalyst make-up) after the NaOH supported molecular sieve catalyst was recovered by filtration, with the results shown in table 5:
TABLE 5 recycle of NaOH-supported molecular sieve catalyst
Figure BDA0003553380080000112
Example 6
145g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 12g of hydrazine hydrate and 1g of KOH-supported alumina catalyst (prepared in example B) are put into a 200ml four-neck flask, stirred and mixed uniformly, heated to 120 ℃ for reaction for 10 hours, cooled after the reaction is finished, washed, cooled and crystallized, and filtered to obtain the antioxidant 1024.
The KOH supported alumina catalyst was recovered by filtration and the above procedure was repeated (without catalyst replacement), with the results shown in table 6:
TABLE 6 Recycling and reusing conditions of KOH-loaded alumina catalyst
Figure BDA0003553380080000121
Comparative example 1
160g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 20g of propane diamine and 1g of sodium ethoxide are put into a 200ml four-mouth bottle, uniformly stirred, heated to 150 ℃ for reaction for 20 hours, and after the reaction is finished, the temperature is reduced to obtain 140g of antioxidant 1019 product, the yield is 87.06%, and the product purity is 99.05%.
Comparative example 2
32g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 6g of hexamethylenediamine and 0.2g of sodium methoxide are put into a 100ml four-mouth bottle, evenly stirred, heated to 150 ℃ for reaction for 20 hours, and after the reaction is finished, the temperature is reduced to obtain 28g of antioxidant 1098, the yield is 85.11 percent, and the purity of the product is 99.11 percent.
Comparative example 3
32g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 6g of hexamethylenediamine and 0.1g of Ca (OH)2 loaded molecular sieve (prepared by the method of the embodiment A) are put into a 100ml four-mouth bottle, stirred and mixed uniformly, heated to 100 ℃ for reaction for 10 hours, and cooled after the reaction is finished, so that 2g of an antioxidant 1098 product is obtained by post-treatment, the yield is 6.08%, and the product purity is 99.44%.
Comparative example 4
32g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 6g of hexamethylenediamine and 0.1g of NaOH loaded molecular sieve (the average particle size of the sieve is 80-90 mu m) are put into a 100ml four-mouth bottle, the mixture is stirred and mixed uniformly, the temperature is increased to 100 ℃ for reaction for 10 hours, 30g of antioxidant 1098 is obtained after the reaction is finished and the temperature is reduced, the yield is 91.19%, and the purity of the product is 99.75%.
The increase of the particle size leads to the reduction of the specific surface area of the catalyst and the deterioration of the catalytic effect, but the catalyst is easy to filter and the purity of the product is increased.
Comparative example 5
32g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 6g of hexamethylenediamine and 0.1g of NaOH supported molecular sieve catalyst (prepared in comparative example A) are put into a 100ml four-neck flask, stirred and mixed uniformly, heated to 100 ℃ for reaction for 10 hours, and cooled, washed, crystallized by cooling and filtered after the reaction is finished to obtain the antioxidant 1098.
The above procedure was repeated (without catalyst make-up) after the NaOH supported molecular sieve catalyst was recovered by filtration, with the results shown in table 7:
TABLE 7 Recycling of NaOH loaded molecular sieves
Figure BDA0003553380080000131
Figure BDA0003553380080000141
Comparative example 6
32g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 6g of hexamethylenediamine and 0.1g of NaOH supported molecular sieve catalyst (prepared in a comparative example B) are put into a 100ml four-neck flask, stirred and mixed uniformly, heated to 100 ℃ for reaction for 10 hours, cooled after the reaction is finished, washed, cooled and crystallized, and filtered to obtain the antioxidant 1098.
The NaOH supported molecular sieve catalyst was recovered by filtration and the above procedure was repeated (without catalyst make-up), with the results shown in table 8:
TABLE 8 recycle of NaOH-supported molecular sieve catalyst
Figure BDA0003553380080000142
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The preparation method of the amide antioxidant comprises the following steps:
the hindered phenol carboxylate of formula I and organic amine are subjected to ammonolysis (amination) reaction under the action of a supported alkaline catalyst to prepare an amide antioxidant, wherein the organic amine has a structure shown in formula II or formula III;
Figure FDA0003553380070000011
in the formula I, R1、R2Each independently selected from H, CH3Any one of t-Bu; r is3Is C1-C20Alkylene of (A), R4Is C1-C20Alkyl groups of (a);
in the formula II, R5、R6Each independently selected from H or C1-C20Alkyl groups of (a);
in the formula III, R5、R6Each independently selected from H or C1-C20Alkyl groups of (a); r7Is C0-C20An alkylene group of (a).
2. The process according to claim 1, wherein R in the formula I1、R2Each independently selected from t-Bu; r3Is C1-C4Alkylene of (A), R4Is methyl or ethyl; more preferably, R3Is C2Alkylene of (A)A group;
in the formula II, R5、R6Each independently selected from H or C1-C4Alkyl groups of (a);
in the formula III, R5、R6Each independently selected from H or C1-C4Alkyl groups of (a); r7Is C0-C6An alkylene group of (a).
3. The preparation method according to claim 1, wherein the active ingredient of the basic supported catalyst is one or more of hydroxide, carbonate, nitrate and fluoride of alkali metal; preferably, the active ingredient is selected from one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium nitrate, sodium nitrate, potassium fluoride and sodium fluoride;
The carrier of the alkaline supported catalyst is selected from one or more of alumina, molecular sieve, zirconia, zinc oxide, silica, carbon black, montmorillonite and activated carbon.
4. The production method according to any one of claims 1 to 3, wherein the supported basic catalyst has an average particle diameter of 5 to 50 μm; preferably, the average particle size of the alkaline supported catalyst is 10-45 μm; more preferably, the average particle size of the alkaline supported catalyst is 30-40 μm.
5. The production method according to any one of claims 1 to 4, wherein the supported catalyst is produced by supporting an active ingredient on a carrier by an impregnation microwave method.
6. The production method according to any one of claims 1 to 5, characterized in that the production method of the basic supported catalyst comprises the steps of: s1. dissolving the active ingredient in an aqueous solution; s2, adding a carrier, controlling the temperature to be between 50 and 90 ℃, and reacting for 12 to 24 hours; s3. and drying the water by evaporation at a high temperature, and radiating the dried water in a microwave generator for 10-60 min.
7. The preparation method according to claim 6, wherein the concentration of the active ingredient is 10 to 30 wt%; the mass ratio of the carrier to the active ingredients is 1: (2-30), preferably 1 (2-10).
8. The preparation method according to claim 6, wherein the operating frequency of the microwave generator is 915MHz to 2450 MHz.
9. The production method according to claim 1 or 2, wherein the supported basic catalyst is added in an amount of 0.5 to 1% by weight based on the hindered phenol-based carboxylate.
10. The method of claim 1 or 2, wherein the temperature of the ammonolysis (amination) reaction is between 50 and 150 ℃.
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