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CN114671777B - Preparation method of amide antioxidant - Google Patents

Preparation method of amide antioxidant Download PDF

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Publication number
CN114671777B
CN114671777B CN202210271353.XA CN202210271353A CN114671777B CN 114671777 B CN114671777 B CN 114671777B CN 202210271353 A CN202210271353 A CN 202210271353A CN 114671777 B CN114671777 B CN 114671777B
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supported
catalyst
formula
reaction
carrier
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CN114671777A (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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Plasma & Fusion (AREA)
  • Optics & Photonics (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

The application relates to a preparation method of an amide antioxidant, which comprises the following steps: the hindered phenol carboxylic ester shown in the 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 the formula II or the formula III;

Description

Preparation method of amide antioxidant
Technical Field
The application 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 for wire, cable and the like that come into contact with metals, particularly copper. The existence of the amide group and the hindered phenol simultaneously ensures that the hindered phenol antioxidant has the efficacy of the hindered phenol antioxidant and the metal passivation capability. Meanwhile, the amide antioxidant has proper melting point and better compatibility, so that the amide antioxidant can be uniformly dispersed in the base material. The sales of the products in the market is in a rapid annual growth trend, has a strong development prospect, and is popular with wire and cable customers.
At present, common amide antioxidants have the marks of 1019, 1098, 1024, 697 and the like. The preparation method is mainly synthesized by the following three processes:
1) The hindered phenol carboxylic ester directly reacts with organic amine to form an amide bond, and the process needs higher reaction temperature, and for an amide antioxidant, the higher reaction temperature can lead to dealkylation of a product, so that the reaction selectivity and the product yield are affected.
2) The hindered phenol carboxylic ester and the acyl chloride reagent form acyl chloride compounds, and then the acyl chloride reagent and the organic amine further form amide bonds, wherein the acyl chloride reagent comprises thionyl chloride, phosphorus trichloride or phosphorus oxychloride and the like, the safety risk in the production process is increased by using the acyl chloride reagent, and the acyl chloride reagent such as the thionyl chloride, the phosphorus trichloride and the like belongs to extremely toxic dangerous reagents, and meanwhile, the acyl chloride reaction process is relatively severe, such as the rapid dropping speed, the failure of a temperature control system and the possibility of causing even explosion of spraying due to the error of the feeding proportion.
3) The hindered phenol carboxylic ester and the organic amine are subjected to ammonolysis (amination) reaction under the action of a catalyst, and common catalysts mainly comprise: basic catalysts, acidic (Lewis acid) catalysts and organotin catalysts, wherein the basic catalysts increase the attack ability of the organic amine by capturing protons of the organic amine during the reaction, so that the basic catalysts react with carbocations of ester groups more easily; in the reaction process of the acid catalyst, metal cations of Lewis acid form nucleophilic ion groups firstly and then react with carbocations to reduce the attack difficulty of the carbocations, so that the organic amine can react with the carbocations more easily; the organotin catalyst is similar to an acidic catalyst, so that the attack difficulty of carbocations is reduced. The process has high requirements on the types of catalysts, and the use of different catalysts has certain limitation, for example, the protonic acid of the acid catalyst can react with the organic amine, so that the nucleophilicity of the organic amine is reduced; organotin catalysts have certain toxicity, particularly the toxicity of trihydrocarbyl stannides (R3 SnX) to human bodies is the greatest, and the EU has issued 89/677/EEC, 1999/51/EC, 2002/62/EC and other regulatory documents to limit the use of organotin compounds; the alkaline catalyst has excellent catalytic potential, but the conventional alkaline catalyst needs to be subjected to post-treatment such as water washing, acid washing and the like after the reaction is finished, the water washing and acid washing process can lead to material loss, and the product yield is low.
Based on the above, it is necessary to develop a process for preparing an amide antioxidant which is safe and easy to control the reaction process and can ensure the purity and yield of the product.
Disclosure of Invention
The application aims to provide a process for synthesizing an amide antioxidant by adopting supported alkaline catalysis, which can reduce the reaction difficulty, can not cause severe and difficult control of the reaction, can recycle the amide antioxidant by a simple filtering method, and is favorable for reducing the production unit consumption and improving the product purity and yield.
The preparation method of the amide antioxidant comprises the following steps:
the hindered phenol carboxylic ester shown in the 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 the formula II or the formula III;
in the formula I, R1 and R2 are respectively and independently selected from any one of H, CH3 and t-Bu; r3 is C1-C20 alkylene, R4 is C1-C20 alkyl;
in formula II, R 5 、R 6 Independently selected from H or C 1 -C 20 Alkyl of (a);
in formula III, R 5 、R 6 Independently selected from H or C 1 -C 20 Alkyl of (a); r is R 7 Is C 0 -C 20 Alkylene groups of (a).
Further, in formula I, R1, R2 are each independently selected from t-Bu; r3 is C1-C4 alkylene, R4 is methyl or ethyl; more preferably, R3 is a C2 alkylene group;
in formula II, R 5 、R 6 Independently selected from H or C 1 -C 4 Alkyl of (a);
in formula III, R 5 、R 6 Independently selected from H or C 1 -C 4 Alkyl of (a); r is R 7 Is C 0 -C 6 Alkylene groups of (a).
Further, the active component of the alkaline 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, sodium fluoride;
the carrier of the alkaline supported catalyst is one or more selected from alumina, molecular sieve, zinc oxide, silica, carbon black, montmorillonite and active carbon.
Further, the average particle diameter of the supported alkaline catalyst is controlled to be 5-50 mu m; preferably, the average particle diameter of the alkaline supported catalyst is 10-45 μm; more preferably, the basic supported catalyst has an average particle diameter of 30 to 40. Mu.m.
Further, the supported catalyst is prepared by supporting an active ingredient on a carrier by an impregnation microwave method.
Further, the preparation method of the alkaline supported catalyst comprises the following steps: s1. the active ingredient is dissolved in an aqueous solution; s2, adding a carrier, controlling the temperature to be 50-90 ℃ and reacting for 12-24 hours; s3. the temperature is increased to evaporate the water, and the water is put into a microwave generator to radiate for 10 to 60 minutes.
Further, the concentration of the active ingredient is 10 to 30wt%; the mass ratio of the carrier to the active ingredients is 1: (2-30), preferably 1 (2-10).
Further, the working frequency of the microwave generator is 915 MHz-2450 MHz.
Further, the addition amount of the supported alkaline catalyst is 0.5-1% of the weight of the hindered phenol carboxylic ester.
Further, the ammonolysis (amination) reaction temperature is 50-150 ℃.
The application has the following positive effects: according to the application, the supported alkaline catalyst is used for catalyzing the reaction of the hindered phenol carboxylic ester and the organic amine, the reaction temperature is reduced, the impurity increase caused by dealkylation is avoided, the whole process route is safe, the product yield is high, and meanwhile, the catalyst participating in the reaction can be completely removed by a simple filtering method and can be reused for multiple times, so that the problems of catalyst treatment procedures, hazardous waste emission and the like are avoided, the production time is saved, and the production yield is improved. The production cost is lower, and the production process is mild and safe.
Detailed Description
The application is described in detail below in connection with the embodiments, but it should be noted that the scope of the application is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present application, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or original description of the present application, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this application may be combined in any combination which is understood to be disclosed or described in this application unless the combination is obviously unreasonable by those skilled in the art.
The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the embodiments but also the end points of each numerical range in the specification, and any combination of these numerical points should be considered as a disclosed or described range of the present application.
Technical and scientific terms used in the present application are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
The application provides a preparation method of an amide antioxidant, which comprises the following steps:
the hindered phenol carboxylic ester shown in the 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 the formula II or the formula III;
in the formula I, R 1 、R 2 Are respectively and independently selected from H, CH 3 Any one of t-Bu; r is R 3 Is C 1 -C 20 Alkylene group, R 4 Is C 1 -C 20 Alkyl of (a);
in formula II, R 5 、R 6 Independently selected from H or C 1 -C 20 Alkyl of (a);
in formula III, R 5 、R 6 Independently selected from H or C 1 -C 20 Alkyl of (a); r is R 7 Is C 0 -C 20 Alkylene groups of (a).
The application adopts the supported alkaline catalyst to prepare the amide antioxidant, can reduce the reaction temperature, avoid the increase of impurities caused by dealkylation, has safe whole process route and high product yield, and can be directly filtered and recovered after the reaction is finished, and the product yield and purity are not affected by repeated use for a plurality of times.
Preferably, in formula I, R 1 、R 2 Each independently selected from t-Bu; r is R 3 Is C 1 -C 4 Alkylene group, R 4 Methyl or ethyl; more preferably, R 3 Is C 2 An alkylene group of (a);
in formula II, R 5 、R 6 Independently selected from H or C 1 -C 4 Alkyl of (a); in formula III, R 5 、R 6 Independently selected from H or C 1 -C 4 Alkyl of (a); r is R 7 Is C 0 -C 6 Alkylene groups of (a).
The alkylene group in the present application means a free divalent radical formed by losing two hydrogen atoms on the same or different carbons of an alkane, e.g. C 2 Alkylene of (C) is-CH 2 -CH 2 -。C 0 Is defined as H. The organic amine of formula II or formula III in the present application includes, but is not limited to, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, dibutylamine, diisobutylamine, pentylamine, isopentylamine, ethylenediamine, propylenediamine, 1,3 propylenediamine, hexamethylenediamine, or a mixture of several thereof.
In order to meet the catalytic efficiency requirement of the catalytic amide antioxidant and reduce the reaction temperature, the active component of the alkaline 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, sodium fluoride. The support of the basic supported catalyst includes, but is not limited to: alumina, molecular sieve, zinc oxide, silica, carbon black, montmorillonite and activated carbon.
The ammonolysis (amination) reaction of the application has the requirement on the average particle diameter of the catalyst to be controlled within the range of 5-50 mu m, and the catalyst is a heterogeneous catalyst which cannot be compatible with raw materials and cannot be uniformly distributed in the reaction process, so that the particle diameter has influence on the reaction speed, the solution consistency and the filtration requirement, and the reaction speed is slow due to the overlarge particle diameter; solutions with too small particle sizes are viscous and the catalyst is not easily filtered off. The average grain diameter 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 diameter of the alkaline supported catalyst is 10-45 μm; more preferably, the basic supported catalyst has an average particle diameter of 30 to 40. Mu.m.
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 a dipping microwave method. The preparation method of the alkaline supported catalyst comprises the following steps: s1. the active ingredient is dissolved in an aqueous solution; s2, adding a carrier, controlling the temperature to be 50-90 ℃ and reacting for 12-24 hours; s3. the temperature is increased to evaporate the water, and the water is put into a microwave generator to radiate for 10 to 60 minutes.
In the application, an alkaline supported catalyst is prepared by adopting an immersion microwave method, 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 adopting microwave heating. The catalyst preparation method has high efficiency and better dispersing effect of active ingredients.
In the preparation method of the supported catalyst, the concentration of the active ingredient is 10-30wt%; for example, 15wt%, 20wt%, 25wt%, 30wt%; 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, the working frequency is 1000MHz, 1200MHz, 1500MHz, 1800MHz, 2000MHz. Wherein, the frequency is too low to firmly combine the alkaline active center with the carrier, and too high frequency can lead to the carrier to generate melting agglomeration and increase the particle size.
The addition amount of the supported alkaline catalyst is 0.5-1% of the weight of the hindered phenol carboxylic ester.
The ammonolysis (amination) reaction temperature 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:
40g of NaOH is dissolved in 200g of water, 4g of molecular sieve is added to control the temperature to 80 ℃ for reaction for 12 hours, then the temperature is increased to evaporate water, and the water is placed in a microwave generator with the working frequency of 2450MHz and radiated for 30 minutes. The average particle diameter was 38.85 μm as measured by a laser particle size distribution analyzer.
Example B
The preparation method of KOH-loaded alumina comprises the following steps:
40g KOH is dissolved in 200g water, 8g alumina is added to control the temperature to 80 ℃ for reaction for 24 hours, then the temperature is increased to evaporate the water, and the water is placed in a microwave generator with the working frequency of 915MHz and radiated for 60 minutes. The average particle diameter was 30.11 μm as measured by a laser particle size distribution analyzer.
Comparative example A
The preparation method (chemical impregnation) of the NaOH loaded molecular sieve comprises the following steps:
40g KOH was dissolved in 200g water, 4g molecular sieves were added to control the temperature at 80℃and reacted for 12 hours, after which the water was evaporated to dryness at elevated temperature, and the average particle size was 37.12. Mu.m, as measured by a laser particle size distribution apparatus.
Comparative example B
The preparation method of the NaOH loaded molecular sieve (muffle furnace heating method) comprises the following steps:
40g KOH is dissolved in 200g water, 4g molecular sieve is added to control the temperature to 80 ℃ for reaction for 12 hours, then the temperature is increased to evaporate the water, and the mixture is placed in a muffle furnace to control the temperature to 800 ℃ for roasting for 12 hours, and is taken out for grinding. The average particle diameter was 80.52 μm as measured by a laser particle size distribution analyzer.
Preparation of amide antioxidant
Example 1
200ml four-mouth bottle is put with 160g of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, 20g of propylene diamine and 0.5g of NaOH loaded molecular sieve catalyst (prepared in example A), stirred and mixed uniformly, heated to 100 ℃ for reaction for 10 hours, cooled after the reaction, washed, decolorized, cooled and crystallized, and filtered to obtain antioxidant 1019.
The above operation was repeated (without replenishing new catalyst) after filtering and recovering the NaOH supported molecular sieve catalyst, and the results are shown in table 1:
table 1 recovery and reuse of NaOH Supported molecular Screen catalysts
Note that: the recovered catalyst was used after washing with solvent, with a portion of the material stuck, and all examples were operated in the same manner.
Example 2
200ml four-necked flask was charged with 160g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 20g of propylene diamine and 1g of KOH-supported alumina catalyst (prepared in example B), stirred and mixed uniformly, heated to 100 ℃ for reaction for 10h, cooled after the reaction, washed, decolorized, cooled and crystallized, and filtered to obtain antioxidant 1019.
The above operation was repeated (without replenishing new catalyst) after the KOH-supported alumina catalyst was recovered by filtration, and the results are shown in Table 2:
TABLE 2 recovery of KOH Supported alumina catalyst
Example 3
Into a 100ml four-port bottle, 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, 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 operation was repeated (without replenishing new catalyst) after filtering and recovering the NaOH supported molecular sieve catalyst, and the results are shown in table 3:
TABLE 3 recovery and reuse of NaOH Supported molecular Screen catalysts
Example 4
Into a 100ml four-port bottle, 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, 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 operation (without replenishing new catalyst) was repeated after the KOH-supported alumina was recovered by filtration, and the results are shown in Table 4:
TABLE 4 recovery of KOH Supported alumina catalyst
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-port 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 operation was repeated (without replenishing new catalyst) after filtering and recovering the NaOH supported molecular sieve catalyst, and the results are shown in table 5:
table 5 recovery and reuse of NaOH Supported molecular Screen catalysts
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-necked 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 above operation was repeated (without replenishing new catalyst) after the KOH-supported alumina catalyst was recovered by filtration, and the results are shown in Table 6:
TABLE 6 recovery of KOH Supported alumina catalyst
Comparative example 1
200ml four-mouth bottle is put with 160g of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, 20g of propylene diamine and 1g of sodium ethoxide, stirred and mixed evenly, heated to 150 ℃ for reaction for 20h, cooled after the reaction is finished and treated to obtain 140g of antioxidant 1019 product with the yield of 87.06% and the product purity of 99.05%.
Comparative example 2
Into a 100ml four-mouth bottle, 32g of methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 6g of hexamethylenediamine and 0.2g of sodium methoxide are put, stirred and mixed uniformly, heated to 150 ℃ for reaction for 20h, cooled and treated after the reaction is finished to obtain 28g of antioxidant 1098, the yield is 85.11%, and the purity of the product is 99.11%.
Comparative example 3
Into a 100ml four-port bottle, 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 according to the method of example A) are put, stirred and mixed uniformly, heated to 100 ℃ for reaction for 10 hours, cooled after the reaction is finished, and then treated to obtain 2g of antioxidant 1098, the yield is 6.08%, and the purity of the product is 99.44%.
Comparative example 4
Into a 100ml four-mouth bottle, 32g of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, 6g of hexamethylenediamine and 0.1g of NaOH-loaded molecular sieve (with the screening average particle size of 80-90 mu m) are put, stirred and mixed uniformly, heated to 100 ℃ for reaction for 10 hours, cooled after the reaction is finished, and treated to obtain 30g of antioxidant 1098, the yield is 91.19%, and the purity of the product is 99.75%.
The specific surface area of the catalyst is reduced after the particle size is increased, the catalytic effect is poor, but the catalyst is easy to filter out, and the purity of the product is increased.
Comparative example 5
Into a 100ml four-mouth bottle, 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, 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 operation was repeated (without replenishing new catalyst) after filtering and recovering the NaOH supported molecular sieve catalyst, and the results are shown in table 7:
table 7 recovery and reuse of NaOH loaded molecular sieves
Comparative example 6
Into a 100ml four-mouth bottle, 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 B) are put, 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 operation was repeated (without replenishing new catalyst) after filtering and recovering the NaOH supported molecular sieve catalyst, and the results are shown in table 8:
table 8 recovery and reuse of NaOH Supported molecular Screen catalysts
While the application has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the application and are intended to be within the scope of the application as claimed.

Claims (12)

1. The preparation method of the amide antioxidant comprises the following steps:
the hindered phenol carboxylic ester shown in the formula I and organic amine are subjected to ammonolysis reaction under the action of a supported alkaline catalyst to prepare an amide antioxidant, wherein the organic amine has a structure shown in the formula III;
in the formula I, R 1 、R 2 Are each independently selected from CH 3 Any one of t-Bu; r is R 3 Is C 1 -C 20 Alkylene group, R 4 Is C 1 -C 20 Alkyl of (a);
in formula III, R 5 、R 6 Each independently selected from H; r is R 7 Is C 0 -C 6 An alkylene group of (a);
the active component of the supported alkaline catalyst is one or more of hydroxide, carbonate, nitrate and fluoride of alkali metal; the carrier of the supported alkaline catalyst is one or more selected from alumina, molecular sieve, zinc oxide, silicon dioxide, carbon black, montmorillonite and active carbon;
the average grain diameter of the load type alkaline catalyst is controlled to be 5-50 mu m; the supported alkaline catalyst is prepared by loading active ingredients on a carrier by an impregnation microwave method.
2. The process of claim 1, wherein R in formula I 1 、R 2 Each independently selected from t-Bu; r is R 3 Is C 1 -C 4 Alkylene group, R 4 Is methyl or ethyl.
3. The process of claim 2, wherein in formula I, R 3 Is C 2 Alkylene groups of (a).
4. The preparation method according to claim 1, wherein the active ingredient of the supported alkaline catalyst is selected from one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium nitrate, sodium nitrate, potassium fluoride, sodium fluoride.
5. The process according to any one of claims 1 to 4, wherein the average particle diameter of the supported basic catalyst is 10 to 45. Mu.m.
6. The process according to claim 4, wherein the average particle diameter of the supported basic catalyst is 30 to 40. Mu.m.
7. The method according to any one of claims 1 to 4, wherein the method for producing the supported basic catalyst comprises the steps of: s1. the active ingredient is dissolved in an aqueous solution; s2, adding a carrier, controlling the temperature to be 50-90 ℃ and reacting for 12-24 hours; s3. the temperature is increased to evaporate the water, and the water is put into a microwave generator to radiate for 10 to 60 minutes.
8. The method of claim 7, wherein the concentration of the active ingredient is 10 to 30wt%; the mass ratio of the carrier to the active ingredients is 1: (2-30).
9. The method according to claim 8, wherein the mass ratio of the carrier to the active ingredient is 1 (2-10).
10. The method of claim 7, wherein the microwave generator operates at a frequency of 915MHz to 2450MHz.
11. The preparation method according to claim 1 or 2, wherein the amount of the supported basic catalyst added is 0.5 to 1% by weight of the hindered phenol carboxylate.
12. The process according to claim 1 or 2, wherein the ammonolysis reaction is carried out at a temperature of 50-150 ℃.
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