Synthesis process of peroxide 2-ethylhexyl tert-amyl carbonate

Abstract

The invention provides a synthesis process of tert-amyl peroxy-2-ethylhexyl carbonate, and relates to the technical field of organic synthesis.The synthesis process comprises the following steps that S1, caustic soda liquid and water are pumped into a reaction kettle; s2, tert-amyl hydroperoxide is added into the reaction kettle for a salt forming reaction; s3, after the salt forming reaction is finished, adding a catalyst, dropwise adding isooctyl chloroformate, and carrying out condensation reaction to obtain a crude product of tert-amyl 2-ethylhexyl peroxide; and S4, carrying out alkali washing and water washing on the peroxide 2-ethylhexyl tert-amyl carbonate crude product to obtain a finished product. The catalyst is a tree-shaped structure catalyst of a silica gel carrier, and has the advantages of high conversion rate and high yield.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to a synthesis process of tert-amylperoxy 2-ethylhexyl carbonate. Background Art

[0002] Tert-amylperoxy 2-ethylhexyl carbonate, abbreviated as TAEC, with the English name Tert-Amylperoxy 2-ethylhexylcarbonate, is mainly prepared from isooctyl chloroformate, tert-amyl hydroperoxide and sodium hydroxide, and its chemical structural formula is: The molecular weight is 260.4, and the molecular formula is C 14 H 28 O4, and the CAS number

[0003] 70833-40-8. TAEC is commonly used as an initiator, which can catalyze and initiate free radical polymerization in polymerization reactions, and can also be used for cross-linking and curing of resin materials in the photovoltaic field. Due to problems such as the easy hydrolysis of isooctyl chloroformate in the raw materials in the existing production process, there are problems of low product yield and conversion rate. In addition, due to the presence of a tert-amylperoxy structure in its structure, the overall steric hindrance is relatively large, and the existing catalysts are difficult to meet the needs of synthesis and preparation. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects of the prior art, and provide a synthesis process of tert-amylperoxy 2-ethylhexyl carbonate, so as to improve the yield and conversion rate of synthesizing tert-amylperoxy 2-ethylhexyl carbonate in the prior art.

[0005] The reaction equation of the tert-amylperoxy 2-ethylhexyl carbonate of the present invention is as follows:

[0006]

[0007] In order to achieve the above and other purposes, the present invention is realized by including the following technical solutions: The present invention first provides a synthesis process of tert-amylperoxy 2-ethylhexyl carbonate, and the synthesis process includes the following steps:

[0008] S1: Pump liquid caustic soda and water into the reaction kettle;

[0009] S2: Add tert-amyl hydroperoxide to the reaction kettle for salt formation reaction;

[0010] S3: After the salt formation reaction is completed, add a catalyst and dropwise add isooctyl chloroformate for condensation reaction to obtain a crude product of tert-amylperoxy 2-ethylhexyl carbonate;

[0011] S4: Wash the crude product of tert-amylperoxy 2-ethylhexyl carbonate with alkali and then with water to obtain the finished product;

[0012] Among them, the preparation of the catalyst includes the following steps:

[0013] (1) Provide an amino-modified silica gel support;

[0014] (2) React 4-aminobutane-1,2,3-triol with methanol and hydrochloric acid to obtain a first intermediate. React the first intermediate with bis(trichloromethyl) carbonate to obtain a second intermediate. React the second intermediate with the amino-modified silica gel support to obtain a third intermediate. React the third intermediate with 1,3-propanediamine and methanol to obtain a polyamino dendrimer product;

[0015] (3) React tert-butyl 4-(2-hydroxyethyl)-4-(2-hydroxypropyl)piperidine-1-carboxylate with 1,4-dichloromethylbutane to obtain a first product, and then react the first product with the polyamino dendrimer product to obtain a polyamino dendrimer product with crown ether;

[0016] (4) React 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid with 3,4-diaminobenzoic acid to obtain a second product,

[0017] React the second product with the polyamino dendrimer product with crown ether to obtain the catalyst.

[0018] In some embodiments, in step (1), the preparation of the amino-modified silica gel support includes: dehydrating the silica gel at 150-200 °C to remove moisture; mixing 50-100 parts of toluene, 1-3 parts of 3-aminopropyltriethoxysilane, and 10-20 parts of silica gel and reacting at 80-90 °C for 8-10 hours, and obtaining the amino-modified silica gel support through filtration, washing, and drying.

[0019] Specifically, the beneficial effect of this embodiment is that the ethoxy group (-OCH2CH3) undergoes a hydrolysis condensation reaction with the silanol group (-Si-OH) on the surface of the silica gel to form a stable Si-O-Si bond, and at the same time, the amino group (-NH2) is introduced onto the surface of the silica gel.

[0020] In some embodiments, in step (2), the preparation of the first intermediate includes: reacting 20-30 parts of 4-aminobutane-1,2,3-triol with 50-60 parts of methanol and 10-15 parts of hydrochloric acid at 60-80 °C for 6-10 hours; obtaining the first intermediate through neutralization, extraction, drying, and distillation.

[0021] Specifically, the beneficial effect of this embodiment is that under acidic catalytic conditions, the hydroxyl group (-OH) of 4-aminobutane-1,2,3-triol reacts with methanol (CH3OH) to activate the hydroxyl group into an ester for subsequent further grafting of the amino group.

[0022] In some embodiments, in step (2), the preparation of the second intermediate includes: reacting 20 - 30 parts of the first intermediate, 0.15 - 0.2 part of bis(trichloromethyl) carbonate, and 50 - 100 parts of dichloromethane at 10 - 20 °C for 2 - 5 hours; filtering and washing to obtain the second intermediate.

[0023] Specifically, the beneficial effect of this embodiment is: introducing NCO onto the first intermediate, facilitating subsequent access to the amino - containing silica support.

[0024] In some embodiments, in step (2), the preparation of the third intermediate includes: reacting 20 - 30 parts of the second intermediate, 15 - 20 parts of the amino - modified silica support, and 80 - 100 parts of N,N - dimethylformamide at 20 - 30 °C for 5 - 10 hours; filtering, washing, and drying to obtain the third intermediate.

[0025] Specifically, the beneficial effect of this embodiment is: grafting the amino - containing silica support.

[0026] In some embodiments, in step (2), the preparation of the poly - amino dendritic product includes: reacting 10 - 20 parts of the third intermediate, 1 - 5 parts of 1,3 - propanediamine, 0.05 - 0.1 part of triethylamine (catalyst), and 50 - 100 parts of methanol at 30 - 50 °C for 10 - 20 hours; filtering and washing to obtain the poly - amino dendritic product.

[0027] Specifically, the beneficial effect of this embodiment is: forming a poly - amino dendritic product through an amidation reaction.

[0028] In some embodiments, in step (3), the preparation of the first product includes: reacting 20 - 30 parts of tert - butyl 4-(2 - hydroxyethyl)-4-(2 - hydroxypropyl)piperidine - 1 - carboxylate with 25 - 30 parts of 1,4 - dichloromethylbutane, 0.1 - 0.2 part of triethylamine (catalyst), and 90 - 100 parts of N,N - dimethylformamide at 60 - 80 °C for 8 - 10 hours; filtering and washing to obtain the first product.

[0029] Specifically, the beneficial effect of this embodiment is: one of the two chlorine functional groups in 1,4 - dichloromethylbutane reacts with the hydroxyl group, and the other facilitates the subsequent formation of a crown ether.

[0030] In some embodiments, in step (3), the preparation of the polyamino dendritic product with crown ether includes the following steps: reacting 20-30 parts of the first product, 30-35 parts of the polyamino dendritic product, 0.1-0.15 parts of triethylamine, and 100-150 parts of N,N-dimethylformamide at 60-80 °C for 8-12 hours; obtaining the polyamino dendritic product with crown ether through filtration and washing.

[0031] Specifically, the beneficial effect of this embodiment is that a polyamino dendritic product with a crown ether structure is formed through the substitution reaction of amino and chlorine, and the polyamino dendritic product can be appropriately in excess.

[0032] In some embodiments, in step (4), the preparation of the second product includes: reacting 20-30 parts of 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid, 6-10 parts of 3,4-diaminobenzoic acid, 50-100 parts of tetrahydrofuran, 25-30 parts of N,N'-dicyclohexylcarbodiimide, and 0.1-0.2 parts of 4-dimethylaminopyridine at 30-40 °C for 8-10 hours; obtaining the second product through filtration and washing.

[0033] Specifically, the beneficial effect of this embodiment is that by reacting 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid and 3,4-diaminobenzoic acid in a molar ratio of about 2:1, the carboxyl groups on two 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acids can be condensed with the two amino groups on 3,4-diaminobenzoic acid respectively to obtain a structure with amide bonds and multiple hydroxyl groups for complexing with chlorine, and the excess carboxyl groups on 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid can subsequently become grafting sites with the polyamino dendritic product.

[0034] In some embodiments, in step (4), the preparation of the catalyst includes: mixing 10-20 parts of the second product, 15-20 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 80-100 parts of N,N-dimethylformamide at 20-30 °C for 1-2 hours, and then adding 18-24 parts of the polyamino dendritic product with crown ether and reacting at 20-30 °C for 12-24 hours; obtaining the catalyst through filtration and washing.

[0035] Specifically, the beneficial effect of this embodiment is that the carboxyl group reacts with the amino group on the polyamino dendritic product with crown ether to form an amide bond.

[0036] The present invention synthesizes a dendritic structure catalyst with a silica gel support. The silica gel support has the characteristics of good mechanical strength, easy modification, and separation and recovery. The catalyst is grafted with crown ether. As a phase transfer catalyst, the crown ether can accelerate the two-phase reaction. The cavity size of the crown ether can match that of sodium ions, and a complex can be formed through coordination. The cavity of the crown ether also provides enough space around the catalytic active center to accommodate large steric hindrance groups such as tert-amyl groups. Reactants can be enriched on the surface or in the internal cavity of the dendritic polymer catalyst to form a local high-concentration environment, accelerating the reaction rate. In addition, the cavity of the crown ether can also play a certain role in encapsulating water molecules, reducing the occurrence of side reactions.

[0037] The amide bond formed by 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid and 3,4-diaminobenzoic acid with a molar ratio of about 2:1, as well as the hydroxyl and double bond groups, can complex with chlorine, reducing the probability of the by-product sodium chloride covering the product formed after the hydrolysis of isooctyl chloroformate, so as to reduce the impact on the stability of the product. The branched structure of the dendritic polymer can generate a specific spatial environment, restricting the orientation of the reactants, thereby improving the selectivity of the reaction.

[0038] A benzene ring is introduced into the catalyst. The oxygen atom in the peroxide bond has lone pair electrons, and these lone pair electrons can have a weak interaction with the π electron cloud of the adjacent aromatic ring. In addition, the presence of the aromatic ring can restrict the rotation or vibration of the peroxide bond through steric hindrance, thereby reducing the possibility of product decomposition and improving the stability of the product. Specific Embodiments

[0039] The following specific examples illustrate the embodiments of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0040] In the following examples, the silica gel was purchased from Dongying Yiming New Materials Co., Ltd. (mesh number: 100-200, specific surface area 300-550m 2 / g), 3-aminopropyltriethoxysilane was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., 4-aminobutane-1,2,3-triol (CAS: 90847-51-1) was purchased from Hubei Jiutian Biopharmaceutical Technology Co., Ltd., bis(trichloromethyl) carbonate (CAS: 32315-10-9) was purchased from Shanghai Yayu Biopharmaceutical Co., Ltd., dichloromethane was purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd., tert-butyl 4-(2-hydroxyethyl)-4-(2-hydroxypropyl)piperidine-1-carboxylate (CAS: 77279-24-4) was purchased from Shandong Carbon Hydrogen Biochemical Co., Ltd., 1,4-dichloromethylbutane (CAS: 13483-19-7) was purchased from Shanghai Huayuan Century Trading Co., Ltd., 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid (CAS: 1138-41-6) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., 3,4-diaminobenzoic acid (CAS: 619-05-6) was purchased from Yancheng Herui'en Technology Co., Ltd. The activator N,N'-dicyclohexylcarbodiimide (CAS: 538-75-0) was purchased from Hubei Hongfuda Biotechnology Co., Ltd., and the activator 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (CAS: 25952-53-8) was purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0041] Example 1

[0042] 1) Alkali preparation: Quantitative water and 30% liquid caustic soda were sent into the reaction kettle through the conveying pipeline, the stirring was started, and the temperature was lowered to 20 °C by turning on the chilled brine.

[0043] 2) Salt formation reaction: When the temperature in the reaction kettle was controlled at about 20 °C, a quantitative amount of 80% tert-amyl hydroperoxide was added dropwise, and the temperature was controlled below 35 °C. After adding tert-amyl hydroperoxide, the reaction continued for 25 - 30 minutes.

[0044] 3) Condensation reaction: When the temperature in the reaction kettle dropped to about 20 °C, the catalyst was added. The addition amount of the catalyst was 0.5% of the mass of isooctyl chloroformate, and then a quantitative amount of 99% isooctyl chloroformate was added dropwise. The dropping rate and the heating rate were controlled, and the reaction temperature was controlled at 28 - 32 °C. After adding isooctyl chloroformate dropwise, it was kept warm for 1 hour, and the temperature was controlled between 28 - 30 °C.

[0045] Among them, the preparation method of the catalyst in the condensation reaction includes the following steps, and the reaction is carried out under nitrogen protection:

[0046] (1) The silica gel was dehydrated at 150 °C to remove the water adsorbed on the surface; 50 parts of toluene, 1 part of 3-aminopropyltriethoxysilane and 10 parts of silica gel were mixed and reacted at 80 °C for 8 hours, and the amino-modified silica gel carrier was obtained through filtration, washing and drying.

[0047] (2) React 20 parts of 4-aminobutane-1,2,3-triol with 50 parts of methanol and 10 parts of hydrochloric acid (37%) at 60 °C for 6 hours to obtain a first intermediate. React 20 parts of the first intermediate, 0.15 parts of bis(trichloromethyl) carbonate, and 50 parts of dichloromethane at 10 °C for 2 hours to obtain a second intermediate. React 20 parts of the second intermediate, 15 parts of amino-modified silica gel support, and 80 parts of N,N-dimethylformamide at 20 °C for 5 hours to obtain a third intermediate. React 10 parts of the third intermediate with 1 part of 1,3-propanediamine, 50 parts of methanol, and 0.05 parts of triethylamine at 30 °C for 10 hours to obtain a polyamino dendritic product;

[0048] (3) React 20 parts of tert-butyl 4-(2-hydroxyethyl)-4-(2-hydroxypropyl)piperidine-1-carboxylate with 25 parts of 1,4-dichloromethylbutane, 0.1 part of triethylamine, and 90 parts of N,N-dimethylformamide at 60 °C for 8 hours to obtain a first product. Then react 20 parts of the first product, 30 parts of the polyamino dendritic product, 0.1 part of triethylamine, and 100 parts of N,N-dimethylformamide at 60 °C for 8 hours to obtain a polyamino dendritic product with crown ether;

[0049] (4) React 20 parts of 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid, 6 parts of 3,4-diaminobenzoic acid, 50 parts of tetrahydrofuran, 25 parts of N,N′-dicyclohexylcarbodiimide, and 0.1 part of 4-dimethylaminopyridine at 30 °C for 8 hours to obtain a second product. Mix 10 parts of the second product, 15 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 80 parts of N,N-dimethylformamide at 20 °C for 1 hour, then add 18 parts of the polyamino dendritic product with crown ether and react at 20 °C for 12 hours to obtain a catalyst.

[0050] 4) Static stratification: Sampling and analysis show that it is qualified when the chloride ion content is <0.01%. Stop stirring and let it stand for stratification. The lower-layer mother liquor is discharged into the acidification kettle for treatment, and the upper-layer product is waiting for alkali washing.

[0051] 5) Alkali washing: Add a certain amount of 3% liquid caustic soda, start stirring for the first alkali washing for about 10 minutes, let it stand for stratification, and the lower-layer alkali washing wastewater is discharged into the alkali washing wastewater kettle for treatment; repeat the above alkali washing operation, let it stand for stratification, and the lower-layer alkali washing wastewater is also discharged into the alkali washing wastewater kettle for treatment. It is qualified when the content of tert-amyl hydroperoxide remaining in the product is <0.01%.

[0052] 6) Water washing: Add a certain amount of soft water, start stirring for the first water washing for about 10 minutes, let it stand for stratification, and the lower-layer water washing wastewater is used as water for preparing alkali; repeat the above water washing operation, let it stand for stratification, and the lower-layer water washing wastewater is also discharged into the water washing wastewater as water for preparing alkali. It is qualified when the pH value of the product is 7.

[0053] 7) Freezing and packaging: Package after reducing the temperature in the kettle to -10°C.

[0054] 8) Storage: Store the product at a temperature below 20°C.

[0055] Example 2

[0056] 1) Alkali preparation: Feed a certain amount of water and 30% liquid alkali into the reaction kettle through the conveying pipeline, start stirring, and cool down to 20°C by opening the chilled brine.

[0057] 2) Salt formation reaction: Control the temperature in the reaction kettle at about 20°C and start dropping a certain amount of 80% tert-amyl hydroperoxide, with the temperature controlled below 35°C. After adding tert-amyl hydroperoxide, continue the reaction for 25 - 30 minutes.

[0058] 3) Condensation reaction: When the temperature in the reaction kettle drops to about 20°C, add the catalyst. The addition amount of the catalyst is 0.5% of the mass of isooctyl chloroformate, and then drop a certain amount of 99% isooctyl chloroformate. Control the dropping rate and the heating rate, and control the reaction temperature at 28 - 32°C. After dropping isooctyl chloroformate, keep the temperature for 1 hour, with the temperature controlled between 28 - 30°C.

[0059] Among them, the preparation method of the catalyst in the condensation reaction includes the following steps, and the reaction is carried out under nitrogen protection:

[0060] (1) Dehydrate the silica gel at 200°C to remove the moisture adsorbed on the surface; mix 100 parts of toluene, 3 parts of 3-aminopropyltriethoxysilane, and 20 parts of silica gel and react at 90°C for 10 hours, and obtain the amino-modified silica gel carrier through filtration, washing, and drying.

[0061] (2) React 30 parts of 4-aminobutane-1,2,3-triol with 60 parts of methanol and 15 parts of hydrochloric acid (37%) at 80°C for 10 hours to obtain the first intermediate. React 30 parts of the first intermediate, 0.2 parts of bis(trichloromethyl) carbonate, and 100 parts of dichloromethane at 20°C for 5 hours to obtain the second intermediate. React 30 parts of the second intermediate, 20 parts of the amino-modified silica gel carrier, and 100 parts of N,N-dimethylformamide at 30°C for 10 hours to obtain the third intermediate. React 20 parts of the third intermediate with 5 parts of 1,3-propanediamine, 100 parts of methanol, and 0.1 part of triethylamine at 50°C for 20 hours to obtain the polyamino dendritic product.

[0062] (3) React 30 parts of tert-butyl 4-(2-hydroxyethyl)-4-(2-hydroxypropyl)piperidine-1-carboxylate with 30 parts of 1,4-dichloromethylbutane, 0.2 parts of triethylamine, and 100 parts of N,N-dimethylformamide at 80 °C for 10 hours to obtain a first product. Then react 30 parts of the first product, 35 parts of a polyamino dendritic product, 0.15 parts of triethylamine, and 150 parts of N,N-dimethylformamide at 80 °C for 12 hours to obtain a polyamino dendritic product with crown ether;

[0063] (4) React 30 parts of 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid with 10 parts of 3,4-diaminobenzoic acid, 100 parts of tetrahydrofuran, 30 parts of N,N′-dicyclohexylcarbodiimide, and 0.2 parts of 4-dimethylaminopyridine at 40 °C for 10 hours to obtain a second product. Mix 20 parts of the second product, 20 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 100 parts of N,N-dimethylformamide at 30 °C for 2 hours, then add 24 parts of the polyamino dendritic product with crown ether and react at 30 °C for 24 hours to obtain a catalyst.

[0064] 4) Static separation: Sampling and analyzing the chloride ion content. When it is less than 0.01%, it is qualified. Stop stirring and perform static separation. The lower-layer mother liquor is discharged into the acidification kettle for treatment, and the upper-layer product is waiting for alkali washing.

[0065] 5) Alkali washing: Add a certain amount of 3% liquid caustic soda, start stirring for the first alkali washing for about 10 minutes, let it stand for separation, and the lower-layer alkali washing wastewater is discharged into the alkali washing wastewater kettle for treatment; repeat the above alkali washing operation, let it stand for separation, and the lower-layer alkali washing wastewater is also discharged into the alkali washing wastewater kettle for treatment. When the content of tert-amyl hydroperoxide remaining in the product is less than 0.01%, it is qualified.

[0066] 6) Water washing: Add a certain amount of soft water, start stirring for the first water washing for about 10 minutes, let it stand for separation, and the lower-layer water washing wastewater is used as water for preparing alkali; repeat the above water washing operation, let it stand for separation, and the lower-layer water washing wastewater is also discharged into the water washing wastewater as water for preparing alkali. When the pH value of the product is 7, it is qualified.

[0067] 7) Freezing and packaging: Lower the kettle temperature to -10 °C and then package.

[0068] 8) Storage: Store the product below 20 °C.

[0069] Example 3

[0070] 1) Prepare alkali: Feed a certain amount of water and 30% liquid caustic soda into the reaction kettle through a conveying pipeline, start stirring, and turn on the chilled brine to cool down to 20 degrees Celsius.

[0071] 2) Salt formation reaction: When the temperature in the reaction kettle is controlled at about 20°C, a quantitative amount of 80% tert-amyl hydroperoxide is added dropwise, and the temperature is controlled below 35°C. After adding tert-amyl hydroperoxide, continue the reaction for 25 - 30 minutes.

[0072] 3) Condensation reaction: When the temperature in the reaction kettle drops to about 20°C, a catalyst is added. The addition amount of the catalyst is 0.5% of the mass of isooctyl chloroformate, and then a quantitative amount of 99% isooctyl chloroformate is added dropwise. Control the dropping rate and the heating rate, and the reaction temperature is controlled at 28 - 32°C. After adding isooctyl chloroformate dropwise, keep the temperature for 1 hour, and the temperature is controlled between 28 - 30°C.

[0073] Among them, the preparation method of the catalyst in the condensation reaction includes the following steps, and the reaction is carried out under nitrogen protection:

[0074] (1) Dehydrate silica gel at 180°C to remove the water adsorbed on the surface; mix 80 parts of toluene, 2 parts of 3-aminopropyltriethoxysilane, and 16 parts of silica gel and react at 85°C for 9 hours. After filtration, washing, and drying, obtain the amino-modified silica gel carrier;

[0075] (2) React 27 parts of 4-aminobutane-1,2,3-triol with 58 parts of methanol and 12 parts of hydrochloric acid (37%) at 65°C for 8 hours to obtain a first intermediate. React 28 parts of the first intermediate, 0.18 parts of bis(trichloromethyl) carbonate, and 80 parts of dichloromethane at 15°C for 4 hours to obtain a second intermediate. React 24 parts of the second intermediate, 17 parts of the amino-modified silica gel carrier, and 90 parts of N,N-dimethylformamide at 25°C for 8 hours to obtain a third intermediate. React 15 parts of the third intermediate with 4 parts of 1,3-propanediamine, 80 parts of methanol, and 0.08 parts of triethylamine at 40°C for 16 hours to obtain a polyamino dendritic product;

[0076] (3) React 28 parts of tert-butyl 4-(2-hydroxyethyl)-4-(2-hydroxypropyl)piperidine-1-carboxylate with 26 parts of 1,4-dichloromethylbutane,

[0077] 0.15 parts of triethylamine, and 90 parts of N,N-dimethylformamide at 70°C for 9 hours to obtain a first product. Then react 28 parts of the first product, 36 parts of the polyamino dendritic product, 0.15 parts of triethylamine, and 120 parts of N,N-dimethylformamide at 70°C for 10 hours to obtain a polyamino dendritic product with crown ether;

[0078] (4) React 22 parts of 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid, 8 parts of 3,4-diaminobenzoic acid, 80 parts of tetrahydrofuran, 28 parts of N,N'-dicyclohexylcarbodiimide, and 0.2 part of 4-dimethylaminopyridine at 35 °C for 9 hours to obtain a second product. Mix 14 parts of the second product, 18 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 80 parts of N,N-dimethylformamide at 20 °C for 2 hours, and then add 20 parts of a polyamino dendrimer product with crown ether and react at 20 °C for 14 hours to obtain a catalyst.

[0079] 4) Static stratification: Sampling and analysis shows that when the chloride ion content is less than 0.01%, it is qualified. Stop stirring and let it stratify statically. The lower-layer mother liquor is discharged into the acidification kettle for treatment, and the upper-layer product is waiting for alkali washing.

[0080] 5) Alkali washing: Add a certain amount of 3% liquid caustic soda, start stirring for the first alkali washing for about 10 minutes, let it stand and stratify. The lower-layer alkali washing wastewater is discharged into the alkali washing wastewater kettle for treatment; repeat the above alkali washing operation, let it stand and stratify, and the lower-layer alkali washing wastewater is also discharged into the alkali washing wastewater kettle for treatment. When the content of tert-amyl hydroperoxide remaining in the product is less than 0.1%, it is qualified.

[0081] 6) Water washing: Add a certain amount of soft water, start stirring for the first water washing for about 10 minutes, let it stand and stratify. The lower-layer water washing wastewater is used as water for preparing alkali; repeat the above water washing operation, let it stand and stratify, and the lower-layer water washing wastewater is also discharged into the water washing wastewater as water for preparing alkali. When the pH value of the product is 7, it is qualified.

[0082] 7) Freezing and packaging: Lower the kettle temperature to -10 °C and then package.

[0083] 8) Storage: Store the product below 20 °C.

[0084] Comparative Example 1

[0085] 1) Prepare alkali: Feed a certain amount of water and 30% liquid caustic soda into the reaction kettle through a conveying pipeline, start stirring, and turn on the chilled brine to cool down to 20 degrees Celsius.

[0086] 2) Salt formation reaction: Control the temperature in the reaction kettle at about 20 °C and start dropping a certain amount of 80% tert-amyl hydroperoxide, with the temperature controlled below 35 °C. After adding tert-amyl hydroperoxide, continue the reaction for 25 - 30 minutes.

[0087] 3) Condensation reaction: When the temperature in the reaction kettle drops to about 20 °C, start adding a catalyst. The addition amount of the catalyst is 0.5% of the mass of isooctyl chloroformate, and then drop a certain amount of 99% isooctyl chloroformate. Control the dropping rate and the heating rate, and control the reaction temperature at 28 - 32 °C. After dropping isooctyl chloroformate, keep it warm for 1 hour, with the temperature controlled between 28 - 30 °C.

[0088] Among them, the preparation method of the catalyst in the condensation reaction includes the following steps, and the reaction is carried out under nitrogen protection:

[0089] (1) Dehydrate silica gel at 150 °C to remove the water adsorbed on the surface; mix 50 parts of toluene, 1 part of 3-aminopropyltriethoxysilane and 10 parts of silica gel, and react at 80 °C for 8 hours. After filtration, washing and drying, the amino-modified silica gel support is obtained;

[0090] (2) React 20 parts of 4-aminobutane-1,2,3-triol with 50 parts of methanol and 10 parts of hydrochloric acid (37%) at 60 °C for 6 hours to obtain a first intermediate. React 20 parts of the first intermediate, 0.15 parts of bis(trichloromethyl) carbonate and 50 parts of dichloromethane at 10 °C for 2 hours to obtain a second intermediate. React 20 parts of the second intermediate, 15 parts of the amino-modified silica gel support and 80 parts of N,N-dimethylformamide at 20 °C for 5 hours to obtain a third intermediate. React 10 parts of the third intermediate with 1 part of 1,3-propanediamine, 50 parts of methanol and 0.05 parts of triethylamine at 30 °C for 10 hours to obtain a polyamino dendritic product;

[0091] (3) React 20 parts of tert-butyl 4-(2-hydroxyethyl)-4-(2-hydroxypropyl)piperidine-1-carboxylate with 25 parts of 1,4-dichloromethylbutane, 0.1 part of triethylamine and 90 parts of N,N-dimethylformamide at 60 °C for 8 hours to obtain a first product. Then react 20 parts of the first product, 30 parts of the polyamino dendritic product, 0.1 part of triethylamine and 100 parts of N,N-dimethylformamide at 60 °C for 8 hours to obtain a polyamino dendritic product catalyst with crown ether.

[0092] 4) Static stratification: Sampling and analysis shows that when the chloride ion content is less than 0.01%, it is qualified. Stop stirring and let it stand for stratification. The lower layer of mother liquor is discharged into the acidification kettle for treatment, and the upper layer of product is waiting for alkali washing.

[0093] 5) Alkali washing: Add a certain amount of 3% liquid caustic soda, start stirring for the first alkali washing for about 10 minutes, let it stand for stratification, and the lower layer of alkali washing wastewater is discharged into the alkali washing wastewater kettle for treatment; repeat the above alkali washing operation, let it stand for stratification, and the lower layer of alkali washing wastewater is also discharged into the alkali washing wastewater kettle for treatment. It is qualified when the content of tert-amyl hydroperoxide remaining in the product is less than 0.1%.

[0094] 6) Water washing: Add a certain amount of soft water, start stirring for the first water washing for about 10 minutes, let it stand for stratification, and the lower layer of water washing wastewater is used as water for preparing alkali; repeat the above water washing operation, let it stand for stratification, and the lower layer of water washing wastewater is also discharged into the water washing wastewater as water for preparing alkali. It is qualified when the pH value of the product is 7.

[0095] 7) Freezing and packaging: Lower the temperature of the kettle to -10 °C and then package.

[0096] 8) Storage: The product is stored at a temperature below 20°C.

[0097] Comparative Example 2

[0098] The process of Comparative Example 2 is similar to that of Example 1, except that no catalyst is added for the reaction.

[0099] The conversion rates and yield test results of the products in Examples 1 to 3 and Comparative Examples 1 to 2 are listed below, as shown in Table 1.

[0100] Table 1

[0101] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Conversion rate 92.7％ 92.0％ 91.8％ 90.3％ 83.4％ Yield 87.7％ 86.8％ 85.1％ 80.6％ 75.5％

[0102] It can be seen from Table 1 that the conversion rates and yields of the products obtained in Examples 1 - 3 with the addition of a catalyst are significantly better than those of Comparative Example 2 without the addition of a catalyst for the reaction. In Comparative Example 1, due to the lack of modification in step (4) of the catalyst preparation, the yield and conversion rate are inferior to those of Examples 1 - 3.

[0103] Therefore, the present invention effectively overcomes various drawbacks in the prior art and has high industrial utilization value. The above embodiments are only illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A synthesis process of tert-amyl 2-ethylhexyl carbonate peroxide, characterized in that, The synthesis process comprises the following steps: S1: Pump liquid caustic soda and water into a reaction kettle; S2: Add tert-amyl hydroperoxide to the reaction kettle for salt formation reaction; S3: After the salt formation reaction is completed, add a catalyst and dropwise add isooctyl chloroformate for condensation reaction to obtain crude tert-amyl 2-ethylhexyl carbonate peroxide; S4: Wash the crude tert-amyl 2-ethylhexyl carbonate peroxide with alkali and then with water to obtain the finished product; Among them, the preparation of the catalyst comprises the following steps: (1) Provide a silica gel carrier modified with amino groups; (2) React 4-aminobutane-1,2,3-triol with methanol and hydrochloric acid to obtain a first intermediate, react the first intermediate with bis(trichloromethyl) carbonate to obtain a second intermediate, react the second intermediate with the amino group-modified silica gel carrier to obtain a third intermediate, and react the third intermediate with 1,3-propanediamine and methanol to obtain a polyamino dendritic product; (3) React tert-butyl 4-(2-hydroxyethyl)-4-(2-hydroxypropyl)piperidine-1-carboxylate with 1,4-dichloromethylbutane to obtain a first product, and then react the first product with the polyamino dendritic product to obtain a polyamino dendritic product with crown ether; (4) React 4-hydroxy-3-(3-methylbut-2-en-1-yl)benzoic acid with 3,4-diaminobenzoic acid to obtain a second product, and react the second product with the polyamino dendritic product with crown ether to obtain the catalyst.

2. The synthesis process according to claim 1, characterized in that: In step (1), the preparation of the amino group-modified silica gel carrier comprises: dehydrating silica gel at 150-200 °C to remove moisture; React 50-100 parts of toluene, 1-3 parts of 3-aminopropyltriethoxysilane and 10-20 parts of silica gel at 80-90 °C for 8-10 hours, and obtain the amino group-modified silica gel carrier through filtration, washing and drying.

3. The synthesis process according to claim 1, characterized in that: In step (2), the preparation of the first intermediate comprises: React 20-30 parts of 4-aminobutane-1,2,3-triol with 50-60 parts of methanol and 10-15 parts of hydrochloric acid at 60-80 °C for 6-10 hours; obtain the first intermediate through neutralization, extraction, drying and distillation.

4. The synthesis process according to claim 1, characterized in that: In step (2), the preparation of the second intermediate comprises: React 20-30 parts of the first intermediate, 0.15-0.2 part of bis(trichloromethyl) carbonate and 50-100 parts of dichloromethane at 10-20 °C for 2-5 hours; obtain the second intermediate through filtration and washing.

5. The synthesis process according to claim 1, characterized in that: In step (2), the preparation of the third intermediate comprises: React 20-30 parts of the second intermediate, 15-20 parts of the amino group-modified silica gel carrier and 80-100 parts of N,N-dimethylformamide at 20-30 °C for 5-10 hours; obtain the third intermediate through filtration, washing and drying.

6. The synthesis process according to claim 1, wherein: In step (2), the preparation of the polyamino dendrimer product includes: reacting 10 - 20 parts of the third intermediate, 1 - 5 parts of 1,3 - propanediamine, 0.05 - 0.1 part of triethylamine, and 50 - 100 parts of methanol at 30 - 50 °C for 10 - 20 hours; and obtaining the polyamino dendrimer product through filtration and washing.

7. The synthesis process according to claim 1, characterized in that: In step (3), the preparation of the first product includes: reacting 20 - 30 parts of tert - butyl 4-(2 - hydroxyethyl)-4-(2 - hydroxypropyl)piperidine - 1 - carboxylate with 25 - 30 parts of 1,4 - dichloromethylbutane, 0.1 - 0.2 part of triethylamine, and 90 - 100 parts of N,N - dimethylformamide at 60 - 80 °C for 8 - 10 hours; and obtaining the first product through filtration and washing.

8. The synthesis process according to claim 1, characterized in that: In step (3), the preparation of the polyamino dendrimer product with crown ether includes the following steps: reacting 20 - 30 parts of the first product, 30 - 35 parts of the polyamino dendrimer product, 0.1 - 0.15 part of triethylamine, and 100 - 150 parts of N,N - dimethylformamide at 60 - 80 °C for 8 - 12 hours; and obtaining the polyamino dendrimer product with crown ether through filtration and washing.

9. The synthesis process according to claim 1, characterized in that: In step (4), the preparation of the second product includes: reacting 20 - 30 parts of 4 - hydroxy - 3-(3 - methylbut - 2 - en - 1 - yl)benzoic acid, 6 - 10 parts of 3,4 - diaminobenzoic acid, 50 - 100 parts of tetrahydrofuran, 25 - 30 parts of N,N′ - dicyclohexylcarbodiimide, and 0.1 - 0.2 part of 4 - dimethylaminopyridine at 30 - 40 °C for 8 - 10 hours; and obtaining the second product through filtration and washing.

10. The synthesis process according to claim 1, characterized in that: In step (4), the preparation of the catalyst includes: mixing 10 - 20 parts of the second product, 15 - 20 parts of 1 - ethyl - 3-(3 - dimethylaminopropyl)carbodiimide, and 80 - 100 parts of N,N - dimethylformamide at 20 - 30 °C for 1 - 2 hours, then adding 18 - 24 parts of the polyamino dendrimer product with crown ether and reacting at 20 - 30 °C for 12 - 24 hours; and obtaining the catalyst through filtration and washing.

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