High-yield diisobutyryl peroxide and synthetic preparation method thereof

Abstract

The invention discloses high-yield diisobutyryl peroxide and a synthetic preparation method thereof, and belongs to the technical field of chemical synthesis. Comprising the following steps: by taking deionized water as a reaction solvent, controlling the temperature at 0-5 DEG C, and meanwhile, under the catalysis of alkali metal, performing peroxidation on isobutyryl chloride to obtain the diisobutyryl peroxide. The yield of the product diisobutyryl peroxide is higher than 90%, the problem that high reaction temperature is needed in an existing preparation method is solved, the production process is simplified, the production cost is reduced, and the production efficiency is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and more specifically relates to high-yield diisobutyryl peroxide and a synthetic preparation method thereof. Background Art

[0002] Diisobutyryl peroxide is an important organic chemical intermediate. It is a colorless to light yellow oily liquid at room temperature with a special smell. It is volatile, insoluble in water, and soluble in organic solvents. It is widely used in the fields of polymer production, pharmaceutical synthesis, fragrance preparation, and rubber and plastic industries, and can be used as a crosslinking agent and auxiliary agent for polymers. In rubber products, diisobutyryl peroxide can improve the hardness, strength and heat resistance of the colloid, making it more resistant to aging and corrosion. In plastic products, diisobutyryl peroxide can promote chemical reactions and improve the thermal stability and physical properties of plastics, such as impact resistance and corrosion resistance. The research on the synthesis and preparation method of diisobutyryl peroxide has always been an important topic in the field of chemical industry. In the field of organic chemistry, the method for synthesizing and preparing diisobutyryl peroxide is mainly catalytic synthesis. In the existing technology, the synthesis and preparation of diisobutyryl peroxide mainly uses liquid alkali as a catalyst. The catalytic efficiency of this method is low, the yield is usually no more than 70%, and the production cost is high. In addition, the reaction temperature of the preparation process needs to be controlled at around 20°C, which places higher demands on the safety control of the production process.

[0003] After searching, the patent application document with Chinese patent application number 202310385783.9 and application publication date July 7, 2023 discloses a method for preparing diisobutyryl peroxide. The preparation method comprises the following steps: at 0°C to 15°C, liquid caustic soda and hydrogen peroxide are reacted in a medium of water and solvent, wherein the mass ratio of liquid caustic soda, water, hydrogen peroxide, solvent and isobutyryl chloride is 2:(1-1.5):(0.8-1.5):(0-0.2):(0.5-1), the reaction time is 10-30 min, stirring is continued for a period of time after the addition is completed, and then the temperature is lowered to 0°C to 10°C, and isobutyryl chloride is slowly added dropwise after the temperature is lowered, the addition time is 0.5-3 h, stirring is continued for a period of time after the addition is completed, stirring is stopped, and after standing for 10-120 min, the upper layer liquid is collected as crude diisobutyryl peroxide, and then the crude diisobutyryl peroxide is subjected to alkali washing, acid washing and brine washing to obtain diisobutyryl peroxide. Although the existing technology can realize the synthesis and preparation of diisobutyryl peroxide to a certain extent, there are still some problems and limitations. First, in the existing methods, the catalytic efficiency of the catalyst is low, resulting in a low yield, which not only affects the production efficiency but also increases the production cost. Secondly, in the existing methods, the reaction temperature needs to be strictly controlled, which not only increases the complexity of the production process but also puts forward higher requirements for the safety control of the production process. These problems limit the application and development of the existing technology in industrial production.

[0004] The applicant is committed to solving the above problems, and on March 28, 2023, disclosed a method for preparing an organic peroxide initiator using an alkaline earth metal catalyst, using an alkaline earth metal catalyst to replace the traditional NaOH catalyst for catalytic synthesis of peroxide initiators, specifically: first add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 5°C to 20°C, add an alkaline earth metal catalyst, stir for 5 to 30 minutes, then start dripping the acyl chloride, drip for 3 to 30 minutes, control the temperature below 10°C, keep warm and stir for 0 to 10 minutes after the dripping, and stand for water separation and purification to complete the preparation. However, in this study, isobutyryl chloride was not used as a raw material to prepare diisobutyryl peroxide as an example. This is because it was found during the research and development process that isobutyryl chloride is more easily hydrolyzed than other acyl chlorides, and the yield of diisobutyryl peroxide prepared using alkaline earth metals as catalysts does not reach 90%.

[0005] Therefore, developing a new, more efficient and safer method for synthesizing diisobutyryl peroxide is an urgent problem to be solved in this field. Summary of the invention

[0006] 1. Problem to be solved

[0007] In view of the problem that the yield of diisobutyryl peroxide in the prior art is low, the present invention provides a high-yield diisobutyryl peroxide synthesis preparation method, which uses alkali metal as a catalyst to achieve a peroxidation reaction at a temperature below 5° C., and the yield obtained is higher than 90%. Furthermore, diisobutyryl peroxide obtained by the above preparation method is provided.

[0008] 2. Technical solution

[0009] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0010] As a first aspect of the present application, the present application provides a high-yield synthesis and preparation method of diisobutyryl peroxide, comprising the following steps: using deionized water as a reaction solvent, controlling the temperature at 0°C to 5°C, and simultaneously under the catalysis of an alkali metal, peroxidizing isobutyryl chloride to obtain diisobutyryl peroxide.

[0011] Furthermore, the alkali metal is one or more combinations of Li2O and Cs2O, preferably Li2O.

[0012] Furthermore, the mixing mass ratio of Li2O and Cs2O is 1:1.

[0013] Further, isobutyryl chloride undergoes a peroxidation reaction with hydrogen peroxide.

[0014] Furthermore, in the reaction system, the mass fractions of deionized water, alkali metal, isobutyryl chloride, and hydrogen peroxide are

[0015]

[0016] Furthermore, the concentration of the hydrogen peroxide is 27.5%; the concentration of the isobutyryl chloride is 98%.

[0017] Furthermore, hydrogen peroxide and deionized water are first added to the reaction kettle, stirring is started, the temperature is controlled at 0°C to 5°C, an alkali metal catalyst is added, and then isobutyryl chloride is added dropwise for 3 to 10 minutes, the temperature is controlled at 0°C to 5°C, and after the addition is completed, the mixture is stirred and kept warm for 0 to 10 minutes, and the mixture is allowed to stand for water separation and purification, and the preparation is completed.

[0018] Furthermore, the reaction time was 1.2 h.

[0019] As a second aspect of the present application, the present application provides diisobutyryl peroxide catalyzed by alkali metal, which is prepared by the above method, wherein the chloride content is controlled within 0.004%.

[0020] 3. Beneficial effects

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The present invention solves the problem of low yield of diisobutyryl peroxide in the existing preparation method: the traditional preparation method of diisobutyryl peroxide uses liquid alkali as a catalyst, the catalytic efficiency is low, and the yield does not exceed 70%; the present invention uses an alkali metal catalyst to increase the yield to more than 90%, significantly improving the production efficiency, reducing the production cost, and improving the economic benefits.

[0023] Compared with traditional liquid alkali catalysts, alkali metals or alkaline earth metals have very obvious advantages. The mechanism of action is that the hydrogen atoms of the hydroperoxide and the chlorine atoms in the functional group of the acyl chloride (-C(O)Cl) will chemically adsorb with the alkaline active center of the alkali metal / alkaline earth metal catalyst, resulting in the cleavage of the OH bond of the hydroperoxide and the C-Cl bond in the acyl chloride compound, thereby catalyzing the peroxidation substitution reaction of the acyl chloride in the hydroperoxide in the forward direction.

[0024] Especially for the isobutyryl chloride raw material involved in the scheme of the present invention, since isobutyryl chloride is easier to hydrolyze than other acyl chlorides, a catalyst is required to be able to rapidly catalyze the reaction normally, and to obtain sufficient advantages in the competitive reaction between the normal synthesis reaction of normal acyl chloride / hydrogen peroxide and the hydrolysis reaction of acyl chloride raw materials, in order to ensure the expected conversion rate. Therefore, with respect to the invention content of this case, by comparing alkali metal catalysts and alkaline earth metal catalysts, alkali metals are the six metal elements in Group IA of the periodic table except hydrogen (H), and alkaline earth metals are metal elements in Group ⅡA of the periodic table. Alkali metal elements are more catalytically active than alkaline earth metals, and the alkaline active center has stronger adsorption. For the ultra-low temperature and high hydrolysis reaction process of diisobutyryl peroxide, the alkali metal catalyst of the present invention can innovatively solve the industry problems of too low catalytic efficiency and too low conversion rate.

[0025] (2) The present invention solves the problem of high reaction temperature required in the existing preparation method: In the traditional preparation method, the reaction temperature needs to be controlled at about 20°C, which puts forward high requirements for the safety control of the production process. The present invention reduces the reaction temperature to below 5°C, reduces the production cost and simplifies the production process, while improving the production safety and the purity and quality of the product. (Since the reaction is carried out in an aqueous solution, the reaction temperature cannot be lower than 0°C. The lower the reaction temperature is above 0°C, the safer it is, but the reaction rate and conversion rate will also be reduced. The higher the reaction temperature, the greater the safety risk. There are extremely high requirements for the heat exchange capacity of the reaction device. If the heat exchange is not timely, it is very easy to get out of control of the temperature. Therefore, the innovation of the second aspect of the present invention is to ensure that the synthesis rate and conversion rate of the initiator are greatly improved through the development and introduction of alkali metal catalysts at the safest synthesis temperature of the initiator of 0 to 5°C, ensuring safety while improving product purity).

[0026] (3) The present invention solves the problem of complex production process in the existing preparation method: the existing diisobutyryl peroxide synthesis preparation method has a complex production process and strict safety control requirements for the production process. The present invention simplifies the production process, reduces production costs and improves production efficiency by innovatively using alkali metal catalysts and lowering the reaction temperature; by lowering the reaction temperature to below 5°C, it not only reduces energy consumption, but also greatly reduces the thermal risk in the production process and improves production safety. At the same time, the simplified production process also reduces safety hazards in the production process, further improving production safety.

[0027] In summary, in general, compared with the prior art, the present invention has the advantages of higher yield, lower reaction temperature, lower production cost, simplified production process and higher production safety, and is a more efficient, safe and environmentally friendly method for synthesizing and preparing diisobutyryl peroxide. DETAILED DESCRIPTION

[0028] The present invention is further described below in conjunction with specific embodiments.

[0029] The invention discloses a high-yield diisobutyryl peroxide synthesis preparation method, which comprises the following steps: firstly, adding hydrogen peroxide and deionized water into a reaction kettle, starting stirring, controlling the temperature at 0°C to 5°C, adding an alkali metal catalyst, and then starting to drop isobutyryl chloride for 3 to 10 minutes, controlling the temperature at 0°C to 5°C, keeping the temperature and stirring for 0 to 10 minutes after the dropwise addition is completed, and standing to separate water for purification to complete the preparation, wherein, in the reaction system, the mass fractions of deionized water, alkali metal, isobutyryl chloride and hydrogen peroxide are respectively

[0030]

[0031] To avoid redundancy, in the reaction systems of Examples 1 to 4, hydrogen peroxide (27.5%): 20 parts, isobutyryl chloride (98%): 35 parts, and deionized water 44.5 parts are used as constants, and the type and amount of alkali metal are changed to illustrate the unexpected technical effects of the present invention.

[0032] Example 1

[0033] formula:

[0034] Hydrogen peroxide (27.5%): 20 parts, Li2O: 0.2 parts, isobutyryl chloride (98%): 35 parts, deionized water: 44.5 parts.

[0035] Process:

[0036] First, add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 0°C~1°C, add catalyst Li2O, and then start to drop isobutyryl chloride for 4~5 minutes, control the temperature at 0°C~1°C, keep warm and stir for 2 minutes after the addition is completed, let it stand to separate the water and purify it, and the preparation is completed.

[0037] Example 2

[0038] formula:

[0039] Hydrogen peroxide (27.5%): 20 parts, Li2O: 0.1 parts, Cs2O: 0.1 parts, isobutyryl chloride (98%): 35 parts, deionized water 44.5 parts.

[0040] Process:

[0041] First, add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 1°C to 2°C, add catalyst Li2O, and then start to drop isobutyryl chloride for 3 to 4 minutes, control the temperature at 1°C to 2°C, keep warm and stir for 10 minutes after the addition is completed, let it stand to separate the water and purify it, and the preparation is completed.

[0042] Example 3

[0043] formula:

[0044] Hydrogen peroxide (27.5%): 20 parts, Li2O: 1.7 parts, isobutyryl chloride (98%): 35 parts, deionized water: 44.5 parts.

[0045] Process:

[0046] First, add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 2°C to 3°C, add catalyst Li2O, and then start to drop isobutyryl chloride for 4 to 5 minutes, control the temperature at 2°C to 3°C, keep warm and stir for 2 minutes after the addition is completed, let it stand to separate the water and purify it, and the preparation is completed.

[0047] Example 4

[0048] formula:

[0049] Hydrogen peroxide (27.5%): 20 parts, Li2O: 0.5 parts, isobutyryl chloride (98%): 35 parts, deionized water: 44.5 parts.

[0050] Process:

[0051] First, add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 4°C to 5°C, add catalyst Li2O, and then start to drop isobutyryl chloride for 4 to 5 minutes, control the temperature at 4°C to 5°C, keep warm and stir for 2 minutes after the addition is completed, let it stand to separate the water and purify it, and the preparation is completed.

[0052] Comparative Example 1 (basically the same as Example 4, except that the alkali metal catalyst is replaced by sodium hydroxide catalyst)

[0053] formula:

[0054] Hydrogen peroxide (27.5%): 20 parts, sodium hydroxide: 0.5 parts, isobutyryl chloride (98%): 35 parts, deionized water 44.5 parts. Process:

[0055] First, add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 4°C to 5°C, add the catalyst sodium hydroxide, and then start to drop isobutyryl chloride for 4 to 5 minutes, control the temperature at 4°C to 5°C, keep warm and stir for 2 minutes after the addition is completed, let it stand to separate the water and purify it, and the preparation is completed.

[0056] Comparative Example 2 (traditional catalyst, traditional preparation method)

[0057] formula:

[0058] Hydrogen peroxide (27.5%): 20 parts, sodium hydroxide: 10 parts, isobutyryl chloride (98%): 35 parts, deionized water 35 parts. Process:

[0059] First, add sodium hydroxide and deionized water to the reaction kettle, start stirring, control the temperature at 10°C to 20°C, start dripping hydrogen peroxide, drip for 30 to 40 minutes, keep warm for 20 minutes after the dripping is completed, start dripping isobutyryl chloride, the dripping temperature is 20 to 40°C, keep warm for 60 minutes after the dripping is completed, let it stand to separate the water and purify, and the preparation is completed.

[0060] Comparative Example 3 (basically the same as Example 1, except that the alkaline metal catalyst is replaced by the alkaline earth metal catalyst)

[0061] formula:

[0062] Hydrogen peroxide (27.5%): 20 parts, CaO: 0.2 parts, isobutyryl chloride (98%): 35 parts, deionized water 44.5 parts.

[0063] Process:

[0064] First, add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 0°C~1°C, add catalyst CaO, and then start to drop isobutyryl chloride for 4~5 minutes, control the temperature at 0°C~1°C, keep warm and stir for 2 minutes after the addition is completed, let it stand to separate the water and purify it, and the preparation is completed.

[0065] Comparative Example 4 (basically the same as Example 1, except that isononanoyl chloride replaces isobutyryl chloride)

[0066] formula:

[0067] Hydrogen peroxide (27.5%): 20 parts, Li2O: 0.2 parts, isononanoyl chloride (98%): 35 parts, deionized water: 44.5 parts.

[0068] Process:

[0069] First, add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 0°C~1°C, add catalyst Li2O, and then start to drop isononanoyl chloride for 4~5 minutes, control the temperature at 0°C~1°C, keep warm and stir for 2 minutes after the addition is completed, let it stand to separate the water and purify it, and the preparation is completed.

[0070] Comparative Example 5 (basically the same as Example 1, except that isononanoyl chloride replaces isobutyryl chloride)

[0071] formula:

[0072] Hydrogen peroxide (27.5%): 20 parts, CaO: 0.2 parts, isononanoyl chloride (98%): 35 parts, deionized water 44.5 parts.

[0073] Process:

[0074] First, add hydrogen peroxide and deionized water to the reactor, start stirring, control the temperature at 0°C~1°C, add catalyst CaO, and then start to drop isononanoyl chloride for 4~5 minutes, control the temperature at 0°C~1°C, keep warm and stir for 2 minutes after the addition is completed, let it stand to separate the water and purify it, and the preparation is completed.

[0075] This product is used in 20m 3 The effect was verified on the polymerization kettle, and the verification data are shown in the following table.

[0076]

[0077] As shown in the table above, it should be emphasized that the preparation time can reflect the catalytic rate of the catalyst. In Comparative Examples 4 and 5, isononanoyl chloride is used as the acyl chloride raw material, and alkali metal is used as the catalyst in Comparative Example 4, and alkaline earth metal is used as the catalyst in Comparative Example 5. The catalytic effects of Comparative Examples 4 and 5 are slightly worse than those of Example 1, indicating that for isononanoyl chloride, the effects of alkali metal catalysts and alkaline earth metal catalysts are similar. Comparative Example 3 is compared with Example 1, and it can be seen that the catalytic effect of the alkaline earth metal in Comparative Example 3 on isobutyryl chloride is not as good as the catalytic effect of the alkali metal in Example 1 on isobutyryl chloride, indicating that for isobutyryl chloride, alkali metal and alkaline earth metal are used as catalysts respectively, but the effects are unexpectedly different. Moreover, the reaction effects of Comparative Examples 1 and 2 are even slower.

[0078] The above shows and describes the basic principles and main features of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A high-yield diisobutyryl peroxide synthesis preparation method, characterized in that: The method comprises the following steps: using deionized water as a reaction solvent, controlling the temperature at 0°C to 5°C, and simultaneously, under the catalysis of an alkali metal, peroxidizing isobutyryl chloride to obtain diisobutyryl peroxide.

2. A high-yield diisobutyryl peroxide synthesis method according to claim 1, characterized in that: The alkali metal is one or more combinations of Li2O and Cs2O.

3. A high-yield diisobutyryl peroxide synthesis method according to claim 2, characterized in that: The mixing mass ratio of Li2O and Cs2O is 1:

1.

4. A high-yield diisobutyryl peroxide synthesis method according to claim 1, characterized in that: Isobutyryl chloride reacts with hydrogen peroxide to form a peroxidation reaction.

5. A high-yield diisobutyryl peroxide synthesis method according to claim 4, characterized in that: The concentration of the hydrogen peroxide is 27.5%; the concentration of the isobutyryl chloride is 98%.

6. A high-yield diisobutyryl peroxide synthesis method according to claim 1, characterized in that: In the reaction system, the mass fractions of deionized water, alkali metal, isobutyryl chloride, and hydrogen peroxide are 7. A high-yield preparation method for diisobutyryl peroxide according to claim 6, characterized in that: First, add hydrogen peroxide and deionized water into the reaction kettle, start stirring, control the temperature at 0°C to 5°C, add an alkali metal catalyst, and then start to drop isobutyryl chloride for 3 to 10 minutes, control the temperature at 0°C to 5°C, keep warm and stir for 0 to 10 minutes after the dropwise addition is completed, and the preparation is completed after standing to separate water and purify.

8. A high-yield preparation method for diisobutyryl peroxide according to any one of claims 1 to 7, characterized in that: The reaction time is 1.2h.

9. A diisobutyryl peroxide using an alkali metal catalyst, characterized in that: The product is prepared by the method of any one of claims 1 to 8, and the chloride content in diisobutyryl peroxide is controlled within 0.004%.

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