Synthesis method of 1, 1, 3, 3-tetramethylbutylperoxy-2-ethylhexanoate

Abstract

The invention provides a synthesis method of 1, 1, 3, 3-tetramethylbutylperoxy-2-ethylhexanoate, and belongs to the field of organic chemistry. By optimizing the reaction conditions, the reaction rate is successfully improved, the reaction time is shortened, the product decomposition loss and the selectivity of side reaction are reduced, and the conversion rate of the target product is improved. According to the method, the crude product is washed by using the mixed solution, and the product purity, quality and stability are effectively improved. According to the method, the labor intensity is reduced, the production safety coefficient is increased, the production efficiency is improved, and the preparation process is more efficient and reliable. Green and environment-friendly raw materials are adopted for preparation, high-yield, high-purity and low-cost preparation is achieved, and the method has positive significance on development of the chemical industry.

Description

Technical Field

[0001] The invention relates to the field of organic chemistry, and in particular to a method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. Background Art

[0002] PVC resin, a widely used plastic material, is widely used in the construction industry and many other fields. In the construction field, PVC resin is used to manufacture various hard products, such as drainage pipes, wire pipes, profiles, etc., providing key support for the water supply and drainage system, electrical system, insulation system, etc. of the construction industry. In addition, PVC resin is also used as packaging materials in the food, medicine, cosmetics and other industries, such as packaging bags, packaging boxes, bottle caps, etc. These packaging materials can effectively protect the products and extend the shelf life, and improve the safety of the products. At the same time, PVC resin can also be processed into artificial leather with wear resistance, folding resistance, and aging resistance, which is widely used in the fields of soles, bags, etc. In addition, PVC resin can also be made into various plastic products such as hoses, hard pipes, films, cable sheaths, etc., which are widely used in the medical, electronics, automobile, home appliances and other industries. In addition, PVC resin is also used in the manufacture of coatings, adhesives, sealants, etc., such as waterproof coatings, adhesives and sealants.

[0003] 1,1,3,3-Tetramethylbutyl peroxy-2-ethylhexanoate has oxidative activity and can initiate polymerization under specific conditions. It is widely used in the polymerization reaction of PVC resin. In addition, 1,1,3,3-Tetramethylbutyl peroxy-2-ethylhexanoate can also be used as a plasticizer and softener to optimize the processing performance and flexibility of PVC resin, and is often used to make soft PVC products. In the production of some PVC products, 1,1,3,3-Tetramethylbutyl peroxy-2-ethylhexanoate can be used as a cross-linking agent to improve the hardness and heat resistance of PVC resin, and is often used to make hard PVC products. In short, as an organic peroxide, 1,1,3,3-Tetramethylbutyl peroxy-2-ethylhexanoate can play a variety of functions in PVC resin, including heat stabilizer, initiator, plasticizer and cross-linker, etc., which is of great significance to improving the processing performance, mechanical properties and heat resistance of polymers. However, its preparation method has not been fully studied and developed, so it is of great theoretical significance and practical application value to study and develop an efficient, environmentally friendly and economical preparation method of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. This preparation method can not only provide high-quality raw materials for rubber, plastics, coatings and other related industries, improve product performance, but also reduce production costs, improve production efficiency, reduce environmental impact, and promote sustainable development. Summary of the invention

[0004] The present invention provides a method for efficiently preparing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. By optimizing the reaction conditions, the reaction rate is significantly improved, the reaction time is greatly shortened, the product decomposition loss and the selectivity of the side reaction are reduced, and the conversion rate of the target product is improved. In the preparation process, the present invention adopts a pH buffer mixed solution to wash the crude product, which can simply and effectively bring impurities into the mixed solution, further improve the product purity, and improve the quality and stability of the product. In addition, due to the shortening of the reaction cycle, the method reduces the labor intensity, increases the production safety factor, and improves the production efficiency, making the preparation process more efficient and reliable. The preparation method provided by the present invention is not only efficient and environmentally friendly, but also simple to operate and has high practical value. At the same time, the method adopts green and environmentally friendly raw materials to prepare 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, achieves high yield, high purity, and low-cost preparation, and has positive significance for promoting the development of the chemical industry.

[0005] To achieve the above-mentioned object of the invention, the technical solution of the present invention is as follows:

[0006] A method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate comprises three steps of synthesis, purification and drying, wherein:

[0007] Synthesis: Under strict experimental conditions, follow the following steps:

[0008] (1) Mixing a hydroperoxide with an alkaline solution, maintaining a mass ratio of the hydroperoxide to the alkali at 1:0.35-0.75.

[0009] (2) Gradually add isooctanoyl chloride dropwise into the above mixed solution while stirring, maintaining the temperature between 5 and 30° C., and ensuring that isooctanoyl chloride is completely added within 70 to 135 minutes.

[0010] (3) Continue stirring the reaction for 20 to 45 minutes to promote the reaction.

[0011] (4) After the reaction is completed, stop stirring and let the mixed solution stand for 25 to 40 minutes, separate the mother liquor, and wash the reaction product until the pH value is 5 to 7.

[0012] (5) The temperature is lowered to 0°C to -15°C to obtain the target product 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.

[0013] A 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, whose chemical structure is shown in the following formula (1):

[0014]

[0015] In step (1), the alkaline solution is an aqueous solution of sodium hydroxide or potassium hydroxide, and its concentration is 40% to 55%. Sodium hydroxide and potassium hydroxide are both common and easily available chemical substances, so their use costs are low and they are suitable for large-scale production and application.

[0016] In the step (2), the mass ratio of isooctanoyl chloride to the solution obtained in the step (1) is 1:1.67-3.2.

[0017] When performing step (2), the temperature is controlled between 10°C and 25°C.

[0018] In step (3), the stirring reaction time should be controlled between 30 and 45 minutes.

[0019] (1) After the preparation process, we obtained the crude product of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. To ensure the purity of the product, we washed it with a saturated sodium chloride solution until it reached a neutral state. Subsequently, we dried it with anhydrous sodium sulfate and filtered it to finally obtain 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. During storage, the product needs to be stored at -20 to -25°C. DETAILED DESCRIPTION

[0020] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Embodiment 1:

[0022] The following is a method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, the method comprising the following steps:

[0023] (1) In a 1000 ml flask, add 37.5 g of 65% sodium hydroxide and 40 g of water, stir and cool to 5°C.

[0024] (2) 41.6 g of hydroperoxide with a concentration of 72% was added dropwise to the solution obtained in step 1, and the reaction was carried out for 30 minutes while the temperature was controlled at 25°C.

[0025] (3) After stirring evenly, slowly drop 63.4 g of 99% isooctanoyl chloride solution into the flask, control the reaction temperature at 20°C, and add the solution in 1.5 hours. After adding the isooctanoyl chloride solution, stir and react for 60 minutes.

[0026] (4) After the reaction is completed, stirring is stopped and the mixture is allowed to stand for 20 minutes. The mother liquor is separated and the reaction product is washed until the pH value is 6.

[0027] (5) A total of 105.6 g of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate with a content of 97% was obtained, and the yield was about 95%.

[0028] Embodiment 2:

[0029] A method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, the method comprising the following steps:

[0030] (1) In a 1000 ml flask, add 37.5 g of 65% sodium hydroxide and 40 g of water, stir and cool to 5°C.

[0031] (2) 41.6 g of hydroperoxide with a concentration of 72% was added dropwise to the solution prepared in step (1). The reaction time was 30 minutes and the temperature was controlled at 25°C.

[0032] (3) After stirring evenly, 63.4 g of 99% isooctanoyl chloride solution was slowly added dropwise to the flask. The reaction temperature was controlled at 30° C. and the addition was completed in 1.5 hours.

[0033] (4) After adding the isooctanoyl chloride solution, stir and react for 60 minutes. After the reaction is completed, stop stirring, let stand for 20 minutes, separate the reaction mother liquor, and wash the reaction product until the pH value is 6.

[0034] (5) A total of 107.6 g of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate with a content of 98% was obtained, and the yield was about 97%.

[0035] Embodiment 3:

[0036] A method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, the method comprising the following steps:

[0037] (1) In a 1000 ml flask, add 37.5 g of 65% sodium hydroxide and 40 g of water, stir and cool to 5°C;

[0038] (2) 41.6 g of 72% hydroperoxide was added dropwise to the solution obtained in step (1), and the reaction was continued for 30 min while the temperature was controlled at 25° C.;

[0039] (3) After stirring evenly, slowly dropwise add 63.4 g of 99% isooctanoyl chloride solution into the flask, control the reaction temperature at 30°C, and add the solution over 2 hours. After adding the isooctanoyl chloride solution, stir and react for 60 minutes;

[0040] (4) After the reaction is completed, stirring is stopped, the reaction mixture is allowed to stand for 20 minutes, the reaction mother liquor is separated, and the reaction product is washed until the pH value is 6;

[0041] (5) A total of 108.4 g of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate with a content of 95% was obtained, and the yield was about 96%.

[0042] The above disclosure is only a preferred embodiment of the present invention, but does not limit the specific implementation of the present invention. All equivalent replacements and improvements based on the technical essence of the present invention should be included in the protection scope of the present invention.

[0043] The solution of the present invention not only covers the technical means disclosed above, but also covers the technical solution formed by any combination of these technical features. The above is only a specific implementation of the present invention. It should be pointed out that without departing from the principle of the present invention, ordinary technicians in this technical field can also make several improvements and modifications, and these improvements and modifications should also be regarded as the protection scope of the present invention.

[0044] The TOPEH prepared in Examples 1 to 3 was subjected to chemical analysis, and the analysis results are shown in Table 1. The sample analysis conditions are as follows:

[0045] (1) Product content is tested using the chemical oxygen content method

[0046] (2) TOHP content measurement method adopts reflux method

[0047] (3) Chloride content was chemically titrated using silver nitrate

[0048] (4) Free acid content is determined by potassium hydroxide chemical titration

[0049] (5) Moisture content was measured by Karl Fischer method

[0050] The test results are shown in Table 1 below:

[0051] Table 1

[0052] Test indicators Example 1 Example 2 Example 3 TOPEH content (%) 93.21％ 95.24％ 95.14％ TOHP content (%) 0.058％ 0.032％ 0.072％ Chloride content (%) 0.00027％ 0.00021％ 0.00026％ Free acid content (%) 0.072％ 0.064％ 0.082％ Product moisture (%) 0.021％ 0.046％ 0.072％

[0053] By comparing the data in Table 1, it can be seen that the TOPV content is ≥90%, the hydroperoxide (in terms of TOHP) is ≤0.1%, H+ is ≤0.1%, and Cl- is ≤0.025%. Example 2 is the most stable and excellent in all indicators.

[0054] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0055] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, characterized in that : Includes the following steps: (1) mixing a hydroperoxide with an alkaline solution, maintaining a mass ratio of the hydroperoxide to the alkali at 1:0.35 to 0.75; (2) gradually adding isooctanoyl chloride dropwise to the above-mentioned mixed solution, stirring while adding dropwise, maintaining the temperature between 5 and 30° C., and ensuring that isooctanoyl chloride is completely added within 70 to 135 minutes; (3) Continue stirring the reaction for 20 to 45 minutes to promote the reaction; (4) After the reaction is completed, stop stirring, let the mixed solution stand for 25 to 40 minutes, separate the mother liquor, and wash the reaction product until the pH value is 5 to 7; (5) The temperature is lowered to 0°C to -15°C to obtain the target product 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.

2. A method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate according to claim 1, characterized in that The mass ratio of isooctanoyl chloride to the solution obtained in step (1) is 1:1.67-3.

2.

3. A method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate according to claim 1, characterized in that : In step (2), the temperature is controlled between 10°C and 25°C.

4. A method for synthesizing 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate according to claim 1, characterized in that In step (3), the stirring reaction time should be controlled within 30 to 45 minutes.

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