Synthesis method of 1, 3, 3, 3-tetramethyl butyl peroxypivalate

Abstract

The invention discloses a synthesis method of 1, 1, 3, 3-tetramethyl butyl peroxypivalate, which comprises the following steps: sequentially adding soft water, isoparaffin and TOHP into a reaction kettle, cooling, dropwise adding inorganic base, keeping for 15 minutes, and cooling to 10 DEG C; after alkalization is finished, pivaloyl chloride is dropwise added, the rotating speed is increased, the temperature is kept for 120 min, water is added after the temperature is kept for 15 min, stirring is stopped after the temperature is kept for 15 min, standing is conducted for 30 min, a separating funnel is used for material separation, and a crude product is obtained; adding glacial acetic acid into the crude product, then adding triisobutyl lithium borohydride, separating by using a separating funnel, then adding a sodium hydroxide solution and soft water, and finally separating to obtain a fine sample; and drying the high-quality sample to obtain the 1, 1, 3, 3-tetramethyl butyl peroxypivalate. The 1, 1, 3, 3-tetramethyl butyl peroxypivalate provided by the invention is simple, safe and environment-friendly to synthesize, and the produced refined product is high in purity and low in water content.

Description

Technical Field

[0001] The invention relates to the field of peroxides in the chemical industry, and in particular to a method for preparing peroxides. Background Art

[0002] In the production of polyvinyl chloride, in addition to the optimal combination of process operating conditions, water-oil ratio, type and amount of dispersants and other additives, the selection of initiator type and amount is also crucial, which has a certain impact on the production, processing and performance of the resin products. Domestic research on initiators is relatively late and there are fewer varieties, while foreign research is more comprehensive. The trend of organic peroxide research is to develop in the direction of multi-function, low operating temperature, low volatility, good thermal stability, and convenient and safe use.

[0003] At present, my country's PVC manufacturers mainly use isopropyl peroxide neodecanoate as an initiator system in combination with other inefficient initiators to produce general-purpose PVC resins. However, the presence of benzene rings in the initiator system causes the presence of benzene carcinogens in PVC products and production wastewater, which in turn causes certain pollution to the environment.

[0004] 1,1,3,3-Tetramethylbutyl peroxypivalate (TOPV) does not contain a benzene ring in its structure. As a highly efficient initiator for polymer synthesis, it is used in small amounts during the polymerization process, is easily dispersed in the polymerization system, and releases heat evenly, making it easy to control. The synthesized PVC products are not easy to change color, produce little irritating odor, and effectively avoid harm to the human body during the production process. It has a low solubility in water and is not easy to volatilize, which can reduce the number of fish eyes in PVC products and ensure that PVC products and production wastewater do not contain benzene-based carcinogens. It is a safe, efficient, and high-efficiency initiator for polymer synthesis with stable product quality. Summary of the invention

[0005] The object of the present invention is to provide a method for synthesizing 1,1,3,3-tetramethylbutyl peroxypivalate (TOPV) to solve the problems mentioned in the background technology.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] The synthesis method of 1,1,3,3-tetramethylbutyl peroxypivalate (TOPV) comprises the following steps:

[0008] S1. Add soft water, isoparaffin, and TOHP to the reactor in sequence, cool to 13°C, rotate at 320 rpm, and start adding inorganic alkali (the reaction temperature cannot exceed 15°C and cannot be lower than 10°C). The addition ends after 30 minutes, and the temperature is lowered to 10°C after 15 minutes;

[0009] S2. After the alkalization is completed, the speed is 350rpm, the reaction temperature is reduced to 7°C, and pivaloyl chloride is added dropwise. Pivaloyl chloride is prepared with an inert solvent to a content of 80% (the temperature is controlled at 11-15°C). After preparation, the hydrolysis degree of the acyl chloride during the addition and reaction process is effectively slowed down. The addition time is 120 minutes. After the addition is completed, the speed is increased to 360rpm, and the temperature is maintained for 120 minutes at 15°C. After the maintenance is completed, 30g of water is added, pH≈12, and the temperature is continued to be maintained at 15°C for 15 minutes. After the maintenance is completed, stirring is stopped, and the mixture is allowed to stand for 30 minutes, and the material is separated with a separatory funnel;

[0010] S3. Add glacial acetic acid to the crude product and stir for 5 minutes, then add lithium triisobutylborohydride and stir at 10°C for 20 minutes. After stirring, let it stand for 10 minutes and then separate the materials with a separatory funnel. Then add sodium hydroxide solution and soft water, stir at 5°C for 20 minutes, and finally separate the materials to obtain a fine sample.

[0011] When the acyl chloride is added dropwise, in order to prevent the hydrolysis of pivaloyl chloride, the acyl chloride is added in a bottom-insertion manner, and the crude material after the reaction is washed with an alkaline washing liquid and a reducing washing liquid, and finally 1,1,3,3-tetramethylbutyl peroxypivalate with a neutral pH is obtained;

[0012] S4. Use a solid desiccant to dry the fine sample to obtain 1,1,3,3-tetramethylbutyl peroxypivalate.

[0013] Furthermore, the chemical structure of 1,1,3,3-tetramethylbutyl peroxypivalate (TOPV) is shown in the following formula (1):

[0014]

[0015] Furthermore, the molecular weight of the 1,1,3,3-tetramethylbutyl peroxypivalate (TOPV) is 230.3.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. The 1,1,3,3-tetramethylbutyl peroxypivalate proposed by the present invention is simple to synthesize, safe and environmentally friendly, and the produced fine product has high purity and low water content. DETAILED DESCRIPTION

[0018] 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.

[0019] Example 1

[0020] The synthesis method of 1,1,3,3-tetramethylbutyl peroxypivalate (TOPV) comprises the following steps:

[0021] S1. First, add 12g of soft water, 10g of isoparaffin, and 111g of TOHP to the reactor in sequence, then cool to 13°C, rotate at 320rpm, and start dripping 88g of sodium hydroxide solution (the reaction temperature cannot exceed 15°C and cannot be lower than 10°C). The dripping ends after 30 minutes, and the temperature is cooled to 10°C after 15 minutes;

[0022] S2. After the alkalization is completed, the speed is 350rpm, the reaction temperature is lowered to 7°C, and 76g of pivaloyl chloride adjusted to 80% concentration with industrial white oil is added dropwise (the temperature is controlled at 11-15°C). The addition time is 120 minutes. After the addition is completed, the speed is increased to 360rpm, and the temperature is maintained for 120 minutes at 15°C. After the maintenance is completed, 30g of water is added, pH≈12, and the temperature is continued to be maintained at 15°C for 15 minutes. After the maintenance is completed, stirring is stopped, and the mixture is allowed to stand for 30 minutes. The material is separated with a separatory funnel to obtain a crude product;

[0023] S3. First, add 10g of glacial acetic acid to the crude product and stir for 5 minutes. Then add 150g of lithium triisobutyl borohydride and stir at 10°C for 20 minutes. After stirring, let it stand for 10 minutes and then separate the materials with a separatory funnel. Then add 10g of sodium hydroxide solution and 200g of soft water, stir at 5°C for 20 minutes, and finally separate the materials to obtain a fine sample.

[0024] S4. Add 8g of silica gel desiccant to the above fine sample and shake it at 0℃ for 20 minutes. Then filter it with filter paper at the same temperature to obtain the required dry sample.

[0025] Example 2

[0026] The synthesis method of 1,1,3,3-tetramethylbutyl peroxypivalate (TOPV) comprises the following steps:

[0027] S1. First, add 12g of soft water, 10g of isoparaffin, and 111g of TOHP to the reactor in sequence, then cool to 13°C, rotate at 320rpm, and start dripping 88g of sodium hydroxide solution (the reaction temperature cannot exceed 15°C and cannot be lower than 10°C). The dripping ends after 30 minutes, and the temperature is cooled to 10°C after 15 minutes.

[0028] S2. After the alkalization is completed, the speed is 350rpm, the reaction temperature is lowered to 7°C, and 88g of pivaloyl chloride adjusted to 80% concentration with dimethyl silicone oil is added dropwise (the temperature is controlled at 11-15°C), and the addition time is 120 minutes. After the addition is completed, the speed is increased to 360rpm, and the temperature is maintained for 120 minutes, and the temperature is 15°C. After the maintenance is completed, 30g of water is added, the PH is ≈ 12, and the temperature is continued to be maintained at 15°C for 15 minutes. After the maintenance is completed, stirring is stopped, and the mixture is allowed to stand for 30 minutes. The material is separated with a separatory funnel to obtain a crude product;

[0029] S3. First, add 10g of glacial acetic acid to the crude product and stir for 5 minutes, then add 133g of lithium aluminum hydride and stir for 20 minutes at 10°C. After stirring, let it stand for 10 minutes and then separate the materials with a separatory funnel. Then add 10g of sodium hydroxide solution and 200g of soft water, stir for 20 minutes at 5°C, and finally separate the materials to obtain a fine sample;

[0030] S4. Add 13g of calcium chloride desiccant to the above fine sample and shake it at 0℃ for 20 minutes. Then filter it with filter paper at the same temperature to obtain the required dry sample.

[0031] Example 3

[0032] The synthesis method of 1,1,3,3-tetramethylbutyl peroxypivalate (TOPV) comprises the following steps:

[0033] S1. First, add 12g of soft water, 10g of isoparaffin, and 111g of TOHP to the reactor in sequence, then cool to 13°C, rotate at 320rpm, and start dripping 88g of sodium hydroxide solution (the reaction temperature cannot exceed 15°C and cannot be lower than 10°C). The dripping ends after 30 minutes, and the temperature is cooled to 10°C after 15 minutes.

[0034] S2. After the alkalization is completed, the speed is 350rpm, the reaction temperature is lowered to 7°C, and 73g of pivaloyl chloride adjusted to 80% concentration with chloroform is added dropwise (the temperature is controlled at 11-15°C). The addition time is 120 minutes. After the addition is completed, the speed is increased to 360rpm, and the temperature is maintained for 120 minutes at 15°C. After the maintenance is completed, 30g of water is added, pH≈12, and the temperature is continued to be maintained at 15°C for 15 minutes. After the maintenance is completed, stirring is stopped, and the mixture is allowed to stand for 30 minutes. The material is separated with a separatory funnel to obtain a crude product;

[0035] S3. First, add 10g of glacial acetic acid to the crude product and stir for 5 minutes, then add 129g of triethylsilane and stir for 20 minutes at 10°C. After stirring, let it stand for 10 minutes and then separate the materials with a separatory funnel, then add 10g of sodium hydroxide solution and 200g of soft water, stir for 20 minutes at 5°C, and finally separate the materials to obtain a fine sample;

[0036] S4. Add 13g of magnesium chloride desiccant to the above fine sample and shake it at 0°C for 20 minutes. Then filter it with filter paper at the same temperature to obtain the desired dry sample.

[0037] The TOPV 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:

[0038] (1) Product content is tested using the chemical oxygen content method

[0039] (2) TOHP content measurement method adopts reflux method

[0040] (3) Chloride content was chemically titrated using silver nitrate

[0041] (4) Free acid content is determined by potassium hydroxide chemical titration

[0042] (5) Moisture content was measured by Karl Fischer method

[0043] The test results are shown in Table 1 below:

[0044] Table 1

[0045]

[0046]

[0047] From the data comparison in Table 1, it can be seen that TOPV content is ≥75%, hydroperoxide (in terms of TOHP) is ≤0.1%, H + ≤0.1%,Cl - ≤0.015%, Example 1 is the most stable and excellent in all indicators.

[0048] 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.

[0049] 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 peroxypivalate, characterized in that: The following steps are involved: S1. Add soft water, isoparaffin, and TOHP to the reactor in sequence, cool to 13°C, rotate at 320 rpm, start dripping inorganic alkali, and stop dripping after 30 minutes. Keep for 15 minutes and then cool to 10°C; S2, after the alkalization is completed, the speed is adjusted to 350rpm, the reaction temperature is lowered to 7°C, pivaloyl chloride is added dropwise, pivaloyl chloride is prepared with an inert solvent to a content of 80%, the dropping time is 120 minutes, after the dropping is completed, the speed is increased to 360rpm, and the temperature is kept at 15°C for 120 minutes. After the maintenance is completed, 30g of water is added, and the temperature is continued to be maintained at 15°C for 15 minutes. After the maintenance is completed, stirring is stopped, and the mixture is allowed to stand for 30 minutes. The material is separated with a separatory funnel to obtain a crude product; S3. Add glacial acetic acid to the crude product and stir for 5 minutes, then add lithium triisobutylborohydride and stir at 10°C for 20 minutes. After stirring, let it stand for 10 minutes and then separate the materials with a separatory funnel. Then add sodium hydroxide solution and soft water, stir at 5°C for 20 minutes, and finally separate the materials to obtain a fine sample. S4. Use a solid desiccant to dry the fine sample to obtain 1,1,3,3-tetramethylbutyl peroxypivalate.

2. The synthetic method of 1,1,3,3-tetramethylbutyl peroxypivalate according to claim 1, characterized in that: The molecular weight of the 1,1,3,3-tetramethylbutyl peroxypivalate is 230.3.

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