A preparation method of 1,1,3,3-tetramethylbutyl peroxypivalate

Abstract

The invention discloses a method for preparing 1,1,3,3-tetramethylbutyl peroxide pivalate, and belongs to the technical field of organic compound preparation. 1,1,3,3-tetramethylbutyl hydroperoxide and pivaloyl chloride are mixed and pumped into a tubular fixed bed reactor filled with a catalyst, and the mass space velocity is 0.04-0.1 g·min ‑1 / g, temperature controlled at 20-35°C, to obtain 1,1,3,3-tetramethylbutyl peroxypivalate; the catalyst is copper-vanadium-molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ] Catalyst. The present invention adopts a tubular fixed bed reactor to prepare 1,1,3,3-tetramethylbutyl peroxide pivalate, and can increase the utilization rate and stability of the catalyst by accurately controlling the flow rate and material residence time, thereby realizing the continuous production of 1,1,3,3-tetramethylbutyl peroxide pivalate.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compound preparation, and particularly relates to a method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate. Background Art

[0002] With the rapid development of the domestic polymer synthesis industry, the quality and demand of initiators for polymer synthesis have increased rapidly. It is well known that azo initiators have long been used as initiators for the synthesis of polymer polyvinyl chloride, but the decomposition rate of azo initiators is relatively low, resulting in a relatively slow polymerization rate, which ultimately affects production efficiency. The peroxide bonds of organic peroxide initiators are easily broken to produce free radicals, thereby efficiently initiating monomer polymerization reactions and enabling the polymerization reaction to reach a higher conversion rate in a shorter period of time. The two raw materials, 1,1,3,3-tetramethylbutyl hydroperoxide and pivaloyl chloride, are relatively easy to obtain in the chemical market, with a relatively stable supply, which can ensure the continuity of production and are suitable for large-scale industrial production. Therefore, choosing these two raw materials as substrates to synthesize organic peroxide initiators can reduce the cost of initiators.

[0003] In the traditional preparation process of organic peroxide initiators, liquid caustic soda (NaOH) is usually added as a catalyst, and liquid caustic soda as a catalyst requires a two-step reaction. In the first step, liquid caustic soda reacts with hydrogen peroxide to produce sodium peroxide salt, and in the second step, sodium peroxide salt reacts with acyl chloride. However, due to the active and unstable nature of sodium peroxide salt, this process will inevitably cause the decomposition of sodium peroxide salt, which greatly hinders the forward reaction and affects the final yield of organic peroxide. Summary of the invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide a method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate.

[0005] To achieve the above object, the present invention is implemented through the following technical solutions:

[0006] A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate comprises the following steps:

[0007] 1,1,3,3-Tetramethylbutyl hydroperoxide and pivaloyl chloride were mixed and pumped into a tubular fixed bed reactor filled with catalyst at a mass space velocity of 0.04-0.1 g·min -1 / g, controlling the temperature at 20-35°C to obtain 1,1,3,3-tetramethylbutyl peroxypivalate;

[0008] The catalyst is copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40]catalyst.

[0009] The molar ratio of 1,1,3,3-tetramethylbutyl hydroperoxide to pivaloyl chloride is 1:(0.95-1.1).

[0010] The copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 The catalyst is prepared by the following method: deionized water, ammonium molybdate, ammonium metavanadate, copper chloride and isopropyl imidazole are stirred and mixed, the pH is adjusted to 6-8 with HCl, the temperature is raised to 120-160°C, the reaction is carried out for 48-96 hours, and the reaction is cooled to room temperature to obtain copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]catalyst.

[0011] The molar ratio of ammonium molybdate, ammonium metavanadate, copper chloride and isopropylimidazole is 1.0:(1.6-2.4):(0.5-1.0):(4.0-5.0).

[0012] Due to the adoption of the above technical solution, the beneficial effects of the present invention include:

[0013] (1) The present invention uses a hydrothermal method to prepare a new type of copper-vanadium molybdenum oxy-cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]catalyst.

[0014] (2) The present invention uses copper-vanadium molybdenum oxide clusters [Cu(1-iPIM)4]3[VMo 12 O 40 ] catalyst replaces traditional NaOH and alkaline earth metal catalysts to catalyze the synthesis of 1,1,3,3-tetramethylbutyl peroxide pivalate. The catalyst has an anion active site and a metal cation active site of a multi-metal oxygen cluster, and is easily chemically adsorbed with the hydrogen atoms of the hydroperoxide and the chlorine atoms in the acyl chloride functional group, promoting the breaking of the OH bond of the hydroperoxide and the C-Cl bond in the acyl chloride compound, thereby catalyzing the forward reaction of 1,1,3,3-tetramethylbutyl hydroperoxide and pivaloyl chloride, effectively improving the yield of 1,1,3,3-tetramethylbutyl peroxide pivalate.

[0015] (3) The present invention adopts a tubular fixed bed reactor to prepare 1,1,3,3-tetramethylbutyl peroxide pivalate, which can increase the utilization rate and stability of the catalyst by accurately controlling the flow rate and material residence time, thereby realizing the continuous production of 1,1,3,3-tetramethylbutyl peroxide pivalate. DETAILED DESCRIPTION

[0016] The invention will be further described below in conjunction with the embodiments, but the invention is not limited to these embodiments.

[0017] Example 1 Copper-vanadium-molybdenum oxy-cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ] Preparation of catalyst:

[0018] 12 g of deionized water, 1.0 mmol of ammonium molybdate, 1.6 mmol of ammonium metavanadate, 0.5 mmol of copper chloride and 4.0 mmol of isopropyl imidazole were stirred and mixed, and the pH was adjusted to 6 with 1 M HCl. The mixture was transferred into a polytetrafluoroethylene-lined stainless steel hydrothermal synthesis reactor, heated to 120 °C, reacted for 96 h, slowly cooled to room temperature (cooling rate 15 °C / h), filtered, washed with 30 g of deionized water, and vacuum dried at 35 °C for 10 h to obtain copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]catalyst.

[0019] Example 2 Copper-vanadium-molybdenum oxy-cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ] Preparation of catalyst:

[0020] 18 g of deionized water, 1.0 mmol of ammonium molybdate, 2.0 mmol of ammonium metavanadate, 0.75 mmol of cupric chloride and 4.5 mmol of isopropyl imidazole were stirred and mixed, and the pH was adjusted to 7 with 1 M HCl. The mixture was transferred into a polytetrafluoroethylene-lined stainless steel hydrothermal synthesis reactor, heated to 145 °C, reacted for 72 h, slowly cooled to room temperature (cooling rate 15 °C / h), filtered, washed with 30 g of deionized water, and vacuum dried at 35 °C for 10 h to obtain copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]catalyst.

[0021] Example 3 Copper-vanadium-molybdenum oxy-cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ] Preparation of catalyst:

[0022] 20 g of deionized water, 1.0 mmol of ammonium molybdate, 2.4 mmol of ammonium metavanadate, 1.0 mmol of cupric chloride and 5.0 mmol of isopropyl imidazole were stirred and mixed, and the pH was adjusted to 8 with 1 M HCl. The mixture was transferred into a polytetrafluoroethylene-lined stainless steel hydrothermal synthesis reactor, heated to 160 °C, reacted for 48 h, slowly cooled to room temperature (cooling rate 15 °C / h), filtered, washed with 30 g of deionized water, and vacuum dried at 35 °C for 10 h to obtain copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12O 40 ]catalyst.

[0023] Example 4 Preparation of 1,1,3,3-tetramethylbutyl peroxypivalate

[0024] 1,1,3,3-Tetramethylbutyl hydroperoxide and pivaloyl chloride were mixed at a molar ratio of 1:0.95, and the filling catalyst (copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo prepared in Example 1) was pumped into the mixture. 12 O 40 ]) in a tube-type fixed bed reactor, the mass space velocity is 0.04 g·min -1 / g, and the temperature was controlled at 20°C to obtain a reaction product solution. The obtained reaction product solution was washed with a 5wt% NaOH solution (the weight of the 5wt% NaOH solution washing liquid was equal to that of the reaction product solution), and then washed with a saturated sodium chloride solution of the same weight as that of the reaction product solution to obtain a crude product, which was dried with anhydrous magnesium sulfate (the weight of anhydrous magnesium sulfate was half of the weight of the crude product) and filtered to obtain 1,1,3,3-tetramethylbutyl peroxypivalate, with a content of 97.87% and a yield of 96.04%.

[0025] Example 5 Preparation of 1,1,3,3-tetramethylbutyl peroxypivalate

[0026] 1,1,3,3-Tetramethylbutyl hydroperoxide and pivaloyl chloride were mixed in a molar ratio of 1:1, and the catalyst (copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo prepared in Example 2) was pumped into the mixture. 12 O 40 ]) in a tube-type fixed bed reactor, the mass space velocity is 0.07 g min -1 / g, and the temperature was controlled at 30°C to obtain a reaction product solution. The obtained reaction product solution was washed with a 5wt% NaOH solution (the weight of the 5wt% NaOH solution washing liquid was equal to that of the reaction product solution), and then washed with a saturated sodium chloride solution of the same weight as that of the reaction product solution to obtain a crude product, which was dried with anhydrous magnesium sulfate (the weight of anhydrous magnesium sulfate was half of the weight of the crude product) and filtered to obtain 1,1,3,3-tetramethylbutyl peroxypivalate, with a content of 99.05% and a yield of 97.86%.

[0027] Example 6 Preparation of 1,1,3,3-tetramethylbutyl peroxypivalate

[0028] 1,1,3,3-Tetramethylbutyl hydroperoxide and pivaloyl chloride were mixed in a molar ratio of 1:1.1, and the catalyst (copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo prepared in Example 3) was pumped into the mixture. 12 O 40]) in a tube-type fixed bed reactor, the mass space velocity is 0.1 g min -1 / g, and the temperature was controlled at 35°C to obtain a reaction product solution. The obtained reaction product solution was washed with a 5wt% NaOH solution (the weight of the 5wt% NaOH solution washing liquid was equal to that of the reaction product solution), and then washed with a saturated sodium chloride solution of the same weight as that of the reaction product solution to obtain a crude product, which was dried with anhydrous magnesium sulfate (the weight of anhydrous magnesium sulfate was half of the weight of the crude product) and filtered to obtain 1,1,3,3-tetramethylbutyl peroxypivalate, with a content of 99.01% and a yield of 98.05%.

[0029] Comparative Example 1

[0030] A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate is substantially the same as that in Example 5, except that the filled copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]The catalyst was replaced with an equal weight of CaO, and the content of the obtained 1,1,3,3-tetramethylbutyl peroxypivalate was 84.12% and the yield was 86.35%.

[0031] Comparative Example 2

[0032] A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate is substantially the same as that in Example 5, except that the filled copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]The catalyst was replaced with an equal weight of MgO, and the content of the obtained 1,1,3,3-tetramethylbutyl peroxypivalate was 75.68%, and the yield was 80.96%.

[0033] Comparative Example 3

[0034] A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate is substantially the same as that in Example 5, except that the filled copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]The catalyst was replaced with an equal weight of MoO3, and the content of the obtained 1,1,3,3-tetramethylbutyl peroxypivalate was 84.29% and the yield was 88.75%.

[0035] Comparative Example 4

[0036] A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate is substantially the same as that in Example 5, except that the filled copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O40 ] catalyst was replaced by an equal weight of [Cu(1-iPIM)4]3[VW 12 O 40 ], the content of 1,1,3,3-tetramethylbutyl peroxypivalate was 90.53%, and the yield was 89.67%.

[0037] [Cu(1-iPIM)4]3[VW 12 O 40 ] prepared by the following method:

[0038] 14 g of deionized water, 1.0 mmol of sodium tungstate, 2.0 mmol of ammonium metavanadate, 0.75 mmol of copper chloride and 4.5 mmol of isopropyl imidazole were stirred and mixed, and the pH was adjusted to 7 with 1 M HCl. The mixture was transferred into a polytetrafluoroethylene-lined stainless steel hydrothermal synthesis reactor, heated to 150 °C, reacted for 72 h, slowly cooled to room temperature (cooling rate 15 °C / h), filtered, washed with 30 g of deionized water, and vacuum dried at 40 °C for 8 h to obtain copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VW 12 O 40 ]catalyst.

[0039] Comparative Example 5

[0040] A preparation method of 1,1,3,3-tetramethylbutyl peroxide pivalate is basically the same as that of Example 5, except that the tubular fixed bed reactor is not filled with a catalyst, and the material pumped into the tubular fixed bed reactor is prepared by the following method: 300g of 1,1,3,3-tetramethylbutyl hydroperoxide is added to a flask, the temperature is controlled at 20°C, 300g of 5wt% NaOH solution is slowly added dropwise (dropwise for 10min), stirred for 30min, and then 248g of pivaloyl chloride is added dropwise (dropwise for 10min), and mixed evenly. The content of 1,1,3,3-tetramethylbutyl peroxide pivalate obtained by the method is 86.65%, and the yield is 75.10%.

[0041] Comparative Example 6

[0042] 0.5 mol of 1,1,3,3-tetramethylbutyl hydroperoxide, 20 g of copper-vanadium molybdenum oxy-cluster [Cu(1-iPIM)4]3[VMo 12 O 40] The catalyst was mixed and stirred, the temperature was controlled at 30°C, 0.5 mol of pivaloyl chloride was slowly added dropwise (dropwise for 10 minutes), and the reaction was kept warm for 25 minutes to obtain a reaction product solution. The obtained reaction product solution was washed with a 5wt% NaOH solution (the weight of the 5wt% NaOH solution washing liquid was equal to that of the reaction product solution), and then washed with a saturated sodium chloride solution of the same weight as the reaction product solution to obtain a crude product, which was dried with anhydrous magnesium sulfate (the weight of anhydrous magnesium sulfate was half the weight of the crude product) and filtered to obtain 1,1,3,3-tetramethylbutyl peroxypivalate, with a content of 88.93% and a yield of 91.37%.

[0043] The manufacturer of the tubular fixed bed reactor used in the examples and comparative examples of the present application is Hebei Zhongyu Instrument Equipment Co., Ltd., the model is ZYYQ-2, and the filling amount of the catalyst is 20g.

[0044] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. However, any equivalent changes, modifications and evolutions made by ordinary technicians in the field without departing from the scope of the technical solution of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate, characterized in that: The following steps are involved: 1,1,3,3-Tetramethylbutyl hydroperoxide and pivaloyl chloride were mixed and pumped into a tubular fixed bed reactor filled with catalyst at a mass space velocity of 0.04-0.1 g·min -1 / g, controlling the temperature at 20-35°C to obtain 1,1,3,3-tetramethylbutyl peroxypivalate; The catalyst is copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]catalyst.

2. A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate according to claim 1, characterized in that: The mixing molar ratio of the 1,1,3,3-tetramethylbutyl hydroperoxide to pivaloyl chloride is 1:(0.95-1.1).

3. A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate according to claim 1, characterized in that: The copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 The catalyst is prepared by the following method: deionized water, ammonium molybdate, ammonium metavanadate, copper chloride and isopropyl imidazole are stirred and mixed, the pH is adjusted to 6-8 with HCl, the temperature is raised to 120-160°C, the reaction is carried out for 48-96 hours, and the reaction is cooled to room temperature to obtain copper-vanadium molybdenum oxygen cluster [Cu(1-iPIM)4]3[VMo 12 O 40 ]catalyst.

4. A method for preparing 1,1,3,3-tetramethylbutyl peroxypivalate according to claim 3, characterized in that: The molar ratio of ammonium molybdate, ammonium metavanadate, copper chloride and isopropylimidazole is 1.0:(1.6-2.4):(0.5-1.0):(4.0-5.0).