Synthesis process of tetrabutylammonium bromide

Abstract

The invention discloses a synthesis process of tetrabutylammonium bromide. The process is characterized by comprising the following steps: (1) taking dibutylamine and n-butyraldehyde as initial raw materials, taking water as a hydrogen source and butanol as a sacrificial reagent under the action of a modified titanium dioxide photocatalyst, and preparing tributylamine by a photocatalytic continuous micro-channel reactor through a reductive amination mechanism; and (2) after concentrating the obtained tributylamine, making the tributylamine directly dissolved in the solvent and mixed with a certain proportion of n-bromobutane, and then enter the next step continuous micro-channel reactor, such that the target product TBAB can be obtained at the high yield after the reaction is performed for3-5 h at the temperature of 60-90 DEG C. Compared with the kettle type reaction, the continuous reaction temperature is low, the reaction time is short, and the process is safe and efficient.

Description

technical field

[0001] The invention belongs to the technical field of chemical synthesis, and specifically refers to a synthesis process of tetrabutylammonium bromide. Background technique

[0002] Tetrabutylammonium bromide (TBAB) has a wide range of uses, as an efficient phase transfer catalyst in organic synthesis, used in alkylation reactions, redox reactions, ester hydrolysis, cyanide halide ion displacement reactions, condensation reactions, addition Synthesis reaction, polymerization reaction, carbene cycloaddition reaction and elimination reaction, etc. It can also be used as bromide ion nucleophile and ionic liquid. It can be used as a molecular sieve template to synthesize ZSM-11 and Silicalite-2 molecular sieves. It can be used as a surfactant in the daily chemical industry and also as a polarographic analysis reagent.

[0003] The synthesis reported in the TBAB literature is mainly obtained by the direct reaction of tri-n-butylamine and brominated n-butane. At...

Examples

Embodiment 1

[0042] Embodiment 1: Preparation of photocatalyst TiO 2 / NiO

[0043] 1g of TiO 2 (P25) powder is added to the solution of nickel acetylacetonate (the solution concentration is kept at 6.0×10 - 4 mol / L~7.0×10 -4 mol / L or so), it was placed in a three-necked flask, and mechanically stirred for 24 hours at room temperature. The final product was washed repeatedly with the same solvent to remove unreacted complexes, and dried at room temperature. Then bake in a muffle furnace at 400°C to 500°C for 1h, repeat the above steps to obtain the photocatalyst TiO 2 / NiO (10.5%).

[0044] The synthesized photocatalyst TiO of embodiment 1 of the present invention 2 / NiO(10.5%) scanning electron microscope picture as figure 1 shown.

Embodiment 2

[0045] Embodiment 2: Preparation of photocatalyst TiO 2 / Fe 2 o 3

[0046] Iron acetylacetonate was added to the mixed solvent of 15ml ethanol and 85ml n-hexane, and the solution concentration was kept at 6.5×10 -4 mol / L, then add 1g of TiO 2 (P25), placed in a three-necked flask, mechanically stirred at room temperature for 24 hours, washed repeatedly with the same solvent, dried at room temperature, and calcined at 400°C to 500°C for 1 hour. Repeat the above steps to obtain different photocatalyst TiO 2 / Fe 2 o 3 (6.5%).

[0047] The synthesized photocatalyst TiO of embodiment 2 of the present invention 2 / Fe 2 o 3 (6.5%) scanning electron microscope picture as figure 2 shown.

Embodiment 3

[0048] Embodiment 3: synthetic tributylamine

[0049] With 50g dibutylamine (0.387mol), 29.29g butyraldehyde (0.406mol), photocatalyst TiO 2 / NiO (10.5%) 1g, n-butanol 100mL, deionized water 10mL were added to the mixer and mixed evenly, pumped into the microchannel reactor, the flow rate was controlled to 10mL / min, under the 100W LED white light After reacting for 2-4 hours under irradiation, monitor the reaction to the end point, filter to remove the photocatalyst, concentrate to remove the solvent, and wash the catalyst once with ethanol and n-butanol, respectively, and then use it for the second catalytic reaction. Gas phase monitoring reaction yield was 90%, purity: 97%.

[0050] Alternate example:

[0051] The preparation method is the same as in Example 3, the difference is that the type and amount of the catalyst and the flow rate of the microchannel reactor are adjusted, and its influence on the reaction is tested respectively, as shown in Table 1.

[0052] Table 1...

technical field

[0001] The invention belongs to the technical field of chemical synthesis, and specifically refers to a synthesis process of tetrabutylammonium bromide. Background technique

[0002] Tetrabutylammonium bromide (TBAB) has a wide range of uses, as an efficient phase transfer catalyst in organic synthesis, used in alkylation reactions, redox reactions, ester hydrolysis, cyanide halide ion displacement reactions, condensation reactions, addition Synthesis reaction, polymerization reaction, carbene cycloaddition reaction and elimination reaction, etc. It can also be used as bromide ion nucleophile and ionic liquid. It can be used as a molecular sieve template to synthesize ZSM-11 and Silicalite-2 molecular sieves. It can be used as a surfactant in the daily chemical industry and also as a polarographic analysis reagent.

[0003] The synthesis reported in the TBAB literature is mainly obtained by the direct reaction of tri-n-butylamine and brominated n-butane. At...

Examples

Embodiment 1

[0042] Embodiment 1: Preparation of photocatalyst TiO 2 / NiO

[0043] 1g of TiO 2 (P25) powder is added to the solution of nickel acetylacetonate (the solution concentration is kept at 6.0×10 - 4 mol / L~7.0×10 -4 mol / L or so), it was placed in a three-necked flask, and mechanically stirred for 24 hours at room temperature. The final product was washed repeatedly with the same solvent to remove unreacted complexes, and dried at room temperature. Then bake in a muffle furnace at 400°C to 500°C for 1h, repeat the above steps to obtain the photocatalyst TiO 2 / NiO (10.5%).

[0044] The synthesized photocatalyst TiO of embodiment 1 of the present invention 2 / NiO(10.5%) scanning electron microscope picture as figure 1 shown.

Embodiment 2

[0045] Embodiment 2: Preparation of photocatalyst TiO 2 / Fe 2 o 3

[0046] Iron acetylacetonate was added to the mixed solvent of 15ml ethanol and 85ml n-hexane, and the solution concentration was kept at 6.5×10 -4 mol / L, then add 1g of TiO 2 (P25), placed in a three-necked flask, mechanically stirred at room temperature for 24 hours, washed repeatedly with the same solvent, dried at room temperature, and calcined at 400°C to 500°C for 1 hour. Repeat the above steps to obtain different photocatalyst TiO 2 / Fe 2 o 3 (6.5%).

[0047] The synthesized photocatalyst TiO of embodiment 2 of the present invention 2 / Fe 2 o 3 (6.5%) scanning electron microscope picture as figure 2 shown.

Embodiment 3

[0048] Embodiment 3: synthetic tributylamine

[0049] With 50g dibutylamine (0.387mol), 29.29g butyraldehyde (0.406mol), photocatalyst TiO 2 / NiO (10.5%) 1g, n-butanol 100mL, deionized water 10mL were added to the mixer and mixed evenly, pumped into the microchannel reactor, the flow rate was controlled to 10mL / min, under the 100W LED white light After reacting for 2-4 hours under irradiation, monitor the reaction to the end point, filter to remove the photocatalyst, concentrate to remove the solvent, and wash the catalyst once with ethanol and n-butanol, respectively, and then use it for the second catalytic reaction. Gas phase monitoring reaction yield was 90%, purity: 97%.

[0050] Alternate example:

[0051] The preparation method is the same as in Example 3, the difference is that the type and amount of the catalyst and the flow rate of the microchannel reactor are adjusted, and its influence on the reaction is tested respectively, as shown in Table 1.

[0052] Table 1...

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