CN102604440B - White carbon black composite powder material and preparation method thereof - Google Patents

Abstract

The invention relates to a white carbon black composite powder material, the white carbon black composite powder material has a strong absorption of ultraviolet-visible spectrum in the range of 220-400nm, and can be used as a good ultraviolet absorbing material; white carbon black The composite powder material has excellent optical properties and can emit very pure red fluorescence, which can be used as a good fluorescent or red light base material. Therefore, it has special significance for the development of materials with optical functions, and has potential application value in optoelectronic functional materials. The preparation method of the white carbon black composite powder material is to utilize hexylcarbazole formaldehyde to oxidize hexylcarbazole formic acid, and then synthesize the white carbon black composite powder material with hexylcarbazole formic acid and activated white carbon black. The method is simple, suitable for industrial production, and has good application prospects.

Description

White carbon black composite powder material and preparation method thereof

technical field

The invention relates to a white carbon black composite powder material and a preparation method thereof.

Background technique

Silica is soluble in caustic and hydrofluoric acid. High temperature resistance, non-combustible, tasteless, odorless, with good electrical insulation.

Due to a series of advantages of silica products, it can be widely used in many fields such as rubber products, agricultural chemicals, daily chemical products, cementing agents, anti-caking agents, paper fillers, etc., and can also be used in fire-fighting agents , feed, cosmetics, matting agents, pigments, paints and many other industries.

However, since silica is a substance that does not absorb ultraviolet rays, and when silica is irradiated by light with an excitation wavelength of 350±5 nm, it hardly fluoresces in the range of 400-700 nm. Therefore, silica cannot be used as an ultraviolet absorber. Matter, nor can it be used as a fluorescent or red light base material, which limits the application of silica.

Contents of the invention

The technical problem to be solved by the present invention is to provide a white carbon black composite powder material, which can absorb ultraviolet rays and can be used as a fluorescent or red light base material; another technical problem to be solved by the present invention The invention provides a preparation method of the white carbon black composite powder material.

In order to solve the above-mentioned technical problems, the invention provides a kind of white carbon black composite powder material, and its preparation method comprises the following steps:

(1) Mix 1.2±0.3 g hexylcarbazole formaldehyde and 2.8±0.3 g potassium dichromate to obtain a mixture, add water and dichloromethane to dissolve the mixture to obtain a mixture, add 30±5 mL to the mixture under stirring water and H ₂ SO ₄ , the volume ratio of water to H ₂ SO ₄ is 1:1, then heat and reflux at 80°C for 1±0.5 hours, cool the reflux at room temperature, add 20±5 mL of water, Extraction, separation and concentration with dichloromethane to obtain a crude product, and then recrystallization of the crude product with a mixture of 10% NaOH and dichloromethane to obtain hexylcarbazole formic acid;

(2) Mix and stir 0.10±0.03g sodium hydroxide and 0.10±0.03g white carbon black, and heat at 200±50°C for 2±0.5 hours to obtain activated white carbon black;

(3) After preheating 50±5 mL of absolute ethanol at 80±5°C for 3-6 minutes, add the activated silica obtained in step (2) and 1.40±0.05 g of hexylcarbazole formic acid to the preheated Stir evenly in the heated absolute ethanol, keep the stirring state, heat and reflux for 48±12 hours, then cool and filter to obtain the crude white carbon black composite powder material, and then wash three times with absolute ethanol to obtain the white carbon black composite powder Material.

The relevant characteristics of the white carbon black composite powder material of the present invention are analyzed and studied below.

1. Ultraviolet visible spectrum absorption test

Weigh a certain amount of hexylcarbazole formaldehyde, hexylcarbazole formic acid, white carbon black, and white carbon black composite powder materials, and make 50 mL solutions with absolute ethanol respectively, with a concentration of 1.0×10 ^-5 mol/L , and then measured with a UV-visible spectrophotometer to study their UV-visible spectral properties.

See accompanying drawing 1 for the comparison result of the ultraviolet spectrograms of the above four substances.

The abscissa in accompanying drawing 1 is wavelength (nm), and ordinate is absorbance (relative intensity); Wherein aldehyde is hexylcarbazole formaldehyde, acid is hexylcarbazole formic acid, composite material is white carbon black composite of the present invention Powder material.

It can be seen from Figure 1 that:

Silica hardly absorbs the ultraviolet-visible spectrum;

Hexylcarbazole formaldehyde and hexylcarbazole formic acid have absorption at 220-350 nm, with absorption peaks at 235±2 nm, 275±2 nm, 290±2 nm and 345±2 nm;

The silica composite powder material has a strong absorption at 220-400 nm, which shifts to the long-wave direction relative to hexylcarbazole formic acid, and the absorption peak at 235±2 nm red shifts to 242±2 nm; The powder material also has a red shift at 275±2 nm, 290±2 nm and 345±2 nm relative to hexylcarbazole formic acid, about 5-10 nm in red shift.

Due to the nano effect of silica and the coordination effect of hexylcarbazole carboxylic acid, the energy level difference between the front molecular orbitals of the silica composite powder material is reduced, and the energy required for the excited transition of electrons is reduced, so the composite powder The UV absorption of the material is red-shifted relative to hexylcarbazole carboxylic acid.

The ultraviolet-visible spectrum absorption test shows that: by using the preparation method of the white carbon black composite powder material of the present invention, the white carbon black that does not absorb ultraviolet rays is transformed into an organic-inorganic composite powder material that can absorb ultraviolet rays.

2. Fluorescence test results of white carbon black, hexylcarbazole formic acid and white carbon black composite powder materials

The fluorescence test results of hexylcarbazole carboxylic acid and white carbon black composite powder materials are shown in Figure 2 and Figure 3 respectively.

The abscissa in accompanying drawings 2 and 3 is the wavelength (nm), and the ordinate is the fluorescence intensity (relative intensity); the carbazole formic acid 1 in the accompanying drawing 2 is hexylcarbazole formic acid, and the composite material EM1 in the accompanying drawing 3 It is the white carbon black composite powder material described in the present invention.

Fluorescent test results showed:

When white carbon black is irradiated by light with an excitation wavelength of 350±5 nm, it hardly fluoresces in the range of 400-700 nm (not shown in the figure);

When hexylcarbazole carboxylic acid is irradiated by light with an excitation wavelength of 350±5 nm, it emits strong fluorescence in the range of 400-600 nm;

When the white carbon black composite powder material is irradiated by light with an excitation wavelength of 350±5 nm, it has strong fluorescence in the range of 400-580 nm, and there is a strong red fluorescence peak at 695±2 nm, which is mainly It is the nano-effect, coordination effect and silanol effect of silica, which partially reduces the energy level difference between the front molecular orbitals of the silica composite powder material, and reduces the energy required for some high-energy π electrons to move back. Therefore, Compared with hexylcarbazole formic acid, silica composite powder has an obvious red fluorescence peak at 695±2 nm in the long-wave direction.

Fluorescence test shows that this white carbon black composite powder material has excellent optical properties, and can emit very pure red fluorescence (685-710 nm range) under the laser excitation of 346 ± 5 nm, white carbon black of the present invention Composite powder material can be used as a good fluorescent or red light base material.

In summary, the white carbon black composite powder material of the present invention has a strong absorption in the ultraviolet-visible spectrum in the range of 220-400 nm, and it can move to the long-wave direction compared with hexylcarbazole formic acid, which can be done very well. Ultraviolet absorbing material; white carbon black composite powder material has excellent optical properties, and can emit very pure red fluorescence, which can be used as a good fluorescent or red light base material. Therefore, it has special significance for the development of materials with optical functions, and has potential application value in optoelectronic functional materials.

The preparation method of the white carbon black composite powder material of the present invention is to utilize hexylcarbazole formaldehyde oxidation to obtain hexylcarbazole formic acid, then synthesize white carbon black composite powder material with hexylcarbazole formic acid and activated white carbon black, The preparation method is simple, suitable for industrial production, and has good application prospects.

Description of drawings

Figure 1: The results of UV-Vis absorption tests of four substances.

Figure 2: Fluorescence spectrum of hexylcarbazole formic acid with an excitation wavelength of 350 nm.

Figure 3: The fluorescence spectrum of the silica composite powder material with an excitation wavelength of 346 nm.

Detailed ways

Example 1:

White carbon black composite powder material, its preparation method comprises the following steps:

(1) Mix 1.2 g of hexylcarbazole formaldehyde and 2.8 g of potassium dichromate to obtain a mixture, add water and dichloromethane to dissolve the mixture to obtain a mixture, add 30 mL of water and H ₂ SO to the mixture under stirring _4. The volume ratio of water and H ₂ SO ₄ is 1:1, and then heated and refluxed at 80°C for 60 minutes, the reflux solution is cooled at room temperature, 20 mL of water is added, extracted and separated with dichloromethane, and concentrated to obtain a crude product , then recrystallize the crude product with a mixed solution of 10% NaOH and dichloromethane to obtain hexylcarbazole formic acid;

(2) Mix and stir 0.1 g sodium hydroxide and 0.1 g white carbon black, and heat at 200°C for 120 minutes to obtain activated white carbon black;

(3) After preheating 50 mL of absolute ethanol at 80 °C for 5 minutes, add the activated silica obtained in step (2) and 1.40 g of hexylcarbazole formic acid into the preheated absolute ethanol and stir After heating and refluxing for 48 hours in a stirring state, cool and filter to obtain the crude white carbon black composite powder material, wash with absolute ethanol three times, and obtain the white carbon black composite powder material of the present invention.

Example 2:

White carbon black composite powder material, its preparation method comprises the following steps:

(1) Mix 0.9 g hexylcarbazole formaldehyde and 2.5 g potassium dichromate to obtain a mixture, add water and dichloromethane to dissolve the mixture to obtain a mixture, add 25 mL of water and H ₂ SO to the mixture under stirring _4. The volume ratio of water to H ₂ SO ₄ is 1:1, and then heated and refluxed at 80°C for 30 minutes, the reflux solution is cooled at room temperature, 15 mL of water is added, extracted and separated with dichloromethane, and concentrated to obtain a crude product , then recrystallize the crude product with a mixed solution of 10% NaOH and dichloromethane to obtain hexylcarbazole formic acid;

(2) Mix and stir 0.07 g sodium hydroxide and 0.07 g white carbon black, and heat at 150°C for 150 minutes to obtain activated white carbon black;

(3) After preheating 45 mL of absolute ethanol at 75°C for 3 minutes, add the activated silica obtained in step (2) and 1.35 g of hexylcarbazole formic acid into the preheated absolute ethanol and stir After heating and refluxing for 48 hours in a stirring state, cool and filter to obtain the crude white carbon black composite powder material, wash with absolute ethanol three times, and obtain the white carbon black composite powder material of the present invention.

Example 3:

White carbon black composite powder material, its preparation method comprises the following steps:

(1) Mix 1.5 g of hexylcarbazole formaldehyde and 3.1 g of potassium dichromate to obtain a mixture, add water and dichloromethane to dissolve the mixture to obtain a mixture, add 35 mL of water and H ₂ SO to the mixture under stirring _4. The volume ratio of water to H ₂ SO ₄ is 1:1, and then heated and refluxed at 80°C for 90 minutes, the reflux solution is cooled at room temperature, 25 mL of water is added, extracted and separated with dichloromethane, and concentrated to obtain a crude product , then recrystallize the crude product with a mixed solution of 10% NaOH and dichloromethane to obtain hexylcarbazole formic acid;

(2) Mix and stir 0.13 g sodium hydroxide and 0.13 g white carbon black, and heat at 250°C for 90 minutes to obtain activated white carbon black;

(3) After preheating 55 mL of absolute ethanol at 85 °C for 6 minutes, add the activated silica obtained in step (2) and 1.45 g of hexylcarbazole formic acid into the preheated absolute ethanol and stir Evenly, keep the stirring state, heat and reflux for 60 hours, cool and filter to obtain the crude white carbon black composite powder material, wash with absolute ethanol three times, and obtain the white carbon black composite powder material of the present invention.

Claims (2)

1. The preparation method of white carbon black composite powder material, comprises the following steps: (1) Mix 1.2±0.3 g hexylcarbazole formaldehyde and 2.8±0.3 g potassium dichromate to obtain a mixture, add water and dichloromethane to dissolve the mixture to obtain a mixture, add 30±5 mL to the mixture under stirring water and H ₂ SO ₄ , the volume ratio of water to H ₂ SO ₄ is 1:1, then heat and reflux at 80°C for 1±0.5 hours, cool the reflux at room temperature, add 20±5 mL of water, Extraction, separation and concentration with dichloromethane to obtain a crude product, and then recrystallization of the crude product with a mixture of 10% NaOH and dichloromethane to obtain hexylcarbazole formic acid; (2) Mix and stir 0.10±0.03g sodium hydroxide and 0.10±0.03g white carbon black, and heat at 200±50°C for 2±0.5 hours to obtain activated white carbon black; (3) After preheating 50±5 mL of absolute ethanol at 80±5°C for 3-6 minutes, mix the activated silica obtained in step (2) with 1.40±0.05 g of hexyl obtained in step (1) Add carbazole carboxylic acid into the preheated absolute ethanol and stir evenly, keep stirring and heat to reflux for 48±12 hours, then cool and filter to obtain the crude white carbon black composite powder material, and then wash three times with absolute ethanol to obtain White carbon black composite powder material. 2. the white carbon black composite powder material that the preparation method of white carbon black composite powder material according to claim 1 makes.

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