WO2022205580A1 - Instant soluble ultrafine solid block carbon black, preparation method for same, and applications thereof - Google Patents

Abstract

An instant soluble ultrafine solid block carbon black, a preparation method for same, and applications thereof. Powder carbon black, an anionic surfactant, a nonionic surfactant, a surfactant, and water are premixed and then milled with zirconium oxide to produce a carbon black nanoemulsion of which the particle size of the carbon black is no higher than 200 nm; the emulsion is baked and molded to produce the solid block carbon black. The technical solution described above has the advantage of being free of dust pollution, can be used conveniently, can be quickly dissolved into block carbon black, has excellent application performance, is applied to the surface of a material by employing conventional methods such as padding and coating, and is then baked to produce a carbon black-modified material.

Description

A kind of instant ultrafine solid block carbon black and its preparation method and application technical field

The invention relates to a preparation technology of a carbon-based material, in particular to the preparation of an environment-friendly solid block carbon black, so as to solve the dust pollution of the existing powdery carbon black.

Background technique

Carbon black is an amorphous carbon, a light, loose, and extremely fine black powder with a very large surface area. Carbon black has the advantages of low price and wide range of raw material sources. However, carbon black has serious carbon black dust pollution in the process of production, processing, packaging and transportation, which not only deteriorates the production environment, but also seriously affects the health of production workers. In the application process of carbon black powder, there are also problems of carbon black dust pollution and deterioration of the production environment, and according to the application requirements, powder carbon black needs to be emulsified and dispersed, which is extremely inconvenient to use. In order to reduce the environmental pollution of powdered carbon black, a carbon black compressor and a block carbon black processing device are used to make block carbon black by mechanical compression (ZL200520033701.1) or extrusion (ZL201820897798.8) to solve the existing problems. Reports of technical problems that the technology is easily packaged in bulk during storage and transportation, polluting the environment, and seriously endangering the health of operators during packaging and use. However, in the process of use, there are still shortcomings such as the need to emulsify and disperse powder carbon black.

technical problem

The purpose of the present invention is to provide a kind of instant ultrafine solid block carbon black, which can directly use the carbon black conveniently, avoid the emulsification and dispersion when the carbon black is used, and reduce the environmental pollution caused by the carbon black dust.

technical solutions

In order to achieve the above purpose of the invention, the technical solution adopted in the present invention is:

An instant type ultrafine solid block carbon black, the preparation method comprising the following steps: mixing powdery carbon black, an auxiliary agent and water and grinding to obtain a carbon black emulsion; after drying the carbon black emulsion, an instant type carbon black emulsion is obtained Ultrafine solid block carbon black.

The invention discloses an ultra-fine carbon black instant solution, and a preparation method thereof comprises the following steps: mixing powdery carbon black, auxiliary agents and water, and then grinding to obtain a carbon black emulsion; and drying the carbon black emulsion to obtain an instant solution type ultrafine solid block carbon black; mixing instant ultrafine solid block carbon black with water to obtain a superfine carbon black instant solution.

The invention discloses a conductive fabric. The preparation method comprises the following steps: mixing powdery carbon black, auxiliary agents and water and then grinding to obtain a carbon black emulsion; and drying the carbon black emulsion to obtain an instant ultrafine solid block carbon black; mixing instant ultrafine solid block carbon black with water to obtain a superfine carbon black quick solution; padding the fabric with the superfine carbon black quick solution and drying to obtain a conductive fabric.

In the present invention, powdery carbon black is a conventional product, which is one or a mixture of pigment carbon black, conductive carbon black and rubber carbon black.

In the present invention, the adjuvant includes a surfactant and a surfactant, wherein the surfactant is an anionic surfactant, a nonionic surfactant; preferably, the adjuvant is an anionic surfactant, a nonionic surfactant, a Active agent composition, more preferably, the auxiliary agent is composed of anionic surfactant, nonionic surfactant and surfactant with a mass ratio of 1:(0.5-0.8):(0.02-0.1). Specifically, the anionic surfactant is a mixture of formaldehyde condensate of sodium methylnaphthalene sulfonate and sodium lignosulfonate; the nonionic surfactant is aliphatic amine polyoxyethylene ether, fatty alcohol polyoxyethylene ether , a mixture of polyether polyols; the surfactant is an amphiphilic surfactant. The forces between carbon black particles include van der Waals force, electrostatic attraction and steric resistance. The van der Waals force between particles increases with the increase of particle size and decreases with the increase of the distance between particles. The electrostatic attraction between carbon black particles can be reduced by adding a dispersant, and the stable dispersion of carbon black in an aqueous system can be promoted by using an effective dispersion method. The key technology is to select an appropriate dispersant. The additive defined in the present invention increases the distance between carbon black particles, thereby preventing the aggregation of carbon black particles, changing the surface charge of the carbon black particles, and preventing the aggregation of carbon black particles through electrostatic repulsion. The anchoring group is adsorbed to the surface of carbon black particles, forming a large number of shells or enhancing the charge on the surface of carbon black, effectively preventing the flocculation and coagulation of the carbon black dispersion system.

In the present invention, grinding is carried out in a conventional zirconia ball milling device, the specific operation of grinding is the prior art, and the grinding time is preferably 2 to 4 hours to obtain a carbon black emulsion with a carbon black particle size not higher than 200 nm.

In the present invention, drying the carbon black emulsion is a conventional technique, and the carbon black emulsion can be placed in a container and dried to obtain solid block carbon black. The container is a conventional product, which can store the carbon black emulsion; drying is a conventional drying method, such as placing the carbon black liquid in a conventional container and drying it at 100-120 ° C for 1-4 hours to obtain solid lump carbon black.

In the present invention, the instant ultra-fine solid block carbon black is mixed with water, and stirred at 700-800 rpm for 2-8 minutes to obtain the ultra-fine carbon black quick solution, which is the creativity of the present invention. The powdery carbon black of the existing product is ground and then dried to obtain the lumpy carbon black, which solves the problem of powder pollution in the transportation and application of the powdery carbon black in the prior art. In particular, the lumpy carbon black of the present invention Black can be instantly dissolved in water, and in the formed instant solution, the particle size of carbon black particles is small, and there is no agglomeration phenomenon, which is a technical effect that cannot be achieved by the existing technology, and significantly improves the environment in the application field of carbon black and reduces dust pollution. .

In the present invention, the fabric can be polyester spandex fabric; the rolling ratio of padding is 85%; the specific padding and drying are conventional techniques.

The method for preparing instant ultrafine solid block carbon black in the present invention is as follows.

(1) Premixing, premixing powdered carbon black, additives and water to obtain a carbon black solution.

(2) Grinding, the carbon black solution is continuously ground in a zirconia grinding device to obtain a carbon black emulsion.

(3) Drying and forming: The carbon black emulsion is placed in a container and dried to obtain instant ultra-fine solid block carbon black.

In the present invention, the mass sum of powdered carbon black, additives and water is 100%, wherein 10-40% of powdered carbon black, 3-15% of additives, and water are the balance; The ratio is 1:(0.5～0.8):(0.02～0.1) of anionic surfactant, nonionic surfactant and surfactant.

The instant ultra-fine solid block carbon black disclosed in the invention has ultra-fine self-dispersion performance, and the solid block carbon black is mixed with water to prepare an ultra-fine self-dispersing carbon black liquid with a carbon black particle size not higher than 200 nm. Then, it is applied to the surface of the material by conventional methods such as padding and coating, and then dried to obtain a carbon black modified material. Therefore, the present invention discloses the application of the above-mentioned instant ultrafine solid block carbon black in the preparation of carbon black modified materials.

The invention provides a preparation technology of ultra-fine solid block carbon black, which integrates "no dust pollution, no waste water discharge, rapid dissolution, and ultra-fine nano-particles", and solves the problems of carbon black dust pollution and easy agglomeration of water-based carbon black. , powdered carbon black can be added with additives and ground into a certain concentration of nano-carbon black emulsion, and then dried to prepare solid block carbon black, and solid block carbon black has the characteristics of rapid dissolution, which can be easily applied to carbon black Modification of other materials to obtain excellent antistatic properties and electrical conductivity.

beneficial effect

Due to the application of the above technical solutions, the present invention has the following advantages compared with the prior art.

(1) It avoids the problem that powdered carbon black is easily packaged to pollute the environment during storage and transportation.

(2) The dust hazard of powdered carbon black to the health of operators is significantly reduced.

(3) The agglomeration phenomenon and environmental pollution caused by powdered carbon black during use are solved.

(4) The massive carbon black that is extremely convenient to use and can dissolve quickly is prepared, which is not only convenient to use, but also the carbon black dissolved in water is still in the ultra-fine and nano-scale, and the particle size of the carbon black is not higher than 200 nm.

(5) The prepared block carbon black can be blended with other materials to obtain excellent application performance.

Description of drawings

Fig. 1 is the particle size test result of the carbon black emulsion prepared in Example 1.

Figure 2 is the particle size test result of the carbon black emulsion prepared in Example 2.

3 is the particle size test result of the carbon black emulsion prepared in Example 3.

4 is the particle size test result of the carbon black emulsion prepared in Example 4.

5 is the particle size test result of the carbon black emulsion prepared in Example 5.

FIG. 6 is the particle size test result of the carbon black emulsion prepared in Example 6. FIG.

7 is the particle size test result of the instant carbon black liquid prepared in Example 7.

8 is the particle size test result of the instant carbon black liquid prepared in Example 8.

9 is the particle size test result of the instant carbon black liquid prepared in Example 9.

10 is the particle size test result of the instant carbon black liquid prepared in Example 10.

11 is the particle size test result of the instant carbon black liquid prepared in Example 11.

12 is the particle size test result of the instant carbon black liquid prepared in Example 12.

13 is the morphology of carbon black in the carbon black emulsion prepared in Example 4 (transmission electron microscope, 500 nm).

14 is the morphology of carbon black in the carbon black emulsion prepared in Example 4 (transmission electron microscope, 200 nm).

Figure 15 is a photo of the solid block carbon black prepared in Example 4.

Embodiments of the present invention

The present invention will be further described below in conjunction with the examples.

All raw materials in the embodiment are commercially available products, such as commercially available carbon black 15F (Anhui Heiyu Pigment New Materials Co., Ltd.), commercially available dispersant MF, commercially available sodium lignosulfonate-N, commercially available octadecylamine Polyoxyethylene ether (EO is 15, 20, 30 respectively), commercially available peregal O (EO is 15, 20, 30 respectively), commercially available polyether polyol HSH-210, commercially available dispersant AKN-2290, Foshan City Qianyou Chemical Co., Ltd., commercially available dispersant RQT-FS, and Henan Richite Chemical Co., Ltd. are all industrial grades. Grinding is a conventional method, using a conventional vertical grinding machine, and the grinding speed is 3000 rpm. The drying of the bulk carbon black prepared from the carbon black liquid is a conventional method. For example, the carbon black liquid is placed in a suitable container and dried at 100 to 120 ° C for 1 to 4 hours. In the following example, 110 ° C is selected to be dried for 2 hours to obtain Solid lump carbon black. The drying of the prepared conductive fabric is a conventional method, such as padding the instant carbon black liquid on the fabric and drying at 140° C. for 5 minutes.

In Examples 1 to 6, the composition (g) of the raw materials is as follows.

.

In the table, the 4th to 9th columns are the detailed composition of the adjuvant.

Example 1.

1000 grams of carbon black 15F, 96 grams of dispersant MF, 97 grams of sodium lignosulfonate-N, 34 grams of octadecylamine polyoxyethylene ether (EO=15), 33 grams of Pinga O15 (EO=15), 34 grams 1 g of polyether polyol HSH-210, 6 g of dispersant RQT-FS and 8700 g of water were pre-mixed to obtain a carbon black solution with a total of 300 g of additives. The carbon black solution was continuously ground in a zirconia ball mill for 2 hours to obtain a carbon black emulsion. The above nanometer carbon black emulsion is placed in a container and dried to obtain solid block carbon black.

Example 2.

1000 grams of carbon black F15, 82 grams of dispersant MF, 81 grams of sodium lignosulfonate-N, 41 grams of octadecylamine polyoxyethylene ether (EO=15), 41 grams of Pinga O15 (EO=15), 41 grams The carbon black solution was prepared by premixing 1 g of polyether polyol HSH-210, 14 g of dispersant RQT-FS and 8700 g of water. The carbon black solution was continuously ground in a zirconia grinding device for 2.5 hours to obtain a carbon black emulsion. The above nanometer carbon black emulsion is placed in a container and dried to obtain solid block carbon black.

Example 3.

Combine 2000 grams of carbon black F15, 157 grams of dispersant MF, 157 grams of sodium lignosulfonate-N, 50 grams of octadecylamine polyoxyethylene ether (EO=15), 45 grams of Pingban plus O15 (EO=15), 78 The carbon black solution was prepared by premixing 1 g of polyether polyol HSH-210, 13 g of dispersant RQT-FS and 7500 g of water. The carbon black solution was continuously ground in a zirconia grinding device for 2.5 hours to obtain a carbon black emulsion. The above nanometer carbon black emulsion is placed in a container and dried to obtain solid block carbon black.

Example 4.

Combine 2000 grams of carbon black 15F, 168 grams of dispersant MF, 200 grams of sodium lignosulfonate-N, 55 grams of octadecylamine polyoxyethylene ether (EO=15), 117 grams of peregal O15 (EO=15), 78 gram polyether polyol HSH, 32 grams of dispersant RQT-FS and 7350 grams of water were premixed to obtain a carbon black solution with a total of 650 grams of abrasive. The carbon black solution was continuously ground in a zirconia grinding device for 3 hours to obtain a carbon black emulsion. The above carbon black emulsion is placed in a container and dried to obtain solid block carbon black.

Example 5.

Combine 3000 grams of carbon black F15, 300 grams of dispersant MF, 314 grams of sodium lignosulfonate-N, 100 grams of octadecylamine polyoxyethylene ether (EO=20), 100 grams of peregal O15 (EO=30), 156 The carbon black solution was prepared by pre-mixing gram of polyether polyol HSH, 30 grams of dispersant RQT-FS and 6000 grams of water, with a total of 1000 grams of abrasive. The carbon black solution was continuously ground in a zirconia grinding device for 3 hours to obtain a carbon black emulsion. The above carbon black emulsion is placed in a container and dried to obtain solid block carbon black.

Example 6.

Combine 3800 grams of carbon black F15, 420 grams of dispersant MF, 356 grams of sodium lignosulfonate-N, 180 grams of octadecylamine polyoxyethylene ether (EO=30), 150 grams of peregal O20 (EO=20), 228 A carbon black solution was prepared by premixing 1 g of polyether polyol HSH-210, 66 g of dispersant RQT-FS and 4800 g of water. The carbon black solution was continuously ground in a zirconia grinding device for 4 hours to obtain a carbon black emulsion. The above nanometer carbon black emulsion is placed in a container and dried to obtain solid block carbon black.

Comparative ratio.

Combine 2000 grams of carbon black 15F, 168 grams of dispersant MF, 200 grams of sodium lignosulfonate-N, 55 grams of octadecylamine polyoxyethylene ether (EO=15), 117 grams of peregal O15 (EO=15), 78 The carbon black solution was prepared by premixing gram polyether polyol HSH and 7382 grams water. The carbon black solution was continuously ground in a zirconia grinding device for 3 hours to obtain a carbon black emulsion. The above-mentioned carbon black emulsion was placed in a container, and the solid block carbon black was obtained by drying, and 15 grams of solid block carbon black (prepared in Example 4) was mixed with 85 grams of water, and stirred with a stirrer at 800 rpm. After 5 minutes, there were particles visible to the naked eye, and the mixture was stirred for another 15 minutes to obtain a carbon black liquid. Trace particles were also seen, and the measured particle size was 286.88 nm.

Combine 2000 grams of carbon black 15F, 168 grams of dispersant MF, 200 grams of sodium lignosulfonate-N, 55 grams of octadecylamine polyoxyethylene ether (EO=15), 117 grams of peregal O15 (EO=15), 78 A carbon black solution was prepared by premixing gram of polyether polyol HSH, 32 grams of dispersant AKN-2290 and 7350 grams of water. The carbon black solution was continuously ground in a zirconia grinding device for 3 hours to obtain a carbon black emulsion with a measured particle size of 226.79 nm.

Disperse 2000 grams of carbon black 15F, 168 grams of dispersant MF, 55 grams of octadecylamine polyoxyethylene ether (EO=15), 117 grams of Pinga O15 (EO=15), 78 grams of polyether polyol HSH, 32 grams of dispersed The carbon black solution was prepared by premixing the agent RQT-FS and 7550 g of water. The carbon black solution was continuously ground in a zirconia grinding device for 3 hours to obtain a carbon black emulsion with a measured particle size of 236.82 nm.

Example 7.

Mix 10 grams of solid lump carbon black (prepared in Example 1) with 90 grams of water, and stir with a stirrer at 700 rpm for 5 minutes to prepare an instant carbon black liquid. Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.

Example 8.

Mix 15 grams of solid lump carbon black (prepared in Example 2) with 85 grams of water, and stir with a stirrer at 800 rpm for 5 minutes to prepare an instant carbon black liquid. Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.

Example 9.

Mix 10 grams of solid block carbon black (prepared in Example 3) with 90 grams of water, and stir with a stirrer at 800 rpm for 5 minutes to prepare an instant carbon black liquid. Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.

Example 10.

Mix 15 grams of solid lump carbon black (prepared in Example 4) with 85 grams of water, and stir with a stirrer at 800 rpm for 5 minutes to prepare an instant carbon black liquid. Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.

Example 11.

Mix 10 grams of solid lump carbon black (prepared in Example 5) with 90 grams of water, and stir with a stirrer at 800 rpm for 5 minutes to prepare an instant carbon black liquid. Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.

Example 12.

Mix 10 grams of solid lump carbon black (prepared in Example 6) with 90 grams of water, and stir with a stirrer at 700 rpm for 5 minutes to prepare an instant carbon black liquid. Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.

Performance Testing.

Particle size of instant carbon black liquid: measured on a nanometer particle sizer, and D50 is used to represent the particle size, and the unit is nm.

Morphology of carbon black: The morphology of instant carbon black liquid is tested by transmission electron microscope, and the morphology of spherical carbon black can be observed.

Electrical conductivity: The sheet resistance of the fabric was tested on a digital four-point probe tester. The test conditions were temperature 20 °C, humidity 65%, and the sample was equilibrated for 24 h.

The test results of the particle size of the instant carbon black liquid are shown in Figures 1 to 12. It can be seen that the D50 particle sizes of the nano-carbon black emulsions of Examples 1 to 6 are 131.49, 111.30, 120.09, 141.10, 154.59 and 140.02 nm, respectively; the D50 particle sizes of the nano-carbon black liquids of Examples 7 to 12 are respectively are 151.63, 142.10, 166.29, 180.37, 184.59 and 164.86nm. This shows that the solid block carbon black prepared by the solution disclosed in the present technology can have excellent water solubility and instant solubility, and the particle size of the dissolved carbon black liquid is not higher than 200 nm. Due to the objective properties, the ground carbon black particles will aggregate, especially when they are dried and then dispersed, the particles aggregate obviously, resulting in a large particle size, exceeding the nanometer level. The present invention effectively solves this problem, and the prepared block carbon black Black not only has strong instant solubility, but also in the dispersed carbon black liquid, the particle size of carbon black particles increases very little.

Figure 13 and Figure 14 are the carbon black morphology (transmission electron microscope) of the carbon black emulsion prepared in Example 4. It can be seen that the carbon black morphology in the prepared nano-carbon black emulsion is mostly nano-scale spherical structure (attached A) in Fig. 13, a small amount of nano-scale sheet-like structures can also be seen (B in Fig. 13), such nano-scale sheet-like structures can be clearly observed (Fig. 14); Fig. 15 shows the implementation The photo of the solid lump carbon black prepared in Example 4, compared with the powdery carbon black without grinding modification, has no dust pollution, and there is obvious orientation in the lump carbon black.

The polyester spandex fabrics prepared from Examples 7 to 12 have been tested for electrical conductivity, and the sheet resistances of the polyester spandex fabrics are 0.0751, 0.0715, 0.0782, 0.0633, 0.0681 and 0.0565 MΩ, respectively, with excellent electrical conductivity.

In order to solve the deficiencies in the production, processing, packaging, transportation and use processes of carbon black, the invention discloses a preparation method of instant ultra-fine solid block carbon black, which can not only prepare solid block carbon black without dust pollution, but also When used, it has the advantages of rapid dissolution and ultra-fine carbon black particle size, which significantly improves the environmental pollution caused by powder carbon black, has the effect of extremely simple use, and can meet the performance requirements of water-based carbon black applications.

Claims (10)

1. An instant ultra-fine solid block carbon black, characterized in that the preparation method of the instant ultra-fine solid block carbon black comprises the following steps: mixing powdery carbon black, an auxiliary agent and water, and then grinding to obtain the carbon black Black emulsion; after drying the carbon black emulsion, instant ultrafine solid block carbon black is obtained.
2. The instant ultrafine solid block carbon black of claim 1, wherein the powdery carbon black is one or a mixture of pigment carbon black, conductive carbon black, and rubber carbon black.
3. The instant ultrafine solid block carbon black according to claim 1, wherein the auxiliary agent comprises a surfactant and a surfactant; the mass sum of the powdery carbon black, auxiliary agent and water is 100%, wherein the powder 10-40% of carbon black, 3-15% of additives, and water as the balance.
4. The instant ultra-fine solid block carbon black according to claim 3, characterized in that the auxiliary agent is an anionic surfactant and a non-ionic surfactant with a mass ratio of 1:(0.5-0.8):(0.02-0.1). and surfactants.
5. The instant ultrafine solid block carbon black according to claim 4, wherein the anionic surfactant is a mixture of formaldehyde condensate of sodium naphthalene sulfonate and sodium lignosulfonate; the nonionic surfactant The surfactant is a mixture of fatty amine polyoxyethylene ether, fatty alcohol polyoxyethylene ether and polyether polyol; the surfactant is an amphiphilic surfactant.
6. The preparation method of instant ultrafine solid block carbon black according to claim 1, characterized in that it comprises the following steps: mixing powdery carbon black, auxiliary agent and water and then grinding to obtain a carbon black emulsion; the carbon black emulsion After drying, instant ultrafine solid block carbon black is obtained.
7. The method for preparing instant ultrafine solid block carbon black according to claim 6, wherein the grinding time is 2-4 hours.
8. A superfine carbon black quick solution, characterized in that the preparation method of the superfine carbon black quick solution comprises the following steps: mixing powdery carbon black, an auxiliary agent and water and then grinding to obtain a carbon black emulsion; the carbon black emulsion; After the black emulsion is dried, the instant superfine solid block carbon black is obtained; the instant superfine solid block carbon black is mixed with water to obtain the superfine carbon black quick solution.
9. A conductive fabric, characterized in that the preparation method of the conductive fabric comprises the following steps: mixing powdery carbon black, auxiliary agents and water, and then grinding to obtain a carbon black emulsion; and drying the carbon black emulsion to obtain an instant solution Type ultrafine solid block carbon black; mixing instant ultrafine solid block carbon black with water to obtain a superfine carbon black quick solution; padding the fabric with the superfine carbon black quick solution and drying to obtain a conductive fabric .
10. The application of the instant ultra-fine solid block carbon black of claim 1 in the preparation of instant carbon black liquid, or the application in the preparation of carbon black modified materials.