阅读说明：本技术 一种电催化联合水热技术改性白炭黑的方法 (Method for modifying white carbon black by combining electrocatalysis with hydrothermal technology ) 是由 洪希杭 王冬 李芳芳 于 2020-06-28 设计创作，主要内容包括：本发明提供一种电催化联合水热技术改性白炭黑的方法,具体合成分为带电催化装置的水热釜的改造与改性白炭黑的制备两道工序。赋予传统的水热反应釜电催化装置,使传统白炭黑与改性药品在封闭的高温高压环境中充分反应的同时也受到电催化作用,在此过程中通过改变反应条件来调整产物的形貌结构,再对所得产物进行物性表征,从而得到分散性好、结晶度高、纯度高、性能优异的改性白炭黑材料。本发明所用改性药品特点是经济性良好、环境友好,实验操作过程灵活方便,具有广阔的实际应用前景。(The invention provides a method for modifying white carbon black by combining electrocatalysis with hydrothermal technology, and the specific synthesis comprises two procedures of modification of a hydrothermal kettle with an electrocatalysis device and preparation of modified white carbon black. Endowing a traditional hydrothermal reaction kettle electro-catalytic device, enabling the traditional white carbon black and modified drugs to be fully reacted in a closed high-temperature high-pressure environment and simultaneously to be subjected to electro-catalytic action, adjusting the shape and structure of a product by changing reaction conditions in the process, and performing physical property characterization on the obtained product, thereby obtaining the modified white carbon black material with good dispersibility, high crystallinity, high purity and excellent performance. The modified medicine used in the invention has the characteristics of good economy, environmental friendliness, flexible and convenient experimental operation process and wide practical application prospect.)

1. The invention provides a method for modifying white carbon black by combining electrocatalysis with hydrothermal technology, and the specific synthetic process comprises 2 steps: the first step is a modification method of a hydrothermal kettle with an electro-catalytic device, and the second step is preparation of modified white carbon black;

the modification method of the hydrothermal kettle with the electro-catalytic device comprises the following specific steps:

firstly, adding 0.5000-1.5000 g of polyvinylidene fluoride into 40-80 mL of N-methyl-2-pyrrolidone solution with the concentration of 0.0100-10.0000 g/mL at room temperature to obtain a mixed solution, and keeping the mixed solution for 0.5-1.5 h at the rotating speed of 400-900 r/min;

secondly, adding 0.5000-1.0000 g of Super P carbon powder as a conductive agent into the solution, and continuously keeping the mixture for 0.5-1.5 hours at the rotating speed of 400-900 r/min;

thirdly, adding 5.0000-10.0000 g of acetylene black under the condition that the stirring speed of the solution is kept unchanged, stirring for 0.5-3 hours at the rotating speed of 300-900 r/min, then adding 0.5000-5.0000 g of platinum nanoparticles with the particle size of 20-1000 nm into the mixture, and stirring for 0.5-1.5 hours to obtain mixed slurry;

fourthly, uniformly coating the mixed slurry on the surfaces of two high-purity graphite carbon electrode rods with the diameter of 6-10 mm and the length of 100-150 mm by using an automatic coating dryer, wherein the coating thickness is 30-100 mu m, and drying at 50-80 ℃ for 12-36 h to obtain a modified electrode;

fifthly, opening two holes with the diameter of 7-11 mm on the top cover of a polytetrafluoroethylene reaction kettle with the volume of 150-300 mL, inserting the two prepared electrodes through the holes, sealing the electrodes and the holes by using a high-temperature-resistant rubber ring, wherein the high-temperature-resistant rubber ring is any one of SN0102, KL-7057, TE-9249, TE-9128, E-120HP, 2301 high-temperature-resistant rubber rings and HR-8767A, and a direct-current voltage of 5-100V can be applied between the two electrodes to obtain the hydrothermal kettle with the electric catalytic device;

the second step is the preparation of the modified white carbon black, and specifically comprises the following steps:

firstly, putting white carbon black with the particle size of 50-1000 nm into the specially-made inner lining of the reaction kettle, adding 40-80 mL of absolute ethyl alcohol and 40-80 mL of distilled water, and preparing 0.0010-10.0000 g/mL of white carbon black suspension;

secondly, continuously stirring the suspension for 8-12 min at the rotating speed of 400-700 r/min, and then adding 0.0500-5.0000 g of methyltrimethoxysilane, 0.0500-5.0000 g of 1-butyl-3-methyl imidazole bromide [ BMIM ] Br and 0.0500-5.0000 g of KCl into the suspension;

thirdly, sealing the reaction kettle, and placing the reaction kettle in an environment at 50-200 ℃ for 0.5-50 h, wherein the external direct current voltage of the electrode is 5-100V;

and fourthly, after the reaction is finished, taking out the reaction kettle, closing the applied voltage, naturally cooling the reaction kettle to room temperature, centrifugally separating the substances in the kettle for 3-6 min at the rotating speed of 4000-8000 r/min, washing the product for 3 times by using distilled water and absolute ethyl alcohol respectively, and finally drying in an oven at the temperature of 50-70 ℃ for 12-24 h to obtain the modified white carbon black material.

[ technical field ]: the invention belongs to the technical field of chemical raw material production, and particularly relates to a method for modifying white carbon black by combining electrocatalysis with hydrothermal technology.

[ technical background ]: with the concept of environmental protection and health going into the heart, the idea of production development in the manufacturing industry is shifted from the pursuit of low price to the 'high quality and good price'. The rubber is a high-elasticity industrial raw material, has various product types, and is widely applied to the fields of solar batteries, aerospace, tires, rubber tubes, cables and the like. However, the development of scientific Technology has made new demands on the functionality of rubber, for example, the mechanical properties of rubber are poor due to poor interaction force between rubber molecular chains, so that it is necessary to modify rubber by reinforcing filler to improve its mechanical properties and thermal stability when producing tires (ZhongB C, Jia Z X, Luo Y F, et al. A method to improve the mechanical properties of rubber-butadiene rubber powder modified silica [ J ]. Composites Science and Technology,2015,117: 46-53; Mundo, Torreya, Fanghong, etc.. the functional modification of white carbon black and the preparation of modified rubber-based Composites and characterization of [ J ]. Composites, 2017,34(1): 67-74.).

The white carbon black has a three-dimensional network structure and comprises SiO as a main component₂The surface of the rubber has a large amount of silanol groups, and the rubber has good heat resistance, high activity and no electricity conduction, and is widely applied to the fields of rubber, coating, paint, plastics, cosmetics, medical appliances and the like (Ohashit, Tohsan A, Ikeda Y.role of in a single generated silicon for rubber science and technology [ J]Polymer International,2017,66(2): 250-. At present, white carbon black is produced mainly by a gas phase method and a precipitation method, and although the white carbon black prepared by the gas phase method has good surface activity, specific surface area, particle size, dispersity and other properties, the process for producing the white carbon black by the gas phase method is complex, the equipment investment is high, and the commercial popularization is not facilitated; the white carbon black prepared by the precipitation method has low purity, difficult control of particle size and poor dispersibility, and cannot meet the requirements of high-grade markets. (Liu FL, Zhu J Q, Liu J H, et al preparation and properties of cosmetic-stearic acid/White Carbon Black composite for thermal storage in building envelope [ J].Energy and Buildings,2018,158:1781-1789；Gao H Y,Song Z Z,Yang L,etal.Synthesis Method of White Carbon Black Utilizing Water-Quenching BlastFurnace Slag[J].Energy&fuels,2016,30(11): 9645-. Therefore, there is an urgent need in the market to functionally modify white carbon black to optimize the product and maximize the profit.

Aiming at the problem, the invention relates to a method for modifying white carbon black by combining electrocatalysis with hydrothermal technology, in particular to a new method for combining a traditional hydrothermal method and an electrocatalysis method, and the prepared white carbon black has good dispersity, large specific surface and high activity, and the performance of the white carbon black is greatly improved compared with that of the traditional white carbon black. The preparation method is simple to operate, the reaction is more sufficient due to the catalysis of the external electric field, the synthesis efficiency is high, and the feasibility, the high efficiency and the novelty are realized.

[ summary of the invention ]: the main content of the invention is to provide a new method for modifying the traditional white carbon black. The method comprises the steps of firstly transforming a traditional hydrothermal reaction kettle, endowing the traditional hydrothermal reaction kettle with an electro-catalytic device, enabling the traditional white carbon black and modified drugs to fully react in a high-temperature and high-pressure closed environment, and simultaneously carrying out electro-catalytic action on the traditional white carbon black and the modified drugs. The morphology structure of the product is controlled by regulating and controlling reaction parameters in the reaction process, so that the functional modification of the white carbon black is realized, and the obtained modified white carbon black has good dispersity, high purity and uniform morphology. The modification method is beneficial to realizing the preparation of the white carbon black with high dispersity and excellent performance, and is expected to meet the requirement of the current market on the white carbon black with high quality.

[ technical solution of the present invention ]:

1. the invention provides a method for modifying white carbon black by combining electrocatalysis with hydrothermal technology, and the specific synthetic process comprises 2 steps: the first step is a modification method of a hydrothermal kettle with an electro-catalytic device, and the second step is preparation of modified white carbon black;

the modification method of the hydrothermal kettle with the electro-catalytic device comprises the following specific steps:

firstly, adding 0.5000-1.5000 g of polyvinylidene fluoride into 40-80 mL of N-methyl-2-pyrrolidone solution with the concentration of 0.0100-10.0000 g/mL at room temperature to obtain a mixed solution, and keeping the mixed solution for 0.5-1.5 h at the rotating speed of 400-900 r/min;

secondly, adding 0.5000-1.0000 g of Super P carbon powder as a conductive agent into the solution, and continuously keeping the mixture for 0.5-1.5 hours at the rotating speed of 400-900 r/min;

thirdly, adding 5.0000-10.0000 g of acetylene black under the condition that the stirring speed of the solution is kept unchanged, stirring for 0.5-3 hours at the rotating speed of 300-900 r/min, then adding 0.5000-5.0000 g of platinum nanoparticles with the particle size of 20-1000 nm into the mixture, and stirring for 0.5-1.5 hours to obtain mixed slurry;

fourthly, uniformly coating the mixed slurry on the surfaces of two high-purity graphite carbon electrode rods with the diameter of 6-10 mm and the length of 100-150 mm by using an automatic coating dryer, wherein the coating thickness is 30-100 mu m, and drying at 50-80 ℃ for 12-36 h to obtain a modified electrode;

fifthly, opening two holes with the diameter of 7-11 mm on the top cover of a polytetrafluoroethylene reaction kettle with the volume of 150-300 mL, inserting the two prepared electrodes through the holes, sealing the electrodes and the holes by using a high-temperature-resistant rubber ring, wherein the high-temperature-resistant rubber ring is any one of SN0102, KL-7057, TE-9249, TE-9128, E-120HP, 2301 high-temperature-resistant rubber rings and HR-8767A, and a direct-current voltage of 5-100V can be applied between the two electrodes to obtain the hydrothermal kettle with the electric catalytic device;

the second step is the preparation of the modified white carbon black, and specifically comprises the following steps:

firstly, putting white carbon black with the particle size of 50-1000 nm into the specially-made inner lining of the reaction kettle, adding 40-80 mL of absolute ethyl alcohol and 40-80 mL of distilled water, and preparing 0.0010-10.0000 g/mL of white carbon black suspension;

secondly, continuously stirring the suspension for 8-12 min at the rotating speed of 400-700 r/min, and then adding 0.0500-5.0000 g of methyltrimethoxysilane, 0.0500-5.0000 g of 1-butyl-3-methyl imidazole bromide [ BMIM ] Br and 0.0500-5.0000 g of KCl into the suspension;

thirdly, sealing the reaction kettle, and placing the reaction kettle in an environment at 50-200 ℃ for 0.5-50 h, wherein the external direct current voltage of the electrode is 5-100V;

and fourthly, after the reaction is finished, taking out the reaction kettle, closing the applied voltage, naturally cooling the reaction kettle to room temperature, centrifugally separating the substances in the kettle for 3-6 min at the rotating speed of 4000-8000 r/min, washing the product for 3 times by using distilled water and absolute ethyl alcohol respectively, and finally drying in an oven at the temperature of 50-70 ℃ for 12-24 h to obtain the modified white carbon black material.

[ advantages and effects of the invention ]: the method for modifying white carbon black by combining electrocatalysis with hydrothermal technology has the following remarkable advantages: (1) the electrocatalysis and hydrothermal technology related by the invention are organically combined to modify the traditional white carbon black, so that the reaction materials are fully contacted under the closed high-temperature and high-pressure condition, the product morphology structure is regulated and controlled by regulating and controlling reaction parameters, the controllability is strong, and the purity and the yield of the modified white carbon black are favorably improved; (2) the traditional hydrothermal reaction kettle is modified by electrocatalysis equipment, so that the catalytic oxidation effect is endowed to the reaction, the reaction is more efficient and stable, the operation process is flexible and convenient, and the problem of secondary pollution is avoided; (3) on the basis of the original traditional white carbon black, the modified material is rich in resources and low in price, the performance of the obtained modified white carbon black is greatly improved, and the modified white carbon black can be commercially produced; (4) the modified white carbon black used in the invention is nano-scale white carbon black modified by electrocatalysis and hydrothermal combined technology, the material has large specific surface area, high dispersity and good high-temperature stability and electrical insulation property, and the modification method has feasibility, high efficiency and novelty.

Drawings

FIG. 1 is a schematic view of an apparatus for preparing modified white carbon black by combining electrocatalysis and hydrothermal technology

Detailed Description

In order to more clearly illustrate the advantages of this patent, the following description will be given by way of example to further illustrate the embodiments and effects of the present invention. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments disclosed herein are intended to be within the scope of the present invention.