阅读说明：本技术 一种补强-阻燃-耐磨的全工业固废型复合橡胶填料及其制备方法 (Reinforcing, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler and preparation method thereof ) 是由 张�浩 李海丽 龙红明 吴胜华 宗志芳 杜晓燕 于 2019-11-04 设计创作，主要内容包括：本发明公开了一种补强-阻燃-耐磨的全工业固废型复合橡胶填料及其制备方法,属于工业固废资源循环利用领域。该填料包括不锈钢渣、粉煤灰、磷渣、镁渣、锰渣、复合助磨剂、表面改性剂和水。所述不锈钢渣、粉煤灰、磷渣、镁渣和锰渣均为工业固体废弃物；所述复合助磨剂为丙三醇、无水乙醇和三乙醇胺的混合物；所述表面改性剂为硬脂酸和硅烷偶联剂KH550的混合物。本发明利用不锈钢渣、粉煤灰、磷渣、镁渣与锰渣进行复合制备全工业固废型补强-阻燃-耐磨复合橡胶填料,不仅降低了橡胶填料成本、拓展了橡胶填料的功能性,而且实现了工业固废的循环利用,促进了企业增效、橡胶制品行业提性能与降成本,符合当前节能环保、循环经济的产业发展要求。(The invention discloses a reinforcing, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler and a preparation method thereof, belonging to the field of recycling of industrial solid waste resources. The filler comprises stainless steel slag, fly ash, phosphorous slag, magnesium slag, manganese slag, a composite grinding aid, a surface modifier and water. The stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are all industrial solid wastes; the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine; the surface modifier is a mixture of stearic acid and a silane coupling agent KH 550. According to the invention, the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are compounded to prepare the full-industrial solid waste type reinforcing-flame-retardant-wear-resistant composite rubber filler, so that the cost of the rubber filler is reduced, the functionality of the rubber filler is expanded, the cyclic utilization of industrial solid waste is realized, the enterprise synergy and the performance improvement and cost reduction of the rubber product industry are promoted, and the industrial development requirements of energy conservation, environmental protection and circular economy at present are met.)

1. The reinforced, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler is characterized by comprising the following components in percentage by weight:

the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are all industrial solid wastes; the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, and the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 4:2: 1-1: 1: 1; the surface modifier is a mixture of stearic acid and a silane coupling agent KH550, and the mass ratio of the stearic acid to the silane coupling agent KH550 is 5: 1-1: 1.

2. The reinforced, flame retardant and wear resistant all-industrial solid waste compounded rubber filler according to claim 1, wherein the stainless steel slag, fly ash, phosphorous slag, magnesium slag and manganese slag all have a particle size of less than 5 mm.

3. A method for preparing the reinforced, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler as defined in claim 1, which comprises the following steps:

(1) mixing stainless steel slag, fly ash, phosphorus slag, magnesium slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 600-900 r/min for 90-120 min to obtain full-industrial solid waste composite micro powder; performing mechanochemical treatment on the composite industrial solid waste micropowder by using a planetary ball mill, wherein the rotating speed is 200-300 r/min, and the time is 72-96 h, so as to obtain the all-industrial solid waste composite micropowder;

(2) mixing a surface modifier with water, and dispersing the mixture by using an ultrasonic disperser, wherein the power of the ultrasonic disperser is 600-900W, and the time of the ultrasonic disperser is 60-90 min, so as to obtain a surface modifier solution;

(3) mixing the all-industrial solid waste composite superfine powder with a surface modifier solution, and stirring the mixture by using a planetary ball mill at the rotating speed of 300-500 r/min for 120-150 min to obtain the modified all-industrial solid waste composite superfine powder, namely the reinforced, flame-retardant and wear-resistant all-industrial solid waste composite rubber filler.

Technical Field

The invention belongs to the field of recycling of industrial solid waste resources, and particularly relates to a reinforced-flame-retardant-wear-resistant all-industrial solid waste type composite rubber filler and a preparation method thereof.

Background

The stainless steel slag, the fly ash, the phosphorus slag, the magnesium slag and the manganese slag are all industrial solid wastes, wherein the stainless steel slag is alkaline and mainly comprises CaO and Fe₂O₃、SiO₂And small amount of ZnO, CuO and Cr₂O₃Heavy metal oxides such as PbO; the fly ash is acidic, and the main component of the fly ash is SiO₂、Al₂O₃(ii) a The phosphorus slag is alkaline, and the main components of the phosphorus slag are CaO and SiO₂、P₂O₅(ii) a The magnesium slag is alkaline, and the main components of the magnesium slag are CaO and SiO₂、MgO₃(ii) a The manganese slag is alkaline and has CaO and SiO as main components₂And MnO. At present, a large amount of stainless steel slag, fly ash, phosphorus slag, magnesium slag and manganese slag are piled up in the open air, thereby not only occupying valuable land, but also polluting the surrounding environment and underground water. Therefore, how to utilize the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag in a large scale and high efficiency to realize the reduction of the environmental burden and the synergy of enterprises is a problem which needs to be solved urgently.

Rubber is used as a polymer material with wide application, and a large amount of filler is required in the preparation and processing process of the rubber so as to improve the mechanical property, the processing property and the filling capacity. At present, the commonly used rubber filler mainly comprises carbon black (8000 yuan/ton), white carbon black (6000 yuan/ton) and the like, but the production of the carbon black and the white carbon black is complex in process, and a large amount of energy and resources are consumed, so that the cost is high.

Disclosure of Invention

The rubber reinforcing agent aims to solve the problems that the main fillers of carbon black and white carbon black in the existing rubber industry are high in price and single in function, namely only reinforcing performance exists; the acid solution is used for modifying alkaline solid waste materials (such as stainless steel slag, phosphorous slag, magnesium slag and manganese slag), so that the problems of unsafe operation and environmental pollution exist; the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are recycled and have low additional value; stainless steel slag, fly ash, phosphorus slag, magnesium slag and manganese slag are easy to abrade and are easy to agglomerate when being directly added into rubber, and the problem of poor compatibility between an inorganic interface and an organic interface exists; the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag all have certain flame retardance, but have the problem of incapability of realizing synergistic flame retardance. The invention provides a reinforced, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler, aiming at solving the problems.

The invention is realized by the following technical scheme.

The invention provides a reinforced, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler, which comprises the following components in percentage by weight:

the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are all industrial solid wastes; the composite grinding aid is a mixture of glycerol, absolute ethyl alcohol and triethanolamine, and the mass ratio of the glycerol to the absolute ethyl alcohol to the triethanolamine is 4:2: 1-1: 1: 1; the surface modifier is a mixture of stearic acid and a silane coupling agent KH550, and the mass ratio of the stearic acid to the silane coupling agent KH550 is 5: 1-1: 1.

As an optimization, the particle sizes of the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are all less than 5 mm.

The invention also provides a preparation method of the reinforced, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler, which comprises the following steps:

(1) mixing stainless steel slag, fly ash, phosphorus slag, magnesium slag, manganese slag and a composite grinding aid, and grinding the mixture by using a planetary ball mill at the rotating speed of 600-900 r/min for 90-120 min to obtain full-industrial solid waste composite micro powder; and performing mechanochemical treatment on the composite industrial solid waste micropowder by using a planetary ball mill, wherein the rotating speed is 200-300 r/min, and the time is 72-96 h, so as to obtain the all-industrial solid waste composite ultrafine powder.

(2) Mixing the surface modifier with water, and dispersing the mixture by an ultrasonic disperser with the power of 600-900W and the time of 60-90 min to obtain a surface modifier solution.

(3) Mixing the all-industrial solid waste composite superfine powder with a surface modifier solution, and stirring the mixture by using a planetary ball mill at the rotating speed of 300-500 r/min for 120-150 min to obtain the modified all-industrial solid waste composite superfine powder, namely the reinforced, flame-retardant and wear-resistant all-industrial solid waste composite rubber filler.

The scientific principle of the invention is as follows:

(1) surfactant molecules of glycerol, absolute ethyl alcohol and triethanolamine in the composite grinding aid are utilized to form a monomolecular adsorption film on the surface of the stainless steel slag to be ground, the surface of fly ash, the surface of phosphorous slag, the surface of magnesium slag and the surface of manganese slag, the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are all fractured in the grinding process, and free electrovalence bonds generated on fracture surfaces of the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are neutralized with ions or molecules provided by the composite grinding aid, so that the aggregation tendency of the solid waste composite micro powder in the whole industry is eliminated or weakened, and the fracture surface is prevented from being compounded.

(2) The stainless steel slag, the fly ash, the phosphorus slag, the magnesium slag and the manganese slag all have porous structures, so that the effect of adsorbing carbon black can be improved, and the contact surface with rubber can be increasedSo as to achieve the reinforcing effect. The stainless steel slag, the phosphorus slag, the magnesium slag and the manganese slag are all SiO₂The CaO system is alkaline, and the right amount of alkalinity can accelerate the rubber vulcanization speed, but the excessive alkalinity causes the rubber brittleness to increase, so that SiO is utilized₂-Al₂O₃The system shows that the acidic fly ash modifies alkaline solid waste materials (such as stainless steel slag, phosphorus slag, magnesium slag and manganese slag), so that the alkalinity of the mixture of the stainless steel slag, the fly ash, the phosphorus slag, the magnesium slag and the manganese slag is reduced, and the reinforcing effect is improved.

(3) The stainless steel slag, the fly ash, the phosphorus slag, the magnesium slag and the manganese slag are promoted to be subjected to mechanochemical treatment by adopting a long-time stirring and grinding mode, namely, the crushing process can lead the materials to have a series of mechanochemical changes such as smaller grain diameter, larger specific surface area, crystal structure distortion, reduced heat effect temperature and the like to form a silicon-phosphorus-iron system, a silicon-phosphorus-magnesium system and a silicon-phosphorus-aluminum system with flame retardant property, thereby improving the flame retardant effect. The manganese slag containing MnO is subjected to catalytic reaction in the rubber vulcanization process, so that the stability of a network structure of a rubber system is improved, and the aim of improving the wear resistance is fulfilled.

(4) Stearic acid and a silane coupling agent KH570 in the surface modifier are utilized to form organic coating layers on the surfaces of the all-industrial solid waste composite superfine powder, so that the agglomeration of the all-industrial solid waste composite superfine powder is reduced, the dispersion effect of the modified all-industrial solid waste composite superfine powder is improved, and the purpose of good compatibility with rubber is achieved.

(5) The stainless steel slag mainly comprises CaO and Fe₂O₃、SiO₂And small amounts of ZnO, CuO and Cr₂O₃And PbO, etc., wherein ZnO, CuO, Cr₂O₃And the heavy metal oxides such as PbO and the like have the promotion effect or the synergistic promotion effect in a rubber system, so that the reinforcement-flame retardance-wear resistance synergistic property of the rubber is improved.

Compared with the prior art, the invention has the following technical effects:

1. the invention solves the problems that the main fillers of carbon black and white carbon black in the existing rubber industry are high in price and single in function, namely only reinforcing performance exists; the acid solution is used for modifying alkaline solid waste materials (such as stainless steel slag, phosphorous slag, magnesium slag and manganese slag), so that the problems of unsafe operation and environmental pollution exist; the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are recycled and have low additional value; stainless steel slag, fly ash, phosphorus slag, magnesium slag and manganese slag are easy to abrade and are easy to agglomerate when being directly added into rubber, and the problem of poor compatibility between an inorganic interface and an organic interface exists; the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag all have certain flame retardance, but have the problem of incapability of realizing synergistic flame retardance.

2. According to the invention, the stainless steel slag, the fly ash, the phosphorous slag, the magnesium slag and the manganese slag are compounded to prepare the full-industrial solid waste type reinforcing-flame-retardant-wear-resistant composite rubber filler, so that the cost of the rubber filler is reduced, the functionality of the rubber filler is expanded, the cyclic utilization of industrial solid waste is realized, the enterprise synergy and the performance improvement and cost reduction of the rubber product industry are promoted, and the industrial development requirements of energy conservation, environmental protection and circular economy at present are met.

Detailed Description

The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.

The invention relates to a preparation method of a reinforced, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler