An impact-resistant rubber floor and its preparation method

Abstract

This invention discloses an impact-resistant rubber flooring and its preparation method, relating to the field of rubber materials. In preparing the impact-resistant rubber flooring, the invention involves reacting pyrrole, 1H-pyrrole-3-methanol, and silica to obtain modified silica; reacting depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, and sodium hydroxide to obtain modified lignin; then reacting the modified lignin with 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol to prepare modified lignin microspheres; and finally, mixing and vulcanizing styrene-butadiene rubber, allyl phosphate, modified silica, modified lignin microspheres, sulfur, and stearic acid to obtain the impact-resistant rubber flooring. The impact-resistant rubber flooring prepared by this invention exhibits excellent impact resistance, anti-aging properties, flame retardant properties, antibacterial properties, and antistatic properties.

Description

Technical Field

[0001] This invention relates to the field of rubber materials, specifically to an impact-resistant rubber floor and its preparation method. Background Technology

[0002] Rubber flooring is made of synthetic rubber and other polymer materials, and is widely used in gyms, training halls, precision instrument manufacturing and storage facilities, nurseries, kindergartens, senior citizen activity centers, and other places requiring vibration damping. Among various types of rubber, styrene-butadiene rubber (SBR) not only has high elasticity but also high strength, high toughness, and high strain performance, playing an important role in the tire industry, footwear manufacturing, conveyor belts, and machinery products.

[0003] However, styrene-butadiene rubber (SBR) is a non-polar unsaturated rubber that cannot crystallize for self-reinforcement. During manufacturing, it typically requires the addition of large amounts of high-quality reinforcing fillers to achieve practical application. Furthermore, when exposed to oxygen, high temperature, low temperature, or light, the rubber products are prone to cross-linking or breakage of the polymer chains, leading to discoloration, whitening, softening and stickiness, hardening and brittleness, surface cracking, and other aging phenomena, thus limiting the application areas of SBR. The impact-resistant rubber flooring prepared by this invention possesses excellent impact resistance, anti-aging properties, flame retardant properties, and antistatic properties, and has broad market prospects. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing impact-resistant rubber flooring to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] An impact-resistant rubber flooring is prepared by reacting pyrrole, 1H-pyrrole-3-methanol with silica to obtain modified silica; reacting depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, and sodium hydroxide to obtain modified lignin; reacting the modified lignin with 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol to obtain modified lignin microspheres; and mixing and vulcanizing styrene-butadiene rubber, allyl phosphate, modified silica, modified lignin microspheres, sulfur, and stearic acid.

[0007] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0008] The silica was soaked in a pyrrole mixed solution for 10-20 minutes, the solid was filtered out, the solid was drained, and then soaked in a ferric chloride hydrochloric acid solution at 3-5℃ for 2-4 hours. After filtration, the filter residue was washed with anhydrous ethanol 3-5 times and dried at 50-60℃ for 6-8 hours to obtain modified silica.

[0009] Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water were mixed in a mass ratio of 1:(1.3~1.7):(3~4):(0.5~0.7):(300~400). The mixture was stirred at 400~600 r / min for 0.5~1.5 h at 60~70 °C. The temperature was then raised to 85~95 °C and stirring was continued for 25~35 min. The mixture was cooled to room temperature and the precipitate was separated by centrifugation. The precipitate was washed 3~5 times with deionized water and anhydrous ethanol, and then dried at 50~60 °C for 6~8 h to obtain modified lignin.

[0010] Modified lignin, 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol were mixed at a mass ratio of 1:(0.05~0.15):(3~5):(0.3~0.5), stirred at 400~600 r / min for 2~4 h at room temperature, filtered, and the filter residue was washed 3~5 times with deionized water and anhydrous ethanol, respectively, and dried at 50~60℃ for 6~8 h to obtain modified lignin microspheres.

[0011] Styrene-butadiene rubber is mixed in an open mill at 100-120℃ for 20-40 minutes. The roller gap of the open mill is adjusted to 1-3mm. At 50-70℃, allyl phosphate, modified silica, modified lignin microspheres, sulfur, and stearic acid are added. The mixture is then formed into triangular bundles and rolled alternately 3-5 times each. The mixture is placed in a mold and vulcanized on a flat vulcanizing machine at 140-160℃ and 14-16MPa for 10-12 hours. After naturally cooling to room temperature, the mixture is removed to obtain impact-resistant rubber flooring.

[0012] As an optimization, the pyrrole mixed solution in step (1) is prepared by mixing pyrrole, 1H-pyrrole-3-methanol and anhydrous ethanol in a mass ratio of 1:(0.3~0.5):(8~12).

[0013] As an optimization, the ferric chloride hydrochloric acid solution in step (1) is prepared by mixing 0.1 mol / L ferric chloride solution and 0.3 mol / L hydrochloric acid solution at a volume ratio of 1:1.

[0014] As an optimization, the method for preparing depolymerized lignin in step (2) is as follows: lithium bromide and 0.3 mol / L hydrochloric acid solution are mixed at a mass ratio of 1:1.7 to obtain a mixed solution; alkali lignin and the mixed solution are mixed at a mass ratio of 1:50, stirred at 400 r / min for 2 h at 110 °C, filtered, the solid is washed 3 times with deionized water, and vacuum dried at 50 °C for 4 h to obtain depolymerized lignin.

[0015] As an optimization, the polyethylene glycol in step (3) is PEG1500 type polyethylene glycol.

[0016] As an optimization, the styrene-butadiene rubber mentioned in step (4) is industrial grade styrene-butadiene rubber.

[0017] As an optimization, the ratio of styrene-butadiene rubber, allyl phosphate, modified silica, modified lignin microspheres, sulfur, and stearic acid in step (4) is 1:0.08:0.3:0.1:0.25:0.05 by mass.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] In preparing impact-resistant rubber flooring, this invention involves reacting pyrrole, 1H-pyrrole-3-methanol, and silica to obtain modified silica; reacting depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, and sodium hydroxide to obtain modified lignin; reacting the modified lignin with 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol to obtain modified lignin microspheres; and mixing and vulcanizing styrene-butadiene rubber, allyl phosphate, modified silica, modified lignin microspheres, sulfur, and stearic acid to obtain the impact-resistant rubber flooring.

[0020] First, modified silica is prepared by reacting pyrrole, 1H-pyrrole-3-methanol, and silica. On the one hand, the in-situ polymerization of pyrrole and 1H-pyrrole-3-methanol on silica forms a conductive polypyrrole layer, giving silica good conductivity. As a filler added to rubber flooring materials, it can effectively improve the antistatic properties of impact-resistant rubber flooring. On the other hand, the hydroxyl groups introduced by 1H-pyrrole-3-methanol are negatively charged and can combine with the positively charged phosphoric acid in allyl phosphate to improve the impact resistance of impact-resistant rubber flooring. Moreover, silica has a physical barrier effect, which can block the diffusion of combustible gases and heat during combustion, thus improving the flame retardant properties of impact-resistant rubber flooring.

[0021] Secondly, the modified lignin prepared by reacting 2,6-di-tert-butylphenol with depolymerized lignin introduces a hindered structure on the lignin, which can effectively scavenge free radicals and improve the anti-aging performance of impact-resistant rubber flooring. 1,3-Diaminoguanidine hydrochloride not only crosslinks lignin to prepare lignin microspheres, but also introduces guanidine salts with cationic antibacterial effects, improving the antibacterial performance of impact-resistant rubber flooring. Furthermore, the large number of negatively charged hydroxyl groups on the lignin can combine with the positively charged phosphoric acid in allyl phosphate to effectively improve the impact resistance of impact-resistant rubber flooring. 1,3-Diaminoguanidine hydrochloride also introduces abundant nitrogen elements, which can have a synergistic flame-retardant effect with phosphorus in allyl phosphate, thereby effectively improving the flame-retardant performance of impact-resistant rubber flooring.

[0022] Introducing allyl phosphate during the vulcanization process of rubber, phosphoric acid, which carries a positive charge, can combine with the numerous negatively charged hydroxyl groups on lignin to effectively improve the impact resistance of the impact-resistant rubber flooring. Furthermore, under heated combustion conditions, phosphoric acid undergoes dehydration polymerization to regenerate polymetaphosphoric acid. Polymetaphosphoric acid can rapidly catalyze the dehydration and carbonization of the rubber flooring to generate a dense protective carbon layer, which isolates oxygen and reduces the thermal decomposition rate of the material. At the same time, it reduces the heat generated by rubber decomposition, thereby improving the flame retardant properties of the impact-resistant rubber flooring. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0024] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0025] A pyrrole mixed solution was prepared by mixing pyrrole, 1H-pyrrole-3-methanol, and anhydrous ethanol at a mass ratio of 1:0.3:8; a ferric chloride hydrochloric acid solution was prepared by mixing 0.1 mol / L ferric chloride solution and 0.3 mol / L hydrochloric acid solution at a volume ratio of 1:1; silica was soaked in the pyrrole mixed solution for 10 min, the solid was filtered out, the solid was drained, and then soaked in the ferric chloride hydrochloric acid solution at 3℃ for 2 h, filtered, the filter residue was washed three times with anhydrous ethanol, and dried at 50℃ for 6 h to obtain modified silica;

[0026] A mixed solution was prepared by mixing lithium bromide and 0.3 mol / L hydrochloric acid solution at a mass ratio of 1:1.7. Alkali lignin was then mixed with the mixed solution at a mass ratio of 1:50 and stirred at 110℃ for 400 r / min for 2 h. The mixture was filtered, and the solid was washed three times with deionized water and dried under vacuum at 50℃ for 4 h to obtain depolymerized lignin. Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water were mixed at a mass ratio of 1:1.3:3:0.5:300 and stirred at 60℃ for 400 r / min for 0.5 h. The mixture was then heated to 85℃ and stirred for 25 min. After cooling to room temperature, the precipitate was separated by centrifugation. The precipitate was washed three times with deionized water and three times with anhydrous ethanol, and dried at 50℃ for 6 h to obtain modified lignin.

[0027] Modified lignin, 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol were mixed at a mass ratio of 1:0.05:3:0.3 and stirred at 400 r / min for 2 h at room temperature. After filtration, the filter residue was washed three times with deionized water and anhydrous ethanol, and dried at 50 °C for 6 h to obtain modified lignin microspheres.

[0028] Styrene-butadiene rubber (SBR) was mixed in a two-roll mill at 100°C for 20 minutes. The roller gap of the two-roll mill was adjusted to 1 mm. At 50°C, 0.08 times the mass of SBR was added to allyl phosphate, 0.3 times the mass of SBR was added to modified silica, 0.1 times the mass of SBR was added to modified lignin microspheres, 0.25 times the mass of SBR was added to sulfur, and 0.05 times the mass of SBR was added to stearic acid. The mixture was then folded into triangular shapes and rolled three times each. The mixture was placed in a mold and vulcanized at 140°C and 14 MPa for 10 hours on a flat vulcanizing machine. After naturally cooling to room temperature, the mixture was removed to obtain impact-resistant rubber flooring.

[0029] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0030] A pyrrole mixed solution was prepared by mixing pyrrole, 1H-pyrrole-3-methanol, and anhydrous ethanol at a mass ratio of 1:0.4:10; a ferric chloride hydrochloric acid solution was prepared by mixing 0.1 mol / L ferric chloride solution and 0.3 mol / L hydrochloric acid solution at a volume ratio of 1:1; silica was soaked in the pyrrole mixed solution for 15 min, the solid was filtered out, the solid was drained, and then soaked in the ferric chloride hydrochloric acid solution at 4℃ for 3 h, filtered, the filter residue was washed 4 times with anhydrous ethanol, and dried at 55℃ for 7 h to obtain modified silica;

[0031] A mixed solution was prepared by mixing lithium bromide and 0.3 mol / L hydrochloric acid solution at a mass ratio of 1:1.7. Alkali lignin was then mixed with the mixed solution at a mass ratio of 1:50 and stirred at 400 r / min for 2 h at 110 °C. The mixture was filtered, and the solid was washed three times with deionized water and dried under vacuum at 50 °C for 4 h to obtain depolymerized lignin. Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water were mixed at a mass ratio of 1:1.5:3.5:0.6:350 and stirred at 500 r / min for 1 h at 65 °C. The mixture was then heated to 90 °C and stirred for another 30 min. After cooling to room temperature, the precipitate was separated by centrifugation. The precipitate was washed four times with deionized water and four times with anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin.

[0032] Modified lignin, 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol were mixed at a mass ratio of 1:0.1:4:0.4 and stirred at 500 r / min for 3 h at room temperature. After filtration, the filter residue was washed four times with deionized water and anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin microspheres.

[0033] Styrene-butadiene rubber (SBR) was mixed in a two-roll mill at 110°C for 30 minutes. The roller gap of the two-roll mill was adjusted to 2 mm. At 60°C, 0.08 times the mass of SBR was added to allyl phosphate, 0.3 times the mass of SBR was added to modified silica, 0.1 times the mass of SBR was added to modified lignin microspheres, 0.25 times the mass of SBR was added to sulfur, and 0.05 times the mass of SBR was added to stearic acid. The mixture was then folded into triangular shapes and rolled 4 times each. The mixture was placed in a mold and vulcanized at 150°C and 15 MPa for 11 hours on a flat vulcanizing machine. After naturally cooling to room temperature, the mixture was removed to obtain impact-resistant rubber flooring.

[0034] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0035] A pyrrole mixed solution was prepared by mixing pyrrole, 1H-pyrrole-3-methanol, and anhydrous ethanol at a mass ratio of 1:0.5:12; a ferric chloride hydrochloric acid solution was prepared by mixing 0.1 mol / L ferric chloride solution and 0.3 mol / L hydrochloric acid solution at a volume ratio of 1:1; silica was soaked in the pyrrole mixed solution for 20 min, the solid was filtered out, the solid was drained, and then soaked in the ferric chloride hydrochloric acid solution at 5℃ for 4 h, filtered, the filter residue was washed 5 times with anhydrous ethanol, and dried at 60℃ for 8 h to obtain modified silica;

[0036] A mixed solution was prepared by mixing lithium bromide and 0.3 mol / L hydrochloric acid solution at a mass ratio of 1:1.7. Alkali lignin was then mixed with the mixed solution at a mass ratio of 1:50 and stirred at 400 r / min for 2 h at 110 °C. The mixture was filtered, and the solid was washed three times with deionized water and dried under vacuum at 50 °C for 4 h to obtain depolymerized lignin. Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water were mixed at a mass ratio of 1:1.7:4:0.7:400 and stirred at 600 r / min for 1.5 h at 70 °C. The mixture was then heated to 95 °C and stirred for another 35 min. After cooling to room temperature, the precipitate was separated by centrifugation. The precipitate was washed five times with deionized water and five times with anhydrous ethanol, and dried at 60 °C for 8 h to obtain modified lignin.

[0037] Modified lignin, 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol were mixed at a mass ratio of 1:0.15:5:0.5 and stirred at 600 r / min for 4 h at room temperature. After filtration, the filter residue was washed 5 times with deionized water and anhydrous ethanol, and dried at 60℃ for 8 h to obtain modified lignin microspheres.

[0038] Styrene-butadiene rubber (SBR) was mixed in a two-roll mill at 120°C for 40 minutes. The roller gap of the two-roll mill was adjusted to 3 mm. At 70°C, 0.08 times the mass of SBR was added to allyl phosphate, 0.3 times the mass of SBR was added to modified silica, 0.1 times the mass of SBR was added to modified lignin microspheres, 0.25 times the mass of SBR was added to sulfur, and 0.05 times the mass of SBR was added to stearic acid. The mixture was then folded into triangular shapes and rolled 5 times each. The mixture was placed in a mold and vulcanized at 160°C and 16 MPa for 12 hours on a flat vulcanizing machine. After naturally cooling to room temperature, the mixture was removed to obtain impact-resistant rubber flooring.

[0039] Comparative Example 1:

[0040] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0041] A pyrrole mixed solution was prepared by mixing pyrrole, 1H-pyrrole-3-methanol, and anhydrous ethanol at a mass ratio of 1:0.4:10; a ferric chloride hydrochloric acid solution was prepared by mixing 0.1 mol / L ferric chloride solution and 0.3 mol / L hydrochloric acid solution at a volume ratio of 1:1; silica was soaked in the pyrrole mixed solution for 15 min, the solid was filtered out, the solid was drained, and then soaked in the ferric chloride hydrochloric acid solution at 4℃ for 3 h, filtered, the filter residue was washed 4 times with anhydrous ethanol, and dried at 55℃ for 7 h to obtain modified silica;

[0042] A mixed solution was prepared by mixing lithium bromide and 0.3 mol / L hydrochloric acid solution at a mass ratio of 1:1.7; alkali lignin and the mixed solution were mixed at a mass ratio of 1:50, stirred at 110℃ and 400 r / min for 2 h, filtered, and the solid was washed three times with deionized water and dried under vacuum at 50℃ for 4 h to obtain depolymerized lignin.

[0043] Depolymerized lignin, 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol were mixed at a mass ratio of 1:0.1:4:0.4 and stirred at 500 r / min for 3 h at room temperature. After filtration, the filter residue was washed four times with deionized water and anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin microspheres.

[0044] Styrene-butadiene rubber (SBR) was mixed in a two-roll mill at 110°C for 30 minutes. The roller gap of the two-roll mill was adjusted to 2 mm. At 60°C, 0.08 times the mass of SBR was added to allyl phosphate, 0.3 times the mass of SBR was added to modified silica, 0.1 times the mass of SBR was added to modified lignin microspheres, 0.25 times the mass of SBR was added to sulfur, and 0.05 times the mass of SBR was added to stearic acid. The mixture was then folded into triangular shapes and rolled 4 times each. The mixture was placed in a mold and vulcanized at 150°C and 15 MPa for 11 hours on a flat vulcanizing machine. After naturally cooling to room temperature, the mixture was removed to obtain impact-resistant rubber flooring.

[0045] Comparative Example 2:

[0046] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0047] A pyrrole mixed solution was prepared by mixing pyrrole, 1H-pyrrole-3-methanol, and anhydrous ethanol at a mass ratio of 1:0.4:10; a ferric chloride hydrochloric acid solution was prepared by mixing 0.1 mol / L ferric chloride solution and 0.3 mol / L hydrochloric acid solution at a volume ratio of 1:1; silica was soaked in the pyrrole mixed solution for 15 min, the solid was filtered out, the solid was drained, and then soaked in the ferric chloride hydrochloric acid solution at 4℃ for 3 h, filtered, the filter residue was washed 4 times with anhydrous ethanol, and dried at 55℃ for 7 h to obtain modified silica;

[0048] A mixed solution was prepared by mixing lithium bromide and 0.3 mol / L hydrochloric acid solution at a mass ratio of 1:1.7. Alkali lignin was then mixed with the mixed solution at a mass ratio of 1:50 and stirred at 400 r / min for 2 h at 110 °C. The mixture was filtered, and the solid was washed three times with deionized water and dried under vacuum at 50 °C for 4 h to obtain depolymerized lignin. Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water were mixed at a mass ratio of 1:1.5:3.5:0.6:350 and stirred at 500 r / min for 1 h at 65 °C. The mixture was then heated to 90 °C and stirred for another 30 min. After cooling to room temperature, the precipitate was separated by centrifugation. The precipitate was washed four times with deionized water and four times with anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin.

[0049] Modified lignin, 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol were mixed at a mass ratio of 1:0.1:4:0.4 and stirred at 500 r / min for 3 h at room temperature. After filtration, the filter residue was washed four times with deionized water and anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin microspheres.

[0050] Styrene-butadiene rubber (SBR) was mixed in a two-roll mill at 110°C for 30 minutes. The roller gap of the two-roll mill was adjusted to 2 mm. At 60°C, modified silica (0.3 times the weight of SBR), modified lignin microspheres (0.1 times the weight of SBR), sulfur (0.25 times the weight of SBR), and stearic acid (0.05 times the weight of SBR) were added. The mixture was then formed into triangular bundles and rolled 4 times each. It was then placed in a mold and vulcanized in a flat vulcanizing machine at 150°C and 15 MPa for 11 hours. After naturally cooling to room temperature, it was removed to obtain impact-resistant rubber flooring.

[0051] Comparative Example 3:

[0052] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0053] A pyrrole mixed solution was prepared by mixing pyrrole, 1H-pyrrole-3-methanol, and anhydrous ethanol at a mass ratio of 1:0.4:10; a ferric chloride hydrochloric acid solution was prepared by mixing 0.1 mol / L ferric chloride solution and 0.3 mol / L hydrochloric acid solution at a volume ratio of 1:1; silica was soaked in the pyrrole mixed solution for 15 min, the solid was filtered out, the solid was drained, and then soaked in the ferric chloride hydrochloric acid solution at 4℃ for 3 h, filtered, the filter residue was washed 4 times with anhydrous ethanol, and dried at 55℃ for 7 h to obtain modified silica;

[0054] A mixed solution was prepared by mixing lithium bromide and 0.3 mol / L hydrochloric acid solution at a mass ratio of 1:1.7. Alkali lignin was then mixed with the mixed solution at a mass ratio of 1:50 and stirred at 400 r / min for 2 h at 110 °C. The mixture was filtered, and the solid was washed three times with deionized water and dried under vacuum at 50 °C for 4 h to obtain depolymerized lignin. Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water were mixed at a mass ratio of 1:1.5:3.5:0.6:350 and stirred at 500 r / min for 1 h at 65 °C. The mixture was then heated to 90 °C and stirred for another 30 min. After cooling to room temperature, the precipitate was separated by centrifugation. The precipitate was washed four times with deionized water and four times with anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin.

[0055] Styrene-butadiene rubber (SBR) was mixed in a two-roll mill at 110°C for 30 minutes. The roller gap of the two-roll mill was adjusted to 2 mm. At 60°C, 0.08 times the mass of SBR was added to allyl phosphate, 0.3 times the mass of SBR was added to modified silica, 0.1 times the mass of SBR was added to modified lignin, 0.25 times the mass of SBR was added to sulfur, and 0.05 times the mass of SBR was added to stearic acid. The mixture was then folded into triangular shapes and rolled 4 times each. The mixture was placed in a mold and vulcanized in a flat vulcanizing machine at 150°C and 15 MPa for 11 hours. After naturally cooling to room temperature, the mixture was removed to obtain impact-resistant rubber flooring.

[0056] Comparative Example 4:

[0057] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0058] A mixed solution was prepared by mixing lithium bromide and 0.3 mol / L hydrochloric acid solution at a mass ratio of 1:1.7. Alkali lignin was then mixed with the mixed solution at a mass ratio of 1:50 and stirred at 400 r / min for 2 h at 110 °C. The mixture was filtered, and the solid was washed three times with deionized water and dried under vacuum at 50 °C for 4 h to obtain depolymerized lignin. Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water were mixed at a mass ratio of 1:1.5:3.5:0.6:350 and stirred at 500 r / min for 1 h at 65 °C. The mixture was then heated to 90 °C and stirred for another 30 min. After cooling to room temperature, the precipitate was separated by centrifugation. The precipitate was washed four times with deionized water and four times with anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin.

[0059] Modified lignin, 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol were mixed at a mass ratio of 1:0.1:4:0.4 and stirred at 500 r / min for 3 h at room temperature. After filtration, the filter residue was washed four times with deionized water and anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin microspheres.

[0060] Styrene-butadiene rubber (SBR) was mixed in a two-roll mill at 110°C for 30 minutes. The roller gap of the two-roll mill was adjusted to 2 mm. At 60°C, 0.08 times the mass of SBR, 0.3 times the mass of SBR, 0.1 times the mass of SBR, modified lignin microspheres, 0.25 times the mass of SBR, and 0.05 times the mass of SBR, stearic acid were added. The mixture was then formed into triangular bundles and rolled 4 times each. The mixture was placed in a mold and vulcanized at 150°C and 15 MPa for 11 hours on a flat vulcanizing machine. After naturally cooling to room temperature, the mixture was removed to obtain impact-resistant rubber flooring.

[0061] Comparative Example 5:

[0062] A method for preparing impact-resistant rubber flooring includes the following preparation steps:

[0063] A mixed solution was prepared by mixing lithium bromide and 0.3 mol / L hydrochloric acid solution at a mass ratio of 1:1.7. Alkali lignin was then mixed with the mixed solution at a mass ratio of 1:50 and stirred at 400 r / min for 2 h at 110 °C. The mixture was filtered, and the solid was washed three times with deionized water and dried under vacuum at 50 °C for 4 h to obtain depolymerized lignin. Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water were mixed at a mass ratio of 1:1.5:3.5:0.6:350 and stirred at 500 r / min for 1 h at 65 °C. The mixture was then heated to 90 °C and stirred for another 30 min. After cooling to room temperature, the precipitate was separated by centrifugation. The precipitate was washed four times with deionized water and four times with anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin.

[0064] Modified lignin, 1,3-diaminoguanidine hydrochloride, deionized water, and polyethylene glycol were mixed at a mass ratio of 1:0.1:4:0.4 and stirred at 500 r / min for 3 h at room temperature. After filtration, the filter residue was washed four times with deionized water and anhydrous ethanol, and dried at 55 °C for 7 h to obtain modified lignin microspheres.

[0065] Styrene-butadiene rubber (SBR) was mixed in a two-roll mill at 110°C for 30 minutes. The roller gap of the two-roll mill was adjusted to 2 mm. At 60°C, 0.08 times the mass of SBR was added to allyl phosphate, 0.1 times the mass of SBR was added to modified lignin microspheres, 0.25 times the mass of SBR was added to sulfur, and 0.05 times the mass of SBR was added to stearic acid. The mixture was then folded into triangular shapes and rolled 4 times each. The mixture was placed in a mold and vulcanized in a flat vulcanizing machine at 150°C and 15 MPa for 11 hours. After naturally cooling to room temperature, the mixture was removed to obtain impact-resistant rubber flooring.

[0066] Test Example 1:

[0067] Impact resistance test: Samples of each embodiment and comparative example were prepared with dimensions of 64mm × 12.7mm × 6.4mm and a notch depth of 10.2mm. The samples were clamped in an impact testing machine with the notched side facing the edge of the pendulum. The pendulum was released to impact the sample. If the sample did not break, a heavier pendulum was used until the sample broke. The impact energy was measured, and the impact strength was calculated as impact energy / sample thickness. The results are shown in Table 1.

[0068] Table 1

[0069] Impact strength (J / m) Impact strength (J / m) Example 1 247.8 Comparative Example 1 244.1 Example 2 248.3 Comparative Example 2 204.3 Example 3 245.6 Comparative Example 3 247.2 Comparative Example 4 205.7 Comparative Example 5 150.7

[0070] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 1 reveals that the impact-resistant rubber flooring prepared by the present invention has good impact resistance.

[0071] By comparison, the impact strength of Examples 1-3 is significantly greater than that of Comparative Example 5, indicating that silica, as an inorganic filler, fills the gaps in the rubber crosslinking network and improves the impact resistance of the impact-resistant rubber flooring.

[0072] By comparison, the impact strength of Examples 1-3 is significantly greater than that of Comparative Example 2, indicating that the introduction of allyl phosphate during the vulcanization process of rubber, with phosphoric acid carrying a positive charge, can combine with the large number of negatively charged hydroxyl groups on lignin to form a positive and negative charge combination, effectively improving the impact resistance of the impact-resistant rubber flooring; the impact strength of Examples 1-3 is significantly greater than that of Comparative Example 4, indicating that the hydroxyl groups introduced by 1H-pyrrole-3-methanol are negatively charged and can combine with the positively charged phosphoric acid in allyl phosphate to form a positive and negative charge combination, improving the impact resistance of the impact-resistant rubber flooring.

[0073] Test Example 2:

[0074] Flame retardant performance test method: Standard specimens were prepared according to GB / T10701-2008 for the examples and comparative examples. The specimen size was 130mm×13mm×3mm. The limiting oxygen index of the standard specimens was tested. The results are shown in Table 2.

[0075] Table 2

[0076] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 31.5 Comparative Example 1 31.1 Example 2 31.3 Comparative Example 2 22.5 Example 3 31.2 Comparative Example 3 27.9 Comparative Example 4 30.5 Comparative Example 5 28.3

[0077] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 2 reveals that the impact-resistant rubber flooring prepared by this invention has good flame-retardant properties.

[0078] By comparison, the limiting oxygen index (LOI) of Examples 1-3 was significantly greater than that of Comparative Example 2, indicating that after allyl phosphate forms a vulcanization system with rubber during vulcanization, phosphoric acid undergoes dehydration polymerization under heated combustion conditions to regenerate polymetaphosphoric acid. Polymetaphosphoric acid can rapidly catalyze the dehydration and carbonization of the rubber flooring to form a dense protective carbon layer, which isolates oxygen and reduces the thermal decomposition rate of the material. At the same time, it reduces the heat generated by rubber decomposition and improves the flame retardant performance of the impact-resistant rubber flooring. The limiting oxygen index of Examples 1-3 was significantly greater than that of Comparative Example 3, indicating that the presence of guanidine salt introduces abundant nitrogen elements, which can have a synergistic flame retardant effect with phosphorus in allyl phosphate, thereby effectively improving the flame retardant performance of the impact-resistant rubber flooring. The limiting oxygen index of Examples 1-3 was significantly greater than that of Comparative Example 5, indicating that silica has a physical barrier effect, which can block the diffusion of combustible gases and heat during combustion, thereby improving the flame retardant performance of the impact-resistant rubber flooring.

[0079] Test Example 3:

[0080] Anti-aging performance test: Samples of each embodiment and comparative example were prepared into specimens with dimensions of 20mm × 4mm × 1mm to obtain original samples. The original tensile strength was tested. Xenon lamps were used to simulate sunlight, and the samples were placed in a xenon lamp accelerated aging test chamber for 360 hours. The experimental atmosphere was air, the temperature was 65℃, the lamp source was 25cm away from the sample, and the radiation intensity was 550W / m². 2 Tensile strength 2 was tested again, and the performance degradation rate was calculated as 1 - tensile strength 1 / tensile strength 2. The results are shown in Table 3.

[0081] Table 3

[0082] performance degradation rate performance degradation rate Example 1 0.011 Comparative Example 1 0.175 Example 2 0.011 Comparative Example 2 0.013 Example 3 0.009 Comparative Example 3 0.010 Comparative Example 4 0.012 Comparative Example 5 0.013

[0083] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 3 reveals that the impact-resistant rubber flooring prepared by this invention has good anti-aging properties.

[0084] By comparison, the performance degradation rate of Examples 1-3 was less than that of Comparative Example 1, indicating that the modified lignin prepared by reacting 2,6-di-tert-butylphenol with depolymerized lignin introduces a hindered structure on the lignin, which can effectively scavenge free radicals and improve the anti-aging performance of impact-resistant rubber flooring.

[0085] Test Example 4:

[0086] Antibacterial performance test: The materials of each example and comparative example were pulverized into powder with a particle size of less than 150 micrometers. The same mass was taken, and the inhibition rate of the materials against Staphylococcus aureus was tested according to the Quine test method. The results are shown in Table 4.

[0087] Table 4

[0088] Antibacterial rate (%) Antibacterial rate (%) Example 1 96.2 Comparative Example 1 96.1 Example 2 96.6 Comparative Example 2 95.9 Example 3 96.5 Comparative Example 3 21.5 Comparative Example 4 96.3 Comparative Example 5 96.2

[0089] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 4 reveals that the impact-resistant rubber flooring prepared by this invention has good antibacterial properties.

[0090] By comparison, the antibacterial rate of Examples 1-3 was significantly greater than that of Comparative Example 3, indicating that 1,3-diaminoguanidine hydrochloride not only played the role of crosslinking lignin, but also introduced guanidine salt with cationic antibacterial effect, thereby improving the antibacterial performance of impact-resistant rubber flooring.

[0091] Test Example 5:

[0092] Antistatic performance testing: The high resistance of the vulcanized rubber was measured using a Keithley 6517B high resistance meter (manufactured by Guangzhou Zhichen Electronics Co., Ltd.). The instrument's current measurement range is 1fA~20mA, and the resistance measurement range is 20MΩ~200MΩ. Each example and test example was cut into 6cm diameter circular pieces for testing. The results are shown in Table 5.

[0093] Table 5

[0094] Resistivity (Ω·cm) Resistivity (Ω·cm) Example 1 2.1×1011 Comparative Example 1 2.0×1011 Example 2 1.9×1011 Comparative Example 2 2.1×1011 Example 3 1.8×1011 Comparative Example 3 1.8×1011 Comparative Example 4 3.5×1015 Comparative Example 5 4.8×1015

[0095] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 5 reveals that the impact-resistant rubber flooring prepared by the present invention has good antistatic properties.

[0096] By comparison, the resistivity of Examples 1-3 is significantly lower than that of Comparative Example 4, indicating that the in-situ polymerization of pyrrole and 1H-pyrrole-3-methanol on silica forms a polypyrrole conductive layer with conductive effect, giving silica good conductivity. As a filler added to rubber flooring materials, it can effectively improve the antistatic performance of impact-resistant rubber flooring.

[0097] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing impact-resistant rubber flooring, characterized in that, The preparation steps include the following: (1) Soak the silica in a pyrrole mixed solution for 10-20 min, filter out the solid, drain the solid, soak it in ferric chloride hydrochloric acid solution at 3-5℃ for 2-4 h, filter, wash the filter residue with anhydrous ethanol 3-5 times, and dry it at 50-60℃ for 6-8 h to obtain modified silica. (2) Depolymerized lignin, 2,6-di-tert-butylphenol, formaldehyde, sodium hydroxide, and deionized water are mixed in a mass ratio of 1:(1.3~1.7):(3~4):(0.5~0.7):(300~400), stirred at 400~600 r / min for 0.5~1.5 h at 60~70℃, heated to 85~95℃ and stirred for 25~35 min, cooled to room temperature, and centrifuged to separate the precipitate. The precipitate is washed 3~5 times with deionized water and anhydrous ethanol, and dried at 50~60℃ for 6~8 h to obtain modified lignin. (3) Mix modified lignin, 1,3-diaminoguanidine hydrochloride, deionized water and polyethylene glycol in a mass ratio of 1:(0.05~0.15):(3~5):(0.3~0.5), stir at 400~600 r / min for 2~4 h at room temperature, filter, wash the filter residue with deionized water and anhydrous ethanol 3~5 times respectively, and dry at 50~60℃ for 6~8 h to obtain modified lignin microspheres; (4) Mix styrene-butadiene rubber with an open mill at 100-120℃ for 20-40 minutes. Adjust the roller gap of the open mill to 1-3 mm. Add allyl phosphate, modified silica, modified lignin microspheres, sulfur, and stearic acid at 50-70℃. Make triangular wraps and roll them crosswise 3-5 times each. Place them in a mold and vulcanize them on a flat vulcanizing machine at 140-160℃ and 14-16 MPa for 10-12 hours. After naturally cooling to room temperature, take them out to obtain impact-resistant rubber flooring. The ratio of styrene-butadiene rubber, allyl phosphate, modified silica, modified lignin microspheres, sulfur, and stearic acid by mass is 1:0.08:0.3:0.1:0.25:0.

05.

2. The method for preparing an impact-resistant rubber flooring according to claim 1, characterized in that, The pyrrole mixed solution in step (1) is prepared by mixing pyrrole, 1H-pyrrole-3-methanol and anhydrous ethanol in a mass ratio of 1:(0.3~0.5):(8~12).

3. The method for preparing an impact-resistant rubber flooring according to claim 1, characterized in that, The ferric chloride hydrochloric acid solution mentioned in step (1) is prepared by mixing 0.1 mol / L ferric chloride solution and 0.3 mol / L hydrochloric acid solution at a volume ratio of 1:

1.

4. The method for preparing an impact-resistant rubber flooring according to claim 1, characterized in that, The method for preparing depolymerized lignin in step (2) is as follows: lithium bromide and 0.3 mol / L hydrochloric acid solution are mixed at a mass ratio of 1:1.7 to obtain a mixed solution; alkali lignin and the mixed solution are mixed at a mass ratio of 1:50, stirred at 110℃ and 400 r / min for 2 h, filtered, the solid is washed 3 times with deionized water, and dried under vacuum at 50℃ for 4 h to obtain depolymerized lignin.

5. The method for preparing an impact-resistant rubber flooring according to claim 1, characterized in that, The polyethylene glycol mentioned in step (3) is PEG1500 type polyethylene glycol.

6. The method for preparing an impact-resistant rubber flooring according to claim 1, characterized in that, The styrene-butadiene rubber mentioned in step (4) is industrial grade styrene-butadiene rubber.

7. An impact-resistant rubber floor prepared by the method of any one of claims 1 to 6.