Application of environment-friendly tire regenerated rubber particles as waterproof roll formula

Abstract

The invention relates to the technical field of regenerated rubber particles, in particular to application of environment-friendly tire regenerated rubber particles as a waterproof coiled material formula, and a preparation method of regenerated modified particles comprises the following steps: premixing 40-60% of regenerated rubber particles subjected to dynamic desulfurization treatment and 15-25% of modified red mud in an internal mixer, controlling the temperature to be 115-125 DEG C, controlling the rotating speed to be 25-35 rpm, and treating for 5 minutes. The oxidation-modified lignin nano-particles are added at intervals in three times, the interval of each adding is 2 min, the temperature is increased to 145 DEG C synchronously in a stepped mode, and the total adding amount of the lignin nano-particles is 9%-15%; and finally, adding 5-10% of seaweed biochar, and stirring at a high speed of 600rpm at the temperature of 90 DEG C to obtain the modified regenerated particles.

Description

Technical Field

[0001] The present invention relates to the technical field of recycled rubber particles, and in particular to the use of an environmentally friendly tire recycled rubber particle as a waterproofing membrane formulation. Background Art

[0002] Traditional waterproofing membranes mostly rely on synthetic rubbers (such as styrene-butadiene rubber, chloroprene rubber) or asphalt, and have problems such as high cost, non-degradability, and environmental pollution. Although recycled tire rubber can reduce costs, its sole use easily leads to insufficient mechanical properties (such as low tensile strength and poor weather resistance). In addition, red mud, as an industrial waste residue of alumina, is prone to cause alkali pollution and radioactive hazards when stacked outdoors for a long time; lignin, as an agricultural and forestry waste, has low utilization rate; the resource utilization of seaweed biochar has not been fully developed. Therefore, there is an urgent need for the use of an environmentally friendly tire recycled rubber particle as a waterproofing membrane formulation, which can make full use of waste resources to improve the performance of waterproofing membranes. Summary of the Invention

[0003] The technical problem to be solved by the present invention is: to provide the use of an environmentally friendly tire recycled rubber particle as a waterproofing membrane formulation, which can make full use of waste resources to improve the waterproof and mechanical properties of the waterproofing membrane.

[0004] To solve the above technical problem, the technical solution adopted by the present invention is: the use of an environmentally friendly tire recycled rubber particle as a waterproofing membrane formulation, and the preparation method of the modified recycled rubber particle:

[0005] Step 1: Premix 40%-60% of the recycled rubber particles treated by dynamic desulfurization and 15%-25% of the modified red mud in a kneader, control the temperature at 115-125°C and the rotation speed at 25 rpm-35 rpm, and process for 5 minutes.

[0006] Step 2: Add the oxidized modified lignin nanoparticles in three intervals, with an interval of 2 minutes each time, and synchronously increase the temperature step by step to 145°C. The total addition amount of the lignin nanoparticles is 9%-15%;

[0007] Step 3: Finally, add 5%-10% of seaweed biochar, and stir at a high speed of 600 rpm and a temperature of 90°C to obtain the modified recycled particles.

[0008] Further, the preparation of the modified red mud: The modified red mud is pickled with 5 mol / L of salt acid and then calcined at 635°C for 30 minutes, so that the pH value is reduced from 12.3 to 7.8, and the specific surface area reaches 125 m 2 / g.

[0009] Further, the seaweed biochar is prepared by pyrolyzing kelp under anaerobic conditions at 600°C for 2 hours, with a porosity of 85% and an iodine adsorption value of 820 mg / g.

[0010] Furthermore, 50% recycled rubber particles, 20% modified red mud, 12% sodium lignin particles, and 8% seaweed biochar.

[0011] Furthermore, the preparation method of the waterproof coiled material comprises the following steps: adding a plasticizer, an antioxidant, a vulcanizing agent, and a vulcanization accelerator to the modified recycled rubber particles, and continuously mixing at 135 - 155°C for 5 - 8 minutes to obtain a mixed rubber;

[0012] Step 2: Vulcanization and molding: placing the mixed rubber in a flat vulcanizer, vulcanizing at 155 - 165°C and a pressure of 14 - 16 MPa for 18 - 22 minutes, and cooling to obtain the waterproof coiled material.

[0013] The beneficial effects of the present invention are as follows: Lignin forms a three-dimensional network skeleton through π-π stacking with recycled rubber particles, and its phenylpropane unit structure enhances the rigidity of the material. F e2 O3 in the modified red mud fills the network gaps to improve the density. The porous structure of the seaweed biochar provides a buffer space for the molecular chain slip. The three work together to increase the tensile strength. The oxygen-containing functional groups of lignin form coordination bonds with metal ions in the modified red mud, and the pores of the biochar anchor the polymer chains, jointly inhibiting crack propagation and improving the tear strength. The phenolic hydroxyl groups of lignin scavenge free radicals, and F e2 O3 in the modified red mud reflects ultraviolet rays, and the graphitized layer of the biochar blocks the penetration of light and oxygen, so that the strength remains above 85% after 500 h of UV aging. Lignin can expose more aromatic ring structures through oxidation modification, reduce the surface energy, and form a hydrophobic film similar to AKD sizing agent. The micropores of the biochar are closed by the lignin hydrophobic film, and the modified red mud particles repair the interface defects, achieving no water leakage under a water pressure of 0.3 MPa for 72 h. Detailed implementation mode

[0014] To illustrate the technical content, the achieved objectives, and the effects of the present invention in detail, the following is described in conjunction with the implementation modes.

[0015] Example 1:

[0016] The preparation method of the modified recycled rubber particles comprises the following steps:

[0017] Step 1: Premix 50% of the recycled rubber particles treated by dynamic desulfurization and 20% of the modified red mud in a mixer, control the temperature at 120°C, the rotation speed at 30 rpm, and process for 5 min.

[0018] Step 2: Add the lignin nanoparticles into Step 1 in three times, with an addition amount of 4% each time, and a gap time of 2 min between each addition, and raise the temperature to 145°C.

[0019] Step 3: Finally, add 8% of the seaweed biochar, stir at a high speed of 600 rpm, and the temperature is 90°C to obtain the modified recycled particles.

[0020] The preparation of modified red mud adopts a method combining acid washing and roasting. The specific steps are as follows: Take industrial red mud, perform acid washing treatment with a 5mol / L hydrochloric acid solution according to a liquid-solid ratio of 10:1, the acid washing temperature is 60°C, the acid washing time is 2 hours, and the stirring speed is maintained at 200rpm during the acid washing process; after the acid washing is completed, wash with deionized water until neutral, and dry at 105°C for 12 hours; place the dried red mud in a muffle furnace, heat it to 635°C at a heating rate of 5°C / min, keep it warm for 30 minutes, and naturally cool to room temperature to obtain modified red mud.

[0021] The preparation of lignin nanoparticles adopts the ultrasonic-assisted method. The specific steps are as follows: Take industrial lignin powder, add deionized water to prepare a suspension with a mass fraction of 5%, and perform ultrasonic treatment for 60 minutes under the conditions of an ultrasonic power of 500W and a frequency of 20kHz; the treated suspension is centrifuged, and the supernatant is taken and freeze-dried to obtain lignin nanoparticles with a particle size range of 50-100nm.

[0022] The preparation of seaweed biochar adopts the pyrolysis method. The specific steps are as follows: Take dried seaweed, under nitrogen protection, heat it to 600°C at a heating rate of 10°C / min, keep it warm for 2 hours and then naturally cool to room temperature to obtain seaweed biochar. The porosity of the prepared seaweed biochar is 85%, and the iodine adsorption value is 850mg / g.

[0023] Example 2:

[0024] The preparation method of modified recycled rubber particles includes the following steps:

[0025] Step 1: Premix 40% of the recycled rubber particles treated by dynamic desulfurization with 15% of the modified red mud in a mixer, control the temperature at 120°C and the rotation speed at 30rpm, and process for 5 minutes.

[0026] Step 2: Add the lignin nanoparticles into Step 1 in three times, with each addition amount being 3%, and the interval time between each addition being 2 minutes, and raise the temperature to 145°C.

[0027] Step 3: Finally, add 5% of the seaweed biochar, stir at a high speed of 600rpm, and the temperature is 90°C to obtain the modified recycled particles.

[0028] The modified red mud is prepared by combining acid washing and roasting. The specific steps are as follows: Take industrial red mud, perform acid washing treatment with 5mol / L hydrochloric acid solution according to a liquid-solid ratio of 10:1, the acid washing temperature is 60°C, the acid washing time is 2 hours, and the stirring speed is maintained at 200rpm during the acid washing process; after the acid washing is completed, wash with deionized water until neutral, and dry at 105°C for 12 hours; place the dried red mud in a muffle furnace, heat it to 635°C at a heating rate of 5°C / min, hold for 30 minutes, and naturally cool to room temperature to obtain the modified red mud.

[0029] The lignin nanoparticles are prepared by an ultrasonic-assisted method. The specific steps are as follows: Take industrial lignin powder, add deionized water to prepare a suspension with a mass fraction of 5%, and perform ultrasonic treatment for 60 minutes under the conditions of an ultrasonic power of 500W and a frequency of 20kHz; the treated suspension is centrifuged, and the supernatant is taken and freeze-dried to obtain lignin nanoparticles with a particle size range of 50-100nm.

[0030] The seaweed biochar is prepared by pyrolysis. The specific steps are as follows: Take the dried seaweed, under nitrogen protection, heat it to 600°C at a heating rate of 10°C / min, hold for 2 hours and then naturally cool to room temperature to obtain the seaweed biochar. The prepared seaweed biochar has a porosity of 85% and an iodine adsorption value of 850mg / g.

[0031] Example 3:

[0032] The preparation method of the modified recycled rubber particles includes the following steps:

[0033] Step 1: Premix 60% of the recycled rubber particles treated by dynamic desulfurization and 25% of the modified red mud in a mixer, control the temperature at 120°C, the rotation speed at 30rpm, and treat for 5 minutes.

[0034] Step 2: Add the lignin nanoparticles into Step 1 in three times, with each addition amount being 5%, and the interval time between each addition being 2 minutes, and raise the temperature to 145°C.

[0035] Step 3: Finally, add 10% of the seaweed biochar, stir at a high speed of 600rpm, and the temperature is 90°C to obtain the modified recycled particles.

[0036] The modified red mud is prepared by combining acid washing and roasting. The specific steps are as follows: Take industrial red mud, perform acid washing treatment with 5 mol / L hydrochloric acid solution according to a liquid-solid ratio of 10:1, the acid washing temperature is 60 °C, the acid washing time is 2 hours, and keep the stirring speed at 200 rpm during the acid washing process; after the acid washing is completed, wash with deionized water until neutral, and dry at 105 °C for 12 hours; place the dried red mud in a muffle furnace, heat it to 635 °C at a heating rate of 5 °C / min, keep it warm for 30 minutes, and then cool it naturally to room temperature to obtain the modified red mud.

[0037] The lignin nanoparticles are prepared by an ultrasonic-assisted method. The specific steps are as follows: Take industrial lignin powder, add deionized water to prepare a suspension with a mass fraction of 5%, and perform ultrasonic treatment for 60 minutes under the conditions of an ultrasonic power of 500 W and a frequency of 20 kHz; after the treatment, the suspension is centrifuged, the supernatant is taken, and the lignin nanoparticles are obtained by freeze-drying, and the particle size range is 50 - 100 nm.

[0038] The seaweed biochar is prepared by pyrolysis. The specific steps are as follows: Take the dried seaweed, under nitrogen protection, heat it to 600 °C at a heating rate of 10 °C / min, keep it warm for 2 hours, and then cool it naturally to room temperature to obtain the seaweed biochar. The porosity of the prepared seaweed biochar is 85%, and the iodine adsorption value is 850 mg / g.

[0039] Comparative Example 1:

[0040] Different from the preparation method of the modified recycled rubber particles in Example 1, step 2 is omitted.

[0041] Comparative Example 2:

[0042] Different from the preparation method of the modified recycled rubber particles in Example 1, step 1 is omitted.

[0043] Comparative Example 3:

[0044] Different from the preparation method of the modified recycled rubber particles in Example 1, step 3 is omitted.

[0045] Experimental group: Add the modified recycled rubber particles obtained in the above Examples 1 - 3 and Comparative Examples 1 - 3 to a plasticizer, an antioxidant, a vulcanizing agent, and a vulcanization accelerator, and continue to mix for 5 - 8 minutes at 135 - 155 °C to obtain a mixed rubber. Place the mixed rubber in a flat vulcanizer and vulcanize it for 18 - 22 minutes at 155 - 165 °C and a pressure of 14 - 16 MPa, and then cool it to obtain a waterproof coiled material, which is divided into Experimental Groups 1 - 6. Experimental Group 7 is the shock-absorbing and waterproof coiled material of butyl rubber produced in Example 1 of the authorized announcement number CN116442610B.

[0046]

[0047] The waterproof coiled materials of experimental groups 1 - 6 and experimental group 7 were tested for their performance with reference to GB / T 328, and their UV aging was tested with GB 18244 - 2000.

[0048] The waterproof coiled materials obtained from the experimental groups were subjected to performance tests, and the results are shown in the following table:

[0049]

[0050]

[0051] As can be seen from the above table:

[0052] The tensile strength of experimental group 1 reached 17.0 Mpa, the elongation at break was 700, the tear strength was 28, there was no leakage in 72 hours, and the UV aging strength was maintained at 88%. Thus, it can be seen that through the synergistic effect of lignin, modified red mud, and biochar and the specific ratio of other additives, the performance of the waterproof coiled materials can be improved.

[0053] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. All equivalent transformations made using the content of the specification of the present invention, directly or indirectly applied in related technical fields, are similarly included in the patent protection scope of the present invention.

Claims

1. Use of an environment-friendly tire recycled rubber granule as a waterproofing membrane formulation, characterized in that, Preparation method of modified recycled rubber particles: Step 1: Premix 40%-60% of the recycled rubber particles treated by dynamic desulfurization and 15%-25% of modified red mud in a mixer, control the temperature at 115-125°C and the rotation speed at 25 rpm - 35 rpm, and process for 5 minutes. Step 2: Add the oxidized modified lignin nanoparticles in three intervals, with an interval of 2 minutes each time, and synchronously increase the temperature step by step to 145°C. The total addition amount of the lignin nanoparticles is 9%-15%. Step 3: Finally, add 5%-10% of seaweed biochar, and stir at a high speed of 600 rpm at a temperature of 90°C to obtain the modified recycled particles.

2. Use of the environmentally friendly tire recycled rubber particles as a waterproofing membrane formulation according to claim 1, characterized in that, Preparation of modified red mud: The modified red mud is pickled with 5 mol / L hydrochloric acid and then calcined at 635 °C for 30 min, reducing the pH from 12.3 to 7.8 and achieving a specific surface area of 125 m 2 / g.

3. Use of the environmentally friendly tire recycled rubber particles as a waterproofing membrane formulation according to claim 1, characterized in that, The seaweed biochar is prepared by pyrolyzing kelp at 600°C under anoxic conditions for 2 hours, with a porosity of 85% and an iodine adsorption value of 820 mg / g.

4. Use of the environment-friendly tire recycled rubber particles as a waterproofing membrane formulation according to claim 1, characterized in that, 50% of recycled rubber particles, 20% of modified red mud, 12% of sodium lignin particles, and 8% of seaweed biochar.

5. The preparation method of the waterproof coiled material according to any one of claims 1-4, characterized in that It includes the following steps: Step 1: Add a plasticizer, an antioxidant, a vulcanizing agent, and a vulcanization accelerator to the modified recycled rubber particles, and continue to mix at 135-155°C for 5-8 minutes to obtain a mixed rubber. Step 2: Vulcanization molding: Place the mixed rubber in a flat vulcanizer and vulcanize at 155-165°C and a pressure of 14-16 MPa for 18-22 minutes, and then cool to obtain a waterproof coiled material.

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