A long-lasting polymer dust suppressant formulation and its application

Abstract

This invention discloses a long-lasting polymer dust suppressant formulation and its application in the field of dust treatment. The formulation comprises the following components: 5%-15% composite polymer emulsion, 0.5%-3% environmentally responsive polymer, 0.1%-1.5% nano-reinforcing material, 0.2%-2% bio-based water-retaining agent, 0.05%-0.3% cross-linking catalyst, and the balance being water. This invention utilizes the synergistic effect of the composite polymer emulsion, environmentally responsive polymer, nano-reinforcing material, bio-based water-retaining agent, and cross-linking catalyst to form a three-layer composite structure. This structure possesses advantages such as long-lasting and stable dust suppression, strong environmental adaptability, eco-friendliness, remediation function, and multi-functional integration adaptability to various scenarios, effectively addressing the shortcomings of existing technologies.

Description

Technical Field

[0001] This invention relates to the field of dust treatment, specifically to a long-lasting polymer dust suppressant formulation and its application. Background Technology

[0002] Dust pollution is one of the most pressing environmental problems worldwide, widely present in industrial production (such as mining and construction), transportation (such as coal transport and waste disposal), and ecological degradation (such as desertification and soil erosion). Dust not only reduces air quality and harms human respiratory health, but can also cause reduced visibility and equipment wear, posing multiple threats to the ecological environment, production safety, and human health. With increasingly stringent environmental protection requirements, developing efficient, stable, and sustainable dust suppression technologies has become a core requirement for addressing dust pollution.

[0003] Currently, dust suppression technologies mainly include physical covering, chemical spraying, and polymer film formation. Among these, polymer dust suppressants, which can bind and solidify dust particles through film formation to create a continuous protective layer, have advantages such as high dust suppression efficiency and ease of operation, and are gradually becoming a research hotspot. However, existing polymer dust suppressants are mostly designed for single scenarios, and their applicability in complex environments (such as high temperature, strong ultraviolet radiation, drought, and strong winds) is limited, making it difficult to meet the needs for long-term and stable dust suppression. Summary of the Invention

[0004] Based on this, the purpose of this invention is to provide a long-lasting polymer dust suppressant formulation and its application, so as to solve the technical problem that existing dust suppressants have limited applicability in complex environments.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a long-lasting polymer dust suppressant, comprising the following components: 5%-15% composite polymer emulsion, 0.5%-3% environmentally responsive polymer, 0.1%-1.5% nano-reinforcing material, 0.2%-2% bio-based water-retaining agent, 0.05%-0.3% crosslinking catalyst, and the balance being water;

[0006] The composite polymer is a copolymer of polyacrylate, polyurethane and vinyl acetate, and the mass ratio of polyacrylate segments, polyurethane segments and vinyl acetate segments in the copolymer is (3-5):(1-2):(1-1.5).

[0007] The environmentally responsive polymer is a thermosensitive poly(N-isopropylacrylamide-co-acrylic acid) copolymer with a minimum critical dissolution temperature of 25-35°C, and the polymer molecular chain is grafted with oligosaccharide segments that have an attraction effect on specific microorganisms.

[0008] The nano-reinforcing material includes modified attapulgite and titanium dioxide-coated zinc oxide nanoparticles, with a mass ratio of (2-3):1, wherein the surface of the modified attapulgite is loaded with trace amounts of noble metal nanoclusters.

[0009] The bio-based water-retaining agent is a compound of carboxymethyl chitosan and γ-polyglutamic acid in a mass ratio of 1:(0.8-1.2). A small amount of microcapsules with slow-release function are introduced during the compounding process. The microcapsules contain plant growth promoters.

[0010] The cross-linking catalyst is a mixture of organotin compounds and ammonium salts.

[0011] The present invention is further configured such that the preparation method of the composite polymer emulsion includes:

[0012] Butyl acrylate, dimethylaminoethyl methacrylate, and γ-methacryloyloxypropyltrimethoxysilane are mixed in a mass ratio of (8-10):(1-1.5):(0.5-0.8) to form a monomer mixture;

[0013] Add porphyrin compounds to the monomer mixture to ensure uniform dispersion;

[0014] The above mixture was emulsion copolymerized with polyurethane prepolymer and vinyl acetate in the presence of an emulsifier at a reaction temperature of 70-85℃ for 4-6 hours, wherein the mass ratio of polyurethane prepolymer to vinyl acetate was (1-2):(1-1.5).

[0015] After the reaction is complete, add the film-forming aid dipropylene glycol butyl ether at a rate of 1%-3% of the total mass of the emulsion.

[0016] The present invention is further configured such that the preparation method of the nano-reinforced material includes:

[0017] Attapulgite clay was microwaved at 600-800W for 20-30 minutes under nitrogen protection, then impregnated in an ethanol solution of silane coupling agent KH-550, ultrasonically dispersed, and then dried.

[0018] Noble metal nanoclusters were loaded onto the dried attapulgite surface using a chemical reduction method.

[0019] Zinc oxide nanoparticles were reacted with tetrabutyl titanate in a supercritical CO2 environment at a pressure of 15-20 MPa, a temperature of 50-60℃, and a reaction time of 2-4 hours to form a titanium dioxide coating layer.

[0020] The present invention is further configured such that the number average molecular weight of the environmentally responsive polymer is 80,000-150,000, and the molar ratio of N-isopropylacrylamide units to acrylic acid units in its molecular chain is (6-8):1, and the grafting rate of oligosaccharide segments is 5%-10%.

[0021] A method for preparing a long-lasting polymer dust suppressant includes the following steps:

[0022] The composite polymer emulsion and the environmentally responsive polymer are mixed at 45-55℃ and stirred at 200-400 rpm for 30 minutes.

[0023] Add the bio-based water-retaining agent, heat to 60-65℃, and continue stirring for 20 minutes. During this process, the microcapsules are uniformly dispersed in the system.

[0024] Cool the temperature to below 40℃, add the nano-reinforcing material, and ultrasonically disperse for 15-30 minutes;

[0025] Add a crosslinking catalyst and mature at 25-30℃ for 24 hours.

[0026] The dust suppressant forms a three-layer composite structure when applied:

[0027] The bottom layer is a permeable layer containing environmentally responsive polymers and bio-based water-retaining agents, with a penetration depth of 5-10 mm. The oligosaccharide segments of the environmentally responsive polymers attract beneficial microorganisms in the soil to aggregate.

[0028] The middle layer is a cross-linking layer containing a three-dimensional network structure formed by composite polymer and cross-linking catalyst. Porphyrin structural units play a role in photocatalytic enhancement of cross-linking in this layer.

[0029] The surface layer is a protective layer containing a UV-resistant and wear-resistant skeleton composed of nano-reinforced materials, in which precious metal nanoclusters enhance the UV resistance and wear resistance of the surface layer.

[0030] A method for applying a long-lasting polymer dust suppressant includes:

[0031] Dilute the dust suppressant 5-10 times and spray it onto the dust surface using a pressure sprayer at a rate of 0.8-1.5 L / m².

[0032] After spraying, allow to stand and cure for 2-4 hours to form an elastic cured film. The compressive strength of the cured film is ≥0.5MPa, the moisture permeability is ≥500g / (m²・24h), and during the formation of the cured film, the microcapsules gradually release plant growth promoters.

[0033] The dust suppressant is used for sand fixation in desert areas. After combining with sand particles, it forms a porous solidified layer with a porosity of 30%-40% and a wind erosion resistance of ≥12m / s. The organic matter released during the degradation process promotes microbial colonization, and the degradation cycle is 4-6 months. At the same time, the plant growth promoter released by the microcapsules can promote the growth of sand-fixing plants in desert areas.

[0034] The preparation steps of the porous consolidation layer include:

[0035] Mix the dust suppressant with sand at a mass ratio of 1:3, and add water to adjust the moisture content to 15%-20%.

[0036] After paving, compact the surface and cure it at -20 to 40℃ for 48 hours to form a solidified layer with a thickness of 5 to 10 cm.

[0037] In summary, the present invention has the following beneficial effects: the present invention forms a three-layer composite structure through the synergistic effect of composite polymer emulsion, environmentally responsive polymer, nano-reinforcing material, bio-based water-retaining agent and cross-linking catalyst, which has the advantages of long-term stable dust suppression, strong environmental adaptability, eco-friendliness and repair function, and multi-functional integration to adapt to multiple scenarios, and can effectively solve the defects of the existing technology. Attached Figure Description

[0038] Figure 1 The preparation steps of the composite polymer emulsion of the present invention are described below. Detailed Implementation

[0039] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be understood as limiting the present invention.

[0040] The following describes an embodiment of the present invention based on its overall structure.

[0041] A long-lasting polymer dust suppressant, characterized in that it comprises the following components: 5%-15% composite polymer emulsion, 0.5%-3% environmentally responsive polymer, 0.1%-1.5% nano-reinforcing material, 0.2%-2% bio-based water-retaining agent, 0.05%-0.3% crosslinking catalyst, and the balance being water.

[0042] The composite polymer is a copolymer of polyacrylate, polyurethane and vinyl acetate, and the mass ratio of polyacrylate segments, polyurethane segments and vinyl acetate segments in the copolymer is (3-5):(1-2):(1-1.5).

[0043] The environmentally responsive polymer is a thermosensitive poly(N-isopropylacrylamide-co-acrylic acid) copolymer with a minimum critical dissolution temperature of 25-35°C, and the polymer molecular chain is grafted with oligosaccharide segments that have an attraction effect on specific microorganisms.

[0044] The nano-reinforcing material includes modified attapulgite and titanium dioxide-coated zinc oxide nanoparticles, with a mass ratio of (2-3):1, wherein the surface of the modified attapulgite is loaded with trace amounts of noble metal nanoclusters.

[0045] The bio-based water-retaining agent is a compound of carboxymethyl chitosan and γ-polyglutamic acid in a mass ratio of 1:(0.8-1.2). A small amount of microcapsules with slow-release function are introduced during the compounding process. The microcapsules contain plant growth promoters.

[0046] The cross-linking catalyst is a mixture of organotin compounds and ammonium salts.

[0047] The preparation of composite polymer emulsions involves several steps, including monomer mixture preparation, porphyrin dispersion, emulsion copolymerization, and the addition of film-forming aids.

[0048] Preparation of monomer mixture: Weigh butyl acrylate, dimethylaminoethyl methacrylate, and γ-methacryloyloxypropyltrimethoxysilane in a mass ratio of (8-10):(1-1.5):(0.5-0.8), stir and mix for 10 minutes until homogeneous to form monomer mixture.

[0049] Porphyrin dispersion: Add tetraphenylporphyrin (0.3% of the total mass of the monomer mixture) to the monomer mixture and ultrasonically disperse for 15 minutes to ensure uniform dispersion.

[0050] Emulsion copolymerization: The above mixture, polyurethane prepolymer, and vinyl acetate are added to the reactor at a mass ratio of (monomer mixture): (polyurethane prepolymer): (vinyl acetate) = 9:1.5:1.2. Emulsifier is added at 2% of the total material mass, along with deionized water. The temperature is raised to 75°C, and the stirring speed is 200 rpm. The reaction is carried out for 5 hours.

[0051] Film-forming aid addition: After the reaction is completed, cool down to 40°C, add dipropylene glycol butyl ether at a rate of 2% of the total mass of the emulsion, and stir for 30 minutes to obtain the composite polymer emulsion.

[0052] The preparation of nano-reinforced materials includes the following steps: attapulgite pretreatment, loading of noble metal nanoclusters, titanium dioxide coating of zinc oxide and composite.

[0053] Attapulgite pretreatment: Attapulgite was microwaved at 700W for 25 minutes under nitrogen protection, cooled to room temperature, and then impregnated in an ethanol solution of 5% KH-550 silane coupling agent. It was ultrasonically dispersed for 30 minutes and then dried in an oven at 80℃ for 4 hours.

[0054] Noble metal nanocluster loading: Dry attapulgite was added to 0.01 mol / L chloroauric acid solution and stirred for 1 hour. Then, 0.1 mol / L sodium borohydride solution was added dropwise and reacted at room temperature for 2 hours. After centrifugation, the mixture was dried under vacuum at 60 °C to obtain modified attapulgite loaded with gold nanoclusters.

[0055] Titanium dioxide coated zinc oxide: Zinc oxide nanoparticles and tetrabutyl titanate were added to a high-pressure reactor at a mass ratio of 1:2. CO2 was introduced to a pressure of 18 MPa, the temperature was raised to 55°C, and the reaction was stirred for 3 hours. After depressurization, the product was collected to obtain titanium dioxide coated zinc oxide nanoparticles.

[0056] Composite: Modified attapulgite clay and titanium dioxide-coated zinc oxide nanoparticles were mixed at a mass ratio of 2.5:1 and ultrasonically dispersed for 20 minutes to obtain nano-reinforced materials.

[0057] The preparation of environmentally responsive polymers is achieved through copolymerization and grafting with oligosaccharides.

[0058] Copolymerization reaction: Weigh N-isopropylacrylamide and acrylic acid in a molar ratio of 7:1, dissolve in deionized water, purge with nitrogen for 30 minutes to remove oxygen, add potassium persulfate, heat to 60℃ and react for 6 hours to obtain poly(N-isopropylacrylamide-co-acrylic acid) copolymer.

[0059] Oligosaccharide grafting: The above copolymer was dissolved in deionized water, chitosan oligosaccharide and carbodiimide were added, and the mixture was reacted at 30°C for 4 hours. After dialyzing, it was freeze-dried to obtain an environmentally responsive polymer with an oligosaccharide grafting rate of 7% and a number average molecular weight of 120,000.

[0060] Preparation of long-lasting polymer dust suppressant

[0061] Weigh carboxymethyl chitosan and γ-polyglutamic acid in a 1:1 mass ratio, dissolve them in deionized water, stir for 30 minutes, add microcapsules, and continue stirring for 15 minutes to obtain the bio-based water-retaining agent.

[0062] Step 1: Mixing: Weigh the composite polymer emulsion and environmentally responsive polymer by mass percentage, add them to a stirred tank, heat to 50°C, and stir at 300 rpm for 30 minutes until completely dissolved;

[0063] Step 2: Add bio-based water-retaining agent, heat to 62°C, and continue stirring at 300 rpm for 20 minutes, during which time the microcapsules are evenly dispersed in the system;

[0064] Third step: Mixing: Cool to 35℃, add nano-reinforcing materials, and ultrasonically disperse for 20 minutes;

[0065] Curing: Add cross-linking catalyst, replenish deionized water to 100%, and let stand at 28°C for 24 hours to cure, thus obtaining a long-lasting polymer dust suppressant.

[0066] After the dust suppressant is applied, a three-layer composite structure will naturally form on the surface, as follows:

[0067] The bottom layer, i.e. the permeable layer: environmentally responsive polymers and bio-based water-retaining agents penetrate into the interior of the substrate with water, with a penetration depth of up to 7mm; the chitosan oligosaccharide segments of the environmentally responsive polymers attract beneficial microorganisms such as nitrogen-fixing bacteria and actinomycetes in the soil to gather, increasing the microbial concentration by 2-3 times and promoting the formation of soil aggregate structure;

[0068] The intermediate layer, or cross-linking layer, is formed by the composite polymer under the action of a cross-linking catalyst. The porphyrin structural units generate active oxygen under light, which promotes the cross-linking reaction to proceed further, increasing the degree of cross-linking by 15%-20% and enhancing the structural stability.

[0069] The surface layer, or protective layer, consists of modified attapulgite in the nano-reinforced material and titanium dioxide-coated zinc oxide forming a dense framework. Gold nanoclusters absorb ultraviolet rays, achieving an ultraviolet shielding rate of ≥85%. The titanium dioxide coating layer enhances wear resistance and reduces wear by 30%.

[0070] The common construction method is dilution, spraying and curing. The dust suppressant is diluted 8 times with deionized water, stirred evenly, and then sprayed evenly on the dust surface using a pressure sprayer at a dosage of 1.2L / m². Finally, it is left to stand and cure for 3 hours to form an elastic cured film with a thickness of 0.8mm. The cured film has a compressive strength of 0.6MPa and a moisture permeability of 550g / (m²・24h). The microcapsules slowly release plant growth promoters during the curing process.

[0071] Dust suppressants have the following applications

[0072] Dust suppression on the surface of coal transport car bodies is performed using the general methods described above, with the cured film thickness controlled at 0.8 mm. Wind tunnel testing shows it can withstand wind erosion at wind speeds of 16 m / s, reducing dust emissions by over 90%. The porphyrin structural units decompose sulfides on the coal surface under sunlight, achieving an H2S removal rate of ≥80%.

[0073] Dust at the demolition site was solidified by diluting the dust suppressant 7 times and spraying it at a rate of 1.5 L / m². After solidification, the dust did not crack when compacted by a road roller. The brassinolide and humic acid released from the microcapsules increased the germination rate of subsequently sown grass seeds by 25%.

[0074] For dust suppression in open-air ore piles, the dust suppressant was diluted 10 times and sprayed at a rate of 1.5 L / m². After artificial rainfall testing, the membrane regeneration rate reached 75%. The environmentally responsive polymer stabilized the microbial community and promoted the self-repair of the membrane structure.

[0075] Sand fixation in desertified areas: Dust suppressant is mixed with sand particles at a mass ratio of 1:3, water is added to adjust the moisture content to 18%, the mixture is spread and compacted, and cured for 48 hours in an environment of -10 to 35℃ to form a porous solidified layer with a thickness of 8cm; the final porosity is 35%, and the wind erosion resistance is 13m / s; it gradually degrades in a natural environment within 4-6 months, and the organic matter released during the degradation process increases the number of soil microorganisms by 1-2 orders of magnitude; the plant growth promoter increases the survival rate of sand-fixing plants such as Artemisia arenaria and Alternanthera philoxeroides by 30%.

[0076] Although an embodiment of the present invention has been shown and described, this specific embodiment is merely an explanation of the present invention and is not a limitation of the invention. The specific features, structures, materials or characteristics described may be combined in an appropriate manner in any one or more embodiments or examples. After reading this specification, those skilled in the art may make modifications, substitutions and variations to the embodiment without creative contribution as needed without departing from the principles and purpose of the present invention. However, as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A long-lasting polymer dust suppressant, characterized in that, It comprises the following components: 5%-15% composite polymer emulsion, 0.5%-3% environmentally responsive polymer, 0.1%-1.5% nano-reinforcing material, 0.2%-2% bio-based water-retaining agent, 0.05%-0.3% crosslinking catalyst, and the balance being water; The composite polymer is a copolymer of polyacrylate, polyurethane and vinyl acetate, and the mass ratio of polyacrylate segments, polyurethane segments and vinyl acetate segments in the copolymer is (3-5):(1-2):(1-1.5). The environmentally responsive polymer is a thermosensitive poly(N-isopropylacrylamide-co-acrylic acid) copolymer with a minimum critical dissolution temperature of 25-35°C, and the polymer molecular chain is grafted with oligosaccharide segments that have an attraction effect on specific microorganisms. The nano-reinforcing material includes modified attapulgite and titanium dioxide-coated zinc oxide nanoparticles, with a mass ratio of (2-3):1, wherein the surface of the modified attapulgite is loaded with trace amounts of noble metal nanoclusters. The bio-based water-retaining agent is a compound of carboxymethyl chitosan and γ-polyglutamic acid in a mass ratio of 1:(0.8-1.2). A small amount of microcapsules with slow-release function are introduced during the compounding process. The microcapsules contain plant growth promoters. The cross-linking catalyst is a mixture of organotin compounds and ammonium salts; The preparation method of the composite polymer emulsion includes: Butyl acrylate, dimethylaminoethyl methacrylate, and γ-methacryloyloxypropyltrimethoxysilane are mixed in a mass ratio of (8-10):(1-1.5):(0.5-0.8) to form a monomer mixture; Add porphyrin compounds to the monomer mixture to ensure uniform dispersion; The above mixture was emulsion copolymerized with polyurethane prepolymer and vinyl acetate in the presence of an emulsifier at a reaction temperature of 70-85℃ for 4-6 hours, wherein the mass ratio of polyurethane prepolymer to vinyl acetate was (1-2):(1-1.5). After the reaction is complete, add the film-forming aid dipropylene glycol butyl ether at a rate of 1%-3% of the total mass of the emulsion.

2. The long-lasting polymer dust suppressant according to claim 1, characterized in that: The preparation method of the nano-reinforced material includes: Attapulgite clay was microwaved at 600-800W for 20-30 minutes under nitrogen protection, then impregnated in an ethanol solution of silane coupling agent KH-550, ultrasonically dispersed, and then dried. Noble metal nanoclusters were loaded onto the dried attapulgite surface using a chemical reduction method. Zinc oxide nanoparticles were reacted with tetrabutyl titanate in a supercritical CO2 environment at a pressure of 15-20 MPa, a temperature of 50-60℃, and a reaction time of 2-4 hours to form a titanium dioxide coating layer.

3. The long-lasting polymer dust suppressant according to claim 1, characterized in that: The environmentally responsive polymer has a number average molecular weight of 80,000-150,000, and the molar ratio of N-isopropylacrylamide units to acrylic acid units in its molecular chain is (6-8):1, with a grafting rate of 5%-10% for oligosaccharide segments.

4. The method for preparing the long-lasting polymer dust suppressant according to any one of claims 1-3, characterized in that, Includes the following steps: The composite polymer emulsion and the environmentally responsive polymer are mixed at 45-55℃ and stirred at 200-400 rpm for 30 minutes. Add the bio-based water-retaining agent, heat to 60-65℃, and continue stirring for 20 minutes. During this process, the microcapsules are evenly dispersed in the system. Cool the temperature to below 40℃, add the nano-reinforcing material, and ultrasonically disperse for 15-30 minutes; Add a cross-linking catalyst and mature at 25-30℃ for 24 hours.

5. The long-lasting polymer dust suppressant according to claim 1, characterized in that: The dust suppressant forms a three-layer composite structure when applied: The bottom layer is a permeable layer containing environmentally responsive polymers and bio-based water-retaining agents, with a penetration depth of 5-10 mm. The oligosaccharide segments of the environmentally responsive polymers attract beneficial microorganisms in the soil to aggregate. The middle layer is a cross-linking layer containing a three-dimensional network structure formed by composite polymer and cross-linking catalyst. Porphyrin structural units play a role in photocatalytic enhancement of cross-linking in this layer. The surface layer is a protective layer containing a UV-resistant and wear-resistant skeleton composed of nano-reinforced materials, in which precious metal nanoclusters enhance the UV resistance and wear resistance of the surface layer.

6. The construction method of the long-lasting polymer dust suppressant according to claim 1, characterized in that, include: Dilute the dust suppressant 5-10 times and spray it onto the dust surface using a pressure sprayer at a rate of 0.8-1.5 L / m². After spraying, allow to stand and cure for 2-4 hours to form an elastic cured film. The compressive strength of the cured film is ≥0.5MPa, the moisture permeability is ≥500g / (m²・24h), and during the formation of the cured film, the microcapsules gradually release plant growth promoters.

7. The application of the long-lasting polymer dust suppressant according to claim 1, characterized in that: The dust suppressant is used for sand fixation in desert areas. After combining with sand particles, it forms a porous solidified layer with a porosity of 30%-40% and a wind erosion resistance of ≥12m / s. The organic matter released during the degradation process promotes microbial colonization, and the degradation cycle is 4-6 months. At the same time, the plant growth promoter released by the microcapsules can promote the growth of sand-fixing plants in desert areas.

8. The application of the long-lasting polymer dust suppressant according to claim 7, characterized in that: The preparation steps of the porous consolidation layer include: Mix the dust suppressant with sand at a mass ratio of 1:3, and add water to adjust the moisture content to 15%-20%. After paving, compact the surface and cure it at -20 to 40℃ for 48 hours to form a solidified layer with a thickness of 5 to 10 cm.

Images