A mine-used conveying belt quick repairing material and a preparation method thereof

Abstract

The application relates to the technical field of repairing materials, and particularly discloses a quick repairing material for a mine conveying belt and a preparation method thereof. The quick repairing material for the mine conveying belt comprises components A and B, and the preparation raw materials of the component A include the following components in parts by weight: polyether polyol 30-50 parts and diphenyl methane diisocyanate 45-80 parts; the preparation raw materials of the component B include the following components in parts by weight: terminal amino polyether 30-50 parts, chain extender 20-40 parts, crosslinking agent 5-10 parts, modified flame retardant 5-10 parts, antistatic agent 1-5 parts and auxiliary agent 1-5 parts; wherein the flame retardant is one of a metal organic framework flame retardant, a metal organic framework flame retardant modified by a phosphorus-based flame retardant and a metal organic framework flame retardant modified by a reaction type DOPO-based flame retardant. The spraying type quick repairing material provided by the application can ensure the physical and chemical properties of the material, and improve the flame retardant property and stability of the material.

Description

Technical Field

[0001] This application relates to the field of repair materials, and in particular to a rapid repair material for mining conveyor belts and its preparation method. Background Technology

[0002] Mining conveyor belts are a crucial transportation tool in the mining industry, enabling the transport of mined raw materials such as coal and ore from mines, and facilitating efficient long-distance transport. However, due to the harsh operating environment in mines, long-term use can cause severe wear and tear on the conveyor belts, thus requiring frequent maintenance and repair.

[0003] To minimize production delays, rapid repair technology for conveyor belts has emerged. Currently, common repair materials used for mining conveyor belts can be broadly categorized into four types: 1. Thermosetting Rubber: Thermosetting rubber is a commonly used conveyor belt repair material. It possesses high strength and wear resistance, effectively repairing damage to mining conveyor belts, such as tears and cuts. It can be used in high-temperature environments, is not easily damaged by heat, and is suitable for high-temperature environments such as mines. However, thermosetting rubber also has some disadvantages: it usually contains harmful substances, which may pollute the environment, making it less environmentally friendly; once thermosetting rubber has cured, it is difficult to reverse, and incorrect repair methods may lead to more severe damage to the conveyor belt; moreover, compared to other repair materials, thermosetting rubber has relatively poor corrosion resistance and may be susceptible to corrosion from chemical substances.

[0004] 2. Cold-rolled aluminum foil: Cold-rolled aluminum foil is a lightweight material with good corrosion resistance, suitable for use in humid and corrosive environments. It can be directly adhered to the conveyor belt surface during repair, eliminating the need for glue or other accessories, making installation simple and convenient. It can be used in high-temperature environments without being easily damaged by heat, making it suitable for high-temperature environments such as mines. It is also suitable for small-area repairs. The main disadvantages of cold-rolled aluminum foil are: compared to other repair materials, its strength is lower and it may not be able to withstand significant mechanical stress; furthermore, its wear resistance is poor, and it may show signs of wear again after prolonged use.

[0005] 3. Polyurea: Polyurea is a high-strength and wear-resistant material that can be used to repair large-area damage on conveyor belts. It has good corrosion resistance and can be used in humid and corrosive environments. It is typically applied to the conveyor belt surface in liquid form, forming a strong coating within minutes, making it easy to apply. It can be used in high-temperature environments without being easily damaged by heat, making it suitable for high-temperature environments such as mines. The main disadvantages of polyurea are: it usually contains harmful substances, which can easily pollute the environment, and it may age after prolonged use, leading to poor repair results.

[0006] 4. Steel Belt Clamps: Steel belt clamps can be used to connect the two ends of a conveyor belt or repair a broken conveyor belt. They typically consist of two steel clamps and some bolts, allowing for quick installation and providing strong bonding force. Steel belt clamps can be quickly installed on-site without complicated operations, and the repair effect is obvious. Made of high-strength steel, they have good wear resistance and can effectively repair damage to mining conveyor belts. Steel belt clamps are suitable for conveyor belts of different sizes, offering high applicability. They are also relatively inexpensive, making them more economical compared to other repair methods. The main disadvantages of steel belt clamps are: their strength is limited by the manufacturing process and may not be able to withstand large mechanical stresses; and improper installation may cause more serious damage to the conveyor belt.

[0007] Therefore, there is an urgent need to develop a repair material that is easy to use, has high strength, and good corrosion resistance. Summary of the Invention

[0008] To improve the wear resistance, corrosion resistance, and environmental performance of rapid repair materials, this application provides a rapid repair material for mining conveyor belts and its preparation method. The spray-applied rapid repair material provided by this invention employs a design that blends multiple resin block copolymers and modified flame retardants. This ensures the material's physical and chemical properties while improving its flame retardant properties, resulting in a material that possesses excellent physical and chemical properties, as well as long-lasting flame retardant performance and stability.

[0009] In the first aspect, this application provides a rapid repair material for mining conveyor belts, employing the following technical solution: A rapid repair material for mining conveyor belts, comprising component A and component B. Component A, by weight, comprises the following raw materials: 30-50 parts polyether polyol and 45-80 parts diphenylmethane diisocyanate; component B, by weight, comprises the following raw materials: 30-50 parts amino-terminated polyether, 20-40 parts chain extender, 5-10 parts crosslinking agent, 5-10 parts modified flame retardant, 1-5 parts antistatic agent, and 1-5 parts additives. The flame retardant is one of the following: a metal-organic framework flame retardant, a phosphorus-based flame retardant modified metal-organic framework flame retardant, and a reactive DOPO-based modified metal-organic framework flame retardant.

[0010] By adopting the above technical solution, in component A, the polyether polyol provides the basic framework for the repair material and imparts flexibility. The reaction between the polyether polyol and diphenylmethane diisocyanate forms hard segments of polyurethane, improving the strength and hardness of the repair material. In component B, on the one hand, the amino-terminated polyether molecular chain ends with amino groups, enabling it to undergo a nucleophilic substitution reaction with diphenylmethane diisocyanate at a relatively fast rate. On the other hand, multiple functional groups of the crosslinking agent react with diphenylmethane diisocyanate, effectively promoting the curing and hardening process of the repair material. This allows the repair material to cure completely in a short time, minimizing production downtime due to conveyor belt failure and ensuring production efficiency. Furthermore, in the presence of chain extenders and crosslinking agents, the reaction between the amino-terminated polyether and the isocyanate groups of diphenylmethane diisocyanate increases the length of the polyurethane molecular chain, while the reaction between the crosslinking agent and diphenylmethane diisocyanate forms a dense crosslinked structure, significantly improving the toughness and stability of the repair material. By alternating soft and hard segments, the repair material can maintain flexibility while also possessing sufficient wear resistance.

[0011] In addition, flame retardants are added to component B. Phosphorus-based and DOPO-based flame retardants undergo a series of reactions during combustion, such as thermal decomposition and oxidation, generating substances like phosphoric acid or metaphosphoric acid and releasing non-flammable gases such as ammonia and water. Phosphoric acid or metaphosphoric acid forms a dense char layer on the resin matrix surface, effectively preventing oxygen from the air from contacting the internal material, thus slowing down or terminating the combustion process. The released gases effectively dilute flammable gases and inhibit combustion, while simultaneously promoting matrix foaming and expansion. Phosphorus-based and DOPO-based flame retardants can capture free radicals generated during combustion in the gas phase, thereby interrupting the chain reaction of combustion and reducing the speed and intensity of combustion. Meanwhile, metal-organic framework flame retardants have a high specific surface area and abundant porous structure, capable of adsorbing flammable gases and smoke particles generated during combustion, causing them to settle on the polymer surface, further reducing the hazards of combustion. Furthermore, the charring effect of transition metal ions in the metal-organic framework flame retardants promotes the formation of a char layer on the polymer surface. This dense char layer covering the material surface can block the intrusion of heat and oxygen, achieving a flame-retardant effect. The addition of antistatic agents can reduce the accumulation of static electricity in materials, thereby reducing the possibility of fires and explosions caused by static electricity accumulation.

[0012] Preferably, the weight ratio of component A to component B is (1-1.1):1.

[0013] By adopting the above technical solution and controlling the weight ratio of component A and component B, it is helpful to form a dense block copolymer cross-linked structure after the two are mixed, which ensures that the material has excellent physical and chemical properties while improving its flame retardant properties.

[0014] Preferably, the phosphorus-based flame retardant modified metal-organic framework flame retardant is obtained by mixing a phosphorus-based flame retardant and a metal-organic framework flame retardant.

[0015] By employing the above-mentioned technical solutions, phosphorus-based flame retardants can form a char layer on the material surface during combustion, thereby isolating oxygen. They can also absorb the heat generated during combustion, reduce heat conduction, and capture free radicals generated during combustion to delay or interrupt combustion. Meanwhile, metal-organic framework flame retardants utilize their high specific surface area and porous structure to adsorb harmful combustion products. The two can complement each other in terms of flame retardancy, thereby further improving the flame retardant performance of repair materials.

[0016] Preferably, the phosphorus-based flame retardant modified metal-organic framework flame retardant is prepared by the following method: The metal-organic framework flame retardant was mixed with a solvent and then a phosphorus-based flame retardant was added. After mixing evenly, the mixture was reacted at 40-120°C for 9-14 hours. The precipitate obtained from the reaction was filtered, washed and dried to obtain a phosphorus-based flame retardant modified metal-organic framework flame retardant.

[0017] By adopting the above technical solution, metal-organic framework flame retardants have a high specific surface area and abundant pore structure, which can adsorb some phosphorus-based flame retardants on their surface to form a stable flame retardant system, which helps to improve the dispersibility of phosphorus-based flame retardants. At the same time, metal-organic framework flame retardants themselves also have a certain flame retardant effect. The synergistic effect of the two can further improve the flame retardant performance of the repair material.

[0018] As a preferred embodiment, the reactive DOPO-based modified metal-organic framework flame retardant is prepared by the following method: S1, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 4,4'-diaminobenzophenone are mixed evenly and heated to 160-200℃ for 2-4 hours. After cooling to 90-110℃, toluene is added. The precipitate obtained from the reaction is filtered and washed, and then mixed with tetrahydrofuran and recrystallized to obtain m-2DOPO-2NH2 mixture. S2. After uniformly mixing the metal-organic framework flame retardant and tetrahydrofuran, add the mixture to the m-2DOPO-2NH2 mixture and react at 40-60℃ for 2-4 hours. Filter, wash and dry the precipitate obtained from the reaction to obtain the reactive DOPO-based modified metal-organic framework flame retardant.

[0019] By adopting the above technical solution, the reactive DOPO-based modified metal-organic framework achieves flame retardancy through the synergistic effect of multiple mechanisms, including phosphorus-oxygen free radical inhibition, char layer formation, and gas-phase flame retardancy. These mechanisms effectively suppress flame spread and heat release, resulting in excellent flame retardancy and significantly reducing fire risk. Furthermore, due to its amino group, it can react with isocyanate components, overcoming the drawbacks of conventional additive liquid flame retardants such as easy release, volatilization, and instability.

[0020] Preferably, the ligands of the MOFs are selected from one or more of 2-methylimidazolium, terephthalic acid, phenyl 1,3,5-tricarboxylic acid, and 2-aminoterephthalic acid; and the metal ions of the MOFs are selected from one or more of chromium ions, iron ions, cobalt ions, zinc ions, aluminum ions, copper ions, zirconium ions, lanthanum ions, cerium ions, and yttrium ions.

[0021] Preferably, the chain extender comprises a polyol and a diamine, wherein the weight ratio of the polyol to the diamine is (1-50):(1-100).

[0022] By adopting the above technical solution, polyols, as chain extenders, can adjust the hard segment structure of polyurethane, extend the length of polymer chains, and provide flexibility to polymer chains; while diamines introduce more rigidity into polymer chains, adjust the balance between soft and hard segments of polyurethane, and the synergy of the two can further improve the strength and stability of the material.

[0023] In some preferred embodiments, the weight ratio of polyol to diamine can be 1:100, 50:1, or 25:50, etc.

[0024] Preferably, the additive is selected from one or more of bismuth carboxylate, molecular sieve, and pigment.

[0025] By employing the above-mentioned technical solutions, bismuth carboxylate, as a metal catalyst, can significantly increase the rate of polyurethane or polyurea synthesis reactions and optimize reaction conditions, thus promoting polymer formation, improving production efficiency, and enhancing the physical properties of the materials. Molecular sieves, with their strong hydrophilicity, can adsorb moisture and carbon dioxide produced during the reaction, helping to solve the problem of carbon dioxide bubble formation during the reaction of polyurethane with water and preventing the negative impact of bubble formation on material properties. Simultaneously, molecular sieves can also reduce the hygroscopic properties of the materials, maintain the mechanical properties of the polymer, and improve the thermal stability and weather resistance of the products. Color pastes are used to adjust the appearance of the materials, meeting the needs of different colored conveyor belts for repair materials.

[0026] Preferably, the additives include bismuth carboxylate, molecular sieve, and color paste, with the weight ratio of bismuth carboxylate, molecular sieve, and color paste being (0.01-0.3):5:5.

[0027] By adopting the above technical solution, the weight ratio of bismuth carboxylate, molecular sieve and pigment is further adjusted, thereby optimizing the performance of the repair material, improving curing efficiency and ensuring the uniformity and stability of the material color.

[0028] In some preferred embodiments, the weight ratio of bismuth carboxylate, molecular sieve, and pigment can be 0.01:5:5, 0.3:5:5, or 0.2:5:5, etc.

[0029] Secondly, this application provides a method for preparing a rapid repair material for mining conveyor belts, employing the following technical solution: A method for preparing a rapid repair material for mining conveyor belts includes the following steps: T1. Heat the polyether polyol to 90-120℃ and then dehydrate it under vacuum. When the temperature drops to 50-60℃, add diphenylmethane diisocyanate, stir for 0.5-1h, then heat to 60-80℃ and continue stirring for 0.5-1h. Heat again to 85-90℃ and react for 2-4h to obtain component A. T2. Mix the terminal amino polyether, chain extender, crosslinking agent, flame retardant, antistatic agent and additives, and stir at 60-80℃ for 1-2 hours to obtain component B. T3. Place components A and B separately in a spraying device and mix and spray them under conditions of 65-70℃ and 1800-2200psi to obtain a rapid repair material.

[0030] By adopting the above technical solution and designing and adjusting the parameters of the raw materials and preparation process of the repair material, the prepared repair material has excellent mechanical properties, flame retardant properties and corrosion resistance, which can extend the service life of the conveyor belt and reduce the number of maintenance and costs.

[0031] In summary, this application includes at least one of the following beneficial technical effects: 1. The sprayable repair material of this application adjusts the raw materials for the preparation of components A and B. The reaction of polyether polyol with diphenylmethane diisocyanate can form hard segments of polyurethane, improving the strength and hardness of the repair material. The amino-terminated polyether in component B can react with the isocyanate groups of diphenylmethane diisocyanate in component A, increasing the length of the polyurethane molecular chain and improving the toughness and stability of the repair material. Through the alternating arrangement of soft and hard segments, the repair material can maintain flexibility while also having sufficient wear resistance. 2. The sprayable rapid repair material of this application has excellent flame retardant properties. By combining inorganic flame retardants and organic flame retardants, its compatibility with polymers can be enhanced or the sensitivity of inorganic materials can be reduced, resulting in better flame retardant properties and effectively preventing production accidents caused by conveyor belt fires. 3. This application introduces a reactive flame retardant into the raw materials for preparing spray-applied polyurea repair materials, which solves the problems of easy precipitation, volatilization and instability of conventionally added liquid flame retardants. It also solves the problems of difficult dispersion, easy agglomeration and sedimentation, and large addition amount of conventionally added solid flame retardants, so that component B has better process fluidity. Attached Figure Description

[0032] Figure 1 This is a comparison chart of the average heat release rates of Examples 8, 11, 14 and Comparative Examples 1-2; Figure 2 This is a comparison chart of the smoke production rates of Examples 9, 12, and 15 and Comparative Examples 1 and 3; Figure 3 This is a comparison chart of tensile strength and elongation at break after different treatments in Example 1. Detailed Implementation

[0033] To make this application easier to understand, the following detailed description will be provided with reference to embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of application of this application. Unless otherwise specified, the raw materials or components used in this application can be obtained commercially or by conventional methods.

[0034] Source of raw materials Polyether polyol, with an effective ingredient content of 99%, is classified as a superior grade product. Amino-terminated polyether, CAS number 9046-10-0, active ingredient content 99%, grade: superior product; 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, CAS No. 35948-25-5, active ingredient content is 99%; 4,4'-Diaminobenzophenone, CAS number 611-98-3, has an active ingredient content of 98%; Ammonium polyphosphate, CAS No. 68333-79-9, has an effective phosphorus content of ≥57% and an effective ingredient content of 98%; Melamine polyphosphate, CAS number 218768-84-4, active ingredient content is 99%, grade is industrial; Polyethylene glycol, with an active ingredient content of 99% and a molecular weight of 200; The molecular sieve is 3A molecular sieve, with an effective ingredient content of 99% and a density of 0.4 g / cm³. 3 .

[0035] Preparation Example 1: In Preparation Example 1, the flame retardant is a metal-organic framework flame retardant Cr-MOF. The ligand of the metal-organic framework flame retardant is terephthalic acid, and the metal ion is chromium ion. The preparation method of Cr-MOF is as follows: A1. Add 2 g of Cr(NO3)3·9H2O to 20 mL of terephthalic acid, and disperse it by ultrasonic for 30 min to obtain a suspension; A2. Transfer the suspension into a high-pressure reactor, place it at 218 °C for 18 h, and centrifuge it at 10000 rpm for 10 min when it cools to 25 °C. Wash the precipitate repeatedly with deionized water to obtain MOF solid; A3. Add 0.46 g of MOF solid to 20 mL of N,N-dimethylformamide, stir for 30 min, then place it at 70 °C for 10 h, centrifuge it, and wash the precipitate repeatedly with methanol to obtain Cr-MOF.

[0036] Preparation Example 2: In Preparation Example 2, the flame retardant is a metal-organic framework flame retardant Al-BDC. The ligand of the metal-organic framework flame retardant is terephthalic acid, and the metal ion is aluminum ion. The preparation method of Al-BDC is as follows: B1. Dissolve 1.5 g of Al(NO3)3·9H2O in 25 mL of water, stir for 20 min, then add 75 mL of terephthalic acid, and stir for 15 min to obtain a mixed solution; B2. Transfer the mixed solution into a high-pressure reactor, place it at 210 °C for 4 h, filter, wash, and dry the precipitate obtained by the reaction to obtain Al-BDC.

[0037] Preparation Example 3: In Preparation Example 3, the flame retardant is a metal-organic framework flame retardant Fe-BDC. The ligand of the metal-organic framework flame retardant is terephthalic acid, and the metal ion is iron ion. The preparation method of Fe-BDC is as follows: C1. Add 25 mL of Fe(NO3)3·9H2O and 10 mL of terephthalic acid to 60 mL of water, stir for 0.5 h to obtain a premixed solution; C2. Add the premixed solution into a high-pressure reactor, place it at 200 °C for 4 h, filter, wash, and dry the precipitate obtained by the reaction to obtain Fe-BDC.

[0038] Preparation Example 4: In Preparation Example 4, the flame retardant is a metal-organic framework flame retardant APP / Cr-MOF modified by a phosphorus-based flame retardant. The phosphorus-based flame retardant is ammonium polyphosphate, and the metal-organic framework flame retardant is Cr-MOF prepared in Preparation Example 1. The preparation method of the flame retardant is as follows: Directly mix ammonium polyphosphate and Cr-MOF in a mass ratio of 1:1 to obtain the flame retardant.

[0039] Preparation Example 5: In Preparation Example 5, the flame retardant is a metal-organic framework flame retardant MPP / Al-BDC modified by a phosphorus-based flame retardant. The phosphorus-based flame retardant is melamine polyphosphate, and the metal-organic framework flame retardant is Al-BDC prepared in Preparation Example 2. The preparation method of the flame retardant is the same as that in Preparation Example 4.

[0040] Preparation Example 6: In Preparation Example 6, the flame retardant is a metal-organic framework flame retardant MPP / Fe-BDC modified by a phosphorus-based flame retardant. The phosphorus-based flame retardant is melamine polyphosphate, and the metal-organic framework flame retardant is Fe-BDC prepared in Preparation Example 3. The preparation method of the flame retardant is the same as that in Preparation Example 4.

[0041] Preparation Example 7: In Preparation Example 7, the flame retardant is a metal-organic framework flame retardant APP@Cr-MOF modified by a phosphorus-based flame retardant. The phosphorus-based flame retardant is ammonium polyphosphate, and the metal-organic framework flame retardant is Cr-MOF prepared in Preparation Example 1. The flame retardant is prepared by a solvothermal method. The specific preparation method is as follows: Dissolve 0.4 g of Cr-MOF in 60 mL of absolute ethanol, then add 0.4 g of ammonium polyphosphate thereto, mix evenly, put it into a reaction kettle, and react at 100 °C for 12 h. After it is cooled to room temperature, filter the precipitate obtained from the reaction, wash the precipitate 3 times with absolute ethanol, and dry it at 80 °C for 12 h to obtain the flame retardant.

[0042] Preparation Example 8: In Preparation Example 8, the flame retardant is a metal-organic framework flame retardant MPP@Al-BDC modified by a phosphorus-based flame retardant. The phosphorus-based flame retardant is melamine polyphosphate, and the metal-organic framework flame retardant is Al-BDC prepared in Preparation Example 2. The preparation method of the flame retardant is the same as that in Preparation Example 7.

[0043] Preparation Example 9: In Preparation Example 9, the flame retardant is a metal-organic framework flame retardant MPP@Fe-BDC modified by a phosphorus-based flame retardant. The phosphorus-based flame retardant is melamine polyphosphate, and the metal-organic framework flame retardant is Fe-BDC prepared in Preparation Example 3. The preparation method of the flame retardant is the same as that in Preparation Example 7.

[0044] Preparation Example 10: In Preparation Example 10, the flame retardant is a reactive DOPO-based modified metal-organic framework flame retardant DOPO-NH2@Cr-MOF, and the metal-organic framework flame retardant is Cr-MOF prepared in Preparation Example 1. The preparation method is as follows: S1. Mix 38.91 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 6.37 g of 4,4'-diaminobenzophenone, heat to 180 °C for melting and stir for 3 h. After cooling to 100 °C, add 150 mL of toluene thereto, filter the precipitate obtained by the reaction, wash with toluene and then mix with 20 mL of tetrahydrofuran for recrystallization to obtain a m-2DOPO-2NH2 mixed solution; S2. Ultrasonically disperse 0.2 g of Cr-MOF in 20 mL of tetrahydrofuran, then add 10 mL of the m-2DOPO-2NH2 mixed solution thereto, react at 50 °C for 3 h, filter the precipitate obtained by the reaction, repeatedly wash with tetrahydrofuran and then dry at 80 °C to obtain the flame retardant.

[0045] Preparation Example 11: In Preparation Example 11, the flame retardant is a reactive DOPO-based modified metal-organic framework flame retardant DOPO-NH2@Al-BDC, and the metal-organic framework flame retardant is Al-BDC prepared in Preparation Example 2. The preparation method of the flame retardant is the same as that of Preparation Example 10.

[0046] Preparation Example 12: In Preparation Example 12, the flame retardant is a reactive DOPO-based modified metal-organic framework flame retardant DOPO-NH2@Fe-BDC, and the metal-organic framework flame retardant is Fe-BDC prepared in Preparation Example 3. The preparation method of the flame retardant is the same as that of Preparation Example 10.

[0047] Examples 1-3: In Examples 1-3, the rapid repair material includes component A and component B. The raw materials and their dosages for preparing component A and component B are shown in Table 1. Among them, the flame retardant is the flame retardant prepared in Preparation Example 1, the chain extender is polyol and diamine, the crosslinking agent is N,N-methylenebisacrylamide, the antistatic agent is polyethylene glycol, and the auxiliary agents are bismuth carboxylate, 3A molecular sieve and color paste.

[0048] The preparation method of the repair material is as follows: T1. Add polyether polyol into a reaction kettle, stir and heat up to 110°C, conduct vacuum dehydration. When it cools down to 55°C, add diphenylmethane diisocyanate, stir for 0.5 h, then heat up to 70°C, stir and mix for another 1 h, and heat to 85°C for reaction for 3 h to obtain Component A; T2. Mix terminal amino polyether, chain extender, crosslinker, modified flame retardant, antistatic agent and auxiliary agent, and stir at 70°C for 1 h to obtain Component B; T3. Place Component A and Component B in separate bins of a high-temperature and high-pressure spraying device respectively, and mix and spray them under the conditions of a temperature of 70°C and a pressure of 2000 psi to obtain a rapid repair material.

[0049] Examples 4 - 5: In Examples 4 - 5, the rapid repair material includes Component A and Component B. The raw materials and their dosages for preparing Component A and Component B are shown in Table 1. The differences between Examples 4 - 5 and Example 1 are that the mass ratios of polyol to diamine in the chain extender are 1:100 and 50:1 respectively, and the rest are the same as in Example 1.

[0050] Table 1. Raw materials and their dosages (kg) for preparing the rapid repair material in Examples 1 - 5 Examples 6 - 16: The differences between Examples 6 - 16 and Example 1 are that the flame retardants are respectively the flame retardants prepared in Preparation Examples 2 - 12, and the rest are the same as in Example 1.

[0051] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is that no flame retardant is added to the raw materials for preparing the rapid repair material, and the rest are the same as in Example 1.

[0052] Comparative Examples 2 - 3: The differences between Comparative Examples 2 - 3 and Example 1 are that the flame retardants are phosphorus-based flame retardants, and the flame retardants added in Comparative Examples 2 - 3 are ammonium polyphosphate and melamine polyphosphate respectively, and the rest are the same as in Example 1.

[0053] Test Example: The performance of the rapid repair materials prepared in Examples 1-16 and Comparative Examples 1-3 was tested, specifically including tensile strength, elongation at break, limiting oxygen index (LOI), and fire rating. Among them, the tensile strength and elongation at break were both tested according to GB / T 528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber", the limiting oxygen index (LOI) was tested according to GB / T 2406.2-2009 "Plastics - Determination of Burning Behavior by the Oxygen Index - Part 2: Room Temperature Tests", and the fire rating was tested according to the UL94 standard. The specific test results are shown in Table 2. To further test the performance of the flame retardant, the average heat release rate of Examples 8, 11, 14 and Comparative Examples 1-2 was tested, and the smoke production rate of Examples 9, 12, 15 and Comparative Examples 1, 3 was tested. The test methods all refer to EN ISO 5660-1 "Determination of the Heat Release Rate of Materials by the Cone Calorimeter", and the test results are as Figure 1-2 . In addition, the anti-ultraviolet aging performance of the repair material prepared in Example 1 was also tested. The specific treatment method of the aging sample is as follows: A specimen with a size of 150 mm × 75 mm was placed in an ultraviolet aging test chamber for continuous ultraviolet light irradiation, and the tensile strength and elongation at break of the specimen were tested after different irradiation times; the specific treatment method of the blank sample was to place the specimen outdoors and expose it to sunlight, and the tensile strength and elongation at break of the specimen were tested after different irradiation times. The detection of tensile strength and elongation at break was carried out according to GB / T 528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber", and the detection results are as Figure 3 .

[0054] Table 2 Example 1 21.9 370 23.0 V-1 Example 2 20.6 361 21.7 V-1 Example 3 21.1 357 22.0 V-1 Example 4 20.2 344 22.6 V-1 Example 5 20.0 340 22.5 V-1 Example 6 21.6 367 22.8 V-1 Example 7 21.4 372 22.6 V-1 Example 8 21.5 337 25.5 V-1 Example 9 20.4 345 25.4 V-1 Example 10 21.4 338 25.6 V-1 Example 11 22.6 355 27.3 V-0 Example 12 21.5 352 26.9 V-0 Example 13 22.6 347 27.1 V-0 Example 14 24.5 377 28.8 V-0 Example 15 24.4 375 28.5 V-0 Example 16 24.4 378 28.8 V-0 Comparative Example 1 25.2 388 21.4 V-1 Comparative Example 2 23.1 362 23.8 V-1 Comparative Example 3 24.0 370 22.2 V-1 It can be seen from the test data in Table 2 that the tensile strength of the rapid repair materials prepared in Examples 1-16 and Comparative Examples 1-3 is 20.0-25.2 MPa, the elongation at break is 337-388%, and the limiting oxygen index is 21.4-28.8%.

[0055] Combined with the test data of Examples 1-3 and Comparative Examples 1-3 Figure 1 and Figure 2 it can be known that after adding the metal-organic framework flame retardant or the phosphorus-based flame retardant alone to the rapid repair material, the average heat release rate and smoke production rate of the material decrease significantly. That is to say, the addition of the flame retardant can significantly improve the flame retardant performance of the material, but it will have a certain impact on the mechanical properties of the material.

[0056] From Figure 3From the detection results, it can be seen that the repair material prepared according to the raw materials and preparation method of the repair material in Example 1 of the present application has excellent anti-ultraviolet aging performance. After long-term ultraviolet irradiation, it can still have high strength and strong toughness.

[0057] From the detection data of Examples 1, 4 and 5, it can be seen that when polyol and diamine are used as chain extenders together, and the weight ratio of polyol to diamine is 25:50, the two can synergistically adjust the balance between hard segments and soft segments in polyurethane, extend the length of polymer chains, and introduce rigidity into the polymer chains at the same time, improving the wear resistance of the repair material.

[0058] Combined with the detection data of Examples 1, 8 - 13 and Comparative Example 1 Figure 1 and Figure 2 it can be seen that after adding a metal-organic framework flame retardant modified by a phosphorus-based flame retardant to the repair material, the limiting oxygen index of the repair material increases, and the average heat release rate and smoke production rate further decrease. That is to say, the flame retardant performance of the material is further improved. However, the addition of the metal-organic framework flame retardant modified by a phosphorus-based flame retardant still has an impact on the mechanical properties of the repair material. Among them, compared with the flame retardant prepared by the solvothermal method and the flame retardant prepared by direct mixing, the former has a more obvious improvement in the flame retardant performance of the repair material and a smaller impact on the mechanical properties of the repair material.

[0059] Combined with the detection data of Examples 1, 14 - 16 and Comparative Example 1 Figure 1 and Figure 2 it can be seen that after adding a reactive DOPO-based modified metal-organic framework flame retardant to the repair material, the limiting oxygen index increases significantly, the flame retardant grade can reach V-0, the average heat release rate and smoke production rate decrease significantly, greatly improving the flame retardant performance of the repair material. Moreover, compared with the metal-organic framework flame retardant and the metal-organic framework flame retardant modified by a phosphorus-based flame retardant, the reactive DOPO-based modified metal-organic framework flame retardant has a more obvious improvement in the flame retardant performance of the repair material and a smaller impact on the mechanical properties of the repair material, and can be used as a preferred flame retardant in the repair material.

[0060] It should be noted that the above-mentioned embodiments are only used to explain the present application and do not constitute any limitation to the present application. The present application has been described by referring to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words rather than limiting words. Modifications can be made to the present application within the scope of the claims of the present application, and the present invention can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and embodiments, it does not mean that the present application is limited to the specific examples disclosed therein. On the contrary, the present application can be extended to all other methods and applications with the same functions.

Claims

1. A rapid repair material for mining conveyor belts, characterized in that: The rapid repair material comprises component A and component B. By weight, component A comprises the following raw materials: 30-50 parts polyether polyol and 45-80 parts diphenylmethane diisocyanate. By weight, component B comprises the following raw materials: 30-50 parts amino-terminated polyether, 20-40 parts chain extender, 5-10 parts crosslinking agent, 5-10 parts flame retardant, 1-5 parts antistatic agent, and 1-5 parts additives. The flame retardant is a reactive DOPO-based modified metal-organic framework flame retardant. The reactive DOPO-based modified metal-organic framework flame retardant was prepared by the following method: S1. Mix 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 4,4'-diaminobenzophenone evenly and heat to 160-200℃ for 2-4 hours. After cooling to 90-110℃, add toluene. Filter and wash the precipitate obtained from the reaction, mix it with tetrahydrofuran and recrystallize to obtain a mixture of m-2DOPO-2NH2. S2. After uniformly mixing the metal-organic framework flame retardant and tetrahydrofuran, add the mixture to the m-2DOPO-2NH2 mixture and react at 40-60℃ for 2-4 hours. Filter, wash and dry the precipitate obtained from the reaction to obtain the reactive DOPO-based modified metal-organic framework flame retardant.

2. The rapid repair material for mining conveyor belts according to claim 1, characterized in that: The weight ratio of component A to component B is (1-1.1):

1.

3. The rapid repair material for mining conveyor belts according to any one of claims 1-2, characterized in that: The ligands of the metal-organic framework flame retardant are selected from one or more of 2-methylimidazole, terephthalic acid, 1,3,5-benzenetricarboxylic acid and 2-aminoterephthalic acid; the metal ions of the metal-organic framework flame retardant are selected from one or more of chromium ions, iron ions, cobalt ions, zinc ions, aluminum ions, copper ions, zirconium ions, lanthanum ions, cerium ions and yttrium ions.

4. The rapid repair material for mining conveyor belts according to claim 1, characterized in that: The chain extender comprises a polyol and a diamine, and the weight ratio of the polyol to the diamine is (1-50):(1-100).

5. The rapid repair material for mining conveyor belts according to claim 1, characterized in that: The additive is selected from one or more of bismuth carboxylate, molecular sieve, and color paste.

6. The rapid repair material for mining conveyor belts according to claim 5, characterized in that: The additives include bismuth carboxylate, molecular sieve, and color paste, and the weight ratio of bismuth carboxylate, molecular sieve, and color paste is (0.01-0.3):5:

5.

7. A method for preparing a rapid repair material as described in any one of claims 1-6, characterized in that: The method includes the following steps: T1. Heat the polyether polyol to 90-120℃ and then dehydrate it under vacuum. When the temperature drops to 50-60℃, add diphenylmethane diisocyanate and mix. Then heat to 60-80℃ and stir for 0.5-1h. Then heat again to 85-90℃ and react for 2-4h to obtain component A. T2. Mix the terminal amino polyether, chain extender, crosslinking agent, flame retardant, antistatic agent and additives, and stir at 60-80℃ for 1-2 hours to obtain component B. T3. Place components A and B separately in a spraying device and mix and spray them under conditions of 65-70℃ and 1800-2200psi to obtain a rapid repair material.

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