Spraying material for reinforcing and supporting mine laneway as well as preparation method and application of spraying material

Abstract

The invention relates to the technical field of spraying, in particular to a spraying material for reinforcing and supporting mine laneways and a preparation method and application of the spraying material. The spraying material is prepared from, by weight, 1-5 parts of metal organic frameworks and 30-40 parts of modified high-molecular polymers. The preparation method of the spraying material comprises the following steps: obtaining the metal organic framework through centrifugal washing, dispersing the pre-prepared modified high-molecular polymer in the metal organic framework to form a mixed solution, and drying the mixed solution at 80 DEG C, thereby obtaining the spraying material. The modified high-molecular polymer and the metal organic framework are uniformly mixed, so that uniform distribution of components in the composite material is ensured, and the stability and the reliability of the material are improved; the preparation method of the spraying material for reinforcing and supporting the mine laneway is simple in process, the protective net formed by copolymerization of acrylonitrile, methyl methacrylate and sodium methallyl sulfonate is selected, and the spraying material not only has excellent curing performance, but also can remarkably improve the overall strength and durability of the laneway.

Description

Technical Field

[0001] The present invention belongs to the field of spraying technology, and specifically refers to a spraying material for reinforcing and supporting mine tunnels, and a preparation method and application thereof. Background Art

[0002] With the surge in my country's coal demand, the coal mining industry has expanded rapidly, but the problems of tunnel strata in underground mining are becoming increasingly serious. Tunnel support has become a top priority to ensure safe production in coal mines. Traditional metal protective nets occupy a core position in tunnel support due to their strong bearing capacity and good protection effect. However, the humidity and strong corrosion of the underground environment pose a challenge to the durability and stability of the metal protective net, affecting its support effect and service life.

[0003] In order to overcome these defects of metal protective nets, fiber protective nets have emerged as an emerging material, which has significant advantages in corrosion resistance and lightweight, but there are also some problems: the performance of fiber protective nets under extreme stress or impact loads may not be stable enough, the protective ability is weakened under high temperature conditions, and the manufacturing cost of high-performance fiber materials is high. Summary of the invention

[0004] In view of the above situation, in order to overcome the defects of the prior art, the present invention provides a spray material for mine tunnel reinforcement and support, and a preparation method and application thereof, in order to solve the problems of insufficient performance and high cost of fiber protective nets in the prior art under extreme stress and high temperature conditions.

[0005] The first aspect of the present application provides a spray material for reinforcing and supporting mine tunnels. The raw materials of the spray material are mixed in a weight ratio of 1-5 parts of a metal organic framework to 30-40 parts of a modified high molecular polymer. The preparation method of the spray material is to obtain the metal organic framework by centrifugal washing, disperse the pre-prepared modified high molecular polymer in the metal organic framework to form a mixed liquid, and dry the mixed liquid at 80°C.

[0006] Optionally, the metal organic framework is a compound formed by the reaction of zinc acetate and 2-methylimidazole, which is obtained by allowing the compound to stand with methanol in a sealed container for 24 hours.

[0007] Optionally, the modified high molecular polymer comprises the following components by weight:

[0008] Aerogel: 1-5 parts;

[0009] New transition metal oxide: 10-20 parts;

[0010] Polymer emulsion: 30-40 parts;

[0011] Flame retardant: 2-8 parts.

[0012] Optionally, the aerogel is a hydrophobically treated silicon aerogel or a carbon aerogel.

[0013] Optionally, the novel transition metal oxide is a glass material composed of a mixture of zirconium oxide, niobium oxide, hafnium oxide, tantalum oxide, vanadium oxide and titanium oxide.

[0014] Optionally, the polymer emulsion is one or more of acrylic emulsion, acetic acid acrylic emulsion, styrene acrylic emulsion, pure acrylic emulsion, and silicone acrylic emulsion.

[0015] Optionally, the flame retardant comprises the following components by weight:

[0016] Hexaphenoxy cyclotriphosphazene: 10-20 parts;

[0017] Bismuth selenide: 1-5 parts.

[0018] Optionally, the bismuth selenide is produced by uniformly mixing elemental selenium and elemental bismuth and subjecting the mixture to a chemical reaction in an inert gas environment.

[0019] Optionally, the hexaphenoxycyclotriphosphazene has a purity of 99%.

[0020] The second aspect of the present application provides an application of a spray material for mine tunnel reinforcement and support. The above-mentioned spray material for mine tunnel reinforcement and support is sprayed on a protective net, and the protective net is made of a copolymer of acrylonitrile, methyl methacrylate and sodium methacrylic sulfonate.

[0021] Therefore, this application has at least the following beneficial effects:

[0022] (1) By uniformly mixing the modified polymer and the metal organic framework by mechanical stirring, ultrasonic dispersion and other methods, the uniform distribution of the components inside the composite material is ensured, local performance differences are avoided, and the stability and reliability of the material are improved;

[0023] (2) In the process of preparing modified polymers, aerogels are introduced. Due to their extremely high porosity and extremely low thermal conductivity, they can significantly improve the thermal insulation performance of polymers. At the same time, the density of aerogels is extremely low, which helps to achieve lightweight polymers and reduce material weight.

[0024] (3) In the process of preparing modified polymers, new transition metal oxides are added, which not only improves the melting point and corrosion resistance of the material, but also significantly enhances the mechanical strength and durability, so that the composite material can still maintain good performance in harsh environments;

[0025] (4) In the process of preparing modified polymers, polymer emulsions can be used as additives to reduce the viscosity of polymers, improve their processing fluidity, and make the processing process smoother. Secondly, the polymer chains in the emulsion can form an interpenetrating network structure with the matrix polymer, enhance the interface bonding force, and improve the overall performance of the composite material.

[0026] (5) In the process of preparing the modified high molecular polymer, the flame retardant can decompose at high temperature to produce flame retardant gas or form a heat insulation layer to prevent the spread of flame and the transfer of heat, thereby improving the flame retardant properties of the high molecular polymer. Among them, the added nano bismuth selenium is not only low in cost, but also hexaphenoxy cyclotriphosphazene can enhance the flame retardant effect;

[0027] (6) The method for preparing the spray material for reinforcing and supporting mine tunnels provided by the present invention has a simple process and is easy to operate. By selecting a protective net formed by copolymerization of acrylonitrile, methyl methacrylate and sodium methacrylate sulfonate and undergoing careful weaving and other processes, the prepared protective net not only has excellent curing performance and stability after the spray material, but also can significantly improve the overall strength and durability of the tunnel; after adding the modified high molecular polymer, the spray material can fill and reinforce the pores and cracks in the tunnel, meeting market demand and showing good economic and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which:

[0029] Figure 1 A schematic diagram of the structure of a protective net provided in an embodiment of the present invention;

[0030] Figure 2 This is a scanning electron microscope image of the spraying material for mine tunnel reinforcement and support provided in Example 4 of the present invention. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0032] In the examples of the present invention, if there is no special description of raw materials or processing techniques, it is indicated that they are all conventional commercially available raw materials or conventional processing techniques in the art.

[0033] The following describes a spray material for mine tunnel reinforcement and support and its preparation method and application in accordance with an embodiment of the present application with reference to the accompanying drawings. In response to the problem of insufficient performance of the fiber protection net mentioned in the above background technology, the present application provides a spray material for mine tunnel reinforcement and support, which can ensure the uniform distribution of components inside the composite material by mixing the modified polymer with the metal organic framework by mechanical stirring, ultrasonic dispersion and other methods, avoiding local performance differences and improving the stability and reliability of the material; in the process of preparing the modified polymer, aerogel is introduced, which can significantly improve the thermal insulation performance of the polymer due to its extremely high porosity and extremely low thermal conductivity. At the same time, the density of aerogel is extremely low, which helps to achieve the lightweight of the polymer and reduce the weight of the material; in the process of preparing the modified polymer, a new transition metal oxide is added, which not only improves the melting point and corrosion resistance of the material, but also significantly enhances the mechanical strength and durability, so that the composite material can still maintain good performance in harsh environments; in the process of preparing the modified polymer, the polymer emulsion is used as an additive to reduce the viscosity of the polymer and improve its processing fluidity, The processing process is made smoother. Secondly, the polymer chains in the emulsion can form an interpenetrating network structure with the matrix polymer, enhance the interface bonding force, and improve the overall performance of the composite material. In the process of preparing the modified polymer, the flame retardant can decompose at high temperature to produce flame-retardant gas or form a heat-insulating layer to prevent the spread of flames and the transfer of heat, thereby improving the flame retardant properties of the polymer. Among them, the added nano bismuth selenium is not only low in cost, but also the hexaphenoxy cyclotriphosphazene can enhance the flame retardant effect. The preparation method of the spraying material for mine tunnel reinforcement and support provided by the present invention has a simple process and is easy to operate. By selecting a protective net formed by copolymerization of acrylonitrile, methyl methacrylate and sodium methyl methacrylate sulfonate, and undergoing careful weaving and other processes, the prepared protective net has not only excellent curing performance and stability after the spraying material, but also can significantly improve the overall strength and durability of the tunnel. After adding the modified polymer, the spraying material can fill and reinforce the pores and cracks in the tunnel, meet market demand, and show good economic and social benefits. Thereby, the problems of insufficient performance and high cost of fiber protection nets under extreme stress and high temperature conditions in the prior art are solved.

[0034] Example 1

[0035] The present application provides a spray material for reinforcing and supporting mine tunnels. The raw materials of the spray material are mixed in a weight ratio of 1 part of a metal-organic framework to 30 parts of a modified high molecular polymer. The preparation method of the spray material is to obtain the metal-organic framework by centrifugal washing, disperse the pre-prepared modified high molecular polymer in the metal-organic framework to form a mixed liquid, and dry the mixed liquid at 80°C.

[0036] The metal organic framework is a compound formed by the reaction of zinc acetate and 2-methylimidazole, and the compound is allowed to stand with methanol in a sealed container for 24 hours.

[0037] The modified high molecular polymer comprises the following components by weight:

[0038] Aerogel: 1 part;

[0039] New transition metal oxides: 10 parts;

[0040] Polymer emulsion: 30 parts;

[0041] Flame retardant: 2 parts.

[0042] The aerogel is a hydrophobically treated silicon aerogel or carbon aerogel.

[0043] Among them, the new transition metal oxide is a glass material composed of a mixture of zirconium oxide, niobium oxide, hafnium oxide, tantalum oxide, vanadium oxide and titanium oxide.

[0044] Wherein, the polymer emulsion is one or more of acrylic emulsion, acetic acid acrylic emulsion, styrene acrylic emulsion, pure acrylic emulsion and silicone acrylic emulsion.

[0045] The flame retardant comprises the following components by weight:

[0046] Hexaphenoxy cyclotriphosphazene: 10 parts;

[0047] Bismuth selenide: 1 part.

[0048] Among them, bismuth selenide is produced by mixing elemental selenium and elemental bismuth evenly and placing them in an inert gas environment for chemical reaction.

[0049] The purity of hexaphenoxycyclotriphosphazene is 99%.

[0050] The present application also provides an application of a spray material for strengthening and supporting a mine tunnel, wherein the spray material for strengthening and supporting a mine tunnel is sprayed on a protective net, and the protective net is made of acrylonitrile, methyl methacrylate and sodium methacrylic acid sulfonate copolymer, such as Figure 1 shown.

[0051] Example 2

[0052] The present application provides a spray material for reinforcing and supporting mine tunnels. The raw materials of the spray material are mixed in a weight ratio of 2 parts of a metal organic framework to 32 parts of a modified high molecular polymer. The preparation method of the spray material is to obtain the metal organic framework by centrifugal washing, disperse the pre-prepared modified high molecular polymer in the metal organic framework to form a mixed liquid, and dry the mixed liquid at 80°C.

[0053] The metal organic framework is a compound formed by the reaction of zinc acetate and 2-methylimidazole, and the compound is allowed to stand with methanol in a sealed container for 24 hours.

[0054] The modified high molecular polymer comprises the following components by weight:

[0055] Aerogel: 2 parts;

[0056] New transition metal oxides: 12 parts;

[0057] Polymer emulsion: 32 parts;

[0058] Flame retardant: 4 parts.

[0059] The aerogel is a hydrophobically treated silicon aerogel or carbon aerogel.

[0060] Among them, the new transition metal oxide is a glass material composed of a mixture of zirconium oxide, niobium oxide, hafnium oxide, tantalum oxide, vanadium oxide and titanium oxide.

[0061] Wherein, the polymer emulsion is one or more of acrylic emulsion, acetic acid acrylic emulsion, styrene acrylic emulsion, pure acrylic emulsion and silicone acrylic emulsion.

[0062] The flame retardant comprises the following components by weight:

[0063] Hexaphenoxy cyclotriphosphazene: 12 parts;

[0064] Bismuth selenide: 2 parts.

[0065] Among them, bismuth selenide is produced by mixing elemental selenium and elemental bismuth evenly and placing them in an inert gas environment for chemical reaction.

[0066] The purity of hexaphenoxycyclotriphosphazene is 99%.

[0067] The present application also provides an application of a spray material for strengthening and supporting a mine tunnel, wherein the spray material for strengthening and supporting a mine tunnel is sprayed on a protective net, and the protective net is made of acrylonitrile, methyl methacrylate and sodium methacrylic acid sulfonate copolymer, such as Figure 1 shown.

[0068] Example 3

[0069] The present application provides a spray material for reinforcing and supporting mine tunnels. The raw materials of the spray material are mixed in a weight ratio of 3 parts of a metal organic framework to 35 parts of a modified high molecular polymer. The preparation method of the spray material is to obtain the metal organic framework by centrifugal washing, disperse the pre-prepared modified high molecular polymer in the metal organic framework to form a mixed liquid, and dry the mixed liquid at 80°C.

[0070] The metal organic framework is a compound formed by the reaction of zinc acetate and 2-methylimidazole, and the compound is allowed to stand with methanol in a sealed container for 24 hours.

[0071] The modified high molecular polymer comprises the following components by weight:

[0072] Aerogel: 3 parts;

[0073] New transition metal oxides: 14 parts;

[0074] Polymer emulsion: 35 parts;

[0075] Flame retardant: 5 parts.

[0076] The aerogel is a hydrophobically treated silicon aerogel or carbon aerogel.

[0077] Among them, the new transition metal oxide is a glass material composed of a mixture of zirconium oxide, niobium oxide, hafnium oxide, tantalum oxide, vanadium oxide and titanium oxide.

[0078] Wherein, the polymer emulsion is one or more of acrylic emulsion, acetic acid acrylic emulsion, styrene acrylic emulsion, pure acrylic emulsion and silicone acrylic emulsion.

[0079] The flame retardant comprises the following components by weight:

[0080] Hexaphenoxy cyclotriphosphazene: 15 parts;

[0081] Bismuth selenide: 3 parts.

[0082] Among them, bismuth selenide is produced by mixing elemental selenium and elemental bismuth evenly and placing them in an inert gas environment for chemical reaction.

[0083] The purity of hexaphenoxycyclotriphosphazene is 99%.

[0084] The present application also provides an application of a spray material for strengthening and supporting a mine tunnel, wherein the spray material for strengthening and supporting a mine tunnel is sprayed on a protective net, and the protective net is made of acrylonitrile, methyl methacrylate and sodium methacrylic acid sulfonate copolymer, such as Figure 1 shown.

[0085] Example 4

[0086] The present application provides a spray material for reinforcing and supporting mine tunnels. The raw materials of the spray material are mixed in a weight ratio of 4 parts of a metal-organic framework to 38 parts of a modified high molecular polymer. The preparation method of the spray material is to obtain the metal-organic framework by centrifugal washing, disperse the pre-prepared modified high molecular polymer in the metal-organic framework to form a mixed liquid, and dry the mixed liquid at 80°C.

[0087] The metal organic framework is a compound formed by the reaction of zinc acetate and 2-methylimidazole, and the compound is allowed to stand with methanol in a sealed container for 24 hours.

[0088] The modified high molecular polymer comprises the following components by weight:

[0089] Aerogel: 4 parts;

[0090] New transition metal oxides: 18 parts;

[0091] Polymer emulsion: 38 parts;

[0092] Flame retardant: 7 parts.

[0093] The aerogel is a hydrophobically treated silicon aerogel or carbon aerogel.

[0094] Among them, the new transition metal oxide is a glass material composed of a mixture of zirconium oxide, niobium oxide, hafnium oxide, tantalum oxide, vanadium oxide and titanium oxide.

[0095] Wherein, the polymer emulsion is one or more of acrylic emulsion, acetic acid acrylic emulsion, styrene acrylic emulsion, pure acrylic emulsion and silicone acrylic emulsion.

[0096] The flame retardant comprises the following components by weight:

[0097] Hexaphenoxy cyclotriphosphazene: 18 parts;

[0098] Bismuth selenide: 4 parts.

[0099] Among them, bismuth selenide is produced by mixing elemental selenium and elemental bismuth evenly and placing them in an inert gas environment for chemical reaction.

[0100] The purity of hexaphenoxycyclotriphosphazene is 99%.

[0101] The present application also provides an application of a spray material for strengthening and supporting a mine tunnel, wherein the spray material for strengthening and supporting a mine tunnel is sprayed on a protective net, and the protective net is made of acrylonitrile, methyl methacrylate and sodium methacrylic acid sulfonate copolymer, such as Figure 1 shown.

[0102] Example 5

[0103] The present application provides a spray material for reinforcing and supporting mine tunnels. The raw materials of the spray material are mixed in a weight ratio of 5 parts of a metal-organic framework to 40 parts of a modified high molecular polymer. The preparation method of the spray material is to obtain the metal-organic framework by centrifugal washing, disperse the pre-prepared modified high molecular polymer in the metal-organic framework to form a mixed liquid, and dry the mixed liquid at 80°C.

[0104] The metal organic framework is a compound formed by the reaction of zinc acetate and 2-methylimidazole, and the compound is allowed to stand with methanol in a sealed container for 24 hours.

[0105] The modified high molecular polymer comprises the following components by weight:

[0106] Aerogel: 5 parts;

[0107] New transition metal oxides: 20 parts;

[0108] Polymer emulsion: 40 parts;

[0109] Flame retardant: 8 parts.

[0110] The aerogel is a hydrophobically treated silicon aerogel or carbon aerogel.

[0111] Among them, the new transition metal oxide is a glass material composed of a mixture of zirconium oxide, niobium oxide, hafnium oxide, tantalum oxide, vanadium oxide and titanium oxide.

[0112] Wherein, the polymer emulsion is one or more of acrylic emulsion, acetic acid acrylic emulsion, styrene acrylic emulsion, pure acrylic emulsion and silicone acrylic emulsion.

[0113] The flame retardant comprises the following components by weight:

[0114] Hexaphenoxy cyclotriphosphazene: 20 parts;

[0115] Bismuth selenide: 5 parts.

[0116] Among them, bismuth selenide is produced by mixing elemental selenium and elemental bismuth evenly and placing them in an inert gas environment for chemical reaction.

[0117] The purity of hexaphenoxycyclotriphosphazene is 99%.

[0118] The present application also provides an application of a spray material for strengthening and supporting a mine tunnel, wherein the spray material for strengthening and supporting a mine tunnel is sprayed on a protective net, and the protective net is made of acrylonitrile, methyl methacrylate and sodium methacrylic acid sulfonate copolymer, such as Figure 1 shown.

[0119] Performance Testing

[0120] The spray materials for mine tunnel reinforcement and support prepared in Examples 1-5 were sprayed on the protective net, and the tensile strength, elongation, porosity and flame retardant properties of the protective net were tested. The performance tests are shown in Table 1 below.

[0121] Table 1 Performance test of protective net

[0122] serial number Tensile strength / Mpa Elongation % Porosity % Flame retardant properties Example 1 3804 10 88.6 Excellent, meets the requirements Example 2 4190 12 89.7 Excellent, meets the requirements Example 3 4563 15 90.2 Excellent, meets the requirements Example 4 4721 17 91.5 Excellent, meets the requirements Example 5 4648 16 90.9 Excellent, meets the requirements

[0123] like Figure 2 As shown in Table 1, the protective net in the embodiment of the present invention has strong tensile strength and high elongation. At the same time, it has excellent properties such as obvious porosity and flame retardancy, and can achieve low-cost large-scale production.

[0124] The spray material for mine tunnel reinforcement and support provided by the present invention is used and sprayed on the protective net. The tensile strength, elongation and porosity of Example 4 are optimal, with a tensile strength of 4721Mpa, an elongation of 17%, and a porosity of 91.5%. At the same time, the flame retardant performance is excellent. It can be seen that the introduced material must be within a certain amount, and adding too much or too little will affect the performance. Therefore, considering the comprehensive performance influence of the spray material for mine tunnel reinforcement and support, the spray material for mine tunnel reinforcement and support of the present invention is sprayed on the protective net at a low cost, which improves the material performance and porosity, and has obvious flame retardant effect, and has a high use value.

[0125] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

[0126] The present invention and its implementation methods are described above, and such description is not restrictive, and the actual application is not limited thereto. In short, if ordinary technicians in the field are inspired by it, without departing from the purpose of the invention, they can design structures and embodiments similar to the technical solution without creativity, which should all fall within the protection scope of the present invention.

Claims

1. A spraying material for strengthening and supporting mine tunnels, characterized in that: The raw materials of the spray material are mixed in a weight ratio of 1-5 parts of a metal organic framework to 30-40 parts of a modified high molecular polymer. The preparation method of the spray material is to obtain the metal organic framework by centrifugal washing, disperse the pre-prepared modified high molecular polymer in the metal organic framework to form a mixed liquid, and dry the mixed liquid at 80°C.

2. The spraying material for mine tunnel reinforcement and support according to claim 1, characterized in that: The metal organic framework is a compound formed by the reaction of zinc acetate and 2-methylimidazole, and the compound is allowed to stand in a sealed container with methanol for 24 hours to obtain the metal organic framework.

3. The spraying material for mine tunnel reinforcement and support according to claim 2, characterized in that: The modified high molecular polymer comprises the following components by weight: Aerogel: 1-5 parts; New transition metal oxide: 10-20 parts; Polymer emulsion: 30-40 parts; Flame retardant: 2-8 parts.

4. The spraying material for mine tunnel reinforcement and support according to claim 3, characterized in that: The aerogel is a hydrophobic treated silicon aerogel or a carbon aerogel.

5. The spraying material for mine tunnel reinforcement and support according to claim 3, characterized in that: The novel transition metal oxide is a glass material composed of a mixture of zirconium oxide, niobium oxide, hafnium oxide, tantalum oxide, vanadium oxide and titanium oxide.

6. The spraying material for mine tunnel reinforcement and support according to claim 3, characterized in that: The polymer emulsion is one or more of acrylic emulsion, acetic acid acrylic emulsion, styrene acrylic emulsion, pure acrylic emulsion and silicone acrylic emulsion.

7. The spraying material for mine tunnel reinforcement and support according to claim 6, characterized in that: The flame retardant comprises the following components by weight: Hexaphenoxy cyclotriphosphazene: 10-20 parts; Bismuth selenide: 1-5 parts.

8. The spraying material for mine tunnel reinforcement and support according to claim 7, characterized in that: The bismuth selenide is produced by uniformly mixing elemental selenium and elemental bismuth and performing a chemical reaction in an inert gas environment.

9. The spraying material for mine tunnel reinforcement and support according to claim 7, characterized in that: The purity of the hexaphenoxy cyclotriphosphazene is 99%.

10. The application of the spraying material for mine tunnel reinforcement and support according to claim 1, characterized in that: The spray material for mine tunnel reinforcement and support as claimed in claim 1 is sprayed on a protective net, and the protective net is copolymerized with acrylonitrile, methyl methacrylate and sodium methacrylic acid sulfonate.

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