An intrinsic flame-retardant self-repairing tunnel surface thin-spray support material and its application

Abstract

The present invention discloses an intrinsic flame retardant self-repairing roadway surface thin spraying support material and its application. The intrinsic flame retardant self-repairing roadway surface thin spraying support material comprises a first component and a second component. The first component comprises, by mass, 40 to 80 parts of isocyanate, 15 to 50 parts of a first polyol, 0 to 10 parts of a viscosity reducer, 1 to 7 parts of a maleimide cross-linking agent, and 0.01 to 0.5 parts of a polymerization inhibitor; the second component comprises, by mass, 60 to 85 parts of a second polyol, 10 to 30 parts of a flame retardant diol, 2 to 10 parts of an antistatic agent, and 0.2 to 2 parts of a catalyst; the flame retardant diol comprises a conjugated structure. The thin spraying support material of the present invention has excellent intrinsic self-repairing performance, intrinsic flame retardant properties, mechanical properties, and strong bonding properties, can realize the self-repair of local cracks in the spray layer, and improve the safety level of the roadway.

Description

Technical Field

[0001] The present invention belongs to the technical field of coal mine tunnel reinforcement and support, and in particular, relates to an intrinsic flame retardant self-repairing tunnel surface thin-spray support material and application thereof. Background Art

[0002] In the process of coal mining, underground mining is the main mining method. In recent years, the total length of newly excavated tunnels in my country has exceeded 12,000 km each year, and coal and semi-coal rock tunnels account for more than 80%. New tunnels and tunnels in operation constitute the largest underground projects in my country. Thin shotcrete support materials on the surface of tunnels are a new direction for the development of tunnel surrounding rock support technology. However, tunnels such as coal mine tunnels generally have large deformations, and superimposed geological disasters such as impact ground pressure can easily cause local cracking of the spray layer of thin shotcrete support materials, which requires repeated spraying of thin shotcrete support materials, and poor bonding performance, which is labor-intensive and seriously restricts the support efficiency. Summary of the invention

[0003] The present invention is based on the inventor's discovery and understanding of the following facts and problems: The deformation of the tunnel is large, and the superposition of geological disasters such as impact ground pressure can easily cause local cracking of the spray layer of the thin spray support material, which requires repeated spraying of the thin spray support material, and the bonding performance is poor, which is labor-intensive and seriously restricts the support efficiency. The thin spray support material has strict requirements on the flame retardant, mechanical and bonding properties of the material. The effect of the traditional additive flame retardant is relatively single. After adding the additive flame retardant, the mechanical and bonding properties of the thin spray support material are seriously weakened, making it difficult to meet the technical requirements of the thin spray support material on the tunnel surface.

[0004] The present invention aims to solve one of the technical problems in the related art to at least a certain extent. To this end, the embodiments of the present invention provide a thin-sprayed support material with intrinsic flame retardant and self-repairing properties and its application. The thin-sprayed support material has excellent intrinsic self-repairing properties, intrinsic flame retardant properties, mechanical properties and strong bonding properties, and can achieve self-repair of local cracks in the sprayed layer, thereby improving the safety level of the tunnel.

[0005] The embodiment of the present invention provides an intrinsic flame-retardant self-repairing tunnel surface thin-spray support material, comprising a first component and a second component, wherein the first component comprises, by mass: 40 to 80 parts of isocyanate, 15 to 50 parts of a first polyol, 0 to 10 parts of a viscosity reducer, 1 to 7 parts of a maleimide cross-linking agent, and 0.01 to 0.5 parts of an inhibitor;

[0006] The second component comprises, by mass, 60 to 85 parts of a second polyol, 10 to 30 parts of a flame retardant diol, 2 to 10 parts of an antistatic agent and 0.2 to 2 parts of a catalyst; the flame retardant diol comprises a conjugated structure.

[0007] The advantages and technical effects brought by the intrinsic flame-retardant self-repairing tunnel surface thin-sprayed support material of the embodiment of the present invention are as follows: the thin-sprayed support material has excellent intrinsic self-repairing performance, intrinsic flame-retardant properties, mechanical properties and strong bonding properties, can achieve self-repair of local cracks in the sprayed layer, and improve the safety level of the tunnel.

[0008] In the embodiment of the present invention, the reversible Diels-Alder (DA) reaction is a type of [4+2] cycloaddition reaction, which can occur between an electron-rich diene and an electron-deficient dienophile, and has the advantages of mild reaction conditions, no need for catalysts, and high reaction efficiency. After the generated adduct is heated, a reverse DA reaction can occur, so that the electron-rich diene and the electron-deficient dienophile can undergo a DA reaction again, and cross-link again to achieve the function of self-repair. The thin-spray support material of the present invention contains both flame-retardant diols and maleimide crosslinkers. The flame-retardant diols include a conjugated structure and are electron-rich dienes; the maleimide crosslinker includes a carbon-carbon double bond and is an electron-deficient dienophile. The flame-retardant diols and the maleimide crosslinker can achieve self-repair of local cracks in the spray layer during the use of the intrinsic flame-retardant self-repairing roadway surface thin-spray support material through the reversible Diels-Alder reaction, and the self-repair rate is good.

[0009] In the embodiment of the present invention, a viscosity reducer can be added to the thin-sprayed support material to reduce the viscosity of the thin-sprayed support material and improve the construction performance of the thin-sprayed support material through the lubrication effect at the molecular level; adding too much viscosity reducer will affect the mechanical properties of the material. An antistatic agent is also added to the thin-sprayed support material to construct a conductive path so that static charges can be quickly dissipated without aggregation, reduce surface resistance, and increase antistatic properties; if too little antistatic agent is added, the surface resistance is high, and if too much is added, the cost will increase and the mechanical properties of the material will be affected. A trace amount of polymerization inhibitor is also added to the thin-sprayed support material to help increase the storage period of the thin-sprayed support material. The thin-sprayed support material has a microphase separation structure of soft segments and hard segments. The hard segment is beneficial to improving the strength of the thin-sprayed support material, and the soft segment is beneficial to improving the toughness of the thin-sprayed support material. By optimizing the number of components in the thin-sprayed support material, it is beneficial to obtain a thin-sprayed support material with excellent strength and toughness properties.

[0010] In some embodiments, the flame retardant diol comprises at least one of the following structural formulas:

[0011] or

[0012] Formula (I) Formula (II)

[0013] Among them, R 1 or R 2 Each is independently selected from unsubstituted or alkyl-substituted pyrrolyl, and unsubstituted or alkyl-substituted furanyl.

[0014] In some embodiments, R 1 or R 2 Each independently selected from , , , , or .

[0015] In some embodiments, in the first component, the isocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, or polyphenyl polymethylene polyisocyanate;

[0016] and / or, the first polyol comprises at least one of a polyether polyol or a polyester polyol;

[0017] and / or, the hydroxyl value of the first polyol is 30 to 500 mg KOH / g;

[0018] And / or, the viscosity reducing agent includes at least one of dimethyl adipate or diisopropyl adipate;

[0019] And / or, the inhibitor includes at least one of orthophosphoric acid, tartaric acid, benzoyl chloride and benzoic acid.

[0020] In some embodiments, in the first component, the maleimide crosslinking agent includes at least one of a bismaleimide crosslinking agent and a trimaleimide crosslinking agent.

[0021] In some embodiments, in the second component, the second polyol includes at least one of a polyether polyol or a polyester polyol;

[0022] and / or, the hydroxyl value of the second polyol is 30 to 500 mg KOH / g;

[0023] And / or, the antistatic agent includes at least one of DS-8, E6019, and TRG-329;

[0024] And / or, the catalyst includes at least one of an organic metal catalyst and an amine catalyst.

[0025] In some embodiments, the organometallic catalyst includes at least one of dibutyltin dilaurate, stannous octoate, lead isooctanoate, and bismuth isooctanoate;

[0026] And / or, the amine catalyst includes at least one of aliphatic amine catalysts, alicyclic amine catalysts, aromatic amine catalysts or alcohol amine catalysts.

[0027] The embodiment of the present invention provides a method for preparing an intrinsic flame-retardant self-repairing tunnel surface thin-spray support material, comprising the following steps:

[0028] 1) reacting an isocyanate, a first polyol, a viscosity reducer, a maleimide crosslinking agent and a polymerization inhibitor to obtain a first component;

[0029] 2) Mixing the second polyol, the flame retardant diol, the antistatic agent and the catalyst to obtain a second component.

[0030] In the embodiment of the present invention, a reaction intermediate is generated in advance by reacting isocyanate and the first polyol in the first component, and the first component and the second component are fully mixed respectively, thereby reducing the strengthening time of the thin-spray support material during use.

[0031] In some embodiments, in step 1), the reaction temperature is 50-120° C.; and / or the reaction time is 2-3 h.

[0032] The embodiment of the present invention provides an application of an intrinsic flame retardant self-repairing tunnel surface thin-spray support material for use in the tunnel. In the embodiment of the present invention, the thin-spray support material has excellent intrinsic self-repairing performance, intrinsic flame retardant properties, mechanical properties and strong bonding properties, can achieve self-repair of local cracks in the spray layer, and can also achieve strong bonding between the thin-spray support material and the tunnel, thereby improving the safety level of the tunnel.

[0033] In some embodiments, the tunnel comprises a coal mine tunnel. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is the thin-sprayed support material for the fracture to be repaired in Example 11 of the present invention.

[0035] Figure 2 It is the repaired thin-sprayed support material in Example 11 of the present invention.

[0036] Figure 3 is the diol compound in Example 3 1 H NMR spectrum.

[0037] Figure 4 is the diol compound in Example 3 31 P NMR spectrum. DETAILED DESCRIPTION

[0038] Embodiments of the present invention are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to be used to explain the present invention, but should not be understood as limiting the present invention.

[0039] The flame retardant diol of the embodiment of the present invention has a structural formula as shown in the following formula (I) or formula (II):

[0040] or

[0041] Formula (I) Formula (II)

[0042] Among them, R 1 or R 2 Each is independently selected from unsubstituted or alkyl-substituted pyrrolyl, and unsubstituted or alkyl-substituted furanyl.

[0043] Flame-retardant diols of the embodiments of the present invention: In the related art, the flame retardant properties of the material are improved by introducing an organic phosphorus flame retardant component containing an aliphatic structure into the polyester polyol, but there are problems such as significant damage to the mechanical properties of the material and poor anti-melting droplet properties. The flame-retardant diol of the present invention introduces a DOPO structure, which has intrinsic flame retardant properties. The furan and / or pyrrole five-membered aromatic heterocyclic structure forms a rigid structure with the bridge ring structure and the DOPO structure, further improving the thermal stability and flame retardant properties of the material. In addition, the unsubstituted or alkyl-substituted pyrrole group contains N elements, which can be flame-retardant with the P element of the DOPO structure, and has more excellent flame retardant properties. The bridge ring ester structure based on 5-norbornene-2,3-dicarboxylic acid and / or acrylpimaric acid can provide an ester group and can improve the bonding strength of the material through hydrogen bonding and strong polarity; it also contains double bonds, which can strengthen the π-π conjugation effect and improve the bonding strength of the material; the chemical properties are stable, and the special nonlinear molecular structure gives the material excellent mechanical properties.

[0044] In the embodiments of the present invention, when the flame retardant diol of the present invention is used in polyurethane, it can give the polyurethane material excellent thermal stability, intrinsic flame retardancy, anti-dripping and mechanical properties. At the same time, the molecular main chain functional groups of the flame retardant diol can produce hydrogen bonding, π-π conjugation and strong polarity with the coal rock substrate, thereby achieving strong bonding, preventing cracking and falling, and improving the safety level of the tunnel.

[0045] In some embodiments, R 1 or R 2 Each is independently selected from unsubstituted or alkyl-substituted pyrrolyl, unsubstituted or alkyl-substituted furanyl; optionally, the alkyl is selected from methyl and ethyl.

[0046] In some embodiments, R 1 or R 2 Each independently selected from , , , , or Wherein, the * is R 1 or R 2 The connection site in the flame retardant diol refers to the R 1 or R 2 The connecting bond (connection site on the five-membered ring) does not represent a carbon atom. In the embodiment of the present invention, by preferably R 1 or R 2 The pyrrolyl or furanyl group is beneficial to further improve the flame retardant properties, thermal stability, anti-dripping properties, adhesion properties and mechanical properties of the flame retardant diol.

[0047] A method for preparing a flame retardant diol according to an embodiment of the present invention comprises the following steps:

[0048] (1) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and a five-membered aromatic heterocyclic derivative (HAOH) to obtain a diol compound (DPH); the five-membered aromatic heterocyclic derivative comprises at least one of a pyrrole derivative or a furan derivative;

[0049] (2) reacting a dibasic acid with oxalyl chloride, and then adding the diol compound to carry out an acylation reaction to obtain a flame retardant diol (DPHE); wherein the dibasic acid comprises at least one of 5-norbornene-2,3-dicarboxylic acid or acrylpimaric acid.

[0050] In the embodiment of the present invention, DOPO reacts with a five-membered aromatic heterocyclic derivative to generate a diol compound; a dibasic acid reacts with oxalyl chloride, and the carboxyl group of the dibasic acid generates an acyl chloride group, which is conducive to efficient reaction with a hydroxyl group; an acylation reaction is carried out between the diol compound and the oxalyl chloride reaction product of the dibasic acid to obtain a flame retardant diol, the dibasic acid has high reactivity and the product has stable chemical properties, the method is simple, the conditions are mild, and it is suitable for mass production.

[0051] In some embodiments, in step (1), the pyrrole derivative comprises at least one of the following structural formulas:

[0052] .

[0053] In the embodiment of the present invention, the pyrrole derivative has small steric hindrance and high reaction activity, and the aldehyde group reacts with DOPO.

[0054] In some embodiments, in step (1), the furan derivative comprises at least one of the following structural formulas:

[0055] .

[0056] In the embodiment of the present invention, the furan derivative has small steric hindrance and high reaction activity, and the aldehyde group reacts with DOPO.

[0057] In some embodiments, in step (1), the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the five-membered aromatic heterocyclic derivative is 1:1.

[0058] In some embodiments, in step (1), the reaction temperature is 80-150°C, specifically, for example, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C; and / or the reaction time is 2-8h, specifically, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h.

[0059] In some embodiments, in step (1), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a five-membered aromatic heterocyclic derivative are reacted in a solvent to obtain a diol compound; optionally, the solvent includes at least one of dioxane or 2-methyltetrahydrofuran.

[0060] In some embodiments, in step (1), after the reaction is completed, the solvent is removed and dried to obtain a diol compound; optionally, the solvent is removed by vacuum distillation; optionally, washing is performed before drying, specifically, washing is performed using chloroform.

[0061] In some embodiments, in step (2), the molar ratio of the dibasic acid to oxalyl chloride is 1:2.

[0062] In some embodiments, in step (2), the reaction temperature is 5-40°C, specifically, for example, 5°C, 15°C, 20°C, 25°C, 30°C, 40°C; and / or the reaction time is 2-5h, specifically, for example, 2h, 3h, 4h, 5h.

[0063] In some embodiments, in step (2), the molar ratio of the dibasic acid to the diol compound is 1:2. In the embodiment of the present invention, the amount of the diol compound is twice that of the dibasic acid, and the two hydroxyl groups of the diol compound have different steric hindrances and different reaction activities. The primary hydroxyl group with small steric hindrance reacts first, and the reaction is selective.

[0064] In some embodiments, in step (2), the temperature of the acylation reaction is 5-40°C, specifically, for example, 5°C, 15°C, 20°C, 25°C, 30°C, 40°C; and / or the time of the acylation reaction is 2-5h, specifically, for example, 2h, 3h, 4h, 5h.

[0065] In some embodiments, in step (2), after the dibasic acid reacts with oxalyl chloride, the diol compound is slowly added.

[0066] In some embodiments, in step (2), the dibasic acid is reacted with oxalyl chloride in a solvent; optionally, the solvent comprises at least one of dichloromethane, chloroform or tetrahydrofuran.

[0067] In some embodiments, in the step (2), after the acylation reaction, suction filtration, reduced pressure distillation, washing and drying are performed to obtain a flame retardant diol.

[0068] In some embodiments, step (2) is performed under an inert gas atmosphere; optionally, the inert gas atmosphere includes nitrogen.

[0069] An intrinsic flame-retardant self-repairing tunnel surface thin-spray support material according to an embodiment of the present invention comprises a first component and a second component, wherein the first component comprises, by mass: 40 to 80 parts of isocyanate, 15 to 50 parts of a first polyol, 0 to 10 parts of a viscosity reducer, 1 to 7 parts of a maleimide cross-linking agent, and 0.01 to 0.5 parts of an inhibitor;

[0070] The second component comprises, by mass, 60 to 85 parts of a second polyol, 10 to 30 parts of a flame retardant diol, 2 to 10 parts of an antistatic agent and 0.2 to 2 parts of a catalyst; the flame retardant diol comprises a conjugated structure.

[0071] The intrinsic flame-retardant self-repairing tunnel surface thin-spray support material of the embodiment of the present invention has excellent intrinsic self-repairing performance, intrinsic flame-retardant properties, mechanical properties and strong bonding properties, can achieve self-repair of local cracks in the spray layer, and improve the safety level of the tunnel.

[0072] In the embodiment of the present invention, the reversible Diels-Alder (DA) reaction is a type of [4+2] cycloaddition reaction, which can occur between an electron-rich diene and an electron-deficient dienophile, and has the advantages of mild reaction conditions, no need for catalysts, and high reaction efficiency. After the generated adduct is heated, a reverse DA reaction can occur, so that the electron-rich diene and the electron-deficient dienophile can undergo a DA reaction again, and cross-link again to achieve the function of self-repair. The thin-spray support material of the present invention contains both flame-retardant diols and maleimide crosslinkers. The flame-retardant diols include a conjugated structure and are electron-rich dienes; the maleimide crosslinker includes a carbon-carbon double bond and is an electron-deficient dienophile. The flame-retardant diols and the maleimide crosslinker can achieve self-repair of local cracks in the spray layer during the use of the intrinsic flame-retardant self-repairing roadway surface thin-spray support material through the reversible Diels-Alder reaction, and the self-repair rate is good.

[0073] In the embodiment of the present invention, a viscosity reducer can be added to the thin-sprayed support material to reduce the viscosity of the thin-sprayed support material and improve the construction performance of the thin-sprayed support material through the lubrication effect at the molecular level; adding too much viscosity reducer will affect the mechanical properties of the material. An antistatic agent is also added to the thin-sprayed support material to construct a conductive path so that static charges can be quickly dissipated without aggregation, reduce surface resistance, and increase antistatic properties; if too little antistatic agent is added, the surface resistance is high, and if too much is added, the cost will increase and the mechanical properties of the material will be affected. A trace amount of polymerization inhibitor is also added to the thin-sprayed support material to help increase the storage period of the thin-sprayed support material. The thin-sprayed support material has a microphase separation structure of soft segments and hard segments. The hard segment is beneficial to improving the strength of the thin-sprayed support material, and the soft segment is beneficial to improving the toughness of the thin-sprayed support material. By optimizing the number of components in the thin-sprayed support material, it is beneficial to obtain a thin-sprayed support material with excellent strength and toughness properties.

[0074] In some embodiments, in the first component, by mass: isocyanate may be 40 parts, 45 parts, 50 parts, 60 parts, 70 parts, 75 parts, 80 parts;

[0075] The first polyol can be 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 50 parts;

[0076] The viscosity reducer can be 0 parts, 0.01 parts, 0.5 parts, 1 parts, 2 parts, 5 parts, 7 parts, 8 parts, 10 parts;

[0077] The maleimide crosslinker can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 6.5 parts, 7 parts;

[0078] The amount of the polymerization inhibitor may be 0.01 part, 0.02 part, 0.05 part, 0.1 part, 0.2 part, 0.4 part, or 0.5 part.

[0079] In some embodiments, in the second component, by weight: the second polyol may be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, or 85 parts by weight;

[0080] The flame retardant diol can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts;

[0081] The antistatic agent can be 2 parts, 4 parts, 6 parts, 8 parts, 10 parts;

[0082] The catalyst can be 0.2 parts, 0.5 parts, 1 part, 1.5 parts, or 2 parts.

[0083] In some embodiments, the flame retardant diol comprises a conjugated structure; alternatively, the flame retardant diol comprises a conjugated carbon-carbon double bond; alternatively, the flame retardant diol comprises at least one of the following structural formulas:

[0084] or

[0085] Formula (I) Formula (II)

[0086] Among them, R 1 or R 2 Each is independently selected from unsubstituted or alkyl-substituted pyrrolyl, and unsubstituted or alkyl-substituted furanyl.

[0087] In the embodiments of the present invention, the unsubstituted or alkyl-substituted pyrrolyl and the unsubstituted or alkyl-substituted furanyl in the flame-retardant diol have a conjugated structure, and can react with the maleimide cross-linker through a reversible Diels-Alder reaction to achieve self-repair of local cracks in the spray layer during the use of the intrinsic flame-retardant self-repairing tunnel surface thin spray support material, thereby improving the self-repair ability.

[0088] In some embodiments, R 1 or R 2 Each is independently selected from unsubstituted or alkyl-substituted pyrrolyl, unsubstituted or alkyl-substituted furanyl; optionally, the alkyl is selected from methyl and ethyl.

[0089] In some embodiments, R 1 or R 2 Each independently selected from , , , , or Wherein, the * refers to R in the flame retardant diol 1 or R 2 The connecting bond (connection site on the five-membered ring) does not represent a carbon atom. In the embodiment of the present invention, by preferably R 1 or R 2 The pyrrolyl or furanyl groups are beneficial to further improve the intrinsic self-healing properties, intrinsic flame retardancy, thermal stability, anti-droplet properties, bonding properties and mechanical properties of the thin-spray support material.

[0090] In some embodiments, in the first component, the isocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, or polyphenyl polymethylene polyisocyanate.

[0091] In some embodiments, in the first component, the first polyol includes at least one of a polyether polyol or a polyester polyol; optionally, the polyether polyol includes at least one of polytetramethylene glycol, polyether polyol YD330N, polyether polyol TMN450, polyether polyol 855, and polyether polyol YD1020; the polyester polyol includes at least one of polyester polyol PD56, polyester polyol PS4027, and polyester polyol YT4200.

[0092] In some embodiments, the hydroxyl value of the first polyol is 30-500 mg KOH / g, specifically, for example, 30 mg KOH / g, 50 mg KOH / g, 100 mg KOH / g, 200 mg KOH / g, 300 mg KOH / g, 400 mg KOH / g, 500 mg KOH / g.

[0093] In some embodiments, in the first component, the viscosity reducing agent includes at least one of dimethyl adipate or diisopropyl adipate.

[0094] In some embodiments, in the first component, the inhibitor includes at least one of orthophosphoric acid, tartaric acid, benzoyl chloride, and benzoic acid.

[0095] In some embodiments, in the first component, the maleimide crosslinker includes at least one of a bismaleimide crosslinker and a trimaleimide crosslinker; optionally, the bismaleimide crosslinker includes at least one of 4,4'-bismaleimidodiphenylmethane and 1,6-dimaleimidohexane; optionally, the trimaleimide crosslinker includes tris(2-maleimidoethyl)amine. In the embodiment of the present invention, the maleimide crosslinker is beneficial to further improve the intrinsic self-healing performance, intrinsic flame retardant performance, thermal stability, anti-melting droplet performance, bonding performance and mechanical properties of the thin spray support material.

[0096] In some embodiments, in the second component, the second polyol includes at least one of a polyether polyol or a polyester polyol; optionally, the polyether polyol includes at least one of polytetramethylene glycol, polyether polyol YD330N, polyether polyol TMN450, polyether polyol 855, and polyether polyol YD1020; the polyester polyol includes at least one of polyester polyol PD56, polyester polyol PS4027, and polyester polyol YT4200.

[0097] In some embodiments, the hydroxyl value of the second polyol is 30-500 mg KOH / g, specifically, for example, 30 mg KOH / g, 50 mg KOH / g, 100 mg KOH / g, 200 mg KOH / g, 300 mg KOH / g, 400 mg KOH / g, 500 mg KOH / g.

[0098] In some embodiments, in the second component, the antistatic agent includes at least one of DS-8, E6019, and TRG-329.

[0099] In some embodiments, in the second component, the catalyst includes at least one of an organic metal catalyst and an amine catalyst; optionally, the organic metal catalyst includes at least one of dibutyltin dilaurate, stannous octoate, lead isooctanoate, and bismuth isooctanoate; optionally, the amine catalyst includes at least one of an aliphatic amine catalyst, an alicyclic amine catalyst, an aromatic amine catalyst, or an alcohol amine catalyst; optionally, the amine catalyst includes at least one of N-methylmorpholine, triethylenediamine, and N,N-dimethylcyclohexylamine.

[0100] In some embodiments, the mass ratio of the first component to the second component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1. In the embodiment of the present invention, when the thin-spray support material is used, the mass ratio of the first component to the second component can be 0.9-1.1:1.

[0101] In some embodiments, the volume ratio of the first component to the second component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1.

[0102] A method for preparing an intrinsic flame-retardant self-repairing tunnel surface thin-spray support material according to an embodiment of the present invention comprises the following steps:

[0103] 1) reacting an isocyanate, a first polyol, a viscosity reducer, a maleimide crosslinking agent and a polymerization inhibitor to obtain a first component;

[0104] 2) Mixing the second polyol, the flame retardant diol, the antistatic agent and the catalyst to obtain a second component.

[0105] In the embodiment of the present invention, a reaction intermediate is generated in advance by reacting isocyanate and the first polyol in the first component, and the first component and the second component are fully mixed respectively, thereby reducing the strengthening time of the thin-spray support material during use.

[0106] In some embodiments, in step 1), the reaction temperature is 50-120°C, specifically, for example, 50°C, 70°C, 80°C, 100°C, 110°C, 120°C; and / or the reaction time is 2-3 h, specifically, for example, 2 h, 2.5 h, 3 h.

[0107] In some embodiments, in step 1), the temperature is cooled to room temperature after the reaction and nitrogen is filled for protection, and the first component is obtained by discharging the material.

[0108] In some embodiments, in step 2), the mixing temperature is 5-40°C, specifically, for example, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 40°C; and / or the mixing time is 2-3h.

[0109] In some embodiments, in step 2), the mixing method is stirring.

[0110] In some embodiments, in step 2), nitrogen is charged at room temperature for protection after mixing or nitrogen is charged at room temperature for protection after mixing, and the second component is obtained by discharging the material.

[0111] An application of an intrinsic flame retardant self-repairing tunnel surface thin-spray support material in an embodiment of the present invention is used in a tunnel. In the embodiment of the present invention, the thin-spray support material has excellent intrinsic self-repairing performance, intrinsic flame retardant properties, mechanical properties and strong bonding properties, can achieve self-repair of local cracks in the spray layer, and can also achieve strong bonding between the thin-spray support material and the tunnel, thereby improving the safety level of the tunnel.

[0112] In some embodiments, it is applied to the surface of the surrounding rock of the tunnel.

[0113] In some embodiments, the roadway comprises a coal mine roadway, and optionally, the coal mine roadway comprises a coal-rock roadway or a semi-coal-rock roadway.

[0114] In some embodiments, the intrinsic flame retardant self-repairing tunnel surface thin-film spray support material is sprayed onto the tunnel surface.

[0115] In some embodiments, the first component and the second component are mixed and sprayed onto the roadway surface; alternatively, the first component and the second component are added into a spraying device for spraying.

[0116] In some embodiments, the curing time after spraying is ≤40 s, specifically, for example, 5 s, 10 s, 20 s, 30 s, 40 s.

[0117] In some embodiments, the mass ratio of the first component to the second component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1.

[0118] In some embodiments, the volume ratio of the first component to the second component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1.

[0119] In some embodiments, the thickness of the intrinsic flame retardant self-repairing tunnel surface thin spray support material on the tunnel surface is 5 to 10 mm, specifically, for example, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm.

[0120] In some embodiments, the intrinsic flame retardant self-repairing tunnel surface thin-spray support material is self-repaired by heating; optionally, the heating temperature is 70-150°C, specifically, for example, 70°C, 80°C, 100°C, 110°C, 120°C, 150°C; the heating time is 2~60min, specifically, for example, 2 min, 5 min, 10 min, 20 min, 30min, 40 min, 50 min, 60 min; the heating method includes direct heating or indirect heating; optionally, hot pressing is performed, and the hot pressing pressure can be 0.3-0.7MPa, specifically, for example, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa.

[0121] The present invention is described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0122] Example 1

[0123] A method for preparing a flame retardant diol comprises the following steps:

[0124] (1) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a five-membered aromatic heterocyclic derivative The reaction was carried out in 2-methyltetrahydrofuran at a molar ratio of 1:1 at 100°C for 5 hours, and the diol compound (6-(hydroxy(5-(hydroxymethyl)-1-methyl-1H-pyrrol-2-yl)methyl)dibenzo[c,e][1,2]phosphine-6-oxide) was obtained after washing with chloroform and drying.

[0125] (2) After reacting 5-norbornene-2,3-dicarboxylic acid and oxalyl chloride at a molar ratio of 1:2 at 40°C for 2 hours, a diol compound was slowly added, and the molar ratio of 5-norbornene-2,3-dicarboxylic acid to the diol compound was 1:2. The reaction was carried out at 30°C for 3 hours. After the reaction was completed, the mixture was filtered, distilled under reduced pressure, washed and dried to obtain a flame retardant diol (bis(5-(hydroxy(6-oxydibenzo[c,e][1,2]phosphin-6-yl)methyl)-1-methyl-1H-pyrrol-2-yl)methyl(1R,2R,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, DPHE1).

[0126]

[0127] DPHE1

[0128] Example 2

[0129] The preparation method is the same as that of Example 1, except that the five-membered aromatic heterocyclic derivative in step (1) is replaced by , and finally obtained the flame retardant diol (bis(1-ethyl-5-(hydroxy(6-oxydibenzo[c,e][1,2]phosphin-6-yl)methyl)-1H-pyrrol-2-yl)methyl(1R,2R,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, DPHE2).

[0130]

[0131] DPHE2

[0132] Example 3

[0133] The preparation method is the same as that of Example 1, except that the five-membered aromatic heterocyclic derivative in step (1) is replaced by , to obtain a diol compound (hydrogen spectrum such as Figure 3 As shown, the phosphorus spectrum is Figure 4 As shown), the flame retardant diol (bis(5-(hydroxy(6-oxydibenzo[c,e][1,2]phosphin-6-yl)methyl)furan-2-yl)methyl(1R,2R,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, DPHE3) was finally obtained.

[0134] Example 4

[0135] The preparation method is the same as that of Example 1, except that the five-membered aromatic heterocyclic derivative in step (1) is replaced by , the 5-norbornene-2,3-dicarboxylic acid in the step (2) is replaced by acrylpimaric acid to finally obtain DPHE4.

[0136] Example 5

[0137] The preparation method is the same as that of Example 1, except that the five-membered aromatic heterocyclic derivative in step (1) is replaced by , the 5-norbornene-2,3-dicarboxylic acid in the step (2) is replaced with acrylpimaric acid to finally obtain DPHE5.

[0138] Example 6

[0139] An intrinsic flame-retardant self-repairing tunnel surface thin-spray support material comprises a first component and a second component, wherein the first component comprises: 53 parts by weight of toluene diisocyanate; 20 parts by weight of polytetrahydrofuran polyol (hydroxyl value 112 mg KOH / g), 17.05 parts by weight of polyether polyol YD330N (hydroxyl value 33 mg KOH / g); 2 parts by weight of bismaleimide (4,4'-bismaleimidodiphenylmethane), 2.9 parts by weight of trimaleimide (tris(2-maleimidoethyl)amine); 5 parts by weight of dimethyl adipate as a viscosity reducer; and 0.05 parts by weight of orthophosphoric acid as an inhibitor;

[0140] The second component includes: 69.9 parts by weight of polyether polyol TMN450 (hydroxyl value 460 mg KOH / g); 24.6 parts by weight of DPHE1 diol; 3 parts by weight of antistatic agent DS-8, 2 parts by weight of E6019; 0.5 parts by weight of organotin catalyst T12;

[0141] The preparation method of the intrinsic flame retardant self-repairing tunnel surface thin spraying support material comprises the following steps:

[0142] 1) Add the first polyol, polymerization inhibitor, isocyanate, viscosity reducer and maleimide crosslinker into a reaction vessel, and react at 80°C for 2.5 hours; cool to room temperature, fill with nitrogen for protection, and discharge to obtain the first component;

[0143] 2) Add the second polyol, flame retardant diol, antistatic agent and catalyst into the reaction container, stir and disperse them evenly at room temperature, fill with nitrogen for protection at room temperature, and discharge to obtain the second component.

[0144] Example 7

[0145] The preparation method is the same as that of Example 6, except that the intrinsic self-repairing thin spray support material includes a first component and a second component, and the first component includes: 40 parts by weight of toluene diisocyanate, 22 parts by weight of polyphenyl polymethylene polyisocyanate; 15 parts by weight of polytetrahydrofuran polyol (hydroxyl value 56 mg KOH / g), 10.05 parts by weight of polyester polyol PD56 (hydroxyl value 52 mg KOH / g); 8 parts by weight of diisopropyl adipate as a viscosity reducer; 2.2 parts by weight of bismaleimide (1,6-dimaleimidohexane), 2.7 parts by weight of trimaleimide (tris(2-maleimidoethyl)amine); 0.05 parts by weight of tartaric acid as an inhibitor;

[0146] The second component includes: 69.9 parts by weight of polyether polyol 855 (hydroxyl value 380 mg KOH / g); 24.6 parts by weight of DPHE1 diol; 5 parts by weight of antistatic agent E6019; and 0.5 parts by weight of catalyst bismuth isooctanoate.

[0147] Example 8

[0148] The preparation method is the same as that of Example 6, except that the intrinsic self-repairing thin-spray support material includes a first component and a second component, and the first component includes: 49 parts by weight of polyphenyl polymethylene polyisocyanate; 42.45 parts by weight of polyester polyol PD56 (hydroxyl value 52 mg KOH / g); 6 parts by weight of viscosity reducer diisopropyl adipate; 1.2 parts by weight of bismaleimide (4,4'-bismaleimide diphenylmethane) and 1.3 parts by weight of trimaleimide (tris(2-maleimideethyl)amine); 0.05 parts by weight of tartaric acid as an inhibitor;

[0149] The second component includes: 32 parts by weight of polytetramethylene glycol (hydroxyl value 448 mg KOH / g), 47.5 parts by weight of polyether polyol 855 (hydroxyl value 380 mg KOH / g); 12.4 parts by weight of DPHE1 diol; 7 parts by weight of antistatic agent TRG-329; 0.5 parts by weight of catalyst dibutyltin dilaurate and 0.6 parts by weight of N-methylmorpholine.

[0150] Example 9

[0151] The preparation method is the same as that of Example 6, except that the intrinsic self-repairing thin-spray support material includes a first component and a second component, and the first component includes: 76 parts by weight of diphenylmethane diisocyanate; 19.45 parts by weight of polyether polyol YD1020 (hydroxyl value 112 mg KOH / g); 2 parts by weight of diisopropyl adipate, a viscosity reducer; 2.5 parts by weight of trimaleimide (tris(2-maleimidoethyl)amine); 0.05 parts by weight of benzoyl chloride, an inhibitor;

[0152] The second component includes: 35 parts by weight of polytetramethylene polyol (hydroxyl value 448 mg KOH / g), 44.5 parts by weight of polyether polyol 855 (hydroxyl value 380 mg KOH / g); 12.4 parts by weight of DPHE2 diol; 3 parts by weight of antistatic agent TRG-329, 4 parts by weight of E6019; 0.1 parts by weight of catalyst triethylenediamine, 1.0 parts by weight of N-methylmorpholine.

[0153] Example 10

[0154] The preparation method is the same as that of Example 6, except that the intrinsic self-repairing thin-spray support material includes a first component and a second component, and the first component includes: 55 parts by weight of diphenylmethane diisocyanate; 35.55 parts by weight of polyether polyol YD330N (hydroxyl value 33 mg KOH / g); 6 parts by weight of diisopropyl adipate, a viscosity reducer; 0.05 parts by weight of orthophosphoric acid, an inhibitor; 1.8 parts by weight of bismaleimide (1,6-dimaleimidohexane) and 1.6 parts by weight of trimaleimide (tris(2-maleimidoethyl)amine);

[0155] The second component includes: 38 parts by weight of polytetramethylene glycol (hydroxyl value 448 mg KOH / g), 35.4 parts by weight of polyester polyol PS4027 (hydroxyl value 408 mg KOH / g); 16 parts by weight of DPHE2 diol; 9 parts by weight of antistatic agent TRG-329; 0.8 parts by weight of catalyst dibutyltin dilaurate and 0.8 parts by weight of N,N-dimethylcyclohexylamine.

[0156] Embodiment 11

[0157] The preparation method is the same as that of Example 10, except that the DPHE2 diol in the second component is replaced by DPHE3 diol.

[0158] Example 12

[0159] The preparation method is the same as that of Example 9, except that the DPHE2 diol in the second component is replaced by DPHE4 diol.

[0160] Example 13

[0161] The preparation method is the same as that of Example 9, except that the DPHE2 diol in the second component is replaced by DPHE5 diol.

[0162] Comparative Example 1

[0163] The preparation method is the same as that of Example 6, except that in the second component, DPHE1 diol is replaced by polyether polyol TMN450 (hydroxyl value 460 mg KOH / g).

[0164] Comparative Example 2

[0165] The preparation method is the same as that of Example 6, except that in the second component, DPHE1 diol is replaced by polyether polyol TMN450 (hydroxyl value 460 mg KOH / g), and the second component also includes 12.40 parts of DOPO.

[0166] Comparative Example 3

[0167] The preparation method is the same as that of Example 6, except that in the second component, 69.9 parts by weight of polyether polyol TMN450 (hydroxyl value 460 mg KOH / g) is adjusted to 54.5 parts by weight; and 24.6 parts by weight of DPHE1 diol is adjusted to 40 parts by weight.

[0168] Comparative Example 4

[0169] The preparation method is the same as that of Example 6, except that in the second component, 69.9 parts by weight of polyether polyol (hydroxyl value 460 mg KOH / g) is adjusted to 86.5 parts by weight; and 24.6 parts by weight of DPHE1 diol is adjusted to 8 parts by weight.

[0170] Comparative Example 5

[0171] The preparation method is the same as that of Example 9, except that in the first component, trimaleimide (tris(2-maleimidoethyl)amine) is 0.5 parts by weight.

[0172] Comparative Example 6

[0173] The preparation method is the same as that of Example 9, except that in the first component, trimaleimide (tris(2-maleimidoethyl)amine) is 10 parts by weight.

[0174] The thin-sprayed support materials obtained in Examples 6 to 13 and Comparative Examples 1 to 6, with a volume ratio of the first component to the second component of 1:1, were tested for tensile strength, elongation at break, and bonding strength in accordance with the "Safety Technical Requirements for Thin-Sprayed Support Materials for Tunnel Surfaces (Trial)" and standard AQ1088-2011, and the oxygen index was tested in accordance with GB / T 2406.2-2009 standard. The results are shown in Table 1.

[0175] Determination of self-repair rate: cut the cured specimens of equal volumes of the first component and the second component, overlap the broken parts, and hot press at 100℃ (pressure 0.5MPa) for 10min to obtain the repaired specimens. Test the tensile strength according to the same standard. The ratio of the tensile strength of the repaired specimen to the specimen before fracture is the self-repair rate.

[0176] Table 1

[0177]

[0178] It can be seen from Table 1 that the intrinsic flame retardant self-repairing tunnel surface thin spraying support materials of Examples 6-13 of the present invention have excellent intrinsic self-repairing performance, intrinsic flame retardant properties, mechanical properties and strong bonding properties, can achieve self-repair of local cracks in the spraying layer, and improve the safety level of the tunnel.

[0179] By comparing Examples 10 and 11, it can be seen that the flame retardant effect of the flame retardant diol of the intrinsic flame retardant self-repairing tunnel surface thin spray support material is further better when the flame retardant diol adopts the pyrrole group than when the flame retardant diol adopts the furan group. This is because the unsubstituted or alkyl-substituted pyrrole group contains the N element, which can synergistically flame retard with the P element of the DOPO structure and has more excellent flame retardant properties.

[0180] It can be seen from Example 6 and Comparative Example 1 that no flame retardant diol is added to Comparative Example 1, and the oxygen index is 23.5%, which does not meet the requirement of the safety regulations that the oxygen index is not less than 28%, and does not have intrinsic flame retardant properties. No flame retardant diol is added in Comparative Example 1, and the maleimide cross-linking agent cannot achieve self-repair of cracks during the use of the thin-sprayed support material through the reversible Diels-Alder reaction, and basically has no self-repair ability. The tensile strength and elongation at break of the thin-sprayed support material in Comparative Example 1 are lower than those in Example 6, and the mechanical properties are poor. In addition, the bonding strength of the thin-sprayed support material in Comparative Example 1 is only 1.9 MPa, and the bonding performance is poor. It is easy to crack and fall when used in the tunnel.

[0181] It can be seen from Example 6 and Comparative Example 2 that the physical doping of DOPO in Comparative Example 2 has obvious disadvantages. Since DOPO is only physically mixed in the thin-spray support material, it is impossible to achieve molecular-level dispersion of covalent bonds, resulting in uneven dispersion of components inside the material, leading to decreased mechanical properties such as tensile strength and elongation at break. In addition, physical doping leads to uneven distribution of flame retardant elements, resulting in aggregation of flammable components, and the oxygen index is also significantly affected, which seriously weakens the flame retardant properties of the material.

[0182] It can be seen from Example 6 and Comparative Example 3 that the excessive amount of flame retardant diol used in Comparative Example 3 will reduce the toughness of the material and reduce the elongation at break, exceeding the requirement of no less than 60% at break in the Safety Technical Requirements (Trial) for Thin Spraying Support Materials on Tunnel Surfaces.

[0183] It can be seen from Example 6 and Comparative Example 4 that the amount of flame retardant diol used in Comparative Example 4 is low, the oxygen index is reduced, the flame retardant performance is reduced, and the self-healing performance is reduced. In addition, when the amount of flame retardant diol used in Comparative Example 4 is low, the mechanical properties and bonding properties are also reduced.

[0184] It can be seen from Example 9 and Comparative Example 5 that in Comparative Example 5, the amount of maleimide cross-linking agent added is too small, and the mechanical properties and self-repairing properties of the thin-spray support material are affected.

[0185] It can be seen from Example 9 and Comparative Example 6 that too much maleimide cross-linking agent is added, the material is brittle, and the requirement of the safety regulations that the elongation at break is not less than 60% is not met.

[0186] Figure 1 It is the thin-sprayed support material for the fracture to be repaired in Example 11 of the present invention, Figure 2 It is the repaired thin-sprayed support material in Example 11 of the present invention. It can be seen that the intrinsic flame-retardant self-repairing tunnel surface thin-sprayed support material of the present invention has excellent intrinsic self-repairing performance, can realize self-repair of local cracks, and improve the safety level of the tunnel.

[0187] In the present invention, the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" etc. mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0188] Although the above embodiments have been shown and described, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. Changes, modifications, substitutions and variations of the above embodiments by those of ordinary skill in the art are all within the scope of protection of the present invention.

Claims

1. An intrinsic flame retardant self-repairing tunnel surface thin spraying support material, characterized in that: It comprises a first component and a second component, wherein the first component comprises, by mass, 40 to 80 parts of isocyanate, 15 to 50 parts of a first polyol, 0 to 10 parts of a viscosity reducer, 1 to 7 parts of a maleimide crosslinker, and 0.01 to 0.5 parts of a polymerization inhibitor; The second component comprises, by mass, 60 to 85 parts of a second polyol, 10 to 30 parts of a flame retardant diol, 2 to 10 parts of an antistatic agent, and 0.2 to 2 parts of a catalyst; the flame retardant diol comprises a conjugated structure; The flame retardant diol comprises at least one of the following structural formulas: or Formula (I) Formula (II) Among them, R 1 or R 2 Each is independently selected from unsubstituted or alkyl-substituted pyrrolyl, and unsubstituted or alkyl-substituted furanyl.

2. The intrinsic flame retardant self-repairing tunnel surface thin spraying support material according to claim 1 is characterized in that: R 1 or R 2 Each independently selected from , , , , or .

3. The intrinsic flame retardant self-repairing tunnel surface thin-spray support material according to claim 1 is characterized in that: In the first component, the isocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate or polyphenyl polymethylene polyisocyanate; and / or, the first polyol comprises at least one of a polyether polyol or a polyester polyol; and / or, the hydroxyl value of the first polyol is 30 to 500 mg KOH / g; And / or, the viscosity reducing agent includes at least one of dimethyl adipate or diisopropyl adipate; And / or, the inhibitor includes at least one of orthophosphoric acid, tartaric acid, benzoyl chloride and benzoic acid.

4. The intrinsic flame retardant self-repairing tunnel surface thin-spray support material according to claim 1 is characterized in that: In the first component, the maleimide crosslinking agent includes at least one of a bismaleimide crosslinking agent and a trimaleimide crosslinking agent.

5. The intrinsic flame retardant self-repairing tunnel surface thin spraying support material according to claim 1 is characterized in that: In the second component, the second polyol includes at least one of a polyether polyol or a polyester polyol; and / or, the hydroxyl value of the second polyol is 30 to 500 mg KOH / g; And / or, the antistatic agent includes at least one of DS-8, E6019, and TRG-329; And / or, the catalyst includes at least one of an organic metal catalyst and an amine catalyst.

6. The intrinsic flame retardant self-repairing tunnel surface thin-spray support material according to claim 5 is characterized in that: The organic metal catalyst includes at least one of dibutyltin dilaurate, stannous octoate, lead isooctanoate, and bismuth isooctanoate; And / or, the amine catalyst includes at least one of aliphatic amine catalysts, alicyclic amine catalysts, aromatic amine catalysts or alcohol amine catalysts.

7. A method for preparing the intrinsic flame retardant self-repairing tunnel surface thin-spray support material according to any one of claims 1 to 6, characterized in that: The following steps are involved: 1) reacting an isocyanate, a first polyol, a viscosity reducer, a maleimide crosslinking agent and a polymerization inhibitor to obtain a first component; 2) Mixing the second polyol, the flame retardant diol, the antistatic agent and the catalyst to obtain a second component.

8. The method for preparing the intrinsic flame-retardant self-repairing tunnel surface thin-spray support material according to claim 7, characterized in that: In the step 1), the reaction temperature is 50-120° C.; and / or the reaction time is 2-3 h.

9. An application of an intrinsic flame retardant self-repairing tunnel surface thin-spray support material, characterized in that: Used for tunnels; the intrinsic flame retardant self-repairing tunnel surface thin spraying support material includes the intrinsic flame retardant self-repairing tunnel surface thin spraying support material described in any one of claims 1-6 or the intrinsic flame retardant self-repairing tunnel surface thin spraying support material prepared by the preparation method described in claim 7 or 8.

10. The use of the intrinsic flame retardant self-repairing tunnel surface thin-spray support material according to claim 9, characterized in that: The tunnel comprises a coal mine tunnel.

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