A kind of halogen-free flame-retardant polyester polyol for mining and its preparation method and application

Abstract

The present invention discloses a halogen-free flame-retardant polyester polyol for mining, and a preparation method and application thereof. The halogen-free flame-retardant polyester polyol for mining contains a five-membered furan and / or pyrrole aromatic heterocyclic structure and a DOPO structure. In the present invention, the halogen-free flame-retardant polyester polyol for mining is a linear flame-retardant polyester polyol macromolecule with a controllable DOPO content and a main chain containing a five-membered furan or pyrrole aromatic heterocyclic structure. The rigid five-membered aromatic heterocyclic structure and DOPO structure of the main chain give the material excellent thermal stability, anti-melting droplet property and intrinsic flame retardant properties, and is suitable for spraying and plugging wind leakage and grouting reinforcement of tunnels.

Description

Technical Field

[0001] The invention belongs to the technical field of mining engineering, and in particular relates to a halogen-free flame-retardant polyester polyol for mining, and a preparation method and application thereof. Background Art

[0002] The total length of newly excavated tunnels in my country exceeds 12,000 km each year, and the consumption of mining support materials is huge, such as spray plugging and grouting reinforcement materials. In the preparation of these materials, polyester polyols are widely used. However, conventional polyester polyurethane materials are extremely easy to burn and difficult to extinguish when encountering open flames. They are also accompanied by serious molten dripping, which causes the fire to spread further and poses a serious threat to the personal safety of people underground. The underground environment has high requirements for flame retardant properties. At present, the relevant technology generally adopts the method of adding flame retardants to improve the flame retardant properties of materials. However, the added flame retardants have the disadvantages of easy migration and precipitation, resulting in poor long-term flame retardancy. In addition, halogen-containing flame retardant elements will release a lot of smoke when burning, which is extremely harmful to health. Therefore, it is of great significance to develop halogen-free intrinsic flame retardant polyester polyols. Summary of the invention

[0003] The present invention is based on the inventor's discovery and understanding of the following facts and problems: At present, materials use external flame retardants to improve their flame retardancy, but external flame retardants have the disadvantages of easy migration and precipitation, resulting in poor long-term flame retardancy. Halogen-containing flame retardant elements release a large amount of smoke when burned, which is extremely harmful to health. In addition, the technology of introducing organic phosphorus flame retardant components containing aliphatic structures into polyester polyols to improve the flame retardancy of materials has the problem of significantly damaging the mechanical properties of the materials and poor anti-melting droplet properties.

[0004] The present invention aims to solve at least one of the technical problems in the related art to a certain extent. To this end, the embodiments of the present invention provide a halogen-free flame-retardant polyester polyol for mining and a preparation method and application thereof. The halogen-free flame-retardant polyester polyol for mining is a linear flame-retardant polyester polyol macromolecule with a controllable DOPO content and a main chain containing a five-membered furan or pyrrole aromatic heterocyclic structure. The rigid five-membered aromatic heterocyclic structure and DOPO structure of the main chain give the material excellent thermal stability, anti-melting droplet resistance and intrinsic flame retardant properties, and at the same time give the material excellent mechanical properties, which is suitable for spraying and plugging wind leakage and grouting reinforcement of tunnels.

[0005] The embodiment of the present invention provides a halogen-free flame-retardant polyester polyol for mining, characterized in that the structural formula of the halogen-free flame-retardant polyester polyol for mining is as follows:

[0006]

[0007] Wherein, R1 is selected from at least one of unsubstituted or alkyl-substituted pyrrolyl and unsubstituted or alkyl-substituted furanyl;

[0008] R2 is selected from C1-C 10 alkylene;

[0009] R3 is selected from C2-C 10 Alkylene, C2-C 10 The ether group;

[0010] n1 is an integer from 1 to 99; n2 is an integer from 0 to 99.

[0011] The advantages and technical effects of the halogen-free flame-retardant polyester polyol for mining of the embodiment of the present invention are as follows: the DOPO content of the halogen-free flame-retardant polyester polyol for mining is controllable, and the linear flame-retardant polyester polyol macromolecule containing a five-membered furan or pyrrole aromatic heterocyclic structure in the main chain, the five-membered aromatic heterocyclic structure and DOPO structure in the main chain are rigid, and have excellent thermal stability, anti-melting droplet and flame retardant properties, and can give polyester polyol materials and polyurethane materials excellent thermal stability, anti-melting droplet and intrinsic flame retardant properties, while giving the materials excellent mechanical properties. In addition, the N in the pyrrole group can cooperate with the adjacent P to retard the flame, further improving the flame retardant properties.

[0012] In some embodiments, R1 is selected from , , , , or .

[0013] The embodiment of the present invention provides a method for preparing a halogen-free flame-retardant polyester polyol for mining, comprising the following steps:

[0014] (1) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with a five-membered aromatic heterocyclic derivative to obtain a diol compound; the five-membered aromatic heterocyclic derivative comprises at least one of a pyrrole derivative or a furan derivative;

[0015] (2) The diol compound, the first polyol, the dibasic acid and the antioxidant are subjected to a condensation polymerization reaction to obtain a halogen-free flame-retardant polyester polyol for mining.

[0016] In the embodiment of the present invention, DOPO and a pyrrole derivative or a furan derivative react to generate a diol compound, and then the diol compound and a dibasic acid or the diol compound and a first polyol and a dibasic acid undergo a condensation reaction to obtain a halogen-free flame-retardant polyester polyol for mining. The halogen-free flame-retardant polyester polyol material for mining has excellent thermal stability, anti-dripping property and intrinsic flame retardant properties.

[0017] In some embodiments, in step (1), the pyrrole derivative comprises at least one of the following structural formulas:

[0018] ;

[0019] And / or, the furan derivative comprises at least one of the following structural formulas:

[0020] .

[0021] In some embodiments, in step (1), the molar ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the five-membered aromatic heterocyclic derivative is 1:1;

[0022] And / or, the reaction temperature is 80-150°C;

[0023] And / or, the reaction time is 2 to 8 h.

[0024] In some embodiments, in step (2), the first polyol includes at least one of ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, 2-ethyl-1,3-hexanediol, and 3-methyl-1,5-pentanediol;

[0025] and / or, the dibasic acid comprises at least one of succinic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, and phthalic acid;

[0026] and / or, the molar ratio of the total amount of the diol compound and the first polyol to the dibasic acid is 1-18:1-10;

[0027] and / or, the molar ratio of the diol compound to the first polyol is 1-18:0-17;

[0028] and / or, the antioxidant comprises at least one of N,N-diphenylethane-1,2-diamine or 2,6-di-tert-butyl-4-methylphenol;

[0029] And / or, the weight of the antioxidant is 0.1% to 2% of the total weight of the diol compound, the first polyol and the dibasic acid.

[0030] In some embodiments, in step (2), the polycondensation reaction is first carried out at 160-200°C and then heated to 210-240°C for reaction; preferably, the polycondensation reaction is carried out at 160-200°C for 2.0-6.0 hours; the reaction is carried out at 210-240°C for 1.0-6.0 hours;

[0031] And / or, after the polycondensation reaction is completed, the acid value is ≤5 mgKOH / g.

[0032] The embodiment of the present invention provides a spraying plugging material, comprising a first component and a second component, wherein the first component comprises, by mass: 30-45 parts of halogen-free flame-retardant polyester polyol for mining, 45-70 parts of a second polyol, 1-5 parts of a foam stabilizer, 0.5-2 parts of water, and 0.1-2 parts of a catalyst;

[0033] The second component comprises, by mass, 5 to 10 parts of halogen-free flame-retardant polyester polyol for mining, 85 to 95 parts of isocyanate and 3 to 7 parts of foaming agent;

[0034] The halogen-free flame-retardant polyester polyol for mining includes at least one of the halogen-free flame-retardant polyester polyol for mining described in the embodiment of the present invention or the halogen-free flame-retardant polyester polyol for mining prepared by the preparation method described in the embodiment of the present invention.

[0035] In the embodiment of the present invention, the spray-coated plugging material is a polyurethane material, and the rigid five-membered aromatic heterocyclic structure and DOPO structure of the main chain of the halogen-free flame-retardant polyester polyol for mining endow the polyurethane material with excellent thermal stability, anti-melting droplet properties and intrinsic flame retardant properties, while endowing the material with excellent mechanical properties. The spray-coated plugging material containing the halogen-free flame-retardant polyester polyol for mining, the main chain functional groups of the molecule can produce hydrogen bonding, π-π conjugation and strong polarity with the coal rock substrate, achieving strong bonding, so that the spray-coated plugging material for mining is tightly bonded to the substrate, better playing a sealing effect, not falling off, and reducing gas accumulation. In addition, the spray-coated plugging material can rapidly foam in large quantities in a short period of time to construct a sealing wall, ensuring the safety of the tunnel and reducing the amount used, which has economic benefits.

[0036] In the embodiments of the present invention, the flame retardant performance is required to be high in coal mines, the spray foaming material requires an oxygen index of not less than 28%, and the spray plugging material is often used in high-gas mines, which has extremely high safety risks. The spray plugging material of the present invention applies halogen-free flame-retardant polyester polyol, which can achieve halogen-free intrinsic flame retardancy, and the oxygen index is higher than 28%. At the same time, the bonding strength and mechanical properties are improved, which greatly improves the safety level of underground mining.

[0037] In some embodiments, the volume ratio of the first component to the second component is 0.9-1.1:1;

[0038] and / or, the second polyol comprises a polyether polyol;

[0039] and / or, the foam stabilizer comprises polysiloxane;

[0040] and / or, the catalyst comprises at least one of N,N-dimethylcyclohexylamine and 2-hydroxy-N,N,N-trimethyl-1-propylamine formate;

[0041] and / or, the isocyanate comprises at least one of diphenylmethylene diisocyanate or polymethylene polyphenyl isocyanate;

[0042] And / or, the blowing agent includes at least one of 1,1,1,3,3-pentafluoropropane or cyclopentane.

[0043] The embodiment of the present invention provides a method for preparing a spray-coated air leakage plugging material, comprising the following steps:

[0044] 1) Mixing the mining halogen-free flame-retardant polyester polyol, the second polyol, the foam stabilizer, water and the catalyst to obtain a first component;

[0045] 2) Mixing the halogen-free flame-retardant polyester polyol for mining and isocyanate to react, thereby obtaining an isocyanate prepolymer; after cooling, adding a foaming agent to obtain a second component.

[0046] In the embodiment of the present invention, the components of the first component are fully mixed to obtain the first component; the mining halogen-free flame-retardant polyester polyol and isocyanate are mixed and reacted to obtain an isocyanate prepolymer, and then a foaming agent is added and mixed to obtain the second component, thereby improving the curing speed during construction.

[0047] In some embodiments, in step 2), the reaction temperature is 50-120° C.; and the reaction time is 2-48 hours.

[0048] The embodiment of the present invention provides a grouting material, comprising a third component and a fourth component, wherein the third component comprises, by mass: 10 to 30 parts of a halogen-free flame-retardant polyester polyol for mining, 60 to 90 parts of a third polyol, and 0.01 to 0.5 parts of a catalyst;

[0049] The fourth component comprises, by mass, 5 to 15 parts of halogen-free flame-retardant polyester polyol for mining, 75 to 90 parts of isocyanate and 2 to 10 parts of plasticizer;

[0050] The halogen-free flame-retardant polyester polyol for mining includes at least one of the halogen-free flame-retardant polyester polyol for mining described in the embodiment of the present invention or the halogen-free flame-retardant polyester polyol for mining prepared by the preparation method described in the embodiment of the present invention.

[0051] In the embodiment of the present invention, the grouting material is a polyurethane material, and the rigid five-membered aromatic heterocyclic structure and DOPO structure of the main chain of the halogen-free flame-retardant polyester polyol for mining endow the polyurethane material with excellent thermal stability, anti-melting droplet properties and intrinsic flame retardant properties, while also endowing the material with excellent mechanical properties. The molecular main chain functional groups of the grouting material can produce hydrogen bonding, π-π conjugation and strong polarity with the coal rock substrate to achieve strong bonding, so that the grouting material is tightly bonded to the broken rock mass, greatly improving the strength of the rock mass, and significantly improving the shear resistance, thereby improving the safety of tunnel excavation.

[0052] In the embodiment of the present invention, the flame retardant performance is required to be high in coal mines, and the oxygen index of the grouting material is required to be not less than 28%. The grouting material of the present invention applies halogen-free flame-retardant polyester polyol, which can achieve halogen-free intrinsic flame retardancy, and the oxygen index is higher than 28%. At the same time, the bonding strength and mechanical properties are improved, which greatly improves the safety level of underground mining.

[0053] In some embodiments, the volume ratio of the third component to the fourth component is 0.9-1.1:1;

[0054] and / or, the third polyol comprises a polyether polyol;

[0055] And / or, the catalyst comprises at least one of stannous octoate or TMR-3;

[0056] and / or, the isocyanate comprises at least one of diphenylmethylene diisocyanate or polymethylene polyphenyl isocyanate;

[0057] And / or, the plasticizer includes at least one of dimethyl adipate or diisopropyl adipate.

[0058] An embodiment of the present invention provides a method for preparing a grouting material, comprising the following steps:

[0059] 1) Mixing the mining-use halogen-free flame-retardant polyester polyol, the third polyol and the catalyst to obtain a third component;

[0060] 2) reacting the halogen-free flame-retardant polyester polyol for mining with isocyanate to obtain an isocyanate prepolymer; after cooling, adding a plasticizer to obtain a fourth component.

[0061] In the embodiment of the present invention, the components of the third component are fully mixed to obtain the third component; the mining halogen-free flame-retardant polyester polyol and isocyanate are mixed and reacted to obtain an isocyanate prepolymer, and then a plasticizer is added and mixed to obtain the fourth component, thereby improving the curing speed during construction.

[0062] In some embodiments, in step 2), the reaction temperature is 50-120° C.; and the reaction time is 2-48 hours.

[0063] The embodiment of the present invention provides an application of a halogen-free flame-retardant polyester polyol for mining or a spray-coated air leakage plugging material or a grouting material for use in a tunnel.

[0064] In the embodiments of the present invention, the halogen-free flame-retardant polyester polyol for mining has intrinsic flame-retardant properties, can give the polyurethane material excellent thermal stability, anti-dripping property, intrinsic flame-retardant properties and mechanical properties, the oxygen index is higher than 28%, the material has strong adhesion with the coal rock substrate, improves the safety of tunnel excavation, and is suitable for tunnel surfaces, for example, coal mine tunnel surfaces.

[0065] In some embodiments, it is used in coal mine tunnels. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 It is the gel permeation chromatography (GPC) curve of Example 4 of the present invention.

[0067] Figure 2 It is a gel permeation chromatography (GPC) curve chart of Example 4 of the present invention. DETAILED DESCRIPTION

[0068] 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.

[0069] A halogen-free flame-retardant polyester polyol for mining according to an embodiment of the present invention has a structural formula as shown below:

[0070]

[0071] Wherein, R1 is selected from at least one of unsubstituted or alkyl-substituted pyrrolyl and unsubstituted or alkyl-substituted furanyl;

[0072] R2 is selected from C1-C 10 alkylene;

[0073] R3 is selected from C2-C 10 Alkylene, C2-C 10 The ether group;

[0074] n1 is an integer from 1 to 99; n2 is an integer from 0 to 99.

[0075] The halogen-free flame-retardant polyester polyol for mining of the embodiment of the present invention has a controllable DOPO content and is a linear flame-retardant polyester polyol macromolecule containing a five-membered furan or pyrrole aromatic heterocyclic structure in the main chain. The five-membered aromatic heterocyclic structure and DOPO structure with rigid main chain have excellent thermal stability, anti-melting droplet and flame retardant properties, and can give polyester polyol materials and polyurethane materials excellent thermal stability, anti-melting droplet and intrinsic flame retardant properties, while giving the materials excellent mechanical properties. In addition, the N in the pyrrole group can cooperate with the adjacent P to retard the flame, further improving the flame retardant properties.

[0076] In some embodiments, the number average molecular weight of the halogen-free flame-retardant polyester polyol for mining is 500-3000, specifically, for example, 500, 1000, 2000, 3000.

[0077] In some embodiments, R1 is selected from at least one of unsubstituted or alkyl-substituted pyrrolyl and unsubstituted or alkyl-substituted furanyl; optionally, the alkyl is selected from methyl and ethyl.

[0078] In some embodiments, R1 is selected from , , , , or . Wherein, the * refers to the connecting bond of R1 in the halogen-free flame-retardant polyester polyol for mining, which does not represent a carbon atom. In the embodiment of the present invention, by preferably selecting the pyrrolyl or furanyl of R1 of the halogen-free flame-retardant polyester polyol for mining, it is beneficial to further improve the thermal stability, anti-dripping property and intrinsic flame retardant property of the halogen-free flame-retardant polyester polyol for mining.

[0079] In some embodiments, R2 is selected from C1-C 10 alkylene;

[0080] In a specific embodiment, R2 is selected from at least one of the following structural formulas:

[0081] , , , , , or ,

[0082] Wherein, the * refers to the connecting bond of R2 in the halogen-free flame-retardant polyester polyol for mining, and does not represent a carbon atom.

[0083] In some embodiments, R3 is selected from C2-C 10 Alkylene, C2-C 10 The ether group;

[0084] In a specific embodiment, R3 is selected from at least one of the following structural formulas:

[0085] ,

[0086] Wherein, the * refers to the connecting bond of R3 in the halogen-free flame-retardant polyester polyol for mining, and does not represent a carbon atom.

[0087] In some embodiments, n1 is an integer of 1-99, specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 40, 60, 80, 90, 99.

[0088] In some embodiments, n2 is an integer from 0 to 99, specifically, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 40, 60, 80, 90, 99.

[0089] A method for preparing a halogen-free flame-retardant polyester polyol for mining according to an embodiment of the present invention comprises the following steps:

[0090] (1) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with a five-membered aromatic heterocyclic derivative to obtain a diol compound; the five-membered aromatic heterocyclic derivative comprises at least one of a pyrrole derivative or a furan derivative;

[0091] (2) The diol compound, the first polyol, the dibasic acid and the antioxidant are subjected to a condensation polymerization reaction to obtain a halogen-free flame-retardant polyester polyol for mining.

[0092] In the embodiment of the present invention, DOPO and a pyrrole derivative or a furan derivative react to generate a diol compound, and then the diol compound and a dibasic acid or the diol compound and a first polyol and a dibasic acid undergo a condensation reaction to obtain a halogen-free flame-retardant polyester polyol for mining. The halogen-free flame-retardant polyester polyol material for mining has excellent thermal stability, anti-dripping property and intrinsic flame retardant properties.

[0093] In some embodiments, in step (1), the pyrrole derivative comprises at least one of the following structural formulas:

[0094] .

[0095] In the embodiment of the present invention, by selecting the type of pyrrole derivative, it is beneficial to further improve the thermal stability, anti-melting and flame retardant properties of the polyester polyol material. At the same time, the N in pyrrole can cooperate with the adjacent P to retard the flame, further improving the flame retardant performance. The pyrrole derivative has small steric hindrance and high reactivity, and the aldehyde group reacts with DOPO.

[0096] In some embodiments, in step (1), the furan derivative comprises at least one of the following structural formulas:

[0097] .

[0098] In the embodiment of the present invention, the type of furan derivative is selected to further improve the thermal stability, anti-drip and flame retardant properties of the polyester polyol material. The furan derivative has small steric hindrance and high reactivity, and the aldehyde group reacts with DOPO.

[0099] 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.

[0100] 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; the reaction time is 2-8 h, specifically, for example, 2 h, 4 h, 6 h, 8 h.

[0101] In some embodiments, in step (1), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and a five-membered aromatic heterocyclic derivative are dissolved in a solvent for reaction; optionally, the solvent comprises at least one of dioxane or 2-methyltetrahydrofuran; optionally, after the reaction, the mixture is washed with chloroform and dried.

[0102] In some embodiments, in the 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.

[0103] In some embodiments, in step (2), the first polyol includes at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, 2-ethyl-1,3-hexanediol, and 3-methyl-1,5-pentanediol; optionally, the propylene glycol includes 1,2-propylene glycol; the butanediol includes at least one of 1,4-butanediol and 1,3-butanediol; the pentanediol includes 1,5-pentanediol; and the hexanediol includes 1,6-hexanediol.

[0104] In some embodiments, in step (2), the dibasic acid includes at least one of succinic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, and phthalic acid; preferably, it includes at least one of succinic acid, adipic acid, suberic acid, and sebacic acid.

[0105] In some embodiments, in step (2), the molar ratio of the total amount of the diol compound and the first polyol to the dibasic acid is 1-18:1-10, specifically, 1-18 (e.g., 1, 2, 3, 5, 8, 10, 15, 16, 18): 1-10 (e.g., 1, 2, 3, 5, 8, 9, 10), preferably, 3-16:2-9;

[0106] Optionally, the molar ratio of the diol compound to the first polyol is 1-18:0-17, specifically, 1-18 (e.g., 1, 2, 3, 5, 8, 10, 12, 15, 18):0-17 (e.g., 0, 1, 2, 3, 5, 8, 9, 10, 11, 15, 17), preferably, 3-12:1-11.

[0107] In the embodiment of the present invention, by adjusting the dosage of the diol compound, the first polyol and the dibasic acid, it is beneficial to adjust the composition and molecular weight of the halogen-free flame-retardant polyester polyol for mining. When the dosage of the diol compound is too low, the content of the flame retardant element is reduced and the flame retardant effect is reduced.

[0108] In some embodiments, in step (2), the antioxidant includes at least one of N,N-diphenylethane-1,2-diamine or 2,6-di-tert-butyl-4-methylphenol; the mass of the antioxidant is 0.1% to 2% of the total mass of the diol compound, the first polyol, and the dibasic acid, specifically, for example, 0.1%, 0.5%, 1%, 1.5%, 2%. In the embodiment of the present invention, the antioxidant is used to improve the reaction stability and reduce the occurrence of side reactions. The amount of the antioxidant is 0.1% to 2%, which is beneficial to further improve the stability of the esterification reaction, while reducing the occurrence of side reactions, and does not affect the performance of the product.

[0109] In some embodiments, in step (2), the polycondensation reaction is first reacted at 160-200°C (for example, 160°C, 170°C, 180°C, 190°C, 200°C), and then the temperature is raised to 210-240°C (for example, 210°C, 220°C, 230°C, 240°C) for reaction; preferably, the polycondensation reaction is reacted at 160-200°C for 2.0-6.0h (for example, 2.0h, 3.0h, 4.0h, 5.0h, 6.0h); the temperature is raised to 210-240°C for reaction for 1.0-6.0h (for example, 1.0h, 2.0h, 3.0h, 4.0h, 5.0h, 6.0h). In the embodiment of the present invention, the polycondensation reaction is first reacted at 160-200°C, and then the temperature is raised to 210-240°C for reaction, which is beneficial to improve the reaction effect of the esterification reaction.

[0110] In some embodiments, in step (2), the diol compound, the first polyol, the dibasic acid and the antioxidant are subjected to a condensation reaction under a protective atmosphere; optionally, the protective atmosphere includes nitrogen, and the reaction is carried out under stirring.

[0111] In some embodiments, after the polycondensation reaction is completed, the acid value is ≤5 mgKOH / g. In the embodiments of the present invention, the acid value is used to evaluate the residual carboxyl content after the polycondensation reaction. The standard for the completion of the polycondensation reaction is an acid value of ≤5 mgKOH / g. If the acid value is greatly reduced, the dibasic acid has been basically reacted, the conversion rate has reached the requirement, and the reaction can be terminated.

[0112] A spraying plugging material for air leakage according to an embodiment of the present invention comprises a first component and a second component, wherein the first component comprises, by mass, 30 to 45 parts of a halogen-free flame-retardant polyester polyol for mining, 45 to 70 parts of a second polyol, 1 to 5 parts of a foam stabilizer, 0.5 to 2 parts of water, and 0.1 to 2 parts of a catalyst;

[0113] The second component comprises, by mass, 5 to 10 parts of halogen-free flame-retardant polyester polyol for mining, 85 to 95 parts of isocyanate and 3 to 7 parts of foaming agent;

[0114] The halogen-free flame-retardant polyester polyol for mining includes at least one of the halogen-free flame-retardant polyester polyol for mining described in the embodiment of the present invention or the halogen-free flame-retardant polyester polyol for mining prepared by the preparation method described in the embodiment of the present invention.

[0115] In the embodiment of the present invention, the spray-coated plugging material is a polyurethane material, and the rigid five-membered aromatic heterocyclic structure and DOPO structure of the main chain of the halogen-free flame-retardant polyester polyol for mining endow the polyurethane material with excellent thermal stability, anti-melting droplet properties and intrinsic flame retardant properties, while endowing the material with excellent mechanical properties. The spray-coated plugging material containing the halogen-free flame-retardant polyester polyol for mining, the main chain functional groups of the molecule can produce hydrogen bonding, π-π conjugation and strong polarity with the coal rock substrate, achieving strong bonding, so that the spray-coated plugging material for mining is tightly bonded to the substrate, better playing a sealing effect, not falling off, and reducing gas accumulation. In addition, the spray-coated plugging material can rapidly foam in large quantities in a short period of time to construct a sealing wall, ensuring the safety of the tunnel and reducing the amount used, which has economic benefits.

[0116] In the embodiments of the present invention, the flame retardant performance is required to be high in coal mines, and the spray foaming material requires an oxygen index of not less than 28%, and is often used in high-gas mines, with extremely high safety risks. The related art generally adopts the method of adding halogen-containing flame retardants to improve the flame retardant performance of the material, but the added halogen-containing flame retardants have the disadvantages of easy migration, precipitation, and large smoke release, resulting in poor long-term flame retardancy, great harm to the human body, and almost no mechanical strength. In addition, it is very easy to burn when encountering an open flame, and it is difficult to extinguish. It is also accompanied by a serious molten drop phenomenon, causing the fire to spread further, posing a serious threat to the personal safety of people underground. The spray-coated plugging wind material of the present invention applies halogen-free flame-retardant polyester polyols therein, which can achieve halogen-free intrinsic flame retardancy, and the oxygen index is higher than 28%. At the same time, the bonding strength and mechanical properties are improved, which greatly improves the safety level of underground mining.

[0117] In some embodiments, in the first component, by mass: the halogen-free flame-retardant polyester polyol for mining can be 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts;

[0118] The second polyol can be 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts;

[0119] The foam stabilizer can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts;

[0120] Water can be 0.5 parts, 1 part, 1.5 parts, 2 parts;

[0121] The catalyst can be 0.1 parts, 0.5 parts, 1 part, 1.5 parts, or 2 parts.

[0122] In some embodiments, in the second component, by mass: the halogen-free flame-retardant polyester polyol for mining can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts;

[0123] Isocyanate can be 85 parts, 88 parts, 90 parts, 92 parts, 95 parts;

[0124] The amount of foaming agent can be 3 parts, 4 parts, 5 parts, 6 parts, or 7 parts.

[0125] In some embodiments, the first component of the halogen-free flame-retardant polyester polyol for mining use and the second component of the halogen-free flame-retardant polyester polyol for mining use may be the same as or different from each other.

[0126] In some embodiments, the mining-grade halogen-free flame-retardant polyester polyol and the second polyol are different.

[0127] 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, 1.0:1, 1.05:1, 1.1:1. In the embodiment of the present invention, the volume ratio of the first component to the second component is 0.9-1.1:1, which is conducive to improving the degree of polymerization and reaction efficiency.

[0128] 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, 1.0:1, 1.05:1, 1.1:1.

[0129] In some embodiments, the second polyol comprises a polyether polyol; alternatively, the second polyol comprises at least one of H307, H310 or H210.

[0130] In some embodiments, the foam stabilizer includes polysiloxane; optionally, the foam stabilizer includes at least one of B8002 or D193. In the embodiment of the present invention, adding a foam stabilizer to the spray-coated air leakage plugging material can stabilize and adjust the pore structure.

[0131] In some embodiments, the catalyst includes at least one of dimethylcyclohexylamine and 2-hydroxy-N,N,N-trimethyl-1-propylamine formate (TMR-2). In the embodiments of the present invention, the catalyst can promote the curing reaction. By selecting the catalyst, it is beneficial to quickly react and cure, accelerate the later curing, and do not affect the early milky time.

[0132] In some embodiments, the isocyanate is a polyisocyanate, and optionally, the isocyanate includes at least one of diphenylmethylene diisocyanate or polymethylene polyphenyl isocyanate.

[0133] In some embodiments, the foaming agent includes at least one of 1,1,1,3,3-pentafluoropropane (HFC-245fa) or cyclopentane. In the embodiment of the present invention, the foaming agent is added to the spray-coated air leakage plugging material to adjust the foaming multiple.

[0134] A method for preparing a spray-coated air leakage plugging material according to an embodiment of the present invention comprises the following steps:

[0135] 1) Mixing the mining halogen-free flame-retardant polyester polyol, the first polyol, the foam stabilizer, water and the catalyst to obtain a first component;

[0136] 2) Mixing the halogen-free flame-retardant polyester polyol for mining and isocyanate to react, thereby obtaining an isocyanate prepolymer; after cooling, adding a foaming agent to obtain a second component.

[0137] In the embodiment of the present invention, the components of the first component are fully mixed to obtain the first component; the mining halogen-free flame-retardant polyester polyol and isocyanate are mixed and reacted to obtain an isocyanate prepolymer, and then a foaming agent is added and mixed to obtain the second component, thereby improving the curing speed during construction.

[0138] In some embodiments, in step 1), the mixing temperature is 5-30°C, specifically, for example, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C; and the mixing time is 1-3h.

[0139] In some embodiments, in step 2), the reaction temperature is 50-120°C, specifically, for example, 50°C, 70°C, 80°C, 100°C, 110°C, 120°C; the reaction time is 2-48h, specifically, for example, 2 h, 2.5h, 3 h, 6 h, 12 h, 24 h, 36 h, 48 h.

[0140] In some embodiments, in step 2), a foaming agent is added after cooling to room temperature.

[0141] A grouting material according to an embodiment of the present invention comprises a third component and a fourth component, wherein the third component comprises, by mass, 10 to 30 parts of a halogen-free flame-retardant polyester polyol for mining, 60 to 90 parts of a third polyol, and 0.01 to 0.5 parts of a catalyst;

[0142] The fourth component comprises, by mass, 5 to 15 parts of halogen-free flame-retardant polyester polyol for mining, 75 to 90 parts of isocyanate and 2 to 10 parts of plasticizer;

[0143] The halogen-free flame-retardant polyester polyol for mining includes at least one of the halogen-free flame-retardant polyester polyol for mining described in the embodiment of the present invention or the halogen-free flame-retardant polyester polyol for mining prepared by the preparation method described in the embodiment of the present invention.

[0144] In the embodiment of the present invention, the grouting material is a polyurethane material, and the rigid five-membered aromatic heterocyclic structure and DOPO structure of the main chain of the halogen-free flame-retardant polyester polyol for mining endow the polyurethane material with excellent thermal stability, anti-melting droplet properties and intrinsic flame retardant properties, while also endowing the material with excellent mechanical properties. The molecular main chain functional groups of the grouting material can produce hydrogen bonding, π-π conjugation and strong polarity with the coal rock substrate to achieve strong bonding, so that the grouting material is tightly bonded to the broken rock mass, greatly improving the strength of the rock mass, and significantly improving the shear resistance, thereby improving the safety of tunnel excavation.

[0145] In the embodiments of the present invention, the flame retardant performance is required to be high in coal mines underground, and the oxygen index of the grouting material is required to be not less than 28%. The relevant technology generally adopts the method of adding halogen-containing flame retardants to improve the flame retardant performance of the material, but the added halogen-containing flame retardants have the disadvantages of easy migration, precipitation, and large smoke release, resulting in poor long-term flame retardancy. In addition, the grouting material has high requirements for shear resistance, and the method of adding flame retardants greatly affects the mechanical properties of the material. The grouting material of the present invention applies halogen-free flame-retardant polyester polyols, which can achieve halogen-free intrinsic flame retardancy, and the oxygen index is higher than 28%. At the same time, the bonding strength and mechanical properties are improved, which greatly improves the safety level of underground mining.

[0146] In some embodiments, in the third component, by mass: halogen-free flame-retardant polyester polyol for mining can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts;

[0147] The third polyol can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts;

[0148] The catalyst can be 0.01 parts, 0.02 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts.

[0149] In some embodiments, in the fourth component, by mass: the mining halogen-free flame-retardant polyester polyol may be 5 parts, 8 parts, 10 parts, 12 parts, or 15 parts;

[0150] Isocyanate can be 75 parts, 78 parts, 80 parts, 85 parts, 88 parts, 90 parts;

[0151] The plasticizer can be 2 parts, 4 parts, 6 parts, 8 parts, or 10 parts.

[0152] In some embodiments, the mining-use halogen-free flame-retardant polyester polyol of the third component and the mining-use halogen-free flame-retardant polyester polyol of the fourth component may be the same as or different from each other.

[0153] In some embodiments, the mining-grade halogen-free flame-retardant polyester polyol and the third polyol are different.

[0154] In some embodiments, the volume ratio of the third component to the fourth component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1.0:1, 1.05:1, 1.1:1. In the embodiment of the present invention, the volume ratio of the third component to the fourth component is 0.9-1.1:1, which is conducive to improving the degree of polymerization and reaction efficiency.

[0155] In some embodiments, the mass ratio of the third component to the fourth component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1.0:1, 1.05:1, 1.1:1.

[0156] In some embodiments, the third polyol comprises a polyether polyol; alternatively, the third polyol comprises at least one of H6007, H6360 or H240M.

[0157] In some embodiments, the catalyst includes at least one of stannous octoate or TMR-3.

[0158] In some embodiments, the isocyanate is a polyisocyanate; optionally, the isocyanate includes at least one of diphenylmethylene diisocyanate or polymethylene polyphenyl isocyanate.

[0159] In some embodiments, the plasticizer includes at least one of dimethyl adipate or diisopropyl adipate. In the embodiments of the present invention, by adding the plasticizer, the grouting material is facilitated to achieve molecular level lubrication and improve construction performance.

[0160] A method for preparing a grouting material according to an embodiment of the present invention comprises the following steps:

[0161] 1) Mixing the mining-use halogen-free flame-retardant polyester polyol, the second polyol and the catalyst to obtain a third component;

[0162] 2) reacting the halogen-free flame-retardant polyester polyol for mining with isocyanate to obtain an isocyanate prepolymer; after cooling, adding a plasticizer to obtain a fourth component.

[0163] In the embodiment of the present invention, the components of the third component are fully mixed to obtain the third component; the mining halogen-free flame-retardant polyester polyol and isocyanate are mixed and reacted to obtain an isocyanate prepolymer, and then a plasticizer is added and mixed to obtain the fourth component, thereby improving the curing speed during construction.

[0164] In some embodiments, in step 1), the mixing temperature is 5-30°C, specifically, for example, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C; and the mixing time is 0.2-3h.

[0165] In some embodiments, in step 2), the reaction temperature is 50-120°C, specifically, for example, 50°C, 70°C, 80°C, 100°C, 110°C, 120°C; the reaction time is 2-48h, specifically, for example, 2 h, 2.5h, 3 h, 6 h, 12 h, 24 h, 36 h, 48 h.

[0166] In some embodiments, in step 2), after cooling to room temperature, a plasticizer is added.

[0167] The application of a halogen-free flame-retardant polyester polyol for mining or a spray-coated air leakage plugging material or a grouting material according to an embodiment of the present invention is used in tunnels.

[0168] In the embodiments of the present invention, the halogen-free flame-retardant polyester polyol for mining has intrinsic flame-retardant properties, can give the polyurethane material excellent thermal stability, anti-dripping property, intrinsic flame-retardant properties and mechanical properties, the oxygen index is higher than 28%, the material has strong adhesion with the coal rock substrate, improves the safety of tunnel excavation, and is suitable for tunnel surfaces, for example, coal mine tunnel surfaces.

[0169] In some embodiments, it is used in coal mine tunnels.

[0170] In some embodiments, the halogen-free flame-retardant polyester polyol for mining is used for spraying air leakage plugging materials or grouting materials.

[0171] In some embodiments, an application of a spray-coated air leakage plugging material is used in tunnels; optionally, in coal mine tunnels; optionally, the first component and the second component are mixed to prepare a foamed body; optionally, the mixture is stirred; optionally, the foaming multiple of the spray-coated air leakage plugging material is more than 16 times, and the foaming time is less than 15s; the oxygen index of the spray-coated air leakage plugging material is higher than 28%; the bonding strength of the spray-coated air leakage plugging material is more than 2.0MPa.

[0172] In the embodiment of the present invention, the conventional spray-coated polyurethane material for plugging air leakage has poor flame retardancy and can only be expanded by 3 to 6 times. After the foaming multiple is large, the oxygen index is lower than 28%, which does not meet the safety requirements, and the flame retardant effect is greatly reduced due to the overflow of the added flame retardant for more than half a year, which endangers the safety of the tunnel. The foaming multiple of the spray-coated air leakage plugging material of the present invention can reach more than 16 times, has intrinsic flame retardant properties, and the oxygen index is higher than 28%, the bonding strength is more than 2.0MPa, can be rapidly foamed in large quantities in a short time, and a sealing wall is constructed, which ensures the safety of the tunnel and reduces the dosage, and has economic benefits.

[0173] In some embodiments, a grouting material is used for tunnels; optionally, for coal mine tunnels; optionally, the third component and the fourth component are mixed to prepare a consolidated body; optionally, the mixture is stirred; optionally, it is used to reinforce coal rock mass in coal mines, and the curing time is <150s.

[0174] In the embodiment of the present invention, the traditionally used polyurethane grouting material for coal mine reinforcement coal rock mass, in order to ensure that the oxygen index is higher than 28%, a large amount of flame retardant is added. After half a year, the flame retardant effect is greatly reduced, which endangers the safety of the roadway. In addition, the addition of excessive flame retardant causes a significant decrease in shear resistance, which can only barely reach the national standard line of 15.0MPa, and there is a safety hazard. In the grouting material of the embodiment of the present invention, a linear flame retardant polyester polyol macromolecule with a controllable DOPO content and a main chain containing a five-membered furan or pyrrole aromatic heterocyclic structure, a rigid five-membered aromatic heterocyclic structure and a DOPO structure are used, which gives the material excellent thermal stability, anti-melting droplet properties and intrinsic flame retardant properties, and at the same time gives the material excellent mechanical properties. In addition, the molecular main chain functional group can produce hydrogen bonding, π-π conjugation and strong polarity with the coal rock substrate to achieve strong bonding. The strong bonding performance can make the grouting material tightly bonded to the broken rock mass, greatly improve the rock mass strength, and significantly improve the shear resistance, thereby improving the safety of roadway excavation.

[0175] 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.

[0176] Example 1

[0177] A method for preparing a halogen-free flame-retardant polyester polyol for mining comprises the following steps:

[0178] (1) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a five-membered aromatic heterocyclic derivative The mixture was reacted in 2-methyltetrahydrofuran at a molar ratio of 1:1 at 120°C for 3 h, and then washed with chloroform and dried to obtain a diol compound (DPH1);

[0179] (DPH1)

[0180] (2) 0.5 mol of DPH1, 0.5 mol of 1,6-hexanediol and 0.8 mol of sebacic acid were mixed in a reactor at a molar ratio of 5:5:8, 1.0% of N,N-diphenylethane-1,2-diamine relative to the total mass of the above reactants was added, nitrogen was introduced into the reactor, and the mixture was reacted at 180° C. for 4 h and then at 230° C. for 4 h under mechanical stirring, with an acid value of ≤5 mgKOH / g, to obtain a halogen-free flame-retardant polyester polyol for mining.

[0181] Example 2

[0182] A method for preparing a halogen-free flame-retardant polyester polyol for mining comprises the following steps:

[0183] (1) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a five-membered aromatic heterocyclic derivative The mixture was reacted in dioxane at a molar ratio of 1:1 at 90°C for 6 h, and then washed with chloroform and dried to obtain a diol compound (DPH2);

[0184] (DPH2)

[0185] (2) 0.2 mol of DPH1 in Example 1, 0.2 mol of DPH2, 0.20 mol of diethylene glycol and 0.45 mol of succinic acid were mixed in a reactor at a molar ratio of 4:4:4:9, 0.3% of N,N-diphenylethane-1,2-diamine relative to the total mass of the above reactants was added, nitrogen was introduced into the reactor, and the mixture was reacted at 165° C. for 3 h and then at 220° C. for 2 h under mechanical stirring, with an acid value of ≤5 mgKOH / g, to obtain a halogen-free flame-retardant polyester polyol for mining.

[0186] Example 3

[0187] A method for preparing a halogen-free flame-retardant polyester polyol for mining comprises the following steps:

[0188] (1) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a five-membered aromatic heterocyclic derivative The mixture was reacted in 2-methyltetrahydrofuran at a molar ratio of 1:1 at 120°C for 3 h, and then washed with chloroform and dried to obtain a diol compound (DPH3);

[0189] (DPH3)

[0190] (2) 0.8 mol of DPH3, 0.3 mol of 1,3-butanediol and 0.8 mol of adipic acid were mixed in a reactor at a molar ratio of 8:3:8, 1.5% of N,N-diphenylethane-1,2-diamine relative to the total mass of the above reactants was added, nitrogen was introduced into the reactor, and the mixture was reacted at 180°C for 4 h and then at 230°C for 4 h under mechanical stirring, with an acid value of ≤5 mgKOH / g, to obtain a halogen-free flame-retardant polyester polyol for mining.

[0191] Example 4

[0192] The preparation method is the same as that of Example 3, except that in step (2), 1.0 mol of DPH3 in Example 3, 0.3 mol of 1,3-butanediol and 0.6 mol of suberic acid are mixed in a reactor at a molar ratio of 10:3:6 to obtain a halogen-free flame-retardant polyester polyol for mining. The GPC curve is as shown in FIG. Figure 1 and Figure 2 shown.

[0193] Example 5

[0194] The preparation method is the same as that of Example 4, except that in step (1), the five-membered aromatic heterocyclic derivative Replace with , to prepare a diol compound (DPH4); in the step (2), DPH3 is replaced by DPH4.

[0195] Example 6

[0196] The preparation method is the same as that of Example 4, except that in step (1), the five-membered aromatic heterocyclic derivative Replace with , to prepare a diol compound (DPH5); in the step (2), DPH3 is replaced by DPH5.

[0197] Example 7

[0198] The preparation method is the same as that of Example 4, except that in step (1), the five-membered aromatic heterocyclic derivative Replace with , to prepare a diol compound (DPH6); in the step (2), DPH3 is replaced by DPH6.

[0199] Table 1

[0200]

[0201] As can be seen from Table 1, the halogen-free flame-retardant polyester polyol for mining is successfully prepared through the polycondensation reaction, and the acid value is low. The diol compound has the ability of polycondensation reaction and the polycondensation reaction activity is high.

[0202] Application Example 1

[0203] A method for preparing a spray-coated air leakage plugging material comprises the following steps:

[0204] 1) 36 parts of the halogen-free flame-retardant polyester polyol for mining of Example 2, 60 parts of polyether polyol H307, 2 parts of foam stabilizer B8002, 1 part of water, 0.5 parts of catalyst N,N-dimethylcyclohexylamine, and 0.5 parts of catalyst TMR-2 were added into a reaction kettle and stirred for 1 hour to obtain a first component.

[0205] 2) Add 5 parts of the flame-retardant polyester polyol for mining of Example 2 and 90 parts of diphenylmethylene diisocyanate into a reaction kettle and react at 50° C. for 24 hours to obtain an isocyanate prepolymer; after cooling to room temperature, add 5 parts of a blowing agent HFC-245fa and mix to obtain a second component.

[0206] When using the spray plugging material, the first component and the second component are stirred and mixed in a volume ratio of 1:1 to prepare a foam, and the test is carried out in accordance with the AQ / T1089-2020 standard and the UL-94 vertical burning test.

[0207] Comparative Example 1

[0208] The preparation method is the same as that of Application Example 1, except that 36 parts of the halogen-free flame-retardant polyester polyol for mining in step 1) are replaced by 36 parts of polyether polyol H307; and 5 parts of the flame-retardant polyester polyol for mining in step 2) are replaced by 5 parts of polyether polyol H307.

[0209] Comparative Example 2

[0210] The preparation method is the same as that of Application Example 1, except that 36 parts of the halogen-free flame-retardant polyester polyol for mining in step 1) are replaced by 36 parts of polyether polyol H307; 5 parts of the flame-retardant polyester polyol for mining in step 2) are replaced by 5 parts of polyether polyol H307;

[0211] In the step 1), 15.3 parts of DOPO are added; in the step 2), 2.1 parts of DOPO are added.

[0212] Table 2

[0213]

[0214] As can be seen from Table 2, in Application Example 1, the oxygen index of the spray-coated air leakage plugging material tested in accordance with the AQ1089-2020 standard is 28.9%, which meets the requirements for use in coal mines. The UL-94 vertical burning test shows that there are no molten droplets during the combustion process of the material, the flame retardant performance reaches the V-0 level, and the bonding strength is 2.9MPa. The bonding strength and mechanical properties are improved, which greatly improves the safety level of underground mining.

[0215] In Comparative Example 1, halogen-free flame-retardant polyester polyol for mining is not used. The UL-94 vertical combustion test shows that there are molten droplets in the combustion process of the material, the flame retardancy is V-2 level, and the oxygen index is lower than 28%. The flame retardancy requirements of coal mines are relatively high. The spray foaming material requires an oxygen index of not less than 28%, and it is often used in high-gas mines, which poses extremely high safety risks.

[0216] In Comparative Example 2, the flame retardancy is improved by adding DOPO flame retardant. When the DOPO content is similar to that of the spray-coated plugging material in Application Example 1, the flame retardancy of the spray-coated plugging material in Comparative Example 2 only reaches the V-1 level, and the oxygen index is lower than 28%. The safety risk is extremely high, and the added flame retardant has the disadvantages of easy migration, precipitation, and large smoke release, resulting in poor long-term flame retardancy, great harm to the human body, and almost no mechanical strength. It is very easy to burn and difficult to extinguish when encountering an open flame, causing the fire to spread further, posing a serious threat to the safety of people underground. In addition, the bonding strength of the spray-coated plugging material in Comparative Example 2 is 0.9 MPa, which is relatively low, which is not conducive to the close bonding of the spray-coated plugging material with the substrate, and the sealing effect is poor, and it is easy to fall off, causing gas accumulation.

[0217] Application Example 2

[0218] A method for preparing a grouting material comprises the following steps:

[0219] 1) 20 parts of the halogen-free flame-retardant polyester polyol for mining use in Example 3, 80 parts of the polyether polyol H6360, 0.05 parts of the catalyst stannous octoate, and 0.05 parts of the catalyst TMR-3 were added into a reaction kettle and stirred for 0.5 hours to obtain a third component.

[0220] 2) Add 10 parts of the halogen-free flame-retardant polyester polyol for mining use in Example 3 and 85 parts of polymethylene polyphenyl isocyanate into a reaction kettle and react at 50° C. for 24 hours to obtain an isocyanate prepolymer; after cooling to room temperature, add 5 parts of a plasticizer, dimethyl adipate, to obtain a fourth component.

[0221] When applying the grouting material, the third component and the fourth component are stirred and mixed in a volume ratio of 1:1 to prepare a consolidated body, and the test is carried out in accordance with the AQ / T1089-2020 standard and the UL-94 vertical burning test.

[0222] Application Example 3

[0223] The preparation method is the same as that of Application Example 2, except that the halogen-free flame-retardant polyester polyol for mining in step 1) and step 2) is replaced by the halogen-free flame-retardant polyester polyol for mining in Example 4.

[0224] Application Example 4

[0225] The preparation method is the same as that of Application Example 2, except that the halogen-free flame-retardant polyester polyol for mining in step 1) and step 2) is replaced by the halogen-free flame-retardant polyester polyol for mining in Example 5.

[0226] Comparative Example 3

[0227] The preparation method is the same as that of Application Example 2, except that 20 parts of the halogen-free flame-retardant polyester polyol for mining in step 1) are replaced by 20 parts of polyether polyol H6360; and 10 parts of the flame-retardant polyester polyol for mining in step 2) are replaced by 10 parts of polyether polyol H6360.

[0228] Comparative Example 4

[0229] The preparation method is the same as that of Application Example 2, except that 20 parts of the halogen-free flame-retardant polyester polyol for mining in step 1) are replaced by 20 parts of polyether polyol H6360; 10 parts of the flame-retardant polyester polyol for mining in step 2) are replaced by 10 parts of polyether polyol H6360;

[0230] In the step 1), 8.8 parts of DOPO are added; in the step 2), 4.4 parts of DOPO are added.

[0231] Table 3

[0232]

[0233] As can be seen from Table 3, in Application Example 2, the oxygen index of the grouting material tested in accordance with the AQ1089-2020 standard is 30.2%, which meets the requirements for use in coal mines. The UL-94 vertical combustion test shows that there are no molten droplets during the combustion process of the material, and the flame retardant performance reaches the V-0 level. The shear strength is 21.5MPa, which meets the shear performance requirements of the grouting material, and the mechanical properties are improved, greatly improving the safety level of underground mining.

[0234] By comparing Application Examples 3 and 4, it can be seen that the oxygen index of Application Example 4 is 35.1%, which is higher than that of Application Example 3. This is because the halogen-free flame-retardant polyester polyol for mining in Application Example 4 uses pyrrole derivatives, and the nitrogen element in the pyrrole ring can be combined with the phosphorus element to form a synergistic flame retardant system. The two can produce a strong synergistic effect and improve the oxygen index.

[0235] In Comparative Example 3, halogen-free flame-retardant polyester polyol for mining is not used. The UL-94 vertical combustion test shows that there are molten droplets during the combustion process of the material, the flame retardant performance is V-2 level, and the oxygen index is lower than 28%. Coal mines have high requirements for flame retardant performance underground, and the grouting material requires an oxygen index of not less than 28%, which poses an extremely high safety risk.

[0236] In Comparative Example 4, the flame retardancy is improved by adding DOPO flame retardant. When the DOPO content is similar to that of the grouting material in Application Example 2, the flame retardancy of the grouting material in Comparative Example 2 only reaches the V-1 level, the oxygen index is lower than 28%, and the safety risk is extremely high. In addition, the added flame retardant has the disadvantages of easy migration, precipitation, and large smoke release, resulting in poor long-term flame retardancy. In addition, the grouting material has very high requirements for shear resistance, and the addition of flame retardants greatly affects the mechanical properties of the material. The shear strength of the grouting material in Comparative Example 4 is only 13.1 MPa, which is relatively low.

[0237] 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.

[0238] 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. A halogen-free flame-retardant polyester polyol for mining, characterized in that: The structural formula of the halogen-free flame-retardant polyester polyol for mining is as follows: Wherein, R1 is selected from at least one of unsubstituted or alkyl-substituted pyrrolyl and unsubstituted or alkyl-substituted furanyl; R2 is selected from C1-C 10 alkylene; R3 is selected from C2-C 10 Alkylene, C2-C 10 The ether group; n1 is an integer from 1 to 99; n2 is an integer from 1 to 99.

2. The halogen-free flame-retardant polyester polyol for mining according to claim 1, characterized in that: R1 is selected from , , , , or .

3. A method for preparing the halogen-free flame-retardant polyester polyol for mining use according to claim 1 or 2, characterized in that: The following steps are involved: (1) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a five-membered aromatic heterocyclic derivative to obtain a diol compound; the five-membered aromatic heterocyclic derivative comprises at least one of a pyrrole derivative and a furan derivative; (2) The diol compound, the first polyol, the dibasic acid and the antioxidant are subjected to a condensation polymerization reaction to obtain a halogen-free flame-retardant polyester polyol for mining.

4. The method for preparing the halogen-free flame-retardant polyester polyol for mining use according to claim 3, characterized in that: In the step (1), the pyrrole derivative comprises at least one of the following structural formulas: ； And / or, the furan derivative comprises at least one of the following structural formulas: 。 5. The method for preparing the halogen-free flame-retardant polyester polyol for mining use according to claim 3, characterized in that: In the step (1), the molar ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the five-membered aromatic heterocyclic derivative is 1:1; And / or, the reaction temperature is 80-150°C; And / or, the reaction time is 2 to 8 h.

6. The method for preparing the halogen-free flame-retardant polyester polyol for mining use according to claim 3, characterized in that: In the step (2), the first polyol includes at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, 2-ethyl-1,3-hexanediol, and 3-methyl-1,5-pentanediol; and / or, the dibasic acid comprises at least one of succinic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, and phthalic acid; and / or, the molar ratio of the total amount of the diol compound and the first polyol to the dibasic acid is 1-18:1-10; and / or, the molar ratio of the diol compound to the first polyol is 1-18:1-17; and / or, the antioxidant comprises at least one of N,N-diphenylethane-1,2-diamine or 2,6-di-tert-butyl-4-methylphenol; And / or, the weight of the antioxidant is 0.1% to 2% of the total weight of the diol compound, the first polyol and the dibasic acid.

7. The method for preparing halogen-free flame-retardant polyester polyol for mining use according to claim 3, characterized in that: In the step (2), the polycondensation reaction is first carried out at 160-200°C and then heated to 210-240°C for reaction; the polycondensation reaction is carried out at 160-200°C for 2.0-6.0 hours; the reaction is carried out at 210-240°C for 1.0-6.0 hours; And / or, after the polycondensation reaction is completed, the acid value is ≤5 mgKOH / g.

8. A spray-coated air leakage plugging material, characterized in that: It comprises a first component and a second component, wherein the first component comprises, by mass, 30-45 parts of halogen-free flame-retardant polyester polyol for mining, 45-70 parts of a second polyol, 1-5 parts of a foam stabilizer, 0.5-2 parts of water, and 0.1-2 parts of a catalyst; The second component comprises, by mass, 5 to 10 parts of halogen-free flame-retardant polyester polyol for mining, 85 to 95 parts of isocyanate and 3 to 7 parts of foaming agent; The halogen-free flame-retardant polyester polyol for mining includes at least one of the halogen-free flame-retardant polyester polyol for mining according to claim 1 or 2 or the halogen-free flame-retardant polyester polyol for mining prepared by the preparation method described in any one of claims 3-7.

9. The spraying air leakage plugging material according to claim 8, characterized in that: The volume ratio of the first component to the second component is 0.9-1.1:1; and / or, the second polyol comprises a polyether polyol; and / or, the foam stabilizer comprises polysiloxane; and / or, the catalyst comprises at least one of N,N-dimethylcyclohexylamine and 2-hydroxy-N,N,N-trimethyl-1-propylamine formate; and / or, the isocyanate comprises at least one of diphenylmethylene diisocyanate or polymethylene polyphenyl isocyanate; And / or, the blowing agent includes at least one of 1,1,1,3,3-pentafluoropropane or cyclopentane.

10. A method for preparing the spray-coated air leakage plugging material according to claim 8 or 9, characterized in that: The following steps are involved: 1) Mixing the mining halogen-free flame-retardant polyester polyol, the second polyol, the foam stabilizer, water and the catalyst to obtain a first component; 2) Mixing the mining-use halogen-free flame-retardant polyester polyol and isocyanate to react and obtain an isocyanate prepolymer; After cooling, a blowing agent is added to obtain a second component.

11. The method for preparing the spray-coated air leakage plugging material according to claim 10, characterized in that: In the step 2), the reaction temperature is 50-120° C. and the reaction time is 2-48 hours.

12. A grouting material, characterized in that: The invention comprises a third component and a fourth component, wherein the third component comprises, by mass, 10 to 30 parts of halogen-free flame-retardant polyester polyol for mining, 60 to 90 parts of a third polyol and 0.01 to 0.5 parts of a catalyst; The fourth component comprises, by mass, 5 to 15 parts of halogen-free flame-retardant polyester polyol for mining, 75 to 90 parts of isocyanate and 2 to 10 parts of plasticizer; The halogen-free flame-retardant polyester polyol for mining includes at least one of the halogen-free flame-retardant polyester polyol for mining according to claim 1 or 2 or the halogen-free flame-retardant polyester polyol for mining prepared by the preparation method described in any one of claims 3-7.

13. The grouting material according to claim 12, characterized in that: The volume ratio of the third component to the fourth component is 0.9-1.1:1; and / or, the third polyol comprises a polyether polyol; And / or, the catalyst comprises at least one of stannous octoate or TMR-3; and / or, the isocyanate comprises at least one of diphenylmethylene diisocyanate or polymethylene polyphenyl isocyanate; And / or, the plasticizer includes at least one of dimethyl adipate or diisopropyl adipate.

14. A method for preparing a grouting material according to claim 12 or 13, characterized in that: The following steps are involved: 1) Mixing the mining-use halogen-free flame-retardant polyester polyol, the third polyol and the catalyst to obtain a third component; 2) reacting the halogen-free flame-retardant polyester polyol for mining with isocyanate to obtain an isocyanate prepolymer; After cooling, a plasticizer is added to obtain a fourth component.

15. The method for preparing the grouting material according to claim 14, characterized in that: In the step 2), the reaction temperature is 50-120° C. and the reaction time is 2-48 hours.

16. Use of the halogen-free flame-retardant polyester polyol for mining according to claim 1 or 2, or the spray plugging material for wind leakage according to claim 8 or 9, or the grouting material according to claim 12 or 13, characterized in that: Used in alleyways.

17. The use according to claim 16, characterized in that Used in coal mine tunnels.

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