Reactive Low-Temperature Reinforcing Materials for Mines, Their Preparation Methods and Applications
The reactive flame-retardant low-temperature reinforcement material for mining uses a prepolymer prepared by reacting a special polyether polyol b with polymethylene polyphenyl polyisocyanate, combined with silane coupling agent KH-550. This solves the problem of the influence of traditional additive flame retardants on material properties and achieves high compressive strength, bonding strength and low heat of reaction.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHANDONG INOV NEW MATERIALS CO LTD
- Filing Date
- 2025-12-16
- Publication Date
- 2026-05-26
AI Technical Summary
When using traditional additive flame retardants, existing mining reinforcement materials may suffer from reduced compressive strength, bonding strength, and flame retardant effect, and the migration of flame retardants may lead to unstable performance.
A reactive flame-retardant low-temperature reinforcement material for mining is adopted. A prepolymer is prepared by reacting a special polyether polyol b with polymethylene polyphenyl polyisocyanate. Combined with silane coupling agent KH-550, a high-density cross-linked network is formed, which enhances the compressive strength and bonding performance of the material. The benzene ring structure inhibits the self-polymerization reaction of isocyanate and reduces the heat of reaction.
It achieves high compressive strength (≥80MPa), high bond strength (≥8MPa) and low reaction temperature (≤90℃), while also possessing excellent flame retardant properties (oxygen index ≥29%), avoiding the damage to the material structure caused by traditional additive flame retardants.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of reinforcement materials technology, specifically to reactive low-temperature reinforcement materials for mining, their preparation methods, and applications. Background Technology
[0002] In various coal mining processes, problems such as roof falls, sidewall collapses, and fires frequently occur, seriously affecting the safety of underground workers and the efficiency of coal mining. To address these issues, the use of mining reinforcement materials in the mineral extraction process is crucial.
[0003] Patent CN119306910A discloses a low-reaction-heat mineral reinforcement material and its preparation method. It involves mixing bisphenol A (a type of polyether polyol) and high-functionality polyether polyol B, using a specific initiator, to reduce the heat of reaction while maintaining the strength of the reinforcement material. Simultaneously, the use of tetrabromobisphenol A-initiated polyether polyol C enhances the flame retardancy, toughness, and strength of the prepolymer, resulting in a reinforcement material with high compressive strength and low heat of reaction. Patent CN120349499A introduces hexahydroxytriphenylene with a star-shaped molecular structure into the synthesis of mineral polyether polyols. The invention forms a highly cross-linked star-shaped structure, balancing rigidity and flexibility while improving the cross-linking density and compressive strength of the product. Secondly, by using bisphenol A, which contains a benzene ring structure, as a raw material for synthesizing the prepolymer, the toughness and strength of the material are improved through the interaction of the benzene rings, resulting in polyurethane materials with high compressive strength and low heat of reaction. However, both of these inventions involve the addition of more than 10% of additive flame retardants, which will inevitably affect the mechanical structure of the material, thereby reducing compressive strength and bonding strength. At the same time, the additive flame retardants will migrate on the material surface, affecting the flame retardant effect. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a reactive low-temperature reinforcing material for mining, thereby resolving the impact of existing technologies on the compressive strength, bonding strength, and flame retardant effect of materials as described in the background section.
[0005] The present invention also provides a preparation method that is simple, easy to implement, and suitable for large-scale production.
[0006] The present invention also provides its applications.
[0007] The reactive low-temperature reinforcement material for mining described in this invention is composed of component A and component B in a mass ratio of 1:(0.95-1.05), wherein:
[0008] Component A consists of the following parts by mass:
[0009] Polyester polyol: 40-60 parts;
[0010] Polyether polyol a: 40~60 parts;
[0011] Silane coupling agent: 1-3 parts;
[0012] Catalyst: 0.5~1.0 parts;
[0013] Component B consists of the following parts by mass:
[0014] Prepolymer: 80-90 parts;
[0015] Additives: 10-20 parts;
[0016] The polyester polyol is PE-B1210 from Shandong Yinuowei Polyurethane Co., Ltd., with a hydroxyl value of 210.8 mgKOH / g, an acid value of 0.94 mgKOH / g, a moisture content of 0.03%, and a viscosity of 5000 cps.
[0017] The polyether polyol a has a functionality of 2 and a hydroxyl value of 280 mgKOH / g, preferably INOVOL C204 from Shandong Yinuowei New Material Co., Ltd.
[0018] The prepolymer is obtained by reacting polyether polyol b with polymethylene polyphenyl polyisocyanate;
[0019] The polyether polyol b has a polycyclic benzene ring structure, a functionality of 3.1, and a hydroxyl value of 207 mgKOH / g. It is a special polyether polyol polymerized with propylene oxide using maltitol, trimethylolpropane, hydroquinone, and triethylene glycol as initiators.
[0020] The prepolymer has an -NCO content of 20 wt%.
[0021] The polymethylene polyphenyl polyisocyanate is PM200.
[0022] The preparation method of the polyether polyol b is as follows:
[0023] A. Add 50wt.% maltitol aqueous solution, trimethylolpropane, hydroquinone, triethylene glycol, and solid KOH into the reactor, seal the reactor and heat it up, and continuously add the first stage of propylene oxide dropwise.
[0024] B. After the internal pressure reaction, the temperature is increased, and a vacuum dehydration operation is performed to control the moisture content of the material in the reactor to be below 0.1%;
[0025] C. Increase the temperature and continuously add the remaining propylene oxide dropwise. After the addition is complete, let it mature for 3 hours.
[0026] D. After removing unreacted monomers, polyether polyol b is obtained through phosphoric acid neutralization, magnesium silicate adsorption, bubbling dehydration, and vacuum filtration.
[0027] The temperature increase mentioned in step A is to raise the temperature to 80-90℃.
[0028] The temperature increase mentioned in step B is to raise the temperature to 95-105℃.
[0029] The temperature increase mentioned in step C is to raise the temperature to 105-115℃.
[0030] The silane coupling agent is KH-550.
[0031] The additive is one or both of dioctyl terephthalate (DOTP) and dibutyl phthalate (DBP), preferably dioctyl terephthalate (DOTP).
[0032] The catalyst is one or both of bismuth neodecanoate and bismuth isooctanoate, preferably bismuth isooctanoate.
[0033] The preparation method of the reactive low-temperature reinforcement material for mining described in this invention comprises the following steps:
[0034] (1) Add the weighed polyester polyol, polyether polyol a, silane coupling agent and catalyst to the reaction vessel, stir and mix at room temperature to obtain component A, and seal and store.
[0035] (2) Add the weighed prepolymer and additives to another reaction vessel, stir and mix at room temperature to obtain component B, and store it in a nitrogen-filled and sealed container;
[0036] (3) After mixing components A and B, grouting and curing are carried out to obtain reactive low-temperature reinforcement material for mining.
[0037] The application of the reactive low-temperature reinforcement material for mining described in this invention involves drilling holes in a scattering pattern around the areas of the coal seam that require reinforcement. A grouting device is used to mix components A and B evenly before grouting. After curing, the reinforcement effect is tested.
[0038] The material has a compressive strength ≥80MPa, a bond strength ≥8MPa, an internal reaction temperature ≤90℃, and an oxygen index ≥29%.
[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0040] 1) This invention employs a reactive flame retardant structure, rather than the traditional additive-based flame retardant, which solves the flame retardant problem at the molecular level and is key to improving material performance. Simultaneously, it avoids the damage to the material's intrinsic structure caused by additives, thus ensuring high compressive strength. While achieving high flame retardant performance, this invention also features low internal heat of reaction, effectively reducing safety risks during use or combustion.
[0041] 2) This invention uses a self-made special polyether polyol b, with maltitol, trimethylolpropane, hydroquinone, and triethylene glycol as initiators. Maltitol, as a high-functionality initiator, acts as a "crosslinking bridge" to connect different molecular chains during polymerization, promoting the formation of a three-dimensional crosslinked network. Trimethylolpropane has a regular and ordered molecular structure, and after polymerization with propylene oxide, it provides a flexible portion for the overall chain segments, enhancing the overall toughness of the sample. Hydroquinone, with its main structural component being benzene rings, provides a rigid portion for the overall chain segments after polymerization with propylene oxide, enhancing the overall strength of the sample. Triethylene glycol can enhance the degree of crosslinking and mechanical strength of the polymer. Compared with monofunctional modifiers, the combination of these four initiators can react with more molecular chains, increasing the number of crosslinking points, making the network structure denser, and resulting in a reasonable combination of rigid and flexible portions within the material's chain segments, significantly improving the material's strength.
[0042] 3) The prepolymer of component B in this invention uses a special polyether polyol b as raw material. The steric hindrance of the benzene ring structure can suppress side reactions such as self-polymerization and trimerization of isocyanate, reducing the generation of additional heat and lowering the reaction temperature of the material. The urea bond structure formed by the prepolymer of polyether polyol with hydroquinone as the initiator and isocyanate will rapidly generate an aromatic carbon layer containing benzene rings at high temperatures through the catalytic action of phenolic hydroxyl groups. This carbon layer structure is dense and has low porosity, which can effectively block oxygen from entering the interior of the substrate, inhibiting combustion from the source and continuously meeting the material's strict requirements for strength and low heat of reaction.
[0043] 4) The silane coupling agent KH-550 selected in this invention can improve the wetting behavior of the material on the coal seam surface and reduce the interfacial tension between the material and the coal seam, thereby effectively improving the interfacial bonding performance between the material and the medium.
[0044] 5) The compressive strength of the material described in this invention is ≥80MPa, the bonding strength is ≥8MPa, the internal reaction temperature is ≤90℃, and the oxygen index is ≥29%. Detailed Implementation
[0045] The present invention will be further described below with reference to the embodiments.
[0046] Unless otherwise specified, all raw materials used in the examples were commercially available.
[0047] PE-B1210: Polyester polyol, Shandong Yinuowei Polyurethane Co., Ltd.;
[0048] INOVOL C204: Polyether polyol a, Shandong Yinuowei New Material Co., Ltd.;
[0049] KH-550: Silane coupling agent, Nanjing Chuangshi Chemical Additives Co., Ltd.;
[0050] Bismuth neodecanoate: Jiangsu Evergreen New Material Technology Co., Ltd.;
[0051] Bismuth isooctanoate: Jiangsu Evergreen New Material Technology Co., Ltd.;
[0052] DOTP: Shandong Lanfan Chemical Co., Ltd.;
[0053] DBP: Shandong Lanfan Chemical Co., Ltd.
[0054] INOVOL C305: Shandong Yinuowei New Materials Co., Ltd.;
[0055] MY-8175: Jinan Meiyu New Materials Co., Ltd., hydroxyl value 176mgKOH / g, acid value 1.35mgKOH / g, moisture 0.05%, viscosity 10280cps;
[0056] PM200: Wanhua Chemical Group Co., Ltd.
[0057] The preparation method of the polyether polyol b used is as follows:
[0058] A. Add 200g of 50wt.% maltitol aqueous solution, 40g of trimethylolpropane, 40.5g of hydroquinone, 14g of triethylene glycol, and 4.3g of solid KOH into a reaction vessel. Seal the vessel and purge it with nitrogen. Then raise the temperature to 85±5℃. Add 150g of propylene oxide dropwise for the first time. During the reaction, control the actual temperature of the materials between 82.5±2.5℃ and control the pressure inside the vessel at 0.25±0.15MPa. After the addition is complete, let it mature for 3 hours.
[0059] B. Heat to 100±5℃ and perform vacuum dehydration for 4 hours to control the moisture content of the material in the reactor to below 0.1%;
[0060] C. Control the temperature inside the polymerization reactor to 110±5℃, add propylene oxide for the second time, control the pressure to 0.25±0.15MPa, add all the remaining 883g of propylene oxide, and let it mature for 3 hours.
[0061] D. Control the temperature inside the reactor at 112.5±2.5℃, and maintain the pressure inside the reactor under vacuum at -0.08 to -0.09 MPa for 1 hour to remove unreacted propylene oxide monomer. Lower the temperature inside the reactor to 80±5℃, add 12.9g of phosphoric acid and 69.35g of water, stir for 1 hour, add 2.07g of magnesium silicate, raise the temperature to 105±5℃, and maintain the pressure inside the reactor under vacuum at -0.08 to -0.09 MPa for 4 hours. Check that the moisture content is below 0.1%, discharge the material, and filter to obtain a qualified polyether polyol product. Polyether polyol b with a hydroxyl value of 207 mgKOH / g and a viscosity of 557 mPa·s is obtained.
[0062] Example 1
[0063] The aforementioned reactive low-temperature reinforcement material for mining is composed of component A and component B, wherein:
[0064] Component A:
[0065] PE-B1210: 600kg;
[0066] INOVOL C204: 400kg;
[0067] KH-550: 10kg;
[0068] Catalyst: bismuth neodecanoate: 5 kg;
[0069] Component B:
[0070] Prepolymer: 900kg;
[0071] DOTP: 100kg;
[0072] The preparation method of the aforementioned reactive low-temperature reinforcement material for mining:
[0073] (1) Add the weighed PE-B1210, INOVOL C204, KH-550 and catalyst bismuth neodecanoate to the reaction vessel and stir and mix at room temperature for 1.5 h to obtain component A, which is then sealed and stored.
[0074] (2) The weighed prepolymer (214.5 kg of polyether polyol b and 685.5 kg of PM200 prepolymerized at 80°C for 2 h, with -NCO content of 20 wt%) and DOTP additive were added to another reactor and stirred at room temperature to obtain component B. The mixture was then sealed and stored under nitrogen.
[0075] Applications of reactive low-temperature reinforcement materials for mining:
[0076] For the areas of the coal seam that require reinforcement, four boreholes were drilled in a radiating pattern in the vicinity, with a depth of 2 meters. Using a grouting device, components A and B were uniformly mixed at a mass ratio of 1:1 and injected into the boreholes. After maturation for 72 hours, the reinforcement effect was tested.
[0077] Example 2
[0078] The aforementioned reactive low-temperature reinforcement material for mining is composed of component A and component B, wherein:
[0079] Component A:
[0080] PE-B1210: 500kg;
[0081] INOVOL C204: 500kg;
[0082] KH-550: 20kg;
[0083] Catalyst: 8 kg of bismuth isooctanoate;
[0084] Component B:
[0085] Prepolymer: 850 kg;
[0086] Additive DOTP: 150kg;
[0087] Preparation method of reactive low-temperature reinforcement materials for mining:
[0088] (1) Add the weighed PE-B1210, INOVOL C204, KH-550 and bismuth isooctanoate catalyst to the reaction vessel and stir and mix at room temperature for 1.5 h to obtain component A, which is then sealed and stored.
[0089] (2) The weighed prepolymer (202.6 kg of polyether polyol b and 647.4 kg of PM200 prepolymerized at 80℃ for 2 h, with -NCO content of 20 wt%) and DOTP additive were added to another reactor and mixed at room temperature to obtain component B. The mixture was then sealed and stored under nitrogen.
[0090] Applications of reactive low-temperature reinforcement materials for mining:
[0091] For the areas of the coal seam that require reinforcement, four boreholes were drilled in a radiating pattern in the vicinity, with a depth of 2 meters. Using a grouting device, components A and B were uniformly mixed at a mass ratio of 1:0.95. The mixture was then injected into the boreholes using the grouting device. After maturation for 72 hours, the reinforcement effect was tested.
[0092] Example 3
[0093] The aforementioned reactive low-temperature reinforcement material for mining is composed of component A and component B, wherein:
[0094] Component A:
[0095] PE-B1210: 400kg;
[0096] INOVOL C204: 600kg;
[0097] KH-550: 30kg;
[0098] Catalyst: bismuth isooctanoate: 10 kg;
[0099] Component B:
[0100] Prepolymer: 800kg;
[0101] Additive DBP: 200kg;
[0102] Preparation method of reactive low-temperature reinforcement materials for mining:
[0103] (1) Add the weighed PE-B1210, INOVOL C204, KH-550 and bismuth isooctanoate catalyst to the reaction vessel and stir and mix at room temperature for 1.5 h to obtain component A, which is then sealed and stored.
[0104] (2) The weighed prepolymer (obtained by prepolymerizing 190.7 kg of polyether polyol b and 609.3 kg of PM200 at 80℃ for 2 h, with -NCO content of 20 wt%) and additive DBP are added to another reactor and stirred at room temperature to obtain component B. It is then sealed and stored under nitrogen.
[0105] Applications of reactive low-temperature reinforcement materials for mining:
[0106] For the areas of the coal seam that require reinforcement, four boreholes were drilled in a radiating pattern in the vicinity, with a depth of 2 meters. Using a grouting device, components A and B were uniformly mixed at a mass ratio of 1:1.05. The mixture was then injected into the boreholes using the grouting device. After maturation for 72 hours, the reinforcement effect was tested.
[0107] Comparative Example 1
[0108] This comparative example is the same as Example 1, except that the prepolymer polyether polyol b in Example 1 is replaced with an equal mass fraction of INOVOL C305, and the remaining steps are the same as in Example 1.
[0109] Comparative Example 2
[0110] This comparative example is the same as Example 2, except that PE-B1210 in Example 2 is replaced with an equal number of parts by mass of MY-8175, and the rest of the steps are the same as in Example 2.
[0111] Comparative Example 3
[0112] This comparative example is the same as Example 3, except that KH-550 in Example 3 is removed, and the rest of the steps are the same as in Example 3.
[0113] The products obtained in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests. The testing standards and results are shown in Table 1.
[0114] Table 1. Testing Standards and Test Results
[0115] The method for testing the gel time is as follows:
[0116]
[0117] At a material temperature of 20℃, measure a total sample volume of 200 mL according to the ratio of components A and B, and pour it into a container with a diameter of 50 mm. Start timing from the moment the materials are mixed (using a mixer at 1000 r / min). After mixing evenly, stop timing when the material has just solidified (the stir bar cannot be removed) and record the time interval. Take the average of three tests as the curing time, accurate to 1 second. The allowable deviation of the curing time in three consecutive measurements should not exceed 10%; otherwise, the cause should be investigated and the test repeated.
[0118] As can be seen from Examples 1-3 in Table 1, the low-temperature reinforcing material for mining prepared by the present invention can achieve a compressive strength ≥80MPa, a bonding strength ≥8MPa, an internal reaction temperature ≤90℃, and an oxygen index ≥29% through the reasonable combination of raw materials of each component. Compared with Example 1, Comparative Example 1 uses INOVOL C305 as the prepolymer in component B. The compressive strength, bond strength, internal reaction temperature, and oxygen index of the material are significantly affected. This is because the reasonable combination of the four initiators in the special polyether polyol b significantly improves the compressive strength and bond strength of the material. The steric hindrance of the benzene ring structure can inhibit the self-polymerization and trimerization side reactions of isocyanate, reduce the generation of additional heat, and keep the reaction temperature low. The urea bond structure formed by the prepolymer of polyether polyol with hydroquinone as the initiator and isocyanate can quickly generate an aromatic carbon layer containing benzene rings at high temperature through the catalytic effect of phenolic hydroxyl groups, which can improve the flame retardant performance. Compared with Example 2, Comparative Example 2 uses polyester polyol MY-8175 instead of PE-B1210, and the flame retardant performance of the material decreases. Compared with Example 3, Comparative Example 3 removes KH-550, and the bond performance of the material decreases sharply.
Claims
1. A reactive mine low temperature reinforcement material, characterized by, It is composed of component A and component B in a mass ratio of 1:(0.95-1.05), wherein: Component A consists of the following parts by mass: Polyester polyol: 40-60 parts; Polyether polyol a: 40~60 parts; Silane coupling agent: 1-3 parts; Catalyst: 0.5~1.0 parts; Component B consists of the following parts by mass: Prepolymer: 80-90 parts; Additives: 10-20 parts; The polyester polyol is PE-B1210 with a functionality of 2.1 and a hydroxyl value of 210.8 mgKOH / g. The polyether polyol a has a functionality of 2 and a hydroxyl value of 280 mgKOH / g; The prepolymer is obtained by reacting polyether polyol b with polymethylene polyphenyl polyisocyanate; The silane coupling agent is KH-550; The polyether polyol b has a polycyclic benzene ring structure, a functionality of 3.1, and a hydroxyl value of 207 mgKOH / g. It is a special polyether polyol polymerized with propylene oxide using maltitol, trimethylolpropane, hydroquinone, and triethylene glycol as initiators. The preparation method of the polyether polyol b is as follows: A. Add maltitol aqueous solution, trimethylolpropane, hydroquinone, triethylene glycol, and solid KOH into the reaction vessel, seal the vessel and heat it up, and continuously add the first stage of propylene oxide dropwise. B. After the internal pressure reaction, the temperature is increased, and a vacuum dehydration operation is performed. C. Increase the temperature and continuously add the remaining propylene oxide dropwise. After the addition is complete, allow it to mature. D. Remove unreacted monomers, and obtain polyether polyol b after neutralization, adsorption, dehydration and filtration; The temperature increase mentioned in step A is to raise the temperature to 80-90℃; The temperature increase mentioned in step B is to raise the temperature to 95-105℃; The temperature increase mentioned in step C is to raise the temperature to 105-115℃.
2. The reaction-type mine low-temperature reinforcement material according to claim 1, characterized by, The additive is one or both of dioctyl terephthalate or dibutyl phthalate.
3. The reactive low-temperature reinforcement material for mining according to claim 1, characterized in that, The catalyst is one or both of bismuth neodecanoate and bismuth isooctanoate.
4. A method for preparing a reactive low-temperature reinforcing material for mining as described in any one of claims 1 to 3, characterized in that, It is prepared by the following steps: (1) Add polyester polyol, polyether polyol a, silane coupling agent and catalyst to the reaction vessel and stir to mix to obtain component A; (2) Add the prepolymer and additives to another reaction vessel and stir to mix to obtain component B; (3) After mixing components A and B, grouting and curing are carried out to obtain reactive low-temperature reinforcement material for mining.
5. The application of a reactive low-temperature reinforcement material for mining as described in any one of claims 1 to 3, characterized in that, For the parts of the coal seam that need reinforcement, boreholes are drilled in a radiating pattern in the vicinity. A grouting device is used to mix components A and B evenly before grouting and curing.