Coal mine reinforcing polyurethane material and preparation method thereof
A balanced formulation of polyether polyols, isocyanate prepolymer, and fumed silica in polyurethane materials addresses the challenges of meeting safety and mechanical standards, enhancing compressive strength and stability for coal rock reinforcement.
Patent Information
- Application Number
- CN202411231194.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-04
- Publication Date
- 2024-12-17
AI Technical Summary
The existing polyurethane materials for coal rock reinforcement face challenges in meeting the new safety standards set by the AQ1089-2020 industry standard, which require a maximum reaction temperature of ≤100°C and compressive strength of ≥60MPa, while maintaining flame retardancy, as adding flame retardants and viscosity reducers often compromises mechanical properties.
A coal mine reinforcement polyurethane material composed of specific components A and B, including polyether polyols, isocyanate prepolymer, crosslinking agents, and fumed silica, with a balanced formulation that achieves a maximum reaction temperature of ≤100°C and compressive strength of ≥60MPa, utilizing cross-linking agents with amino groups and benzene ring segments to form a cross-linked network structure, and fumed silica to enhance material density and strength.
The material meets the safety and mechanical requirements of the AQ1089-2020 standard, providing effective reinforcement with improved compressive strength and stability, suitable for coal rock reinforcement applications.
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polyurethane and relates to a coal mine reinforcement polyurethane material and a preparation method thereof. Background Art
[0002] The geological conditions for underground coal mining are complex and changeable. With the increase in mining depth and the large-scale promotion and application of comprehensive top coal caving mining technology, the working environment continues to deteriorate, often causing accidents such as surrounding rock collapse and water leakage, posing a huge threat to the safe production of coal mines and the safety of underground construction workers.
[0003] Polyurethane grouting materials have the characteristics of good permeability, good adhesion, controllable curing speed and high strength. They can quickly and effectively reinforce and deal with accidents such as coal wall spalling and roof collapse. Therefore, polyurethane grouting materials have been widely promoted and applied in underground coal mines.
[0004] However, the reaction process of polyurethane materials is an exothermic reaction. Local heat accumulation may occur during underground construction, which may easily cause fires and bring safety hazards. In response to safety risks in use, the maximum reaction temperature of polyurethane materials for coal rock reinforcement in my country's current safety production industry standard (AQ1089-2020) is reduced from ≤140℃ in the original standard (AQ1089-2011) to ≤100℃, and the compressive strength is reduced from ≥60MPa to ≥40MPa. In the research and development process of polyurethane materials for coal rock reinforcement, it was found that in order to meet the requirements of the maximum reaction temperature (≤100℃) and flame retardancy (oxygen index ≥28), a large amount of flame retardants and viscosity reducers need to be added, which often causes a significant decrease in physical and mechanical properties such as compressive strength. Therefore, under the new safety standards, new means are urgently needed to improve the physical and mechanical properties of polyurethane materials for coal rock reinforcement. Summary of the invention
[0005] The invention proposes a coal mine reinforcement polyurethane material and provides a preparation method thereof. The material has a maximum reaction temperature of ≤100°C and a compressive strength of ≥60MPa, and has broad application prospects in the field of coal rock reinforcement.
[0006] The technical solution of the present invention is achieved in this way: Technical Theme 1 A coal mine reinforcement polyurethane material, comprising component A and component B in a mass ratio of 0.8-1.2:1; wherein, by mass, component A comprises: 70-90 parts of polyether polyol A, 10-30 parts of polyether polyol B, 0.1-3.0 parts of a catalyst, 10-40 parts of a flame retardant, 1-20 parts of a crosslinking agent, and 0.5-3 parts of fumed silica; Component B includes: 100-140 parts of isocyanate prepolymer, 10-30 parts of flame retardant and 5-20 parts of toughening agent; The cross-linking agent is 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 1-20:1-10:1-10; The polyether polyol A is a polyether polyol with a functionality of 2-4, a hydroxyl value of 150-500 mgKOH / g, and a viscosity of 200-1000 mPa.s at 25°C; The polyether polyol B is a polyether polyol having a functionality of 2-6, a hydroxyl value of 150-450 mgKOH / g, and a viscosity of 50-3500 mPa.s at 25°C; The cross-linking agent is selected from one or more of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline); The preparation method of the isocyanate prepolymer comprises: mixing 5-30 parts of polyether polyol C with 70-120 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 70-90° C. for 3-5 hours to obtain the isocyanate prepolymer; The polyether polyol C is composed of YD-1020, YD-6205 and YD-450K in a mass ratio of 30-50:1-10:1-10.
[0007] Preferably, the cross-linking agent is 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 1-20:1-10:1-10.
[0008] Preferably, the crosslinking agent is 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 5-15:2-5:3-5.
[0009] Preferably, the polyether polyol C is composed of YD-1020, YD-6205 and YD-450K in a mass ratio of 40:4:5.
[0010] Preferably, the polyether polyol C is dehydrated before being mixed with phenyl polymethylene polyisocyanate, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 100-120° C. for dehydration for 1.5-3 hours, and then cooling to 25-40° C. for standby use.
[0011] Preferably, the catalyst is an organic metal catalyst and / or an organic amine catalyst.
[0012] Preferably, the organic metal catalyst is dibutyltin dilaurate and / or stannous octoate, and the organic amine catalyst is N,N-dimethylcyclohexylamine and / or A33.
[0013] Preferably, the flame retardant is selected from one or more of tris(1,3-dichloro-2-propyl) phosphate (TDCP), triethyl phosphate (TEP), dimethyl methyl phosphate (DMMP), tris(2-chloroethyl) phosphate (TCEP), and tris(1-chloro-2-propyl) phosphate (TCPP).
[0014] Preferably, the toughening agent is dioctyl phthalate and / or dibutyl phthalate.
[0015] Preferably, the particle size of the fumed silica is 10-20 microns.
[0016] Technical Theme 2 The present invention also provides a method for preparing the coal mine reinforcement polyurethane material as described in the first technical subject, comprising the following steps: A. Mix polyether polyol A, polyether polyol B, catalyst, flame retardant and fumed silica, stir evenly at room temperature, then heat to 80-100°C and add crosslinking agent, stir for 1-2h, and mix evenly to obtain component A; B. Mix the isocyanate prepolymer, toughening agent and flame retardant, and stir evenly at room temperature to obtain component B; C. Mix component A and component B in proportion and react.
[0017] Preferably, the stirring rate of the mixing reaction is 100-500 rpm.
[0018] When the above-mentioned coal mine reinforcement polyurethane material is used, component A and component B are mixed in a specified proportion through a special double-liquid grouting pump and then injected into the cracks or cavities of the coal rock mass to be reinforced for solidification.
[0019] The working principle and beneficial effects of the present invention are: 1. The polyurethane material for coal rock reinforcement provided in the present invention optimizes the formulas of component A and component B respectively, so that the maximum reaction temperature of the polyurethane material is ≤100°C and the compressive strength is ≥60MPa, meeting the safety production industry standard (AQ1089-2020).
[0020] 2. In the present invention, on the one hand, a small amount of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) are added to the A component formula to introduce amino groups and benzene ring segments into the reaction system, and the amino groups react with the isocyanate in the B component to obtain urea groups (-NHCONH-) and biuret groups (-NHCON(R)CONH-) to form a cross-linked network structure. At the same time, the benzene ring segments increase the hard segment content and improve the rigidity of the material. On the other hand, the addition of fumed silica fills and stabilizes the internal structure of the material, thereby improving the density and strength of the material. On the other hand, the B component uses three different types of polyether polyols (with different functionalities, hydroxyl values and molecular weights) to carry out composite modification of polyphenyl polymethylene polyisocyanate, so that it reacts with the polyether polyol and the crosslinking agent in the A component to form a structure with a higher crosslinking density.
[0021] In summary, the urea-based hard segment, benzene ring hard segment, cross-linked structure, and fumed silica filling work together to greatly improve the compressive strength of polyurethane. DETAILED DESCRIPTION
[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0023] In the following examples and comparative examples, the raw materials used can all be purchased from commercial sources.
[0024] Among them, polyether polyol YD-303, YD-305, YD-307, polyether polyol YD-204, YD-8310, YD-8335, polyether polyol YD-1020, polyether polyol YD-6205, polyether polyol YD-450K are all provided by Hebei Yadong Chemical Group Co., Ltd.; the parameters are as follows: raw materials Functionality Hydroxyl value mg KOH / g Viscosity mPa·s, 25℃ Molecular weight g / mol YD-303 3 475 450 354 YD-305 3 350 320 481 YD-307 3 235 250 716 YD-204 2 280 70 401 YD-8310 4.5 320 1300 789 YD-8335 4 360 3300 623 YD-1020 2 110 160 1000 YD-6205 4.5 380 2500 660 YD-450K 3.4 450 2500 424 Dibutyltin dilaurate, stannous octoate, N,N-dimethylcyclohexylamine, and A33 (i.e., 33% triethylenediamine solution, a solution obtained by dissolving triethylenediamine in diethylene glycol, with a mass fraction of triethylenediamine of 33%) were all provided by Xindian Chemical Materials (Shanghai) Co., Ltd.
[0025] One or more of tris(1,3-dichloro-2-propyl) phosphate (TDCP), triethyl phosphate (TEP), dimethyl methyl phosphate (DMMP), tris(2-chloroethyl) phosphate (TCEP), and tris(1-chloro-2-propyl) phosphate (TCPP) are provided by Zhejiang Wansheng Co., Ltd.
[0026] 3-Chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester, and 4,4'-methylenebis(2-methyl-6-diethylaniline) were provided by Suzhou Xiangyuan New Materials Co., Ltd., Sanmenxia Xiawei Chemical Co., Ltd., and Changshu Yongli Chemical Co., Ltd., respectively.
[0027] Fumed silica, particle size 15 μm, was provided by Wacker Chemical Fumed Silica (Zhangjiagang) Co., Ltd.
[0028] The polyphenyl polymethylene polyisocyanate used was PM200, which was provided by Wanhua Chemical Group Co., Ltd.
[0029] Dioctyl phthalate and dibutyl phthalate were both provided by Blue Sail Group Co., Ltd.
[0030] Example 1 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 75 parts of polyether polyol YD-305, 25 parts of polyether polyol YD-8310, 0.1 parts of dibutyltin dilaurate, 0.5 parts of N,N-dimethylcyclohexylamine, 5 parts of TDCP, 10 parts of dimethyl methyl phosphate, 25 parts of tris(1-chloro-2-propyl) phosphate, 15 parts of crosslinking agent, and 1.0 parts of fumed silica; Component B: 125 parts of isocyanate prepolymer, 10 parts of tris(2-chloroethyl)phosphate, 14 parts of tris(1-chloro-2-propyl)phosphate and 12 parts of dibutyl phthalate; The cross-linking agent is composed of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 1:1:1; (2) Mix polyether polyol YD-305, polyether polyol YD-8310, dibutyltin dilaurate, N,N-dimethylcyclohexylamine, TDCP, dimethyl methyl phosphate, tri(1-chloro-2-propyl) phosphate, and fumed silica, stir evenly at room temperature, then heat to 80°C and add the crosslinking agent, stir for 1 hour, and mix evenly to obtain component A; (3) Mixing isocyanate prepolymer, dibutyl phthalate, tri(2-chloroethyl) phosphate and tri(1-chloro-2-propyl) phosphate, stirring evenly, to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 25 parts of polyether polyol C with 100 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 70°C for 5 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020, YD-6205 and YD-450K in a mass ratio of 30:2:1; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 0.8:1, stir evenly at a low speed (200 rpm), pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm, and take out the sample after solidification.
[0031] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 98.6°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 65.1Mpa.
[0032] Example 2 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, 17 parts of cross-linking agent, and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; The crosslinking agent is composed of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 10:3:4; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C and add crosslinking agent, stir for 1 hour, mix evenly, and obtain component A; (3) Mix isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stir evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol C with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020, YD-6205 and YD-450K in a mass ratio of 40:4:5; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0033] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 98.5°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 66.4Mpa.
[0034] Example 3 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by mass: 90 parts of polyether polyol YD-307, 10 parts of polyether polyol YD-8335, 1.0 parts of A33, 0.1 parts of stannous octoate, 10 parts of triethyl phosphate, 5 parts of tri(2-chloroethyl) phosphate, 20 parts of tri(1-chloro-2-propyl) phosphate, 12 parts of crosslinking agent, and 3 parts of fumed silica; Component B: 120 parts of isocyanate prepolymer, 10 parts of TDCP, 10 parts of dimethyl methyl phosphate and 20 parts of dioctyl phthalate; The crosslinking agent is composed of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 6:2:4; (2) Mix polyether polyol YD-307, polyether polyol YD-8335, A33, stannous octoate, triethyl phosphate, tri(2-chloroethyl) phosphate, tri(1-chloro-2-propyl) phosphate, and fumed silica, stir evenly, then heat to 80°C and add a crosslinking agent, stir for 2 hours, and mix evenly to obtain component A; (3) Mixing isocyanate prepolymer, dioctyl phthalate, TDCP and dimethyl methyl phosphate, stirring evenly, to obtain component B; wherein the preparation method of isocyanate prepolymer comprises: mixing 20 parts of polyether polyol C with 100 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain isocyanate prepolymer; the polyether polyol C comprises YD-1020, YD-6205 and YD-450K in a mass ratio of 50:10:4; before mixing the polyether polyol C and phenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1.2:1, stir evenly at a low speed (400 rpm), pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm, and take out the sample after solidification.
[0035] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 97.5°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 64.3Mpa.
[0036] Example 4 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, 17 parts of cross-linking agent, and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; The cross-linking agent is composed of 3-chloro-4,4'-diaminodiphenylmethane and 3,5-diamino-4-chlorobenzoic acid isobutyl ester in a mass ratio of 10:3; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C and add crosslinking agent, stir for 1 hour, mix evenly, and obtain component A; (3) Mix isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stir evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol C with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020, YD-6205 and YD-450K in a mass ratio of 40:4:5; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0037] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 98.3°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 64.6Mpa.
[0038] Example 5 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, 17 parts of cross-linking agent, and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; The crosslinking agent is composed of 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 3:4; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C and add crosslinking agent, stir for 1 hour, mix evenly, and obtain component A; (3) Mix isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stir evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol C with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020, YD-6205 and YD-450K in a mass ratio of 40:4:5; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0039] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 98.7°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 62.8Mpa.
[0040] Example 6 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, 17 parts of cross-linking agent 4,4'-methylenebis(2-methyl-6-diethylaniline), and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C and add crosslinking agent, stir for 1 hour, mix evenly, and obtain component A; (3) Mix isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stir evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol C with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020, YD-6205 and YD-450K in a mass ratio of 40:4:5; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0041] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 97.9°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 61.2Mpa.
[0042] Example 7 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, 17 parts of cross-linking agent, and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; The crosslinking agent is composed of 3-chloro-4,4'-diaminodiphenylmethane and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 10:4; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C and add crosslinking agent, stir for 1 hour, mix evenly, and obtain component A; (3) Mix isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stir evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol C with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020, YD-6205 and YD-450K in a mass ratio of 40:4:5; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0043] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 98.4°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 63.5Mpa.
[0044] Comparative Example 1 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, 17 parts of cross-linking agent, and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; The crosslinking agent is composed of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 10:3:4; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C and add crosslinking agent, stir for 1 hour, mix evenly, and obtain component A; (3) Mixing isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stirring evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol YD-1020 with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; before mixing the polyether polyol YD-1020 and the polyphenyl polymethylene polyisocyanate, the mixture is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0045] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 99.8°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 60.7Mpa.
[0046] Comparative Example 2 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, 17 parts of cross-linking agent, and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; The crosslinking agent is composed of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 10:3:4; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C and add crosslinking agent, stir for 1 hour, mix evenly, and obtain component A; (3) Mix isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stir evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol C with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020 and YD-6205 in a mass ratio of 40:4; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0047] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 99.5°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 62.3Mpa.
[0048] Comparative Example 3 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, 17 parts of cross-linking agent, and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; The crosslinking agent is composed of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 10:3:4; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C and add crosslinking agent, stir for 1 hour, mix evenly, and obtain component A; (3) Mix isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stir evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol C with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020 and YD-450K in a mass ratio of 40:5; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0049] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 99.2°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 63.1Mpa.
[0050] Comparative Example 4 A method for preparing a coal mine reinforcement polyurethane material comprises the following steps: (1) Preparation of materials: Prepare component A by weight: 70 parts of polyether polyol YD-303, 30 parts of polyether polyol YD-204, 2.5 parts of A33, 5 parts of TDCP, 30 parts of tris(1-chloro-2-propyl) phosphate, and 1.0 part of fumed silica; Component B: 140 parts of isocyanate prepolymer, 5 parts of triethyl phosphate (TEP), 20 parts of tri(1-chloro-2-propyl) phosphate and 10 parts of dibutyl phthalate; (2) Mix polyether polyol YD-303, polyether polyol YD-204, A33, TDCP, tri(1-chloro-2-propyl) phosphate and fumed silica, stir evenly, then heat to 80°C, stir for 1 hour, and mix evenly to obtain component A; (3) Mix isocyanate prepolymer, dibutyl phthalate, triethyl phosphate (TEP) and tri(1-chloro-2-propyl) phosphate, and stir evenly to obtain component B; wherein the preparation method of the isocyanate prepolymer comprises: mixing 30 parts of polyether polyol C with 110 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 80°C for 4 hours to obtain the isocyanate prepolymer; the polyether polyol C comprises YD-1020, YD-6205 and YD-450K in a mass ratio of 40:4:5; before mixing the polyether polyol C with the polyphenyl polymethylene polyisocyanate, the polyether polyol C is subjected to a dehydration treatment, and the dehydration treatment comprises: adding the polyether polyol to a reaction kettle, passing nitrogen protection, heating to 110°C for dehydration for 2 hours, and then cooling to 40°C for standby use; (4) Mix component A and component B in a mass ratio of 1:1, stir evenly at a low speed (300 rpm), and pour into a cylindrical mold with a diameter of 50 mm and a height of 100 mm. After solidification, take out the sample.
[0051] The maximum reaction temperature was measured in accordance with AQ / T 1089-2020, and the maximum reaction temperature was 94.6°C. After the sample was placed at room temperature for 3 days, the compressive strength was measured in accordance with AQ / T 1089-2020, and the compressive strength was 35.8Mpa.
[0052] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A coal mine reinforcement polyurethane material, It is characterized in that It comprises component A and component B in a mass ratio of 0.8-1.2:1; wherein, by mass, component A comprises: 70-90 parts of polyether polyol A, 10-30 parts of polyether polyol B, 0.1-3.0 parts of catalyst, 10-40 parts of flame retardant, 1-20 parts of crosslinking agent, and 0.5-3 parts of fumed silica; Component B includes: 100-140 parts of isocyanate prepolymer, 10-30 parts of flame retardant and 5-20 parts of toughening agent; The polyether polyol A is a polyether polyol with a functionality of 2-4, a hydroxyl value of 150-500 mgKOH / g, and a viscosity of 200-1000 mPa.s at 25°C; The polyether polyol B is a polyether polyol having a functionality of 2-6, a hydroxyl value of 150-450 mgKOH / g, and a viscosity of 50-3500 mPa.s at 25°C; The cross-linking agent is selected from one or more of 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline); The preparation method of the isocyanate prepolymer comprises: mixing 5-30 parts of polyether polyol C with 70-120 parts of polyphenyl polymethylene polyisocyanate, and keeping the mixture at 70-90° C. for 3-5 hours to obtain the isocyanate prepolymer; The polyether polyol C is composed of YD-1020, YD-6205 and YD-450K in a mass ratio of 30-50:1-10:1-10.
2. A coal mine reinforcement polyurethane material according to claim 1, It is characterized in that The cross-linking agent is 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 1-20:1-10:1-10.
3. A coal mine reinforcement polyurethane material according to claim 1, It is characterized in that The cross-linking agent is 3-chloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4-chlorobenzoic acid isobutyl ester and 4,4'-methylenebis(2-methyl-6-diethylaniline) in a mass ratio of 5-15:2-5:2-5.
4. A coal mine reinforcement polyurethane material according to claim 1, It is characterized in that The polyether polyol C is composed of YD-1020, YD-6205 and YD-450K in a mass ratio of 40:4:
5.
5. A coal mine reinforcement polyurethane material according to claim 1, It is characterized in that The catalyst is an organic metal catalyst and / or an organic amine catalyst.
6. A coal mine reinforcement polyurethane material according to claim 5, It is characterized in that The organic metal catalyst is dibutyltin dilaurate and / or stannous octoate; the organic amine catalyst is N,N-dimethylcyclohexylamine and / or A33.
7. A coal mine reinforcement polyurethane material according to claim 1, It is characterized in that The flame retardant is selected from one or more of tris(1,3-dichloro-2-propyl) phosphate, triethyl phosphate, dimethyl methyl phosphate, tris(2-chloroethyl) phosphate, and tris(1-chloro-2-propyl) phosphate.
8. A coal mine reinforcement polyurethane material according to claim 1, It is characterized in that The toughening agent is dioctyl phthalate and / or dibutyl phthalate.
9. A coal mine reinforcement polyurethane material according to claim 1, It is characterized in that The particle size of the fumed silica is 10-20 microns.
10. The method for preparing the coal mine reinforcement polyurethane material according to any one of claims 1 to 9, It is characterized in that The following steps are involved: A. Mix polyether polyol A, polyether polyol B, catalyst, flame retardant and fumed silica, stir evenly at room temperature, then heat to 80-100°C and add crosslinking agent, stir for 1-2h, and mix evenly to obtain component A; B. Mix the isocyanate prepolymer, toughening agent and flame retardant, and stir evenly at room temperature to obtain component B; C. Mix component A and component B in proportion and react.