Tunnel gushing mud blocking material and preparation method thereof

Abstract

The invention discloses a tunnel gushing mud plugging material and a preparation method thereof. The plugging material comprises a polyurethane prepolymer, epoxy resin A, organosilicon polyether modified epoxy resin and a curing agent, the organosilicon polyether modified epoxy resin is prepared according to the following steps: S1, in an inert atmosphere, performing primary ring opening polymerization on polyethylene polyamine and propylene oxide under the action of a catalyst to obtain hydroxyl-terminated hyperbranched polyether; then adding an epoxy compound with alkenyl and epoxy resin B, and carrying out secondary ring opening polymerization to obtain alkenyl-terminated hyperbranched polyether modified epoxy resin; s2, mixing and reacting the alkenyl-terminated hyperbranched polyether modified epoxy resin with a silane compound containing a silicon hydrogen group and an alkoxy group in the presence of a platinum catalyst to obtain the organosilicon polyether modified epoxy resin. The plugging material provided by the invention has good fluidity and water resistance.

Description

Technical Field

[0001] The present application relates to the field of polymer sealing materials, and in particular to a tunnel mud-gushing plugging material and a preparation method thereof. Background Art

[0002] In tunnel construction, mud and water inrush in tunnels refers to the phenomenon that mud and water in loose soil layers or cracks around the tunnel suddenly rush into the tunnel due to the pressure of groundwater during tunnel excavation. This phenomenon will not only cause construction interruption, but may also cause damage to the tunnel structure and even cause serious safety accidents. At present, sealing cracks with grouting sealing materials is an effective way to solve the problem of mud and water inrush in tunnels.

[0003] At present, the commonly used grouting plugging materials mainly include cement slurry, chemical slurry (such as epoxy resin, polyurethane, etc.) and composite slurry. These materials each have their own characteristics and advantages. Cement slurry is low-cost and widely available, and is suitable for plugging larger cracks and voids. However, it has a long curing time, low early strength, and poor permeability to small cracks. The epoxy resin in the chemical slurry has good adhesion and chemical corrosion resistance, fast curing speed, and is suitable for rapid plugging and reinforcement. However, epoxy resin has obvious problems of high shrinkage and high hardness, which may cause gaps between the plugging material and the substrate, affecting the plugging effect, and even requiring rework and repair. In order to overcome the above-mentioned shortcomings of epoxy resin, researchers tried to add polyurethane, using its micro-expansion effect to effectively solve the shrinkage problem. At the same time, the interpenetrating network structure formed by polyurethane and epoxy resin can significantly improve the strength and toughness of the material.

[0004] Although the composite material of epoxy resin and polyurethane has improved the performance of plugging materials to a certain extent, epoxy resin still has the problems of high viscosity and poor fluidity, which limits its ability to penetrate and fill small gaps. Especially under complex geological conditions, it is difficult to ensure the uniform distribution of plugging materials, affecting the overall plugging effect. Summary of the invention

[0005] In order to solve the defect of epoxy-polyurethane plugging material in fluidity, the present application provides a tunnel mud plugging material and a preparation method thereof.

[0006] In a first aspect, the present application provides a tunnel mud plugging material, which includes the following raw materials in parts by weight: 50-70 parts of polyurethane prepolymer, 20-30 parts of epoxy resin A, 10-20 parts of silicone polyether modified epoxy resin, 3-7 parts of curing agent; The organosilicon polyether modified epoxy resin is prepared according to the following steps: S1, in an inert atmosphere, a polyethylene polyamine and propylene oxide are subjected to a primary ring-opening polymerization under a catalyst to obtain a terminal hydroxyl hyperbranched polyether; then an epoxy compound having an alkenyl group and an epoxy resin B are added to carry out a secondary ring-opening polymerization to obtain a terminal alkenyl hyperbranched polyether modified epoxy resin; S2. The terminal olefin hyperbranched polyether modified epoxy resin is mixed with a silicon hydrogen group and an alkoxy silane compound under a platinum catalyst to obtain an organosilicon polyether modified epoxy resin.

[0007] In any of the above technical solutions, the mass ratio of the polyethylene polyamine to propylene oxide, the epoxy compound having an alkenyl group and the epoxy resin is 1:8-10:3-5:40-60.

[0008] In any of the above technical solutions, the polyethylene polyamine is selected from one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0009] In any of the above technical solutions, the epoxy compound having an alkenyl group is selected from one or more of allyl glycidyl ether, glycidyl methacrylate, and vinyl ethylene oxide.

[0010] In any of the above technical solutions, the silicon hydrogen group and alkoxy silane compound has the following general formula: (RO) n S H 4-n , n is greater than or equal to 2.

[0011] Exemplarily, the silicon hydrogen group and alkoxy silane compound is selected from one or more of trimethoxysilane, triethoxysilane, ethyldimethoxysilane and methyldimethoxysilane.

[0012] It should be noted that when there are multiple alkoxy groups, the resin and the cement matrix can be effectively cross-linked, thereby improving the mechanical strength of the plugging material after curing.

[0013] In any of the above technical solutions, the mass ratio of the terminal olefin hyperbranched polyether modified epoxy resin to the silicon hydrogen group and alkoxy silane compound is 1:2-4.

[0014] In any of the above technical solutions, in step S1, the catalyst is double metal cyanide (DMC), and the reaction temperature of the ring-opening polymerization is 90-120°C.

[0015] In any of the above technical solutions, the time for the one-time ring-opening polymerization is 5 to 10 hours.

[0016] In any of the above technical solutions, the time for the secondary ring-opening polymerization is 8 to 12 hours.

[0017] In any of the above technical solutions, the epoxy resin B is bisphenol A epoxy resin, and the epoxy equivalent is 180 to 200 g / mol.

[0018] In any of the above technical solutions, the -NCO% content of the polyurethane prepolymer is about 15% to 25%.

[0019] It should be noted that the polyurethane prepolymer of the present application can be directly purchased from the market, or can be prepared by reacting polyol with polyisocyanate.

[0020] In any of the above technical solutions, the epoxy resin A is selected from one or more of E-35, E-44, and E-51.

[0021] In any of the above technical solutions, the platinum catalyst is one or more of an alcohol solution of chloroplatinic acid, a platinum catalyst coordinated with tetrahydrofuran, and a platinum catalyst coordinated with divinyltetramethylsiloxane.

[0022] In any of the above technical solutions, the curing agent is an amine curing agent and an organic tin chelate in a mass ratio of 8 to 10:1.

[0023] In any of the above technical solutions, the amine curing agent is selected from one or two of DMP-30, HDG-A / B epoxy resin curing accelerator, tertiary amine accelerator (triethylamine, triethanolamine, BMDA, DBU, DMP-10, pyridine), quaternary ammonium salt accelerator, and fatty amine accelerator.

[0024] In any of the above technical solutions, the organic tin catalyst is stannous octoate or dibutyltin dilaurate.

[0025] In step S1 of the present application, a hydroxyl-terminated polyether with a hyperbranched structure is obtained by a first ring-opening polymerization, and then a hyperbranched polyether terminated with an alkenyl group is obtained by a second ring-opening polymerization and grafted onto the surface of the epoxy resin. In step S2, the alkenyl group is subjected to addition polymerization with the silicon hydrogen group in the silicon hydrogen group and alkoxysilane compound, thereby introducing the siloxane group into the epoxy resin.

[0026] The above-mentioned reaction-grafted organosilicon polyether chain segment has a lower cohesive energy density and higher flexibility, and can reduce the viscosity of epoxy resin. At the same time, the chain segment can increase the slip ability between molecules, reduce the entanglement between epoxy resin molecular chains and the interaction force between molecules, thereby improving the fluidity of epoxy resin. In addition, the organosilicon polyether chain segment contains hydrophobic organosilicon groups, which can effectively repel water molecules and improve the water resistance of the material.

[0027] In addition, the siloxane groups contained in the silicone chain segments introduced by the epoxy resin have good cross-linking reaction properties. The silanol groups formed when they come into contact with water can form good chemical connections with the polyurethane prepolymer and the tunnel cement matrix, thereby improving the bonding strength of the sealing material and its mechanical strength after curing.

[0028] It should be noted that the amount of organosilicon polyether modified epoxy resin in this application should be appropriate, and excessive amount may affect the mechanical properties of the plugging material after curing. Therefore, it is compounded with conventional epoxy resin A in this application.

[0029] In any of the above technical solutions, the raw materials of the material also include 10 to 30 parts of silane coupling agent modified calcium carbonate.

[0030] In any of the above technical solutions, the silane coupling agent modified calcium carbonate is composed of calcium carbonate, isocyanate coupling agent and phenyl silane coupling agent in a mass ratio of 100:3-6:1-5.

[0031] In any of the above technical solutions, the isocyanate coupling agent is selected from 3-isocyanate propyl trimethoxy silane and / or 3-isocyanate propyl triethoxy silane.

[0032] In any of the above technical solutions, the phenylsilane coupling agent is selected from one or more of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and phenylmethyldimethoxysilane.

[0033] In any of the above technical solutions, the median particle size of the calcium carbonate is 1 to 50 μm, more preferably 10 to 20 μm.

[0034] Exemplarily, the median particle size of the calcium carbonate is 5 μm, 10 μm, 15 μm, 25 μm or 30 μm.

[0035] The doping of calcium carbonate filler can significantly improve the mechanical strength of the plugging material so that it can withstand greater pressure loads. The present application uses a silane coupling agent to modify it, on the one hand to improve its surface properties and promote its effective dispersion in the resin matrix; on the other hand, by introducing an isocyanate silane coupling agent, it can react and crosslink with the resin matrix, especially the polyurethane prepolymer, to enhance the interfacial bonding force and improve the compressive strength of the material after curing. In addition, a phenyl silane coupling agent is used to enhance the hydrophobicity and water resistance of the material after curing.

[0036] In a second aspect, the present application provides a method for preparing a tunnel mud plugging material, which comprises the following steps: According to the ratio of any of the above-mentioned plugging materials, the polyurethane prepolymer, epoxy resin A and silicone polyether modified epoxy resin are uniformly mixed to obtain a resin mixture; Mix the resin mixture with the curing agent and stir well.

[0037] In summary, this application has the following beneficial effects: The present application adds an appropriate amount of silicone polyether modified epoxy resin into the epoxy-polyurethane composite resin system, which effectively improves the current epoxy resin's lack of fluidity, improves its penetration and filling effect on cracks, and improves the plugging effect. Secondly, the resin also effectively enhances the anti-seepage and water-resistant properties of the plugging material. Thirdly, it introduces multiple siloxane groups, which can effectively connect the resin matrix and the tunnel cement matrix, further improving the bonding strength and mechanical strength of the plugging material. DETAILED DESCRIPTION

[0038] Preparation Example Preparation Example 1-1, a silicone polyether modified epoxy resin, is prepared according to the following steps: S1. Add 100g triethylenetetramine and 900g propylene oxide into a reactor, introduce nitrogen, and try to exhaust the air in the reactor. Add 50ppm of double metal cyanide (DMC) catalyst to the above reaction materials, heat to 105℃, and carry out a ring-opening polymerization reaction for 6h. After the reaction is completed, cool and vacuum to remove unreacted monomers to obtain terminal hydroxyl hyperbranched polyether. Then add 380g allyl glycidyl ether and 500g bisphenol A epoxy resin (epoxy equivalent is 180g / mol) and 50ppm double metal cyanide (relative to the amount of allyl glycidyl ether and bisphenol A epoxy resin) to the reactor, heat to 115℃, carry out secondary ring-opening polymerization, and react for 10h; after the reaction is completed, cool and vacuum to remove unreacted raw materials to obtain terminal olefin hyperbranched polyether modified epoxy resin.

[0039] S2. Take 100g of terminal olefin hyperbranched polyether modified epoxy resin and 300g of trimethoxysilane into a reaction kettle, stir evenly, then add 50ppm of divinyltetramethylsiloxane coordinated platinum catalyst (0.5% platinum content), heat to 80°C, react for 8h, cool after the reaction, vacuum to remove unreacted trimethoxysilane, and obtain silicone polyether modified epoxy resin.

[0040] Preparation Example 1-2, a silicone polyether modified epoxy resin, is prepared according to the following steps: S1. Put 100g of tetraethylenepentamine and 1000g of propylene oxide into a reactor, pass nitrogen, and try to exhaust the air in the reactor. Add 60ppm of double metal cyanide (DMC) catalyst of the above reaction materials, heat to 110℃, and carry out a ring-opening polymerization reaction for 6h. After the reaction is completed, cool and vacuum remove unreacted monomers to obtain terminal hydroxyl hyperbranched polyether. Then add 460g of allyl glycidyl ether and 420g of bisphenol A epoxy resin (epoxy equivalent is 180g / mol) and 50ppm of double metal cyanide (relative to the amount of allyl glycidyl ether and bisphenol A epoxy resin) into the reactor, heat to 110℃, carry out secondary ring-opening polymerization, and react for 12h; after the reaction is completed, cool and vacuum remove unreacted raw materials to obtain terminal olefin hyperbranched polyether modified epoxy resin.

[0041] S2. Take 100g of terminal olefin hyperbranched polyether modified epoxy resin and 360g of methyldimethoxysilane and put them into a reaction kettle, stir them evenly, then add 50ppm of divinyltetramethylsiloxane coordinated platinum catalyst (0.5% platinum content), heat to 90°C, react for 6h, cool after the reaction, vacuum to remove unreacted methyldimethoxysilane, and obtain silicone polyether modified epoxy resin.

[0042] Preparation Example 1-3, a silicone polyether modified epoxy resin, is prepared according to the following steps: S1. Add 100g triethylenetetramine and 850g propylene oxide into a reactor, introduce nitrogen, and try to exhaust the air in the reactor. Add 50ppm of double metal cyanide (DMC) catalyst to the above reaction materials, heat to 105℃, and carry out a ring-opening polymerization reaction for 6h. After the reaction is completed, cool and vacuum to remove unreacted monomers to obtain terminal hydroxyl hyperbranched polyether. Then add 320g glycidyl methacrylate and 600g bisphenol A epoxy resin (epoxy equivalent is 200g / mol) and 70ppm double metal cyanide (relative to the amount of allyl glycidyl ether and bisphenol A epoxy resin) to the reactor, heat to 115℃, carry out secondary ring-opening polymerization, and react for 8h; after the reaction is completed, cool and vacuum to remove unreacted raw materials to obtain terminal olefin hyperbranched polyether modified epoxy resin.

[0043] S2. Take 100g of terminal olefin hyperbranched polyether modified epoxy resin and 200g of trimethoxysilane into a reaction kettle, stir evenly, then add 50ppm of divinyltetramethylsiloxane coordinated platinum catalyst (0.5% platinum content), heat to 80°C, react for 7h, cool after the reaction, vacuum to remove unreacted trimethoxysilane, and obtain silicone polyether modified epoxy resin.

[0044] Preparation Example 1-4, a hyperbranched polyether modified epoxy resin, is prepared according to the following steps: 100g triethylenetetramine and 900g propylene oxide were put into the reactor, nitrogen was introduced, and the air in the reactor was exhausted as much as possible. 50ppm double metal cyanide (DMC) catalyst was added to the above reaction materials, the temperature was raised to 105℃, and a ring-opening polymerization reaction was carried out for 6h. After the reaction was completed, the mixture was cooled, and the unreacted monomers were removed by vacuum to obtain a terminal hydroxyl hyperbranched polyether. Then 900g bisphenol A epoxy resin (epoxy equivalent of 180g / mol) and 50ppm double metal cyanide (the amount of bisphenol A epoxy resin) were added to the reactor, the temperature was raised to 115℃, and a secondary ring-opening polymerization was carried out for 8h; after the reaction was completed, the mixture was cooled, and the unreacted raw materials were removed by vacuum to obtain a hyperbranched polyether modified epoxy resin.

[0045] Preparation Example 2-1, a silane coupling agent modified calcium carbonate, prepared according to the following method: Add 1000g calcium carbonate (median particle size 15μm), 45g 3-isocyanatepropyltrimethoxysilane, 30g phenyltrimethoxysilane and 25% anhydrous ethanol by mass of calcium carbonate into the reactor, stir and mix, heat to 60°C, stir and react for 2h, release the material after the reaction is completed, remove the upper layer of anhydrous ethanol after standing for a period of time, and then transfer the precipitate to a 110°C oven and dry it for 2h.

[0046] Preparation Example 2-2, a silane coupling agent modified calcium carbonate, prepared according to the following method: Add 1000g calcium carbonate (median particle size 20μm), 30g 3-isocyanatepropyltrimethoxysilane, 15g phenyltrimethoxysilane and 25% anhydrous ethanol by mass of calcium carbonate into the reactor, stir and mix, heat to 60°C, stir and react for 1.5h, release the material after the reaction is completed, remove the anhydrous ethanol on the upper layer after standing for a period of time, and then transfer the precipitate to a 110°C oven and dry it for 2h.

[0047] Preparation Example 2-3, a silane coupling agent modified calcium carbonate, prepared according to the following method: Add 1000g calcium carbonate (median particle size 10μm), 60g 3-isocyanatepropyltrimethoxysilane, 50g phenyltrimethoxysilane and 25% anhydrous ethanol by mass of calcium carbonate into the reactor, stir and mix, heat to 60℃, stir and react for 2h, release the material after the reaction is completed, remove the anhydrous ethanol on the upper layer after standing for a period of time, and then transfer the precipitate to a 110℃ oven and dry it for 2h.

[0048] Preparation Example 2-4, a silane coupling agent-modified calcium carbonate, differs from Preparation Example 2-1 in that 3-isocyanatepropyltrimethoxysilane is replaced with an equal amount of phenyltrimethoxysilane.

[0049] Preparation Example 2-5, a silane coupling agent-modified calcium carbonate, is different from Preparation Example 2-1 in that phenyltrimethoxysilane is replaced by an equal amount of 3-isocyanatepropyltrimethoxysilane.

[0050] Example 1, a tunnel mud plugging material, the preparation steps are as follows: 6 kg of polyurethane prepolymer (-NCO content is 20%), 2.3 kg of epoxy resin A (E-44), 1.5 kg of silicone polyether modified epoxy resin of Preparation Example 1-1 and 1.9 kg of silane coupling agent modified calcium carbonate of Preparation Example 2-1 were mixed evenly to obtain a resin mixture. Epoxy resin A (E-44) Add 0.45 kg of DMP-30 and 0.05 kg of dibutyltin dilaurate to the resin mixture, and stir to obtain the mixture.

[0051] Example 2, a tunnel mud plugging material, the preparation steps are as follows: 5.2 kg of polyurethane prepolymer (-NCO content is 20%), 2.8 kg of epoxy resin A (E-51, 2.0 kg of silicone polyether modified epoxy resin of Preparation Example 1-2 and 1.2 kg of silane coupling agent modified calcium carbonate of Preparation Example 2-2 were mixed evenly to obtain a resin mixture.

[0052] Add 0.56 kg DMP-30 and 0.07 kg dibutyltin dilaurate to the resin mixture, and stir to obtain the mixture.

[0053] Example 3, a tunnel mud plugging material, the preparation steps are as follows: 6.5 kg of polyurethane prepolymer (-NCO content is 25%), 2.0 kg of epoxy resin A (E-44), 1.1 kg of silicone polyether modified epoxy resin of Preparation Example 1-3 and 2.8 kg of silane coupling agent modified calcium carbonate of Preparation Example 2-3 were mixed evenly to obtain a resin mixture.

[0054] Add 0.36 kg of DMP-30 and 0.04 kg of dibutyltin dilaurate to the resin mixture, and stir to obtain the mixture.

[0055] Example 4, a tunnel mud plugging material, is different from Example 1 in that the silane coupling agent-modified calcium carbonate of Preparation Example 2-1 is replaced by an equal amount of the silane coupling agent-modified calcium carbonate of Preparation Example 2-4.

[0056] Example 5, a tunnel mud plugging material, is different from Example 1 in that the silane coupling agent-modified calcium carbonate of Preparation Example 2-1 is replaced by an equal amount of the silane coupling agent-modified calcium carbonate of Preparation Example 2-5.

[0057] Example 6, a tunnel mud plugging material, differs from Example 1 in that no silane coupling agent-modified calcium carbonate is added.

[0058] Comparative Example Comparative Example 1, a tunnel mud plugging material, is different from Example 6 in that the organosilicon polyether modified epoxy resin of Preparation Example 1-1 is replaced by an equal amount of the organosilicon polyether modified epoxy resin of Preparation Example 1-4.

[0059] Comparative Example 2, a tunnel mud plugging material, is different from Example 6 in that the silicone polyether-modified epoxy resin of Preparation Example 1-1 is replaced by an equal amount of E-44 epoxy resin.

[0060] Performance testing The implementation standard of this application refers to the provisions of JC / T 1041-2007 "Epoxy Resin Grouting Materials for Concrete Cracks".

[0061] 1. Initial viscosity: According to the provisions of GB / T 2794-1995, the initial viscosity of the plugging material is measured using a rotational viscometer.

[0062] 2. Impermeability pressure: measured in accordance with the provisions of 6.2.8 of GB / T 18445-2001.

[0063] 3. Compressive strength: measured in accordance with the relevant provisions of compression test in GB / T 2567-2008.

[0064] 4. Bond strength: Measured in accordance with the provisions of Section 7.9 of JC / T 1041-2007.

[0065] Table 1. Performance test results It can be seen from Examples 1 to 6 and Comparative Examples 1 to 2 and Table 1 that the embodiments of the present application use an appropriate amount of silicone polyether modified epoxy resin in the epoxy-polyurethane system, which can effectively alleviate the problem of poor fluidity of the epoxy-polyurethane plugging material and ensure the filling and plugging effect of the plugging material on the cracks caused by mud and water inrush in the tunnel.

[0066] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A tunnel mud plugging material, characterized in that: The invention comprises the following raw materials in parts by weight: 50-70 parts of polyurethane prepolymer, 20-30 parts of epoxy resin A, 10-20 parts of silicone polyether modified epoxy resin, 3-7 parts of curing agent; The organosilicon polyether modified epoxy resin is prepared according to the following steps: S1, in an inert atmosphere, a polyethylene polyamine and propylene oxide are subjected to a primary ring-opening polymerization under a catalyst to obtain a terminal hydroxyl hyperbranched polyether; then an epoxy compound having an alkenyl group and an epoxy resin B are added to carry out a secondary ring-opening polymerization to obtain a terminal alkenyl hyperbranched polyether modified epoxy resin; S2. The terminal olefin hyperbranched polyether modified epoxy resin is mixed with a silicon hydrogen group and an alkoxy silane compound under a platinum catalyst to obtain an organosilicon polyether modified epoxy resin.

2. The material according to claim 1, characterized in that The mass ratio of the polyethylene polyamine to propylene oxide, the epoxy compound having an alkenyl group and the epoxy resin is 1:8-10:3-5:40-60.

3. The material according to claim 1, characterized in that The polyethylene polyamine is selected from one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

4. The material according to claim 1, characterized in that The epoxy compound having an alkenyl group is selected from one or more of allyl glycidyl ether, glycidyl methacrylate, and vinyl ethylene oxide.

5. The material according to claim 1, characterized in that The silicon hydrogen group and alkoxy silane compound is selected from one or more of trimethoxy silane, triethoxy silane, ethyl dimethoxy silane and methyl dimethoxy silane.

6. The material according to claim 1, characterized in that In step S1, the catalyst is double metal cyanide, and the reaction temperature of the ring-opening polymerization is 90-120°C.

7. The material according to claim 1, characterized in that The curing agent is an amine curing agent and an organic tin chelate in a mass ratio of 8 to 10:

1.

8. The material according to claim 1, characterized in that The raw materials of the material also include 10 to 30 parts of silane coupling agent modified calcium carbonate.

9. The material according to claim 1, characterized in that The silane coupling agent modified calcium carbonate comprises calcium carbonate, isocyanate coupling agent and phenyl silane coupling agent in a mass ratio of 100:3-6:1-5.

10. A method for preparing a tunnel mud plugging material, characterized in that: The steps include: According to the material ratio described in any one of claims 1 to 9, the polyurethane prepolymer and the epoxy resin A are uniformly mixed to obtain a resin mixture; Mix the resin mixture with the curing agent and stir well.

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