WO2020103621A1 - 用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料及制备方法 - Google Patents

用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料及制备方法

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Publication number
WO2020103621A1
WO2020103621A1 PCT/CN2019/112042 CN2019112042W WO2020103621A1 WO 2020103621 A1 WO2020103621 A1 WO 2020103621A1 CN 2019112042 W CN2019112042 W CN 2019112042W WO 2020103621 A1 WO2020103621 A1 WO 2020103621A1
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WIPO (PCT)
Prior art keywords
water
grouting material
preparation
initiator
absorbing resin
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PCT/CN2019/112042
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English (en)
French (fr)
Inventor
李术才
刘人太
马晨阳
陈孟军
刘衍凯
王振军
张春雨
李修浩
段少龙
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山东大学
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Publication date
Application filed by 山东大学 filed Critical 山东大学
Priority to US17/275,998 priority Critical patent/US11905352B2/en
Publication of WO2020103621A1 publication Critical patent/WO2020103621A1/zh

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    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D11/00—Lining tunnels, galleries or other underground cavities, e.g. large underground chambers; Linings therefor; Making such linings in situ, e.g. by assembling
    • E21D11/38—Waterproofing; Heat insulating; Soundproofing; Electric insulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the invention belongs to the technical field of plugging materials for underground engineering, and particularly relates to an expanded polymer grouting material for blocking high-pressure large-flow karst surge water and a preparation method thereof.
  • Water inrush is one of the major geological disasters in underground engineering.
  • the construction of underground engineering in China is getting more and more attention, and the geological conditions facing it are gradually becoming more complicated.
  • the structure is prone to geological disasters such as landslides, water inrush and large deformation of surrounding rocks. Especially in the water-rich fracture zone, the surrounding rock is relatively broken, and the amount of water inrush is large.
  • the environmentally friendly elastic propylene chloride grouting material includes component A: Acrylic ester, cross-linking agent I, cross-linking agent II, accelerator; component B: water, initiator.
  • the environment-friendly elastic acrylate grouting material has the advantages of low grouting viscosity, consolidation elongation of more than 200%, environmental protection and other advantages, and can be used for anti-seepage and plugging of expansion joints in a long-term water environment.
  • the grouting material has the advantages of environmental protection and non-toxicity. It is suitable for anti-seepage and plugging of expansion joints, but it is not suitable for operation under high-pressure and large-flow water flow. It is easy to be diluted and difficult to gel, and the two-component grouting material limits its Use and development.
  • Chinese patent document 201711475087.8 discloses an acrylate aqueous solution grouting material and preparation method thereof.
  • the grouting material includes: component A is an acrylate aqueous solution, crosslinking agent and accelerator; component B is water, water-based polymer emulsion and initiator Agent.
  • the acrylic acid aqueous solution grouting material has the characteristics of low grouting viscosity, high strength, low shrinkage in dry environment, etc., and significantly increases the risk of plugging.
  • this acrylate grouting material is mainly used to control sewer water penetration, stabilization and solidification of loose soil, and is not suitable for blocking high-pressure large-flow surge water, because component B is easily diluted by dynamic water and cannot be made
  • the gelation of component A, the form of its two-component grouting material limits its use in plugging water.
  • Chinese patent document 201010172263.2 discloses a quick-setting high-strength expansive mine sealing material, which is prepared from raw materials high-aluminum cement, citric acid, lime, gypsum and sodium lauryl sulfate.
  • the material can be rapidly solidified under the condition of high water-cement ratio, the volume expansion during the solidification process (the maximum free expansion rate can reach more than 10% in one day), and the strength of the consolidated body is high (the strength reaches 3-4MPa in one day).
  • this quick-setting high-strength expansive mine sealing material is an inorganic chemical material, which is mainly used for the reinforcement of mine surrounding rock and the sealing of grouting holes. It has a certain expansion effect, but the expansion ratio is only 10%, and it cannot achieve Blocking treatment of rushing water in karst pipeline and broken zone.
  • Chinese patent document 201110007241.5 discloses a polymer polymerization reinforced water plugging grouting material for underground engineering and its construction process.
  • the grouting material is composed of two low-viscosity liquid substances of resin and catalyst.
  • the grouting material is composed of resin and catalyst. It consists of a low-viscosity liquid component that forms an inert foam after the reaction and has a very high expansion rate.
  • this polymer polymer reinforced water plugging grouting material belongs to polyurethane grouting material, which is derived from the reaction of polyether polyol and polyisocyanate, has the characteristics of foam expansion, and is suitable for coal rock reinforcement, crack filling and leakage Water prevention, but the polymer polymer reinforced water plugging grouting material is easily diluted under the condition of large flow surge water, forming a band-shaped gel along the direction of water flow, which is carried deep into the formation without a surge water seal The effect of blocking.
  • Chinese patent document 201711162326.4 discloses an expansive soft rock roadway grouting material, the grouting material is composed of a matrix component and an externally mixed component, the matrix component includes ultrafine cement, fly ash, silica fume, externally mixed group Points include high-efficiency water reducer and graphite powder stabilizer.
  • the slurry made of the grouting material has good fluidity and stability, high early and late strength, good impermeability and durability, and can inhibit the deformation of the surrounding rock during the grouting process of the expansive soft rock roadway during the grouting process to avoid the slurry injection.
  • the surrounding rock cracks are closed, which can significantly improve the injectability of the surrounding rock cracks of the expansive soft rock roadway and the performance of water blocking and reinforcement.
  • the grouting material is an inorganic chemical material, mainly composed of cement fly ash, which is used to improve the injectability of the surrounding rock cracks of the expansive soft rock roadway and the performance of water plugging and reinforcement.
  • the main engineering problems solved are caused by the surrounding rock cracks
  • the seepage water disaster is not suitable for the geological disaster of high-pressure and large-flow surge water in karst pipelines.
  • the present invention aims to provide an expanded polymer grouting material for high-pressure and large-flow karst inrush water treatment and a preparation method thereof.
  • the polymer grouting material of the present invention can effectively be stuck between the rocks in the water-rich fracture zone after water absorption and expansion, continuously accumulate, increase the viscous force of the water in the fissures, reduce the water cross section of the water-rich fracture zone, and effectively reduce The flow of inrush water can realize the treatment of inrush water in the water-rich broken zone.
  • the polymer grouting material of the present invention effectively solves the technical problem that the grouting material is difficult to retain under the condition of water inrush; at the same time, the grouting material of the present invention is green and pollution-free, and the expansion time is adjustable from 1 to 60 minutes.
  • the expansion ratio is as high as 101-304 times.
  • the first object of the present invention is to provide a method for preparing an expanded polymer grouting material for treatment of high-pressure and large-flow karst inrush water.
  • the second object of the present invention is to provide an expanded polymer grouting material prepared by the above method.
  • the third object of the present invention is to provide a composition of an expanded polymer grouting material prepared by the above method.
  • the fourth object of the present invention is to provide the preparation method of the above-mentioned expanded polymer grouting material, the product prepared therefrom, and the application of the composition of the product.
  • the present invention discloses a method for preparing an expanded polymer grouting material for high-pressure large-flow karst inrush water treatment, which includes the following steps:
  • the synthesis method of the precursor used in the present invention is a static solution polymerization method. In this method, a polymerization monomer and a crosslinking agent and other additives are formulated into a solution, and then placed at a certain temperature to react, the operation is simple and the cost is low;
  • step (2) Add an initiator to the precursor obtained in step (1), raise the temperature, obtain a hydrogel after the reaction, and pulverize the hydrogel to obtain a primary polymer water-absorbing resin;
  • step (3) Spray the surface cross-linking agent on the surface of the primary polymer water-absorbing resin obtained in step (2), and then dry the product for use; spraying the surface cross-linking agent on the surface can effectively regulate the cross-linking of the surface of the primary polymer water-absorbing resin Degree, so that the primary polymer water-absorbing resin has the characteristics of delayed expansion and high gel strength;
  • the inorganic water-conducting agent is prepared as a suspension, and the suspension is sprayed onto the product obtained by drying in step (3), and dried to obtain a granular expanded polymer grouting material.
  • step (1) the mass concentration of the acrylic acid is 25-45%. Tests show that as the monomer concentration increases, the water absorption rate of the polymer water-absorbent resin decreases to varying degrees. When the monomer concentration is less than 25%, it is difficult to polymerize to form a gel, and due to the presence of excessive water-soluble substances, it is not accurate The water absorption rate of the superabsorbent resin was measured. In addition, deionized water can be used to dilute acrylic acid to a set concentration, which is convenient and does not introduce impurities.
  • the polymer water-absorbing resin comonomer includes polyvinyl alcohol, acrylamide, methacrylamide or acrylonitrile. These resin-based superabsorbent resins are rich in raw materials, low in price, and have the characteristics of anti-corrosion and anti-change, can be stored for a long time, and have excellent comprehensive water absorption performance;
  • the raw material of the slurry water blocking material is, for example, starch, hydroxyethyl cellulose, methyl cellulose or carboxymethyl cellulose as a polymer water-absorbing resin comonomer.
  • step (1) the addition ratio of the polymer water-absorbing resin comonomer is 0.5-20% of the mass of acrylic acid in step (1).
  • the polymer water-absorbing resin comonomer mainly plays a role of further strengthening the water-absorbing performance of the grouting material, and its addition amount should be controlled between 0.5-20%, and the effect of too little addition is not obvious.
  • there is an additional process which increases the complexity of the process; too much addition is not conducive to the regulation of the expansion time and expansion ratio of the grouting material.
  • the addition ratio of the crosslinking agent is 0.5-2% of the mass of acrylic acid in step (1).
  • the type and cross-linking degree of the cross-linking agent have a great influence on the water absorption rate of the high water-absorbent resin.
  • the water absorption capacity of the resin decreases with the increase of the cross-linking degree. From the perspective of improving the water absorption rate of the water-absorbent resin, the Under the premise that the water-absorbent resin does not dissolve, the degree of cross-linking should be reduced as much as possible, but the resin after water absorption shows the elastic behavior of rubber, and its gel strength is proportional to the degree of cross-linking. Reducing the degree of cross-linking will cause the gel strength to decrease.
  • the present invention controls the amount of cross-linking agent between 0.5% -1.2%.
  • the crosslinking agent includes N, N-methylenebisacrylamide, dipentaerythritol hexaacrylate, pentaerythritol tetraester, pentaerythritol triallyl ether, pentaerythritol triacrylate, polyethylene glycol diacrylate A composition of one or more of glycidyl ether, ethoxylated glycerol triacrylate, and ethylene glycol dimethacrylate.
  • step (1) the polymerization reaction time is 1-1.5h.
  • step (2) the addition ratio of the initiator is 0.1-0.7% of the mass of acrylic acid in step (1).
  • the amount of initiator used is too large, the decomposition of free radicals increases and the polymerization rate increases, resulting in an increase in crosslink density, a decrease in relative molecular mass, and a decrease in the rate of water absorption.
  • the initiator includes: an inorganic peroxide initiator, an azo initiator, and a redox initiator.
  • the inorganic peroxide initiator includes potassium persulfate, sodium persulfate, and ammonium persulfate;
  • the azo initiator includes azobisisobutyronitrile, azobisisoheptanonitrile, and azobisiso Dimethyl butyrate, etc .;
  • the redox initiators include ammonium persulfate / sodium bisulfite, hydrogen peroxide / ferrous sulfate, ammonium persulfate / ferrous sulfate, potassium persulfate / ferrous chloride, etc.
  • the substance before "/" means oxidation initiator, and the substance
  • the temperature increase means gradually raising the reaction temperature from 0 to 85 ° C, and the initiator is an inorganic peroxide initiator, an azo initiator, and a redox initiator Composition, the mass ratio of the inorganic peroxide initiator, azo initiator and redox initiator is 1-5: 1-5: 1-7.
  • the use of the above three different types of initiators can more effectively initiate the polymerization reaction, because both inorganic peroxide initiators and azo initiators are thermal decomposition initiators.
  • the compound is thermally decomposed As a free radical, it is used to initiate free radical polymerization of olefinic and diene monomers.
  • Inorganic peroxide-based initiators require a relatively high temperature to initiate polymerization, above 65 °C; azo initiators require polymerization to initiate temperatures between 50-65 °C; and redox initiator systems use oxidants
  • the free radicals generated by the electron transfer between the reducing agent and the reducing agent initiate the polymerization reaction, which has the characteristic that it can initiate the polymerization reaction at a lower temperature than the thermal decomposition initiator. Therefore, the present invention selects three different types of initiators for combination.
  • the reaction temperature is lower, and the precursor can initiate the polymerization reaction under the action of the redox initiator.
  • azos The initiator decomposes by heat and begins to participate in the reaction.
  • the inorganic peroxide initiator When the temperature rises above 65 ° C, the inorganic peroxide initiator also begins to participate in the reaction.
  • the reaction temperature if the reaction temperature is too low, the reaction rate is slow, and within a certain period of time, the proportion of the precursor converted into an effective cross-linked structure is low, and some polymers exhibit water solubility.
  • the copolymer has a low water absorption capacity.
  • reaction temperature is too high, the reaction is too violent, resulting in shorter molecular chains between the cross-linked structures of the products, and the polymer chains cannot fully swell to absorb more moisture, and as the reaction temperature increases, the degree of thermal cross-linking increases The water absorption capacity of the high water-absorbent resin is reduced. Therefore, when the initiator is a thermal decomposition initiator, it is recommended to select the reaction temperature between 65-85 °C, which can match the reaction characteristics of the three types of initiators and effectively improve Reaction rate reduces production energy consumption.
  • the surface crosslinking agent includes a combination of one or more of water, polyol, glycidyl ether, ethylene carbonate, propylene carbonate, and polyvalent metal compound.
  • the polyhydric alcohol includes ethylene glycol, propylene glycol or glycerin
  • the polyvalent metal compound includes silver nitrate and copper chloride.
  • the low cross-linking degree inside the polymer water-absorbing resin gives it good water absorption capacity, while the surface A higher degree of cross-linking can give it a high gel strength;
  • the second advantage is that: as the degree of cross-linking increases, the water absorption rate decreases, so by adjusting the degree of cross-linking on the surface of the primary polymer water-absorbing resin, the high The molecular water-absorbent resin has the effect of delaying expansion, which can ensure that the particulate material has enough time to enter the depth of the water-rich crushing zone, so that the leakage plugging material in the crushing zone has the dual effects of expansion and filling and internal compaction.
  • step (3) the addition ratio of the surface crosslinking agent is 3-6% of the mass of the primary polymer water-absorbing resin in step (2).
  • the inorganic water-conducting agent includes: fumed silica, nano titanium dioxide or activated alumina powder, and the addition ratio of the inorganic water-conducting agent is 0.5 of the mass of the primary polymer water-absorbing resin in step (2) -1.5%.
  • the inorganic water-conducting agent suspension may be formed by mixing an inorganic water-conducting agent and water.
  • the grouting material prepared by the invention is a granular polymer water-absorbent resin material, but its surface area size and surface structure have a great influence on the water absorption rate. Although the smaller the diameter of the particulate particles, the larger the surface area, the faster the water absorption rate. However, if the particle diameter is too small, “agglomeration” will occur, that is, a soft gel will form on the surface of the grouting material immediately after contact with water, preventing water molecules from entering the water-absorbing material, that is, forming a surface gelation, like Like the open dough, it becomes a sandwich that does not absorb water. The particles cannot fully contact the water, but the water absorption rate is reduced.
  • the present invention coats the surface of the prepared grouting material with an inorganic water-conducting agent, so that the surface of the grouting material is not easy to gel after encountering water, and does not hinder the uniform penetration of water into the particles. Because the granular water-conducting agent coated on the surface of the grouting material can separate the granular grouting material and avoid direct contact between the grouting material particles, there is a certain gap between the grouting material particles, and the water molecules can Enter, thus avoiding the "reunion phenomenon".
  • the drying conditions are: ventilation drying at 100-120 ° C for 20-60 min.
  • the present invention provides another method for preparing an expanded polymer grouting material for the treatment of high-pressure and large-flow karst inrush water, which differs from the foregoing first method for preparing a grouting material in that: a precursor is prepared in step (1) At the time, the acrylic acid is first incompletely neutralized with an alkaline solution to obtain an incomplete neutralizing solution containing acrylic acid.
  • the degree of neutralization of the incomplete neutralizing solution is maintained between 40% and 90%, and then the above incomplete After the neutralizing solution is mixed with the cross-linking agent, and then polymerized with the polymer water-absorbing resin comonomer to obtain a precursor, the subsequent steps are the same as the previous steps (2)-(4); preferably, choose slowly in an ice water bath Add alkaline solution to the acrylic acid solution to neutralize.
  • the alkaline solution includes sodium hydroxide, calcium hydroxide or a mixture of the two, and the concentration of the alkaline solution is 20-50 wt%.
  • Neutralization degree refers to the degree of neutralization reaction.
  • a part of acrylic acid is neutralized by alkaline solution.
  • 50% of acrylic monomers in acrylic acid solution are neutralized, that is, the degree of neutralization is 50%.
  • the neutralization degree is low, the acrylic acid concentration is high, the activity is high, the polymerization rate is fast, and the self-polymerization reaction easily occurs, forming a polymer with an excessively high cross-linking degree, which reduces the product's water absorption performance; as the neutralization degree increases, it slows If the neutralization degree is too high, the sodium carboxylate concentration in the system will be too high, the reaction rate will decrease, the product cross-linking degree will become lower, and the water solubility will increase, which will easily cause the product water absorption rate to decrease, so In this invention, it is recommended to keep the neutralization degree of incomplete neutralization solution between 40% -90%.
  • the reason for the neutralization of acrylic acid is: first, due to the high flexibility of the acrylic molecular chain, when the molecular weight is high, the molecular weight is highly curled, a large number of carboxyl functional groups are curled inside, which does not effectively absorb water, and the molecule is under acidic conditions The carboxyl groups on the chain are difficult to ionize and hydrate, so acrylic acid must partially neutralize the molecular chains of the polymer obtained after salt formation to produce electrostatic repulsion, resulting in a product with a high water absorption rate. Secondly, when the degree of neutralization of acrylic acid is less than 90%, the liquid absorption rate will increase with the increase of the degree of neutralization.
  • the degree of neutralization When the degree of neutralization is greater than 90%, the liquid absorption rate will decrease with the increase of the degree of neutralization. Because when the neutralization degree is low, the acrylic acid concentration is high and the activity is high. The polymerization rate is fast and the self-polymerization reaction occurs easily. The formed polymer crosslinking degree is too high, and the water absorption rate decreases. When the neutralization degree is high, the reaction rate decreases and crosslinking If the temperature is too low, the water solubility will increase, and the water absorption rate of the product will decrease.
  • the present invention discloses the expanded polymer grouting material obtained by the above preparation method, which is characterized in that the grouting material has a core-shell structure and is a polyacrylic acid series polymer water-absorbent resin, in which step (2) is obtained
  • the primary polymer water-absorbent resin is the core, and the surface cross-linking agent and the water-conducting agent added in step (3) and step (4) respectively form a shell.
  • the present invention provides another composition of the expanded polymer grouting material.
  • the composition includes the present The expanded polymer grouting material and carrier liquid prepared by the invention; wherein, the mass ratio of the expanded polymer grouting material and carrier liquid is 1-2: 1-5.
  • the expansion rate is too fast when injected into the gushing water. Generally, it takes a long time for the expanded polymer grouting material to be injected deep into the crushing zone. It will appear that the expanded polymer grouting material is fully expanded before it reaches the desired depth, so that the superior performance of the expanded polymer grouting material cannot be fully utilized to achieve the purpose of plugging. Therefore, the present invention proposes to use the carrier fluid to suppress the expansion of the expanded polymer grouting material, bring it into the water-rich formation deep in the crushing zone, and absorb water to expand within a controlled time to complete the plugging.
  • the carrying liquid is environmentally friendly and pollution-free, and has no environmental impact on groundwater.
  • the carrier fluid includes one or two of glycerin and ethanol.
  • the conditions required for the carrier fluid described in the present invention are not exhaustive, as long as it is beneficial to suppress the expansion of the expanded polymer grouting material and can bring the expanded polymer grouting material deep into the crushing belt to absorb water within a controlled time It can also be used as a carrier fluid after swelling to complete the blockage.
  • a technical idea similar to the carrying liquid proposed by the present invention can also be used, and a suitable carrier is used to carry the grouting material to a suitable location before plugging is achieved.
  • the present invention discloses the above-mentioned expanded polymer grouting material for high-pressure large-flow karst inrush water treatment and its preparation method, the application of the expanded polymer grouting material composition in the field of construction engineering, especially in the treatment of inrush water inrush Application.
  • the present invention has achieved the following beneficial effects:
  • the expanded polymer grouting material prepared by the present invention has super water absorption and expansion performance that is green and pollution-free, the gelation time is adjustable from 1 to 60 minutes, and the expansion ratio is up to 101-304 times.
  • the expansion time of the expanded polymer grouting material prepared by the present invention is stable and controllable, so that the expansion speed can be adjusted according to engineering needs to ensure that the slurry has good operability and engineering applicability.
  • the small particle grouting material can effectively reduce the fluidity of water in the cracks of the fracture zone after water absorption and increase the viscosity of the water in the cracks Stagnant force reduces its flow rate.
  • the large-particle polymer water-absorbent resin can effectively be stuck between the rocks in the water-rich fracture zone after water absorption and expansion, and continuously accumulate to reduce the water cross-section of the water-rich fracture zone and effectively reduce the water inflow.
  • the expanded polymer grouting material prepared by the present invention can form a viscoelastic body after absorbing water, and it can deform under a certain pressure without being restricted by the shape of pores and cracks; and the expanded polymer grouting material of the present invention
  • the plugging time is short. As long as the water-absorbing resin with the appropriate particle size and injection pressure are selected, effective plugging can be achieved in a short time.
  • the expanded polymer grouting material composition prepared by the present invention when sealing the water-rich crushing zone, the expanded polymer grouting material with a smaller particle size is injected first, and then the expanded with a larger particle size is injected
  • the polymer grouting material can form a longer blocking shielding belt, and at the same time obtain better blocking effect and pressure bearing capacity.
  • FIG. 1 is a visual simulation of the present invention for plugging a high-pressure large-flow inrush water device.
  • FIG. 2 is an SEM image of the expanded polymer grouting material prepared in Example 1.
  • Example 3 is an SEM image of the expanded polymer grouting material prepared in Example 2.
  • FIG. 4 is an unexpanded state diagram of the expanded polymer grouting material prepared in Example 3.
  • FIG. 4 is an unexpanded state diagram of the expanded polymer grouting material prepared in Example 3.
  • Example 5 is a state diagram of the expanded polymer grouting material prepared in Example 3 after expansion.
  • the existing cement-based grouting material has the effect of being cheap, environmentally friendly and strengthening the fault fracture zone, this kind of material not only has a longer initial setting time, but also has a higher resistance to water washout Poor, easy to be scoured in water-rich formations, resulting in low retention rate of these materials in the formation when water is plugged, and the grouting plugging effect is not ideal; while ordinary chemical grouting materials have controllable gel time Advantages, but under the erosion of moving water, it is easy to form a linear consolidation body along the water flow and be washed out by the water. Therefore, the present invention provides an expanded polymer grouting material for the treatment of high-pressure large-flow karst inrush water and its preparation method. The present invention will be further described below with reference to the drawings and specific embodiments.
  • a method for preparing an expanded polymer grouting material for treatment of high-pressure and large-flow karst inrush water includes the following steps:
  • Potassium persulfate dimethyl azobisisobutyrate: potassium persulfate / ferrous chloride is prepared according to a mass ratio of 2: 1: 1 to obtain an initiator, and 0.108 g of the initiator is added to the step ( 1) In the obtained precursor solution, gradually increase the temperature from 4 ° C to 75 ° C (rate 2 ° C / min), react for 15 minutes to obtain a hydrogel, and pulverize the hydrogel to obtain a primary polymer water-absorbing resin;
  • a method for preparing an expanded polymer grouting material for the treatment of high-pressure and large-flow karst inrush water is the same as that in Example 1, except that in step (2), the initiator is only potassium persulfate, which is a kind of The inorganic peroxide initiator is also an oxidation initiator, that is, compared with Example 1, Experimental Example 1 does not add an azo initiator.
  • a preparation method of expanded polymer grouting material for high-pressure and large-flow karst inrush water treatment includes the following steps:
  • the hydrogen peroxide: azobisisoheptanonitrile: potassium persulfate / ferrous chloride is prepared according to a mass ratio of 1: 2: 7 to obtain an initiator, and 0.152 g of the initiator is added to step (1) to obtain In the precursor solution, gradually increase the temperature from 10 ° C to 70 ° C (rate 3 ° C / min), react for 15 minutes to obtain a hydrogel, and crush the hydrogel to obtain a primary polymer water-absorbing resin;
  • step (3) Prepare water: glycerol: ethylene carbonate: silver nitrate according to the mass ratio of 100: 30: 20: 3 to obtain a surface crosslinking agent, and spray the surface crosslinking agent to the one obtained in step (2)
  • the surface of the primary polymer water-absorbent resin, the addition ratio of the surface cross-linking agent is 3.5% of the mass of the primary polymer water-absorbent resin, and then the resin is placed in a 100 ° C oven and reacted for 60 minutes;
  • a method for preparing an expanded polymer grouting material for treatment of high-pressure and large-flow karst inrush water is the same as that in Example 2, except that the temperature is gradually increased from 45 ° C to 70 ° C.
  • a preparation method of expanded polymer grouting material for high-pressure and large-flow karst inrush water treatment includes the following steps:
  • Potassium persulfate dimethyl azobisisobutyrate potassium persulfate / ferrous chloride is prepared according to a mass ratio of 2: 1: 1 to obtain an initiator, and 0.165g of the initiator is added to the step (1 ) In the obtained precursor solution, gradually increase the temperature from 15 ° C to 75 ° C (rate 2 ° C / min), react for 15 minutes to obtain a hydrogel, and pulverize the hydrogel to obtain a primary polymer water-absorbing resin;
  • step (3) Prepare water: ethylene glycol: ethylene carbonate: silver nitrate according to a mass ratio of 100: 30: 20: 3 to obtain a surface crosslinking agent, and spray the surface crosslinking agent to the one obtained in step (2)
  • the surface of the primary polymer water-absorbent resin, the addition ratio of the surface cross-linking agent is 6% of the mass of the primary polymer water-absorbent resin, and then the resin is placed in a 100 ° C oven and reacted for 60 minutes;
  • a method for preparing an expanded polymer grouting material for treatment of high-pressure and large-flow karst inrush water is the same as that in Example 3, except that no surface cross-linking agent is added.
  • a preparation method of expanded polymer grouting material for high-pressure and large-flow karst inrush water treatment includes the following steps:
  • Ammonium persulfate azobisisobutyronitrile: hydrogen peroxide / ferrous sulfate is prepared according to a mass ratio of 2: 2: 3 to obtain an initiator, and 0.035g of the initiator is added to the one obtained in step (1)
  • the precursor solution gradually increase the temperature from 0 ° C to 85 ° C (rate 2 ° C / min), react for 25 minutes to obtain a hydrogel, and pulverize the hydrogel to obtain a primary polymer water-absorbing resin;
  • the glycidyl ether: propylene glycol: propylene carbonate: silver nitrate is prepared according to a mass ratio of 100: 20: 30: 5 to obtain a surface crosslinking agent, and the surface crosslinking agent is sprayed to the one obtained in step (2)
  • the surface of the primary polymer water-absorbent resin, the addition ratio of the surface cross-linking agent is 5% of the mass of the primary polymer water-absorbent resin, and then the resin is placed in an oven at 110 ° C and reacted for 40 minutes;
  • step (3) Mix the nano-titanium dioxide with 20g of water and fully stir to obtain a suspension, the mass of the nano-titanium dioxide is 0.5% of the mass of the primary polymer water-absorbing resin in step (2), and then spray the suspension to the step (3 ) The surface of the obtained water-absorbent resin, then put the obtained product in a drying oven, dry it at 105 °C for 30 minutes, then cool to room temperature; Finally, recycle steps (3) and (4) twice to obtain particles Like expanded polymer grouting material.
  • a method for preparing an expanded polymer grouting material for the treatment of high-pressure and large-flow karst inrush water is the same as that in Example 4, except that step (4) does not include the step of adding a water-conducting agent, only the step (3) The final product is ventilated and dried.
  • a preparation method of expanded polymer grouting material for high-pressure and large-flow karst inrush water treatment includes the following steps:
  • step (3) Prepare ethylene glycol: propylene glycol: copper chloride in a mass ratio of 100: 40: 3 to obtain a surface crosslinking agent, and spray the surface crosslinking agent to the primary polymer water-absorbing resin obtained in step (2) On the surface, the addition ratio of the surface crosslinking agent is 3% of the mass of the primary polymer water-absorbent resin, and then the resin is placed in an oven at 115 ° C and reacted for 30 minutes;
  • a method for preparing an expanded polymer grouting material for treatment of high-pressure and large-flow karst inrush water is the same as that in Example 5, except that in step (1), acrylic acid is completely neutralized into sodium acrylate.
  • a preparation method of expanded polymer grouting material for high-pressure and large-flow karst inrush water treatment includes the following steps:
  • step (3) Prepare ethylene glycol: propylene glycol: copper chloride in a mass ratio of 100: 40: 3 to obtain a surface crosslinking agent, and spray the surface crosslinking agent to the primary polymer water-absorbing resin obtained in step (2) On the surface, the addition ratio of the surface cross-linking agent is 5.5% of the mass of the primary polymer water-absorbing resin, and then the resin is placed in an oven at 120 ° C. and reacted for 20 min;
  • step (3) (4) Mix the activated alumina powder (particle size 60-80nm) with 15g of water and fully stir to obtain a suspension, the mass of the activated alumina powder is 1.5% of the mass of the primary polymer water-absorbing resin in step (2), Then spray the suspension onto the surface of the water-absorbent resin obtained in step (3), then put the obtained product in a drying oven, ventilate and dry at 100 ° C for 20 min, then cool to room temperature; finally, step (3) and (4) Recycle twice to obtain granular expanded polymer grouting material.
  • a preparation method of expanded polymer grouting material for high-pressure and large-flow karst inrush water treatment includes the following steps:
  • Potassium persulfate azobisisobutyronitrile: potassium persulfate / ferrous chloride is prepared according to a mass ratio of 5: 1: 7 to obtain an initiator, and 0.08g of the initiator is added to step (1) to obtain In the precursor solution, gradually increase the temperature from 15 ° C to 65 ° C (rate 2 ° C / min), react for 20 minutes to obtain a hydrogel, and crush the hydrogel to obtain a primary polymer water-absorbing resin;
  • step (3) Prepare ethylene glycol: propylene glycol: silver nitrate according to the mass ratio of 100: 40: 1 to obtain a surface crosslinking agent, and spray the surface crosslinking agent onto the surface of the primary polymer water-absorbing resin obtained in step (2)
  • the addition ratio of the surface cross-linking agent is 4% of the mass of the primary polymer water-absorbing resin, and the resin is placed in an oven at 105 ° C and reacted for 35 minutes;
  • step (3) Mix titanium dioxide with 18g of water and stir thoroughly to obtain a suspension, the mass of the gas-phase titanium dioxide is 0.9% of the mass of the primary polymer water-absorbing resin in step (2), and then spray the suspension to step (3) The surface of the obtained water-absorbent resin, then put the obtained product in a drying oven, dry it at 120 ° C for 20 minutes, then cool to room temperature; finally, recycle steps (3) and (4) twice to obtain granular form Of expanded polymer grouting material.
  • the same method was used to test the expansion effect of the expanded polymer grouting materials prepared in Examples 1, 2 and 4-7, and the expansion rates were 101, 217, 304, 186, 264, and 288 times, respectively.
  • the material has good water absorption and expansion rate.
  • the present invention uses the following visual simulation to block the high-pressure large-flow surge water device (as shown in FIG. 1), and effectively tested the dynamic The water-blocking capacity of the expanded polymer grouting materials prepared in the examples and experimental examples under water conditions, to determine reasonable grouting water-blocking parameters and to evaluate the plugging effect, to provide a theory for further in-depth study of the new material grouting water-blocking process basis.
  • the visual simulation of plugging high-pressure large-flow inrush water device includes four parts: dynamic water supply system, expanded polymer grouting material injection system, slurry storage and slurry pipeline system, data collection and processing system; slurry storage and transportation
  • the slurry pipeline system is composed of a detachable and reorganized acrylic pipeline, a screw jack, a metal filter, and a slurry-water collection tank.
  • the inlet of the pipeline is connected to a water supply system with a regulated water source through a high-pressure hose, and a flow valve is provided on the high-pressure hose ;
  • a slurry-water collection tank is provided at the outlet of the acrylic tube;
  • a slurry injection hole is provided at the front of the acrylic tube, and a flow valve is provided on the grouting tube connected to the injection hole;
  • the data collection and processing system includes moving water installed on the acrylic tube Flow sensor, high-definition photography system.
  • a flow sensor and a water flow pressure sensor are used to collect and record the water flow velocity and water pressure at different locations of dynamic water grouting in real time, and to achieve automatic measurement of the test process by connecting with a computer control system.
  • Step 1 The grouting pump is connected to the grouting flower tube through a high-pressure infusion tube, the syring tube is inserted into the grouting hole at the inlet end of the acrylic tube, and the grouting pressure sensor and grouting flow sensor are arranged.
  • Step 2 According to the geological conditions of the crushing zone encountered in the construction, determine the flow and velocity of the inrush water, adjust the pressure controller of the water supply system to provide dynamic water conditions similar to the project, and arrange the water flow in the bottom middle of the acrylic tube Flow sensor and water pressure sensor adjust the screw jack to adjust the acrylic tube to a horizontal state.
  • Step 3 Connect the flow sensor and pressure sensor to the data collection device, set the collection frequency and data storage parameters.
  • Step 4 Add granular grouting material to the grouting pump. Adjust the pressure controller to provide different dynamic water flow rates for the cross-line. After the flow rate is stable, turn on the grouting pump and set the grouting pressure to a predetermined value.
  • Step 5 Stop the grouting after the granular grouting material has diffused to the outlet boundary or the moving water flow is completely blocked by the granular material. Observation and real-time monitoring and recording of hydraulic plugging of granular grouting materials at different flow rates.
  • Step 6 Remove the acrylic tube of the plugging pressure test section and connect it to the dynamic water supply device through a flange. After the connection is completed, slowly apply water pressure to the particulate plugging material to test the ultimate pressure bearing capacity of the plugging section. Quantitative evaluation of the sealing effect.
  • Step 8 Change the different test conditions to obtain the effect of the amount of expanded polymer grouting material on the diffusion law of the slurry and the plugging of dynamic water at different dynamic water flow rates.
  • Step 9 Clean the granular material and the granular material injection system and test platform.
  • the expanded polymer grouting material prepared by the invention has an excellent gushing water blocking effect.
  • the grouting material prepared in the experimental example can also be plugged when the flow rate and flow rate of the gushing water are small when the usage amount is the same as the example, but the plugging length is significantly higher than the example, which is due to the preparation of the experimental example
  • the grouting material has a low water absorption rate and cannot achieve rapid expansion, which needs to flow with the water flow for a longer time.
  • the grouting material prepared in the experimental example cannot achieve effective plugging.
  • the amount of grouting material must be increased to achieve effective plugging.
  • the plugging length is generally higher than the examples. This is due to the low water absorption rate and expansion rate of the grouting materials prepared in the experimental examples. It is impossible to achieve rapid expansion plugging in high-pressure and large-flow surge water, but is washed away by the water flow. Afterwards, a linear distribution is formed. Even if the grouting material in this distribution form expands later, it can no longer effectively block.

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Abstract

一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，属于地下工程封堵材料技术领域。所述方法包括：1)在丙烯酸中加入交联剂；然后加入高分子吸水树脂共聚单体进行聚合反应，得到前驱体；2)在步骤1)中得到的前驱体中加入引发剂，升温，反应后得到水凝胶，将水凝胶绞碎，得到初级高分子吸水树脂；3)将表面交联剂喷洒到步骤2)得到的初级高分子吸水树脂表面，再将产物烘干；4)将无机导水剂制备成悬浊液，将该悬浊液喷洒到步骤3)得到的产物上，烘干，即得膨胀高分子注浆材料。

Description

[根据细则37.2由ISA制定的发明名称]　用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料及制备方法 技术领域
本发明属于地下工程封堵材料技术领域，尤其涉及一种用于封堵高压大流量岩溶突涌水的膨胀高分子注浆材料及制备方法。
背景技术
涌突水是地下工程的主要地质灾害之一，我国地下工程建设越来越受到重视，面临的地质条件也逐渐复杂起来，在地下工程的建设过程中，极易遇到富水断层等不良地质构造，容易发生塌方、突涌水及围岩大变形等地质灾害。特别是富水破碎带区域，围岩比较破碎，涌水量较大。
实践表明，注浆是治理涌突水的有效技术手段，例如，中国专利文献201610770793.4公开了一种环保型弹性丙烯酸盐灌浆材料及使用方法，所述环保型弹性丙烯盐酸灌浆材料包括A组份：丙烯酸酯、交联剂I、交联剂II、促进剂；B组份：水、引发剂。该环保型弹性丙烯酸盐灌浆材料具有注浆粘度低，固结物延伸率可达200％以上，环保等优点，可用于长期有水环境伸缩移动缝的防渗堵漏。然而，该灌浆材料具有环保无毒的优点，适用于伸缩缝的防渗堵漏，但不适宜在高压大流量水流下作业，易被稀释，难以胶凝，且双组份灌浆材料限制了其使用与发展。
中国专利文献201711475087.8公开了一种丙烯酸盐水溶液灌浆材料及其制备方法，该灌浆材料包括：A组份为丙烯酸盐水溶液、交联剂和促进剂；B组份为水、水性高分子乳液和引发剂。该丙烯酸盐水溶液灌浆材料具有注浆粘度低，强度高，干燥环境收缩率低等特点，显著提高堵漏风险。然而，这种丙烯酸盐灌浆料主要用于控制下水道水渗透、稳固和凝固疏松的土壤，并不适用于封堵高压大流量突涌水，因为B组分易在动水冲刷下被稀释而无法使得A组分胶凝，其双组份灌浆材料的形式限制了在涌水封堵方面的使用。
中国专利文献201010172263.2公开了一种速凝高强膨胀性矿山封孔材料,它由原料高铝水泥、柠檬酸、石灰、石膏、十二烷基硫酸钠配制而成。该材料可在高水灰比的条件下快速凝固、凝固过程中体积膨胀(1天最大自由膨胀率可达10％以上)，且固结体强度较高(1天强度达3～4MPa)。但该速凝高强膨胀性矿山封孔材料属于无机化学材料，主要用作对矿山围岩的加固及注浆孔的封堵，具有一定的膨胀效果，但膨胀倍率仅为10％，并不能实现对岩溶管道及破碎带突涌水的封堵治理。
中国专利文献201110007241.5公开了一种地下工程用高分子聚合加固堵水注浆材料及其施工工艺，该注浆材料由树脂和催化剂两种低粘度液态物组成，该注浆材料由树脂和催化剂两种低粘度液态组分组成，反应后生成惰性泡沫，有很高的膨胀率。然而，这种高分子聚合加固堵水注浆材料属于聚氨酯类灌浆材料，由聚醚多元醇与多异氰酸酯反应而来，具有发泡膨胀的特点，适用于煤岩体加固、裂缝填补及渗漏水的防治，但该高分子聚合加固堵水注浆材料易在大流量突涌水条件下被稀释，沿水流前进方向形成条带状凝胶体，被携带至地层深处，不具有突涌水封堵的效果。
中国专利文献201711162326.4公开了一种膨胀性软岩巷道注浆材料，该注浆材料由基体组分和外掺组分组成，基体组分包括超细水泥、粉煤灰、硅粉，外掺组分包括高效减水剂、石墨粉稳定剂。该注浆材料制成的浆液流动性和稳定性好、早后期强度高、抗渗性和耐久性好，能够抑制膨胀性软岩巷道注浆过程围岩吸水膨胀产生的变形，避免浆液注入引起的围岩裂隙闭合，应用后能显著提高膨胀性软岩巷道围岩裂隙的可注性和堵水加固性能。但该注浆材料属于无机化学材料，主要由水泥粉煤灰组成，用作提高膨胀性软岩巷道围岩裂隙的可注性和堵水加固性能，主要解决的工程问题是围岩裂隙引起的渗漏水灾害，并不适用于岩溶管道中高压大流量的突涌水地质灾害。
另外，对于隧道及煤矿开挖过程中存在的突涌水灾害而言，其涉及的不仅是如何封堵的问题，还必须考虑封堵材料的环保性、封堵效果、封堵方式等问题，但在大裂隙突涌水工况下，以水泥为主体的注浆材料虽然具有价格便宜、环保且加固断层破碎带的效果，但这类材料不仅初终凝时间较长，而且抗水冲刷性较差，在富水地层中易被冲刷，导致这类材料在涌水封堵时在地层中留存率低，每米单耗水泥几吨仍然达不到封堵结束标准，注浆封堵效果不理想。而普通化学类注浆材料，如聚氨酯灌浆材料，虽然具有胶凝时间可控的优势，但是在动水冲刷下，容易顺水流形成线状固结体被水冲出。为此，针对隧道及煤矿开挖过程中存在的突涌水灾害，急需研发胶凝时间可控、堵水能力强、具有膨胀性能的绿色化学注浆材料。
发明内容
针对上述现有技术中存在的问题，本发明旨在提供一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料及制备方法。本发明的高分子注浆材料在吸水膨胀后可有效地卡在富水破碎带岩块之间，不断积聚，增加裂隙中水的粘滞力，减少富水破碎带的过水断面，有效降低涌水流量，实现富水破碎带的突涌水治理。本发明的高分子注浆材料有效地解决了注浆材料在涌水条件下难以留存的技术难题；同时，本发明的注浆堵水材料具有绿色无污染、膨 胀时间在1-60分钟可调，膨胀倍率高达101-304倍的特点。
本发明的第一目的，提供用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法。
本发明的第二目的，提供上述方法制备的膨胀高分子注浆材料。
本发明的第三目的，提供上述方法制备的膨胀高分子注浆材料的组合物。
本发明的第四目的，提供上述膨胀高分子注浆材料的制备方法及其制备的产品以及该产品的组合物的应用。
为实现上述目的，具体的，本发明公开了下述技术方案：
首先，本发明公开一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，包括如下步骤：
(1)在丙烯酸中加入交联剂；然后加入高分子吸水树脂共聚单体进行聚合反应，得到前驱体；通过聚合反应可以将高分子吸水树脂共聚单体接枝到丙烯酸单体表面，进一步增加丙烯酸单体的吸水性，提高注浆材料的封堵性能。另外，本发明采用的前驱体的合成方法为静态溶液聚合法，这种方法是将聚合单体和交联剂等添加剂配成溶液，再置于一定温度下反应，操作简单、成本低；
(2)在步骤(1)中得到的前驱体中加入引发剂，升温，反应后得到水凝胶，将水凝胶绞碎，得到初级高分子吸水树脂；
(3)将表面交联剂喷洒到步骤(2)得到的初级高分子吸水树脂表面，再将产物烘干，备用；在表面喷洒表面交联剂可以有效调控初级高分子吸水树脂表面的交联度，从而使初级高分子吸水树脂具备延迟膨胀以及高胶凝强度的特性；
(4)将无机导水剂制备成悬浊液，将该悬浊液喷洒到步骤(3)烘干得到的产物上，烘干，即得颗粒状的膨胀高分子注浆材料。
步骤(1)中，所述丙烯酸的质量浓度为25-45％。试验表明：随着单体浓度的增加，高分子吸水树脂吸水倍率有不同程度的下降，当单体浓度低于25％时，难以聚合形成凝胶，并且由于过量水溶性物质的存在，不能准确地测定高吸水树脂的吸水倍率。另外，可用去离子水将丙烯酸稀释至设定浓度，既方便也不会引入杂质。
步骤(1)中，所述高分子吸水树脂共聚单体包括聚乙烯醇、丙烯酰胺、甲基丙烯酰胺或丙烯腈。这些树脂类高吸水性树脂原料来源丰富、价格低廉，而且具有防腐防变，能够长期保存、综合吸水性能优良的特点；但也不排除淀粉系及纤维素系高分子吸水树脂作为超高膨 胀注浆堵水材料的原料，例如：用淀粉、羟乙基纤维素、甲基纤维素或羧甲基纤维素等作为高分子吸水树脂共聚单体。
步骤(1)中，所述高分子吸水树脂共聚单体的添加比例为步骤(1)中丙烯酸质量的0.5-20％。在本发明中，高分子吸水树脂共聚单体主要起的是进一步强化注浆材料吸水性能的作用，其添加量宜控制在0.5-20％之间，添加量过少起到的作用不明显，反而多了一道工序，增加了工艺的复杂性；而添加量过多，不利于对注浆材料膨胀时间、膨胀倍率的调控。
步骤(1)中，所述交联剂的添加比例为步骤(1)中丙烯酸质量的0.5-2％。交联剂的种类和交联度对高吸水树脂的吸水倍率有较大的影响，树脂的吸水能力随交联度的增大而降低，从提高吸水树脂的吸水倍率的角度来考虑，在保证吸水树脂不溶解的前提下，应尽可能降低交联度，但是吸水后的树脂显示出橡胶的弹性行为，其凝胶强度与交联度成正比，降低交联度会导致凝胶强度下降。在岩体破碎带注浆治理过程中，要保证高分子吸水树脂能够有效的卡在地层中，不被水流冲出，就要具有合适的交联度，既要保证一定的凝胶强度，又要尽可能提高其吸水倍率，因此，本发明将交联剂的用量控制在0.5％-1.2％之间。
步骤(1)中，所述交联剂包括N,N-亚甲基双丙烯酰胺、双季戊四醇六丙烯酸酯、季戊四醇四酯、季戊四醇三烯丙基醚、季戊四醇三丙烯酸酯、聚乙二醇二缩水甘油醚、乙氧基化甘油三丙烯酸酯、乙二醇二甲基丙烯酸酯中的一种或多种的组合物。
步骤(1)中，所述聚合反应的时间为1-1.5h。
步骤(2)中，所述引发剂的添加比例为步骤(1)中丙烯酸质量的0.1-0.7％。引发剂用量过多时，分解自由基增多，聚合速率加快，导致交联密度增加、相对分子质量降低、吸水倍率下降。
步骤(2)中，所述引发剂包括：无机过氧化物引发剂、偶氮类引发剂、氧化还原引发剂。
进一步地，所述无机过氧化物引发剂包括过硫酸钾、过硫酸钠、过硫酸铵；所述偶氮类引发剂包括偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯等；所述氧化还原类引发剂包括过硫酸铵/亚硫酸氢钠、过氧化氢/硫酸亚铁、过硫酸铵/硫酸亚铁、过硫酸钾/氯化亚铁等，所述氧化还原类引发剂中，过硫酸铵/亚硫酸氢钠、过氧化氢/硫酸亚铁、过硫酸铵/硫酸亚铁、过硫酸钾/氯化亚铁、过氧化氢/硫酸亚铁中，所述“/”前的物质表示氧化类引发剂，“/”后物质表示还原类引发剂，每一组氧化还原引发剂同时使用，其中，氧化类引发剂与还原类引发剂的质量比为1：3-8。引发剂可以直接影响聚合反应过程能否顺利进行，也会影响聚合反应速率，还会影响产品储存期。
进一步地，步骤(2)中，所述升温指：将反应温度逐步从0升至85℃，且所述引发剂为无机过氧化物引发剂、偶氮类引发剂、氧化还原引发剂三者的组合物，所述无机过氧化物引发剂、偶氮类引发剂、氧化还原引发剂三者的质量比为1-5：1-5：1-7。
同时采用上述三种不同类型的引发剂能够更有效地引发聚合反应的进行，因为无机过氧化物类引发剂与偶氮类引发剂均属于热分解引发剂，在一定的温度下，化合物受热分解为自由基，用于引发烯类、双烯类单体的自由基聚合。无机过氧化物类引发剂引发聚合反应时所需温度较高，约在65℃以上；偶氮类引发剂引发聚合反应所需温度在50-65℃之间；而氧化还原引发体系是利用氧化剂和还原剂之间的电子转移所生成的自由基引发聚合反应，其较热分解引发剂具有可以在更低温度下引发聚合反应的特点。因此，本发明选择三种不同类型的引发剂进行组合后，在反应初期，反应温度较低，前驱体能够在氧化还原引发剂的作用下引发聚合反应，随着温度不断升高，偶氮类引发剂受热分解，开始参与反应，当温度上升到65℃以上时，无机过氧化物引发剂也开始参与到反应中来。另外，对于热引发剂引发的二元共聚反应，若反应温度太低，反应速率较慢，在一定时间内，前驱体转化为有效的交联结构的比例较低，部分高分子呈现水溶性，共聚物的吸水能力较低。但若反应温度过高，反应太剧烈，导致产物交联结构之间的分子链变短，高分子链不能充分膨胀而吸收更多的水分，并且随着反应温度升高，热交联程度增大，高吸水树脂的吸水能力下降，因此，在引发剂为热分解引发剂的时候，推荐将反应温度选择在65-85℃之间，这样可以与三类引发剂的反应特点匹配，有效提高反应速率，降低生产能耗。
步骤(3)中，所述表面交联剂包括水、多元醇、缩水甘油醚、碳酸乙烯酯、碳酸丙烯酯和多价金属化合物中的一种或多种的组合物。
进一步地，所述多元醇包括乙二醇、丙二醇或丙三醇，所述多价金属化合物包括硝酸银、氯化铜。初级高分子吸水树脂经过表面处理后，使树脂颗粒内部交联度低，而表面交联度高，其优势一在于：高分子吸水树脂内部的低交联度赋予其良好的吸水能力，而表面较高的交联度可赋予其高的胶凝强度；其优势二在于：由于随着交联度的增加而吸水率下降，因此，通过调控初级高分子吸水树脂表面的交联度，使高分子吸水树脂具备了延迟膨胀的效果，从而能够保证颗粒材料有足够的时间进入富水破碎带深处，使得破碎带内的堵漏材料具有扩张填充和内部挤紧压实的双重效果。
步骤(3)中，所述表面交联剂的添加比例为步骤(2)中初级高分子吸水树脂质量的3-6％。
步骤(4)中，所述无机导水剂包括：气相二氧化硅、纳米二氧化钛或活性氧化铝粉，所 述无机导水剂的添加比例为步骤(2)中初级高分子吸水树脂质量的0.5-1.5％。进一步地，所述无机导水剂悬浊液可由无机导水剂与水混合而成。
本发明制备的注浆材料是一种颗粒状的高分子吸水树脂材料，但其表面积大小以及表面结构对吸水速率影响很大，虽然颗粒物粒子的直径越小，表面积越大，吸水速率越快，但是粒子直径过小时会产生“团聚现象”，即与水接触后马上在注浆材料表面形成一层软凝胶，阻碍水分子进入吸水材料内部，也就是形成了表面胶凝化，像“未和开的面团”一样，成了芯不吸水的夹芯物，粒子之间无法充分与水接触，反而使吸水速率下降。在保证一定颗粒大小的条件下，本发明在制备的注浆材料表面裹附无机导水剂，这样在注浆材料遇水后表面不易凝胶化，不会阻碍水均匀的渗透到颗粒内部，因为在注浆材料表面裹覆的颗粒状的导水剂可以隔开颗粒状的注浆材料，避免注浆材料颗粒之间直接接触，使注浆材料颗粒之间存在一定的缝隙，水分子可以进入，从而避免了“团聚现象”。
步骤(3)、(4)中，所述干燥的条件为：在100-120℃下通风干燥20-60min。
其次，本发明提供另一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，和前述第一种注浆材料制备方法的区别在于：步骤(1)中制备前驱体时，首先用碱液对丙烯酸进行不完全中和，得到含有丙烯酸的不完全中和液，所述不完全中和液的中和度保持在40％-90％之间，然后将上述不完全中和液与交联剂混合后，再与高分子吸水树脂共聚单体进行聚合反应，得到前驱体，后续步骤与前述步骤(2)-(4)一致；优选地，选择在冰水浴中缓慢地向丙烯酸溶液中加入碱液进行中和。
所述碱液包括氢氧化钠、氢氧化钙或两者的混合液，碱液的浓度为20-50wt％。
中和度，是指中和反应进行的程度，在本发明中，是利用碱液使丙烯酸被中和掉一部分，例如，丙烯酸溶液中50％的丙烯酸单体被中和，即中和度为50％。当中和度较低时，丙烯酸浓度高，活性大，聚合速率快，容易发生自聚合反应，形成交联度过高的聚合物，使产物吸水性能降低；随着中和度的增加，既减缓了反应速率，又降低了交联度；如果中和度过高，体系中羧酸钠浓度过高，反应速率下降，产物交联度变低，水溶性增强，易导致产物吸水倍率下降，因此，本发明推荐将不完全中和液的中和度保持在40％-90％之间。
对丙烯酸进行中和的原因是：首先，由于丙烯酸分子链具有较高的柔性，分子量高时，分子量高度蜷曲，大量的羧基官能团蜷曲在内部，起不到有效的吸水作用，且酸性条件下分子链上的羧基难以电离及水合，因此丙烯酸必须部分中和成盐后得到的高聚物分子链之间才能产生静电斥力，使产物具有高的吸水倍率。其次当丙烯酸中和度小于90％时，吸液倍率会 随中和度的增加而增加，当中和度大于90％时，吸液倍率反而会随中和度的增加而减小。因为中和度较低时，丙烯酸浓度高活性大，聚合速度快易发生自聚反应，形成的聚合物交联度过高，吸水倍率下降，中和度较高时，反应速率下降，交联度过低导致水溶性增强，导致产物吸水倍率下降。
再次，本发明公开上述制备方法得到的膨胀高分子注浆材料，其特点是：该注浆材料是具有核壳结构，是一种聚丙烯酸系列的高分子吸水树脂，其中，步骤(2)得到的初级高分子吸水树脂为内核，步骤(3)和步骤(4)分别加入的表面交联剂和导水剂形成了外壳。
再其次，基于本发明制备的用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的特点，本发明提供另一种该膨胀高分子注浆材料的组合物，所述组合物包括本发明制备的膨胀高分子注浆材料和携带液；其中，膨胀高分子注浆材料和携带液的质量比为1-2：1-5。
因为本发明制备的膨胀高分子注浆材料具有超强吸水性，在注入涌水中时膨胀速率太快，一般情况下，膨胀高分子注浆材料注入破碎带深处需要很长的时间，这就会出现膨胀高分子注浆材料还未到达期望深度即完全膨胀，这样则不能很好的发挥膨胀高分子注浆材料的优越性能而达到堵漏的目的。因此，本发明提出用携带液抑制膨胀高分子注浆材料的膨胀，将其带入破碎带深处的富水地层中，并在控制时间内吸水膨胀，从而完成封堵。
本发明推荐的携带液需要具备的条件为：
(1)在一定的时间内，能抑制膨胀高分子注浆材料的膨胀；
(2)具有良好的悬浮和携带颗粒的能力；
(3)在室温、高温或高压下，自身性质比较稳定；
(4)当高分子吸水树脂进入富水破碎带后，能立刻使高分子吸水树脂与水充分接触，使高分子吸水树脂在破碎带中吸水膨胀，从而封堵涌水；
(5)高分子吸水树脂与携带液不能发生化学反应；
(6)携带液环保无污染，对地下水不产生环境影响。
优选地，所述携带液包括丙三醇、乙醇中的一种或两种。本发明所述的携带液需要同时具备的条件并非穷举，只要有利于抑制膨胀高分子注浆材料的膨胀，并能够将膨胀高分子注浆材料带入破碎带深处后在控制时间内吸水膨胀，完成封堵，也可以作为携带液。另外，对于其他通过膨胀实现涌水封堵的注浆材料而言，也可以采用类似本发明提出的携带液的技术思路，采用合适的载体将注浆材料携带到合适的位置后再实现封堵。
最后，本发明公开了上述用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料及其制 备方法，膨胀高分子注浆材料的组合物在建筑工程领域的应用，尤其在涌突水治理中的应用。
与现有技术相比，本发明取得了如下有益效果：
(1)本发明制备的膨胀高分子注浆材料具有绿色无污染、胶凝时间在1-60分钟可调，且膨胀倍率高达101-304倍的超强吸水膨胀性能。
(2)本发明制备的膨胀高分子注浆材料的膨胀时间稳定可控，从而可以根据工程需要进行调控在膨胀速度，保证浆液具有良好的可操作性和工程适用性。
(3)本发明制备的不同级配的膨胀高分子注浆材料组合物中，小颗粒的注浆材料在吸水膨胀后可有效地降低破碎带裂隙中水的流动性，增加裂隙中水的粘滞力，减小其流动速度。大颗粒的高分子吸水树脂在吸水膨胀后可有效地卡在富水破碎带岩块之间，不断积聚，减少富水破碎带的过水断面，有效的降低涌水流量。
(4)本发明制备的膨胀高分子注浆材料吸水后能够形成粘弹性体，其在一定的压力下可发生变形，不受孔隙和裂缝形状的限制；而且本发明的膨胀高分子注浆材料封堵时间短，只要选择了合适粒径的吸水树脂及注入压力，一般在很短时间内即可实现有效封堵。
(5)本发明制备的膨胀高分子注浆材料组合物的使用方法中，在封堵富水破碎带时，先注入较小粒径的膨胀高分子注浆材料，再注入大粒径的膨胀高分子注浆材料，能够形成较长的封堵屏蔽带的同时，获得更佳的封堵效果和承压能力。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。
图1为本发明可视化的模拟封堵高压大流量突涌水装置。
图2为实施例1制备的膨胀高分子注浆材料的SEM图。
图3为实施例2制备的膨胀高分子注浆材料的SEM图。
图4为实施例3制备的膨胀高分子注浆材料的未膨胀的状态图。
图5为实施例3制备的膨胀高分子注浆材料的膨胀后的状态图。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申 请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
正如背景技术所介绍的，现有的以水泥为主体的注浆材料虽然具有价格便宜、环保且加固断层破碎带的效果，但这类材料不仅初终凝时间较长，而且抗水冲刷性较差，在富水地层中易被冲刷，导致这类材料在涌水封堵时在地层中留存率低，注浆封堵效果不理想；而普通化学类注浆材料虽然具有胶凝时间可控的优势，但是在动水冲刷下，容易顺水流形成线状固结体被水冲出。因此，本发明一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料及制备方法，下面结合附图和具体实施方式对本发明做进一步的说明。
实施例1
1、一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，包括如下步骤：
(1)用去离子水稀释丙烯酸单体，得到浓度为45％的丙烯酸溶液80g，然后在丙烯酸溶液中加入0.2g N,N-亚甲基双丙烯酰胺，用磁力搅拌器搅拌10min；然后加入1.5g聚乙烯醇聚合反应1.5h，得到前驱体溶液；
(2)将过硫酸钾：偶氮二异丁酸二甲酯：过硫酸钾/氯化亚铁按照质量比为2:1:1配制，得到引发剂，将0.108g该引发剂加入步骤(1)得到的前驱体溶液中，逐步将温度从4℃升至75℃(速率2℃/min)，反应15分钟得到水凝胶，将水凝胶绞碎得到初级高分子吸水树脂；
(3)将水：丙三醇：碳酸乙烯脂：硝酸银按照质量比100:30:30:5的比例配制，得到表面交联剂，将该表面交联剂喷洒到步骤(2)得到的初级高分子吸水树脂表面，所述表面交联剂的添加比例为初级高分子吸水树脂质量的4.5％，然后将树脂放于100℃烘箱中，反应60min。
(4)取1.6g的气相二氧化硅，与30g水混合，充分搅拌得到悬浊液，将该悬浊液喷洒到步骤(3)得到的吸水树脂表面，然后将得到的产物放入烘干箱内，在120℃之间通风干燥30min后冷却至室温；最后将步骤(3)和(4)再循环两次，即得颗粒状的膨胀高分子注浆材料。
试验例1
1、一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，同实施例1，区别在于：步骤(2)中，引发剂仅为过硫酸钾，这既是一种无机过氧化物引发剂，也是一种氧化类引发剂，即和实施例1相比，实验例1未添加偶氮类引发剂。
实施例2
一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，包括如下步骤：
(1)用去离子水稀释丙烯酸单体，得到浓度为30％的丙烯酸溶液80g，在冰水浴中缓慢加入质量分数为20％的氢氧化钠对丙烯酸水溶液进行中和，得到含有丙烯酸的不完全中和液，其中和度为45％；然后在该不完全中和液中加入0.252g季戊四醇四酯，用磁力搅拌器搅拌8min；然后加入1.8g聚乙烯醇聚合反应1.0h，得到前驱体溶液；
(2)将过氧化氢：偶氮二异庚腈：过硫酸钾/氯化亚铁按照质量比为1:2:7配制，得到引发剂，将0.152g该引发剂加入步骤(1)得到的前驱体溶液中，逐步将温度从10℃升至70℃(速率3℃/min)，反应15分钟得到水凝胶，将水凝胶绞碎得到初级高分子吸水树脂；
(3)将水：丙三醇：碳酸乙烯脂：硝酸银按照质量比100:30:20:3的比例配制，得到表面交联剂，将该表面交联剂喷洒到步骤(2)得到的初级高分子吸水树脂表面，所述表面交联剂的添加比例为初级高分子吸水树脂质量的3.5％，然后将树脂放于100℃烘箱中，反应60min；
(4)将气相二氧化硅与25g水混合充分搅拌得到悬浊液，所述气相二氧化硅的质量为步骤(2)中初级高分子吸水树脂质量的1％，再将该悬浊液喷洒到步骤(3)得到的吸水树脂表面，然后将得到的产物放入烘干箱内，在100℃之间通风干燥60min后冷却至室温；最后将步骤(3)和(4)再循环两次，即得颗粒状的膨胀高分子注浆材料。
试验例2
1、一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，同实施例2，区别在于：逐步将温度从45℃升至70℃。
实施例3
一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，包括如下步骤：
(1)用去离子水稀释丙烯酸单体，得到浓度为30％的丙烯酸溶液120g，在冰水浴中缓慢加入质量分数为30％的氢氧化钙对丙烯酸水溶液进行中和，得到含有丙烯酸的不完全中和液，其中和度为60％；然后在该不完全中和液中加入0.720g季戊四醇三烯丙基醚，用磁力搅拌器搅拌11min；然后加入3.6g丙烯酰胺聚合反应1.5h，得到前驱体溶液；
(2)将过硫酸钾：偶氮二异丁酸二甲酯过硫酸钾/氯化亚铁按照质量比为2:1:1配制，得到引发剂，将0.165g该引发剂加入步骤(1)得到的前驱体溶液中，逐步将温度从15℃升至75℃(速率2℃/min)，反应15分钟得到水凝胶，将水凝胶绞碎得到初级高分子吸水树脂；
(3)将水：乙二醇：碳酸乙烯脂：硝酸银按照质量比100:30:20:3的比例配制，得到表面交联剂，将该表面交联剂喷洒到步骤(2)得到的初级高分子吸水树脂表面，所述表面交联 剂的添加比例为初级高分子吸水树脂质量的6％，然后将树脂放于100℃烘箱中，反应60min；
(4)将气相二氧化硅与20g水混合充分搅拌得到悬浊液，所述气相二氧化硅的质量为步骤(2)中初级高分子吸水树脂质量的1.2％，再将该悬浊液喷洒到步骤(3)得到的吸水树脂表面，然后将得到的产物放入烘干箱内，在120℃之间通风干燥20min后冷却至室温；最后将步骤(3)和(4)再循环两次，即得颗粒状的膨胀高分子注浆材料。
试验例3
1、一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，同实施例3，区别在于：不添加表面交联剂。
实施例4
一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，包括如下步骤：
(1)用去离子水稀释丙烯酸单体，得到浓度为25％的丙烯酸溶液140g，在冰水浴中缓慢加入质量分数为50％的氢氧化钙对丙烯酸水溶液进行中和，得到含有丙烯酸的不完全中和液，其中和度为40％；然后在该不完全中和液中加入0.5g乙氧基化甘油三丙烯酸酯，用磁力搅拌器搅拌7min；然后加入5g聚乙烯醇聚合反应1.2h，得到前驱体溶液；
(2)将过硫酸铵：偶氮二异丁腈：过氧化氢/硫酸亚铁按照质量比为2:2:3配制，得到引发剂，将0.035g该引发剂加入步骤(1)得到的前驱体溶液中，逐步将温度从0℃升至85℃(速率2℃/min)，反应25分钟得到水凝胶，将水凝胶绞碎得到初级高分子吸水树脂；
(3)将缩水甘油醚：丙二醇：碳酸丙烯酯：硝酸银按照质量比100:20:30:5的比例配制，得到表面交联剂，将该表面交联剂喷洒到步骤(2)得到的初级高分子吸水树脂表面，所述表面交联剂的添加比例为初级高分子吸水树脂质量的5％，然后将树脂放于110℃烘箱中，反应40min；
(4)将纳米二氧化钛与20g水混合充分搅拌得到悬浊液，所述纳米二氧化钛的质量为步骤(2)中初级高分子吸水树脂质量的0.5％，再将该悬浊液喷洒到步骤(3)得到的吸水树脂表面，然后将得到的产物放入烘干箱内，在105℃之间通风干燥30min后冷却至室温；最后将步骤(3)和(4)再循环两次，即得颗粒状的膨胀高分子注浆材料。
试验例4
1、一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，同实施例4，区别在于：步骤(4)中不包括添加导水剂的步骤，仅是将步骤(3)最终得到的产物进行通风干燥。
实施例5
一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，包括如下步骤：
(1)用去离子水稀释丙烯酸单体，得到浓度为35％的丙烯酸溶液80g，在冰水浴中缓慢加入质量分数为40％的氢氧化钠对丙烯酸水溶液进行中和，得到含有丙烯酸的不完全中和液，其中和度为80％；然后在该不完全中和液中加入0.14g聚乙二醇二缩水甘油醚，用磁力搅拌器搅拌15min；然后加入0.028g丙烯腈聚合反应1.5h，得到前驱体溶液；
(2)将过硫酸钠：偶氮二异丁酸二甲酯：过硫酸铵/硫酸亚铁按照质量比为1:2:5配制，得到引发剂，将0.168g该引发剂加入步骤(1)得到的前驱体溶液中，逐步将温度从5℃升至70℃(速率3℃/min)，反应30分钟得到水凝胶，将水凝胶绞碎得到初级高分子吸水树脂；
(3)将乙二醇：丙二醇：氯化铜按照质量比100:40:3的比例配制，得到表面交联剂，将该表面交联剂喷洒到步骤(2)得到的初级高分子吸水树脂表面，所述表面交联剂的添加比例为初级高分子吸水树脂质量的3％，然后将树脂放于115℃烘箱中，反应30min；
(4)将气相二氧化硅与25g水混合充分搅拌得到悬浊液，所述气相二氧化硅的质量为步骤(2)中初级高分子吸水树脂质量的1.4％，再将该悬浊液喷洒到步骤(3)得到的吸水树脂表面，然后将得到的产物放入烘干箱内，在100℃之间通风干燥20min后冷却至室温；最后将步骤(3)和(4)再循环两次，即得颗粒状的膨胀高分子注浆材料。
试验例5
1、一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，同实施例5，区别在于：步骤(1)中将丙烯酸完全中和成丙烯酸钠。
实施例6
一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，包括如下步骤：
(1)用去离子水稀释丙烯酸单体，得到浓度为35％的丙烯酸溶液80g，在冰水浴中缓慢加入质量分数为40％的氢氧化钠对丙烯酸水溶液进行中和，得到含有丙烯酸的不完全中和液，其中和度为90％；然后在该不完全中和液中加入0.42g聚乙二醇二缩水甘油醚，用磁力搅拌器搅拌15min；然后加入4.2g甲基丙烯酰胺聚合反应1.5h，得到前驱体溶液；
(2)将过硫酸钠：偶氮二异丁酸二甲酯：硫酸铵/亚硫酸氢钠按照质量比为1:3:5配制，得到引发剂，将0.196g该引发剂加入步骤(1)得到的前驱体溶液中，逐步将温度从5℃升至70℃(速率3℃/min)，反应30分钟得到水凝胶，将水凝胶绞碎得到初级高分子吸水树脂；
(3)将乙二醇：丙二醇：氯化铜按照质量比100:40:3的比例配制，得到表面交联剂，将 该表面交联剂喷洒到步骤(2)得到的初级高分子吸水树脂表面，所述表面交联剂的添加比例为初级高分子吸水树脂质量的5.5％，然后将树脂放于120℃烘箱中，反应20min；
(4)将活性氧化铝粉(粒径60-80nm)与15g水混合充分搅拌得到悬浊液，所述活性氧化铝粉的质量为步骤(2)中初级高分子吸水树脂质量的1.5％，再将该悬浊液喷洒到步骤(3)得到的吸水树脂表面，然后将得到的产物放入烘干箱内，在100℃之间通风干燥20min后冷却至室温；最后将步骤(3)和(4)再循环两次，即得颗粒状的膨胀高分子注浆材料。
实施例7
一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，包括如下步骤：
(1)用去离子水稀释丙烯酸单体，得到浓度为40％的丙烯酸溶液100g，在冰水浴中缓慢加入质量分数为25％的氢氧化钙对丙烯酸水溶液进行中和，得到含有丙烯酸的不完全中和液，其中和度为70％；然后在该不完全中和液中加入0.72g乙二醇二甲基丙烯酸酯，用磁力搅拌器搅拌12min；然后加入1.8g聚乙烯醇和1g蒙脱土聚合反应1.5h，得到前驱体溶液；
(2)将过硫酸钾：偶氮二异丁腈：过硫酸钾/氯化亚铁按照质量比为5:1:7配制，得到引发剂，将0.08g该引发剂加入步骤(1)得到的前驱体溶液中，逐步将温度从15℃升至65℃(速率2℃/min)，反应20分钟得到水凝胶，将水凝胶绞碎得到初级高分子吸水树脂；
(3)将乙二醇：丙二醇：硝酸银按照质量比100:40:1的比例配制，得到表面交联剂，将该表面交联剂喷洒到步骤(2)得到的初级高分子吸水树脂表面，所述表面交联剂的添加比例为初级高分子吸水树脂质量的4％，将树脂放于105℃烘箱中，反应35min；
(4)将二氧化钛与18g水混合充分搅拌得到悬浊液，所述气相二氧化钛的质量为步骤(2)中初级高分子吸水树脂质量的0.9％，再将该悬浊液喷洒到步骤(3)得到的吸水树脂表面，然后将得到的产物放入烘干箱内，在120℃之间通风干燥20min后冷却至室温；最后将步骤(3)和(4)再循环两次，即得颗粒状的膨胀高分子注浆材料。
性能测试：
1、对实施例1和2制备的膨胀高分子注浆材料在扫描电镜下观察微观结构，结果分别如图2和图3所示，从图3中可以看出，本发明制备的膨胀高分子注浆材料呈现出了明显的核壳结构，其中，步骤(2)得到的初级高分子吸水树脂为内核，而步骤(3)和(4)中分别添加的表面交联剂和导水剂这形成了外壳；而图2中外壳已经完全将内核包覆在了内部。
2、对实施例3制备的膨胀高分子注浆材料的膨胀效果进行测试，结果如图4、5所示，图4中左侧的小烧杯中装有150g未膨胀的注浆材料(大约5ml)，右侧大烧杯中是800ml自 来水，将未膨胀的注浆材料加入大烧杯中的自来水后结果如图5所示，可以看出，自来水已经完全被吸收，注浆材料的体积膨胀到了大约810-820ml，膨胀率达到了162倍。采用同样的方法对实施例1、2以及4-7制备的膨胀高分子注浆材料的膨胀效果进行测试，膨胀率分别为101、217、304、186、264、288倍说明本发明的注浆材料具有良好的吸水率和膨胀率。
3、为了研究高分子吸水树脂在含水构造中的扩散机制和封堵涌水的效果，本发明利用如下可视化的模拟封堵高压大流量突涌水装置(如图1所示)，有效地测试了动水条件下实施例和实验例制备的膨胀高分子注浆材料的堵水能力，确定合理的注浆堵水参数并对封堵效果进行评价，为进一步深入研究新材料注浆堵水工艺提供理论基础。所述可视化的模拟封堵高压大流量突涌水装置包括：动水供水系统、膨胀高分子注浆材料注入系统、储浆及输浆管道系统、数据采集与处理系统等四部分；储浆及输浆管路系统由可拆卸重组的亚克力管道、螺纹式千斤顶、金属过滤网、浆—水收集槽组成，管路进口处通过高压软管与稳压水源供水系统相连，高压软管上设置流量阀；亚克力管出口处设有浆—水收集槽；亚克力管前部设有浆液注入孔，与注入孔相连的注浆管上设置流量阀；数据采集与处理系统包括安装在亚克力管道上的动水流量传感器，高清摄影系统。如下装置所示，采用流量传感器，水流压力传感器对动水注浆不同位置处的水流流速及水流压力进行实时采集记录，并通过与计算机控制系统地连接实现试验过程的自动化量测。
测试膨胀高分子注浆材料封堵突涌水实验步骤如下：
步骤1：注浆泵通过高压输液管与注浆花管相连，花管插入亚克力管进口端的注浆孔内，并布置好注浆压力传感器与注浆流量传感器。
步骤2：根据施工中遇到的破碎带地质条件，确定突涌水的流量及流速，调整供水系统压力控制仪来提供与工程相似的动水条件，并在亚克力管的底部中间部分均布置好水流流量传感器及水流压力传感器，调整螺纹式千斤顶，把亚克力管调整至水平状态。
步骤3：将流量传感器和压力传感器连接至数据采集装置，设定采集频率及数据存储参数。
步骤4：注浆泵中加入颗粒类注浆材料。调整压力控制仪，给交叉管路提供不同的动水流速，待流速稳定后开启注浆泵，将注浆压力设为预定值。
步骤5：待颗粒类注浆材料扩散至出水口边界或者将动水水流被颗粒类材料封堵完全之后停止注浆。观测并实时监测记录不同流量下颗粒类注浆材料水压封堵情况。
步骤6：拆取封堵压力测试段亚克力管，与动水供水装置通过法兰盘连接，连接完成后， 慢慢给颗粒类封堵材料施加水压，测试封堵段极限承压能力，从而对封堵效果进行定量评价。
步骤8：改变不同试验条件，可以得到不同动水流速下膨胀高分子注浆材料用量对浆液扩散规律和动水封堵的影响。
步骤9：清洗颗粒类材料及颗粒类材料注入系统及试验平台。
表1
Figure PCTCN2019112042-appb-000001
表2
Figure PCTCN2019112042-appb-000002
表3
Figure PCTCN2019112042-appb-000003
表4
Figure PCTCN2019112042-appb-000004
Figure PCTCN2019112042-appb-000005
表5
Figure PCTCN2019112042-appb-000006
从表1-5可以看出，在流量为10L/min的条件下，仅用150g实施例1-5制备的膨胀高分子注浆材料，在225g携带液作用下即可成功封堵突涌水。实验过程中，通过调整供水系统水压，提供不同的水流流速及流量。随着水流流量的增大，调整高分子吸水树脂的注入量均能有效的对涌水进行封堵，且封堵效果显著，当调节到流量为50L/min的高压大流量突涌水条件下时，用500g高分子吸水树脂在750g携带液作用下即可成功封堵突涌水，说明本发明制备的膨胀高分子注浆材料具有优异的突涌水封堵效果。而实验例制备的注浆材料在使用量和实施例相同的情况下，当涌水的流量、流速较小时，也可以实现封堵，但封堵长度明显高于实施例，这是由于实验例制备的注浆材料的吸水率低，无法实现快速膨胀，需要随水流流动更长时间造成的。而当调节到流量为30L/min以上的高压大流量突涌水条件下时，实验例制备的注浆材料这无法实现有效的封堵，必须加大注浆材料的用量后才能实现有效封堵，而且封堵长度普遍高于实施例，这是由于实验例制备的注浆材料的吸水率、膨胀率等较低，在高压大流量突涌水中无法实现快速膨胀封堵，而是被水流冲散后形成线状分布，这种分布形式的注浆材料即使在后续膨胀，也无法再实现有效封堵。
以上所述仅为本申请的优选实施例，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (23)

  1. 一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，其特征在于：所述方法包括如下步骤：
    (1)在丙烯酸中加入交联剂；然后加入高分子吸水树脂共聚单体进行聚合反应，得到前驱体；
    (2)在步骤(1)的前驱体中加入引发剂，升温，反应后得到水凝胶，将水凝胶绞碎，得到初级高分子吸水树脂；
    (3)将表面交联剂喷洒到步骤(2)的初级高分子吸水树脂表面，将得到的产物烘干，备用；
    (4)将无机导水剂制备成悬浊液，将该悬浊液喷洒到步骤(3)烘干得到的产物上，烘干，即得膨胀高分子注浆材料；
    其中所述高分子吸水树脂共聚单体包括聚乙烯醇、丙烯酰胺、甲基丙烯酰胺或丙烯腈；
    所述交联剂包括N,N-亚甲基双丙烯酰胺、双季戊四醇六丙烯酸酯、季戊四醇四酯、季戊四醇三烯丙基醚、季戊四醇三丙烯酸酯、聚乙二醇二缩水甘油醚、乙氧基化甘油三丙烯酸酯、乙二醇二甲基丙烯酸酯中的一种或多种的组合物；
    所述表面交联剂包括水、多元醇、缩水甘油醚、碳酸乙烯酯、碳酸丙烯酯和多价金属化合物中的一种或多种的组合物；
    所述无机导水剂包括气相二氧化硅、纳米二氧化钛或活性氧化铝粉。
  2. 一种用于高压大流量岩溶突涌水治理的膨胀高分子注浆材料的制备方法，其特征在于：如权利要求1所述的制备方法中，步骤(1)中制备前驱体时，首先用碱液对丙烯酸进行不完全中和，得到含有丙烯酸的不完全中和液，然后将该不完全中和液与交联剂混合后，再与高分子吸水树脂共聚单体进行聚合反应，得到前驱体，后续步骤与权利要求1所述的制备方法中步骤(2)-(4)一致。
  3. 如权利要求2所述的制备方法，其特征在于，所述不完全中和液的中和度保持在40％-90％之间。
  4. 如权利要求2所述的制备方法，其特征在于，所述碱液包括氢氧化钠、氢氧化钙或两者的混合液。
  5. 如权利要求2所述的制备方法，其特征在于，所述碱液的质量浓度为20-50％。
  6. 如权利要求1或2所述的制备方法，其特征在于：步骤(1)中，所述丙烯酸的质量浓度为25-45％；
  7. 如权利要求6所述的制备方法，其特征在于：步骤(1)中，所述高分子吸水树脂共聚单体的添加比例为步骤(1)中丙烯酸质量的0.5-20％。
  8. 如权利要求6所述的制备方法，其特征在于：步骤(1)中，所述交联剂的添加比例为步骤(1)中丙烯酸质量的0.5-2％。
  9. 如权利要求6所述的制备方法，其特征在于：步骤(2)中，所述引发剂的添加比例为步骤(1)中丙烯酸质量的0.1-0.7％；
  10. 如权利要求6所述的制备方法，其特征在于：步骤(3)中，所述表面交联剂的添加比例为步骤(2)中初级高分子吸水树脂质量的3-6％；
  11. 如权利要求6所述的制备方法，其特征在于：步骤(4)中，所述无机导水剂的添加比例为初级高分子吸水树脂质量的0.5-1.5％。
  12. 如权利要求1或2所述的制备方法，其特征在于：
    步骤(2)中，所述引发剂包括：无机过氧化物引发剂、偶氮类引发剂、氧化还原引发剂。
  13. 如权利要求12所述的制备方法，其特征在于：所述无机过氧化物引发剂包括过硫酸钾、过硫酸钠、过硫酸铵；
    所述偶氮类引发剂包括偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯；
    所述氧化还原类引发剂包括过硫酸铵/亚硫酸氢钠、过氧化氢/硫酸亚铁、过硫酸铵/硫酸亚铁、过硫酸钾/氯化亚铁；其中“/”前的物质表示氧化类引发剂，“/”后物质表示还原类引发剂，每一组氧化还原引发剂同时使用；所述氧化类引发剂与还原类引发剂的质量比为1：3-8。
  14. 如权利要求1或2所述的制备方法，其特征在于：
    所述多元醇包括乙二醇、丙二醇或丙三醇；所述多价金属化合物包括硝酸银、氯化铜。
  15. 如权利要求1或2所述的制备方法，其特征在于：步骤(2)中，所述升温指：将反应温度逐步从0升至85℃，且所述引发剂为无机过氧化物引发剂、偶氮类引发剂、氧化还原引发剂三者的组合物。
  16. 如权利要求15所述的制备方法，其特征在于：所述无机过氧化物引发剂、偶氮类引发剂、氧化还原引发剂三者的质量比为1-2：1-2：1-7。
  17. 如权利要求1或2所述的制备方法，其特征在于：步骤(1)中，所述聚合反应的时间为1-1.5h；步骤(3)和(4)中，所述烘干的条件均为：在100-120℃下通风干燥20-60min。
  18. 权利要求1-17任一项所述的方法制备的膨胀高分子注浆材料，其特征在于：所述注浆材料具有核壳结构，其中，步骤(2)得到的初级高分子吸水树脂为内核，步骤(3)和步 骤(4)分别加入的表面交联剂和导水剂为外壳。
  19. 一种膨胀高分子注浆材料的组合物，其特征在于：所述组合物由膨胀高分子注浆材料和携带液组成；所述膨胀高分子注浆材料为权利要求1-17任一项所述的制备方法得到的膨胀高分子注浆材料。
  20. 如权利要求19所述的组合物，其特征在于：所述携带液包括丙三醇、乙醇中的一种或两种。
  21. 如权利要求19所述的组合物，其特征在于：所述膨胀高分子注浆材料和携带液的质量比为1-2：1-5。
  22. 如权利要求1-17任一项所述的制备方法或如权利要求18所述的膨胀高分子注浆材料或如权利要求19-21任一项所述的膨胀高分子注浆材料的组合物在建筑工程领域中的应用。
  23. 如权利要求22所述的应用，其特征在于，所述建筑工程领域中的应用为在涌突水治理中的应用。
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