WO2021098505A1 - 一种岩溶管道型涌水高效封堵超高膨胀注浆材料及其制备、使用方法和应用 - Google Patents

一种岩溶管道型涌水高效封堵超高膨胀注浆材料及其制备、使用方法和应用 Download PDF

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WO2021098505A1
WO2021098505A1 PCT/CN2020/126274 CN2020126274W WO2021098505A1 WO 2021098505 A1 WO2021098505 A1 WO 2021098505A1 CN 2020126274 W CN2020126274 W CN 2020126274W WO 2021098505 A1 WO2021098505 A1 WO 2021098505A1
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water
grouting material
cross
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preparation
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French (fr)
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李术才
刘人太
马晨阳
陈孟军
白继文
王振军
张华胜
段少龙
田嘉伟
张咪
张春雨
李修浩
盛祥超
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Shandong University
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    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
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    • C04B26/06—Acrylates
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    • 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
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    • C08L33/24—Homopolymers or copolymers of amides or imides
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Definitions

  • the invention belongs to the technical field of underground engineering plugging materials, and in particular relates to a karst pipeline type water gushing high-efficiency plugging ultra-high expansion grouting material, and a preparation, use method and application thereof.
  • the key problem of the frequent occurrence of water inrush disasters in the process of tunnel construction is that the mechanism of water inrush and collapse disasters in karst areas is extremely complicated, and the technical level of disaster control is extremely high.
  • domestic and foreign researchers have developed different grouting materials and proposed different treatment methods for different engineering problems.
  • the karst water-rich area has the characteristics of strong water source supplementation, complex geological structure, strong hydraulic connectivity, and presents a pressure state, large flow, fast flow velocity, etc., which makes the existing grouting materials and treatment technology systems lack of pertinence, and it is difficult to achieve the above disasters.
  • the effective sealing and reinforcement treatment of the tunnel has led to a high-risk state of tunnel construction and engineering operations.
  • the prior patent of the present invention proposes an expanding polymer grouting material for the treatment of high-pressure and large-flow karst inrush water and a preparation method thereof.
  • the grouting material includes an acrylic acid solution and a crosslinking agent. , Initiator, surface crosslinking agent, carrier fluid.
  • the expandable polymer grouting material has the technical advantages of an expansion ratio as high as 101-304 times, an adjustable expansion rate, environmental protection and no pollution, and a high-efficiency plugging treatment effect on karst water gushing, which significantly improves the efficiency of underground engineering water gushing treatment.
  • the present invention proposes a karst pipeline type water-gushing efficient plugging ultra-high expansion grouting material and its preparation and use methods And application.
  • the present invention uses molecular structure design theory to design acrylic resin particles and carrier fluid from the perspectives of water swelling rate, salt resistance, gel coagulation rate, and inrush water blocking performance.
  • the composition and structure of the cross-linked curing liquid The grouting material proposed by the present invention can efficiently treat high-pressure and large-flow karst water inrush, improve and increase the efficiency of water inrush blocking, and further promote the construction of major underground projects in my country.
  • the first object of the present invention is to provide a method for preparing a karst pipeline type water gushing material for efficiently plugging an ultra-high expansion grouting material.
  • the second object of the present invention is to provide an ultra-high expansion grouting material prepared by the above method.
  • the third object of the present invention is to provide a method for using the ultra-high expansion grouting material prepared by the above method.
  • the fourth object of the present invention is to provide the application of the ultra-high expansion grouting material prepared by the above preparation method.
  • the present invention discloses a preparation method of a karst pipeline-type water gushing efficient plugging ultra-high expansion grouting material, which includes the following steps:
  • this synthesis method is a static solution polymerization method, which is to combine polymerized monomers with crosslinking Coupling agent and other additives are prepared into a solution, and then reacted at a certain temperature, with simple operation and low cost.
  • step (2) Add an initiator to the precursor obtained in step (1), obtain a colloidal polymer after the temperature rise reaction, the colloidal polymer is crushed and dried to obtain primary polymer water-absorbing resin particles.
  • the gelling catalyst is a combination of polyethylene glycol (PEG), p-di-o-chloroaniline (MOCA) and polyether polyol; the cross-linking curing liquid B is a substance that can react with water.
  • the mass fraction of the acrylic acid solution is 10-80%.
  • the synthesis process of high molecular polymer particles is a free radical copolymerization reaction, and a lot of heat is released during the reaction; as the monomer concentration increases, the reaction rate increases, and the heat released by the reaction is less likely to be dissipated, leading to the reaction.
  • the present invention recommends The mass fraction of acrylic acid solution is 10-80%.
  • the mass fraction of the acrylic acid solution can be appropriately increased or decreased based on the above range, such as 10.01%, 10.1%, 80.01% or 80.1%, etc., which still fall into the scope of the present invention.
  • the addition amount of other components, raw materials, etc. involved in the subsequent, process parameters, etc. can also be adjusted according to the actual situation, and will not be repeated hereafter.
  • the hydrophilic group-containing active substance includes any one or a mixture of several of starch, polyvinyl alcohol, polyacrylamide, acrylamide, etc., or several of the above substances Any one or a mixture of several of the solutions, such as starch solution, polyvinyl alcohol solution, etc. These raw materials have abundant sources, low prices, and excellent water absorption properties.
  • the cellulose-based polymer water-absorbent resin mentioned in the previous patent of the present invention (authorized announcement number: CN 109535306 B) is not excluded as an active substance containing hydrophilic groups, such as hydroxyethyl cellulose, a Base cellulose or carboxymethyl cellulose, etc.
  • the crosslinking agent includes any one or more of N,N-methylenebisacrylamide, divinylbenzene, isocyanate, dipentaerythritol hexaacrylate, and pentaerythritol tetraester Compositions.
  • step (1) the addition ratio of the crosslinking agent is 0.3-2% of the mass of acrylic acid in step (1).
  • the type of crosslinking agent and the degree of crosslinking have a greater impact on the water absorption rate of high molecular polymer particles.
  • the degree of crosslinking As the amount of crosslinking agent increases, high molecular polymer particles On the contrary, its water absorption capacity decreases, but the gel strength increases. From the perspective of increasing the water absorption rate of high molecular polymer particles, it is recommended to reduce the degree of crosslinking as much as possible on the premise that the high molecular polymer particles can be synthesized. Therefore, the present invention controls the amount of crosslinking agent to be 0.3-2 %between.
  • the initiator is an inorganic peroxide initiator, for example, sodium persulfate, potassium persulfate, ammonium persulfate, and the like.
  • Initiators are generally compounds with weak bonds that are easily decomposed into active species. They are also called free radical initiators, which refer to a class of compounds that are easily decomposed into primary free radicals by heat.
  • step (2) the amount of the initiator added is 0.1-0.7% of the mass of acrylic acid in step (1), and the initiation reaction rate at this time is more appropriate.
  • step (2) the temperature of the polymerization reaction is 65-90°C, and the reaction time is 23-119 min.
  • the drying conditions are: ventilating and drying at 100-200° C. for 20-120 min.
  • the drying temperature is higher than 200°C, the high molecular polymer particles are unstable, and the obtained high molecular polymer particles A are prone to yellowing, the drying temperature is too low, and the required drying time is too long, which affects production efficiency.
  • step (3) the mass ratio of polyethylene glycol (PEG): p-di-o-chloroaniline (MOCA): polyether polyol in the gelling catalyst is (1-5): ( 1-5): (2-5).
  • PEG polyethylene glycol
  • MOCA p-di-o-chloroaniline
  • the gelling catalyst is configured as an aqueous solution; it is convenient to spray uniformly on the surface of the primary polymer water-absorbing resin particles.
  • the gelling catalyst is configured as an aqueous solution with a mass fraction of 50-90%. If the mass fraction of the gelling catalyst solution is less than 50%, the drying time will be prolonged and energy consumption will be increased. If the mass fraction of the gelling catalyst solution is higher than 90%, it will be difficult for the gelling catalyst to evenly penetrate the surface of each particle.
  • the amount of the gelling catalyst solution accounts for 1-10% of the total mass of the particles.
  • the function of the gelling catalyst is to promote the reaction process of the crosslinked solidified liquid B and water after the high molecular polymer particles A absorb water and expand, accelerate the gelation reaction process, and improve the efficiency of water gushing blocking.
  • the present invention provides another method for preparing the precursor.
  • the difference from the foregoing preparation method is that: when preparing the precursor in step (1), the acrylic acid is first incompletely neutralized with lye to obtain The incomplete neutralization liquid of acrylic acid is mixed with the crosslinking agent and then polymerized with the active material containing the hydrophilic group to obtain the precursor.
  • the degree of neutralization of the incomplete neutralization liquid is controlled at 60-90%. Tests have shown that when the neutralization is too low, the viscosity of the gel produced by the reaction is too large, and it is difficult to grind for subsequent operations. When the neutralization is too high, the carboxylate concentration in the system is too high, the reaction rate decreases, the product crosslinking degree becomes low, and the water solubility increases, which easily leads to a decrease in the water absorption rate of the product.
  • the lye includes any one or a mixture of sodium hydroxide, calcium hydroxide, and potassium hydroxide.
  • the mass fraction of the lye is controlled between 10-60%, because too high concentration of the lye will cause the acrylic acid solution and the lye to react quickly and release a lot of heat, which is not conducive to the operation of the production personnel and affects the production efficiency. If the concentration of lye is too low, the amount of lye added will be too large, and the water content of the formed colloidal polymer will be too high, which is difficult to dry and increases production energy consumption.
  • the degree of neutralization refers to the degree of progress of the neutralization reaction.
  • a part of acrylic acid is neutralized by alkali solution.
  • 10% of acrylic acid monomer in the acrylic acid solution is neutralized, that is, the degree of neutralization is 10%.
  • Changing the degree of neutralization of acrylic acid can change the ratio of the two groups -COOH and -COONa, which have different hydrophilicities in the resin, thereby affecting the water absorption performance of the product.
  • the activity of acrylic acid is higher than that of sodium acrylate. If the degree of neutralization is lower, the acidity is higher, and the polymerization reaction is difficult to control.
  • the present invention recommends keeping the neutralization degree of the incomplete neutralization solution between 40-90%.
  • the present invention discloses the preparation method of the cross-linked solidified liquid B, which includes the following steps:
  • Synthesize prepolymer Add polyisocyanate dropwise to the dehydrated polyether polyol under heating, and after completion, the temperature will be raised to carry out the polymerization reaction, and the temperature will be lowered when the end of the reaction is reached, and the resulting prepolymer will be stored in a sealed container. In a dry container.
  • step S1 the vacuum heating conditions are: dehydration at 110-120°C and vacuum degree -0.08-0.1MPa for 2.5-4h, and cooling to below 50°C after completion.
  • the polyether polyol is a difunctional or trifunctional low-molecular-weight hydrophilic polyether.
  • difunctional or trifunctional low-molecular-weight hydrophilic polyether has low viscosity, good fluidity, good toughness and high elasticity. It not only has waterproof ability, but excellent elastic deformation performance can greatly reduce the damage caused by deformation during waterproofing. .
  • the plasticizer includes any one or a mixture of phthalates, terephthalates, isophthalates, and the like.
  • step S1 the added mass ratio of the polyether polyol and the plasticizer is 2.94-5.88:1-2.05.
  • step S2 the isocyanate is toluene diisocyanate (TDI) or polymethylene polyphenyl polyisocyanate (PAPI) or diphenylmethane diisocyanate (MDI) or a combination thereof.
  • TDI toluene diisocyanate
  • PAPI polymethylene polyphenyl polyisocyanate
  • MDI diphenylmethane diisocyanate
  • step S2 the heating conditions are heating to no more than 50° C., controlling the temperature to be constant and the dripping is completed within 30 minutes, the dripping is completed, and the stirring is uniform.
  • step S2 the temperature at which the temperature is raised to perform the polymerization reaction is 80-85°C.
  • samples are taken every 30 minutes to determine the% content of -NCO, until the content is basically unchanged, which is the end of the reaction.
  • the -NCO% when the -NCO% is controlled at 7-12%, it is the end of the reaction. As the content of -NCO% in the system increases, the viscosity gradually decreases, the gel time becomes faster, and the amount of water contained decreases. With the increase of -NCO% content, the hard segment content of the system increases, the soft segment content decreases, the corresponding hydrophilic group decreases, and the amount of water contained decreases. If you continue to increase the -NCO% content to more than 12%, the slurry reacts violently with water, and the reaction rate is very fast. It is easy to cause the polymer particles A to expand completely in the future, and the cross-linked solidified liquid B has reacted to form a gel, which reduces the material Expansion performance. Therefore, the preferred formula of the present invention is to control the -NCO% content of the reaction system between 7-12%.
  • the diluent is acetone.
  • the added amount of the diluent is 15-35% of the mass of the prepolymer, more preferably 25-35%.
  • the viscosity of the slurry obtained from the reaction will decrease, and the viscosity will decrease greatly between 15% and 35%.
  • acetone is added continuously, the viscosity of the slurry will still decrease but the trend is slow; the amount of water in the slurry increases with the increase of the amount of acetone. After increasing, it decreases, and the overall change is small; as the amount of acetone increases, the gel time is prolonged, and the compressive strength of the gel is weakened to a certain extent. Therefore, the overall performance of the grouting material obtained when the diluent in the above-mentioned range is used as the solvent of the crosslinking solidified liquid B in the present invention is better.
  • the present invention discloses the ultra-high expansion grouting material obtained by the above preparation method, which is characterized in that: the grouting material comprises high molecular polymer particles A and a cross-linking solidification liquid B, and the high molecular polymer particles A It has a mosaic core-shell structure and is a polyacrylic acid series polymer water-absorbing resin.
  • the primary polymer water-absorbing resin obtained in step (2) is the core, and the gelling catalyst added in step (3) is partially attached to the surface of the core to form At the same time, part of the gelling catalyst penetrates into the inner core to form a mosaic structure.
  • this mosaic core-shell structure after infiltration, the remaining amount of the catalyst can be enough for catalysis after subsequent expansion, and if it is only attached to the surface of the core, the surface area of the polymer particles A after expansion
  • the sharp increase results in the inability to provide enough catalyst to catalyze the full reaction of the cross-linked curing liquid B that is in large contact with the surface of the high molecular polymer particle A.
  • the severe surface expansion may also cause some of the catalyst to fall off and cause losses, which further aggravates the reduction of the catalyst. Therefore, by infiltrating part of the gelling catalyst into the inner core to form an inlaid structure, the catalyst can be pre-stored and supplemented.
  • the present invention provides a method for using the ultra-high expansion grouting material, specifically: before use, the high molecular polymer particles A and the cross-linking curing liquid B are stored separately; when used, the high molecular weight The polymer particles A and the cross-linking solidification liquid B are stirred to make them fully mixed; and then the obtained mixed liquid is used as a grouting material and injected into the cracks of the rock mass fracture zone.
  • the high molecular polymer particles A rapidly absorb water and expand, and the volume expansion is more than 200 times of the original.
  • the cross-linking solidification liquid B reacts with the water in the crushing zone and the water on the surface of the high molecular polymer particles, effectively removing the expanded polymer
  • the polymer particles A are bonded together to more firmly bond the polymer particles A and the broken rock mass in the formation to form a gel consolidation body to realize the treatment of inrush water in the water-rich fracture zone. Effectively solve the technical problem that grouting materials are difficult to retain under water gushing conditions.
  • the mass ratio of the high molecular polymer particles A and the cross-linking curing liquid B is (1-3): (1-5).
  • a catalyst or retarder can be added to the cross-linked curing liquid B before use to control the solidification rate of the cross-linked curing liquid B after encountering water.
  • the catalyst is composed of m-toluene diamine, triethylene diamine and dibutyl tin dilaurate.
  • the ratio of m-toluenediamine: triethylenediamine: dibutyltin dilaurate is 1-2:1-2:2-4 in order.
  • Amine and tin catalysts have a "synergistic effect", that is, when tertiary amine catalysts and organotin catalysts are used together, the catalytic effect will be stronger than when a single type of catalyst is used.
  • the added amount of the catalyst is 2 to 5% of the mass of the cross-linking curing liquid B.
  • Different water gushing geological environments have different requirements for the performance of the slurry. Especially for high-pressure and large-flow water inrush, the slurry needs to have a faster condensation rate, but for the treatment of water inrush from wide fissures, the slurry needs to diffuse deep into the formation. Therefore, different geological environments have different requirements for the setting time of the slurry.
  • the present invention realizes the control of the solidification speed of the slurry by adjusting the amount of catalyst.
  • the retarder is an organic weak acid compound; for example, tartaric acid, citric acid and the like.
  • the cross-linking curing fluid B has a higher reactivity and a faster reaction rate, and it usually gels within ten seconds. Based on this, in some cases, in order to increase the penetration radius of the slurry in the formation, the slurry should be extended according to engineering needs. For gel time, adding a certain amount of retarder is essential.
  • the amount of the retarder is controlled between 8-12%, and the gel time of the cross-linked curing liquid B is adjustable from tens of seconds to hundreds of seconds.
  • the present invention discloses the application of the ultra-high expansion grouting material in the field of construction engineering, especially the application in the plugging of karst water inrush.
  • the present invention has achieved the following beneficial effects:
  • the volume of high molecular polymer particles A rapidly expands after encountering water, and the volume increase is 55-204 times or more than the original expansion ratio.
  • the catalyst on the surface of the particles is exposed, which effectively promotes the cross-linking curing liquid B and the crushing zone.
  • the gelation reaction process of water effectively binds the expanded high molecular polymer particles A to form a gel consolidated body, realizing the treatment of inrush water in the water-rich fracture zone.
  • the cross-linked curing liquid B not only plays the role of suspending and carrying the high molecular polymer particles A, but also can be used in the high molecular polymer particles.
  • a surface catalyst reacts with the water in the formation to effectively bond the expanded polymer particles A, and more firmly bond the polymer particles A to the broken rock mass in the formation.
  • a flexible consolidation body is formed to realize the treatment of water inrush in the water-rich karst area, and effectively solve the technical problem that the grouting material is difficult to retain under the condition of water inrush.
  • the coagulation time of the material of the present invention is stable and controllable. With the material of the present invention, the coagulation of the slurry can be effectively controlled according to the needs of the project to ensure that the slurry has good operability and engineering applicability.
  • the ultra-high expansion polymer grouting material prepared in the present invention realizes the full composite of multi-component materials, achieves the purpose of super-superposition effect of each component, and achieves the effect of effectively blocking the water gushing in the water-rich karst area. Moreover, this grouting material has the technical advantages of convenient operation and safer.
  • Fig. 1 is a physical effect diagram of high molecular polymer particles A prepared in Example 1 of the present invention.
  • Fig. 2 is a physical effect diagram of the cross-linking solidified liquid B prepared in Example 1 of the present invention.
  • FIG. 3 is an actual effect diagram of an expanded polymer grouting material configured by polymer particles A and cross-linking curing liquid B prepared in Example 1 of the present invention.
  • Fig. 4 is a physical effect diagram of the expanded polymer grouting material described in Fig. 3 after being swollen with water.
  • FIG. 5 is an SEM image of high molecular polymer particles A prepared in Example 1 of the present invention.
  • Example 6 is an SEM image of a consolidated body formed by cross-linking high molecular polymer particles A prepared in Example 1 of the present invention.
  • the present invention proposes a karst pipeline type water-gushing efficient plugging ultra-high expansion grouting material and the same Preparation and use methods; the present invention will be further described below with reference to the drawings and specific embodiments.
  • the preparation of an ultra-high expansion grouting material for efficient plugging of karst pipeline-type water gushing includes the following steps:
  • Acrylic acid neutralization stage firstly, 36 parts of 10% acrylic acid solution and 5 parts of 20% acrylamide copolymer solution are prepared with ice water, and 12 parts of 10% lye are added to obtain the degree of neutralization. It is a 60% acrylic acid solution.
  • step (3) Drying and pulverizing stage: the colloidal polymer obtained in step (3) is crushed, and then dried in a drying oven at 100° C. to a constant weight, and the sieved particles are crushed to obtain primary polymer water-absorbing resin particles.
  • the gelling catalyst polyethylene glycol: p-di-o-chloroaniline: polyether polyol mass ratio of 5 parts of cross-linked curing liquid B is 2:1:2 in order
  • the solution is sprayed uniformly onto the primary polymer water-absorbing resin particles obtained in step (3), and then placed in an oven at 160° C. and air-dried again to obtain polymer particles A for use.
  • Polyether polyol dehydration add 50 parts of polyoxypropylene glycol N204 (hydroxyl value 255mgKOH/g, functionality of 2) and 17 parts of phthalate into a container equipped with a stirrer and a thermometer for heating And start stirring, heat up and vacuum, dehydrate at 110°C and vacuum degree -0.08MPa for 3h, then cool to below 50°C, put it in a dry container and keep it tightly closed for later use.
  • the high-molecular polymer particles A prepared in this example and the cross-linking curing liquid B were mixed uniformly at a mass ratio of 1:1 to prepare an expanded polymer grouting material, and various performance indicators were tested. The results are shown in Table 1.1 -1.3 as shown.
  • the method for testing the expansion ratio of polymer particles A is (the same method is used in other embodiments): Take 1g of polymer particles A and put it into a 400 mesh gauze, immerse it in an aqueous solution, and filter with filter paper after the material fully absorbs water and swells. The residual moisture on the dry surface, and record the change in the quality of its water absorption.
  • the swelling ratio Sw (unit: (g/g)) is calculated by the following formula:
  • M 0 and M n are the masses of the dried and water-absorbed polymer particles A, respectively.
  • the cross-linked solidified liquid B reacts with ten times of water, and the average gel time test method (other examples adopt the same method) is: accurately weigh 10 g of cross-linked solidified liquid B into a beaker, add 100 ml of water, and record the time when the water is added At time t 1 , stir it evenly (about 10 s) and then stand still to obtain a white emulsion, and then use a glass rod to continuously detect the change in viscosity. When the glass rod leaves the liquid surface and there is a wire drawing phenomenon, it is deemed that the sample has been gelled.
  • Test method for the maximum expansion ratio of the expanded polymer grouting material (the same method is used in other embodiments): prepare the slurry according to the proportion, take 1 part of the expanded polymer grouting material and place it in 100 parts of pure water, and wait until the material fully absorbs water and expands , Use filter paper to filter out the residual moisture on the surface and record the change in its water absorption quality.
  • the swelling ratio Sw (unit: (g/g)) is calculated by the following formula:
  • M 2 and M 1 are the masses of the swelling polymer grouting material before and after encountering water (unit: g).
  • Exterior Relative density B reacts with ten times water, average gel time Light yellow liquid 1.05 86.5s
  • the preparation of an ultra-high expansion grouting material for efficiently plugging karst pipeline type water gushing includes the following steps:
  • Acrylic acid neutralization stage firstly, 36 parts of 80% acrylic acid solution and 5 parts of 10% acrylamide copolymer solution are prepared with ice water, and 24 parts of 60% lye are added to obtain the degree of neutralization. It is a 90% acrylic acid solution neutralization solution.
  • step (3) Drying and pulverizing stage: the colloidal polymer obtained in step (3) is crushed, and then dried in a drying oven at 200° C. to a constant weight, and the sieved particles are crushed to obtain primary polymer water-absorbing resin particles.
  • Polyether polyol dehydration 25 parts of polyether polyol PEG1000 (hydroxyl value 112mgKOH/g, functionality 2) and 75 parts of polyether polyol 505S (hydroxyl value 56.3mgKOH/g, functionality 3) Add 35 parts of phthalate into a container equipped with a stirrer and a thermometer to heat and start stirring, increase the temperature and vacuumize, dehydrate for 2.5h under the conditions of 120°C, vacuum degree -0.1MPa, and then cool to below 50°C , Put it in a dry container and keep tightly closed for later use.
  • the polymer particles A prepared in this embodiment and the cross-linking curing liquid B are mixed uniformly at a mass ratio of 3:5 to prepare an expanded polymer grouting material, and various performance indicators are tested. The results are shown in Table 2.1 -2.3 shown.
  • Exterior Relative density B reacts with ten times water, average gel time Light yellow liquid 1.08 104.5s
  • A B Exterior Maximum expansion ratio of A+B in pure water S A+B A+B reacts with ten times of water, average gel time 3:5 Light yellow liquid 72.6g/g 29.8s
  • the preparation of an ultra-high expansion grouting material for efficiently plugging karst pipeline type water gushing includes the following steps:
  • Acrylic acid neutralization stage firstly, 36 parts of 40% acrylic acid solution and 5 parts of 10% acrylamide copolymer solution are prepared with ice water, and 12 parts of 50% lye are added to obtain the degree of neutralization. It is a 75% acrylic acid neutralizer.
  • step (3) Drying and pulverizing stage: the colloidal polymer obtained in step (3) is crushed, and then dried in a drying oven at 200°C to a constant weight, and the sieved particles are crushed to obtain primary polymer water-absorbing resin particles.
  • Polyether polyol dehydration 35 parts of polyether polyol PEG1000 (hydroxyl value 112mgKOH/g, functionality 2) and 65 parts of polyether polyol 505S (hydroxyl value 56.3mgKOH/g, functionality 3) Add 35 parts of isophthalate into a container equipped with a stirrer and a thermometer to heat and start stirring. The temperature is raised and vacuumed, dehydrated at 110°C and vacuum -0.095MPa for 3h, and then cooled to below 50°C. Put it in a dry container and keep it tightly closed for later use.
  • the high molecular polymer particles A prepared in this embodiment and the cross-linking curing liquid B are mixed uniformly at a mass ratio of 2:3 to prepare an expanded high molecular grouting material, and various performance indicators are tested. The results are shown in Table 3.1 -3.3 shown.
  • Exterior Relative density B reacts with ten times water, average gel time Light yellow liquid 1.12 98.7s
  • the preparation of an ultra-high expansion grouting material for efficiently plugging karst pipeline type water gushing includes the following steps:
  • Acrylic acid neutralization stage Firstly, 36 parts of 30% acrylic acid solution and 8 parts of 10% acrylamide copolymer solution are prepared with ice water, and 9.6 parts of 50% lye are added to obtain the degree of neutralization. It is a neutralization solution of 80% acrylic acid solution.
  • step (3) Drying and pulverizing stage: the colloidal polymer obtained in step (3) is crushed, and then dried in a drying oven at 200° C. to a constant weight, and the sieved particles are crushed to obtain primary polymer water-absorbing resin particles.
  • gelling catalyst of cross-linking curing liquid B polyethylene glycol: p-di-o-chloroaniline: polyether polyol mass ratio in order of 1:2:3 is configured to a mass fraction of 50%
  • the solution is sprayed uniformly on the primary polymer water-absorbing resin particles obtained in step (3), and placed in an oven at 160° C. and air-dried again to obtain polymer particles A.
  • Polyether polyol dehydration 25 parts of polyether polyol N330 (hydroxyl value 57mgKOH/g, functionality of 2) and 75 parts of polyether polyol N310 (hydroxyl value of 165mgKOH/g, functionality of 3) and Add 35 parts of terephthalate into a container equipped with a stirrer and a thermometer to heat and start stirring. The temperature is raised and vacuumed, dehydrated at 115°C and a vacuum of -0.095MPa for 2.5 hours, and then cooled to below 50°C. Put it in a dry container and keep it tightly closed for later use.
  • the high molecular polymer particles A prepared in this embodiment and the cross-linking curing liquid B are mixed uniformly at a mass ratio of 2:1 to prepare an expanded high molecular grouting material, and various performance indicators are tested. The results are shown in Table 4.1 -4.3 shown.
  • Exterior Relative density B reacts with ten times water, average gel time Light yellow liquid 1.09 84.2s
  • the preparation of an ultra-high expansion grouting material for efficiently plugging karst pipeline type water gushing includes the following steps:
  • Acrylic acid neutralization stage Firstly, 36 parts of 50% acrylic acid solution and 10 parts of 10% acrylamide copolymer solution are prepared with ice water, and 14 parts of 50% lye are added to obtain the degree of neutralization. It is a 75% acrylic acid solution neutralization solution.
  • step (3) Drying and pulverizing stage: the colloidal polymer obtained in step (3) is crushed, and then dried in a drying oven at 100° C. to a constant weight, and the sieved particles are crushed to obtain primary polymer water-absorbing resin particles.
  • Polyether polyol dehydration 30 parts of polyether polyol N210 (hydroxyl value 117mgKOH/g, functionality of 2) and 70 parts of polyether polyol N220 (hydroxyl value of 57mgKOH/g, functionality of 3) and Add 30 parts of isophthalate into a container equipped with a stirrer and thermometer to heat and start stirring. The temperature is raised and vacuumed, dehydrated at 120°C and vacuum -0.095MPa for 2.5 hours, and then cooled to below 50°C Put it in a dry container and keep it tightly closed for later use.
  • the high molecular polymer particles A prepared in this embodiment and the cross-linking curing liquid B are mixed uniformly at a mass ratio of 3:2 to prepare an expanded high molecular grouting material, and various performance indicators are tested. The results are shown in Table 5.1 -5.3 shown.
  • Exterior Relative density B reacts with ten times water, average gel time Light yellow liquid 1.10 83.5s
  • the preparation of an ultra-high expansion grouting material for efficiently plugging karst pipeline type water gushing includes the following steps:
  • Acrylic acid neutralization stage firstly, 36 parts of 30% acrylic acid solution and 5 parts of 10% acrylamide copolymer solution are prepared with ice water, and 8.4 parts of 30% lye are added to obtain the degree of neutralization. It is a 70% acrylic acid solution neutralization solution.
  • step (3) Drying and pulverizing stage: the colloidal polymer obtained in step (3) is crushed, and then dried in a drying oven at 100° C. to a constant weight, and the sieved particles are crushed to obtain primary polymer water-absorbing resin particles.
  • the gelling catalyst (polyethylene glycol: p-di-o-chloroaniline: polyether polyol mass ratio of 5 parts of cross-linked curing liquid B is 2:1:2 in order) is configured to a mass fraction of 50%
  • the solution is sprayed uniformly on the primary polymer water-absorbing resin particles obtained in step (3), and placed in an oven at 160° C. and air-dried again to obtain polymer particles A for use.
  • Polyether polyol dehydration 30 parts of polyether polyol N303 (hydroxyl value 560mgKOH/g, functionality 2) and 70 parts of polyether polyol N240 (hydroxyl value 28mgKOH/g, functionality 3) are combined with Add 30 parts of isophthalate into a container equipped with a stirrer and thermometer to heat and start stirring. The temperature is raised and vacuumed, dehydrated at 110°C and vacuum -0.08MPa for 4 hours, and then cooled to below 50°C. Put it in a dry container and keep it tightly closed for later use.
  • the high molecular polymer particles A prepared in this embodiment and the cross-linking curing liquid B are mixed uniformly at a mass ratio of 1:1 to prepare an expanded high molecular grouting material, and various performance indicators are tested. The results are shown in Table 6.1 -6.3 shown.
  • Exterior Relative density B reacts with ten times water, average gel time Light yellow liquid 1.11 91.5s
  • the preparation of an ultra-high expansion grouting material for efficiently plugging karst pipeline type water gushing includes the following steps:
  • Acrylic acid neutralization stage Firstly, 36 parts of 50% acrylic acid solution and 10 parts of 10% acrylamide copolymer solution are prepared with ice water, and 14 parts of 50% lye are added to obtain the degree of neutralization. It is a 75% acrylic acid solution neutralization solution.
  • step (3) Drying and pulverizing stage: the colloidal polymer obtained in step (3) is crushed, and then dried in a drying oven at 100° C. to a constant weight, and the sieved particles are crushed to obtain primary polymer water-absorbing resin particles.
  • Polyether polyol dehydration 30 parts of polyether polyol N210 (hydroxyl value 117mgKOH/g, functionality of 2) and 70 parts of polyether polyol N220 (hydroxyl value of 57mgKOH/g, functionality of 3) and Add 20 parts of isophthalate into a container equipped with a stirrer and a thermometer to heat and start stirring. The temperature is raised and vacuumed, dehydrated at 115°C and vacuum -0.095MPa for 3.5 hours, and then cooled to below 50°C. Put it in a dry container and keep it tightly closed for later use.
  • step (3) Take 75 parts of the prepolymer synthesized in step (2), add 25 parts of acetone diluent, add 8 parts of retarder tartaric acid, and stir evenly to obtain cross-linked solidified liquid B.
  • the high-molecular polymer particles A prepared in this example and the cross-linking curing liquid B were mixed uniformly at a mass ratio of 3:4 to prepare an expanded polymer grouting material, and various performance indicators were tested. The results are shown in Table 7.1 -7.3 shown.
  • Exterior Relative density B reacts with ten times water, average gel time Light yellow liquid 1.11 256.5s
  • A B Exterior Maximum expansion ratio of A+B in pure water S A+B A+B reacts with ten times of water, average gel time 3:4 Light yellow liquid 75.3g/g 187.5s
  • the preparation of an ultra-high expansion grouting material for efficiently plugging karst pipeline type water gushing includes the following steps:
  • Acrylic acid neutralization stage Firstly, 36 parts of 50% acrylic acid solution and 10 parts of 10% acrylamide copolymer solution are prepared with ice water, and 14 parts of 50% lye are added to obtain the degree of neutralization. It is a 75% acrylic acid solution neutralization solution.
  • step (3) Drying and pulverizing stage: the colloidal polymer obtained in step (3) is crushed, and then dried in a drying oven at 100° C. to a constant weight, and the sieved particles are crushed to obtain primary polymer water-absorbing resin particles.
  • Polyether polyol dehydration 30 parts of polyether polyol N210 (hydroxyl value 117mgKOH/g, functionality of 2) and 70 parts of polyether polyol N220 (hydroxyl value of 57mgKOH/g, functionality of 3) and Add 20 parts of isophthalate into a container equipped with a stirrer and thermometer to heat and start stirring. The temperature is raised and vacuumed, dehydrated at 120°C and vacuum -0.095MPa for 3 hours, and then cooled to below 50°C. Put it in a dry container and keep it tightly closed for later use.
  • step (3) Take 70 parts of the prepolymer synthesized in step (2), add 30 parts of acetone diluent, 12 parts of retarder citric acid, and stir evenly to obtain cross-linked solidified liquid B.
  • the high-molecular polymer particles A prepared in this example and the cross-linking curing liquid B were mixed uniformly at a mass ratio of 3:4 to prepare an expanded polymer grouting material, and various performance indicators were tested. The results are shown in Table 8.1 -8.3 shown.
  • Exterior Relative density B reacts with ten times water, average gel time Light yellow liquid 1.08 341.5s
  • A B Exterior Maximum expansion ratio of A+B in pure water S A+B A+B reacts with ten times of water, average gel time 3:4 Light yellow liquid 95.8g/g 287.5s
  • the expansion ratio of the high molecular polymer particle A is as high as 55-204 times or more after encountering water. This is because the cross-linking curing liquid B reacts with the water in the formation under the action of the surface catalyst of the high molecular polymer particle A, effectively bonding the expanded high molecular polymer particle A, and more firmly and the polymer
  • the polymer particles A are bonded together to form an elastic consolidated body, which is more beneficial to the treatment of water inrush in karst areas. "Swelling in contact with water and blocking water with water” effectively solves the problem of grouting materials that are difficult to retain under water inrush conditions. technical challenge.
  • the coagulation time of the grouting material prepared by the present invention can be controlled by the amount of catalyst added, and can be effectively controlled according to engineering needs, ensuring that the slurry has good operability and engineering applicability.
  • the multi-component material is fully compounded, the super-superposition effect of each component is achieved, and the effect of effectively blocking the water gushing in the water-rich karst area is achieved.
  • this grouting material has the technical advantages of convenient operation and more efficient.

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Abstract

本发明属于地下工程封堵材料技术领域，尤其涉及一种岩溶管道型涌水高效封堵超高膨胀注浆材料及其制备、使用方法和应用。该注浆材料包含高分子聚合物颗粒体A与交联固化液B，所述高分子聚合物颗粒体A具有镶嵌式核壳结构，其中，初级高分子吸水树脂为内核，胶凝催化剂部分附着在内核表面形成了外壳，同时，还有部分胶凝催化剂渗入内核形成镶嵌结构；使用前将高分子聚合物颗粒体A与交联固化液B搅拌，使其充分混合；然后将得到的混合液作为注浆材料注入岩体破碎带的裂隙中，即可。本发明提出的注浆材料可高效的治理高压大流量岩溶突涌水，改善并提高涌水封堵效率，进一步促进我国重大地下工程建设。

Description

一种岩溶管道型涌水高效封堵超高膨胀注浆材料及其制备、使用方法和应用 技术领域
本发明属于地下工程封堵材料技术领域，尤其涉及一种岩溶管道型涌水高效封堵超高膨胀注浆材料及其制备、使用方法和应用。
背景技术
本发明背景技术中公开的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
随着社会的快速发展，交通工程发展迅猛，基础设施建设的步伐持续加快，铁路、隧道、公路、矿山等项目日益增多。特别是随着21世纪海上丝绸之路的大力实施，我国东部沿海地区对城际、省际交通建设提出了巨大需求。截至2018年底，我国建成的公路、铁路隧道数量超过3万座，总里程超3.5万km。此外，我国在建隧道线路5289km，规划隧道线路超过2.8万km。然而我国地形地貌复杂多变，建设中经常穿越岩溶区，由于裂隙、管道、溶洞等不良地质构造极为发育，水力联系通畅，致灾性强常，地下工程建设过程中常遭遇突涌水引发的灾难。施工期突涌水、岩层失稳坍塌等灾害对隧道安全构成了重大威胁，造成严重的经济损失、工程停滞、环境破坏，甚至人员伤亡，严重威胁社会稳定与经济发展。
隧道建设过程中突涌水灾害频发的关键问题在于岩溶区隧道突水塌方灾害发生机理极为复杂，对灾害控制技术水平要求极高。虽然国内外相关学者针对不同的工程问题，研发了不同的注浆材料，提出了不同的治理方法。然而岩溶富水区具有水源补充性强、地质构造复杂、水力联通强且呈现压力状态、流量大、流速快等特点，使得现有的注浆材料与治理技术体系缺乏针对性，难以实现上述灾害的有效封堵与加固治理，导致隧道工程建设与工程运营一直处于高风险状态。
本发明的在先专利(授权公告号：CN 109535306 B)提出了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，该注浆材料包括丙烯酸溶液、交联剂、引发剂、表面交联剂、携带液。该膨胀高分子注浆材料具有膨胀倍率高达101-304倍、膨胀速率可调、环保无污染、对岩溶涌水具有高效封堵治理效果的技术优势，显著提高了地下工程突涌水治理效率。然而，本发明人在后续的进一步研究中发现：尽管这种膨胀高分子注浆材料堵水依靠丙烯酸树脂颗粒遇水迅速膨胀，颗粒体积迅速增长，颗粒相互挤压，形成封堵体进而实现涌水封堵，但是，该专利明确指出该灌浆材料的携带液只具有携带运输丙烯酸树脂颗粒的效果，并不能与颗粒本身反应，综上，该携带液不具有使丙烯酸树脂颗粒交联固化的能力。
发明内容
针对上述现有技术中存在的问题，为了进一步提高注浆材料对岩溶突涌水的封堵效果，本发明提出了一种岩溶管道型涌水高效封堵超高膨胀注浆材料及其制备、使用方法和应用。本发明通过研究高聚物结构与性能的关系，运用分子结构设计理论，分别从遇水膨胀倍率、耐盐性能、胶凝固化速率、突涌水封堵性能等角度设计丙烯酸树脂颗粒及携带液(下文称为交联固化液)的组成和结构。本发明提出的注浆材料可高效的治理高压大流量岩溶突涌水，改善并提高涌水封堵效率，进一步促进我国重大地下工程建设。
本发明的第一目的，提供一种岩溶管道型涌水高效封堵超高膨胀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超高膨胀注浆材料。
本发明的第三目的，提供上述方法制备的超高膨胀注浆材料的使用方法。
本发明的第四目的，提供上述制备方法制备的超高膨胀注浆材料的应用。
为实现上述目的，具体的，本发明公开了下述技术方案：
首先，本发明公开一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备方法，包括如下步骤：
(1)在丙烯酸溶液中加入交联剂，然后加入含亲水基团的活性物质进行聚合反应，得到前驱体；这种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，升温反应后得到胶状聚合物，将所述胶状聚合物绞碎后烘干，得到初级高分子吸水树脂颗粒。
(3)将胶凝催化剂均匀喷洒到所述初级高分子吸水树脂颗粒上，然后干燥，从而在胶凝催化剂表面通过交联形成了具有催化交联固化液B形成凝胶的壳结构，且部分胶凝催化剂渗入初级高分子吸水树脂颗粒中，得到具有镶嵌式核壳结构的高分子聚合物颗粒体A；
所述胶凝催化剂为聚乙二醇(PEG)、对二邻氯苯胺甲烷(MOCA)和聚醚多元醇的组合物；所述交联固化液B为能够与水反应的物质。
进一步地，步骤(1)中，所述丙烯酸溶液的质量分数为10-80％。高分子聚合物颗粒的合成过程是一种自由基共聚反应，反应过程中放出大量的热；随着单体浓度的增加，反应速率随之加快，反应放出的热量就越不容易散发，导致反应的自加速效应越明显，高分子聚合物颗粒在合成过程中容易产生爆聚，使聚合物分子链变短，从而影响高分子聚合物颗粒的吸水性能。当单体浓度低于10％时，难以聚合形成凝胶，并且由于过量水溶性物质的存在，会对聚合物颗粒的凝胶强度产生不利影响，且会增加生产能耗，因此，本发明推荐丙烯酸溶液的质量分数为10-80％。
应当理解的是，也可以根据实际情况，在上述范围的基础上适当增大或者减小丙烯酸溶液的质量分数，例如10.01％、10.1％、80.01％或者80.1％等，其仍然落入本发明的保护范围内。除此之外，后续涉及的其他组分、原料等的添加量，工艺参数等也可以根据实际情况进行调节，此后不再赘述。
进一步地，步骤(1)中，所述含亲水基团的活性物质包括：淀粉、聚乙烯醇、聚丙烯酰胺、丙烯酰胺等中的任意一种或者几种的混合物，或者上述几种物质的溶液中的任意一种或者几种的混合物，如淀粉溶液、聚乙烯醇溶液等。这些原料来源丰富、价格低廉，而且具有优异的吸水性能。同样地，也不排除本发明在先专利(授权公告号：CN 109535306 B)中提及的纤维素系高分子吸水树脂作为含亲水基团的活性物质，如：羟乙基纤维素、甲基纤维素或羧甲基纤维素等。
进一步地，步骤(1)中，所述交联剂包括N,N-亚甲基双丙烯酰胺、二乙烯基苯、异氰酸酯、双季戊四醇六丙烯酸酯、季戊四醇四酯中的任意一种或多种的组合物。
进一步地，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0.3-2％。实验表明：交联剂的种类和交联度对高分子聚合物颗粒的吸水倍率有较大的影响，对于同一种交联剂而言，随着交联剂用量的增多，高分子聚合物颗粒的吸水能力反而降低，但是凝胶强度升高。从提高高分子聚合物颗粒吸水倍率的角度来考虑，在保证高分子聚合物颗粒能够合成的前提下，推荐尽可能降低交联度，因此，本发明将交联剂的用量控制在0.3-2％之间。
进一步地，步骤(2)中，所述引发剂为无机过氧化物引发剂，例如，过硫酸钠、过硫酸钠钾、过硫酸铵等。引发剂一般是带有弱键、易分解成活性种的化合物，又称自由基引发剂，指一类容易受热分解成初级自由基的化合物。
进一步地，步骤(2)中，所述引发剂用量为添加比例为步骤(1)中丙烯酸质量的0.1-0.7％，此时的引发反应速率较为合适。
步骤(2)中，所述聚合反应的温度为65-90℃，反应时间为23-119min。
进一步地，步骤(2)中，所述干燥的条件为：在100-200℃下通风干燥20-120min。烘干温度高于200℃时，高分子聚合物颗粒不稳定，得到的高分子聚合物颗粒A容易泛黄，烘干温度过低，所需的烘干时间过久，影响生产效率。
进一步地，步骤(3)中，所述胶凝催化剂中聚乙二醇(PEG)：对二邻氯苯胺甲烷(MOCA)：聚醚多元醇的质量比依次序为(1-5)：(1-5)：(2-5)。
优选地，将胶凝催化剂配置成水溶液；便于进行均匀喷洒在初级高分子吸水树脂颗粒表面。
进一步地，将胶凝催化剂配置成质量分数为50-90％的水溶液。若胶凝催化剂溶液质量分数低于50％，延长烘干时间，增加能耗，胶凝催化剂溶液质量分数高于90％，会造成胶凝催化剂难以均匀的渗透进每个颗粒表面。
进一步地，步骤(3)中，所述胶凝催化剂溶液用量占颗粒总质量的1-10％。胶凝催化剂的作用是使高分子聚合物颗粒A吸水膨胀后促进交联固化液B与水的反应进程，加速胶凝反应进程，提高涌水封堵效率。
其次，本发明提供另一种用于制备所述前驱体的方法，和前述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，采用该不完全中和液与交联剂混合后，再与含亲水基团的活性物质进行聚合反应，得到前驱体。
进一步地，可以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。
进一步地，所述不完全中和液的中和度控制在60-90％。试验表明，当中和度过低时，反应生成的凝胶粘度太大，难以绞碎进行后续操作。中和度过高时，体系中羧酸盐浓度过高，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。
所述碱液包括氢氧化钠、氢氧化钙、氢氧化钾中的任意一种或者几种的混合物。
进一步地，所述碱液质量分数控制在10-60％之间，因为碱液浓度太高会造成丙烯酸溶液与碱液迅速反应，放出大量热，不利于生产人员操作，影响生产效率。碱液浓度太低，会使得碱液加入量过大，形成的胶状聚合物含水量过高，难以烘干，增加生产能耗。
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10％的丙烯酸单体被中和，即中和度为10％。改变丙烯酸中和度，可以使树脂中亲水性不大相同的两种基团-COOH和-COONa的比例发生变化，从而影响产物吸水性能。从反应动力学来考虑，丙烯酸活性比丙烯酸钠高，若中和度较低，酸度较高，聚合反应不易控制，产物中低分子聚合物较多，吸水倍率较低，中和度过高时，分子间发生了氢键交联反应，形成致密的网状结构，从而使得产物吸水倍率下降，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。
再次，本发明公开所述交联固化液B的制备方法，包括如下步骤：
S1、聚醚多元醇脱水：将聚醚多元醇和增塑剂混合均匀后，在真空加热条件下进行脱水，完成后冷却，即得脱水聚醚多元醇，放入干燥的容器内密闭保存备用。
S2、合成预聚体：在加热条件下将多异氰酸酯滴加至所述脱水聚醚多元醇中，完成后升温进行聚合反应，达到反应终点后降温出料，将得到的预聚体保存在密封干燥的容器中。
S3、在所述预聚体中加入稀释剂，搅拌均匀，即得到交联固化液B。
进一步地，步骤S1中，所述真空加热条件为：在110～120℃、真空度-0.08～0.1MPa条件下脱水2.5-4h，完成后冷却至50℃以下。
进一步地，步骤S1中，所述聚醚多元醇为二官能度或三官能度的低分子量亲水型聚醚。例如： 聚氧化丙烯二醇N204、聚醚多元醇N220、聚醚多元醇N240、聚醚多元醇N310、聚醚多元醇505S。二官能度或三官能度的低分子量亲水型聚醚粘度低，流动性好，成品韧性好弹性高，不仅可以防水能力，优异的弹性形变性能可以大大减少防水过程中因为形变而引起的破损。
进一步地，步骤S1中，所述增塑剂包括邻苯二甲酸酯、对苯二甲酸酯、间苯二甲酸酯等中的任意一种或者多种的混合物。
进一步地，步骤S1中，所述聚醚多元醇和增塑剂的添加质量比为2.94-5.88：1-2.05。
进一步地，步骤S2中，所述的异氰酸酯为甲苯二异氰酸酯(TDI)或多亚甲基多苯基多异氰酸酯(PAPI)或二苯基甲烷二异氰酸酯(MDI)或其组合。
进一步地，步骤S2中，所述加热条件为加热至不超过50℃，并控制温度恒定且滴加在30min内完成，滴加完毕，搅拌均匀。
进一步地，步骤S2中，所述升温进行聚合反应的温度为80～85℃。可选地，每隔30min取样测定-NCO的％含量，直到该含量基本不变时即为反应终点。
进一步地，所述-NCO％控制在7-12％时为反应终点，随着体系中-NCO％含量的增大，黏度逐渐变小，凝胶时间变快，包水量下降，这是因为随着-NCO％含量的增加，体系硬段含量增加，软段含量减少，相应的亲水基团减少，包水量下降。若继续增加-NCO％含量至12％以上，浆液与水反应比较剧烈，反应速率很快，易造成聚合物颗粒A未来得及完全膨胀，交联固化液B已反应形成凝胶，降低了材料的膨胀性能。因此，本发明优选配方为将反应体系的-NCO％含量控制在7-12％之间。
进一步地，步骤S3中，所述的稀释剂为丙酮，优选地，所述稀释剂的添加量为预聚体质量的15-35％，更优选为25-35％。随着丙酮用量的增加，反应所得浆液黏度随之降低，在15～35％之间黏度下降幅度较大，继续加入丙酮，浆液黏度仍下降但趋势较缓；包水量随着丙酮用量的增加先增大后减小，总体变化较小；随着丙酮用量的增多，凝胶时间随之延长，凝胶体的抗压强度有一定程度的减弱。因此，本发明采用上述范围内的稀释剂作为交联固化液B的溶剂时得到的注浆材料的总体性能更好。
再其次，本发明公开上述制备方法得到的超高膨胀注浆材料，其特点是：该注浆材料包含高分子聚合物颗粒体A与交联固化液B，所述高分子聚合物颗粒体A具有镶嵌式核壳结构，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)加入的胶凝催化剂部分附着在内核表面形成了外壳，同时，还有部分胶凝催化剂渗入内核形成镶嵌结构。
这种镶嵌式核壳结构的技术优势是：进行渗透后才能在后续膨胀后使催化剂的保有量足够用于催化，而如果仅仅是附着在内核表面，在高分子聚合物颗粒体A膨胀后表面积急剧增大，导致无法提供足够的催化剂用于催化与高分子聚合物颗粒体A表面大量接触的交联固化液B进行充分反应。而且剧烈的表面膨胀也可能导致部分催化剂脱落造成损失，进一步加加剧了催化剂的减少。因此，通过将部分胶凝催化剂渗入内核形成镶嵌结构，可以起到预存和补充催化剂的作用。
再其次，本发明提供一种所述超高膨胀注浆材料的使用方法，具体为：使用前，所述高分子聚合物颗粒体A、交联固化液B分开存放；使用时，将高分子聚合物颗粒体A与交联固化液B搅拌，使其充分混合；然后将得到的混合液作为注浆材料注入岩体破碎带的裂隙中，即可。
高分子聚合物颗粒体A迅速吸水膨胀，体积膨胀高达原来的200倍以上，交联固化液B与破碎带中的水及高分子聚合物颗粒表面的水反应，有效的把膨胀后的高分子聚合物颗粒体A粘结起来，更加牢固的与把高分子聚合物颗粒体A与地层中的破碎岩体粘结在一起，形成凝胶固结体，实现富水破碎带的突涌水治理，有效的解决注浆材料在涌水条件下难以留存的技术难题。
进一步地，所述高分子聚合物颗粒体A、交联固化液B的质量比为(1-3)：(1-5)。
进一步地，使用前可根据工程需要，在所述交联固化液B中添加催化剂或缓凝剂，控制交联固化液B遇水后凝固速率。
进一步地，所述催化剂由间甲苯二胺，三亚乙基二胺和二月桂酸二丁基锡的复配而成。优选地，间甲苯二胺：三亚乙基二胺：二月桂酸二丁基锡的比例依次序为1-2：1-2：2-4。胺、锡催化剂存在着“协同效应”，即叔胺类催化剂和有机锡催化剂在共同使用时催化效果会比使用单类催化剂更强。
进一步地，所述催化剂的添加量为交联固化液B质量的2-5％。不同的涌水地质环境对浆液的性能有不同的要求，尤其对于高压大流量突涌水而言，需要浆液具有较快的凝结速率，但对于宽大裂隙涌水治理而言，浆液需要扩散到地层深处。因此不同的地质环境对浆液的凝结时间提出了不同要求。为了实现浆液凝固时间可控，本发明通过调节催化剂用量，实现控制浆液的固结速度。
进一步地，所述缓凝剂为有机弱酸类化合物；例如酒石酸、柠檬酸等。交联固化液B反应活性较高，反应速率较快，则通常在十几秒钟就可以凝胶，基于此，在一些情况下，为了提高浆液在地层中的渗透半径，依据工程需要延长浆液凝胶时间，加入一定量的缓凝剂是必不可少的。
进一步地，所述缓凝剂用量控制在8-12％之间，交联固化液B凝胶时间在几十秒到几百秒之间可调。
最后，本发明公开所述超高膨胀注浆材料在建筑工程领域的应用，尤其在岩溶突涌水封堵中的应用。
与现有技术相比，本发明取得了如下有益效果：
(1)高分子聚合物颗粒A在遇水后体积迅速膨胀，体积增长为原来膨胀倍率高达55-204倍甚至以上，颗粒表面的催化剂暴露出来，有效促进交联固化液B与破碎带中的水的胶凝反应进程，有效的把膨胀后的高分子聚合物颗粒体A粘结起来，形成凝胶固结体，实现富水破碎带的突涌水治理。
(2)相比于本发明的在先专利(授权公告号：CN 109535306 B)，交联固化液B不仅起到悬浮和携带高分子聚合物颗粒A的作用，还可在高分子聚合物颗粒A表面催化剂作用下与地层中的水发生反应，有效的把膨胀后的高分子聚合物颗粒A粘结起来，更加牢固的与把高分子聚合物颗粒A与地层中的破碎岩体粘结在一起，形成具有弹性的固结体，实现富水岩溶区的突涌水治理，有效的解决注浆材料在涌水条件下难以留存的技术难题。
(3)本发明材料凝结时间稳定可控，采用本发明材料，在浆液凝结方面可以根据工程需要进行有效调控，保证浆液具有良好的可操作性和工程适用性。
(4)本发明的制备的超高膨胀高分子注浆材料实现了多组分材料充分复合，达到了各组分超叠加效应的目的，达到了有效封堵富水岩溶区涌水的效果。而且这种注浆材料具有操作便捷、更加安全的技术优势。
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为本发明实施例1制备的高分子聚合物颗粒体A的实物效果图。
图2为本发明实施例1制备的交联固化液B的实物效果图。
图3为本发明实施例1制备的高分子聚合物颗粒A与交联固化液B配置成的膨胀高分子注浆材料的实物效果图。
图4为图3所述的膨胀高分子注浆材料遇水膨胀后的实物效果图。
图5为本发明实施例1制备的高分子聚合物颗粒体A的SEM图。
图6为本发明实施例1制备的高分子聚合物颗粒体A交联形成的固结体的SEM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。
正如前文所述，针对现有技术中存在的问题，为了进一步提高注浆材料对岩溶突涌水的封堵效果，本发明提出了一种岩溶管道型涌水高效封堵超高膨胀注浆材料及其制备、使用方法；下面结合附图和具体实施方式对本发明进一步说明。
实施例1
一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备，包括如下步骤：
1、高分子聚合物颗粒体A的制备：
(1)丙烯酸中和阶段：首先用冰水配置质量分数为10％的丙烯酸溶液36份及20％的丙烯酰胺共聚体溶液5份，加入质量分数10％的碱液12份，得到中和度为60％的丙烯酸溶液。
(2)引发聚合反应阶段：将0.072份交联剂N,N-亚甲基双丙烯酰胺配置成质量分数为50％的溶液，加入到步骤(1)配置好的丙烯酸中和液中，并均匀搅拌1h，然后加入由0.025份过硫酸钾配置的质量分数为50％的引发剂溶液，升温到80℃，反应23min，生成胶状聚合物。
(3)干燥粉碎阶段：将步骤(3)得到的胶状聚合物绞碎，然后置于干燥炉中于100℃烘干至恒重，并粉碎筛分颗粒，得到初级高分子吸水树脂颗粒。
(4)将5份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇质量比依次序为2:1:2)配置成质量分数为50％的溶液，均匀喷洒到步骤(3)得到的初级高分子吸水树脂颗粒上，然后置于160℃烘箱里再次鼓风干燥，得到高分子聚合物颗粒A，备用。
2、交联固化液B的制备：
(1)聚醚多元醇脱水：将50份聚氧化丙烯二醇N204(羟值255mgKOH/g，官能度为2)和17份邻苯二甲酸酯加入装有搅拌器、温度计的容器中加热并开动搅拌，升温并抽真空，在110℃、真空度-0.08MPa条件下脱水3h，然后冷却至50℃以下，放入干燥的容器内密闭保存备用。
(2)合成预聚体：在干燥的三口瓶中准确加入脱水后的聚醚多元醇100份,升温到50℃，开动搅拌，缓慢地滴加28份甲苯二异氰酸酯(TDI)，控制温度使滴加在30min内完成。滴加完毕，搅拌均匀后，升温到80℃反应，反应期间每隔30min取样测定-NCO％含量(用盐酸-二正丁胺法检测)，直到-NCO质量％含量稳定在7.0％，即反应终点。降温出料，所得预聚体保存在密封干燥的容器中。
(3)取步骤(2)合成的预聚体80份，加入丙酮稀释剂20份，加入甲苯二胺：三亚乙基二胺：二月桂酸二丁基锡＝1：1：2的催化剂4份，搅拌均匀，即得到交联固化液B。
将本实施例制备的高分子聚合物颗粒A与交联固化液B按质量比为1:1混合均匀，制得膨胀高分子注浆材料，对其各项性能指标进行测试，结果如表1.1-1.3所示。
高分子聚合物颗粒A膨胀倍率测试方法为(其他实施例采用同样的方法)：取高分子聚合物颗粒A1g装入400目纱网中，浸入水溶液中，待材料充分吸水膨胀后，用滤纸滤干表面的残余水分，并记录其吸水质量变化情况。溶胀比Sw(单位：(g/g))由下式计算：
Figure PCTCN2020126274-appb-000001
其中M 0和M n分别为干燥的和吸水后的高分子聚合物颗粒A的质量。
交联固化液B与十倍水反应,平均胶凝时间测试方法(其他实施例采用同样的方法)为：准确称取10g交联固化液B于烧杯中，加入100ml水，记录加入水时的时间t 1，并迅速搅拌均匀(约10s)后静置，得到白色乳浊液，之后用玻璃棒不断探测粘度的变化。当玻璃棒离开液面出现拉丝现象时，视该试样已经胶凝化，记录时t 2，胶凝时间t＝t 2-t 1，多次实验取平均值作为B与十倍水反应平均胶凝时间。
膨胀高分子注浆材料最大膨胀倍率的测试方法(其他实施例采用同样的方法)：按比例配置浆液，取1份膨胀高分子注浆材料置于100份纯水中，待材料充分吸水膨胀后，用滤纸滤干表面的残余水分，并记录其吸水质量变化情况。溶胀比Sw(单位：(g/g))由下式计算：
Figure PCTCN2020126274-appb-000002
其中M 2和M 1分别为遇水前后膨胀高分子注浆材料的质量(单位：g)。
记录注浆材料的成胶时间，多次测试取平均值。
膨胀高分子注浆材料与十倍水反应平均胶凝时间的测试方法(其他实施例采用同样的方法)：准确称取10g膨胀高分子注浆材料于烧杯中，加入100ml水，记录加入水时的时间t 3，并迅速搅拌均匀后静置，得到白色乳浊液，之后膨胀高分子注浆材料体积不断增长，直到烧杯中水全部被吸收并形成凝胶体时记录时t 4，胶凝时间t＝t 4-t 3，多次实验取平均值作为膨胀高分子注浆材料与十倍水反应平均胶凝时间。
表1.1高分子聚合物颗粒A性能测试
A在纯水中最大膨胀倍率Sw 在Cl离子浓度为0.5g/L的NaCl溶液中膨胀倍率Sw
204g/g 72.8g/g
表1.2交联固化液B性能测试
外观 相对密度 B与十倍水反应,平均胶凝时间
浅黄色液体 1.05 86.5s
表1.3膨胀高分子注浆材料性能测试
A：B 外观 A+B在纯水中最大膨胀倍率S A+B A+B与十倍水反应,平均胶凝时间
1：1 浅黄色液体 108g/g 65.2s
实施例2
一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备，包括如下步骤：
1、高分子聚合物颗粒体A的制备：
(1)丙烯酸中和阶段：首先用冰水配置质量分数为80％的丙烯酸溶液36份及10％的丙烯酰胺共聚体溶液5份，加入质量分数60％的碱液24份，得到中和度为90％的丙烯酸溶液中和液。
(2)引发聚合反应阶段：将0.09份交联剂N,N-亚甲基双丙烯酰胺配置成质量分数为50％的溶液，将5份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇＝2:1:2)配置成质量分数为50％的溶液，加入到步骤(1)配置好的丙烯酸中和液中，并均匀搅拌1h。然后0.03份过硫酸 钾配置的质量分数为50％的引发剂溶液，升温到80℃，反应57min，生成胶状聚合物。
(3)干燥粉碎阶段：将步骤(3)得到的胶状聚合物绞碎，然后置于干燥炉中于200℃烘干至恒重，并粉碎筛分颗粒，得到初级高分子吸水树脂颗粒。
(4)将10份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇质量比依次序为2：1：2)配置成质量分数为50％的溶液，匀喷洒到步骤(3)得到的初级高分子吸水树脂颗粒上，并置于160℃烘箱里再次鼓风干燥，得到高分子聚合物颗粒A，备用。
2、交联固化液B的制备：
(1)聚醚多元醇脱水：将25份聚醚多元醇PEG1000(羟值112mgKOH/g，官能度为2)和75份聚醚多元醇505S(羟值56.3mgKOH/g，官能度为3)与35份邻苯二甲酸酯加入装有搅拌器、温度计的容器中加热并开动搅拌，升温并抽真空，在120℃、真空度-0.1MPa条件下脱水2.5h，然后冷却至50℃以下，放入干燥的容器内密闭保存备用。
(2)合成预聚体：在干燥的三口瓶中准确加入脱水后的聚醚多元醇100份,升温到50℃，开动搅拌，缓慢地滴加56份二苯基甲烷二异氰酸酯(MDI)，控制温度使滴加在30min内完成。滴加完毕，搅拌均匀后，升温至85℃反应，反应期间每隔30min取样测定-NCO％含量(用盐酸-二正丁胺法检测)，直到-NCO质量％含量稳定在8.2％，即反应终点。降温出料，所得预聚体保存在密封干燥的容器中。
(3)取预聚体65份，并加入丙酮稀释剂35份，加入甲苯二胺：三亚乙基二胺：二月桂酸二丁基锡＝1：1：2的催化剂2份，搅拌均匀，即得到交联固化液B。
将本实施例制备的高分子聚合物颗粒A与交联固化液B按质量比为3:5混合均匀，制得膨胀高分子注浆材料，对其各项性能指标进行测试，结果如表2.1-2.3所示。
表2.1高分子聚合物颗粒A性能测试
A在纯水中最大膨胀倍率Sw 在Cl离子浓度为0.5g/L的NaCl溶液中膨胀倍率Sw
161.7g/g 34.5g/g
表2.2交联固化液B性能测试
外观 相对密度 B与十倍水反应,平均胶凝时间
浅黄色液体 1.08 104.5s
表2.3膨胀高分子注浆材料性能测试
A：B 外观 A+B在纯水中最大膨胀倍率S A+B A+B与十倍水反应,平均胶凝时间
3：5 浅黄色液体 72.6g/g 29.8s
实施例3
一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备，包括如下步骤：
1、高分子聚合物颗粒体A的制备：
(1)丙烯酸中和阶段：首先用冰水配置质量分数为40％的丙烯酸溶液36份及10％的丙烯酰胺共聚体溶液5份，加入质量分数50％的碱液12份，得到中和度为75％的丙烯酸中和液。
(2)引发聚合反应阶段：将0.05份交联剂N,N-亚甲基双丙烯酰胺配置成质量分数为50％的溶液加入到步骤(1)配置好的丙烯酸中和液中，并均匀搅拌1h。然后加入由0.025份过硫酸铵配置的质量分数为50％的引发剂溶液，升温到80℃，反应88min，生成胶状聚合物。
(3)干燥粉碎阶段：将步骤(3)得到的胶状聚合物绞碎，然后置于干燥炉中于200℃烘干至恒 重，并粉碎筛分颗粒，得到初级高分子吸水树脂颗粒。
(4)将10份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇质量比依次序为1:1:4)配置成质量分数为50％的溶液，均匀喷洒到步骤(3)得到的初级高分子吸水树脂颗粒上，并置于160℃烘箱里再次鼓风干燥，得到高分子聚合物颗粒A，备用。
2、交联固化液B的制备：
(1)聚醚多元醇脱水：将35份聚醚多元醇PEG1000(羟值112mgKOH/g，官能度为2)和65份聚醚多元醇505S(羟值56.3mgKOH/g，官能度为3)与35份间苯二甲酸酯加入装有搅拌器、温度计的容器中加热并开动搅拌，升温并抽真空，在110℃、真空度-0.095MPa条件下脱水3h，然后冷却至50℃以下，放入干燥的容器内密闭保存备用。
(2)合成预聚体：在干燥的容器中准确加入脱水后的聚醚多元醇100份，升温到50℃，开动搅拌，缓慢地滴加56份多亚甲基多苯基多异氰酸酯(PAPI)，控制温度使滴加在30min内完成。滴加完毕，搅拌均匀后，升温至85℃反应，反应期间每隔30min取样测定-NCO％含量(用盐酸-二正丁胺法检测)，直到-NCO质量％含量稳定在9.8％，即反应终点。降温出料，所得预聚体保存在密封干燥的容器中。
(3)取步骤(2)合成的预聚体70份，加入丙酮稀释剂30份，加入甲苯二胺：三亚乙基二胺：二月桂酸二丁基锡＝1：1：2的催化剂3份，搅拌均匀，即得到交联固化液B。
将本实施例制备的高分子聚合物颗粒A与交联固化液B按质量比为2:3混合均匀，制得膨胀高分子注浆材料，对其各项性能指标进行测试，结果如表3.1-3.3所示。
表3.1高分子聚合物颗粒A性能测试
A在纯水中最大膨胀倍率Sw 在Cl离子浓度为0.5g/L的NaCl溶液中膨胀倍率Sw
183.6g/g 56.4g/g
表3.2交联固化液B性能测试
外观 相对密度 B与十倍水反应,平均胶凝时间
浅黄色液体 1.12 98.7s
表3.3膨胀高分子注浆材料性能测试
A：B 外观 A+B在纯水中最大膨胀倍率S A+B A+B与十倍水反应,平均胶凝时间
2：3 浅黄色液体 85.4g/g 46.5s
实施例4
一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备，包括如下步骤：
1、高分子聚合物颗粒体A的制备：
(1)丙烯酸中和阶段：首先用冰水配置质量分数为30％的丙烯酸溶液36份及10％的丙烯酰胺共聚体溶液8份，加入质量分数50％的碱液9.6份，得到中和度为80％的丙烯酸溶液中和液。
(2)引发聚合反应阶段：将0.05份交联剂N,N-亚甲基双丙烯酰胺配置成质量分数为50％的溶液，加入到步骤(1)配置好的丙烯酸中和液中，并均匀搅拌1h，然后加入由0.05份过硫酸铵配置的质量分数为50％的引发剂溶液，升温到80℃，反应119min，生成胶状聚合物。
(3)干燥粉碎阶段：将步骤(3)得到的胶状聚合物绞碎，然后置于干燥炉中于200℃烘干至恒重，并粉碎筛分颗粒，得到初级高分子吸水树脂颗粒。
(4)将5份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇质量比依 次序为1:2:3)配置成质量分数为50％的溶液，均匀喷洒到步骤(3)得到的初级高分子吸水树脂颗粒上，并置于160℃烘箱里再次鼓风干燥，得到高分子聚合物颗粒A。
2、交联固化液B的制备：
(1)聚醚多元醇脱水：将25份聚醚多元醇N330(羟值57mgKOH/g，官能度为2)和75份聚醚多元醇N310(羟值165mgKOH/g，官能度为3)与35份对苯二甲酸酯加入装有搅拌器、温度计的容器中加热并开动搅拌，升温并抽真空，在115℃、真空度-0.095MPa条件下脱水2.5h，然后冷却至50℃以下，放入干燥的容器内密闭保存备用。
(2)合成预聚体：在干燥的容器中准确加入脱水后的聚醚多元醇100份，升温到50℃，开动搅拌，缓慢地滴加50份多亚甲基多苯基多异氰酸酯(PAPI)，控制温度使滴加在30min内完成。滴加完毕，搅拌均匀后，升温至85℃反应，反应期间每隔30min取样测定-NCO％含量(用盐酸-二正丁胺法检测)，直到-NCO质量％含量稳定在10.2％，即反应终点。降温出料，所得预聚体保存在密封干燥的容器中。
(3)取步骤(2)合成的预聚体70份，加入丙酮稀释剂30份，加入甲苯二胺：三亚乙基二胺：二月桂酸二丁基锡＝1：1：2的催化剂8份，搅拌均匀，即得到交联固化液B。
将本实施例制备的高分子聚合物颗粒A与交联固化液B按质量比为2:1混合均匀，制得膨胀高分子注浆材料，对其各项性能指标进行测试，结果如表4.1-4.3所示。
表4.1高分子聚合物颗粒A性能测试
A在纯水中最大膨胀倍率Sw 在Cl离子浓度为0.5g/L的NaCl溶液中膨胀倍率Sw
195.2g/g 66.8g/g
表4.2交联固化液B性能测试
外观 相对密度 B与十倍水反应,平均胶凝时间
浅黄色液体 1.09 84.2s
表4.3膨胀高分子注浆材料性能测试
A：B 外观 A+B在纯水中最大膨胀倍率S A+B A+B与十倍水反应,平均胶凝时间
2：1 浅黄色液体 94.3g/g 57.3s
实施例5
一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备，包括如下步骤：
1、高分子聚合物颗粒体A的制备：
(1)丙烯酸中和阶段：首先用冰水配置质量分数为50％的丙烯酸溶液36份及10％的丙烯酰胺共聚体溶液10份，加入质量分数50％的碱液14份，得到中和度为75％的丙烯酸溶液中和液。
(2)引发聚合反应阶段：将0.27份交联剂N,N-亚甲基双丙烯酰胺配置成质量分数为50％的溶液，加入到步骤(1配置好的丙烯酸中和液中，并均匀搅拌1h，然后加入由0.09份过硫酸铵配置的质量分数为50％的引发剂溶液，升温到80℃，反应119min，生成胶状聚合物。
(3)干燥粉碎阶段：将步骤(3)得到的胶状聚合物绞碎，然后置于干燥炉中于100℃烘干至恒重，并粉碎筛分颗粒，得到初级高分子吸水树脂颗粒。
(4)将5份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇＝聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇质量比依次序为2:1:2)配置成质量分数为50％的溶液，均匀喷洒到步骤(3)得到的初级高分子吸水树脂颗粒上，并置于160℃烘箱里再次鼓风干燥，得到高分子聚合物颗 粒A，备用。
2、交联固化液B的制备：
(1)聚醚多元醇脱水：将30份聚醚多元醇N210(羟值117mgKOH/g，官能度为2)和70份聚醚多元醇N220(羟值57mgKOH/g，官能度为3)与30份间苯二甲酸酯加入装有搅拌器、温度计的容器中加热并开动搅拌，升温并抽真空，在120℃、真空度-0.095MPa条件下脱水2.5h，然后冷却至50℃以下，放入干燥的容器内密闭保存备用。
(2)合成预聚体：在干燥的容器中按配方量准确加入脱水后的聚醚多元醇，升温到50℃，开动搅拌，缓慢地滴加56份甲苯二异氰酸酯(TDI)，控制温度使滴加在30min内完成。滴加完毕，搅拌均匀后，升温至85℃反应，反应期间每隔30min取样测定-NCO％含量(用盐酸-二正丁胺法检测)，直到-NCO质量％含量稳定在11.3％，即反应终点。降温出料，所得预聚体保存在密封干燥的容器中。
(3)取步骤(2)合成的预聚体75份，加入丙酮稀释剂25份，加入甲苯二胺：三亚乙基二胺：二月桂酸二丁基锡＝1：1：2的催化剂5份，搅拌均匀，即得到交联固化液B。
将本实施例制备的高分子聚合物颗粒A与交联固化液B按质量比为3:2混合均匀，制得膨胀高分子注浆材料，对其各项性能指标进行测试，结果如表5.1-5.3所示。
表5.1高分子聚合物颗粒A性能测试
A在纯水中最大膨胀倍率Sw 在Cl离子浓度为0.5g/L的NaCl溶液中膨胀倍率Sw
174.5g/g 46.5g/g
表5.2交联固化液B性能测试
外观 相对密度 B与十倍水反应,平均胶凝时间
浅黄色液体 1.10 83.5s
表5.3膨胀高分子注浆材料性能测试
A：B 外观 A+B在纯水中最大膨胀倍率S A+B A+B与十倍水反应,平均胶凝时间
3：2 浅黄色液体 78.3g/g 40.1s
实施例6
一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备，包括如下步骤：
1、高分子聚合物颗粒体A的制备：
(1)丙烯酸中和阶段：首先用冰水配置质量分数为30％的丙烯酸溶液36份及10％的丙烯酰胺共聚体溶液5份，加入质量分数30％的碱液8.4份，得到中和度为70％丙烯酸溶液中和液。
(2)引发聚合反应阶段：将0.1份交联剂N,N-亚甲基双丙烯酰胺配置成质量分数为50％的溶液，加入到步骤(1)配置好的丙烯酸中和液中，并均匀搅拌1h，然后加入由0.05份过硫酸钾配置的质量分数为50％的引发剂溶液，升温到80℃，反应105min，生成胶状聚合物。
(3)干燥粉碎阶段：将步骤(3)得到的胶状聚合物绞碎，然后置于干燥炉中于100℃烘干至恒重，并粉碎筛分颗粒，得到初级高分子吸水树脂颗粒。
(4)将5份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇质量比依次序为2:1:2)配置成质量分数为50％的溶液，均匀喷洒到步骤(3)得到的初级高分子吸水树脂颗粒上，并置于160℃烘箱里再次鼓风干燥，得到高分子聚合物颗粒A，备用。
2、交联固化液B的制备：
(1)聚醚多元醇脱水：将30份聚醚多元醇N303(羟值560mgKOH/g，官能度为2)和70份聚 醚多元醇N240(羟值28mgKOH/g，官能度为3)与30份间苯二甲酸酯加入装有搅拌器、温度计的容器中加热并开动搅拌，升温并抽真空，在110℃、真空度-0.08MPa条件下脱水4h，然后冷却至50℃以下，放入干燥的容器内密闭保存备用。
(3)合成预聚体：在干燥的容器中按配方量准确加入脱水后的聚醚多元醇，升温到50℃，开动搅拌，缓慢地滴加56份甲苯二异氰酸酯(TDI)，控制温度使滴加在30min内完成。滴加完毕，搅拌均匀后，升温至85℃反应，反应期间每隔30min取样测定-NCO％含量(用盐酸-二正丁胺法检测)，直到-NCO质量％含量稳定在10.9％，即反应终点。降温出料，所得预聚体保存在密封干燥的容器中。
(4)取步骤(2)合成的预聚体75份，加入丙酮稀释剂25份，加入甲苯二胺：三亚乙基二胺：二月桂酸二丁基锡＝1：1：2的催化剂4份，搅拌均匀，即得到交联固化液B。
将本实施例制备的高分子聚合物颗粒A与交联固化液B按质量比为1:1混合均匀，制得膨胀高分子注浆材料，对其各项性能指标进行测试，结果如表6.1-6.3所示。
表6.1高分子聚合物颗粒A性能测试
A在纯水中最大膨胀倍率Sw 在Cl离子浓度为0.5g/L的NaCl溶液中膨胀倍率Sw
185.1g/g 52.9g/g
表6.2交联固化液B性能测试
外观 相对密度 B与十倍水反应,平均胶凝时间
浅黄色液体 1.11 91.5s
表6.3膨胀高分子注浆材料性能测试
A：B 外观 A+B在纯水中最大膨胀倍率S A+B A+B与十倍水反应,平均胶凝时间
1：1 浅黄色液体 84.2g/g 41.8s
实施例7
一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备，包括如下步骤：
1、高分子聚合物颗粒体A的制备：
(1)丙烯酸中和阶段：首先用冰水配置质量分数为50％的丙烯酸溶液36份及10％的丙烯酰胺共聚体溶液10份，加入质量分数50％的碱液14份，得到中和度为75％的丙烯酸溶液中和液。
(2)引发聚合反应阶段：将0.31份交联剂N,N-亚甲基双丙烯酰胺配置成质量分数为50％的溶液，加入到步骤(1配置好的丙烯酸中和液中，并均匀搅拌1h，然后加入由0.11份过硫酸铵配置的质量分数为50％的引发剂溶液，升温到80℃，反应119min，生成胶状聚合物。
(3)干燥粉碎阶段：将步骤(3)得到的胶状聚合物绞碎，然后置于干燥炉中于100℃烘干至恒重，并粉碎筛分颗粒，得到初级高分子吸水树脂颗粒。
(4)将2份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇＝聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇质量比依次序为2:1:2)配置成质量分数为50％的溶液，均匀喷洒到步骤(3)得到的初级高分子吸水树脂颗粒上，并置于160℃烘箱里再次鼓风干燥，得到高分子聚合物颗粒A，备用。
2、交联固化液B的制备：
(1)聚醚多元醇脱水：将30份聚醚多元醇N210(羟值117mgKOH/g，官能度为2)和70份聚醚多元醇N220(羟值57mgKOH/g，官能度为3)与20份间苯二甲酸酯加入装有搅拌器、温度计的容器中加热并开动搅拌，升温并抽真空，在115℃、真空度-0.095MPa条件下脱水3.5h，然后冷却至50℃ 以下，放入干燥的容器内密闭保存备用。
(2)合成预聚体：在干燥的容器中按配方量准确加入脱水后的聚醚多元醇，升温到50℃，开动搅拌，缓慢地滴加56份甲苯二异氰酸酯(TDI)，控制温度使滴加在30min内完成。滴加完毕，搅拌均匀后，升温至85℃反应，反应期间每隔30min取样测定-NCO％含量(用盐酸-二正丁胺法检测)，直到-NCO质量％含量稳定在12.0％，即反应终点。降温出料，所得预聚体保存在密封干燥的容器中。
(3)取步骤(2)合成的预聚体75份，加入丙酮稀释剂25份，加入缓凝剂酒石酸8份，搅拌均匀，即得到交联固化液B。
将本实施例制备的高分子聚合物颗粒A与交联固化液B按质量比为3:4混合均匀，制得膨胀高分子注浆材料，对其各项性能指标进行测试，结果如表7.1-7.3所示。
表7.1高分子聚合物颗粒A性能测试
A在纯水中最大膨胀倍率Sw 在Cl离子浓度为0.5g/L的NaCl溶液中膨胀倍率Sw
186.2g/g 43.2g/g
表7.2交联固化液B性能测试
外观 相对密度 B与十倍水反应,平均胶凝时间
浅黄色液体 1.11 256.5s
表7.3膨胀高分子注浆材料性能测试
A：B 外观 A+B在纯水中最大膨胀倍率S A+B A+B与十倍水反应,平均胶凝时间
3：4 浅黄色液体 75.3g/g 187.5s
实施例8
一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备，包括如下步骤：
1、高分子聚合物颗粒体A的制备：
(1)丙烯酸中和阶段：首先用冰水配置质量分数为50％的丙烯酸溶液36份及10％的丙烯酰胺共聚体溶液10份，加入质量分数50％的碱液14份，得到中和度为75％的丙烯酸溶液中和液。
(2)引发聚合反应阶段：将0.23份交联剂N,N-亚甲基双丙烯酰胺配置成质量分数为50％的溶液，加入到步骤(1配置好的丙烯酸中和液中，并均匀搅拌1h，然后加入由0.1份过硫酸铵配置的质量分数为50％的引发剂溶液，升温到80℃，反应119min，生成胶状聚合物。
(3)干燥粉碎阶段：将步骤(3)得到的胶状聚合物绞碎，然后置于干燥炉中于100℃烘干至恒重，并粉碎筛分颗粒，得到初级高分子吸水树脂颗粒。
(4)将3份交联固化液B的胶凝催化剂(聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇＝聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇质量比依次序为1:1:2)配置成质量分数为50％的溶液，均匀喷洒到步骤(3)得到的初级高分子吸水树脂颗粒上，并置于160℃烘箱里再次鼓风干燥，得到高分子聚合物颗粒A，备用。
2、交联固化液B的制备：
(1)聚醚多元醇脱水：将30份聚醚多元醇N210(羟值117mgKOH/g，官能度为2)和70份聚醚多元醇N220(羟值57mgKOH/g，官能度为3)与20份间苯二甲酸酯加入装有搅拌器、温度计的容器中加热并开动搅拌，升温并抽真空，在120℃、真空度-0.095MPa条件下脱水3h，然后冷却至50℃以下，放入干燥的容器内密闭保存备用。
(2)合成预聚体：在干燥的容器中按配方量准确加入脱水后的聚醚多元醇，升温到50℃，开动 搅拌，缓慢地滴加60份甲苯二异氰酸酯(TDI)，控制温度使滴加在30min内完成。滴加完毕，搅拌均匀后，升温至85℃反应，反应期间每隔30min取样测定-NCO％含量(用盐酸-二正丁胺法检测)，直到-NCO质量％含量稳定在10.9％，即反应终点。降温出料，所得预聚体保存在密封干燥的容器中。
(3)取步骤(2)合成的预聚体70份，加入丙酮稀释剂30份，加入缓凝剂柠檬酸12份，搅拌均匀，即得到交联固化液B。
将本实施例制备的高分子聚合物颗粒A与交联固化液B按质量比为3:4混合均匀，制得膨胀高分子注浆材料，对其各项性能指标进行测试，结果如表8.1-8.3所示。
表8.1高分子聚合物颗粒A性能测试
A在纯水中最大膨胀倍率Sw 在Cl离子浓度为0.5g/L的NaCl溶液中膨胀倍率Sw
191.2g/g 55g/g
表8.2交联固化液B性能测试
外观 相对密度 B与十倍水反应,平均胶凝时间
浅黄色液体 1.08 341.5s
表8.3膨胀高分子注浆材料性能测试
A：B 外观 A+B在纯水中最大膨胀倍率S A+B A+B与十倍水反应,平均胶凝时间
3：4 浅黄色液体 95.8g/g 287.5s
参考图1-6，并结合表1-8的测试数据，可以看出：高分子聚合物颗粒A在遇水后膨胀倍率高达55-204倍甚至以上。这是因为交联固化液B在高分子聚合物颗粒A表面催化剂作用下与地层中的水发生反应，有效的把膨胀后的高分子聚合物颗粒A粘结起来，更加牢固的与把高分子聚合物颗粒A粘结在一起，形成具有弹性的固结体，更有益于岩溶区的突涌水治理，“遇水膨胀、以水堵水”有效的解决注浆材料在涌水条件下难以留存的技术难题。
另外，本发明制备的注浆材料凝结时间可通过催化剂添加量控制，可以根据工程需要进行有效调控，保证浆液具有良好的可操作性和工程适用性。实现了多组分材料充分复合，达到了各组分超叠加效应的目的，达到了有效封堵富水岩溶区涌水的效果。而且这种注浆材料具有操作便捷、更加高效的技术优势。
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 (16)

  1. 一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备方法，其特征在于，包括如下步骤：
    (1)在丙烯酸溶液中加入交联剂，然后加入含亲水基团的活性物质进行聚合反应，得到前驱体；
    (2)在步骤(1)中得到的前驱体中加入引发剂，升温反应后得到胶状聚合物，将所述胶状聚合物绞碎后烘干，得到初级高分子吸水树脂颗粒；
    (3)将胶凝催化剂均匀喷洒到所述初级高分子吸水树脂颗粒上，然后干燥，从而在胶凝催化剂表面通过交联形成了具有催化交联固化液B形成凝胶的壳结构，且部分胶凝催化剂渗入初级高分子吸水树脂颗粒中，得到具有镶嵌式核壳结构的高分子聚合物颗粒体A；
    所述胶凝催化剂为聚乙二醇、对二邻氯苯胺甲烷和聚醚多元醇的组合物；所述交联固化液B为能够与水反应的物质。
  2. 如权利要求1所述的制备方法，其特征在于，所述丙烯酸溶液的质量分数为10-80％；
    或者，步骤(1)中，所述含亲水基团的活性物质包括：所述含亲水基团的活性物质包括：淀粉、聚乙烯醇、聚丙烯酰胺、丙烯酰胺等中的任意一种或者几种的混合物，或者上述几种物质的溶液中的任意一种或者几种的混合物；
    或者，步骤(1)中，所述交联剂包括N,N-亚甲基双丙烯酰胺、二乙烯基苯、异氰酸酯、双季戊四醇六丙烯酸酯、季戊四醇四酯中的任意一种或多种的组合物；
    或者，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0.3-2％；
    或者，步骤(2)中，所述引发剂为无机过氧化物引发剂，优选为过硫酸钠、过硫酸钾或过硫酸铵；
    或者，步骤(2)中，所述引发剂用量为添加比例为步骤(1)中丙烯酸质量的0.1-0.7％；
    或者，步骤(3)中，所述胶凝催化剂溶液用量占颗粒总质量的1-10％。
  3. 如权利要求1所述的制备方法，其特征在于，步骤(3)中，所述胶凝催化剂中聚乙二醇：对二邻氯苯胺甲烷：聚醚多元醇的质量比依次序为(1-5)：(1-5)：(2-5)；
    或者，步骤(2)中，所述干燥的条件为：在100-200℃下通风干燥20-120min；
    或者，步骤(2)中，所述聚合反应的温度为65-90℃，反应时间为23-119min；
    或者，将所述胶凝催化剂配置成水溶液。
  4. 如权利要求3所述的制备方法，其特征在于，将胶凝催化剂配置成质量分数为50-90％的水溶液。
  5. 如权利要求1-4任一项所述的制备方法，其特征在于，所述交联固化液B的制备方法为：
    S1、聚醚多元醇脱水：将计量的聚醚多元醇和增塑剂混合均匀后，在真空加热条件下进行脱水，完成后冷却，即得脱水聚醚多元醇，放入干燥的容器内密闭保存备用；
    S2、合成预聚体：在加热条件下将多异氰酸酯滴加至所述脱水聚醚多元醇中，完成后升温进行聚合反应，达到反应终点后降温出料，将得到的预聚体保存在密封干燥的容器中；
    S3、在所述预聚体中加入稀释剂，搅拌均匀，即得到交联固化液B。
  6. 如权利要求4所述的制备方法，其特征在于，步骤S1中，所述真空加热条件为：在110～120℃、真空度-0.080～0.1MPa条件下脱水2.5-4h，完成后冷却至50℃以下；
    或者，步骤S1中，所述聚醚多元醇为二官能度或三官能度的低分子量亲水型聚醚；优选为聚氧化丙烯二醇N204、聚醚多元醇N220、聚醚多元醇N240、聚醚多元醇N310、聚醚多元醇505S；
    或者，步骤S1中，所述增塑剂包括邻苯二甲酸酯、对苯二甲酸酯、间苯二甲酸酯等中的任意一种或者多种的混合物；
    或者，步骤S1中，所述聚醚多元醇和增塑剂的添加质量比为2.94-5.88：1-2.05；
    或者，步骤S2中，所述的异氰酸酯为甲苯二异氰酸酯或多亚甲基多苯基多异氰酸酯或二苯基甲烷二异氰酸酯或其组合；
    或者，步骤S2中，所述加热条件为加热至不超过50℃，并控制温度恒定且滴加在30min内完成，滴加完毕，搅拌均匀；
    或者，步骤S2中，所述升温进行聚合反应的温度为80～85℃；优选地，每隔30min取样测定-NCO的％含量，直到该含量不变时即为反应终点；优选地，所述-NCO％控制在7-12％时为反应终点；
    或者，步骤S3中，所述的稀释剂为丙酮。
  7. 如权利要求5所述的制备方法，其特征在于，所述稀释剂的添加量为预聚体质量的15-35％。
  8. 如权利要求6所述的制备方法，其特征在于，为25-35％。
  9. 一种岩溶管道型涌水高效封堵超高膨胀注浆材料的制备方法，其特征在于，如权利要求1-7任一项所述的制备方法中，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，采用该不完全中和液与交联剂混合后，再与含亲水基团的活性物质进行聚合反应，得到前驱体；后续步骤与权利要求1-5任一项所述的制备方法中步骤(2)、(3)一致。
  10. 如权利要求8所述的制备方法，其特征在于，所述不完全中和液的中和度控制在60-90％；
    或者，所述碱液包括氢氧化钠、氢氧化钙、氢氧化钾中的任意一种或者几种的混合物；优选地，所述碱液质量分数控制在10-60％之间；
    或者，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。
  11. 权利要求1-9任一项所述方法制备的超高膨胀注浆材料，其特征在于，该注浆材料包含高分子聚合物颗粒体A与交联固化液B，所述高分子聚合物颗粒体A具有镶嵌式核壳结构，该注浆材料具有镶嵌式核壳结构，其中，步骤(2)得到的初级高分子吸水树脂为内核，步骤(3)加入的胶凝催化剂部分附着在内核表面形成了外壳，同时，还有部分胶凝催化剂渗入内核形成镶嵌结构。
  12. 如权利要求10所述方法制备的超高膨胀注浆材料，其特征在于，所述超高膨胀注浆材料的使用方法，具体为：将高分子聚合物颗粒体A与交联固化液B搅拌，使其充分混合；然后将得到的混合液作为注浆材料注入岩体破碎带的裂隙中，即可。
  13. 如权利要求10所述方法制备的超高膨胀注浆材料，其特征在于，所述高分子聚合物颗粒体A、交联固化液B的质量比为(1-3)：(1-5)；
    或者，使用前在所述交联固化液B中添加催化剂或缓凝剂，控制交联固化液B遇水后凝固速率；
    或者，所述催化剂由间甲苯二胺，三亚乙基二胺和二月桂酸二丁基锡的复配而成；优选地，所述间甲苯二胺：三亚乙基二胺：二月桂酸二丁基锡的比例依次序为1-2：1-2：2-4；
    或者，所述催化剂的添加量为交联固化液B质量的2-5％；
    或者，所述缓凝剂为有机弱酸类化合物。
  14. 如权利要求12所述方法制备的超高膨胀注浆材料，其特征在于，所述缓凝剂为酒石酸、柠檬酸。
  15. 如权利要求10所述方法制备的超高膨胀注浆材料，其特征在于，所述缓凝剂用量控制在8-12％之间。
  16. 权利要求1-9任一项所述的方法制备的超高膨胀注浆材料在建筑工程领域的应用，优选为在岩溶突涌水封堵中的应用。
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