• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The invention relates to mining and can be used in the repair of mine workings, the construction and repair of tunnels. The goal is to improve the quality of reinforcement by improving the adherence of the composition to the rocks. The fractures and faults present on the surface of the walls of the workings or tunnels, or in previously drilled wells, are pressurized with a mixture based on polyisocyanates (PIZ) and the aqueous solution of alkali metal silicate until they are completely filled. The composition of the mixture includes a catalyst (K), promoting the trimerization of PIC, in the amount of 6.0 - 14.5 mol per 1 mol of NCO groups. The solution of alkali metal silicate and PIZ is used in a molar ratio in the range of 0.8-1.4. As PIC, 4,4-diphenylmethane diisocyanate (MDI) is used - a product of the phosgenization of aniline-formaldehyde condensates or its prepolymer. The prepolymer used is the product of the interaction of crude MDI and polyoxysiloxane, initiated by glycol with a hydroxyl number of 40-200. The amount of K in the mixture is assumed to be 8.5 - 13.8, in particular, 10.2 - 13.3 mmol per 1 mole of the isocyanate groups NCO. The molar ratio of NCO / SIO 2 is 0.85-1.15. The use of a specified amount of K, determined by the number of NCO and PIZ groups, ensures the formation of an interlaced inorganic and organic three-chamber structure with excellent mechanical strength. 4 hp f-ly, 2 ill., 3 tables.
    公开号:SU1493116A3
    申请号:SU853908700
    申请日:1985-06-06
    公开日:1989-07-07
    发明作者:Хильтерхаус Карл-Хайнц；Норкус Ханс
    申请人:Квт Кунстштофферфаренстехник Гмбх Унд Ко. (Фирма)；Ф.Виллих Гмбх Унд Ко. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of mining, namely to the fastening of mine workings, and can also be used in their repair, construction and repair of tunnels.
    The aim of the invention is to improve the quality of reinforcement by improving the adhesion of the composition to the rocks.
    FIG. Figure 1 shows the dependence of tensile and flexural strength for polymer products on the molar ratio of the amount of catalyst to the amount of NCO-rpynn in the reaction mixture; in fig. 2 shows the dependence of tensile strength and bending for molar products on molar on
    04
    Carrying NCO groups to silica in the reaction mixture.
    The method is carried out as follows.
    In cracks and faults present on the surface of walls, workings or tunnels, or in pre-drilled wells, a mixture based on polyisocyanates and an aqueous solution of alkali metal silicate is injected under pressure until they are completely filled. The composition of the mixture additionally contains a catalyst promoting the trilization of the polyisocyanate in the amount of 6.0-14.5 mol per 1 mol of NCO groups. Polyisocyanate and alkali metal silicate solution are used in molar ratio between 0.8 and 1.4. As a polyisocyanate, 4,4-diphenylmethane diisocyanate (go) is used - the product of the phosgenization of aniline-formaldehyde condensates or its prepolymer, which is used as a product of the interaction of crude MDI and polyoxyloxane, initiated by glycol, with a hydroxy number of 40-200. The amount of catalyst in the mixture is taken equal to 8.5-13.8 and, in particular, 10.2-13.3 mmol per 1 mole of NCO isocyanate groups. The molar ratio of NCO / SiOj is equal to 0.85-1.15. By using a specific catalyst in an amount determined by the number of NCO groups in the polyisocyanate, an organo-mineral product can be obtained in which organic and inorganic structures form a three-dimensional interlaced grill so that during the reaction no increase in the volume of the reaction mixture occurs, whereby the final the product is obtained dense and having a high strength interconnected grid, which provides excellent strengthening of the coal seam, rock and group nta
    When a polyisocyanate and a solution of liquid glass are added to the reaction mixture, which provides for the trimerization of the polyisocyanate catalyst in a certain amount, the amount of carbon dioxide gas (COj) produced is sufficient for optimal curing of the inorganic component of the reaction mixture and trimerization of the polyiso
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    the poster turns out to be sufficient to form an organic structure. Thus, the use of a certain amount of catalyst ensures the formation of an interwoven inorganic and organic three-chamber structure with excellent mechanical strength. Polyisocyanates can be trimerised in aqueous solutions of alkali metal silicate. In the process of trimerisation, the reaction between water and NCO groups is largely suppressed, which makes it possible by appropriate changes in the composition of the reaction mixture to control the amount of gaseous carbon dioxide and play it to react with the liquid. During the reaction, two mutually intertwining polymeric structures.
    In the first stage of the reaction, a part of the polyisocyanate reacts with water, as a result of which polyurethane is formed and CO gas is released. The CO formed during the reaction instantaneously reacts with the component of the liquid glass solution, as a result of which a compound is formed (in this case, Me means an alkali metal, for example sodium or potassium). The binding of an alkali metal oxide contained in a liquid glass solution () ensures the release of SiO from which silicic acid is formed. During the reaction, a significant amount of heat is released, ensuring the next step of the reaction is the trimerization of a certain part of the polyisrolate remaining after the first step of the reaction. The products trimerized in the first stage of the reaction in the second stage of the reaction are at least partially additionally trimextractable, thereby forming a branched high-molecular polymer structure.
    When using this method, excellent adhesion between the reaction product of the polyisocyanate and liquid glass and coal, rock or soil is achieved after a short period of time. After approximately 2 hours, the formation strengthened by this method has a flexural and tensile strength, ek51
    vivalen-1CH (this is the flexural and tensile strength which, when using polyurethane, is reached only after approximately 4 hours. The system used to strengthen the proposed system has the particular advantage that the hardness of the strengthened formation increases over time. So, For example, the tensile and flexural strength measured after 90 hours is approximately 10 N / mm.
    The proposed method and system can be used to strengthen wet and aquifer formations, and the water contained in the rock does not adversely affect the curing process of the polymer structure.
    A solid product in a hardened form, which should be turned into a monolithic mass, can be obtained by this method even in water or, for example, in aquifer sand. Thus, the proposed method can be successfully used to strengthen coal seams and rocks in mines, as well as to strengthen rocks, stones and / or soil in structures of various types, for example, in tunnels.
    Due to the high content of inorganic substances, the reaction product obtained by the proposed method is characterized by less flammability as compared with organic reinforcing materials. When tested for low temperature carbonization of this material in a quartz tube, the resulting pairs are characterized by reduced toxicity. In addition, the electrical resistance of this material is so high that this is sufficient to prevent the occurrence of electrostatic charges. The temperature of spontaneous combustion when the powdered reaction product is mixed with coal is not reduced.
    The system used to strengthen the rocks by the dacha method is convenient for use: the substances used as a catalyst remain in suspension and compared to the commonly used amines, on
    for example, triethylenediamine, and organic compounds, such as tin dibutyldilaurate, are practically odorless and harmless to humans.
    The necessary components of the reaction mixture used to strengthen the rocks of the proposed method are a liquid glass solution, a polyisocyanate and a catalyst that provides for the trimerization of polyisocyanates. To ensure satisfactory consolidation of the rock, the molar ratio of catalyst to the NCO groups contained in the polyisocyanate must be within strictly defined limits.
    The proposed method may be
    implemented using aqueous solutions of alkali metal silicates, commonly used in compositions for strengthening rocks, for example, using solutions
    of the liquid glass described in EP-B-0000579 and Germany 2460834. Due to the availability and low viscosity, it is preferable to use sodium liquid glass. Preferably
    use liquid glass solutions with a relatively high solids content, for example, with a solid inorganic component content in the range of 40-60 wt.%, and the best results are obtained when the solids content is in the range of 46-52 wt.%. Theoretically, in the implementation of the proposed invention
    more concentrated solutions of liquid glass can be used, however, such solutions have too high viscosity, which creates certain difficulties in their application, and
    therefore, such liquid glass solutions are not of practical value.
    Preferably, the molar ratio and in the liquid glass solution used is relatively high and is in the range of about 2.09-3.44. The best results are obtained when this molar ratio is in the range of about 2.48 to 3.17, and the best when this ratio is in the range of 2.70 to 2.95.
    The content in the specified limits promotes the formation in the product of a three-dimensional lattice of inorganic silicic acid,
    At concentrations lower than this, liquid glass has a high viscosity, which makes it unsuitable for practical use. The presence in the mixture of even very small amounts of CO causes precipitation of liquid glass and impairs the homogeneity of the reaction mixture, as a result of which the characteristics of the product are unsatisfactory.
    If the molar ratio for significantly exceeds the specified value, the presence of a large amount of CO in the mixture is required to completely solidify the liquid glass in the reaction mixture. However, such an increase in the amount is achieved by reducing the amount of the trimerized product. Consequently, the ratio of urea / three
    The measured product shifts towards urea, as a result of which the amount of the trimerized product contained in the final reaction product and which strengthens it, decreases. This leads to unsatisfactory results.
    To obtain a product with optimum mechanical strength, it is necessary to select the composition and amount of liquid glass used in the reaction mixture in accordance with the amount of catalyst used. Excellent reinforcement results, especially those obtained by the proposed method, provide the molar ratio of NCO / SiO in the mixture of polyisocyanate and liquid glass solution in the range of 0.8-1.4, preferably in the range of 0.85-1.15. Best results are achieved when the molar ratio of NCO / SiOj is about 1.0.
    In the composition of the reaction mixture, it is preferable to use concentrated solutions of liquid glass, since in this case the maximum limitation of the amount of water in the product is ensured and thus the harmful effect of water on the strength characteristics of the final product is prevented. In addition, with

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    by excessively diluting the reaction mixture, the amount of heat released during the reaction may not be sufficient to initiate the trimerization reaction. The lower limit of the relative content of liquid glass in the reaction mixture is determined by the fact that the amount of liquid glass must be sufficient to form the inorganic structure of the product. To form the inorganic structure of the product, it is necessary that in the reaction mixture at 1 wt. polyisocyanate was present 0.2 wt. liquid glass, preferably 0.5. The permissible upper limit in relation to the content of liquid glass for a given composition is determined from the condition that the amount 00 released during the reaction becomes further insufficient for the connection contained in liquid glass. In this case, as in the case of too high a water content, complete curing of the product becomes impossible. In the case of a 48/50 sodium liquid glass solution, for which the molar ratio is approximately 2.85, the upper limit of the content of water glass in the reaction mixture is approximately 1.6-1.7 parts by weight. on 1 ma.ch. polyisocyanate. When using liquid glass of different composition, the limiting amounts of the liquid glass solution in the reaction mixture may differ from those indicated.
    The proposed method of strengthening the formations can be performed using commonly used polyisocyanates. In addition, MCO products commonly used in the manufacture of polyurethanes can be used.
    In accordance with the invention, it is preferable to use polyisomatane anatates, which are easily trimerized to form a three-dimensional organic structure, in order to obtain a strengthening product. Such polyisocyanates include compounds in which, if possible, the NCO groups participating in the reaction are not completely spatially complex. A specific example of such a spatially uncomplicated 1101CH) zolshpotsmanatl is 4,4-diphoylmetaidium eocyanpt (also in the form of the product of the phosgenization of the anilineformaldegnd condensate (crude MDI).
    In accordance with the invention, it is preferable to use polyisocyanates containing approximately 10-55% g-roe NCO based on the weight of the isocyanate. The most preferred isocyanates include polyisocyanates containing 24-36, and even better 28-32 wt.% NCO groups. With a lower content of NCO groups in the polyisocyanate, the formation of a three-dimensional organic structure is difficult. If the content of NCO groups in the polyisocyanate used is higher than the specified upper limit, too much gaseous CO may be released during the reaction, and this may result in a reconversion of the organic component of the final product.
    The third component is a catalyst that provides for the trimerization of the polyisocyanate component of the reaction mixture. As such a catalyst, trimerization catalysts used for production can be used. polyurethanes. Tertiary amines and amino alcohols are preferably used as a trimerization catalyst. Examples of suitable trimerization catalysts are 2,4,6-tri (dimethylamiomethyl) phenol and Mannich products having the structural formula
    HE
    where R - is a radical in ortho or para position and having the formula
    ./RI RI
    where N is an integer of 1-3; R, and R are the same or different groups, in luces, methyl, cn or hydroxyl groups.
    In accordance with the invention, mixtures of these catalysts can also be used in the composition of the reaction mixture.
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    In carrying out the present invention, the molar ratio of catalyst to NCO groups in the reaction mixture is a critical factor, since an excellent reinforcement of the formation is achieved only when this molecular ratio is within a strictly defined narrow range. Taking into account the composition and amount of liquid glass used in the composition of the reaction mixture, the indicated molar ratio is determined by the following criteria:
    the amount of catalyst should be sufficient to carry out the trimerization reaction necessary to form a three-dimensional organic structure;
    The amount of catalyst in the reaction mixture should not be so high that it promotes an uncontrolled reaction, since this will produce too much COj and water will evaporate causing foaming of the reaction mixture, as a result of which the mechanical strength of the final proves to be insufficient.
    If the composition and amount of the liquid glass solution is selected in accordance with the principles of the invention, in the reaction mixture, per mole of NCO groups, in general, 6.0-14.5 mmol of catalyst should be present, preferably 8.5-13.8 or even better. , 2-13.3 mmol of catalyst.
    If the amount of catalyst in the reaction mixture is below the specified lower limit, the formation of a three-dimensional polymer c-structure is limited. If the catalyst content in the reaction mixture is too high, the inorganic component of the product is not sufficiently cured, and due to intense heat generation during the exothermic reaction, some expansion of the product occurs. In order to further control the trimerization reaction, an additional catalyst may be included in the composition of the reaction mixture. As such an additional catalyst can serve as a compound of ferric iron, for example, trichloric iron (FeClj), which often contains
    lives in various technical polyisocyanates and is formed in them during their production. Additional catalysts which are known per se are suitable trialkyl phosphates, for example trimethylphospholine, alkali metal salts of carboxylic acids, for example sodium acetate or sodium maleate, or transition metal compounds, for example antimony oxide (), zirconium chloride (ZiOCl), antimony tichloride (SbClj) and CuCl chloride.
    The best physical properties of the reinforcing material obtained by the inventive method are achieved when the polyisocyanate and the water glass have a composition and are taken in such quantities that they obtain the preferred ratio of catalyst to the number of NCO groups and at the same time establish the preferred NCO / SiOj ratios, the amount of catalyst in the reaction mixture being chosen by TakHM, that the amount of gaseous gas formed during the reaction COj is sufficient for complete precipitation from liquid glass. These conditions are satisfied in cases where mixtures are used in which there are 6.0-14.5, preferably 8.5-13.8, and preferably 10.2-13.3 mmol of catalyst per 1 mole of the NCO groups. , and in which the polyisocyanate and alkali metal silicate solution are used in such amounts that the molar ratio of NCO / SiO is in the range of 0.8-1.4, preferably in the range of 0.85-1.5. Liquid glass may have a generally preferred composition in which the molar ratio of SiO / MejG is in the range of 2.09-3.44, preferably in the range of 2.48-3.17.
    To achieve satisfactory consolidation of the coal seam, rock, soil, and brickwork, it is desirable that the catalyst be uniformly distributed throughout the reaction mixture during the reaction between the polyisocyanate and the water glass solution. Usually, the catalyst is added to the liquid glass solution, however, in this case as well
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    The production of one hundred saw blade dispersion is not ensured, since the mixture is dehomogenized (stratified) during storage.
    The tendency of the reaction mixture to dehomogenize can be reduced or completely suppressed by adding antimony trioxide to the catalyst-containing reaction mixture. The addition of antimony trioxide maintains the catalyst in a dispersed state. This fact does not depend on the amount of catalyst present in the reaction mixture, and the addition of antimony trioxide has a positive effect not only on the proposed system, but generally in any process of obtaining organic-mineral products from polyisocyanates and liquid glass solutions using trimerization catalysts. Antimony trioxide should be added to the composition of the reaction mixture in an amount of about 5-100, preferably 20-50 and even better 30-40 wt.% Of the amount of the catalyst used.
    The proposed method of preparing a reinforcing material does not require the addition of a foaming agent to the reaction mixture, however, depending on the specific composition of the reaction mixture and on other conditions of the reaction, a strictly metered amount of foaming agent may be added to the mixture. The amount of blowing agent added to the reaction mixture should be small enough so that product expansion does not occur during the polymerization. I
    Suitable for use in
    as a blowing agent, substances are volatile substances that are in a liquid state at room temperature and evaporate during the exothermic reaction of a water glass with a polyisocyanate. Examples of such volatile substances are monofluorotrichloromethane, dichlorodifluoromethane and trichlorotrifluoroethane. Preferably, the amount of volatile substance added to the reaction mixture does not exceed 3.5 wt.% Of the total mass of the reaction mixture. The best results are obtained when the content is
    flue pep1RG1V, hn relactive mixture is in the range of 1-2.8 wt.%. Such a small amount of volatile matter does not cause expansion of the foaming product during the trimerization reaction. Moreover, at the beginning of the reaction, the volatile substance is completely removed from the p-reaction mixture, where there remain various voids and channels, which are formed by a solution of alkali metal silicate, which remains in the reaction mass. mixes. In addition, the action of volatile substances significantly improves the mechanical characteristics of the product used as a reinforcing material. In accordance with the principles of the invention, any significant expansion of the reaction products is unacceptable, since only dense products are able to withstand the pressure of a reinforced rock or brickwork. On the other hand, the products remain so elastic that they allow rock to be displaced by a few millimeters.
    Stable Isolating substances and substances that create crystallization centers can be added to the reaction mixture. Substances that form crystallization centers include, for example, finely divided solid materials: silica or alumina, which can be used in combination with zinc stearate, amorphous silicic acids or metal silicates. Of these substances forming crystallization centers, silicon dioxide precipitating from a colloidal solution of liquid glass is preferred.
    Suitable stabilizers are polysiloxane based silicone oils. The amount of stabilizer added to the reaction mixture may be in the range of about 0.5-2.0, preferably 0.8-1.4 wt.% Of the total mass of the reaction mixture.
    Depending on the desired characteristics of the reinforcing material and the environmental conditions in which the material is to be found, appropriate additives can be added to the reaction mixture. To such add
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    Cams, for example, are organic compounds having groups that react with the isocyanate groups of the polyisocyanate. Examples of such compounds are polyhydric alcohols: polyesters and polyether polyhydric alcohols, as well as phosphoric acid esters, for example, three uranium-chlorine-ethyl-phosphanate or three (3) -isopropyl phosphanate used in the production of polyurethanes. The amount of polyhydric alcohol added to the reaction mixture must be so small that it does not have a detrimental effect on the formation of a three-dimensional organic structure and an inorganic structure entwined with it. The maximum amount of polyhydric alcohol or phosphoric acid ester added to the reaction mixture should be in the range of 2-45, preferably in the range of 10-20% by weight, based on the weight of the isocyanate of the component.
    In order to reduce the flammability of the final product, it is possible to add substances to the reaction mixture to slow down and prevent the final product from burning. As such substances, flame retardants used in the plastics industry, such as phosphates or borates, can be added to the reaction mixture. The amount of ignition inhibitor added to the reaction mixture may be in the range of 2-30% by weight of the amount of the isocyanate component.
    Fillers can also be added to the reaction mixture to increase the mechanical strength of the final product. Examples of suitable fillers are diatomaceous earth, alumina hydrate, magnesium silicate, powdered asbestos, chalk asbestos fiber and fiberglass. The amount of filler added to the reaction mixture is determined mainly by the viscosity of the mixture. Preferably, the amount of filler added to the reaction mixture is in the range of 0.1-30% by weight, based on the weight of the liquid glass solution used.
    If desired, pigments or dyes can also be added to the reaction mixture.
    In the implementation of the proposed1 method of strengthening the formations, two components (A) and (B) are initially prepared. Component (A) is a liquid glass solution containing a catalyst and a compound that maintains the catalyst in the dispersion state, as well as a polyhydric alcohol, an ignition inhibitor, fillers, and a dye. Component (B) is a polyisocyanate and may additionally contain a volatile substance and a stabilizing agent. In addition, the composition of the component (B) may include fillers that are compatible with the other components, and other of these additives. Since antimony trioxide is a suitable dispersing agent for the catalyst and can simultaneously serve as a co-catalyst, it can also be included in component (A).
    The prepared components (A) and (B) are thoroughly mixed. The starting time of the resulting mixture is generally in the range of 5-100 seconds or more, and this time can be changed, if required. To obtain the required starting time, components (A) and (B) or a mixture of these components can be cooled or heated respectively. The injection of the reaction mixture into a reinforced formation is carried out in the usual way, for example, through wells or injection tubes in a coal seam, rock, soil or brickwork. The feed of the reaction mixture to the formation can be carried out under pressure. The components of the reaction mixture can be placed in the compartments of a sectioned sleeve, which is inserted into the reinforced formation. After inserting such a sleeve into the formation to displace the components of the reaction mixture, the partitions between the sections are destroyed.
    The reaction between components (A) and (B) begins with the reaction between the NCO isocyanate groups and the water contained in the liquid glass solution. This reaction is exothermic and, on the one hand, promotes evaporation of volatile substances in the mixture, and, on the other hand, initiates catalytic trimerization
    remaining of common groups. The carbon dioxide gas liberating in the reaction process reacts with oxide and fir-tree metal entering into the composition of liquid glass, as a result of which alkali metal carbonate is formed and alkali metal oxide is eliminated from liquid glass. During the reaction, the remaining silicic acid forms a three-dimensional inorganic structure, firmly combined with the simultaneously formed organic polymer, with the result that a material with high strength and interlaced lattice is formed, providing excellent strengthening of the coal seam, rock, soil or masonry. Remaining in the channels formed as a result of evaporation of the volatile substance, the alkali metal carbonate solution gives the reinforcing material additional strength.
    When implementing the proposed method of reinforcing formations, a two-component system consisting of components (L) and (B) can be chosen so that the DPA of its insertion; already existing equipment without its modifications can be used in the reinforced formation. After the two KOMnoHeiiToD are mixed, the reaction mixture for a certain period of time passes from the LIQUID-O state to the normal state. Depending on the TOHKtjH of the reinforced rock and its temperature, the reaction mixture retains its plastic state for a shorter or longer period; -; .. yes time, and then goes r - solid - O. that notion. Even under unfavorable conditions, for example in the case of pulverized, wet or even wet rock, this fortified material has high adhesion; . in relation to coal, rock and brick. Due to the use of special catalysts in the reaction mixture, several consistent reactions take place in which the liquid components react in such a way that in any case the final product is solid and the character is due to high adhesion.
    94.48 0.5
    1.5 3.44
    93.00 5.00
    2.00
    These examples show the strength of the reaction products for stretching and bending versus mmol of catalyst / mol NCO and mol NCO / mol SiOj.
    Example 1. The prepared component (A) had the following composition in wt.%:
    Sodium liquid
    glass 48/50
    Antimony trioxide
    2,4,6-tri- (dimethylaminomethyl) -phenol
    Water
    Prepared separately component (B) had the following composition, wt.%:
    Polyphenylpolymethylene polyisocyanate,
    containing NCO groups in the amount of 31 wt.%
    Trichlorofluoromethane
    Stabilizing
    agent
    When two components (A) and (c) are mixed in a 4: 3 weight ratio (11.36 mmol of catalyst per 1 mole of NCO isocyanate groups), after about 1 minute, the reaction mixture starts to turn into a gel. After 2 minutes, the temperature of the reaction mixture begins to increase and the mixture turns into a solid organic product.
    In order to test the resulting product for breaking and bending, two stones were used, held in a fixed position at a distance of 5 mm from each other using adhesive tape attached to the front surfaces of the stones. After intensive mixing of the reaction mixture with a wooden rod from the bubbles, the reaction mixture was poured into the gap between the two stones shortly before gelation began.
    The tensile and flexural strength of the bond between the two stones, formed using this reinforcing material, was determined after 2 hours at a temperature of 20 ° C; after 2 hours at a temperature of 50 ° C (the sample was placed in a drying chamber); through Vh at a temperature of 20 ° C (for measuring the tensile and flexural strength the instrument was used
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    used in chemical laboratories for the processing of hlcn).
    Examples 2-5 (comparative examples 1 and 2).
    The mixing of components (A) and (B) was carried out in a certain ratio. In all cases, tensile and flexural strength measurements were made exactly as indicated in Example 1.
    Example 6 Samples of reinforcing material prepared by the method described in Example 1 were tested to determine the tensile and flexural strength as a function of the ratio of the amount of catalyst used in the reaction mixture to the molar amount of isocyanate NCO groups. in the polyisocyanate used, with an unchanged molar ratio of NCO / SiO of 1.0. The test results are shown in Table. one.
    Table 1 .
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    Example 7. Samples of the reinforcing material prepared by the method described in Example 1 were tested to determine the tensile and flexural strengths as a function of the molar ratio of NCO / SiO at a constant ratio of mmol of catalyst / mol of NCO of about 11 ,eight. The test results are shown in Table. 2
    Table 2
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    This test report shows the practical application of the proposed method of reinforcing formations in a coal mine.
    1. Description of the test.
    1.1. Forget.
    Formation thickness 5.2 m max.
    Advance of a zabo: 3 m / days
    Rock disturbance: the shale layer is reduced in the roof of the excavation.
    1.1.1. Long slaughter.
    In the test zone, coal has a tendency to collapse textural cracks in the formation.
    1.1.2.Transport generation. Promoted end of production by
    breed interlayer (average thickness 1m). The reinforcement was carried out by the injection of the reinforcing composition in the lower part of the coal seam.
    1.1.3.Krovl generation. Strengthening the end of the movement
    long bottom was made of anhydride bulk.
    1.2. The time spent working to strengthen the coal seam of the rock was carried out at night.
    1.3.Equipment.
    For testing, a standard injection system of pipelines was used, and no changes were made to it.
    On the day of testing the reaction mixture, a two-component pump with a capacity of 15 liters per minute was used in the coal seam and rock.
    The mixing ratio is 1: 1 (volume).
    Pipeline length: approximately 350 m.
    Pipeline diameter: 13 mm (component A).
    Pipeline diameter: 20 mm (component B).
    Distributing system: intermediate taps with a bore diameter of 13 mm.
    Injection equipment: a common pipe with a downhole packer.
    1.4. Testing.
    In 35 wells, 171 containers were installed, each with a capacity of 30 liters (Table 3).
    Table3
    As a result, when using this reinforcing material using existing standard equipment, no problems arise. The ease of use of the new reinforcing material is due to its relatively high fluidity and satisfactory injection characteristics. The reaction parameters of the components of the reaction mixture are selected according to the specific conditions of use. After turning off the pump, there was only a slight leakage of liquid material from cracks in the rock. Depending on the fracture of the rock
    The new material penetrates the rock to the mean: it is distributed evenly throughout the rock. Adhesion strengthened: to e; o material in relation to coal and g. of rock of the character of a satisfactory.
    The checks carried out before each night shift showed that in all cases after the coal was dredged, the bottom face remained the shape of the right ledge and the rock and coal were not collapsed. Obrubshvani rocks from the roof was not observed. The zones that existed earlier had collapsed neither the rocks were reinforced with this material.
    The coal and rock strengthened by the new material are quite easily processed by pneumatic tools. Thus, a coal bed reinforced with a new material, for example in an advanced long bottom hole, can be made using a hand tool. In addition, the injection equipment after the injection of the reinforcing composition in one well can be used to inject the composition into another well.
    The proposed method is carried out as follows.
    In the zone adjacent to the vertical concrete shaft with a dome-shaped lower end at a depth of approximately 780 m, water circulated around the void in the rock near the outer surface of the concrete shields of the mine lining at a rate of approximately 20 l / min. about 4 units. which caused severe chemical damage to concrete.
    A series of wells were drilled to fill the voids in order to protect the rock formation from water in the shields. Each well was closed by a packer, through which the two-component composition was injected into the voids near the well. Work on the injection of the reaction mixture was carried out using a high-pressure pump with a capacity of 6–40 l / min.
    with atmospheric pressure at the outlet.
    Components (A) and (B) were fed into the wells along separate hoses through a static mixer located directly in front of the packer. The volume ratio of the components (A) and (B) at the mixer output was 1: 1.
    The rock was strengthened by injecting this reaction mixture through a packer and an integrated mixer into longitudinal cracks and associated voids until either the pump working pressure reached a value above 130 bar, or the reaction mixture began to flow from near the well. The wells in the walls of the shaft were located in a staggered order at a distance of 5–10 m from one another.

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    The reinforcement of the rock around the shaft shaft was carried out until all the voids located near the outer surface of the concrete lining were filled with this reinforcing material. All work was completed within two days. Circulation of water in the near-wellbore zone ceased and the leakage of reinforcing material through the concrete mixtures of the shaft lining gradually stopped.
    权利要求:
    Claims (4)
    [1]
    1. The method of strengthening and compaction of coal massifs, rocks, soil in mine workings, as well as walls of tunnels and building structures, including drilling wells, forcing them into cracks, and / nli fractures under pressure from a mixture based on polyisocyanates and an aqueous solution of silicate alkali metals before they are completely filled, in order to improve the quality of strengthening by improving the adhesion of the composition to the rocks, a catalyst is additionally introduced that promotes the trimerization of polyisocyanate in the amount of 6.0- 14.5 mol per 1 mol of NCO groups, while the polyisocyanate and alkali metal silicate solution are used in a molar ratio of 0.8-1.4 NCO / SiOi.
    [2]
    2. A method according to claim 1, characterized in that 4,4-diphenyl methanediisocyanate (MD11) is used as the polyisocyanate - the product. -Posgenization of aniline-formaldehyde condensates or its prepolymer.
    [3]
    3. A method according to claim 2, characterized in that the product of the interaction between the crude IDN and polyoxyoxane initiated by a glycol with a hydroxyl number of 40-200 is used as the prepolymer.
    [4]
    4. Method according to paragraphs. 1-3, in which the amount of catalyst in the mixture is assumed to be in the range of 8.5-13.8, in particular 10.2-13.3 mmol per 1 mole of the isocyanate NCO groups.
    3. The method according to paragraphs. 1-4, characterized in that the molar ratio of NCO / SiO is 0., 85-1.15.
    H / ffMffSO C, lr)
    3.0 .5Ü 15 W
    0.5
    -r11r
    5 IN 1 IN 9 W and 1 13 J 15 16 FIG. 1
    / WOW / 7A / WW7 / Z7 W CO
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    同族专利:
    公开号 | 公开日
    HUT38663A|1986-06-30|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE3421085A|DE3421085C1|1984-06-06|1984-06-06|Process for solidifying and sealing coal and / or rock and earth formations|
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