Early strength resin anchoring agent and preparation method thereof

Abstract

The invention discloses an early-strength resin anchoring agent and a preparation method thereof, the resin anchoring agent is composed of daub and a curing agent, the daub comprises the following raw materials: self-made high-activity vinyl ester resin, a high-strength coarse filler, a high thixotropic agent, a composite accelerator, a low shrinkage agent, a silane coupling agent and a flexibilizer; the curing agent comprises the following raw materials: a surfactant, water, a thickening agent, a composite initiator, a fine filler, aluminum hydroxide and calcium chloride; the prepared early-strength resin anchoring agent has the excellent characteristics of high early-stage bearing speed, capability of applying high prestress in time after curing, shock resistance, low shrinkage, high shear, easiness in mixing, good self-repairing property, good load transmission and the like, and can meet the construction requirements of quickly bearing and applying high prestress and the like in the construction of a prestressed resin anchor rod; and active and timely supporting of the prestressed resin anchor rod in geotechnical engineering is ensured. Therefore, the method has huge application and popularization prospects.

Description

Technical Field

[0001] This invention relates to the field of support material technology, specifically to an early-strength resin anchoring agent and its preparation method. Background Technology

[0002] Resin anchor bolt (cable) support mainly consists of anchor bolts, resin anchoring agent, nuts, trays, and anchoring components. Its principle involves injecting resin anchoring agent into the anchor bolt (cable) hole. After mixing and curing, the anchor bolt (cable) is bonded to the surrounding rock as an organic whole. By fully utilizing the material and structural properties of the components themselves, it actively improves and enhances the self-supporting capacity of the surrounding rock, effectively controlling its stability and meeting the various functions required for support. Resin anchor bolts play a vital role in geotechnical engineering and are widely used in geotechnical projects such as mines, tunnels, water conservancy and hydropower, and military underground engineering.

[0003] Currently, the resin anchoring agents used in resin anchor bolt (cable) support are divided into inorganic and organic anchoring agents: (1) Inorganic anchoring agents have advantages such as controllable gel time, low raw material price, good water resistance, and good volume stability. For example, Chinese Patent CN 111234711 A discloses a high-durability inorganic rebar adhesive and its preparation method, which uses modified magnesium matrix as the main coagulant to prepare a high-durability inorganic rebar adhesive with controllable gel time, high early strength, high bonding strength, high temperature resistance, good rebar protection performance, good water resistance, good volume stability, and non-toxic and environmentally friendly properties. However, this type of inorganic rebar adhesive has the following disadvantages: slow gelation speed and low early strength. Achieving a high anchoring force requires a long curing time, which cannot meet the requirements of rapid load bearing. Chinese Patent CN 108726962 A discloses a fast-setting inorganic rebar adhesive, which has good fast-setting and early strength performance by using various additives, but its rebar protection performance is poor.

[0004] (2) Organic anchoring agents have excellent comprehensive properties such as fast curing speed, strong environmental adaptability, high mechanical properties, large load-bearing capacity, simple construction and mature development. For example, Chinese patent CN115197666A discloses an injection-type rebar anchoring adhesive for high-speed rail and its preparation method. It adopts the island toughening theory, combines inorganic nanomaterials to toughen epoxy resin, and combines it with alicyclic amine composite curing agent. It also adds additives that can increase performance to prepare modified epoxy rebar anchoring adhesive for high-speed rail. The mixer with equal proportion double tube structure is convenient to use, has a good mixing effect, and is energy-saving and environmentally friendly. However, this rebar anchoring adhesive has disadvantages such as a load-bearing capacity of no more than 72kN in 1 minute and a large curing shrinkage rate.

[0005] The aforementioned conventional resin anchors suffer from problems such as slow load-bearing capacity, inability to apply high prestress promptly, poor vibration resistance, high propulsion resistance, large shrinkage, decreased shear strength, and reduced load transfer. Currently, the fastest resin anchor used in China is the CKa type, with a gel time of 8-25 seconds, a waiting time of 10-30 seconds, and a load-bearing time of 5 minutes. This relatively long construction and load-bearing time cannot meet the requirements for rapid mechanized construction of prestressed resin anchors in tunnels. Furthermore, low ambient temperatures and water accumulation in boreholes during tunnel construction further slow down the gelation and curing time of the resin anchor, prolonging the load-bearing time, affecting construction efficiency, and resulting in poor fatigue and impact resistance.

[0006] Rock drills or anchor bolt trolleys are now widely used for anchor bolt construction in geotechnical engineering projects such as mines, tunnels, water conservancy and hydropower, and military underground engineering. This has greatly improved the efficiency of anchor bolt construction and ensured construction quality. Geotechnical engineering projects often encounter complex and challenging conditions such as high-stress roadways, extra-large cross-section roadways, roadways affected by intense mining, roadways left along the goaf, and soft rock roadways.

[0007] For corrosion protection, prestressed anchor bolts in water conservancy and hydropower projects require an annular thickness of no less than 20mm. Anchor bolts with diameters of 32mm and 36mm correspond to borehole diameters of 72mm and 76mm, respectively. An excessively large annular thickness (half the difference between the borehole diameter and the anchor bolt diameter) does not meet the "three-diameter matching" requirement. This results in poor mixing of the mortar and hardener within a large annular thickness, easily leading to a "glove" effect, causing significant creep and shrinkage of the anchor bolt, decreased shear strength, reduced load transfer, and ultimately, poor support effectiveness.

[0008] Based on this, the present invention provides an early-strength resin anchoring agent and its preparation method to solve the above problems. Summary of the Invention

[0009] To address the technical problems existing in the prior art, the present invention aims to provide an early-strength resin anchoring agent and its preparation method. The prepared resin anchoring agent has excellent characteristics such as rapid early load-bearing, timely application of high prestress after curing, seismic resistance, low shrinkage, high shear strength, easy mixing, and good load transfer. It can meet the construction requirements of rapid load-bearing and application of high prestress in the construction of prestressed resin anchors, and ensure that geotechnical engineering achieves active and timely support of prestressed resin anchors.

[0010] To achieve the above objectives, the present invention provides the following technical solution: A first aspect of the present invention provides an early-strength resin anchoring agent, said early-strength resin anchoring agent being composed of putty and a curing agent, wherein, The putty comprises the following raw materials in parts by weight: 90-100 parts of high-activity vinyl ester resin, 300-400 parts of high-strength coarse filler, 1.0-2.0 parts of high thixotropic agent, 5.0-10.0 parts of composite accelerator, 1.5-3.0 parts of low-shrinkage agent, 2.0-3.0 parts of silane coupling agent, and 5.0-10.0 parts of toughening agent; The curing agent comprises the following raw materials in parts by weight: 11-13 parts surfactant, 21-23 parts water, 0.5-0.6 parts thickener, 10-15 parts composite initiator, 50-55 parts fine filler, 0.4-0.6 parts aluminum hydroxide, and 1-2 parts calcium chloride.

[0011] Preferably, the composite accelerator is selected from tertiary aromatic amines or tertiary alkyl amines, wherein the tertiary aromatic amine is one or a combination of two or more of N,N-dimethyltoluidine, N,N-diisopropanol-toluidine, N-methyl-N-(2-hydroxyethyl)-toluidine, and N,N-dimethyl-(2-hydroxyethyl)-toluidine; and the tertiary alkyl amine is N,N-dimethyloctylamine and / or N,N-dimethyldecylamine.

[0012] Preferably, the amount of the composite accelerator is 0.2 to 0.6 wt% of the mass of the highly active vinyl ester resin. By selecting appropriate types and amounts of composite accelerators according to actual needs, the anchoring agent can be rapidly cured in low-temperature and wet environments, and it also possesses fast load-bearing performance, adapting to rapid mechanized construction of prestressed resin anchors under low-temperature and wet conditions, meeting the requirements of active and timely support.

[0013] Preferably, the high thixotropic agent is nano-fumed silica. The selected nano-fumed silica has a small number of silanol groups on its surface that interact to form a three-dimensional network structure, which can improve the thixotropy of the resin anchoring agent putty, reduce the pushing resistance during anchor construction, promote the workability of the resin anchoring agent, facilitate the rapid mechanization of prestressed anchor support in geotechnical engineering, meet the requirements of timely application of prestress, and at the same time prevent the anchoring agent from flowing out of the anchor hole, ensuring the density of the anchoring.

[0014] Preferably, the high-strength coarse filler is quartz sand with a particle size of 40-200 mesh.

[0015] Preferably, the amount of the high-strength coarse filler is 3 to 4 times the mass of the high-activity vinyl ester resin.

[0016] Preferably, the amount of the low-shrinkage agent is 0.3 to 0.5 wt% of the total mass of the putty; the addition of an appropriate amount of low-shrinkage agent can reduce the shrinkage problem that exists during the construction of early-strength resin anchoring agent and ensure that the anchoring effect reaches the best.

[0017] Preferably, the amount of the silane coupling agent is 0.3-0.5 wt% of the total mass of the putty; the general structural formula of the silane coupling agent is RSiX3, where R is selected from amino, mercapto, vinyl, epoxy, cyano, and methylpropylvinyloxy groups, etc., because these groups have strong reactivity with different matrix resins; X is selected from hydrolyzable groups, such as halogens, alkoxy groups, acyloxy groups, etc. The silane coupling agent is further preferably KH-550, KH-560, or KH-570.

[0018] Preferably, the toughening agent is nitrile rubber; Preferably, the composite initiator is selected as a combination of at least one solid peroxide (e.g., benzoyl peroxide, 2,4-dichlorobenzoyl peroxide) and at least one liquid peroxide (e.g., tert-butyl peroxide, tert-butyl maleate peroxide) as needed.

[0019] Preferably, the surfactant is polymethyl ethylene glycol ether.

[0020] Preferably, the amount of surfactant used is 11 to 13 wt% of the total mass of the curing agent.

[0021] Preferably, the amount of aluminum hydroxide used is 0.4 to 0.6 wt% of the total mass of the curing agent; and the amount of calcium chloride used is 1 to 2 wt% of the total mass of the curing agent.

[0022] A second aspect of the present invention provides a method for preparing the above-mentioned early-strength resin anchoring agent, comprising the following steps: S1. Add the high-activity vinyl ester resin, composite accelerator and high thixotropic agent to the first premixing device equipped with a shear dispersion device in sequence according to the formula ratio, stir and premix to obtain resin premix; S2. Add the high-strength coarse filler, low-shrinkage agent, silane coupling agent and toughening agent to the first mixing reactor equipped with a twin-screw stirrer, stir and mix to obtain the composite filler; S3. Add the composite filler obtained in step S2 to the first premixing device containing the resin premix in step S1, stir and mix, and then carry out the first decompression reaction to obtain component A, i.e. putty. S4. Add polymethyl ethylene glycol ether, tap water, thickener, composite initiator, aluminum hydroxide, and calcium chloride to the second mixing reactor according to the formula ratio, stir and premix, then add fine filler, stir, and carry out the second depressurization reaction to obtain component B, i.e., curing agent; S5. Separate the obtained putty and curing agent into rolls according to a certain ratio to obtain early-strength resin anchoring agent.

[0023] Preferably, in step S1, the premixing process is as follows: first, the highly active vinyl ester resin and the composite accelerator are stirred and premixed, with the stirring speed set to 500-800 r / min and the stirring time to 5-10 min; then, the high thixotropic agent is added, with the stirring speed set to 1000-1200 r / min and the stirring time to 10-15 min.

[0024] Preferably, in step S2, the stirring speed is set to 40-50 r / min and the stirring time is 20-30 min.

[0025] Preferably, in step S3, when stirring and mixing, the speed is set to 300-500 r / min, and the stirring is carried out for 20-30 min. Then the speed is adjusted to 46-80 r / min, and the vacuum valve is opened at the same time to control the temperature below 45°C and carry out the reduced pressure reaction for 15-20 min. Preferably, in step S4, during the stirring premixing, the rotation speed is set to 500-800 r / min and the stirring time is 20-30 min; after adding the fine filler, the rotation speed is first set to 400-500 r / min and stirred for 25-30 min, and then the rotation speed is adjusted to 46-80 r / min. At the same time, the vacuum valve is opened and the temperature is controlled below 40 degrees Celsius to carry out the second decompression reaction for 15-20 min.

[0026] Preferably, in steps S3 and S4, the vacuum level during the first and second decompression reactions is controlled to be no less than 0.075 MPa. Setting a certain vacuum level here is beneficial to remove a large number of air bubbles introduced during the high-speed shear dispersion of components A and B, increasing the contact area between the resin anchor and the anchoring substrate, improving the degree of encapsulation and density of the resin anchor and the reinforcing bar or drilled substrate, and enhancing the bonding strength of the resin anchor.

[0027] Compared with the prior art, the beneficial effects of the present invention are: (1) This invention has developed an early-strength resin anchoring agent by self-making and selecting suitable high-activity vinyl ester resin, composite accelerator and curing agent, inorganic filler and other substances. It has the characteristics of fast load bearing, rapid application of high prestress, low shrinkage, corrosion resistance, seismic resistance and self-healing. It realizes the mechanized and rapid construction of prestressed resin anchor rods in geotechnical engineering, meets the requirement of tensioning not less than 72kN 1 minute after mixing, adapts to the requirements of mechanized and rapid construction and tunnel construction environment (low temperature, water presence), and active and timely support. It overcomes the shortcomings of ordinary resin anchoring agents, such as low early strength and poor waterproof performance, which cannot meet the requirements of rapid mechanized construction of anchor rod support in railway tunnels. The developed anchoring material has a wide range of applications and has great application and promotion prospects.

[0028] (2) In the preparation of the curing agent, a composite initiator (a combination of at least one solid peroxide and at least one liquid peroxide) is used to replace the existing single initiator. The composite initiator obtained after the two are combined has good miscibility, low decomposition temperature and high initiation activity. The use of composite initiators to prepare curing agents enables the final early-strength resin anchoring agent to be cured quickly at low temperature, bear load quickly, and apply high prestress quickly, meeting the mechanized construction requirements of prestress tension greater than 72kN in 1 minute. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] This invention provides an early-strength resin anchoring agent, which is composed of putty and a curing agent, wherein, The putty comprises the following raw materials in parts by weight: 90-100 parts of high-activity vinyl ester resin, 300-400 parts of high-strength coarse filler, 1.0-2.0 parts of high-thixotropic agent, 5.0-10.0 parts of composite accelerator, 1.5-3.0 parts of low-shrinkage agent, 2.0-3.0 parts of silane coupling agent, and 5.0-10.0 parts of toughening agent; The curing agent comprises the following raw materials in parts by weight: 11-13 parts surfactant, 21-23 parts water, 0.5-0.6 parts thickener, 10-15 parts composite initiator, 50-55 parts fine filler, 0.4-0.6 parts aluminum hydroxide, and 1-2 parts calcium chloride.

[0031] In this invention, the composite accelerator can be selected from at least one tertiary aromatic amine and at least one tertiary alkyl amine as needed, so that the anchoring agent can be cured quickly in low temperature and water environment, and also has fast load-bearing performance, which can adapt to the rapid mechanized construction of prestressed resin anchor rods under low temperature and water conditions, and meet the requirements of active and timely support.

[0032] In this invention, under complex geological conditions of high ground stress in the surrounding rock of tunnels, conventional resin anchoring agents have low thixotropy and high viscosity, resulting in high propulsion resistance during anchor bolt construction. By adding a high thixotropic agent (nano-fumed silica), the interaction of a small number of silanol groups on its surface forms a three-dimensional network structure, which can improve the thixotropy of the resin anchoring agent, reduce propulsion resistance, and promote the mixing and workability of the resin anchoring agent. This is beneficial for the rapid mechanization of prestressed anchor bolt support in geotechnical engineering, meeting the requirement of timely application of prestress, while preventing the anchoring agent from flowing out of the anchor hole and ensuring the density of the anchoring.

[0033] In this invention, the mortar uses high-strength coarse filler (40-200 mesh quartz sand) with optimal filler ratio and particle size morphology, and the ratio of high-activity vinyl ester resin to filler is 1:3-4. Different shapes, particle sizes, and quantities of inorganic fillers impart different properties to the resin anchoring agent. Existing conventional resin anchoring agents use heavy calcium carbonate powder as filler, which has an irregular shape. When preparing resin anchoring agents from irregularly shaped powder materials, many voids exist between the materials, resulting in poor compaction between the resin anchoring agent and the anchoring substrate during prestressed anchor construction, affecting the bonding strength of the resin anchoring agent. In contrast, the quartz sand selected in this invention is a regularly shaped powder material, which improves packing performance, reduces voids, and makes the material more dense and homogeneous, improving the compressive strength, electrical insulation properties, flowability, thermal stability, and corrosion resistance of the resin anchoring agent.

[0034] In this invention, the addition of a low-shrinkage agent can reduce the shrinkage problem that exists during the construction of high-strength resin anchoring agent, ensuring that the anchoring effect reaches the best. In this invention, the amount of silane coupling agent used is 0.3-0.5 wt% of the total mass of the adhesive. The addition of an appropriate amount of silane coupling agent enables the coupling of the highly reactive vinyl ester resin (unsaturated resin) and the inorganic filler, thereby improving the bonding strength of the anchoring agent. The general structural formula of the silane coupling agent is RSiX3, where R is selected from amino, mercapto, vinyl, epoxy, cyano, and methylpropylvinyloxy groups, etc., because these groups have strong reactivity with different matrix resins; X is selected from hydrolyzable groups, such as halogens, alkoxy groups, acyloxy groups, etc. The silane coupling agent is further preferably KH-550, KH-560, or KH-570.

[0035] Because silane coupling agents can interact with both hydroxyl groups in inorganic materials and long molecular chains in organic polymers, they can couple two materials with different properties, thereby improving various material properties. Quartz sand, after special surface treatment, possesses oleophilic and hydrophobic properties, making it easily dispersed in organic material systems. The addition of an appropriate amount of silane coupling agent can couple highly reactive vinyl ester resins and inorganic fillers, improving the bonding strength of early-strength resin anchoring agents.

[0036] In this invention, the addition of an appropriate amount of toughening agent enables the resulting resin anchor to suppress the development of crazes under high ground stress and strong seismic geological conditions. It can also promptly adapt to changes in geological conditions, improving the seismic resistance and self-healing properties of the resin anchor. After curing, the rubber forms "islands" of a "sea-island structure" within the resin system, ultimately achieving the goal of toughening the main resin system.

[0037] In this invention, the high-strength coarse filler is quartz sand with a particle size of 40-200 mesh. Inorganic fillers of different shapes, particle sizes, and quantities can impart different properties to the resin anchoring agent. Conventional resin anchoring agents use heavy calcium carbonate powder, which has an irregular shape. When preparing resin anchoring agents from irregularly shaped powder materials, many voids exist between the materials. During the construction of prestressed anchor rods, the density between the resin anchoring agent and the anchoring substrate is poor, affecting the bonding strength of the resin anchoring agent. The quartz sand selected in this invention is a regularly shaped powder material, which can improve packing performance, reduce voids, and make the material more dense and homogeneous, thereby improving the compressive strength, electrical insulation performance, flowability, thermal stability, and corrosion resistance of the resin anchoring agent.

[0038] In this invention, based on the crazing-shear band theory, the main reason for the toughening effect of the toughening agent is the large-scale generation of crazing and shear bands and the interaction between them. The first important function of rubber particles is to act as stress concentration centers, inducing a large number of crazing and shear bands. The generation and development of these crazing or shear bands require a significant amount of energy. The proportion of crazing and shear bands is related to the matrix properties; the greater the toughness of the matrix, the higher the proportion of shear bands. It is also related to the deformation rate; as the deformation rate increases, the proportion of crazing increases. The second important function of rubber particles is to control the development of crazing and terminate it in a timely manner. During the application of external force, the rubber particles deform, not only generating a large number of small crazing or shear bands and absorbing a large amount of energy, but also terminating the crazing in a timely manner to prevent it from developing into destructive cracks. After curing, the rubber forms "islands" of a "sea-island structure" in the resin system, ultimately achieving the goal of toughening the main resin system. The addition of an appropriate amount of toughening agent (nitrile rubber) to the mortar can inhibit the development of silver streaks in the resin anchor under high ground stress and strong vibration geological conditions. It can also promptly repair and adapt to new geological conditions when geological conditions change, thereby improving the seismic resistance and self-healing performance of the resin anchor. This solves the problem of roadway support under complex and difficult conditions in geotechnical engineering, such as roadways with high ground stress, extra-large cross-section roadways, roadways affected by strong mining, roadways left along the goaf, and soft rock roadways.

[0039] In this invention, the addition of an appropriate amount of thickener can make the curing agent into a viscous liquid, preventing the curing agent from leaking out of the film, reducing the moisture loss of the curing agent, and extending the shelf life of the anchoring agent. This is because the hydrophobic backbone in the thickener molecule associates with surrounding water molecules through hydrogen bonds, increasing the fluid volume of the polymer itself and reducing the space for free movement of particles, thereby increasing the viscosity of the system; viscosity can also be increased through the entanglement of molecular chains, manifested as high viscosity at static and low shear, and low viscosity at high shear. This is because at static or low shear rates, the cellulose molecular chains are in a disordered state, making the system highly viscous; while at high shear rates, the molecules are arranged in an ordered manner parallel to the flow direction, making it easy for them to slide against each other, so the viscosity of the system decreases.

[0040] In this invention, a mixture of at least one liquid peroxide and at least one solid peroxide is selected as the composite initiator. The solid peroxide can be, for example, benzoyl peroxide or 2,4-dichlorobenzoyl peroxide; the liquid peroxide can be, for example, tert-butyl peroxide or tert-butyl maleate peroxide. The liquid and solid peroxides exhibit good miscibility, lower decomposition temperature, and higher initiator activity. By adding an appropriate amount of the composite initiator, the early-strength resin anchoring agent can achieve rapid low-temperature curing, fast load-bearing capacity, and rapid application of high prestress, meeting the actual mechanized construction requirements of tensioning greater than 72 kN per minute. In this invention, the surfactant is polymethyl ethylene glycol ether. Polymethyl ethylene glycol ether can form a large number of micelles in water and effectively reduce the interfacial tension between the two phases, so that the liquid and solid can exist stably in water. This demonstrates the emulsifying, dispersing, foaming, and solubilizing effects of the surfactant, and improves the storage stability of the curing agent.

[0041] In this invention, appropriate amounts of aluminum hydroxide and calcium chloride are added to the curing agent. The added aluminum hydroxide (a commonly used inorganic flame retardant) can release moisture and absorb heat, forming a protective layer at high temperatures; the added calcium chloride can lower the freezing point, ensuring that the curing agent does not freeze when the resin anchoring agent is below zero degrees Celsius.

[0042] The highly active vinyl ester resin prepared in this invention has the following characteristics compared with ordinary unsaturated polyester resin: fast gel time, short resin exothermic peak time, high exothermic peak value, high compressive strength, high elastic modulus, and thermal stability (see Table 1).

[0043] Table 1

[0044] Example 1 An early-strength resin anchoring agent, composed of putty and curing agent; wherein, The putty is composed of the following raw materials in parts by weight: 90 parts of high-activity vinyl ester resin, 300 parts of high-strength coarse filler, 1.0 part of high thixotropic agent, 5.0 parts of composite accelerator, 1.5 parts of low-shrinkage agent, 2.0 parts of silane coupling agent, and 5.0 parts of toughening agent. The curing agent is composed of the following raw materials in parts by weight: 11 parts polymethyl ethylene glycol ether, 21 parts tap water, 0.5 parts thickener, 10 parts composite initiator, 50 parts fine filler, 0.4 parts aluminum hydroxide, and 1 part calcium chloride.

[0045] The preparation method of the above-mentioned early-strength resin anchoring agent includes the following steps: S1. Add the high-activity vinyl ester resin and composite accelerator to the resin premix tank equipped with a shear dispersion device at room temperature. Set the rotation speed to (500-800) r / min and stir for (5-10) min. Then add the high thixotropic agent and set the rotation speed to (1000-1200) r / min. Stir for (10-15) min to obtain the resin premix.

[0046] S2. Add the filler, low shrinkage agent, silane coupling agent and toughening agent to a mixing vessel equipped with a twin-screw agitator. Set the speed to (40-50) r / min and turn on the dust collection device at the same time. Stir for 20-30 minutes to obtain high-strength composite filler.

[0047] S3. Add the specified weight of composite filler into the resin premix tank, set the speed to (300-500) r / min, stir for (20-30) min, set the low speed stirring to (46-80) r / min, open the vacuum valve at the same time, stir for (15-20) min, control the temperature to below 45 degrees, and then prepare component A. S4. Weigh out polymethyl ethylene glycol ether, tap water, thickener, composite initiator, aluminum hydroxide, and calcium chloride and add them to the curing agent mixing tank. Set the speed to (500-800) r / min and stir for 20-30 min. Add fine filler and set the speed to (400-500) r / min. Stir for (25-30) min and set the low-speed stirring to (46-80) r / min. At the same time, open the vacuum valve and control the temperature below 40 degrees Celsius to prepare component B. S5. The prepared components A and B are packaged separately in a certain proportion into rolls to obtain the early-strength resin anchoring agent.

[0048] Example 2 The preparation method of the early-strength resin anchoring agent provided in this embodiment is largely the same as that in Example 1. The main difference lies in the specific proportions of the raw materials used, as follows: An early-strength resin anchoring agent, composed of putty and curing agent; wherein, The putty is composed of the following raw materials in parts by weight: 95 parts of high-activity vinyl ester resin, 350 parts of high-strength coarse filler, 1.5 parts of high thixotropic agent, 7.5 parts of composite accelerator, 2.3 parts of low-shrinkage agent, 2.5 parts of silane coupling agent, and 7.5 parts of toughening agent. The curing agent is composed of the following raw materials in parts by weight: 11 parts surfactant, 21 parts tap water, 0.5 parts thickener, 10 parts composite initiator, 50 parts fine filler, 0.4 parts aluminum hydroxide, and 1 part calcium chloride. Example 3 The preparation method of the early-strength resin anchoring agent provided in this embodiment is largely the same as that in Example 1. The main difference lies in the specific proportions of the raw materials used, as follows: An early-strength resin anchoring agent, composed of putty and curing agent; wherein, The putty comprises the following raw materials in parts by weight: 100 parts of high-activity vinyl ester resin, 400 parts of high-strength coarse filler, 2.0 parts of high thixotropic agent, 10.0 parts of composite accelerator, 3.0 parts of low-shrinkage agent, 3.0 parts of silane coupling agent, and 10.0 parts of toughening agent; (Water-based) curing agent, comprising the following raw materials in parts by weight: 11 parts surfactant, 21 parts tap water, 0.5 parts thickener, 10 parts composite initiator, 50 parts fine filler, 0.4 parts aluminum hydroxide, and 1 part calcium chloride.

[0049] Example 4 The preparation method of the early-strength resin anchoring agent provided in this embodiment is largely the same as that in Example 1. The main difference lies in the specific proportions of the raw materials used, as follows: An early-strength resin anchoring agent, composed of putty and curing agent; wherein, The putty comprises the following raw materials in parts by weight: 100 parts of high-activity vinyl ester resin, 400 parts of high-strength coarse filler, 2.0 parts of high thixotropic agent, 10.0 parts of composite accelerator, 3.0 parts of low-shrinkage agent, 3.0 parts of silane coupling agent, and 10.0 parts of toughening agent; (Water-based) curing agent, comprising the following raw materials in parts by weight: 12 parts surfactant, 22 parts tap water, 0.5 parts thickener, 12 parts composite initiator, 52.5 parts fine filler, 0.5 parts aluminum hydroxide, and 1.5 parts calcium chloride.

[0050] Example 5 The preparation method of the early-strength resin anchoring agent provided in this embodiment is largely the same as that in Example 1. The main difference lies in the specific proportions of the raw materials used, as follows: An early-strength resin anchoring agent, composed of putty and curing agent; wherein, The putty is composed of the following raw materials in parts by weight: 100 parts of high-activity vinyl ester resin, 400 parts of high-strength coarse filler, 2.0 parts of high thixotropic agent, 10.0 parts of composite accelerator, 3.0 parts of silane coupling agent, and 10.0 parts of toughening agent; The curing agent is composed of the following raw materials in parts by weight: 12 parts polymethyl ethylene glycol ether, 22 parts tap water, 0.5 parts thickener, 12 parts composite initiator, 52.5 parts fine filler, 0.5 parts aluminum hydroxide, and 1.5 parts calcium chloride. Example 6 The preparation method of the early-strength resin anchoring agent provided in this embodiment is largely the same as that in Example 1. The main difference lies in the specific proportions of the raw materials used, as follows: An early-strength resin anchoring agent, composed of putty and curing agent; wherein, The putty is composed of the following raw materials in parts by weight: 100 parts of high-activity vinyl ester resin, 400 parts of high-strength coarse filler, 2.0 parts of high thixotropic agent, 10.0 parts of composite accelerator, 1.5-3.0 parts of low-shrinkage agent, and 3.0 parts of silane coupling agent; The curing agent is composed of the following raw materials in parts by weight: 12 parts polymethyl ethylene glycol ether, 22 parts tap water, 0.5 parts thickener, 12 parts composite initiator, 52.5 parts fine filler, 0.5 parts aluminum hydroxide, and 1.5 parts calcium chloride.

[0051] Comparative Example 1 In this comparative example, the high-activity vinyl ester resin was replaced with ordinary unsaturated polyester resin, and the rest was the same as in Example 3.

[0052] Comparative Example 2 In this comparative example, the composite accelerator was replaced with a common accelerator, and the rest was the same as in Example 3.

[0053] Comparative Example 3 Except for replacing the early-high-strength composite initiator with a single initiator, the comparative example is the same as in Example 3.

[0054] Comparative Example 4 Commercially available ordinary ultra-fast resin anchoring agent products.

[0055] Performance testing The resin anchoring agents obtained by Examples 1-6 and Comparative Examples 1-4 of this invention were tested according to MT / T146.1-2011, DL / T5703-2014, BS6319-6:1984, and BS2782 Part 3, respectively. The test results are shown in Table 2.

[0056] Table 2

[0057] In summary, compared with the resin anchoring agents in Comparative Examples 1-4, the early high-strength resin anchoring agents provided in Examples 1-6 have the following advantages: 1. Shrinkage rate: ≤0.3%; 2. 4-day boiling test in different corrosive media: the specimen condition is better than good, with good corrosion resistance; 3. Good thixotropy; 4. 8 million fatigue test: passed, with good seismic resistance and self-healing performance; 5. Elastic modulus ≥4GPa, shear strength ≥24MPa; 6. Half-strength time ≤30min; 7. 2min Bausch hardness: ≥70HBa; 8. When supporting tunnel anchor bolts, the anchoring force is greater than 72kN for 1min of equal strength, and should not be less than the maximum force of the matching anchor bolt body for 5min of equal strength; 9. 24h compressive strength is not less than 70MPa, and the pull-out force test index is not less than 100kN; 10. Adaptable to tunnel construction environment (low temperature, presence of water).

[0058] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A kind of early-strength resin anchoring agent, characterized in that, The early-strength resin anchoring agent is composed of putty and a curing agent, wherein... The putty comprises the following raw materials in parts by weight: 90-100 parts of high-activity vinyl ester resin, 300-400 parts of high-strength coarse filler, 1.0-2.0 parts of high thixotropic agent, 5.0-10.0 parts of composite accelerator, 1.5-3.0 parts of low-shrinkage agent, 2.0-3.0 parts of silane coupling agent, and 5.0-10.0 parts of toughening agent; The curing agent comprises the following raw materials in parts by weight: 11-13 parts surfactant, 21-23 parts water, 0.5-0.6 parts thickener, 10-15 parts composite initiator, 50-55 parts fine filler, 0.4-0.6 parts aluminum hydroxide, and 1-2 parts calcium chloride.

2. The early-strength resin anchoring agent according to claim 1, characterized in that, The composite accelerator is selected from tertiary aromatic amines or tertiary alkyl amines; wherein the tertiary aromatic amine is one or a combination of two or more of N,N-dimethyltoluidine, N,N-dimethyl-p-toluidine, N,N-diisopropanol-p-toluidine, N-methyl-N-(2-hydroxyethyl)-p-toluidine, and N,N-dimethyl-(2-hydroxyethyl)-p-toluidine; the tertiary alkyl amine is N,N-dimethyloctylamine and / or N,N-dimethyldecylamine; the amount of the composite accelerator is 0.2 to 0.6 wt% of the mass of the high-activity vinyl ester resin.

3. The early-strength resin anchoring agent according to claim 1, characterized in that, The high thixotropic agent is nano-fumed silica; the high-strength coarse filler is quartz sand with a particle size of 40-200 mesh, and the amount of the high-strength coarse filler is 3-4 times the mass of the high-activity vinyl ester resin.

4. The early-strength resin anchoring agent according to claim 1, characterized in that, The amount of the low-shrinkage agent is 0.3-0.5 wt% of the total mass of the putty; the amount of the silane coupling agent is 0.3-0.5 wt% of the total mass of the putty; the amount of aluminum hydroxide is 0.4-0.6 wt% of the total mass of the curing agent; and the amount of calcium chloride is 1-2 wt% of the total mass of the curing agent.

5. The early-strength resin anchoring agent according to claim 1, characterized in that, The silane coupling agent is any one of KH-550, KH-560 or KH-570; the toughening agent is nitrile rubber.

6. A method for preparing an early-strength resin anchoring agent according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Add the high-activity vinyl ester resin, composite accelerator and high thixotropic agent to the first premixing device equipped with a shear dispersion device in sequence according to the formula ratio, stir and premix to obtain resin premix; S2. Add the high-strength coarse filler, low-shrinkage agent, silane coupling agent and toughening agent to the first mixing reactor equipped with a twin-screw stirrer, stir and mix to obtain the composite filler; S3. Add the composite filler obtained in step S2 to the first premixing device containing the resin premix in step S1, stir and mix, and then carry out the first decompression reaction to obtain component A, i.e. putty. S4. Add polymethyl ethylene glycol ether, tap water, thickener, composite initiator, aluminum hydroxide, and calcium chloride to the second mixing reactor according to the formula ratio, stir and premix, then add fine filler, stir, and carry out the second depressurization reaction to obtain component B, i.e., curing agent; S5. Separate the obtained putty and curing agent into rolls according to a certain ratio to obtain early-strength resin anchoring agent.

7. The method for preparing the early-strength resin anchoring agent according to claim 6, characterized in that: In step S1, the premixing process is as follows: first, the highly active vinyl ester resin and the composite accelerator are stirred and premixed. The stirring speed is set to 500-800 r / min and the stirring time is 5-10 min. Then, the high thixotropic agent is added, and the stirring speed is set to 1000-1200 r / min and the stirring time is 10-15 min.

8. The method for preparing the early-strength resin anchoring agent according to claim 6, characterized in that: In step S2, the stirring speed is set to 40-50 r / min and the stirring time is 20-30 min. In step S3, when stirring and mixing, the speed is set to 300-500 r / min and stirred for 20-30 min. Then the speed is adjusted to 46-80 r / min. At the same time, the vacuum valve is opened and the temperature is controlled below 45℃ to carry out the reduced pressure reaction for 15-20 min. In step S4, during the premixing process, the stirring speed is set to 500-800 r / min and the stirring time is 20-30 min. After adding the fine filler, the stirring speed is first set to 400-500 r / min and stirred for 25-30 min. Then, the stirring speed is adjusted to 46-80 r / min. At the same time, the vacuum valve is opened and the temperature is controlled below 40 degrees Celsius to carry out the second decompression reaction for 15-20 min.

9. The method for preparing the early-strength resin anchoring agent according to claim 8, characterized in that: In steps S3 and S4, the vacuum level during the first and second decompression reactions is controlled to be no less than 0.075 MPa.

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