A waterproof anchoring agent for water-containing soft rock and a method for preparing the same

Abstract

The present application relates to the technical field of anchoring agent, and particularly relates to a waterproof anchoring agent for water-containing soft rock and a preparation method thereof, the waterproof anchoring agent comprises A component and B component, the A component comprises resin mortar, accelerator and coupling agent, the resin mortar comprises modified unsaturated polyester resin, calcium carbonate, dolomite and mica powder, the modified unsaturated polyester resin comprises palmitoleic acid monoglyceride and conjugated triene pyridine; the B component comprises benzoyl peroxide, chlorobenzene, diphenyl and polyether polyol, the polyether polyol is prepared by ring-opening polymerization of bisphenol A introduced into propylene oxide; the waterproof anchoring agent prepared by the present application overcomes the problems that the anchorage cable body and the traditional resin anchoring agent have low bonding stiffness and are easy to slide and deform in the mudified roadway, so that high pre-tightening force cannot be applied, the utilization rate of the anchorage cable is low, and the anchorage cable cannot realize efficient control of the deformation of the roadway surrounding rock; the waterproof anchoring agent can be used for efficient anchoring of the anchorage cable in the mudified roadway surrounding rock.

Description

Technical Field

[0001] This invention relates to the field of anchoring agent technology, and in particular to a waterproof anchoring agent for water-bearing soft rock and its preparation method. Background Technology

[0002] Anchor cable support is widely used in mining engineering to reinforce surrounding rock. Anchor cable support technology reinforces rock mass through prestressed anchor cables. In essence, it applies prestress to the rock mass through anchor cables and reinforces it with some resin anchoring agents to limit the development of harmful deformation of the rock mass. It can significantly improve the stress state of the surrounding rock, enhance the self-supporting capacity of the surrounding rock, and thus maintain the stability of the surrounding rock.

[0003] Soft rock is a complex rock mechanical medium exhibiting significant plastic deformation under specific environmental conditions. It can be broadly classified into two categories: geological soft rock and engineering soft rock. Geological soft rock refers to loose, loose, soft, and weak rock layers characterized by low strength, high porosity, poor cementation, significant influence from tectonic cutting and weathering, or the presence of abundant expansive clay minerals. These rocks are mostly mudstone, shale, siltstone, and argillaceous rocks, and are naturally formed complex geological media. Engineering soft rock refers to engineering rock masses capable of significant plastic deformation under engineering forces. Soft rock readily absorbs water, undergoing mudification, softening, and disintegration upon contact with water. The rock's resistance to softening by water depends primarily on the content of hydrophilic and easily soluble minerals, as well as the degree of development of pores and microfractures within the rock.

[0004] Due to the characteristics of soft rock, when anchor cable support is carried out in soft rock areas of mining engineering and in muddy roadway surrounding rock, the residual mud-water mixture in the borehole results in low bonding stiffness between the anchor cable body and the traditional resin anchoring agent in the muddy roadway surrounding rock. This makes it easy to slip and deform, resulting in the inability to apply high preload, low anchor cable utilization, and inability to achieve efficient control of roadway surrounding rock deformation by anchor cables. Summary of the Invention

[0005] This invention provides a waterproof anchoring agent for water-bearing soft rock and its preparation method, which solves the defects of the prior art where the anchor cable body and traditional resin anchoring agent have low bonding stiffness in muddy roadway surrounding rock, are prone to sliding deformation and thus cannot apply high preload, have low anchor cable utilization, and cannot achieve efficient control of roadway surrounding rock deformation by anchor cable, thereby achieving efficient anchoring of anchor cable in muddy roadway surrounding rock.

[0006] This invention provides a waterproof anchoring agent for water-bearing soft rock, wherein the waterproof anchoring agent comprises, by weight, 100 parts of component A and 4-7 parts of component B;

[0007] The A component, by weight, comprises: 93-97 parts resin putty, 0.02 parts accelerator, and 0.04 parts coupling agent;

[0008] Component B, by mass, comprises: 44 parts peroxybenzoyl peroxide, 16 parts chlorobenzene, 0.6-0.8 parts biphenyl, and 38-39 parts polyether polyol.

[0009] According to the present invention, a waterproof anchoring agent for water-bearing soft rock is provided, wherein the resin mortar comprises, by weight, 13-15 parts of modified unsaturated polyester resin, 72-74 parts of calcium carbonate, 4 parts of dolomite, and 4 parts of mica powder.

[0010] According to the present invention, a waterproof anchoring agent for water-bearing soft rock is provided, wherein the modified unsaturated polyester resin is prepared by reacting maleic succinic anhydride, diethylene glycol, phosphoric acid, palmitole monoglyceride, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone, conjugated trienepyridine and styrene.

[0011] According to the present invention, a waterproof anchoring agent for water-bearing soft rock is provided, wherein the polyether polyol is prepared by ring-opening polymerization of propylene oxide with the introduction of bisphenol A.

[0012] According to the present invention, a waterproof anchoring agent for water-bearing soft rock is provided, wherein the accelerator is DMA accelerator and the coupling agent is a silane coupling agent.

[0013] This invention also provides a method for preparing a waterproof anchoring agent for water-bearing soft rock, comprising the following steps:

[0014] S1. Palmitoleic acid monoglyceride was prepared using palmitoleic acid, isopropylidene glycerol, sulfonic acid resin, toluene and hydrochloric acid; conjugated trienepyridine was prepared using α-enoyl-α-aminocarbamoyl dithiocarbamate, dimethylformamide, diethyl malonate and potassium carbonate.

[0015] S2. Modified unsaturated polyester resin is prepared using palmitoleic acid monoglyceride and conjugated triene pyridine prepared in step S1, as well as maleic anhydride, diethylene glycol, phosphoric acid, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone, and styrene; polyether polyol is obtained by ring-opening polymerization of bisphenol A in propylene oxide.

[0016] S3. According to the mass fraction, take 13-15 parts of the modified unsaturated polyester resin prepared in step S2, mix it with 72-74 parts of calcium carbonate, 4 parts of dolomite and 4 parts of mica powder, and stir at a speed of 1200-1500 rpm for 30-50 min to obtain resin putty. Then add 0.02 parts of accelerator and 0.04 parts of coupling agent, place it in an anchoring agent mixer, and stir at a speed of 1200-1500 rpm for 30-50 min to obtain component A. According to the mass fraction, take 44 parts of benzoyl peroxide, 16 parts of chlorobenzene, 0.6-0.8 parts of biphenyl and 38-39 parts of polyether polyol, mix them, and stir evenly to obtain component B.

[0017] S4. According to the mass fraction, take 100 parts of component A prepared in step S3 and 4 to 7 parts of component B prepared in step S3, mix them, stir evenly, and then package them to obtain a waterproof anchoring agent for water-bearing soft rock.

[0018] According to the present invention, a method for preparing a waterproof anchoring agent for water-bearing soft rock is provided. In step S1, the preparation process of palmitoleic acid monoglyceride is as follows: under a nitrogen atmosphere, palmitoleic acid, isopropylidene glycerol, sulfonic acid resin and toluene are mixed in a mass ratio of 10:4~6:0.2~0.8:30, heated to 120~130℃, reacted for 2~4h, cooled to room temperature, and an equal volume of 0.8~1mol / L hydrochloric acid is added. After stirring evenly, the mixture is allowed to stand and separate into layers. Then, it is washed with deionized water 3~5 times and vacuum dehydrated to obtain palmitoleic acid monoglyceride.

[0019] In step S1, the preparation process of conjugated triene pyridine is as follows: α-enoyl-α-aminoformyl dithiocarbamate, dimethylformamide and diethyl malonate are mixed at a mass ratio of 6-8:5:3, stirred at 100-200 rpm for 4-6 hours, heated to 78-82℃, and then potassium carbonate (0.05-0.07 times the mass of diethyl malonate) is added. After stirring evenly, the mixture is transferred to a saturated sodium chloride solution, stirred evenly, and extracted with diethyl ether. After washing with water, drying, and separation by column chromatography, conjugated triene pyridine is obtained.

[0020] According to the present invention, a method for preparing a waterproof anchoring agent for water-bearing soft rock is provided, wherein the isopropylidene glycerol is prepared by the following method: glycerol, acetone and sulfonic acid resin are mixed in a mass ratio of 1-3:20:0.15, heated to 50-60°C, reacted for 1-2 hours, filtered while hot and then subjected to vacuum distillation to obtain isopropylidene glycerol.

[0021] According to the present invention, a method for preparing a waterproof anchoring agent for water-bearing soft rock is provided. In step S2, the preparation process of the modified unsaturated polyester resin is as follows: the palmitoleic acid monoglyceride prepared in step S1, maleic anhydride, diethylene glycol, phosphoric acid, and deionized water are mixed in a mass ratio of 4-6:40:12:0.3:5-6. After stirring evenly, the mixture is heated to 125-135°C under a nitrogen atmosphere. Dicyclopentadiene, at a mass ratio of 1.1-1.3 times that of the maleic anhydride, is added dropwise at a rate of 3-5 mL / min. The reaction is maintained at this temperature for 2-4 hours. Then, phthalic anhydride, at a mass ratio of 0.7-0.8 times that of the maleic anhydride, diethylene glycol, at a mass ratio of 0.15-0.25 times that of the maleic anhydride, and the mass ratio of the maleic anhydride are added. Add 0.55–0.65 times the mass of 1,2-propanediol and 0.01–0.02 times the mass of maleic succinic anhydride as a polymerization inhibitor, hydroquinone, to a temperature of 195–205°C. After reacting for 30–50 minutes, cool to 160–180°C. Then add 0.01–0.02 times the mass of maleic succinic anhydride as a polymerization inhibitor, 0.1–0.2 times the mass of maleic succinic anhydride as palmitole monoglyceride prepared in step S1, and 0.1–0.2 times the mass of maleic succinic anhydride as conjugated trienepyridine prepared in step S1. After reacting for 2–4 hours, cool to 90–100°C. Then add 1.2–1.4 times the mass of maleic succinic anhydride as styrene, stir until homogeneous, and cool to room temperature to obtain a modified unsaturated polyester resin.

[0022] According to the present invention, a method for preparing a waterproof anchoring agent for water-bearing soft rock is provided. In step S2, the preparation method of polyether polyol is as follows: under a nitrogen atmosphere, bisphenol A and a catalyst bimetallic cyanide complex are mixed at a mass ratio of 13-15:0.2, heated to 130-140°C, and reacted for 1-2 hours. Then, 0.3-0.5 times the mass of bisphenol A of propylene oxide is added and the pressure is increased to 0.10-0.15 MPa. After reacting for 4-6 hours, another 0.3-0.5 times the mass of bisphenol A of propylene oxide is added, and the reaction continues for 1-2 hours. The mixture is then evacuated and cooled to 85-95°C. Finally, 0.03-0.05 times the mass of bisphenol A of polyether antioxidant is added and stirred evenly to obtain polyether polyol.

[0023] This invention provides a waterproof anchoring agent for water-bearing soft rock and its preparation method. Palmitoleic acid monoglyceride is prepared by using palmitoleic acid, isopropylidene glycerol, sulfonic acid resin, toluene, and hydrochloric acid. Conjugated triene pyridine is prepared using α-enoyl-α-aminoformyl dithiocarbamate, dimethylformamide, diethyl malonate, and potassium carbonate. Modified unsaturated polyester resin is prepared using the prepared palmitoleic acid monoglyceride and conjugated triene pyridine. This resin is then mixed with calcium carbonate, dolomite, and mica powder to prepare a resin putty. An accelerator and a coupling agent are added to obtain component A. A polyether polyol is prepared by ring-opening polymerization of bisphenol A in propylene oxide. Benzoyl peroxide, chlorobenzene, and biphenyl are added to prepare component B. Finally, the waterproof anchoring agent for water-bearing soft rock is prepared by mixing components A and B. The prepared waterproof anchoring agent overcomes the problems of low bonding stiffness between the anchor cable body and traditional resin anchoring agents in muddy roadways, which makes it easy to slide and deform, thus preventing the application of high preload, low anchor cable utilization, and inability to achieve efficient control of roadway surrounding rock deformation. It can be used for efficient anchoring of anchor cables in muddy roadways. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0025] Figure 1 This is a schematic flowchart of the preparation method of the waterproof anchoring agent for water-bearing soft rock provided by the present invention. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0027] This invention provides a waterproof anchoring agent for water-bearing soft rock. The waterproof anchoring agent comprises, by weight, 100 parts of component A and 4-7 parts of component B; wherein, component A comprises, by weight, 93-97 parts of resin putty, 0.02 parts of accelerator, and 0.04 parts of coupling agent; and component B comprises, by weight, 44 parts of benzoyl peroxide, 16 parts of chlorobenzene, 0.6-0.8 parts of biphenyl, and 38-39 parts of polyether polyol.

[0028] Specifically, the resin mortar, by weight, comprises 13-15 parts modified unsaturated polyester resin, 72-74 parts calcium carbonate, 4 parts dolomite, and 4 parts mica powder. The modified unsaturated polyester resin is prepared by reacting maleic anhydride, diethylene glycol, phosphoric acid, palmitole monoglyceride, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone, conjugated trienepyridine, and styrene. The polyether polyol is obtained by ring-opening polymerization of propylene oxide with the introduction of bisphenol A. The accelerator is DMA; the coupling agent is a silane coupling agent.

[0029] This invention also provides a method for preparing a waterproof anchoring agent for water-bearing soft rock, see [link to relevant documentation]. Figure 1 As shown, it includes the following steps:

[0030] S1. Palmitoleic acid monoglyceride was prepared using palmitoleic acid, isopropylidene glycerol, sulfonic acid resin, toluene and hydrochloric acid; conjugated trienepyridine was prepared using α-enoyl-α-aminocarbamoyl dithiocarbamate, dimethylformamide, diethyl malonate and potassium carbonate.

[0031] S2. Modified unsaturated polyester resin is prepared using palmitoleic acid monoglyceride and conjugated triene pyridine prepared in step S1, as well as maleic anhydride, diethylene glycol, phosphoric acid, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone, and styrene; polyether polyol is obtained by ring-opening polymerization of bisphenol A in propylene oxide.

[0032] S3. According to the mass fraction, take 13-15 parts of the modified unsaturated polyester resin prepared in step S2, mix it with 72-74 parts of calcium carbonate, 4 parts of dolomite and 4 parts of mica powder, and stir at a speed of 1200-1500 rpm for 30-50 min to obtain resin putty. Then add 0.02 parts of accelerator and 0.04 parts of coupling agent, place it in an anchoring agent mixer, and stir at a speed of 1200-1500 rpm for 30-50 min to obtain component A. According to the mass fraction, take 44 parts of benzoyl peroxide, 16 parts of chlorobenzene, 0.6-0.8 parts of biphenyl and 38-39 parts of polyether polyol, mix them, and stir evenly to obtain component B.

[0033] S4. According to the mass fraction, take 100 parts of component A prepared in step S3 and 4 to 7 parts of component B prepared in step S3, mix them, stir evenly, and then package them to obtain a waterproof anchoring agent for water-bearing soft rock.

[0034] Specifically, in step S1, the preparation process of palmitoleic acid monoglyceride is as follows: under a nitrogen atmosphere, palmitoleic acid, isopropylidene glycerol, sulfonic acid resin and toluene are mixed in a mass ratio of 10:4-6:0.2-0.8:30, heated to 120-130℃, reacted for 2-4 hours, cooled to room temperature, and an equal volume of 0.8-1 mol / L hydrochloric acid is added. After stirring evenly and allowing to stand for separation, the mixture is washed 3-5 times with deionized water and then dehydrated under vacuum to obtain palmitoleic acid monoglyceride. The isopropylidene glycerol used is prepared by the following method: glycerol, acetone and sulfonic acid resin are mixed in a mass ratio of 1-3:20:0.15, heated to 50-60℃, reacted for 1-2 hours, filtered while hot, and then distilled under reduced pressure to obtain isopropylidene glycerol.

[0035] In step S1, the preparation process of conjugated triene pyridine is as follows: α-enoyl-α-aminoformyl dithiocarbamate, dimethylformamide and diethyl malonate are mixed in a mass ratio of 6-8:5:3, stirred at 100-200 rpm for 4-6 hours, heated to 78-82℃, and then potassium carbonate (0.05-0.07 times the mass of diethyl malonate) is added. After stirring evenly, the mixture is transferred to a saturated sodium chloride solution, stirred evenly, and extracted with diethyl ether. After washing with water, drying, and separation by column chromatography, conjugated triene pyridine is obtained.

[0036] In step S2, the preparation process of the modified unsaturated polyester resin is as follows: Palmitoleic acid monoglyceride prepared in step S1, along with maleic succinic anhydride, diethylene glycol, phosphoric acid, and deionized water, are mixed in a mass ratio of 4–6:40:12:0.3:5–6. After stirring evenly, the mixture is heated to 125–135°C under a nitrogen atmosphere. Dicyclopentadiene, at a rate of 3–5 mL / min, is added dropwise at a ratio of 1.1–1.3 times the mass of maleic succinic anhydride. The reaction is maintained at this temperature for 2–4 hours. Then, phthalic anhydride at a ratio of 0.7–0.8 times the mass of maleic succinic anhydride, diethylene glycol at a ratio of 0.15–0.25 times the mass of maleic succinic anhydride, and dicyclopentadiene at a ratio of 0.55–0.65 times the mass of maleic succinic anhydride are added. 2-Propanediol and hydroquinone (0.01–0.02 times the mass of maleic succinic anhydride) were added as polymerization inhibitors. The mixture was heated to 195–205°C and reacted for 30–50 minutes. Then, the temperature was lowered to 160–180°C. Next, hydroquinone (0.01–0.02 times the mass of maleic succinic anhydride), palmitole monoglyceride (0.1–0.2 times the mass of maleic succinic anhydride), and conjugated trienepyridine (0.1–0.2 times the mass of maleic succinic anhydride) prepared in step S1 were added. The mixture was reacted for 2–4 hours. Then, the temperature was lowered to 90–100°C. Finally, styrene (1.2–1.4 times the mass of maleic succinic anhydride) was added. The mixture was stirred until homogeneous and then cooled to room temperature to obtain the modified unsaturated polyester resin.

[0037] In step S2, the polyether polyol is prepared as follows: Under a nitrogen atmosphere, bisphenol A and the catalyst bimetallic cyanide complex are mixed at a mass ratio of 13-15:0.2, heated to 130-140℃, and reacted for 1-2 hours. Then, 0.3-0.5 times the mass of bisphenol A of propylene oxide is added and the pressure is increased to 0.10-0.15 MPa. After reacting for 4-6 hours, another 0.3-0.5 times the mass of bisphenol A of propylene oxide is added, and the reaction continues for 1-2 hours. The mixture is then evacuated and cooled to 85-95℃. Finally, 0.03-0.05 times the mass of bisphenol A of polyether antioxidant is added and stirred until homogeneous to obtain the polyether polyol.

[0038] The waterproof anchoring agent prepared by this invention for water-bearing soft rock overcomes the problems of low bonding stiffness between the anchor cable body and traditional resin anchoring agents in muddy roadways, which makes it easy to slide and deform, thus preventing the application of high preload, low anchor cable utilization, and inability to achieve efficient control of roadway surrounding rock deformation. It can be used for efficient anchoring of anchor cables in muddy roadways.

[0039] The following comparative description, using specific embodiments and comparative examples, illustrates the waterproof anchoring agent for water-bearing soft rock of the present invention and its preparation method. The testing methods for various indicators of the waterproof anchoring agents prepared in the embodiments and comparative examples are as follows:

[0040] Curing speed: The curing time was recorded when preparing the waterproof anchoring agents of Examples 1-3 and Comparative Examples 1-6.

[0041] Compressive strength: The waterproof anchoring agents prepared in Examples 1-3 and Comparative Examples 1-6 were subjected to compressive strength tests.

[0042] Waterproofing: The waterproof anchoring agents prepared in Examples 1-3 and Comparative Examples 1-6 were immersed in deionized water for 24 hours, and then the compressive strength was tested again.

[0043] Example 1:

[0044] (1) Glycerin, acetone and sulfonic acid resin were mixed in a mass ratio of 1:20:0.15, heated to 50°C, reacted for 1 h, filtered while hot and then distilled under reduced pressure to obtain isopropylidene glycerol; under a nitrogen atmosphere, palmitoleic acid, isopropylidene glycerol, sulfonic acid resin and toluene were mixed in a mass ratio of 10:4:0.2:30, heated to 120°C, reacted for 2 h, cooled to room temperature, and an equal volume of 0.8 mol / L hydrochloric acid was added. After stirring evenly, the mixture was allowed to stand and separate into layers, washed three times with deionized water and then dehydrated under vacuum to obtain palmitoleic acid monoglyceride;

[0045] α-Oenyl-α-aminoformyl dithiocarbamate, dimethylformamide, and diethyl malonate were mixed in a mass ratio of 6:5:3 and stirred at 100 rpm for 4 h. The mixture was then heated to 78 °C, and potassium carbonate (0.05 times the mass of diethyl malonate) was added. After stirring until homogeneous, the mixture was transferred to a saturated sodium chloride solution, stirred until homogeneous, extracted with diethyl ether, washed with water, dried, and separated by column chromatography to obtain conjugated trienepyridine.

[0046] (2) Maleic anhydride, diethylene glycol, phosphoric acid, palmitole monoglyceride, and deionized water were mixed in a mass ratio of 40:12:0.3:4:5. After stirring evenly, the mixture was heated to 125°C under a nitrogen atmosphere. Dicyclopentadiene (1.1 times the mass of maleic anhydride) was added dropwise at a rate of 3 mL / min. The mixture was kept at this temperature for 2 hours. Then, phthalic anhydride (0.7 times the mass of maleic anhydride), diethylene glycol (0.15 times the mass of maleic anhydride), and 1,2-dicyclopentadiene (0.55 times the mass of maleic anhydride) were added. Propylene glycol and hydroquinone (0.01 times the mass of maleic succinic anhydride) were added as polymerization inhibitors. The mixture was heated to 195°C and reacted for 30 minutes. Then, the temperature was lowered to 160°C, and hydroquinone (0.01 times the mass of maleic succinic anhydride), palmitole monoglyceride (0.1 times the mass of maleic succinic anhydride), and conjugated trienepyridine (0.1 times the mass of maleic succinic anhydride) were added. After reacting for 2 hours, the temperature was lowered to 90°C, and styrene (1.2 times the mass of maleic succinic anhydride) was added. The mixture was stirred evenly and then cooled to room temperature to obtain the modified unsaturated polyester resin.

[0047] (3) Modified unsaturated polyester resin, calcium carbonate, dolomite, and mica powder are mixed and stirred at 1200 rpm for 30 min to obtain resin putty. Then, accelerator and coupling agent are added. The mass ratio of modified unsaturated polyester resin, calcium carbonate, dolomite, mica powder, accelerator, and coupling agent is 13:72:4:4:0.02:0.04. The mixture is placed in an anchoring agent mixer and stirred at 1200 rpm for 30 min to obtain component A. Under a nitrogen atmosphere, bisphenol A and the catalyst bimetallic cyanide are mixed. The complex was mixed at a mass ratio of 13:0.2, heated to 130℃, and reacted for 1 hour. Then, 0.3 times the mass of bisphenol A in propylene oxide was added, and the pressure was increased to 0.10 MPa. After reacting for 4 hours, another 0.3 times the mass of bisphenol A in propylene oxide was added, and the reaction continued for 1 hour. The mixture was then evacuated and cooled to 85℃. Finally, 0.03 times the mass of bisphenol A in an antioxidant for polyether was added, and the mixture was stirred until homogeneous to obtain polyether polyol. Benzoyl peroxide, chlorobenzene, biphenyl, and polyether polyol were mixed at a mass ratio of 44:16:0.6:38 and stirred until homogeneous to obtain component B.

[0048] (4) The mass ratio of component A to component B is 100:4. After mixing evenly, the mixture is packaged to obtain a waterproof anchoring agent.

[0049] Example 2:

[0050] (1) Glycerin, acetone and sulfonic acid resin were mixed in a mass ratio of 2:20:0.15, heated to 55°C, reacted for 1.5 h, filtered while hot and then distilled under reduced pressure to obtain isopropylidene glycerol; under a nitrogen atmosphere, palmitoleic acid, isopropylidene glycerol, sulfonic acid resin and toluene were mixed in a mass ratio of 10:5:0.6:30, heated to 125°C, reacted for 3 h, cooled to room temperature, and an equal volume of 0.9 mol / L hydrochloric acid was added. After stirring evenly, the mixture was allowed to stand and separate into layers, washed 4 times with deionized water and then dehydrated under vacuum to obtain palmitoleic acid monoglyceride;

[0051] α-Oenyl-α-aminoformyl dithiocarbamate, dimethylformamide, and diethyl malonate were mixed in a mass ratio of 7:5:3 and stirred at 150 rpm for 5 h. The mixture was then heated to 80 °C, and potassium carbonate (0.06 times the mass of diethyl malonate) was added. After stirring until homogeneous, the mixture was transferred to a saturated sodium chloride solution, stirred until homogeneous, extracted with diethyl ether, washed with water, dried, and separated by column chromatography to obtain conjugated trienepyridine.

[0052] (2) Maleic anhydride, diethylene glycol, phosphoric acid, palmitole monoglyceride, and deionized water were mixed in a mass ratio of 40:12:0.3:5:5.5. After stirring evenly, the mixture was heated to 130°C under a nitrogen atmosphere. Dicyclopentadiene (1.2 times the mass of maleic anhydride) was added dropwise at a rate of 4 mL / min. The reaction was maintained at this temperature for 3 hours. Then, phthalic anhydride (0.75 times the mass of maleic anhydride), diethylene glycol (0.2 times the mass of maleic anhydride), and 1,2-(dicyclopentadiene) (0.60 times the mass of maleic anhydride) were added. Propylene glycol and hydroquinone (0.015 times the mass of maleic succinic anhydride) were heated to 200°C and reacted for 40 minutes. Then, the temperature was lowered to 170°C, and hydroquinone (0.015 times the mass of maleic succinic anhydride), palmitole monoglyceride (0.15 times the mass of maleic succinic anhydride), and conjugated trienepyridine (0.15 times the mass of maleic succinic anhydride) were added. After reacting for 3 hours, the temperature was lowered to 95°C, and styrene (1.3 times the mass of maleic succinic anhydride) was added. After stirring evenly, the mixture was cooled to room temperature to obtain the modified unsaturated polyester resin.

[0053] (3) Modified unsaturated polyester resin, calcium carbonate, dolomite, and mica powder were mixed and stirred at 1400 rpm for 40 min to obtain resin putty. Then, accelerator and coupling agent were added. The mass ratio of modified unsaturated polyester resin, calcium carbonate, dolomite, mica powder, accelerator, and coupling agent was 14:73:4:4:0.02:0.04. The mixture was placed in an anchoring agent mixer and stirred at 1400 rpm for 40 min to obtain component A. Under a nitrogen atmosphere, bisphenol A and the catalyst bimetallic cyanide complex were mixed. Mix the components at a mass ratio of 14:0.2, heat to 135℃, react for 1.5 h, add 0.4 times the mass of bisphenol A in propylene oxide and pressurize to 0.13 MPa, react for 5 h, then add another 0.4 times the mass of bisphenol A in propylene oxide, continue reacting for 1.5 h, evacuate and cool to 90℃, add 0.04 times the mass of bisphenol A in polyether antioxidant, stir evenly to obtain polyether polyol; mix peroxide, benzoyl peroxide, chlorobenzene, biphenyl and polyether polyol at a mass ratio of 44:16:0.7:38.5, stir evenly to obtain component B;

[0054] (4) The mass ratio of component A to component B is 100:5.5. After mixing evenly, the mixture is packaged to obtain a waterproof anchoring agent.

[0055] Example 3:

[0056] (1) Glycerin, acetone and sulfonic acid resin were mixed in a mass ratio of 3:20:0.15, heated to 60°C, reacted for 2 hours, filtered while hot and then distilled under reduced pressure to obtain isopropylidene glycerol; under a nitrogen atmosphere, palmitoleic acid, isopropylidene glycerol, sulfonic acid resin and toluene were mixed in a mass ratio of 10:6:0.8:30, heated to 130°C, reacted for 4 hours, cooled to room temperature, and an equal volume of 1 mol / L hydrochloric acid was added. After stirring evenly, the mixture was allowed to stand and separate into layers, washed 5 times with deionized water and then dehydrated under vacuum to obtain palmitoleic acid monoglyceride;

[0057] α-Oenyl-α-aminoformyl dithiocarbamate, dimethylformamide, and diethyl malonate were mixed in a mass ratio of 8:5:3 and stirred at 200 rpm for 6 h. The mixture was then heated to 82 °C, and potassium carbonate (0.07 times the mass of diethyl malonate) was added. After stirring until homogeneous, the mixture was transferred to a saturated sodium chloride solution, stirred until homogeneous, extracted with diethyl ether, washed with water, dried, and separated by column chromatography to obtain conjugated trienepyridine.

[0058] (2) Maleic anhydride, diethylene glycol, phosphoric acid, palmitole monoglyceride, and deionized water were mixed in a mass ratio of 40:12:0.3:6:6. After stirring evenly, the mixture was heated to 135°C under a nitrogen atmosphere. Dicyclopentadiene (1.3 times the mass of maleic anhydride) was added dropwise at a rate of 5 mL / min. The mixture was kept at this temperature for 4 hours. Then, phthalic anhydride (0.8 times the mass of maleic anhydride), diethylene glycol (0.25 times the mass of maleic anhydride), and 1,2-dicyclopentadiene (0.65 times the mass of maleic anhydride) were added. Propylene glycol and hydroquinone (0.02 times the mass of maleic succinic anhydride) were added as a polymerization inhibitor. The mixture was heated to 205°C and reacted for 50 minutes. Then, the temperature was lowered to 180°C, and hydroquinone (0.02 times the mass of maleic succinic anhydride), palmitole monoglyceride (0.2 times the mass of maleic succinic anhydride), and conjugated trienepyridine (0.2 times the mass of maleic succinic anhydride) were added. After reacting for 4 hours, the temperature was lowered to 100°C, and styrene (1.4 times the mass of maleic succinic anhydride) was added. The mixture was stirred evenly and then cooled to room temperature to obtain the modified unsaturated polyester resin.

[0059] (3) Modified unsaturated polyester resin, calcium carbonate, dolomite, and mica powder are mixed and stirred at 1500 rpm for 50 min to obtain resin putty. Then, accelerator and coupling agent are added. The mass ratio of modified unsaturated polyester resin, calcium carbonate, dolomite, mica powder, accelerator, and coupling agent is 15:74:4:4:0.02:0.04. The mixture is placed in an anchoring agent mixer and stirred at 1500 rpm for 50 min to obtain component A. Under a nitrogen atmosphere, bisphenol A and the catalyst bimetallic cyanide complex are mixed. The compounds were mixed at a mass ratio of 15:0.2, heated to 140℃, and reacted for 2 hours. Then, 0.5 times the mass of bisphenol A in propylene oxide was added, and the pressure was increased to 0.15 MPa. After reacting for 6 hours, another 0.5 times the mass of bisphenol A in propylene oxide was added, and the reaction continued for 2 hours. The mixture was then evacuated and cooled to 95℃. Finally, 0.05 times the mass of bisphenol A in polyether antioxidant B was added, and the mixture was stirred until homogeneous to obtain polyether polyol. Benzoyl peroxide, chlorobenzene, biphenyl, and polyether polyol were mixed at a mass ratio of 44:16:0.8:39 and stirred until homogeneous to obtain component B.

[0060] (4) The mass ratio of component A to component B is 100:7. After mixing evenly, the mixture is packaged to obtain a waterproof anchoring agent.

[0061] Comparative Example 1:

[0062] The composition of Comparative Example 1 is the same as that of Example 2. The difference between the preparation method of this waterproof anchoring agent and Example 2 is that palmitole monoglyceride is not prepared. The modified unsaturated polyester resin is prepared by reacting conjugated trienepyridine with maleic anhydride, diethylene glycol, phosphoric acid, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone and styrene.

[0063] Comparative Example 2:

[0064] The composition of Comparative Example 2 is the same as that of Example 2. The difference between the preparation method of this waterproof anchoring agent and that of Example 2 is that the preparation of conjugated triene pyridine is not carried out. The modified unsaturated polyester resin is prepared by reacting palmitole monoglyceride with maleic anhydride, diethylene glycol, phosphoric acid, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone and styrene.

[0065] Comparative Example 3:

[0066] The composition of Comparative Example 3 is the same as that of Example 2. The only difference between this waterproof anchoring agent and Example 2 is that the polyether polyol is not prepared; a commercially available polyether polyol is used, purchased from Nantong Jiaxian International Trade Co., Ltd.

[0067] Comparative Example 4:

[0068] The composition of Comparative Example 4 is the same as that of Example 2. The difference between the preparation method of this waterproof anchoring agent and Example 2 is that component B is only a combination curing agent including benzoyl peroxide, chlorobenzene and biphenyl.

[0069] Comparative Example 5:

[0070] The composition of Comparative Example 5 is the same as that of Example 2. The difference between the preparation method of this waterproof anchoring agent and Example 2 lies in step (2). Step (2) is modified as follows: maleic anhydride, diethylene glycol, phosphoric acid and deionized water are mixed in a mass ratio of 40:12:0.3:5.5. After stirring evenly, the mixture is heated to 130°C under a nitrogen atmosphere. Dicyclopentadiene with a mass of 1.2 times that of maleic anhydride is added dropwise at a rate of 4 mL / min. The mixture is kept at this temperature for 3 hours. Then, phthalic anhydride with a mass of 0.75 times that of maleic anhydride, diethylene glycol with a mass of 0.2 times that of maleic anhydride, and dicyclopentadiene are added. 1,2-propanediol (0.60 times the mass of maleic anhydride) and hydroquinone (0.015 times the mass of maleic anhydride) were added. The mixture was heated to 200℃ and reacted for 40 min. Then, the temperature was lowered to 170℃, and hydroquinone (0.015 times the mass of maleic anhydride), palmitole monoglyceride (0.15 times the mass of maleic anhydride), and conjugated trienepyridine (0.15 times the mass of maleic anhydride) were added. After reacting for 3 h, the temperature was lowered to 95℃, and styrene (1.3 times the mass of maleic anhydride) was added. The mixture was stirred until homogeneous and then cooled to room temperature to obtain the modified unsaturated polyester resin.

[0071] Comparative Example 6:

[0072] The composition of Comparative Example 6 is the same as that of Example 2. The difference between the preparation method of this waterproof anchoring agent and Example 2 lies in step (2). Step (2) is modified as follows: maleic anhydride, diethylene glycol, phosphoric acid, palmitole monoglyceride and deionized water are mixed in a mass ratio of 40:12:0.3:5:5.5. After stirring evenly, the mixture is heated to 130°C under a nitrogen atmosphere. Dicyclopentadiene with a mass of 1.2 times that of maleic anhydride is added dropwise at a rate of 4 mL / min. The mixture is kept at this temperature for 3 hours. Then, phthalic anhydride with a mass of 0.75 times that of maleic anhydride and maleic anhydride are added. 0.2 times the mass of diethylene glycol, 0.60 times the mass of maleic anhydride of 1,2-propanediol, and 0.015 times the mass of maleic anhydride of hydroquinone (polymerization inhibitor) were added. The mixture was heated to 200°C and reacted for 40 minutes. Then, the temperature was lowered to 170°C, and 0.015 times the mass of maleic anhydride of hydroquinone (polymerization inhibitor) and 0.15 times the mass of maleic anhydride of conjugated trienepyridine were added. After reacting for 3 hours, the temperature was lowered to 95°C, and 1.3 times the mass of maleic anhydride of styrene was added. The mixture was stirred evenly and then cooled to room temperature to obtain the modified unsaturated polyester resin.

[0073] Table 1 below shows the performance analysis results of the waterproof anchoring agents prepared using Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention:

[0074] Table 1:

[0075] Example 1 16.5 75 72 Example 2 16.2 77 73 Example 3 17 71 68 Comparative Example 1 24 74 68 Comparative Example 2 21 76 69 Comparative Example 3 17.1 63 49 Comparative Example 4 17.2 61 58 Comparative Example 5 22 68 62 Comparative Example 6 23 69 64

[0076] By comparing the experimental data of the examples and comparative examples in Table 1, it can be clearly found that the waterproof anchoring agents prepared using Examples 1, 2, and 3 have short curing time and excellent waterproof and compressive strength.

[0077] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 1 and 2 reveals that a modified unsaturated polyester resin prepared from palmitole monoglyceride, conjugated triene pyridine, maleic anhydride, diethylene glycol, phosphoric acid, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone, and styrene enhances the curing reactivity and accelerates the curing speed. This process also improves the flexibility of the resin mortar, coordinates with the metal expanding agent, and encapsulates and evenly disperses calcium carbonate, dolomite, and mica powder within the resin mortar, reducing porosity in the waterproof anchoring agent and enhancing its waterproofness.

[0078] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 3 and 4 reveals that the polyether polyol prepared by introducing bisphenol A into propylene oxide for ring-opening polymerization enhances compatibility. Simultaneously, the mixture of benzoyl peroxide, chlorobenzene, and biphenyl forms a multi-component curing system. When mixed with component A, benzoyl peroxide undergoes thermal decomposition, transforming into a large number of free radicals. These free radicals can react with the modified unsaturated resin and form hydrogen bonds, resulting in a cured, three-dimensionally cross-linked network structure that enhances the compressive strength of the anchoring agent.

[0079] Comparison of experimental data from Examples 1, 2, and 3 and Comparative Examples 5 and 6 reveals that adding palmitole monoglyceride in the initial stage of modified unsaturated polyester resin preparation allows for the sequential reaction of palmitole monoglyceride with unsaturated acids and diols, introducing long chains and double bonds into the unsaturated polyester resin. Adding palmitole monoglyceride and conjugated trienepyridine in the later stage of the reaction enhances the curing reaction activity and accelerates the curing speed.

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A waterproof anchoring agent for water-bearing soft rock, characterized in that, The waterproof anchoring agent, by weight, comprises: 100 parts of component A and 4-7 parts of component B; The A component, by mass, comprises: 93-97 parts resin putty, 0.02 parts accelerator, and 0.04 parts coupling agent; Component B, by mass, comprises: 44 parts peroxide benzoyl peroxide, 16 parts chlorobenzene, 0.6-0.8 parts biphenyl, and 38-39 parts polyether polyol; The resin putty, by weight, comprises: 13-15 parts modified unsaturated polyester resin, 72-74 parts calcium carbonate, 4 parts dolomite, and 4 parts mica powder; wherein the modified unsaturated polyester resin is prepared by reacting maleic anhydride, diethylene glycol, phosphoric acid, palmitole monoglyceride, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone, conjugated trienepyridine, and styrene.

2. The waterproof anchoring agent for water-bearing soft rock according to claim 1, characterized in that, The polyether polyol is prepared by ring-opening polymerization of propylene oxide with the introduction of bisphenol A.

3. The waterproof anchoring agent for water-bearing soft rock according to claim 1, characterized in that, The accelerator is DMA; the coupling agent is a silane coupling agent.

4. A method for preparing a waterproof anchoring agent for water-bearing soft rock, characterized in that, Includes the following steps: S1. Palmitoleic acid monoglyceride was prepared using palmitoleic acid, isopropylidene glycerol, sulfonic acid resin, toluene and hydrochloric acid; conjugated trienepyridine was prepared using α-enoyl-α-aminocarbamoyl dithiocarbamate, dimethylformamide, diethyl malonate and potassium carbonate. S2. Modified unsaturated polyester resin is prepared using palmitoleic acid monoglyceride and conjugated triene pyridine prepared in step S1, as well as maleic anhydride, diethylene glycol, phosphoric acid, dicyclopentadiene, phthalic anhydride, 1,2-propanediol, hydroquinone, and styrene; polyether polyol is obtained by ring-opening polymerization of bisphenol A in propylene oxide. S3. According to the mass fraction, take 13-15 parts of the modified unsaturated polyester resin prepared in step S2, mix it with 72-74 parts of calcium carbonate, 4 parts of dolomite and 4 parts of mica powder, and stir at a speed of 1200-1500 rpm for 30-50 min to obtain resin putty. Then add 0.02 parts of accelerator and 0.04 parts of coupling agent, place it in an anchoring agent mixer, and stir at a speed of 1200-1500 rpm for 30-50 min to obtain component A. According to the mass fraction, take 44 parts of benzoyl peroxide, 16 parts of chlorobenzene, 0.6-0.8 parts of biphenyl and 38-39 parts of polyether polyol, mix them, and stir evenly to obtain component B. S4. According to the mass fraction, take 100 parts of component A prepared in step S3 and 4-7 parts of component B prepared in step S3, mix them, stir evenly, and then package them to obtain a waterproof anchoring agent for water-bearing soft rock.

5. The method for preparing the waterproof anchoring agent for water-bearing soft rock according to claim 4, characterized in that, In step S1, the preparation process of palmitoleic acid monoglyceride is as follows: under a nitrogen atmosphere, palmitoleic acid, isopropylidene glycerol, sulfonic acid resin and toluene are mixed in a mass ratio of 10:4~6:0.2~0.8:30, heated to 120~130℃, reacted for 2~4 hours, cooled to room temperature, and an equal volume of 0.8~1mol / L hydrochloric acid was added. After stirring evenly, the mixture was allowed to stand and separate into layers. Then, it was washed with deionized water 3~5 times and vacuum dehydrated to obtain palmitoleic acid monoglyceride. In step S1, the preparation process of conjugated triene pyridine is as follows: α-enoyl-α-aminoformyl dithiocarbamate, dimethylformamide and diethyl malonate are mixed in a mass ratio of 6~8:5:3, stirred at a rate of 100~200 rpm for 4~6 h, heated to 78~82℃, and then potassium carbonate of 0.05~0.07 times the mass of the diethyl malonate is added. After stirring evenly, the mixture is transferred to a saturated sodium chloride solution, stirred evenly and extracted with diethyl ether. After washing with water, drying and separation by column chromatography, conjugated triene pyridine is obtained.

6. The method for preparing the waterproof anchoring agent for water-bearing soft rock according to claim 5, characterized in that, The isopropylidene glycerol is prepared by the following method: glycerol, acetone and sulfonic acid resin are mixed in a mass ratio of 1~3:20:0.15, heated to 50~60℃, reacted for 1~2 hours, filtered while hot and then distilled under reduced pressure to obtain isopropylidene glycerol.

7. The method for preparing the waterproof anchoring agent for water-bearing soft rock according to claim 4, characterized in that, In step S2, the preparation process of the modified unsaturated polyester resin is as follows: Palmitoleic acid monoglyceride prepared in step S1, maleic anhydride, diethylene glycol, phosphoric acid, and deionized water are mixed in a mass ratio of 4-6:40:12:0.3:5-6. After stirring evenly, the mixture is heated to 125-135℃ under a nitrogen atmosphere. Dicyclopentadiene, at a rate of 3-5 mL / min, is added dropwise at a ratio of 1.1-1.3 times the mass of the maleic anhydride. The reaction is maintained at this temperature for 2-4 hours. Then, phthalic anhydride at a ratio of 0.7-0.8 times the mass of the maleic anhydride, diethylene glycol at a ratio of 0.15-0.25 times the mass of the maleic anhydride, and dicyclopentadiene at a ratio of 0.55-0.65 times the mass of the maleic anhydride are added. 2-Propanediol and hydroquinone (0.01-0.02 times the mass of maleic succinic anhydride) were heated to 195-205°C and reacted for 30-50 minutes. Then, the temperature was lowered to 160-180°C, and hydroquinone (0.01-0.02 times the mass of maleic succinic anhydride), palmitole monoglyceride (0.1-0.2 times the mass of maleic succinic anhydride), and conjugated trienepyridine (0.1-0.2 times the mass of maleic succinic anhydride) prepared in step S1 were added. After reacting for 2-4 hours, the temperature was lowered to 90-100°C, and styrene (1.2-1.4 times the mass of maleic succinic anhydride) was added. After stirring evenly, the mixture was cooled to room temperature to obtain the modified unsaturated polyester resin.

8. The method for preparing the waterproof anchoring agent for water-bearing soft rock according to claim 4, characterized in that, In step S2, the polyether polyol is prepared as follows: Under a nitrogen atmosphere, bisphenol A and the catalyst bimetallic cyanide complex are mixed at a mass ratio of 13~15:0.2, heated to 130~140℃, and reacted for 1~2 hours. Then, 0.3~0.5 times the mass of bisphenol A of propylene oxide is added and the pressure is increased to 0.10~0.15 MPa. After reacting for 4~6 hours, another 0.3~0.5 times the mass of bisphenol A of propylene oxide is added, and the reaction continues for 1~2 hours. The mixture is then evacuated and cooled to 85~95℃. Finally, 0.03~0.05 times the mass of bisphenol A of polyether antioxidant is added and stirred until homogeneous to obtain the polyether polyol.

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