CN116904012A - Polymer touch type anchoring agent for grouting anchor rod - Google Patents
Polymer touch type anchoring agent for grouting anchor rod Download PDFInfo
- Publication number
- CN116904012A CN116904012A CN202310857459.2A CN202310857459A CN116904012A CN 116904012 A CN116904012 A CN 116904012A CN 202310857459 A CN202310857459 A CN 202310857459A CN 116904012 A CN116904012 A CN 116904012A
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- China
- Prior art keywords
- anchoring agent
- component
- parts
- grouting
- thixotropic
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- 238000004873 anchoring Methods 0.000 title claims abstract description 67
- 229920000642 polymer Polymers 0.000 title claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 16
- 239000004111 Potassium silicate Substances 0.000 claims abstract description 15
- 229910052913 potassium silicate Inorganic materials 0.000 claims abstract description 15
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 12
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- HAVACXTVLQTJNR-UHFFFAOYSA-N CCCC[Se]=O Chemical compound CCCC[Se]=O HAVACXTVLQTJNR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940096992 potassium oleate Drugs 0.000 claims abstract description 6
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 229920002521 macromolecule Polymers 0.000 claims description 9
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims description 7
- 108010064470 polyaspartate Proteins 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- -1 polymethylene Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010276 construction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
- E21D20/00—Setting anchoring-bolts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention belongs to the technical field of anchoring agents, and relates to a macromolecular thixotropic anchoring agent for grouting an anchor rod. The anchoring agent comprises a component A and a component B, wherein the component A comprises water glass consisting of sodium silicate solution and potassium silicate solution and a catalyst consisting of potassium oleate and monobutyl selenium oxide; the component B comprises isocyanate substances, amino-terminated resin, thixotropic agent and a solvent. The macromolecular thixotropic anchoring agent prepared by the method has low viscosity, good fluidity and good thixotropic property; the method has the advantages of quick setting time, high temperature sensitivity, quick early strength development, high compressive strength of the finally formed concretion, good toughness, capability of meeting most engineering demands, simple preparation method, easy operation, environmental protection and no pollution, and solves the problems of low thixotropy, slow setting time and easy flowing of the polyurethane-water glass anchoring agent after the anchoring agent is injected into the top surface in the prior art.
Description
Technical Field
The invention belongs to the technical field of anchoring agents, and particularly relates to a polymer thixotropic anchoring agent for grouting an anchor rod.
Background
At present, in the tunnel (hole) construction process, a new Olympic method is mainly adopted for construction, wherein the spray anchor support which is most widely applied is one of key technologies. The construction of the anchor rod of the anchor spray support is an important link, and the construction is rapid and convenient, the process is mature, the performance is stable and is favored by construction units, and the anchor rod construction is not separated from the use of an anchoring agent.
The traditional cement mortar anchoring agent has slow increase of anchoring strength, and is easy to shrink, so that the later anchoring force is reduced. The polyurethane-water glass anchoring material is used as a novel polymer anchoring agent, has the advantages of safe application, high reliability, excellent mechanical property, low cost, simple components and the like, and has been widely applied to the field of underground engineering in recent years. However, a great amount of engineering practices show that the existing polyurethane-water glass anchoring agent has low thixotropy and slow setting time, and the anchoring agent is easy to flow after being injected into the top surface, so that the engineering technical problem can not be solved in certain specific environments, and certain cement mortar anchoring agent or chemical anchoring agent can not be replaced. Therefore, how to develop an anchoring agent with high thixotropy and fast setting time is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polymer thixotropic anchoring agent for grouting an anchor rod. The problems of low thixotropy and slow setting time of the polyurethane-water glass anchoring agent and easy flowing of the anchoring agent after being injected into the top surface in the prior art are solved.
In order to achieve the above purpose, the invention provides a macromolecule touch type anchoring agent for grouting an anchor rod, which comprises a component A and a component B;
the component A comprises the following components in parts by mass: 90-130 parts of water glass and 4-12 parts of catalyst;
the component B comprises the following components in parts by mass: 90-130 parts of isocyanate substances, 16-32 parts of amino-terminated resins, 8-10 parts of thixotropic agents and 8-10 parts of solvent promoters.
Further, the water glass is a mixture of sodium silicate solution and potassium silicate solution, and the mixing volume ratio is 4:1.
Preferably, the modulus of the sodium silicate solution is 2.1-2.8, and the Baume degree is 43-50 De; the modulus of the potassium silicate solution is 3.7-4.0, and the Baume degree is 35-40 Bes.
Modulus and baume are important properties of sodium silicate solution and potassium silicate solution, the larger the modulus is, the larger the Si content is, the larger the binding force is, but the more difficult the binding force is to be dissolved in water, so that a proper modulus range is selected; baume represents the concentration of a solution, the greater the concentration, the more sodium silicate and silicate are present.
The beneficial effects of the above-mentioned preferred scheme are: the sodium silicate and potassium silicate selected by the invention have modulus and baume degree ranges, so that the final reinforcing material has good solubility and cohesive force.
Further, the catalyst is a mixture of potassium oleate and monobutyl selenium oxide, and the mixing mass ratio is 2:1.
The catalyst selected by the invention is used for promoting the combination of water glass and polyurethane, and can accelerate the reaction of amino-terminated resin and isocyanate groups.
Further, the isocyanate substance is one or more of isophorone diisocyanate, polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate and toluene diisocyanate.
Further, the amino-terminated resin is one or more of polyether glycol resin, polyether triol resin and polyaspartic acid ester.
Further, the thixotropic agent is one or more of fumed silica, precipitated silica, surface modified calcium carbonate and xanthan gum.
The isocyanate (-NCO) group has a highly unsaturated structure, and the amino group in the terminal amino resin structure is in steric hindrance surrounding of a steric crown structure, and the ester part in the structure has induction effect to cause reaction with isocyanate (-NCO) component, and can react with water to generate carbamic acid, and rapidly decompose into CO 2 And amine, make the concretion body obtained finally have higher compressive strength and better toughness, the catalyst that the invention chooses can accelerate the reaction of amine-terminated resin and isocyanato.
Further, the cosolvent is one or more of castor oil formate, ethylene glycol diacetate, tributyl citrate and dioctyl phthalate.
On the other hand, the invention also provides a preparation method of the macromolecule thixotropic anchoring agent for grouting the anchor rod, which comprises the following steps:
s1, adding a catalyst into water glass, and stirring for 30-60 min to obtain a component A;
s2, adding amino-terminated resin, thixotropic agent and cosolvent into isocyanate substances, and stirring for 30-60 min to obtain the component B.
Further, the stirring speed in the step S1 is 120-150 rpm.
Further, the stirring speed in the step S2 is 50-110 rpm.
On the other hand, the invention also provides application of the polymer thixotropic anchoring agent for grouting the anchor rod in grouting reinforcement.
Furthermore, the application method is to mix and inject the component A and the component B according to the volume ratio of 1:1 for anchoring.
Compared with the prior art, the technical scheme has the following beneficial effects:
the polymer touch type anchoring agent provided by the invention has good thixotropic property, quick setting time, low viscosity and good fluidity, can effectively enhance the connection between an anchor rod and surrounding rock, and improves the strength of an anchoring body. The anchoring body has higher compressive strength and good toughness, and can meet the requirements of most engineering. The polymer trigger type anchoring agent provided by the invention has low reaction temperature, can react at the temperature of 0 ℃ or below, and has no high-temperature potential safety hazard; meanwhile, the material does not contain organic flame retardant components, belongs to a novel environment-friendly material, has no influence on the environment after being injected into a stratum, and completely meets the environment-friendly requirement. The polymer touch type anchoring agent provided by the invention has stable performance, good injectability and wide application range, and can be used for rock-soil anchoring in the fields of coal bed geology, water conservancy and hydropower, underground engineering, subway tunnels and the like. Meanwhile, the preparation method of the polymer touch type anchoring agent provided by the invention is simple and easy to operate, and the used polyurea raw material does not need to be prepolymerized, so that the cost and the energy consumption are reduced.
The formula raw materials of the macromolecule touch type anchoring agent provided by the invention do not use modified MDI, the material performance is relatively stable, and the influence by a compounding factor is small. The solidifying strength of the material can reach more than 40MPa, the compressive strength of the anchoring body is higher, the toughness is good, most engineering requirements can be met, and the material is very suitable for stratum geological anchoring with higher requirements.
The high-molecular thixotropic anchoring agent provided by the invention has the advantages of quick setting time and high temperature sensitivity, and can be used for adjusting the temperature according to actual engineering requirements to obtain the quick, medium and slow thixotropic anchoring agents with different setting times. The initial setting can be reached about 10s at the highest speed.
The polymer touch type anchoring agent provided by the invention can improve the strength of a consolidated body, ensure that the strength of the consolidated body is more than 30MPa, is convenient to adjust the reaction speed by adding the catalyst, and can control the curing time of a material to be even about 2 minutes.
The polymer touch type anchoring agent A, B provided by the invention does not react with water in the mixing reaction process, can be coagulated and formed underwater, has small influence on strength, and can strengthen rock mass in a water environment. The modified silicate anchoring agent A, B provided by the invention has the advantages of low reaction temperature and no high-temperature potential safety hazard in the mixing reaction process, and is particularly suitable for reinforcing treatment of high-temperature high-gas coal mines.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The sodium silicate solution and the potassium silicate solution are mixed according to the volume ratio of 4:1, the modulus of the sodium silicate solution is 2.5, the Baume degree is 46 Bese, the modulus of the potassium silicate solution is 3.7, and the Baume degree is 36 Bese; the catalyst is prepared by mixing potassium oleate and monobutyl selenium oxide in a mass ratio of 2:1; the isocyanate substance is toluene diisocyanate; the amino-terminated resin is polyaspartic acid ester; the thixotropic agent is fumed silica; the used cosolvent is tributyl citrate.
It is worth noting that the isocyanate group (-NCO) of the isocyanate substance defined by the invention has a highly unsaturated structure, the amino group in the amino-terminated resin structure is in steric hindrance surrounding of a steric crown structure, the part of the ester in the structure plays a role of inducing to react with isocyanate (-NCO) component, and can also react with water to generate carbamic acid and be rapidly decomposed into CO 2 An amine; the thixotropic agent can accelerate the reaction; the selected cosolvent is used for achieving the solubilization effect by destroying non-covalent bonds such as hydrogen bonds, salt bridges, hydrophobic effects and the like in the biological macromolecular structure. Therefore, in the embodiments of the present invention, the isocyanate-based material, the amino-terminated resin, the thixotropic agent, and the solvent are selected from the different raw material types defined by the present invention, and the properties of the final product are not or only little affected.
In the specific implementation process, the inventor finds that the sodium silicate solution and the potassium silicate solution are selected, and the performance of the final product is not greatly changed when any one of the modulus and the baume degree in the limit is selected, so that the specific modulus and the baume degree in the embodiment can be equally replaced by the numerical value in the limit range of the invention, and the performance of the final product is not influenced or is little influenced.
Example 1
The macromolecule touch type anchoring agent for grouting the anchor rod comprises the following components in parts by mass:
a component: 100 parts of water glass and 5 parts of catalyst;
and the component B comprises the following components: 100 parts of toluene diisocyanate, 15 parts of polyaspartic acid ester, 10 parts of fumed silica and 10 parts of tributyl citrate.
Preparation of a macromolecule trigger type anchoring agent for grouting an anchor rod:
s1, a component A: sequentially adding 100 parts by weight of water glass and 5 parts by weight of catalyst into a stirrer, and stirring at a rotating speed of 130r/min for 30 minutes to obtain solution A;
s2, a component B: 100 parts of toluene diisocyanate, 15 parts of polyaspartic acid ester, 10 parts of fumed silica and 10 parts of tributyl citrate are sequentially added into a stirrer, and stirred for 20 minutes at a rotating speed of 110r/min to obtain liquid B.
Example 2
The macromolecule touch type anchoring agent for grouting the anchor rod comprises the following components in parts by mass:
a component: 110 parts of water glass and 10 parts of catalyst;
and the component B comprises the following components: 110 parts of toluene diisocyanate, 25 parts of polyaspartic acid ester, 10 parts of fumed silica and 10 parts of tributyl citrate.
Preparation of a macromolecule trigger type anchoring agent for grouting an anchor rod:
s1, a component A: sequentially adding 110 parts by weight of water glass and 10 parts by weight of catalyst into a stirrer, and stirring at a rotating speed of 150r/min for 25 minutes to obtain a solution A;
s2, a component B: 110 parts of toluene diisocyanate, 25 parts of polyaspartic acid ester, 10 parts of fumed silica and 10 parts of tributyl citrate are sequentially added into a stirrer, and stirred at a rotating speed of 120r/min for 20 minutes to obtain liquid B.
Comparative example 1
Preparation of the anchoring agent:
the difference compared to example 1 is that only the thixotropic agent is not added to the B component, otherwise the same as in example 1.
Comparative example 2
Preparation of the anchoring agent:
the only difference compared to example 1 is that the catalyst is monobutyl selenium oxide, otherwise identical to example 1.
Comparative example 3
Preparation of the anchoring agent:
the only difference compared to example 1 is that the catalyst is potassium oleate, otherwise the same as example 1.
Comparative example 4
The only difference compared with example 1 is that the mass ratio of potassium oleate and monobutyl selenium oxide in the catalyst is 1:1, the other is the same as in example 1.
Comparative example 5
The difference compared to example 1 is that only sodium silicate solution is used for water glass, and the other is the same as example 1.
Comparative example 6
The difference compared to example 1 is that only potassium silicate solution is used for water glass, and the other is the same as example 1.
Comparative example 7
Compared with example 1, the difference is that the compounding ratio of the sodium silicate solution and the potassium silicate solution in the water glass is 1:1, the other is the same as in example 1.
Comparative example 8
The difference compared to example 1 is that the sodium silicate solution in the water glass has a modulus of 3.5, a Baume of 55 Bese, and a potassium silicate solution has a modulus of 4.5, a Baume of 45 Bese, otherwise the same as in example 1.
Comparative example 9
Conventional cement slurries are used as anchoring agents.
Test examples
The anchoring tests, test methods and standards were carried out with respect to the anchoring agents prepared in examples 1 to 2 and comparative examples 1 to 9, respectively, with reference to the "petrophysical mechanical property test procedure".
The anchoring agents prepared in examples 1 to 2 and comparative examples 1 to 9 were anchored by injecting A, B liquid into crushed rock at a volume ratio of 1:1 using a two-liquid grouting pump.
The performance indexes of examples 1-2 and comparative examples 1-9 are shown in Table 1.
TABLE 1
From the data of example 1 compared to the data of comparative example 1, it can be seen that the thixotropic agent has a significant improvement in the properties of the anchoring agent; compared with the data of the embodiment 1, the catalyst proportion selected by the invention can effectively improve the initial setting time, the curing time and the strength of the consolidated body of the anchoring agent; compared with the data of the comparative example 7 and the data of the comparative example 8 and the data of the example 1, it can be seen that the proportion of the water glass selected by the invention, the modulus and the baume degree of the water glass can effectively improve the performance of the anchoring agent; while the data of comparative examples 2 and 3 compared with the data of comparative example 4 and example 1, it can be seen that the composite catalyst has better performance improvement for the anchoring agent than the single catalyst; by comparing the data of comparative examples 5 and 6 with the data of examples 1 and 7, it can be seen that the compounding of sodium silicate and potassium silicate improves the performance of the anchoring agent over sodium silicate or potassium silicate alone.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The macromolecule touch type anchoring agent for grouting the anchor rod is characterized by comprising a component A and a component B;
the component A comprises the following components in parts by mass: 90-130 parts of water glass and 4-12 parts of catalyst;
the component B comprises the following components in parts by mass: 90-130 parts of isocyanate substances, 16-32 parts of amino-terminated resins, 8-10 parts of thixotropic agents and 8-10 parts of solvent promoters.
2. The polymer trigger type anchoring agent for grouting bolts according to claim 1, wherein the water glass is a mixture of sodium silicate solution and potassium silicate solution, and the mixing volume ratio is 4:1.
3. The polymer trigger type anchoring agent for grouting bolts according to claim 2, wherein the sodium silicate solution has a modulus of 2.1-2.8 and a baume degree of 43-50 °be; the modulus of the potassium silicate solution is 3.7-4.0, and the Baume degree is 35-40 Bes.
4. The macromolecule touch type anchoring agent for grouting anchors according to claim 1, wherein the catalyst is a mixture of potassium oleate and monobutyl selenium oxide, and the mixing mass ratio is 2:1.
5. The polymer touch type anchoring agent for grouting bolts according to claim 1, wherein the isocyanate substance is one or more of isophorone diisocyanate, polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, toluene diisocyanate; the amino-terminated resin is one or more of polyether glycol resin, polyether triol resin and polyaspartic acid ester; the thixotropic agent is one or more of fumed silica, precipitated silica, surface modified calcium carbonate and xanthan gum.
6. The polymer trigger type anchoring agent for grouting bolts according to claim 1, wherein the cosolvent is one or more of castor oil formate, ethylene glycol diacetate, tributyl citrate and dioctyl phthalate.
7. A method of preparing a polymeric thixotropic anchoring agent for a grouting bolt as defined in any one of claims 1 to 6, comprising the steps of:
s1, adding a catalyst into water glass, and stirring for 30-60 min to obtain a component A;
s2, adding amino-terminated resin, thixotropic agent and cosolvent into isocyanate substances, and stirring for 30-60 min to obtain the component B.
8. The method according to claim 7, wherein the stirring in step S1 is performed at a rotational speed of 120 to 150rpm; the stirring speed in the step S2 is 50-110 rpm.
9. Use of a polymeric thixotropic anchoring agent for grouting bolts according to any one of claims 1 to 6 for grouting reinforcement.
10. The use according to claim 9, characterized in that it is anchored by mixing and injecting the a and B components in a volume ratio of 1:1.
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