CN116875142A - Mining composite thin spraying material and preparation method thereof - Google Patents
Mining composite thin spraying material and preparation method thereof Download PDFInfo
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- CN116875142A CN116875142A CN202310722910.XA CN202310722910A CN116875142A CN 116875142 A CN116875142 A CN 116875142A CN 202310722910 A CN202310722910 A CN 202310722910A CN 116875142 A CN116875142 A CN 116875142A
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000005065 mining Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000005507 spraying Methods 0.000 title claims description 14
- 238000002156 mixing Methods 0.000 claims abstract description 60
- 239000007921 spray Substances 0.000 claims abstract description 54
- 239000004816 latex Substances 0.000 claims abstract description 50
- 229920000126 latex Polymers 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004568 cement Substances 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- 239000010881 fly ash Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims abstract description 25
- -1 retarder Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000013530 defoamer Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 62
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 42
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 42
- 229910000831 Steel Inorganic materials 0.000 claims description 28
- 239000010959 steel Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- CCESTPXUODXQEN-UHFFFAOYSA-N 1-[diethyl(propyl)silyl]ethanamine Chemical compound NC(C)[Si](CC)(CC)CCC CCESTPXUODXQEN-UHFFFAOYSA-N 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 19
- 229920001155 polypropylene Polymers 0.000 claims description 19
- 239000003995 emulsifying agent Substances 0.000 claims description 18
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- 239000002480 mineral oil Substances 0.000 claims description 14
- 235000010446 mineral oil Nutrition 0.000 claims description 14
- 239000011118 polyvinyl acetate Substances 0.000 claims description 14
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 14
- WPJGWJITSIEFRP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrate Chemical group O.NC1=NC(N)=NC(N)=N1 WPJGWJITSIEFRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims description 10
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 9
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 125000005394 methallyl group Chemical group 0.000 claims description 9
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 9
- 238000010556 emulsion polymerization method Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229920005646 polycarboxylate Polymers 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 239000011398 Portland cement Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000008204 material by function Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003245 coal Substances 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011435 rock Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003469 silicate cement Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
- C08F263/04—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids on to polymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
- C09D1/08—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement with organic additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- 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)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application discloses a mining composite thin spray material and a preparation method thereof, wherein the mining composite thin spray material is prepared by mixing a component A and a component B according to a mass ratio of 1-3:1; the component A comprises the following raw materials in parts by weight: 40-55 parts of polymer emulsion, 0.05-0.5 part of dispersing agent, 0.01-0.1 part of defoamer and 3-5 parts of water; the component B comprises the following raw materials in parts by weight: 30-40 parts of white cement, 8-10 parts of slag, 10-15 parts of fly ash, 0.1-0.5 part of water reducer, 0.05-0.2 part of retarder, 5-8 parts of reinforcing fiber and 3-6 parts of functional material. The application takes the modified VAE latex as polymer emulsion, takes white cement, slag, fly ash, retarder, reinforcing fiber, functional material and other materials as powder, and the mining composite thin spray material prepared by mixing has higher compressive strength and flexural strength, and simultaneously has high bonding strength, thus being capable of forming good bonding with coal mine tunnels.
Description
Technical Field
The application belongs to the field of mine reinforcement, and particularly relates to a mining composite thin spraying material and a preparation method thereof.
Background
Along with the rapid development of economy, the demand for energy is increasingly increased, the number of coal mine wells is increased year by year, the mining of coal mine is gradually developed from shallow mining to deep mining, soft surrounding rock which is easy to weather and deliquesce is frequently encountered, so that the integrity of rock stratum is damaged, the strength is lost to be a dispersion, the local collapse of a roadway is caused, and the safety of mine production is seriously endangered, so that soft rock protection becomes one of the main problems of coal mine safety mining. A Thin Spraying Lining (TSL) is a technology for surface protection by spraying a film, and the principle is that spraying powder and emulsion are sprayed out after being uniformly stirred by special pneumatic spraying equipment, so that a high-toughness, large-deformation and airtight non-reactive film is formed on the surface of a roadway and is tightly attached to the surfaces of a coal rock body and a supporting structure of the roadway, thereby isolating moist air and moisture in the roadway and preventing gas of the coal rock body from escaping. The novel thin spraying technology can rapidly seal the roadway, prevent surrounding rock from weathering and support structure from oxidation, prevent gas of coal rock mass from escaping, prolong the roadway service life and ensure mine safety production.
The existing thin spray materials are divided into a reactive type and a non-reactive type according to the film forming mechanism. The reactive material is mainly polyurethane/polyurea material, has high film forming speed and high strength, but needs to be heated in the spraying process, has extremely high equipment requirement, and is difficult to meet the underground explosion-proof safety requirement. On the other hand, the isocyanate component of such materials may react with water and is not suitable for use in high humidity downhole operations. The non-reactive material is prepared by taking a cement-based material as a main material, adding a small amount of high-molecular polymer as a binder, and has low cost, but a large amount of pores still exist in the material, the adhesive force is low, the brittleness is large (the elongation at break is less than 5%), the shrinkage and cracking are easy, the surface is dull and rough after spraying, and the standard construction of a roadway still needs to be achieved through a brightening process in subsequent engineering. Therefore, a mining composite thin-spray material which has high curing speed, good bonding performance and high compression resistance after molding and is not suitable for shrinkage cracking is needed to meet the requirement of mine tunnel reinforcement.
Disclosure of Invention
In order to solve the defects in the background art, the application aims to provide the mining composite thin spray material and the preparation method thereof, wherein modified VAE latex is used as polymer emulsion, white cement, slag, fly ash, retarder, reinforcing fiber, functional material and other materials are used as powder materials, and the mining composite thin spray material prepared by mixing has higher compressive strength and flexural strength, and meanwhile, the bonding strength is high, so that good bonding can be formed with coal mine tunnels.
The aim of the application can be achieved by the following technical scheme:
a mining composite thin spraying material is prepared by mixing a component A and a component B according to a mass ratio of 1-3:1; the component A comprises the following raw materials in parts by weight: 40-55 parts of polymer emulsion, 0.05-0.5 part of dispersing agent, 0.01-0.1 part of defoamer and 3-5 parts of water; the component B comprises the following raw materials in parts by weight: 30-40 parts of white cement, 8-10 parts of slag, 10-15 parts of fly ash, 0.1-0.5 part of water reducer, 0.05-0.2 part of retarder, 5-8 parts of reinforcing fiber and 3-6 parts of functional material;
the polymer emulsion is modified VAE latex, and the modified VAE emulsion is high-solid-content composite latex prepared by emulsion polymerization of VAE emulsion and polyvinyl acetate;
the retarder is a zwitterionic retarder prepared by taking 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, acryloyloxyethyl trimethyl ammonium chloride and methallyl polyoxyethylene ether as monomers through aqueous solution free radical polymerization;
the functional material is composed of sodium silicate and CaSO 4 Whisker, aminopropyl triethylsilane and polyvinyl alcohol according to the mass ratio of 1:0.5:1:3 mixing.
Further preferably, the white cement is one of white Portland cement, white sulphoaluminate cement or white aluminate cement.
Further preferably, the slag is iron ore tailings with continuous grading of 0.3-4.75 mm particle size, the activity index of the fly ash 28d is more than or equal to 105%, the particle size is less than or equal to 2 mu m, and the specific surface area is 12000-15000 m 2 /kg。
Further preferably, the reinforcing fibers are polyvinyl alcohol fibers, polypropylene fibers and steel fibers according to the mass ratio of 6-8: 1:1, mixing; the length of the polyvinyl alcohol fiber is 4-8 mm, and the diameter is 0.03-0.05 mm; the length of the polypropylene fiber is 4-8 mm, and the diameter is 0.02-0.04 mm; the steel fibers are end hook type copper plating steel fibers, the length is 10-14 mm, and the diameter is 0.18-0.2 mm.
Further preferably, the dispersing agent is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate, the defoaming agent is mineral oil or organic silicon defoaming agent, and the water reducing agent is sulfonated melamine water reducing agent or polycarboxylate water reducing agent.
Further preferably, the preparation method of the mining composite thin spray material comprises the following steps:
s1, preparing modified VAE latex by an emulsion polymerization method, and mixing the modified VAE latex, a dispersing agent and a defoaming agent in proportion by stirring to obtain a component A;
s2, preparing a retarder through free radical polymerization of aqueous solution, and mixing the retarder with white cement, slag, fly ash, a water reducing agent, reinforcing fibers and functional materials in proportion to obtain a component B;
s3, the component A and the component B are mixed according to the mass ratio of 1-3: 1, mixing and stirring to obtain the mining composite thin spray material slurry.
Further preferably, the modified VAE latex comprises the following raw materials in parts by weight: 15-30 parts of VAE emulsion, 20-40 parts of polyvinyl acetate, 0.5-2 parts of composite emulsifier, 0.2-1 part of initiator and 3-5 parts of water, and the preparation method of the modified VAE emulsion comprises the following steps:
(1) Mixing and stirring the composite emulsifier and water, heating to 50-60 ℃, adding the VAE emulsion and the initiator into the composite emulsifier solution, and stirring and heating to 70-80 ℃;
(2) A micropump is used for controlling the dropping speed to drop the polyvinyl acetate monomer, and the reaction is continued for 1-2 hours after the monomer is added dropwise;
(3) And (3) raising the temperature of the system to 80-90 ℃ ‚, preserving heat for 1-3 hours, and cooling to obtain the modified VAE latex.
Further preferably, the composite emulsifier is prepared from OP emulsifier, sodium dodecyl sulfate and polyvinyl alcohol according to a mass ratio of 1:2: 1.
Further preferably, the preparation method of the retarder comprises the following steps:
A. 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, acryloyloxyethyl trimethyl ammonium chloride and methallyl polyoxyethylene ether are dissolved in a reactor in proportion, and the pH value of the system is regulated to 7-10 by sodium hydroxide solution under the cooling condition;
B. introducing nitrogen for 20-30 min, adding an initiator at the water bath temperature of 55-65 ℃, and continuing to perform heat preservation reaction for 3-5 h;
C. and precipitating the polymer obtained by the reaction by using anhydrous hexanol, washing the polymer for a plurality of times by using acetone, and then drying the polymer in a vacuum oven at a low temperature for 12-24 hours to obtain the retarder.
Further preferably, the molar ratio of the 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, acryloyloxyethyl trimethyl ammonium chloride and methallyl polyoxyethylene ether is 10:4:2:0.01.
the application has the beneficial effects that:
the mining composite thin spray material takes the modified VAE latex as polymer emulsion, takes white cement, slag, fly ash, retarder, reinforcing fiber, functional material and other materials as powder, has higher compressive strength and flexural strength, has high bonding strength, and can form good bonding with coal mine tunnels.
The modified VAE latex is prepared by emulsion polymerization of VAE emulsion and polyvinyl acetate, and the polyvinyl acetate colloidal particles with wide particle size distribution in the emulsion can fill gaps ‚ among the colloidal particles with large particle size, so that the particles are close to the aim of preparing the emulsion with multi-particle size distribution and high solid content. And then ‚ polyvinyl acetate small particles enter a hydration layer of the VAE particles, ‚ increases the particle size of the VAE, increases the content of large particles, and contributes to the reduction of the viscosity of the system, so that the mining composite thin-spray material is conveniently mixed with the component B.
The mixing of the polyvinyl alcohol fiber, the polypropylene fiber and the steel fiber can effectively play a bridging role in the mining composite thin spray material, and when the mining composite thin spray material is subjected to bending load, and cracks appear and start to expand, the bridging role of the fibers transmits crack expansion force to surrounding non-cracking areas, so that the further expansion of the cracks is delayed, and the breaking strength of the mining composite thin spray material is further improved.
The friction adhesion force between the steel fiber and the matrix plays a role in debonding, so that the development of matrix cracks is effectively restrained, the polyvinyl alcohol fiber and the polypropylene fiber are distributed in the matrix in a filiform form, and the adhesion force between the matrix and the fibers is also enhanced by the cross-formed reticular structure.
The application can hydrolyze aminopropyl triethylsilane to generate silanol, and simultaneously spontaneously polycondense to form organic siloxane (containing-OH and-NH) 2 ) According to the properties of the composite thin spray material, an aminopropyl triethylsilane hydrolysate is introduced into a polyvinyl alcohol system, and the organosilicon-polyvinyl alcohol copolymer interpenetrating network hydrogel based on the aminopropyl triethylsilane hydrolysis still has excellent mechanical strength while maintaining high water content, on one hand, the water retention property of the polyvinyl alcohol is utilized, free water molecules in the association system are utilized, the viscosity of the whole composite thin spray material system for mines is enhanced, meanwhile, due to the existence of the aminopropyl triethylsilane, air is introduced in the stirring process of the composite thin spray material for mines, a certain amount of bubbles are formed, the flowing speed of the water molecules is reduced, so that the water retention is enhanced to a certain extent, the bubbles can also have a lubricating effect, the fluidity of the composite thin spray material for mines is enhanced, and the construction performance is improved.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the embodiment of the application, the white silicate cement, the white sulphoaluminate cement or the white aluminate cement are all commercial PW-1 325 or PW-1 425 white cement, the slag is iron ore tailing ore with the particle size of 0.3-4.75 mm and continuous grading, the activity index of the fly ash 28d is more than or equal to 105 percent, the particle size is less than or equal to 2 mu m, and the specific surface area is 12000-15000 m 2 The length of the polyvinyl alcohol fiber is 4-8 mm, and the diameter is 0.03-0.05 mm; the length of the polypropylene fiber is 4-8 mm, and the diameter is 0.02-0.04 mm; the steel fibers are end hook type copper plating steel fibers,the length is 10-14 mm, and the diameter is 0.18-0.2 mm.
Example 1: a mining composite thin spray material is prepared by mixing a component A and a component B according to a mass ratio of 3:1; the component A comprises the following raw materials in parts by weight: 40 parts of modified VAE latex, 0.5 part of sodium dodecyl benzene sulfonate, 0.01 part of organosilicon defoamer and 5 parts of water; the component B comprises the following raw materials in parts by weight: 30 parts of white silicate cement, 10 parts of slag, 10 parts of fly ash, 0.5 part of polycarboxylate water reducer, 0.05 part of retarder, 6.4 parts of polyvinyl alcohol fiber, 0.8 part of polypropylene fiber, 0.8 part of steel fiber, 0.6 part of sodium silicate and CaSO 4 Whisker 0.2 parts, aminopropyl triethylsilane 0.6 parts and polyvinyl alcohol 1.7 parts.
The preparation method of the mining composite thin spray material comprises the following steps:
s1, preparing modified VAE latex by an emulsion polymerization method, and mixing the modified VAE latex with sodium dodecyl benzene sulfonate, an organosilicon defoamer and water in proportion by stirring to obtain a component A;
s2, preparing a retarder through free radical polymerization of aqueous solution, and mixing the retarder with white silicate cement, slag, fly ash, polycarboxylate water reducer, polyvinyl alcohol fiber, polypropylene fiber, steel fiber, sodium silicate and CaSO 4 Mixing the whisker, the aminopropyl triethylsilane and the polyvinyl alcohol in proportion to obtain a component B;
s3, mixing the component A and the component B according to a mass ratio of 3:1, mixing and stirring to obtain the mining composite thin spray material slurry.
The modified VAE latex is modified VAE latex and comprises the following raw materials in parts by weight: 15 parts of VAE emulsion, 40 parts of polyvinyl acetate, 0.12 part of OP emulsifier, 0.25 part of sodium dodecyl sulfate, 0.12 part of polyvinyl alcohol, 1 part of initiator and 3 parts of water, and the preparation method of the modified VAE latex comprises the following steps:
(1) Mixing and stirring an OP emulsifier, sodium dodecyl sulfate, polyvinyl alcohol and water, heating to 60 ℃, adding a VAE emulsion and an initiator into a composite emulsifier solution, and heating to 70 ℃ with stirring;
(2) A micropump is used for controlling the dropping speed to drop the polyvinyl acetate monomer, and the reaction is continued for 2 hours after the monomer is added dropwise;
(3) The system temperature is raised to 80 ℃ ‚, and the modified VAE latex is obtained after heat preservation and cooling for 3 hours.
The preparation method of the retarder comprises the following steps:
A. 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, acryloxyethyl trimethyl ammonium chloride and methallyl polyoxyethylene ether are mixed according to the molar ratio of 10:4:2:0.01 is dissolved in a reactor, and the pH value of the system is regulated to 7 by sodium hydroxide solution under the cooling condition;
B. introducing nitrogen for 30min, adding an initiator at the water bath temperature of 55 ℃, and continuing to perform heat preservation reaction for 5h;
C. the polymer obtained by the reaction is precipitated by using anhydrous hexanol, washed by acetone for a plurality of times, and then dried for 12 hours in a vacuum oven at low temperature, thus obtaining the retarder.
Example 2: a mining composite thin spray material comprises a component A and a component B according to a mass ratio of 2:1, mixing; the component A comprises the following raw materials in parts by weight: 48 parts of modified VAE latex, 0.3 part of sodium dodecyl sulfate, 0.05 part of mineral oil and 4 parts of water; the component B comprises the following raw materials in parts by weight: 35 parts of white sulphoaluminate cement, 9 parts of slag, 12 parts of fly ash, 0.3 part of sulfonated melamine water reducer, 0.12 part of retarder, 4.5 parts of polyvinyl alcohol fiber, 0.7 part of polypropylene fiber, 0.8 part of steel fiber, 0.7 part of sodium silicate and CaSO 4 0.4 part of whisker, 0.7 part of aminopropyl triethylsilane and 2.2 parts of polyvinyl alcohol;
the preparation method of the mining composite thin spray material comprises the following steps:
s1, preparing modified VAE latex by an emulsion polymerization method, and mixing the modified VAE latex with sodium dodecyl sulfate, mineral oil and water in proportion by stirring to obtain a component A;
s2, preparing a retarder through free radical polymerization of an aqueous solution, and mixing the retarder with white sulphoaluminate cement, slag, fly ash, sulfonated melamine water reducer, polyvinyl alcohol fiber, polypropylene fiber, steel fiber, sodium silicate and CaSO 4 Mixing the whisker, the aminopropyl triethylsilane and the polyvinyl alcohol in proportion to obtain a component B;
s3, mixing the component A and the component B according to the mass ratio of 2:1, mixing and stirring to obtain the mining composite thin spray material slurry.
The modified VAE latex is modified VAE latex and comprises the following raw materials in parts by weight: 20 parts of VAE emulsion, 30 parts of polyvinyl acetate, 0.25 part of OP emulsifier, 0.5 part of sodium dodecyl sulfate, 0.25 part of polyvinyl alcohol, 0.6 part of initiator and 4 parts of water, and the preparation method of the modified VAE emulsion comprises the following steps:
(1) Mixing and stirring the composite emulsifier and water, heating to 55 ℃, adding the VAE emulsion and the initiator into the composite emulsifier solution, and stirring and heating to 75 ℃;
(2) A micropump is used for controlling the dropping speed to drop the polyvinyl acetate monomer, and the reaction is continued for 1-2 hours after the monomer is added dropwise;
(3) The system temperature is raised to 85 ℃ ‚, and the modified VAE latex is obtained after the system temperature is kept for 2 hours and cooled.
The preparation method of the retarder comprises the following steps:
A. 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, acryloxyethyl trimethyl ammonium chloride and methallyl polyoxyethylene ether are mixed according to the molar ratio of 10:4:2:0.01 is dissolved in a reactor, and the pH value of the system is regulated to 8 by sodium hydroxide solution under the cooling condition;
B. introducing nitrogen for 25min, adding an initiator at the water bath temperature of 60 ℃, and continuing to perform heat preservation reaction for 4h;
C. the polymer obtained by the reaction is precipitated by using anhydrous hexanol, washed by acetone for a plurality of times, and then dried for 18 hours in a vacuum oven at low temperature, thus obtaining the retarder.
Example 3: a mining composite thin spray material is prepared by mixing a component A and a component B according to a mass ratio of 1:1; the component A comprises the following raw materials in parts by weight: 55 parts of modified VAE latex, 0.05 part of sodium dodecyl benzene sulfonate, 0.1 part of mineral oil and 3 parts of water; the component B comprises the following raw materials in parts by weight: 40 parts of white aluminate cement, 8 parts of slag, 15 parts of fly ash, 0.1 part of polycarboxylate water reducer, 0.2 part of retarder, 3.8 parts of polyvinyl alcohol fiber, 0.6 part of polypropylene fiber, 0.6 part of steel fiber, 1.1 part of sodium silicate and CaSO 4 0.5 part of whisker, 1.1 part of aminopropyl triethylsilane and 3.4 parts of polyvinyl alcohol;
the preparation method of the mining composite thin spray material comprises the following steps:
s1, preparing modified VAE latex by an emulsion polymerization method, and mixing the modified VAE latex with sodium dodecyl benzene sulfonate, mineral oil and water in proportion to obtain a component A;
s2, preparing a retarder through free radical polymerization of aqueous solution, and mixing the retarder with white aluminate cement, slag, fly ash, polycarboxylate water reducer, polyvinyl alcohol fiber, polypropylene fiber, steel fiber, sodium silicate and CaSO 4 Mixing the whisker, the aminopropyl triethylsilane and the polyvinyl alcohol in proportion to obtain a component B;
s3, the component A and the component B are mixed according to the mass ratio of 1:1, mixing and stirring to obtain the mining composite thin spray material slurry.
The modified VAE latex is modified VAE latex and comprises the following raw materials in parts by weight: the preparation method of the modified VAE latex comprises the following steps of:
(1) Mixing and stirring the composite emulsifier and water, heating to 50 ℃, adding the VAE emulsion and the initiator into the composite emulsifier solution, and stirring and heating to 80 ℃;
(2) A micropump is used for controlling the dropping speed to drop the polyvinyl acetate monomer, and the reaction is continued for 1h after the monomer is added dropwise;
(3) The system temperature is raised to 90 ℃ ‚, and the modified VAE latex is obtained after heat preservation and cooling for 1 h.
The preparation method of the retarder comprises the following steps:
A. 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, acryloxyethyl trimethyl ammonium chloride and methallyl polyoxyethylene ether are mixed according to the molar ratio of 10:4:2:0.01 is dissolved in a reactor, and the pH value of the system is regulated to 10 by sodium hydroxide solution under the cooling condition;
B. introducing nitrogen for 20min, adding an initiator at the water bath temperature of 65 ℃, and continuing to perform heat preservation reaction for 3h;
C. the polymer obtained by the reaction is precipitated by using anhydrous hexanol, washed by acetone for a plurality of times, and then dried for 24 hours in a vacuum oven at low temperature, thus obtaining the retarder.
Comparative example 1
A mining composite thin spray material comprises a component A and a component B according to a mass ratio of 2:1, mixing; the component A comprises the following raw materials in parts by weight: 48 parts of VAE emulsion, 0.3 part of sodium dodecyl sulfate, 0.05 part of mineral oil and 4 parts of water; the component B comprises the following raw materials in parts by weight: 35 parts of white sulphoaluminate cement, 9 parts of slag, 12 parts of fly ash, 0.3 part of sulfonated melamine water reducer, 0.12 part of retarder, 4.5 parts of polyvinyl alcohol fiber, 0.7 part of polypropylene fiber, 0.8 part of steel fiber, 0.7 part of sodium silicate and CaSO 4 0.4 part of whisker, 0.7 part of aminopropyl triethylsilane and 2.2 parts of polyvinyl alcohol;
the preparation method of the mining composite thin spray material comprises the following steps:
s1, mixing the VAE emulsion, sodium dodecyl sulfate, mineral oil and water in proportion by stirring to obtain a component A;
s2, preparing a retarder through free radical polymerization of an aqueous solution, and mixing the retarder with white sulphoaluminate cement, slag, fly ash, sulfonated melamine water reducer, polyvinyl alcohol fiber, polypropylene fiber, steel fiber, sodium silicate and CaSO 4 Mixing the whisker, the aminopropyl triethylsilane and the polyvinyl alcohol in proportion to obtain a component B;
s3, mixing the component A and the component B according to the mass ratio of 2:1, mixing and stirring to obtain the mining composite thin spray material slurry.
The retarder was prepared in the same manner as in example 2.
Comparative example 2
A mining composite thin spray material comprises a component A and a component B according to a mass ratio of 2:1, mixing; the component A comprises the following raw materials in parts by weight: 48 parts of modified VAE latex, 0.3 part of sodium dodecyl sulfate, 0.05 part of mineral oil and 4 parts of water; the component B comprises the following raw materials in parts by weight: 35 parts of white sulphoaluminate cement, 9 parts of slag, 12 parts of fly ash, 0.3 part of sulfonated melamine water reducer, 4.5 parts of polyvinyl alcohol fiber, 0.7 part of polypropylene fiber, 0.8 part of steel fiber, 0.7 part of sodium silicate and CaSO 4 0.4 part of whisker, 0.7 part of aminopropyl triethylsilane and 2.2 parts of polyvinyl alcohol;
the preparation method of the mining composite thin spray material comprises the following steps:
s1, preparing modified VAE latex by an emulsion polymerization method, and mixing the modified VAE latex with sodium dodecyl sulfate, mineral oil and water in proportion by stirring to obtain a component A;
s2, mixing white sulphoaluminate cement, slag, fly ash, sulfonated melamine water reducer, polyvinyl alcohol fiber, polypropylene fiber, steel fiber, sodium silicate and CaSO 4 Mixing the whisker, the aminopropyl triethylsilane and the polyvinyl alcohol in proportion to obtain a component B;
s3, mixing the component A and the component B according to the mass ratio of 2:1, mixing and stirring to obtain the mining composite thin spray material slurry.
The preparation of the modified VAE latex described above was the same as in example 2.
Comparative example 3
A mining composite thin spray material comprises a component A and a component B according to a mass ratio of 2:1, mixing; the component A comprises the following raw materials in parts by weight: 48 parts of modified VAE latex, 0.3 part of sodium dodecyl sulfate, 0.05 part of mineral oil and 4 parts of water; the component B comprises the following raw materials in parts by weight: 35 parts of white sulphoaluminate cement, 9 parts of slag, 12 parts of fly ash, 0.3 part of sulfonated melamine water reducer, 0.12 part of retarder, 0.7 part of sodium silicate and 0.7 part of CaSO 4 0.4 part of whisker, 0.7 part of aminopropyl triethylsilane and 2.2 parts of polyvinyl alcohol;
the preparation method of the mining composite thin spray material comprises the following steps:
s1, preparing modified VAE latex by an emulsion polymerization method, and mixing the modified VAE latex with sodium dodecyl sulfate, mineral oil and water in proportion by stirring to obtain a component A;
s2, preparing a retarder through free radical polymerization of aqueous solution, and then mixing the retarder with white sulphoaluminate cement, slag, fly ash, sulfonated melamine water reducer, sodium silicate and CaSO 4 Mixing the whisker, the aminopropyl triethylsilane and the polyvinyl alcohol in proportion to obtain a component B;
s3, mixing the component A and the component B according to the mass ratio of 2:1, mixing and stirring to obtain the mining composite thin spray material slurry.
The preparation method of the modified VAE latex and retarder is the same as in example 2.
Comparative example 4
A mining composite thin spray material comprises a component A and a component B according to a mass ratio of 2:1, mixing; the component A comprises the following raw materials in parts by weight: 48 parts of modified VAE latex, 0.3 part of sodium dodecyl sulfate, 0.05 part of mineral oil and 4 parts of water; the component B comprises the following raw materials in parts by weight: 35 parts of white sulphoaluminate cement, 9 parts of slag, 12 parts of fly ash, 0.3 part of sulfonated melamine water reducer, 0.12 part of retarder, 4.5 parts of polyvinyl alcohol fiber, 0.7 part of polypropylene fiber and 0.8 part of steel fiber;
the preparation method of the mining composite thin spray material comprises the following steps:
s1, preparing modified VAE latex by an emulsion polymerization method, and mixing the modified VAE latex with sodium dodecyl sulfate, mineral oil and water in proportion by stirring to obtain a component A;
s2, preparing a retarder through free radical polymerization of an aqueous solution, and mixing the retarder with white sulphoaluminate cement, slag, fly ash, sulfonated melamine water reducer, polyvinyl alcohol fiber, polypropylene fiber and steel fiber according to a proportion to obtain a component B;
s3, mixing the component A and the component B according to the mass ratio of 2:1, mixing and stirring to obtain the mining composite thin spray material slurry.
The preparation method of the modified VAE latex and retarder is the same as in example 2.
Performance detection
1. Mechanical property test
The mining composite thin spray materials prepared in examples 1 to 3 and comparative examples 1 to 4 were prepared into standard samples according to test requirements, and the following tests were performed, respectively, to obtain data shown in table 1.
(1) Flexural strength test and compressive Strength test
The test piece specification is 40 x 160 mm by using a universal tester under the standard of Polymer modified Cement mortar test procedure DL/T5126-2001. The flexural strength formula is:whereinf b In order to achieve the flexural strength, the steel plate is provided with a plurality of steel plates,Pin order to maximize the breaking load,Lto try outThe distance between the fulcrums during the test,bis the side length of the section of the test piece. The compressive strength formula is: />Whereinf c In order to achieve a compressive strength, the steel sheet is,Pis the maximum breaking load to be applied,Sis the area under pressure during testing.
(2) Compressive Strength test
Tensile strength and elongation at break test pieces were 20 x 2 x 80 mm in size and tested using a universal tester. The tensile strength and elongation at break are calculated as follows. Tensile strength formula:wherein T is the tensile strength of the steel sheet,Pfor the maximum tensile force to be reached,Bthe width of the middle of the test piece is the width of the middle of the test piece,Dthe average thickness of the test piece. Elongation at break formula: />WhereinEIs the elongation at break of the steel sheet,L 0 is the distance of the marked line before the test of the test piece,L 1 is the distance of the marked line after the test piece breaks.
Table 1 results of mechanical test of mining composite thin spray materials
As can be seen from the data in Table 1, the flexural strength, compressive strength and pull rope strength of the test pieces in comparative example 3 and comparative example 4 are significantly reduced as compared with those in examples 1 to 3, wherein the reinforcing fiber is not added in comparative example 3, and the reinforcing fiber has obvious effect on improving the mechanical properties of the mining composite thin spray material, while the reinforcing fiber in comparative example 4 is lack of sodium silicate and CaSO 4 The whisker can strengthen the mining composite thin spraying material.
2. Adhesive strength test
Processing lignite into small pieces with the length of 4cm and the length of 1cm by adopting an 8-shaped die method, placing the coal pieces in the middle of the 8-shaped die, fixing the cross section of the 8-shaped die bonded by the 4cm and the 4cm, and thenThe groove of the die is filled with mining composite thin spraying material, the die is disassembled after one day, the die is maintained in a standard maintenance room for 28 days, the clamps adopted on two sides are two semicircular steel rings which are processed together with the 8-shaped die, a universal tester is used for tensile testing, and the calculation formula of the bonding strength is as follows:where Bs is the bonding strength, P 'is the test piece debonding load, and S' is the test piece bonding area. The data obtained are shown in table 2 below.
Table 2 results of test of bond strength of mining composite thin spray material
As can be seen from the data in table 2, the adhesive strength of the modified VAE latex in comparative example 1 is obviously lower than that of examples 1 to 3, and the adhesive performance of the modified VAE latex in comparative example 4 is slightly lower than that of examples 1 to 3, probably because the adhesive property of the composite thin spray material for mining is enhanced to a certain extent due to the compounding of the aminopropyl triethylsilane and the polyvinyl alcohol.
The foregoing has shown and described the basic principles, principal features and advantages of the application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present application, and various changes and modifications may be made without departing from the spirit and scope of the application, which is defined in the appended claims.
Claims (10)
1. A mining composite thin spraying material is characterized in that a component A and a component B are mixed according to a mass ratio of 1-3:1; the component A comprises the following raw materials in parts by weight: 40-55 parts of polymer emulsion, 0.05-0.5 part of dispersing agent, 0.01-0.1 part of defoamer and 3-5 parts of water; the component B comprises the following raw materials in parts by weight: 30-40 parts of white cement, 8-10 parts of slag, 10-15 parts of fly ash, 0.1-0.5 part of water reducer, 0.05-0.2 part of retarder, 5-8 parts of reinforcing fiber and 3-6 parts of functional material;
the polymer emulsion is modified VAE latex, and the modified VAE emulsion is high-solid-content composite latex prepared by emulsion polymerization of VAE emulsion and polyvinyl acetate;
the retarder is a zwitterionic retarder prepared by taking 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, acryloyloxyethyl trimethyl ammonium chloride and methallyl polyoxyethylene ether as monomers through aqueous solution free radical polymerization;
the functional material is prepared from sodium silicate and CaSO 4 Whisker, aminopropyl triethylsilane and polyvinyl alcohol according to the mass ratio of 1:0.5:1:3 mixing.
2. The mining composite thin-spray material of claim 1, wherein the white cement is one of white Portland cement, white sulfoaluminate cement, or white aluminate cement.
3. The mining composite thin spray material according to claim 1, wherein the slag is iron ore tailing ore with continuous gradation of 0.3-4.75 mm particle size, the activity index of the fly ash 28d is more than or equal to 105%, the particle size is less than or equal to 2 μm, and the specific surface area is 12000-15000 m 2 /kg。
4. The mining composite thin spray material according to claim 1, wherein the reinforcing fibers are polyvinyl alcohol fibers, polypropylene fibers and steel fibers according to a mass ratio of 6-8: 1:1, mixing; the length of the polyvinyl alcohol fiber is 4-8 mm, and the diameter is 0.03-0.05 mm; the length of the polypropylene fiber is 4-8 mm, and the diameter is 0.02-0.04 mm; the steel fibers are end hook type copper plating steel fibers, the length is 10-14 mm, and the diameter is 0.18-0.2 mm.
5. The mining composite thin spray material according to claim 1, wherein the dispersing agent is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate, the defoaming agent is mineral oil or an organosilicon defoaming agent, and the water reducing agent is a sulfonated melamine water reducing agent or a polycarboxylate water reducing agent.
6. The method for preparing the mining composite thin spray material according to any one of claims 1 to 5, which is characterized by comprising the following steps:
s1, preparing modified VAE latex by an emulsion polymerization method, and mixing the modified VAE latex, a dispersing agent and a defoaming agent in proportion by stirring to obtain a component A;
s2, preparing a retarder through free radical polymerization of aqueous solution, and mixing the retarder with white cement, slag, fly ash, a water reducing agent, reinforcing fibers and functional materials in proportion to obtain a component B;
s3, the component A and the component B are mixed according to the mass ratio of 1-3: 1, mixing and stirring to obtain the mining composite thin spray material slurry.
7. The method for preparing the mining composite thin-spray material according to claim 6, wherein the modified VAE latex comprises the following raw materials in parts by weight: 15-30 parts of VAE emulsion, 20-40 parts of polyvinyl acetate, 0.5-2 parts of composite emulsifier, 0.2-1 part of initiator and 3-5 parts of water, and the preparation method of the modified VAE emulsion comprises the following steps:
(1) Mixing and stirring the composite emulsifier and water, heating to 50-60 ℃, adding the VAE emulsion and the initiator into the composite emulsifier solution, and stirring and heating to 70-80 ℃;
(2) A micropump is used for controlling the dropping speed to drop the polyvinyl acetate monomer, and the reaction is continued for 1-2 hours after the monomer is added dropwise;
(3) And (3) raising the temperature of the system to 80-90 ℃ ‚, preserving heat for 1-3 hours, and cooling to obtain the modified VAE latex.
8. The preparation method of the mining composite thin spray material according to claim 7, wherein the composite emulsifier comprises an OP emulsifier, sodium dodecyl sulfate and polyvinyl alcohol according to a mass ratio of 1:2: 1.
9. The method for preparing the mining composite thin spray material according to claim 6, wherein the method for preparing the retarder comprises the following steps:
A. 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, acryloyloxyethyl trimethyl ammonium chloride and methallyl polyoxyethylene ether are dissolved in a reactor in proportion, and the pH value of the system is regulated to 7-10 by sodium hydroxide solution under the cooling condition;
B. introducing nitrogen for 20-30 min, adding an initiator at the water bath temperature of 55-65 ℃, and continuing to perform heat preservation reaction for 3-5 h;
C. and precipitating the polymer obtained by the reaction by using anhydrous hexanol, washing the polymer by using acetone for multiple times, and drying the polymer in a vacuum oven at a low temperature for 12-24 hours to obtain the retarder.
10. The preparation method of the mining composite thin spray material according to claim 9, wherein the molar ratio of the 2-acrylamide-2-methylpropanesulfonic acid, the itaconic acid, the acryloyloxyethyl trimethyl ammonium chloride and the methallyl polyoxyethylene ether is 10:4:2:0.01.
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