CN105111411A - Epoxy-modified polyurethane-water glass composite grouting material - Google Patents
Epoxy-modified polyurethane-water glass composite grouting material Download PDFInfo
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- CN105111411A CN105111411A CN201510226836.8A CN201510226836A CN105111411A CN 105111411 A CN105111411 A CN 105111411A CN 201510226836 A CN201510226836 A CN 201510226836A CN 105111411 A CN105111411 A CN 105111411A
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- water glass
- epoxy
- modified polyurethane
- solubilizing agent
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 26
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 12
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- -1 polyoxyethylene Polymers 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- 239000004359 castor oil Substances 0.000 claims description 11
- 235000019438 castor oil Nutrition 0.000 claims description 11
- 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 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- ORVGYTXFUWTWDM-UHFFFAOYSA-N silicic acid;sodium Chemical compound [Na].O[Si](O)(O)O ORVGYTXFUWTWDM-UHFFFAOYSA-N 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 229940096992 potassium oleate Drugs 0.000 claims 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 description 6
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 19
- 239000003245 coal Substances 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011435 rock Substances 0.000 abstract description 7
- 239000006260 foam Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 2
- 230000002265 prevention Effects 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000007906 compression Methods 0.000 description 14
- 230000006835 compression Effects 0.000 description 14
- 238000013019 agitation Methods 0.000 description 9
- 238000010276 construction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- YONVOYAHRUTYTG-UHFFFAOYSA-N ethyl carbamate;hydrate Chemical compound O.CCOC(N)=O YONVOYAHRUTYTG-UHFFFAOYSA-N 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000003701 inert diluent Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000007569 slipcasting Methods 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000036632 reaction speed Effects 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
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002789 polymer coal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- 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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
The invention relates to an epoxy-modified polyurethane-water glass composite grouting material, and a preparation method and application thereof. The epoxy-modified polyurethane-water glass composite grouting material is composed of two independent components, i.e., a component A and a component B, in a volume ratio of 1: 1, wherein the component A comprises water glass, a solubilizer and a catalyst, and the component B comprises polyisocyanate performed polymer and an epoxy active flexibilizer. Through introduction of the epoxy active flexibilizer into the component B, the viscosity of a slurry system is improved, and shearing strength and toughness of a jet-grouted solid are improved; a part of a trimerization catalyst is added into the component A, so release of excess CO2 due to reaction of an isocyanate group with water is effectively inhibited, and the formed jet-grouted solid is compact, does not foam when coming across water and has good mechanical properties; so the epoxy-modified polyurethane-water glass composite grouting material can be extensively applied to fields like reinforcement of coal and rock mass of a coal mine, seepage prevention and leak stoppage.
Description
Technical field
The invention belongs to matrix material synthesis field, especially relate to a kind of epoxy modified polyurethane-water glass combined casting material and preparation method thereof.
Background technology
Under action of underground and when running into geological fault, karst collapse col umn, faling apart in tunnel, face roof coal body shortcake, causes roadway deformation, roof collapse, and coal side slabbing, brings hidden danger to safety in production.
Be usually used in that underground coal mine coal and rock is reinforced at present, leak stopping urethane-water glass injecting paste material because of good penetrability, the low and self flame retardance of reaction heat (meeting a fire carbonization does not burn bright), existing a lot of research and actual construction application among a small circle at present.But it is large without the urethane-water glass injecting paste material induration fragility of toughness reinforcing process, resistance to compression, anti-shear performance all can not meet the demand of application preferably, this type of material is after being circulated into cracks in coal seam, due to self resistance to compression, shear behavior is not enough, very easily causes the generation of repeated wall caving and roof fall accident under mining pressure and coal Gravitative Loads.
Two component injecting paste material comes slip casting viscosity and the plasticity of regulation system often through adding inert diluent or softening agent in polyurethane component, all have and relate in following patent CN103756291A, CN104177052A, CN102964565A and CN1068163A.But the introducing of inert diluent or softening agent, also can cause the decline of material mechanical performance while improving system plasticity.And part inert diluent or softening agent in curing reaction exothermic process from cured article surface transport, ooze out, underground coal mine water body environment often also can be affected and destroy.
Stage urethane-water glass injecting paste material now, for meeting quick-setting practice of construction requirement, adds catalyzer to promote reaction system fast setting in water glass solution of being everlasting.Because water glass belongs to indissoluble alkaline matter, must stir by mechanical forced when production and practice of construction and ensure that catalyzer temporarily can be uniformly dispersed in water glass solution, after leaving standstill for some time, there is layering in catalyst component and water glass, brings inconvenience to actual production and construction.
Patent of invention CN1068163A discloses a kind of two component water glass type chemical slip casting material, and containing inflatable thinner in this pair of component chemical slip casting material, induration ultimate compression strength index obtained in its specific embodiment is only up to 89.0kg/cm
2(about 8.7MPa), well below People's Republic of China's safety in production standard A Q-1089-2011 " polymer coal and rock strengthening agent " ultimate compression strength index>=40MPa requirement.
The patent application CN102964565A of Shandong Dongda Inov New Material Co., Ltd., discloses a kind of silicate modified polyurethane high molecule material.Its component A is the mixture of polyphenyl polymethylene polyisocyanates and modification MDI, NCO content is more than 29%, although the mechanical performance indexs such as this material ultimate compression strength, cohesive strength can meet AQ1089-2011 standard-required, but owing to lacking flexible reaction segment in material cured system, lack the catalyst component regulating curing reaction speed, the physical indexs such as final product gel time, toughness and slip resistance are difficult to the practice of construction requirement meeting the aspects such as coal and rock reinforcing, leak stopping.
Summary of the invention
The object of the invention is to the defect existed for prior art, there is provided a kind of set time adjustable, epoxy modified polyurethane-water glass combined casting material that resistance to compression, bonding and shear behavior are excellent, solves catalyst component and the inconsistent technical barrier of water glass simultaneously.
For achieving the above object, the technical solution used in the present invention is: prepare a kind of epoxy modified polyurethane-water glass composite chemical injecting paste material, by two kinds, independently component A and B component form, during construction, component A and B component are solidified according to the ratio hybrid reaction that volume ratio is 1:1.
Component A comprises the following component according to weight percent meter:
Liquid silicic acid sodium silicate: 91.0% ~ 99.5%;
Solubilizing agent: 0.2% ~ 6.0%;
Catalyzer: 0.3% ~ 3.0%;
B component comprises the following component according to weight percent meter:
Polyisocyanates performed polymer: 75.0% ~ 85.0%;
Epoxy-reactive toughner: 15.0% ~ 25.0%.
Described component A is added drop-wise in sodium silicate water glass by the mixing solutions of solubilizing agent and catalyzer, being a kind of completely limpid, clear homogeneous, isotropy and can stablizing the component reaching 1 year at-10 ~ 45 DEG C of temperature of formation.
In described component A, catalyst component comprises two (dimethylaminoethyl) ether kicker and the 50.0% potassium oleate aqueous solution isocyanate trimerization catalyst of mass ratio 1:3 ~ 6.
The nonionogenic tenside using HLB to be 15-18 in described component A and glycerol mixture are as the solubilizing agent of catalyst component.In solubilizing agent, one or more the composition in castor oil polyoxyethylene (90) ether, peregal C-125 and stearic acid polyoxy 3 vinyl acetate SG-50 selected by tensio-active agent.
The polyisocyanates performed polymer of described B component reacts obtained by polyphenyl polymethylene polyisocyanates and castor oil polyhydric alcohol, and its performed polymer product is brown liquid, and NCO content is 20.0% ~ 29.0%.
Epoxy-reactive toughner in described B component is containing one or both the composition in epoxy terminated polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl ether.
A kind of epoxy modified polyurethane-water glass composite chemical injecting paste material, its preparation process comprises the following steps:
(1) component A material is prepared: first the catalyst component mixing of the solubilizing agent of 0.2% ~ 6.0% and 0.3% ~ 3.0% is made into composite assistant component; Under stirring at normal temperature condition, composite assistant is slowly instilled in the liquid silicic acid sodium silicate solution of 91.0% ~ 99.5%, after being uniformly mixed, namely obtain transparent component A qualified product;
(2) prepare B component material: by castor oil polyhydric alcohol (water content is less than 0.08%), polyphenyl polymethylene polyisocyanates adds reactor, under agitation, 80 DEG C of reactions were cooled to 40 DEG C after 4 hours.Add epoxy toughening agent after sampling detection NCO% content is qualified, be uniformly mixed, obtain B component qualified product.
During use, the component A prepared and B component to be mixed according to the volume ratio of 1:1 with pneumatic high-voltage grouting pump and inject coal and rock, to minute fissure, there is microdilatancy curing reaction in infiltration, reaches the object of reinforcing firm support coal and rock.Described high-pressure injection pump is the pneumatic Double-liquid mud-injection pump that our company produces.
As everyone knows, the ultimate compression strength of urethane-water glass induration, adhesive property and B component isocyanic ester and performed polymer NCO content proportional within the specific limits, when B component isocyanic ester and performed polymer NCO content thereof exceed a certain limit value, then corresponding component A water glass cannot absorb more isocyanic ester and water and reacts and generate CO
2, cause final reactant expand and lose due mechanical property.We find in an experiment, by balancing and adjust ratio and the content of contained kicker and catalyst for trimerization in component A, make part isocyanate groups generation trimerization reaction in B component, decrease isocyanic ester and generate CO based on water reaction
2quantity, the final induration formed is closely knit not to foam, mechanical property significantly increases.
The principle of solidification that the present invention relates to: when after the 1:1 mixing by volume of A, B component, contained by part polyisocyanates and prepolymer, NCO group and water generate polyureas and carbonic acid gas under the effect of kicker, and carbonic acid gas can generate sodium carbonate and precipitated silicic acid with silicate reaction; Part isocyanate groups autohemagglutination under the effect of catalyst for trimerization generates the three-dimensional net structure containing isocyanide urea ester ring; Epoxy-reactive toughner open loop under catalyst action containing epoxy group(ing) and ether generates cancellated build macromole.
The epoxy modified polyurethane that the present invention obtains-water glass combined casting material product quality index is as follows:
(1) set time: 60s ~ 300s;
(2) ultimate compression strength :≤40Mpa;
(3) slip resistance :≤15Mpa;
(4) bonding strength :≤3Mpa;
(5) flame retardant resistance: do not fire.
The invention has the beneficial effects as follows: in invention, preferred solubilizing agent obviously can improve the consistency of catalyst component and sodium silicate water glass, improves the production of product A component, the convenience of construction; By balancing and adjust ratio and the content of contained kicker and catalyst for trimerization in component A, part isocyanate group self-polymeric reaction is made to generate isocyanurate ring, add cross-linking density, the stuctures and properties of cured article is significantly improved and enhanced, decreases CO simultaneously
2produce, be conducive to controlling curing reaction speed and suppressing foaming; The active epoxy toughening agent with flexible and elasticity macromolecular chain segment introduced in polymkeric substance, the final cured article of gained has better ultimate compression strength, cohesive strength and slip resistance, has certain toughness, can adapt to the distortion of coal and rock; Product is cheap, easy construction, safely fire-retardant, good mechanical performance, meets the user demand of coal mining enterprise completely, meets green chemical industry and Sustainable development requirement.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
(1) preparation of polyisocyanates performed polymer
By castor oil polyhydric alcohol (water content is less than 0.08%) 7.0kg, polyphenyl polymethylene polyisocyanates 78.0kg adds reactor, under agitation, 80 DEG C of isothermal reactions 4 hours, stopped reaction is cooled to 40 DEG C, it is 26.5% that sampling detects NCO content, obtains fading in palm fibre polyisocyanate prepolymers.
(2) B component preparation
Under normal temperature, polyisocyanate prepolymers 85.0kg and Polyethylene Glycol Bisglycidyl Ether 15.0kg is added reactor, is uniformly mixed, obtain B component qualified product.
(3) composite assistant preparation
Solubilizing agent (glycerine 5Kg, castor oil polyoxyethylene (90) ether 0.3Kg) is added 50% potassium oleate aqueous solution 2.0kg, two (dimethylaminoethyl) ether 0.3kg mix, stir, obtain composite assistant.
(4) component A preparation
Composite assistant 7.6kg is loaded separating funnel, and under agitation condition, slowly instillation is equipped with in 92.4kg liquid silicic acid sodium silicate solution, controls rate of addition and dropwises at 0.5 hour, must clarify, transparent component A qualified product.
Component A and B component are obtained induration according to volume ratio 1:1 static mixer is mixing cured through high-pressure pneumatic grouting pump.
Product quality indicator:
Set time: 160s(initial temperature 20 DEG C);
Ultimate compression strength: 49.9Mpa;
Slip resistance: 17.2Mpa;
Cohesive strength: 3.5Mpa.
Embodiment 2:
(1) preparation of polyisocyanates performed polymer
By castor oil polyhydric alcohol (water content is less than 0.08%) 9.0kg, polyphenyl polymethylene polyisocyanates 71.0kg adds reactor, under agitation, 80 DEG C of isothermal reactions 4 hours, stopped reaction is cooled to 40 DEG C, it is 25.0% that sampling detects NCO content, obtains fading in palm fibre polyisocyanate prepolymers.
(2) B component preparation
Under normal temperature, polyisocyanate prepolymers 80.0kg and polypropylene glycol diglycidyl ether 20.0kg is added reactor, is uniformly mixed, obtain B component qualified product.
(3) composite assistant preparation
Solubilizing agent (glycerine 3Kg, peregal C-1250.2Kg) is added 50% potassium oleate aqueous solution 1.4kg, two (dimethylaminoethyl) ether 0.4kg to mix, stir, obtain composite assistant.
(4) component A preparation
Composite assistant 4.0kg is loaded separating funnel, and under agitation condition, slowly instillation is equipped with in 92.4kg liquid silicic acid sodium silicate solution, controls rate of addition and dropwises at 0.5 hour, must clarify, transparent component A qualified product.
Component A and B component are obtained induration according to volume ratio 1:1 static mixer is mixing cured through high-pressure pneumatic grouting pump.
Product quality indicator:
Set time: 130s(initial temperature 20 DEG C);
Ultimate compression strength: 41.9Mpa;
Slip resistance: 16.0Mpa;
Cohesive strength: 3.8Mpa.
Embodiment 3:
(1) preparation of polyisocyanates performed polymer
By castor oil polyhydric alcohol (water content is less than 0.08%) 10.0kg, polyphenyl polymethylene polyisocyanates 80.0kg adds reactor, under agitation, 80 DEG C of isothermal reactions 4 hours, stopped reaction is cooled to 40 DEG C, it is 28.5% that sampling detects NCO content, obtains fading in palm fibre polyisocyanate prepolymers.
(2) B component preparation
Under normal temperature, polyisocyanate prepolymers 90.0kg and polypropylene glycol diglycidyl ether 20.0kg is added reactor, is uniformly mixed, obtain B component qualified product.
(3) composite assistant preparation
Solubilizing agent (glycerine 3.5Kg, polyoxyethylene stearic acid ester SG-500.5Kg) is added 50% potassium oleate aqueous solution 2.0kg, two (dimethylaminoethyl) ether 0.5kg to mix, stir, obtain composite assistant.
(4) component A preparation
Composite assistant 6.5kg is loaded separating funnel, and under agitation condition, slowly instillation is equipped with in 93.5kg liquid silicic acid sodium silicate solution, controls rate of addition and dropwises at 0.5 hour, must clarify, transparent component A qualified product.
Component A and B component are obtained induration according to volume ratio 1:1 static mixer is mixing cured through high-pressure pneumatic grouting pump.
Product quality indicator:
Set time: 90s(initial temperature 20 DEG C);
Ultimate compression strength: 52.5Mpa;
Slip resistance: 18.7Mpa;
Cohesive strength: 4.3Mpa.
Embodiment 4:
(1) preparation of polyisocyanates performed polymer
By castor oil polyhydric alcohol (water content is less than 0.08%) 13.0kg, polyphenyl polymethylene polyisocyanates 65.0kg adds reactor, under agitation, 80 DEG C of isothermal reactions 4 hours, stopped reaction is cooled to 40 DEG C, it is 23.0% that sampling detects NCO content, obtains fading in palm fibre polyisocyanate prepolymers.
(2) B component preparation
Under normal temperature, polyisocyanate prepolymers 80.0kg and polypropylene glycol diglycidyl ether 20.0kg is added reactor, is uniformly mixed, obtain B component qualified product.
(3) composite assistant preparation
By solubilizing agent (glycerine 5.6Kg, castor oil polyoxyethylene (90) ether 0.3Kg, polyoxyethylene stearic acid ester SG-500.6kg) add 50% potassium oleate aqueous solution 1.6kg, two (dimethylaminoethyl) ether 0.2kg and mix, stir, obtain composite assistant.
(4) component A preparation
Composite assistant 8.0kg is loaded separating funnel, and under agitation condition, slowly instillation is equipped with in 92.0kg liquid silicic acid sodium silicate solution, controls rate of addition and dropwises at 0.5 hour, must clarify, transparent component A qualified product.
Component A and B component are obtained induration according to volume ratio 1:1 static mixer is mixing cured through high-pressure pneumatic grouting pump.
Product quality indicator:
Set time: 180s(initial temperature 20 DEG C);
Ultimate compression strength: 40.0Mpa;
Slip resistance: 15.9Mpa;
Cohesive strength: 3.0Mpa.
In the present invention, there is provided a kind of epoxy modified polyurethane-water glass combined casting material, product is two-component materials, wherein employs by the solubilizing agent prepared in component A, significantly improve the consistency of catalyst component and sodium silicate water glass, and serve the effect of thinner; Collocation employs catalyst for trimerization in the catalyst, promotes the trimerization reaction of isocyanate groups, decreases the reaction that isocyanate groups meets water, thus effectively controls CO
2produce, avoid too much CO
2generation and the impact of release on its mechanics mechanical property; The active epoxy toughening agent with flexible and elasticity macromolecular chain segment is introduced in B component, enhance the ultimate compression strength of product, cohesive strength and slip resistance, drastically increase the toughness of product, make the use that it more can adapt under varying environment in Coal-body Structure; Thing is cheap, easy construction, safely fire-retardant, good mechanical performance, meets the user demand of coal mining enterprise completely, meets green chemical industry and Sustainable development requirement.
Although describe the application with reference to specific embodiment, should be appreciated that term used to illustrate and exemplary and nonrestrictive.Spirit or the essence of invention is not departed from because the application can specifically implement in a variety of forms, so be to be understood that, above-described embodiment is not limited to any aforesaid details, and should explain widely in the spirit and scope that claim limits, therefore fall into the adjustment of the whole formulation content in claim or its equivalent scope or all should be claim to the choice for use of allied substances contained.
Claims (7)
1. epoxy modified polyurethane-water glass combined casting material, is characterized in that, described epoxy modified polyurethane-water glass composite grouting material is made up of according to volume ratio 1:1 component A and B component, wherein:
Component A comprises the following component according to weight percent meter:
Liquid silicic acid sodium silicate: 91.0% ~ 99.5%;
Solubilizing agent: 0.2% ~ 6.0%;
Catalyzer: 0.3% ~ 3.0%;
B component comprises following component by weight percentage:
Polyisocyanates performed polymer: 75.0% ~ 85.0%;
Epoxy-reactive toughner: 15.0% ~ 25.0%.
2. a kind of epoxy modified polyurethane according to claim 1-water glass combined casting material, it is characterized in that, select HLB to be the nonionogenic tenside of 15-18 and the glycerol mixture solubilizing agent as catalyst component in described component A, in solubilizing agent, glycerine is 5 ~ 10:1 ~ 5 with surfactant qualities ratio.
3. solubilizing agent according to claim 1, it is characterized in that, be applied to can to make in component A catalyzer and sodium silicate water glass solution fully miscible, obtain completely limpid, clear homogeneous, isotropy and the component A composition reaching 1 year can be stablized at-10 DEG C ~ 45 DEG C.
4. the solubilizing agent as requested described in 3, is characterized in that described HLB is one or more the composition that the tensio-active agent of 15-18 can select in castor oil polyoxyethylene (90) ether, peregal C-125 and polyoxyethylene stearic acid ester SG-50.
5. a kind of epoxy modified polyurethane according to claim 1-water glass combined casting material, it is characterized in that, in described component A, catalyzer is two (dimethylaminoethyl) ether kicker and the 50% potassium oleate aqueous solution isocyanate group catalyst for trimerization mixture that is made into of 1:3 ~ 6 in mass ratio.
6. a kind of epoxy modified polyurethane-water glass composite grouting material according to claim 1, it is characterized in that, in described B component, polyisocyanates performed polymer reacts obtained by polyphenyl polymethylene polyisocyanates and castor oil polyhydric alcohol, its performed polymer product is brown liquid, and NCO content is 20.0% ~ 29.0%.
7. a kind of epoxy modified polyurethane according to claim 1-water glass combined casting material, it is characterized in that, in described B component, epoxy-reactive toughner is containing one or both the composition in epoxy terminated polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl ether.
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| CN106543688A (en) * | 2016-11-22 | 2017-03-29 | 山东科技大学 | A kind of organic/inorganic nano combined casting material and preparation method thereof |
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| CN110055026A (en) * | 2019-04-25 | 2019-07-26 | 王鹏 | A kind of gap-grouting material and preparation method thereof |
| CN110452656A (en) * | 2019-08-23 | 2019-11-15 | 垣曲县宏远特种防水材料有限公司 | A kind of phenol aldehyde modified base polyurethane prepolymer for use as-sodium metasilicate two-component consolidation grouting material |
| CN110452656B (en) * | 2019-08-23 | 2021-09-14 | 垣曲县宏远特种防水材料有限公司 | Phenolic aldehyde modified polyurethane prepolymer-sodium silicate two-component reinforced grouting material |
| CN111234172A (en) * | 2020-01-17 | 2020-06-05 | 阳泉煤业（集团）有限责任公司 | Epoxy resin/water glass/polyurethane composite reinforced material and preparation method thereof |
| CN112225523A (en) * | 2020-10-20 | 2021-01-15 | 陕西煤业化工技术研究院有限责任公司 | Silicate modified polyurethane reinforcing material and preparation method and application thereof |
| CN115505087A (en) * | 2021-06-23 | 2022-12-23 | 煤炭科学技术研究院有限公司 | Special composite catalyst for mine water glass modified polyurethane grouting material and preparation method thereof |
| CN115505087B (en) * | 2021-06-23 | 2023-09-15 | 煤炭科学技术研究院有限公司 | Composite catalyst special for mining water glass modified polyurethane grouting material and preparation method thereof |
| CN114573783A (en) * | 2022-03-07 | 2022-06-03 | 河北浩威旭光新材料科技有限公司 | Filling reinforcing material for reinforcing coal rock mass in coal mine and using method thereof |
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