CN117285697A - Single-component water-soluble polyurethane grouting material and preparation method thereof - Google Patents
Single-component water-soluble polyurethane grouting material and preparation method thereof Download PDFInfo
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- CN117285697A CN117285697A CN202310431818.8A CN202310431818A CN117285697A CN 117285697 A CN117285697 A CN 117285697A CN 202310431818 A CN202310431818 A CN 202310431818A CN 117285697 A CN117285697 A CN 117285697A
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- 239000000463 material Substances 0.000 title claims abstract description 90
- 239000004814 polyurethane Substances 0.000 title claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 56
- 229920000570 polyether Polymers 0.000 claims abstract description 56
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 29
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims abstract description 19
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- CVAWAQKMBDKROW-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene;isocyanic acid Chemical compound N=C=O.CC1=CC=C(N=C=O)C=C1N=C=O CVAWAQKMBDKROW-UHFFFAOYSA-N 0.000 claims 3
- 238000012856 packing Methods 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 69
- 239000002002 slurry Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- -1 TDI isocyanate Chemical class 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229920006333 epoxy cement Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LUEHNHVFDCZTGL-UHFFFAOYSA-N but-2-ynoic acid Chemical compound CC#CC(O)=O LUEHNHVFDCZTGL-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing 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
- C08G18/70—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
- C08G18/7607—Compounds of C08G18/7614 and of C08G18/7657
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- 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
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Sealing Material Composition (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a single-component water-soluble polyurethane grouting material and a preparation method thereof, wherein the single-component water-soluble polyurethane grouting material comprises the following raw materials in parts by mass: 1-10 parts of polymethylene polyphenyl isocyanate, 8-20 parts of toluene diisocyanate, 5-15 parts of polyether triol, 45-60 parts of polyether tetrol, 25-40 parts of a composite solvent and 0-0.05 part of inorganic acid; the composite solvent is composed of dibutyl phthalate: dimethyl carbonate: acetone=1: (0-1.02): (1.02-2.50) raw materials in mass ratio; the method comprises the following steps: weighing raw materials; mixing polymethylene polyphenyl isocyanate, toluene diisocyanate and inorganic acid, stirring and heating to obtain a mixed solution A; vacuum dehydrating polyether triol and polyether tetrol, and cooling to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding a composite solvent after reaction to obtain a polyurethane grouting material, and sealing and preserving; the highest water-packing capacity can reach 32 times.
Description
Technical Field
The invention relates to the technical field of building waterproof materials, in particular to a single-component water-soluble polyurethane grouting material and a preparation method thereof.
Background
Polyurethane materials are grouting materials with the largest variety, the largest application range and the largest dosage in the existing chemical grouting materials, and can be generally divided into two types according to the material characteristics: hydrophilic (water-soluble) and hydrophobic (oil-soluble), the hydrophilic polyurethane grouting material is prepared by polymerizing polyisocyanate and high molecular weight multi-functional hydrophilic polyether polyol, and is easy to disperse in water and self-emulsify when meeting water; good hydrophilicity, large water-coating amount and immediate polymerization reaction when meeting water; the consolidation has the dual functions of elastic water stop and expansion water stop; the hydrophobic polyurethane grouting material has no hydrophilicity, foams after meeting water, generates secondary pressure, can be poured into micro cracks, and the formed foam has certain strength, thus being applicable to waterproof plugging occasions with reinforcement. The other classification method is divided into a single component and a double component according to the components. The one-component polyurethane grouting material has the advantage of convenient use, but in order to ensure lower viscosity, polyether polyol with relatively high two-functionality or molecular weight is generally used as a raw material, which determines that the one-component polyurethane grouting material is mostly a flexible elastic material, and the two-component polyurethane grouting material can provide a material with high strength, but needs to be prepared before use, and is inconvenient.
In the prior art, as the patent number is CN20081010392. X, pentaerythritol polyoxyethylene polyoxypropylene ether for a polyurethane waterproof grouting material and a preparation method thereof are disclosed, pentaerythritol is subjected to ring-opening polymerization with epoxide under the condition of a catalyst to prepare pentaerythritol polyether polyol, and in theory, the pentaerythritol is independently synthesized into polyether polyol, so that the water coating amount of a cured product of polyurethane can be obviously improved by 25 times, but the water coating amount of the cured product of polyurethane can not meet the higher-demand plugging waterproof engineering, so that the grouting material with higher water coating amount needs to be developed.
Meanwhile, the prior art has the following defects:
the traditional inorganic grouting material and other water-soluble polyurethane grouting materials are generally suitable for a still water environment, and can not play a role in blocking water in an environment with large water inflow and high water flow speed; the existing grouting material has poor water-packing performance and small water-packing quantity.
Disclosure of Invention
The invention aims to provide a single-component water-soluble polyurethane grouting material and a preparation method thereof, which solve the problem that the existing material is suitable for a still water environment and cannot play a role in quick water shutoff in an environment with large water inflow and high water flow speed.
The invention is realized in such a way that the single-component water-soluble polyurethane grouting material comprises the following raw materials in parts by mass:
1-10 parts of polymethylene polyphenyl isocyanate
Toluene Diisocyanate (TDI) 8-20 parts
5-15 parts of polyether triol
45-60 parts of polyether tetraol
25-40 parts of composite solvent
0-0.05 parts of inorganic acid;
the compound solvent is prepared from dibutyl phthalate: dimethyl carbonate: acetone=1: (0-1.02): (1.02-2.50) mass ratio of raw materials.
In the field, the proportion of raw materials and the selection of the raw materials have great influence on the performance of the materials, polyether triol and polyether tetrol are polyols with extremely strong hydrophilicity, have good compatibility with water, have the functionality ranging from 3 to 4, and have better water-packing property as the functionality is larger, and the two factors determine the high Bao Shuixing of the materials in advance; the polyether triol and the polyether tetrol are combined with the polymethylene polyphenyl isocyanate and the toluene diisocyanate, the content of the-NCO groups after the reaction is in an optimal range in the dosage range described by the invention, and the material can have an optimal water-coating effect after being subjected to water reaction, so that the water-coating amount of the material in the invention can reach 32 times as high as that of the material in combination with water, and compared with the prior material, the water-coating amount of the material is high, and the material has remarkable progress.
According to the proportion of polyether triol, polyether tetrol and polyisocyanate, the content of slurry-NCO groups is in an optimal range, the slurry is uniformly dispersed in water at the temperature of 12-35 ℃ to form emulsion, free-NCO groups in the slurry can quickly react with water, the gel time is short, a good water-stopping effect is formed, and a waterproof elastic colloidal solidified body has good water-stopping performance.
Compared with the prior art, the grouting material disclosed by the invention can be well applied to environments with large water inflow and high water flow speed, so that the application range is wide and the applicability is high; simultaneously, the slurry is filled into the crack, the slurry permeates to the periphery of the crack (forms primary permeation) and then reacts, when the slurry reacts with water to form an elastic consolidated body substance, free isocyanate groups release CO when meeting water 2 The gas, with the help of the gas pressure, the slurry can be further pressed into the gaps of the structure, so that the porous structure or stratum can be completely filled and compacted, the porous structure or stratum has the characteristic of secondary infiltration, and the porous structure or stratum is infiltrated into the gaps of concrete to generate larger infiltration radius and solidification volume, so that the solidification body with large volume, good impermeability and good water shutoff effect is finally formed.
The consolidated body formed by the reaction has good extensibility, elasticity and impermeability, and can be permanently kept in shape in water.
The NCO% of the synthesized product in the invention is 5% -7%.
The invention further adopts the technical scheme that: the grouting material comprises the following raw materials in parts by mass:
1-5 parts of polymethylene polyphenyl isocyanate
Toluene Diisocyanate (TDI) 10-15 parts
5-10 parts of polyether triol
45-52 parts of polyether tetraol
33-40 parts of composite solvent
0-0.02 parts of inorganic acid.
The gel time of the polyurethane grouting material in the scheme is 15s-40s, and the water coating amount is 25-32 times.
The invention further adopts the technical scheme that: the grouting material comprises the following raw materials in parts by mass:
1.7 parts of polymethylene polyphenyl isocyanate
Toluene Diisocyanate (TDI) 9.27 parts
Polyether triol 5.15 parts
46.34 parts of polyether tetraol
37.58 parts of composite solvent
Inorganic acid 0.02 parts.
By adopting the combination, the obtained grouting material has optimal performance, and the water-coating quantity can reach 32 times.
The invention further adopts the technical scheme that: the inorganic acid is phosphoric acid with the concentration of 85 percent.
The phosphoric acid is low in cost and nonvolatile, and can inhibit side reactions of isocyanate; ensuring the purity of the product.
The invention further adopts the technical scheme that: the isocyanate content of the polymethylene polyphenyl isocyanate is 30.5-32%, and the viscosity at 25 ℃ is 150-250 mPa.s. PAPI has large reactivity, low vapor pressure, low volatility and little harm to human body, and provides good rigidity for the material.
The invention further adopts the technical scheme that: the isocyanate content of the toluene diisocyanate is 48% -48.2%, and the viscosity at 25 ℃ is 3 mPas-4 mPas. The TDI isocyanate content is 48% -48.2%, the viscosity is low, and good flexibility and elongation are provided for the material.
The invention further adopts the technical scheme that: the molecular weight of the polyether tetraol is 7000-8000, and the functionality is 3.5-4.5. The polyether tetrol has strong hydrophilicity and high functionality, so that the material has good dispersibility and water-packing property in water.
The invention further adopts the technical scheme that: the polyether triol has a molecular weight of 4200-4800 and a functionality of 2.8-3.5. The polyether triol has relatively small molecular weight and high functionality, and provides certain strength for the material.
The invention also provides a preparation method of the single-component water-soluble polyurethane grouting material, wherein the grouting material is the grouting material, and the preparation method comprises the following steps:
step one: respectively weighing raw materials with corresponding proportions for standby;
step two: mixing polymethylene polyphenyl isocyanate, toluene diisocyanate and inorganic acid in proportion, stirring and heating to 40-50 ℃ to obtain a mixed solution A for later use; vacuum dewatering polyether triol and polyether tetrol at 100-120 deg.c for 1.5-2 hr, and cooling to 40-50 deg.c to obtain mixed liquid B;
step three: and (3) adding the mixed solution A into the mixed solution B in batches, heating to 80-85 ℃ for reaction for 2-2.5 hours, adding a composite solvent, and obtaining the polyurethane grouting material, and sealing and preserving.
In the prior art, the water packing capacity of the grouting material is 25 times at most, and the highest water packing capacity of the grouting material can be 32 times.
Polymethylene polyphenyl isocyanate (PAPI): the PAPI is a crude MDI, the content of the MDI is about 50%, and the damage to human body is small under the condition of common good ventilation because the vapor pressure of the MDI is much lower than that of TDI.
Toluene Diisocyanate (TDI): is a main reaction raw material of polyurethane products, reacts with water to generate carbon dioxide, is easy to react with compounds containing active hydrogen atoms, and reacts with dihydric alcohol to form linear polyurethane or polyurethane resin.
Polyether polyol: is the main reaction material of polyurethane products, and compared with polyester polyol, the polyurethane products synthesized by polyether polyol have good water resistance and low temperature resistance.
Composite solvent: can reduce the hardness of polyurethane products, improve the plasticity (ductility) of the products and improve the brittleness of the foam.
Phosphoric acid: the phosphoric acid is low in cost and nonvolatile, and can inhibit side reactions of isocyanate.
In the raw materials of the invention, TDI and PAPI jointly provide the-NCO groups required by the system, and polyether triol and polyether tetrol jointly provide the-OH groups required by the system; the content of the-NCO groups in the invention is in an optimal range, so that the material can form a good water-in-water effect after being reacted with water.
The raw materials are prepared into polyurethane grouting materials according to the proportion, so that polyurethane with lower viscosity and high water-packing capacity is produced.
The invention has the beneficial effects that: the polyether triol and the polyether tetrol are polyols with extremely strong hydrophilicity, have good compatibility with water, have the functionality ranging from 3 to 4, have higher functionality and better water-packing property, and the two factors determine the high Bao Shuixing of the material in advance; the polyether triol and the polyether tetrol are combined with the polymethylene polyphenyl isocyanate and the toluene diisocyanate, the content of the-NCO groups after the reaction is in an optimal range in the dosage range recorded by the invention, and the material can have an optimal water-coating effect after the material is reacted in water, so that the water-coating amount of the material in the invention can reach 32 times at most when the material is combined with water;
according to the proportion of polyether triol, polyether tetrol and polyisocyanate, the content of slurry-NCO groups is in an optimal range, the slurry is uniformly dispersed in water to form emulsion at the temperature of 12-35 ℃, free-NCO groups in the slurry can quickly react with water, the gel time is short, a good water-stopping effect is formed, and a waterproof elastic colloidal solidified body has good water-stopping performance;
compared with the prior art, the grouting material disclosed by the invention can be well applied to environments with large water inflow and high water flow speed, so that the application range is wide and the applicability is high; simultaneously, the slurry is filled into the crack, the slurry permeates to the periphery of the crack (forms primary permeation) and then reacts, when the slurry reacts with water to form an elastic consolidated body substance, free isocyanate groups release CO when meeting water 2 The gas, by means of gas pressure, the slurry can be further pressed into the gaps of the structure, so that the porous structure or stratum can be completely filled and compacted, and the porous structure or stratum has the characteristic of secondary infiltration, and the porous structure or stratum is infiltrated into the gaps of concrete to generate larger infiltration radius and solidificationThe volume is large, so that a solidified body with good impermeability and good water shutoff effect is finally formed;
the concretion formed by the reaction has good extensibility, elasticity and impermeability, and keeps the original shape in water permanently;
in the prior art, the water packing capacity of the grouting material is 25 times at most, and the highest water packing capacity of the grouting material can be 32 times.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be noted that the tables are only used for being combined with the disclosure of the present invention for the people skilled in the art to understand and read, and are not limited to the practical limitation of the present invention, so that the present invention is not limited to the technical essential significance, and any structural modification, proportional relation change or size adjustment should still fall within the scope of the disclosure of the present invention without affecting the efficacy and achievement of the present invention. Also, the terms such as "upper," "lower," "left," "right," "middle," and "a" and the like recited in the present specification are merely for descriptive purposes and are not intended to limit the scope of the invention, but are intended to provide relative positional changes or modifications without materially altering the technical context in which the invention may be practiced.
Example 1:
as shown in table 1, the formulation of the single-component water-soluble polyurethane grouting material of this example is: comprises 1.7 parts by weight of polymethylene polyphenyl isocyanate (PAPI, wherein the-NCO content is 31%, the viscosity is 200 mPa.s at 25 ℃), 9.27 parts by weight of toluene diisocyanate (TDI-80); 5.15 parts of polyether triol, 46.34 parts of polyether tetrol and 37.58 parts of a composite solvent (compounded by dibutyl phthalate, dimethyl carbonate, acetone=1:1.02:1.02 mass ratio) and 0.02 part of inorganic acid.
Example 2:
as shown in table 1, the formulation of the single-component water-soluble polyurethane grouting material of this example is: comprises 1.8 parts by weight of polymethylene polyphenyl isocyanate (PAPI, wherein the-NCO content is 31%, the viscosity is 200 mPa.s at 25 ℃), and 10.16 parts by weight of toluene diisocyanate (TDI-80); 5.64 parts of polyether triol, 50.79 parts of polyether tetrol, 31.6 parts of a composite solvent (compounded by dibutyl phthalate: acetone=1:2.5 mass ratio) and 0 part of inorganic acid.
The mass parts of the raw materials in the single-component water-soluble polyurethane grouting materials in examples 1 and 2 are shown in the following table 1.
Table 1 the respective raw materials in examples 1 and 2 were in parts by weight
Example 3:
preparation and construction methods of grouting materials in the above examples 1-2
The preparation method comprises the following steps:
1) According to the mass ratio of the raw materials of each component, respectively weighing the corresponding parts by mass of polymethylene polyphenyl isocyanate, toluene diisocyanate, polyether triol, polyether tetrol and inorganic acid.
2) Polymethylene polyphenyl isocyanate; toluene diisocyanate and inorganic acid are mixed according to a certain proportion, stirred and heated to 45 ℃ for standby; dehydrating polyether triol and polyether tetrol for 2 hours at a high temperature of 100 ℃, cooling to 45 ℃, then dropwise adding isocyanate mixed liquid into polyether mixed liquid in batches, heating to 85 ℃ for reacting for 2.5 hours, adding a composite solvent to obtain a single-component water-soluble polyurethane grouting material, and sealing and preserving;
the construction method comprises the following steps:
3) During site construction, the joint surface is firstly treated, surface dirt is removed, the joint surface is ensured to be clean, and states such as the trend and depth of the joint are checked. The method comprises the steps of carrying out a first treatment on the surface of the
4) Setting grouting holes, drilling inclined holes (45 degrees) along two sides of the seam, wherein the hole distance is 20 cm-30 cm, and in the embodiment, the hole distance is 25cm, so that slurry can effectively infiltrate into cracks or gaps, and impurities in the holes are blown clean by compressed gas;
5) Sealing the joint of the buried pipe, burying a grouting pipe (box) by using a plugging king or epoxy cement, and sealing the joint surface;
6) Washing the seam, flushing the seam surface by using pressurized water, knowing the series connection condition among all holes, and checking the sealing effect;
7) Grouting under pressure, wherein grouting pressure is determined according to design requirements, the highest pressure is not more than a structural allowable value and is 0.3MPa in the embodiment, and a vertical seam is filled from the lowest position from bottom to top; the horizontal seam proceeds from one end to the other. When pure slurry appears in the adjacent holes, suspending grouting and ligating the pipeline; the grouting pipe is moved to an adjacent hole to continue grouting, and grouting is carried out on a specified pressure screen until the grouting end standard is reached;
8) After solidification, removing the grouting pipe, and sealing with a plugging agent or epoxy cement;
comparative example 1:
LW water-soluble polyurethane (water-soluble type) developed by the eastern survey design institute: raw materials comprise 1. Toluene diisocyanate TDI;2. ethylene oxide-propylene oxide copolyethers: the hydrophilicity of the polyoxyethylene segment and the hydrophobicity of the polyoxypropylene segment make the polyether have widely varying surface activities, which have emerged in a variety of products ranging from oil-soluble to water-soluble.
And (3) performance detection:
the single-component water-soluble polyurethane grouting materials prepared by the method of the example 3 are adopted for detection in comparative example 1 and examples 1 and 2, and main performance parameters are shown in table 2:
table 2 main properties of single-component water-soluble polyurethane grouting material
As is clear from Table 2, the grouting material obtained in example 1 has short gel time, low viscosity and high solid content, the water packing capacity of the slurry can be up to 32 times, and the grouting material reacts immediately after meeting water to form a waterproof elastic gelatinous solidified body with large volume, good impermeability and good water blocking effect, and has good water blocking performance. The grouting material obtained in the example 2 has short gel time, low viscosity and high solid content, and the water packing property of the slurry can reach 25 times.
As can be seen from Table 2, the performance indexes of the single-component water-soluble polyurethane grouting materials of examples 1-2 all meet the requirements of WPU products in polyurethane grouting materials (JC/T2041-2020). The single-component water-soluble polyurethane grouting material of the embodiment 1 achieves the excellent effects of short gel time, relatively low viscosity, large water-packing quantity and high solid content, can maximally meet the anti-seepage and plugging requirements of expansion joints, cracks, water-flushing blocking, foundation water flowing prevention and the like existing in various projects, has excellent water-packing performance, and can play a role in water-blocking and reinforcing in environments with large water-flushing quantity and high water flow speed.
The slurry in the invention disperses, emulsifies and foams by itself after meeting water, and immediately carries out chemical reaction to form a watertight elastic gelatinous concretion body which has good water stopping performance, and the elastic gelatinous concretion body formed after reaction has good extensibility, elasticity, impermeability and low temperature resistance, and keeps the original shape permanently in water. The water-based adhesive has small viscosity and good pourability after being mixed with water, and the consolidated body is harmless, nontoxic and pollution-free to human body after being soaked in water.
Compared with common grouting liquid, the grouting material of the invention can not be washed away by water, the consolidation area is enlarged by flowing water instead, and the water-containing quantity is 25-32 times. The slurry is poured into the cracks, and then permeates into the periphery of the cracks (primary permeation is formed), the reaction is immediately carried out, the foaming expansion generates secondary permeation, and the permeation into the concrete gaps generates larger permeation radius and solidification volume, so that the solidification body with large volume, good impermeability and good water shutoff effect is finally formed. The chemical stability is high, the acid, alkali, salt and organic solvent are resistant, the surface is smooth and wear-resistant, no mildew is generated, and the consolidated body has good durability.
The grouting material prepared by the invention can release CO when reacting with water to form an elastic concretion substance 2 The gas, by means of gas pressure, the slurry can be further pressed into the voids of the structure to make the structure porousThe structure or stratum can be fully filled and compacted. Has the characteristic of secondary osmosis. The grouting material has large water-packing quantity, good hydrophilicity and pourability, and the viscosity and solidification speed of the slurry can be adjusted according to the requirement. The invention improves the water-packing quantity of the grouting liquid and eliminates the defect of small water-packing quantity of the traditional grouting liquid. Solves the application defect at the present stage and increases the application field of polyurethane.
The invention also provides a preparation method and a reasonable process.
The single-component water-soluble polyurethane grouting material achieves the excellent effects that the gel time is 15-40 s and the water coating amount is 25-32 times.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. A single-component water-soluble polyurethane grouting material is characterized in that: the grouting material comprises the following raw materials in parts by mass:
1-10 parts of polymethylene polyphenyl isocyanate
Toluene Diisocyanate (TDI) 8-20 parts
5-15 parts of polyether triol
45-60 parts of polyether tetraol
25-40 parts of composite solvent
0-0.05 parts of inorganic acid;
the compound solvent is prepared from dibutyl phthalate: dimethyl carbonate: acetone=1: (0-1.02): (1.02-2.50) mass ratio of raw materials.
2. The single-component water-soluble polyurethane grouting material according to claim 1, wherein the grouting material comprises the following raw materials in parts by mass:
1-5 parts of polymethylene polyphenyl isocyanate
Toluene Diisocyanate (TDI) 10-15 parts
5-10 parts of polyether triol
45-52 parts of polyether tetraol
33-40 parts of composite solvent
0-0.02 parts of inorganic acid.
3. The single-component water-soluble polyurethane grouting material according to claim 2, wherein the grouting material comprises the following raw materials in parts by mass:
1.7 parts of polymethylene polyphenyl isocyanate
Toluene Diisocyanate (TDI) 9.27 parts
Polyether triol 5.15 parts
46.34 parts of polyether tetraol
37.58 parts of composite solvent
Inorganic acid 0.02 parts.
4. A one-component water-soluble polyurethane grouting material as claimed in any one of claims 1 to 3, wherein the inorganic acid is phosphoric acid with a concentration of 85%.
5. A one-component water-soluble polyurethane grouting material according to any one of claims 1 to 3, wherein the polymethylene polyphenyl isocyanate has an isocyanate content of 30.5% to 32% and a viscosity of 150 mPa-s to 250 mPa-s at 25 ℃.
6. A one-component water-soluble polyurethane grouting material according to any one of claims 1 to 3, wherein the toluene diisocyanate has an isocyanate content of 48 to 48.2% and a viscosity of 3 to 4 mPa-s at 25 ℃.
7. A one-component water-soluble polyurethane grouting material as claimed in any one of claims 1 to 3, wherein the polyether tetrol has a molecular weight of 7000 to 8000 and a functionality of 3.5 to 4.5.
8. A one-component water-soluble polyurethane grouting material as claimed in any one of claims 1 to 3, wherein the polyether triol has a molecular weight 4200 to 4800 and a functionality of 2.8 to 3.5.
9. A method for preparing a single-component water-soluble polyurethane grouting material, wherein the grouting material is as claimed in any one of claims 1 to 8, and the preparation method comprises the following steps:
step one: respectively weighing raw materials with corresponding proportions for standby;
step two: mixing polymethylene polyphenyl isocyanate, toluene diisocyanate and inorganic acid in proportion, stirring and heating to 40-50 ℃ to obtain a mixed solution A for later use; vacuum dewatering polyether triol and polyether tetrol at 100-120 deg.c for 1.5-2 hr, and cooling to 40-50 deg.c to obtain mixed liquid B;
step three: and (3) adding the mixed solution A into the mixed solution B in batches, heating to 80-85 ℃ for reaction for 2-2.5 hours, adding a composite solvent, and obtaining the polyurethane grouting material, and sealing and preserving.
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