CN116790097A - Epoxy composite grouting material with low viscosity, high strength and low shrinkage - Google Patents
Epoxy composite grouting material with low viscosity, high strength and low shrinkage Download PDFInfo
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- CN116790097A CN116790097A CN202310878691.4A CN202310878691A CN116790097A CN 116790097 A CN116790097 A CN 116790097A CN 202310878691 A CN202310878691 A CN 202310878691A CN 116790097 A CN116790097 A CN 116790097A
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000004593 Epoxy Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 2
- 239000001667 (E)-4-furan-2-ylbut-3-en-2-one Substances 0.000 claims 1
- GBKGJMYPQZODMI-SNAWJCMRSA-N (e)-4-(furan-2-yl)but-3-en-2-one Chemical compound CC(=O)\C=C\C1=CC=CO1 GBKGJMYPQZODMI-SNAWJCMRSA-N 0.000 claims 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims 1
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 16
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 6
- 239000013530 defoamer Substances 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- KQGFKPKZUOFZSV-UHFFFAOYSA-N furan-2-carbaldehyde;propan-2-one Chemical compound CC(C)=O.O=CC1=CC=CO1 KQGFKPKZUOFZSV-UHFFFAOYSA-N 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
-
- 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
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a low-viscosity/high-strength/low-shrinkage epoxy composite grouting material and a preparation method thereof, wherein polyether polyol and toluene diisocyanate are used for preparing polyurethane prepolymer at 70 ℃ by weight, then epoxy resin is added to obtain grouting liquid, and a composite curing agent, a composite diluent, an accelerator, a defoaming agent and the like are added to obtain the final grouting material after curing. The polyurethane and the epoxy resin can effectively form a network interpenetrating structure, enhance the mechanical property of materials, have the advantages of low viscosity, high strength, quick solidification and low shrinkage, have the viscosity below 200mpa.s, have the strength far exceeding the standard strength of the grouting industry, have the initial setting time within 90min and the shrinkage within 1 percent, and therefore, the invention well solves the problem that most grouting materials cannot have the advantages at the same time and has very good application prospect in practical application.
Description
Technical Field
The invention relates to the field of chemical grouting, in particular to an epoxy composite grouting material with low viscosity, high strength and low shrinkage.
Background
With the rapid development of the economy in China, the demands of the infrastructures are increasing, and many planned and under-built important infrastructures are beginning to be deployed to poor geological areas such as soft foundations, rich groundwater, mud-containing broken belts and the like. Under the influence of engineering geology and hydrogeology conditions, the problems of large deformation of soft foundations, water and mud gushing in tunnel engineering, special earthwork Cheng Shiwen and other geotechnical engineering diseases are increasingly prominent, and the engineering safety is seriously influenced. In order to solve such engineering problems, grouting materials are required to have the advantages of low viscosity, high strength, quick solidification and the like. At present, cement grouting materials are still the most widely used in practical grouting engineering, but the traditional cement grouting materials have the defects of poor permeability and incapability of well performing grouting repair due to large particles and poor fluidity, and the grouting materials are required to be quickly solidified due to the influence of environmental factors so as to achieve the effects of seepage prevention and water shutoff. However, most chemical grouting materials cannot simultaneously have various advantages such as low viscosity, high strength, fast curing, low shrinkage and the like, and generally, the low viscosity, the high strength and the fast curing are contradictory, and are difficult to simultaneously meet, when a system has more diluent, the low viscosity can be obtained, and the strength and the curing time of the materials can be influenced to a certain extent, and vice versa. The single epoxy resin has a certain shrinkage rate, and the self-made polyurethane modified epoxy resin is used in the patent, so that the shrinkage rate can be effectively improved. Therefore, the patent develops the low-shrinkage grouting material with the advantages of low viscosity, high strength, quick solidification and the like aiming at special use environments.
An Interpenetrating Polymer Network (IPN) is a novel polymer blend consisting of two or more polymers in network form. On the premise that two polymers have good compatibility, due to the strong polarity of rigid molecular segments, the two polymers are combined together through physical entanglement, so that polymers with different functions form a stable combination, and the polymers have synergistic effect on performance, so that the mechanical performance of the material can be well improved, and a covalent bond (chemical crosslinking) point occasionally exists between two different types of chains of the grafted IPN. The properties of the IPN material formed from the high molecular polymer can be adjusted by selecting raw materials, changing the proportions of the components and improving the processing technique. At present, the IPN structure is widely applied to various industries, but few reports in the grouting field exist, the IPN structure can be effectively formed by adopting polyurethane and epoxy resin, and various properties of the material are obviously enhanced.
Disclosure of Invention
Most epoxy resins have the disadvantages of high shrinkage, high viscosity, slow curing, high brittleness and the like, meanwhile, polyurethane slurry has the problems of large internal reaction heat release, poor heat conduction, performance after curing and the like when being used as a single material in the grouting field, and general grouting materials are difficult to have the advantages of low viscosity, high strength, fast curing and low shrinkage at the same time, and the invention provides the epoxy grouting material with low viscosity/high strength/fast curing/low shrinkage.
The technical scheme adopted by the invention for realizing the purpose is as follows: the epoxy grouting material with low viscosity, high strength, fast curing and low shrinkage has polyurethane and epoxy resin in certain weight ratio, and has different performance and determined optimal ratio
The polyurethane is self-made isocyanate-terminated polyurethane, and the mass ratio of the-OH/-NCO is 1:1.5-1:2.
Further polyurethanes were yellowish in liquid viscosity between 700 and 900 mpa.s.
The epoxy value of the further epoxy resin is between 30 and 51.
The further curing agent is a self-prepared composite curing agent, comprising T31, 593 and diethylenetriamine, and can provide certain strength and maintain certain toughness.
The further diluent is a compound diluent of acetone-furfural, and the two can be subjected to chemical reaction to generate furan resin, so that a denser crosslinked network is formed.
The invention also provides a preparation method of the epoxy grouting material with low viscosity, high strength, quick curing and low shrinkage, which comprises the following steps:
1. weighing a certain amount of polyether polyol, and vacuum drying at 120 ℃ for 2 hours, wherein the vacuum degree is 0.09-0.1MPa.
2. Transferring the dried polyether polyol into a three-neck flask with a condenser pipe, adding isocyanate according to a certain proportion, and reacting for 3 hours under the conditions of mechanical stirring and 70 ℃ to obtain the polyurethane prepolymer.
3. Mixing the polyurethane prepolymer obtained in the last step with epoxy resin according to a preset proportion, adding a catalyst, and reacting for 3 hours at 70 ℃ to finally obtain the polyurethane-epoxy IPN emulsion.
4. Adding the mixed emulsion obtained in the last step into a furfural solution and a defoaming agent to serve as a component A, taking a T31/593/diethylenetriamine curing agent, acetone and DMP-30 as a component B, and uniformly mixing the two components A, B to obtain the final grouting material, and curing at room temperature for 7d to form.
The further curing agent was 40% of EP, furfural was 20% of EP, acetone was 15% of EP, and DMP-30 was 2% of EP.
The invention has the beneficial effects that: the invention adopts polyurethane and epoxy resin as resin matrix to prepare the polymer grouting material. On the basis of retaining the excellent comprehensive performance of the epoxy resin slurry, the purposes of reducing the shrinkage and the material cost and improving the mechanical and thermal properties are achieved through the IPN structure synergistic modification, the bottleneck of single polyurethane and epoxy resin serving as the slurry performance is broken through, and a new idea is provided for chemical slurry modification. In order to solve the problems that the slurry is difficult to simultaneously have low viscosity, high strength, quick solidification and low shrinkage, the composite curing agent and the composite diluent are automatically prepared, and the problem can be obviously solved. The grouting material has various performances meeting national standards, and has good application prospects in engineering.
Drawings
The drawings of the present invention are described as follows:
FIG. 1 is an infrared view of a polyurethane/epoxy IPN emulsion of the present invention
FIG. 2 is an AFM image of the IPN structure of example 3 of the present invention
Detailed Description
The invention is described in further detail below with reference to examples and figures:
example 1
(1) Preparation of polyurethane prepolymer: 100g of hydrophilic polyether polyol is weighed, dried in vacuum for 2 hours at 120 ℃, the dried polyether polyol is cooled to room temperature, then 13.05g of TDI is added into a three-necked flask, the mixture is stirred uniformly, the temperature is raised to 70 ℃, and the reaction is carried out for 2 hours under the condition of mechanical stirring, so as to obtain the PU prepolymer.
Example 2
(1) Preparation of polyurethane-epoxy resin emulsion: 1017.45g of epoxy resin was weighed and blended with the PU prepolymer obtained in example 1, and 5.65g of a catalyst (dibutyltin dilaurate) was added, and reacted again in a three-necked flask at 70℃for 3 hours to obtain a PU-EP IPN emulsion.
(2) Weighing 203.49g of furfural, 1g of defoamer and the PU-EP IPN emulsion obtained in the step (1), mixing uniformly, and obtaining a component A; 203.49g of T31, 101.75g of 593, 101.75g of diethylenetriamine as a curing agent, 152.62g of acetone and 20.34g of DMP-30 (2, 4, 6-tris (dimethylaminomethyl) phenol) are weighed, and are uniformly mixed and stirred to obtain a component B; and finally, uniformly mixing the A, B components, pouring the mixture into a mold, and curing the mixture for 7d at room temperature or curing the mixture for 2h at 60 ℃.
Comparative example 1
(1) 100g of epoxy resin was weighed.
(2) Weighing 20g of furfural, 0.1g of defoamer and the PU-EP IPN emulsion obtained in the step (1), mixing uniformly, and obtaining a component A; 20g of T31, 10g of 593, 10g of diethylenetriamine as a curing agent, 15g of acetone and 2g of DMP-30 (2, 4, 6-tris (dimethylaminomethyl) phenol) are weighed, and are uniformly mixed and stirred to obtain a component B; and finally, uniformly mixing the A, B components, pouring the mixture into a mold, and curing the mixture for 7d at room temperature or curing the mixture for 2h at 60 ℃.
Example 3
(1) Preparation of polyurethane-epoxy resin emulsion: 452.2g of epoxy resin was weighed out and blended with the PU prepolymer obtained in example 1, and 2.82g of catalyst (dibutyltin dilaurate) was added, and reacted again in a three-necked flask at 70℃for 3 hours to obtain a PU-EP IPN emulsion.
(2) Weighing 90.44g of furfural, 0.45g of defoamer and the PU-EP IPN emulsion obtained in the step (1), mixing uniformly, and obtaining a component A; 90.44g of T31, 45.2g of 593, 45.2g of diethylenetriamine as a curing agent, 67.83g of acetone and 9.04g of DMP-30 (2, 4, 6-tris (dimethylaminomethyl) phenol) are weighed, and are uniformly mixed and stirred to obtain a component B; and finally, uniformly mixing the A, B components, pouring the mixture into a mold, and curing the mixture for 7d at room temperature or curing the mixture for 2h at 60 ℃.
Example 4
(1) Preparation of polyurethane-epoxy resin emulsion: 263.78g of epoxy resin was weighed out and blended with the PU prepolymer obtained in example 1, and 1.88g of a catalyst (dibutyltin dilaurate) was added, and reacted again in a three-necked flask at 70℃for 3 hours to obtain a PU-EP IPN emulsion.
(2) Weighing 52.76g of furfural, 0.26g of defoamer and the PU-EP IPN emulsion obtained in the step (1), mixing uniformly, and obtaining a component A; 52.76g of T31, 26.38g of 593, 26.38g of diethylenetriamine as a curing agent, 39.57g of acetone and 5.28g of DMP-30 (2, 4, 6-tris (dimethylaminomethyl) phenol) are weighed, and the materials are uniformly mixed and stirred to obtain a component B; and finally, uniformly mixing the A, B components, pouring the mixture into a mold, and curing the mixture for 7d at room temperature or curing the mixture for 2h at 60 ℃.
Example 5
(1) Preparation of polyurethane-epoxy resin emulsion: 169.58g of epoxy resin was weighed out and blended with the PU prepolymer obtained in example 1, and 1.41g of a catalyst (dibutyltin dilaurate) was added, and reacted again in a three-necked flask at 70℃for 3 hours to obtain a PU-EP IPN emulsion.
(2) Weighing 33.92g of furfural, 1g of defoamer and the PU-EP IPN emulsion obtained in the step (1), mixing uniformly, and obtaining a component A; 33.92g of T31, 16.96g of 593, 16.96g of diethylenetriamine as a curing agent, 25.44g of acetone and 3.39g of DMP-30 (2, 4, 6-tris (dimethylaminomethyl) phenol) are weighed, and are uniformly mixed and stirred to obtain a component B; and finally, uniformly mixing the A, B components, pouring the mixture into a mold, and curing the mixture for 7d at room temperature or curing the mixture for 2h at 60 ℃.
Table 1 comparison of the properties of the respective examples and comparative examples
The test results show that: as can be seen from FIG. 1, the ratio of polyurethane to epoxy is 0-10 at 1730cm -1 Is free from the characteristic peak of polyurethane, and 1730cm with the addition of polyurethane -1 Gradually appear with a peak of 2279cm -1 The characteristic peak of-NCO at the position also gradually appears, and the peak is 910cm -1 The peak of the epoxy group is slightly changed, and the polyurethane prepolymer is further generated due to the partial ring opening of the epoxy group and the reaction of the epoxy group with-NCO.
The obvious IPN structure can be seen in FIG. 2, wherein the brighter part of polyurethane and the darker part of polyurethane are epoxy resin, and the bright parts are alternately arranged, so that the polyurethane and the epoxy have good compatibility, and a denser IPN crosslinked network structure is formed.
From Table one can see that the tensile, compressive, impact strength of the slurry increases and then decreases with the polyurethane content. When the epoxy resin content is 80% and the polyurethane is 20% (the embodiment 3 of the patent), the tensile strength, the compression strength and the impact strength reach the maximum, the tensile strength reaches 110Mpa, the impact strength is 35Mpa, the strength is obviously improved compared with pure epoxy, which shows that as the epoxy content is increased, the crosslinking density of the graft interpenetrating network in the composite material is increased, when the composite material is subjected to tensile stress, the IPN structure is favorable for stress transmission, the effective number of stress concentration chains is improved, and the chain segment movement makes the two-phase interface more easily form locking ring, interpenetration and entanglement effects, so that the mixing capacity of two components is 'forced', the interpenetrating degree of two polymer matrix networks is further improved, and a 'synergistic effect' is generated. However, when the epoxy content is further increased, the properties of the material start to decrease because when the epoxy content is excessively large, the epoxy self-aggregates and phase separates from the polyurethane, and the domain size between the two phases becomes large, resulting in the degradation of the properties of the composite material. The bonding strength under the dry condition is far higher than the body strength of the concrete, and the bonding strength with the concrete under the wet condition can reach 3.2Mpa, thereby conforming to the standard. Meanwhile, the viscosity of the material is less than 200mpa.s, the standard of the super-permeability grouting material is met, and the material can effectively permeate into micro cracks. The initial setting time is about 90min (adjustable), and can meet various use environments. The table shows that the polyurethane can effectively reduce the shrinkage of the grouting material, has the shrinkage within 1 percent and very small shrinkage, and can better play a role in preventing seepage and plugging in the practical application process.
The present invention is not limited to the contents of the embodiments. Various changes and modifications within the technical scope of the present invention will be apparent to those skilled in the art, and any changes and modifications are intended to be within the scope of the present invention.
Claims (8)
1. The low-viscosity high-strength low-shrinkage epoxy composite grouting material is characterized by comprising 40-10 parts of polyurethane and 60-90 parts of epoxy resin by weight; the polyurethane is a prepolymer synthesized from polyether polyol and isocyanate by a native polymerization method; the epoxy value of the epoxy resin is between 0.30 and 0.51; the two resins can form a remarkable interpenetrating polymer network structure (IPN) to enhance the mechanical property of the material.
2. The isocyanate according to claim 1 comprises any one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI).
3. The epoxy composite grouting material with low viscosity, high strength and low shrinkage according to claim 1, wherein the polyurethane contains a small amount of reactive-NCO groups, the content of the reactive-NCO groups is 4% -7%, the epoxy composite grouting material has a micro-expansion effect, the shrinkage rate of the cured high polymer material is remarkably reduced, and the curing is mainly carried out by cohesive force and adhesion force generated by polar groups in molecules.
4. The low-viscosity/high-strength/low-shrinkage epoxy composite grouting material according to claim 1, wherein the curing agent used by the material is a composite curing agent and comprises any three of 651, TV6034, T31, T33, 593, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and ethylenediamine, the composite curing agent has lower viscosity, the amine value is 320-360mg KOH/g in the range of 300-800mpa.s, the active hydrogen equivalent is 180, and the grouting material can be rapidly cured at normal temperature and has excellent mechanical properties; therefore, the composite curing agent is adopted, the performances of the three curing agents can be combined, and finally the grouting material with excellent comprehensive performances is obtained.
5. The low viscosity/high strength/low shrinkage epoxy composite grouting material according to claim 1, wherein the diluent used in the material is a furfural-acetone composite diluent, and the mass ratio of furfural to acetone comprises 3: 1. 2: 1. 1.5: 1. 1:1, when furfural and acetone are mixed, the two react to generate furan, so that the mechanical property of the material can be further enhanced.
6. The low viscosity/high strength/cure fast/low shrinkage epoxy grouting material according to claim 1, wherein the polyurethane resin is between 10% and 40% of the system and the epoxy resin is between 60% and 90% of the system.
7. The preparation method of the epoxy composite grouting material with low viscosity, high strength and low shrinkage is characterized by comprising the following steps:
s01, weighing polyether polyol and isocyanate according to a proportion, and reacting for 3 hours at 70 ℃ to obtain the polyurethane prepolymer.
S02, weighing epoxy resin and polyurethane prepolymer according to a proportion, carrying out blending reaction, adding 0.5% of catalyst, and reacting for 3 hours at 70 ℃ to obtain the PU-EP IPN emulsion.
S03, uniformly mixing a curing agent, acetone, an accelerator and a defoaming agent according to a certain mass ratio to obtain a curing system.
S04, mixing the grouting material and the curing system, uniformly stirring, pouring into a mold, and curing at room temperature or heating to obtain the final grouting material.
8. The method for preparing the low viscosity/high strength/low shrinkage epoxy composite grouting material according to claim 7, wherein the curing process is 7d at room temperature or 2h at 60 ℃.
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