CN112940219B - One-component environment-friendly polyurethane grouting resin reacting in water and production method thereof - Google Patents

One-component environment-friendly polyurethane grouting resin reacting in water and production method thereof Download PDF

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CN112940219B
CN112940219B CN202110239692.5A CN202110239692A CN112940219B CN 112940219 B CN112940219 B CN 112940219B CN 202110239692 A CN202110239692 A CN 202110239692A CN 112940219 B CN112940219 B CN 112940219B
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water
resin
grouting
reaction kettle
grouting resin
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CN112940219A (en
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岳瑞峰
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Suzhou Pien High Tech Material Technology Co ltd
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/4266Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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Abstract

The invention relates to a single-component environment-friendly polyurethane grouting resin reacting in water and a production method thereof. The technical scheme is that the composite material is prepared by taking a non-TDI polymer as a main resin component and assisting with an environment-friendly high-boiling point diluent, a non-PAEs plasticizer, an organic silicon foam stabilizer, a balanced foaming gel catalyst and a flame retardant. The invention provides a water-reaction single-component environment-friendly polyurethane grouting resin material which does not contain TDI free monomers and PAEs plasticizers and can be used for common cargo transportation. In the grouting construction engineering, a catalyst can be reasonably added according to needs, the foaming speed is adjusted, and the construction is flexible and simple; the hydrophobic closed-cell foam structure formed by curing has high compressive strength, has excellent sealing effect on the cracks of the building structure, and has long-acting plugging effect on the water body leakage in the cracks.

Description

Water-reactive single-component environment-friendly polyurethane grouting resin and production method thereof
Technical Field
The invention relates to the technical field of grouting resin, in particular to a single-component environment-friendly polyurethane grouting resin reacting when meeting water and a production method thereof.
Background
The grouting water plugging is to utilize high pressure mechanical power to inject chemical grouting material into the cracks of the building structure, when the grout meets the water in the cracks, the water can be rapidly dispersed, emulsified, expanded and solidified, the solidified foam structure fills the cracks in the building structure, and water flow is completely plugged outside the building structure, so as to achieve the purpose of water stopping and plugging. The solidified foam can play a role in three aspects of chemical linking, high-strength anchor bolts, high-pressure filling and the like on cracks.
The polyurethane grouting resin can be divided into two-component grouting resin and one-component grouting resin. The bi-component grouting resin is also called A, B grouting resin in popular terms, wherein the component A is prepared by taking a hydroxyl-terminated polymer as a main material and assisting with a foaming agent, a catalyst, a flame retardant, a diluting agent and other various auxiliary agents; while the B component is generally simpler and is generally a polyisocyanate. When in use, the A, B components are mixed by special equipment, injected to a construction operation surface under high pressure and foamed on site to form a solid foam structure layer, thereby playing a role of consolidation and water shutoff on a building structure. The bi-component grouting resin is a current relatively universal high-molecular grouting material, and A, B components are produced respectively from the perspective of material preparation, so that the complexity of product production is increased; from the construction angle, to slip casting construction equipment requirement higher, need adopt biliquid material syringe pump and injection gun, equipment is very easily blockked up, and after the construction was accomplished, equipment washs comparatively complicacy. The single-component grouting resin is a single-component resin material formed by taking polyisocyanate resin as a main material and assisting other auxiliary agents. When in use, the grouting resin is conveyed to a construction working face through a high-pressure injection gun, and after the resin is contacted with water in the working face, the resin can be quickly emulsified, foamed and solidified to form a solid foam structure layer, so that the effect of solidifying and plugging water is achieved on a building structure. Compared with the two-component grouting resin, the single-component grouting resin is simpler and easier to implement from the production angle, the construction angle and the requirement on construction equipment.
Disclosure of Invention
In view of the problems in the prior art, the invention discloses a water-reactive single-component environment-friendly polyurethane grouting resin which adopts the technical scheme that a non-TDI polymer is used as a main resin component, and an environment-friendly high-boiling point diluent, a non-PAEs plasticizer, an organic silicon foam stabilizer, a balanced foaming gel catalyst and a flame retardant are used as auxiliary materials to prepare the water-reactive single-component environment-friendly polyurethane grouting resin.
In a preferred embodiment of the present invention, the non-TDI polymer is an-NCO terminated polyurethane prepolymer formed by polymerization of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) monomer and oligomer polyol, and the diphenylmethane diisocyanate (MDI) is produced by petawa
Figure GDA0003696324480000012
Figure GDA0003696324480000013
The isophorone diisocyanate (IPDI) is produced by adopting Coresian
Figure GDA0003696324480000011
I, the oligomer polyol is polycaprolactone diol (PCL), and the polycaprolactone diol (PCL) is selected from one of PLACCEL 210N and PLACCEL 205H which are produced by DAICEL in Japan and have a molecular weight of 500-2000.
In a preferred embodiment of the present invention, the non-TDI polymer is a homopolymer formed from a polyisocyanate monomer, and is one of polymethylene polyphenyl polyisocyanate (PAPI) and hexamethylene diisocyanate Trimer (HDI-Trimer), and the polymethylene polyphenyl polyisocyanate (PAPI) is PM200 produced by takawawa and PM200 produced by kojishi
Figure GDA0003696324480000021
44V40L, wherein the hexamethylene diisocyanate Trimer (HDI-Trimer) is produced by Kostek
Figure GDA0003696324480000022
N 3300。
As a preferable scheme of the invention, the environment-friendly high-boiling point diluent is selected from one of mixed dibasic acid ester (DBE) and propylene carbonate.
In a preferred embodiment of the present invention, the non-PAEs plasticizer is one selected from tributyl citrate and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) produced by eastman.
In a preferable embodiment of the present invention, Niax L-1542 and Niax L-1507 are selected as the silicone foam stabilizer.
As a preferable scheme of the invention, the balanced foaming gel catalyst is one of N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine and 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine.
A production method of a water-reactive single-component environment-friendly polyurethane grouting resin is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: raw material treatment: dehydrating polycaprolactone diol (PCL) for 2 hours in a vacuum drying oven at 90 ℃ and under the vacuum degree of 0.1MPa before use; soaking dibasic acid ester (DBE), propylene carbonate, tributyl citrate, and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) in molecular sieve; diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) are directly used;
step two: preparing a polyurethane prepolymer: putting polycaprolactone diol (PCL) into a reaction kettle with a thermometer, a stirring device, a condensation reflux pipe, a constant pressure dropping funnel and an N2 aerating device according to the proportion of the formula, and raising the temperature of the reaction kettle to 80 ℃; at the temperature, isophorone diisocyanate (IPDI) is added into the reaction kettle dropwise and reacts for 3 hours at the temperature; adding diphenylmethane diisocyanate (MDI) into the reaction kettle to react for 1 hour to finally obtain a polyurethane prepolymer;
step three: reducing the temperature of the reaction kettle to 60 ℃, and adding an environment-friendly high-boiling point diluent to dilute the prepolymer to obtain a low-viscosity prepolymer solution;
step four: reducing the temperature of the reaction kettle to 50 ℃, then adding a non-TDI polymer, a non-PAEs plasticizer and an organic silicon foam stabilizer into the reaction kettle, uniformly mixing to obtain a grouting resin main liquid for later use, and testing the viscosity of the grouting resin;
step five: adding a balanced foaming gel catalyst into the grouting at room temperature and uniformly mixing;
step six: then adding tap water accounting for 10% of the weight of the main grouting liquid, and recording the emulsifying time, the foam rising time and the final foam curing time;
step seven: the cured foam was used to test the expansion coefficient and foam strength.
The invention has the beneficial effects that: the invention provides a water-reaction single-component environment-friendly polyurethane grouting resin material which does not contain TDI free monomers and PAEs plasticizers and can be used for common cargo transportation. In the grouting construction engineering, a catalyst can be reasonably added according to needs, the foaming speed is adjusted, and the construction is flexible and simple; the hydrophobic closed-cell foam structure formed by curing has high compressive strength, has excellent sealing effect on the cracks of the building structure, and has long-acting plugging effect on the water body leakage in the cracks.
Detailed Description
Example 1
The invention relates to a water-reactive single-component environment-friendly polyurethane grouting resin which is prepared by taking a non-TDI polymer as a main resin component and assisting in preparation of an environment-friendly high-boiling point diluent, a non-PAEs plasticizer, an organic silicon foam stabilizer, a balanced foaming gel catalyst and a flame retardant.
The non-TDI polymer is an-NCO-terminated polyurethane prepolymer formed by the polymerization reaction of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) monomer and oligomer polyol, and the diphenylmethane diisocyanate (MDI) is produced by Nitidowawa
Figure GDA0003696324480000035
The isophorone diisocyanate (IPDI) is produced by adopting Coresian
Figure GDA0003696324480000031
I, the oligomer polyol is polycaprolactone diol (PCL), and the polycaprolactone diol (PCL) is selected from one of PLACCEL 210N and PLACCEL 205H which are produced by DAICEL in Japan and have a molecular weight of 500-2000.
The non-TDI polymer is a homopolymer formed by polyisocyanate monomers, one of polymethylene polyphenyl polyisocyanate (PAPI) and hexamethylene diisocyanate Trimer (HDI-Trimer) is selected, and the polymethylene polyphenyl polyisocyanate (PAPI) is selected from PM200 produced by Vanda Wawawa and PM200 produced by Corcisco
Figure GDA0003696324480000032
44V40L, wherein the hexamethylene diisocyanate Trimer (HDI-Trimer) is produced by Colesine
Figure GDA0003696324480000033
N3300。
The non-TDI polymer is poly HDI biuret and is prepared by adopting Corsia
Figure GDA0003696324480000034
N 3400。
The environment-friendly high-boiling point diluent is one of mixed dibasic acid ester (DBE) and propylene carbonate.
The non-PAEs plasticizer is one of tributyl citrate and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) produced by Isemann.
The organosilicon foam stabilizer is selected from Niax L-1542 and Niax L-1507.
The balance type foaming gel catalyst is one of N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine and 1,3, 5-tri (dimethylaminopropyl) hexahydrotriazine.
A production method of a water-reactive single-component environment-friendly polyurethane grouting resin is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: raw material treatment: before use, PLACCEL 210N is dehydrated for 2 hours in a vacuum drying oven at the temperature of 90 ℃ and the vacuum degree of 0.1 MPa; soaking dibasic acid ester (DBE), propylene carbonate, tributyl citrate, and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) in molecular sieve; diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) are directly used;
step two: preparing a polyurethane prepolymer: adding PLACCEL 210N into a reaction kettle with a thermometer, a stirring device, a condensation reflux pipe, a constant pressure dropping funnel and a nitrogen aeration device according to a proportion, and raising the temperature of the reaction kettle to 80 ℃; at the temperature, isophorone diisocyanate (IPDI) is added into the reaction kettle dropwise, and the reaction lasts for 3 hours at the temperature; adding diphenylmethane diisocyanate (MDI) into the reaction kettle to react for 1 hour to finally obtain a polyurethane prepolymer;
step three: reducing the temperature of the reaction kettle to 60 ℃, and adding propylene carbonate to dilute the prepolymer to obtain a low-viscosity prepolymer solution;
step four: the temperature of the reaction kettle is reduced to 50 ℃, and then
Figure GDA0003696324480000041
Adding 44V40L, tributyl citrate, Niax L-1542 and Niax L-1507 into a reaction kettle, uniformly mixing to obtain a grouting resin main liquid for later use, and testing the viscosity of the grouting resin;
step five: adding N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine into the grouting at room temperature and uniformly mixing;
step six: then adding tap water accounting for 10% of the weight of the main grouting liquid, and recording the emulsifying time, the foam rising time and the final foam curing time;
step seven: the cured foam was used to test the expansion coefficient and foam strength.
Example 2
A production method of a water-reactive single-component environment-friendly polyurethane grouting resin is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: raw material treatment: before use, PLACCEL 210N is dehydrated for 2 hours in a vacuum drying oven at the temperature of 90 ℃ and the vacuum degree of 0.1 MPa; soaking mixed dibasic acid ester (DBE), propylene carbonate, tributyl citrate, and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) in molecular sieve; diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) are directly used;
step two: preparing a polyurethane prepolymer: according to the formula proportion, PLACCEL 210N is put into a reaction kettle with a thermometer, a stirring device, a condensation reflux pipe, a constant pressure dropping funnel and a nitrogen aeration device, and the temperature of the reaction kettle is raised to 80 ℃; at the temperature, isophorone diisocyanate (IPDI) is added into the reaction kettle dropwise and reacts for 3 hours at the temperature; then adding diphenylmethane diisocyanate (MDI) into the reaction kettle to react for 1 hour to finally obtain a polyurethane prepolymer;
step three: reducing the temperature of the reaction kettle to 60 ℃, and adding propylene carbonate to dilute the prepolymer to obtain a low-viscosity prepolymer solution;
step four: the temperature of the reaction kettle is reduced to 50 ℃, and then the PM200,
Figure GDA0003696324480000051
ultra N3300, 2,2, 4-trisAdding methyl-1, 3-pentanediol diisobutyrate (TXIB), Niax L-1542 and Niax L-1507 into a reaction kettle, uniformly mixing to obtain a grouting resin main liquid for later use, and testing the viscosity of the grouting resin;
step five: adding N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine into the grouting at room temperature and uniformly mixing;
step six: then adding tap water with 10% of the weight of the main grouting liquid, and recording the emulsifying time, the foam rising time and the final foam curing time;
step seven: the cured foam was used to test the expansion coefficient and foam strength.
Example 3
A production method of a water-reactive single-component environment-friendly polyurethane grouting resin is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: raw material treatment: dewatering PLACCEL 205H in a vacuum drying oven at 90 deg.C and 0.1MPa for 2 hr before use; soaking dibasic acid ester (DBE), propylene carbonate, tributyl citrate, and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) in molecular sieve; diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) are directly used;
step two: preparing a polyurethane prepolymer: according to the formula proportion, PLACCEL 205H is put into a reaction kettle with a thermometer, a stirring device, a condensation reflux pipe, a constant pressure dropping funnel and a nitrogen aeration device, and the temperature of the reaction kettle is raised to 80 ℃; at the temperature, isophorone diisocyanate (IPDI) is added into the reaction kettle dropwise and reacts for 3 hours at the temperature; adding diphenylmethane diisocyanate (MDI) into the reaction kettle to react for 1 hour to finally obtain a polyurethane prepolymer;
step three: cooling the temperature of the reaction kettle to 60 ℃, and adding DBE to dilute the prepolymer to obtain a low-viscosity prepolymer solution;
step four: the temperature of the reaction kettle is reduced to 50 ℃, and then the PM200,
Figure GDA0003696324480000052
ultra N3300, 2,2, 4-trisAdding methyl-1, 3-pentanediol diisobutyrate (TXIB), Niax L-1542 and Niax L-1507 into a reaction kettle, uniformly mixing to obtain a grouting resin main liquid for later use, and testing the viscosity of the grouting resin;
step five: adding 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine into the grouting at room temperature and uniformly mixing;
step six: then adding tap water with 10% of the weight of the main grouting liquid, and recording the emulsifying time, the foam rising time and the final foam curing time;
step seven: the cured foam was used to test the expansion coefficient and foam strength.
Example 4
A production method of a water-reactive single-component environment-friendly polyurethane grouting resin is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: raw material treatment: before use, PLACCEL 205H is dehydrated for 2 hours in a vacuum drying oven at the temperature of 90 ℃ and the vacuum degree of 0.1 MPa; soaking mixed dibasic acid ester (DBE), propylene carbonate, tributyl citrate, and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) in molecular sieve; diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) are directly used;
step two: preparing a polyurethane prepolymer: according to the formula proportion, PLACCEL 205H is put into a reaction kettle with a thermometer, a stirring device, a condensation reflux pipe, a constant pressure dropping funnel and a nitrogen aeration device, and the temperature of the reaction kettle is raised to 80 ℃; at the temperature, isophorone diisocyanate (IPDI) is added into the reaction kettle dropwise and reacts for 3 hours at the temperature; adding diphenylmethane diisocyanate (MDI) into the reaction kettle to react for 1 hour to finally obtain a polyurethane prepolymer;
step three: cooling the temperature of the reaction kettle to 60 ℃, and adding DBE to dilute the prepolymer to obtain a low-viscosity prepolymer solution;
step four: the temperature of the reaction kettle is reduced to 50 ℃, and then the PM200,
Figure GDA0003696324480000061
ultra N3300, 2,2, 4-trisAdding methyl-1, 3-pentanediol diisobutyrate (TXIB), Niax L-1542 and Niax L-1507 into a reaction kettle, uniformly mixing to obtain a grouting resin main liquid for later use, and testing the viscosity of the grouting resin;
step five: adding 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine into the grouting at room temperature and uniformly mixing;
step six: then adding tap water accounting for 10% of the weight of the main grouting liquid, and recording the emulsifying time, the foam rising time and the final foam curing time;
step seven: the cured foam was used to test the expansion coefficient and foam strength.
Table of the grouting resin raw material ingredients of the examples:
Figure GDA0003696324480000062
Figure GDA0003696324480000071
grouting resin test results for each example:
Figure GDA0003696324480000072
parts not described in detail herein are prior art.
Although the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the above embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art without departing from the scope of the present invention.

Claims (8)

1. A water-reactive single-component polyurethane grouting resin is characterized in that a non-TDI polymer is used as a main resin component, and comprises a non-TDI polycaprolactone type polyurethane prepolymer and a non-TDI polyisocyanate homopolymer, and the grouting resin is prepared by high-boiling point diluent, a non-PAEs plasticizer, an organic silicon foam stabilizer, a balanced foaming gel catalyst and a flame retardant in an auxiliary manner; the non-TDI series polycaprolactone type polyurethane prepolymer is an-NCO end-capped polyurethane prepolymer formed by the polymerization reaction of diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) monomers and oligomer polyol; the oligomer polyol is polycaprolactone diol (PCL); the non-TDI polyisocyanate homopolymer is a homopolymer formed by non-TDI polyisocyanate monomers and comprises polymethylene polyphenyl polyisocyanate (PAPI) and a Trimer of hexamethylene diisocyanate (HDI-Trimer).
2. The water-reactive single-component polyurethane grouting resin as claimed in claim 1, wherein: the diphenylmethane diisocyanate (MDI) is produced by selecting fumitory
Figure FDA0003669612530000011
MDI-100, the isophorone diisocyanate (IPDI) is produced by adopting Coresi
Figure FDA0003669612530000012
I, selecting one of PLACCEL 210N and PLACCEL 205H produced by Japanese DAICEL with the molecular weight of 500-2000 from the polycaprolactone diol (PCL).
3. The water-reactive single-component polyurethane grouting resin as claimed in claim 1, wherein: the polymethylene polyphenyl polyisocyanate (PAPI) is produced by PM200 produced by Wanhua nicotinate and Corcission
Figure FDA0003669612530000013
44V40L, wherein the hexamethylene diisocyanate Trimer (HDI-Trimer) is produced by Kostek
Figure FDA0003669612530000014
N 3300。
4. The water-reactive single-component polyurethane grouting resin as claimed in claim 1, wherein: the high boiling point diluent is selected from one of mixed dibasic acid ester (DBE) and propylene carbonate.
5. The water-reactive single-component polyurethane grouting resin as claimed in claim 1, wherein: the non-PAEs plasticizer is one of tributyl citrate and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) produced by Isemann.
6. The water-reactive single-component polyurethane grouting resin as claimed in claim 1, wherein: the organosilicon foam stabilizer is selected from Niax L-1542 and Niax L-1507.
7. The water-reactive single-component polyurethane grouting resin as claimed in claim 1, wherein the water-reactive single-component polyurethane grouting resin comprises: the balance type foaming gel catalyst is one of N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine and 1,3, 5-tri (dimethylaminopropyl) hexahydrotriazine.
8. A production method of a water-reactive single-component polyurethane grouting resin is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: raw material treatment: dehydrating polycaprolactone diol (PCL) for 2 hours in a vacuum drying oven at 90 ℃ and under the vacuum degree of 0.1MPa before use; soaking dibasic acid ester (DBE), propylene carbonate, tributyl citrate, and 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) in molecular sieve; diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) are directly used;
step two: preparing a polyurethane prepolymer: putting polycaprolactone diol (PCL) into a reaction kettle with a thermometer, a stirring device, a condensation reflux pipe, a constant pressure dropping funnel and an N2 aeration device according to the formula proportion, and raising the temperature of the reaction kettle to 80 ℃; at the temperature, dropwise adding isophorone diisocyanate (IPDI) into a reaction kettle, and reacting for 3 hours at the temperature; then adding diphenylmethane diisocyanate (MDI) into the reaction kettle to react for 1 hour to finally obtain a polyurethane prepolymer;
step three: reducing the temperature of the reaction kettle to 60 ℃, and adding mixed dibasic acid ester (DBE) or propylene carbonate to dilute the prepolymer to obtain a low-viscosity prepolymer solution;
step four: the temperature of a reaction kettle is reduced to 50 ℃, then non-TDI polyisocyanate homopolymer polymethylene polyphenyl polyisocyanate (PAPI), hexamethylene diisocyanate Trimer (HDI-Trimer), tributyl citrate or 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate (TXIB) and an organic silicon foam stabilizer are added into the reaction kettle and mixed uniformly to obtain grouting resin main liquid for later use, and the viscosity of the grouting resin is tested;
step five: adding a balanced foaming gel catalyst into the grouting at room temperature and uniformly mixing;
step six: then adding tap water accounting for 10% of the weight of the main grouting liquid, and recording the emulsifying time, the foam rising time and the final foam curing time;
step seven: the cured foam was used to test the expansion coefficient and foam strength.
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