Bi-component polyurethane grouting material and construction method and catalyst thereof

Abstract

The invention discloses a two-component polyurethane grouting material, a construction method thereof and a catalyst. The two-component polyurethane grouting material comprises a first component and a second component, the first component comprises silane modified nano silicate, a thermosetting phenolic aldehyde emulsion, a thermosetting urea formaldehyde emulsion, a thermosetting acrylic emulsion, a composite catalyst and water; the composite catalyst is prepared by the following method: diisocyanate and polyol are used as reaction monomers, and the reaction monomers, dibutyltin dilaurate, p-toluenesulfonic acid and polyol amine are mixed and reacted to prepare the composite catalyst; the second component is prepared from polymethylene polyphenyl polyisocyanate, selective diisocyanate, hydroxylated castor oil and polyether polyol; during construction, the first component and the second component are mixed and grouted. The bi-component polyurethane grouting material disclosed by the invention has the characteristics of high strength, excellent flowing water adaptability, excellent durability, good environmental protection property, convenience and reliability in construction and the like, and is beneficial to construction under harsh working conditions such as flowing water.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building materials, in particular to a two-component polyurethane grouting material for repairing concrete structures, waterproofing and plugging, and a construction method thereof. The material is suitable for complex working conditions such as flowing water environment, damp base, crack grouting, etc., has the characteristics of fast curing, strong bonding, good diffusion, environmental friendliness, etc., and can be widely used in the fields of water conservancy projects, underground tunnels, bridges, industrial floors, etc. for structure reinforcement and waterproofing treatment. BACKGROUND

[0002] Chemical grouting technology is a key technical means for treating concrete structure leakage, reinforcing soft foundation and handling engineering defects, and is widely used in the fields of water conservancy and hydropower, underground engineering, tunnels and bridges, mining and building repair, etc. An ideal grouting material should have excellent groutability (low viscosity), fast curing characteristics, excellent mechanical strength, good environmental adaptability (such as water resistance, chemical resistance) and convenient construction. As an important branch of chemical grouting materials, polyurethane (PU) grouting material has been developed and applied for decades due to its adjustable curing rate, high expansion ratio and good adhesion. However, with the increasing complexity of engineering environment and the continuous improvement of environmental safety requirements, the limitations of traditional polyurethane grouting materials and their derivative technologies have gradually become apparent, mainly in the following aspects: (1) The contradiction between environmental safety and mechanical properties is prominent. Traditional oil-based polyurethane grouting materials usually rely on high volatile organic compounds (VOC) as solvents or plasticizers (such as phthalate plasticizers), which not only pollute the environment, but also pose a threat to the health of construction personnel, and can easily cause fire or poisoning accidents in closed spaces such as mines. Although water glass modified polyurethane (WG / PU) materials significantly improve the flame retardant and anti-static properties and reduce the reaction heat by introducing inorganic water glass components, their mechanical strength is still inferior to that of pure polyurethane systems. At the same time, practice shows that the WG / PU system has reaction imbalance and is prone to water outflow, efflorescence, foaming and other abnormal phenomena, resulting in a sharp drop in strength (which can be lower than 5 MPa), which cannot meet the reinforcement requirements.

[0003] (2) The adaptability to dynamic water environment and wet surface is poor. For the working conditions with seepage water or wetness, the performance of grouting materials faces severe challenges. Although the single-component polyurethane grouting material is simple to construct, its curing depends on the reaction with environmental moisture, which is easily washed away under dynamic water conditions, and the strength after curing is generally low, making it difficult to be used for structural reinforcement. The two-component system can form high-strength consolidated body under waterless conditions through formula design, but its hydrophobic property often leads to a significant decrease in the bonding strength with the wet surface. There are reports that the wet adhesion and low-temperature reactivity are improved to some extent by introducing phthalic anhydride polyester polyol and latent curing agent, but the fundamental problem of hydrophilic-hydrophobic interface compatibility has not been completely solved.

[0004] (3) The challenge of single function and long-term durability. The existing grouting materials have relatively single function, and it is difficult to balance "water blocking" and "reinforcement". Hydrophobic materials are good at water blocking but have low strength, and hydrophilic or high-strength materials are suitable for reinforcement but have no effect on dynamic water. In addition, the durability of the material is also a big test. Ordinary polyurethane materials are prone to aging and strength decay under long-term immersion, dry-wet cycle or chemical medium erosion. Although the introduction of water glass improves the fire resistance, its inherent brittleness and possible alkali-aggregate reaction risk limit its application range. Developing a material that can quickly plug and permanently reinforce with excellent long-term durability is an urgent need for engineering practice.

[0005] (4) The bottleneck of material compatibility and construction precision control. The compounding of organic polyurethane and inorganic materials is an effective way to improve the comprehensive performance, but the poor compatibility between the two is the core technical bottleneck. Generally, the compatibility between oily isocyanate and aqueous water glass is poor, and simple physical blending will lead to serious phase separation, resulting in mechanical properties of the composite material significantly lower than the theoretical value.

[0006] In summary, the grouting materials on the current market have different degrees of deficiencies in environmental protection, performance, adaptability and function. SUMMARY

[0007] The purpose of the present application is to overcome one or more of the deficiencies in the prior art and to provide an improved two-component polyurethane grouting material.

[0008] The present application also provides a construction method of the above-mentioned two-component polyurethane grouting material.

[0009] The present application also provides a catalyst for the above-mentioned two-component polyurethane grouting material.

[0010] To achieve the above-mentioned purpose, a technical solution adopted by the present application is: A two-component polyurethane grouting material, comprising a first component and a second component; The first component comprises silane modified nano-silicate, thermosetting phenolic emulsion, thermosetting urea-formaldehyde emulsion, thermosetting acrylic emulsion, composite catalyst and water; the composite catalyst is prepared by mixing and reacting diisocyanate, polyol as reaction monomers, di-n-butyltin dilaurate, p-toluene sulfonic acid and polyol amine. The second component comprises polymethylene polyphenyl polyisocyanate, optional diisocyanate, hydroxylated castor oil and polyether polyol.

[0011] In some embodiments of the present application, the silane modified nano-silicate is prepared by drying nano-silicate, activating surface hydroxyl groups, and then reacting with silane coupling agent.

[0012] Further, the nano-silicate comprises nano-sodium silicate and / or nano-kaolin.

[0013] Further, the average particle size of the nano-silicate is 50-100 nm.

[0014] Further, the surface hydroxyl groups of the nano-silicate are activated by a plasma treatment instrument.

[0015] Further, the grafting rate of the silane coupling agent in the silane modified nano-silicate is controlled to be 5%-8%.

[0016] According to some specific aspects of the present application, the method for preparing the silane modified nano-silicate comprises: The nano-silicate is dried at 100-130°C or vacuum dried (after drying, the system still contains trace amount of water, generally 0.1%-0.5%), and then the surface hydroxyl groups are activated in a plasma treatment instrument; the silane coupling agent (for example, silane coupling agent WD50, KH550, KH560, KH570, IPST, etc.) is reacted (the reaction temperature can be 20-30°C) under nitrogen protection, and the grafting rate is controlled to be 5%-8%, to obtain the silane modified nano-silicate.

[0017] In the present application, the nano-silicate is modified by silane, which can improve its dispersibility in the system, and on the other hand, through the control of nano-scale, it can realize deep penetration in the concrete cracks, and then improve the underwater bonding strength through ion exchange or chemical bonding.

[0018] Further, in the present application, the silane modified nano-silicate can provide enhanced skeleton structure and improve water resistance, especially, when it penetrates into the concrete cracks, it can increase the strength of the repair with its high strength, and at the same time, it can also participate in the reaction through the residual hydroxyl groups on its surface, to form a lasting and stable effect.

[0019] In some embodiments of the present application, the molar ratio of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine is (4-8):(1-5):(0.2-4) in the preparation of the composite catalyst.

[0020] Further, the molar amount of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine is sequentially decreased.

[0021] According to some preferred and specific aspects of the present application, the molar ratio of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine is (4-6):(2.5-3.5):(1-2.4).

[0022] In some embodiments of the present application, the addition amount of the reaction monomer is 60%-100% of the total addition amount of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine in mass percentage in the preparation of the composite catalyst.

[0023] In some embodiments of the present application, the mass ratio of the diisocyanate to the polyhydric alcohol in the reaction monomer is 1:(0.8-1.2).

[0024] In some embodiments of the present application, the temperature of the mixed reaction is controlled to be 55-65℃ in the preparation of the composite catalyst.

[0025] In some embodiments of the present application, the mixed reaction is controlled to be carried out under stirring in the preparation of the composite catalyst.

[0026] In some embodiments of the present application, the polyhydric alcohol amine comprises triethanolamine.

[0027] In some embodiments of the present application, the diisocyanate comprises isophorone diisocyanate in the preparation of the composite catalyst.

[0028] In some embodiments of the present application, the polyhydric alcohol comprises ethylene glycol in the preparation of the composite catalyst.

[0029] In some embodiments of the present application, the hydroxylated castor oil is prepared by the following method: reacting castor oil with glycerol to form a first intermediate; then mixing the first intermediate with performic acid to obtain a second intermediate; reacting the second intermediate with maleic anhydride to obtain the hydroxylated castor oil.

[0030] Further, in the process of preparing the first intermediate, the molar ratio of the castor oil to the glycerol is controlled to be 1:0.5-0.7.

[0031] Further, in the process of preparing the first intermediate, the temperature of the reaction is controlled to be 210-230℃.

[0032] Further, in the process of preparing the first intermediate, the reaction is carried out under the protection of a protective gas. Further, the protective gas includes but is not limited to nitrogen, helium and the like.

[0033] Further, in the process of preparing the second intermediate, the temperature of the reaction is controlled to be 60-65℃.

[0034] Further, in the process of preparing the second intermediate, the peroxymethanoic acid is generated by reacting hydrogen peroxide with formic acid in a molar ratio of 1.8-2.2:1.

[0035] Further, the epoxy value of the second intermediate is controlled to be greater than or equal to 0.35 mol / 100g.

[0036] Further, the mass ratio of the second intermediate to maleic anhydride is controlled to be 9-11:1, and the temperature of the reaction is controlled to be 70-90℃.

[0037] According to some specific aspects of the present application, the method for preparing the hydroxylated castor oil comprises: adding castor oil and glycerol into a reaction kettle in a molar ratio of 1:0.5-0.7, and reacting at 210-230℃ under the protection of nitrogen to generate monoglyceride; cooling the above product to 55-60℃, slowly adding peroxymethanoic acid solution generated by pre-reacting hydrogen peroxide (which can be achieved by adding hydrogen peroxide) and formic acid in a molar ratio of 1.8-2.2:1, controlling the temperature of the reaction to be 60-65℃, and reacting. After the reaction is completed, washing with alkaline water and separating the liquid to obtain modified castor oil. The modified castor oil is reacted with maleic anhydride in a mass ratio of 9-11:1, and the reaction is carried out under stirring at 70-90℃. An appropriate amount of ethanol is added to terminate the reaction, and the hydroxylated castor oil is obtained after washing and drying.

[0038] In some embodiments of the present application, in the first component, the silane-modified nanosilicate is 30-40 parts by weight, the thermosetting phenolic emulsion is 10-20 parts by weight, the thermosetting urea-formaldehyde emulsion is 5-15 parts by weight, the thermosetting acrylic emulsion is 5-20 parts by weight, the composite catalyst is 0.5-5 parts by weight, the low-temperature activity promoter is 0-8 parts by weight, and the water is 10-40 parts by weight.

[0039] Further, the low-temperature activity promoter includes N,N-dimethylcyclohexylamine (DMCHA, such as commercially available from Arkema, industrial grade 99%), N,N-dimethylethanolamine (DMEA, such as commercially available from BASF, purity >99%), or triethylenediamine (TEDA, A-33 solution, such as commercially available from Evonik, content 33wt.%), etc.

[0040] In some embodiments of the present application, the solid content of the thermosetting phenolic emulsion is 45%-55%.

[0041] In some embodiments of the present application, the solid content of the thermosetting urea-formaldehyde emulsion is 50%-60%.

[0042] In some embodiments of the present application, the solid content of the thermosetting acrylic emulsion is 45%-55%.

[0043] In the present application, the thermosetting phenolic emulsion, the thermosetting urea-formaldehyde emulsion, and the thermosetting acrylic emulsion are all thermosetting, so that part of the active functional groups in the system remain and can participate in the curing reaction. They can be commercially available or prepared according to conventional methods in the art.

[0044] In some embodiments of the present application, in the second component, the polymeric MDI is 40-50 parts by weight, the diisocyanate is 0-20 parts by weight, the hydroxylated castor oil is 10-35 parts by weight, the polyether polyol is 10-25 parts by weight, the nanosilica is 0-6 parts by weight, and the polymerization inhibitor is 0-1 part by weight.

[0045] Further, in the second component, the diisocyanate can be selected from TDI, diphenylmethane diisocyanate (MDI), HDI, IPDI, HMDI, or a combination of two or more of any of the foregoing, etc. It can be commercially available, such as commercially available from Wanhua Chemical, BASF, Covestro, etc.

[0046] Further, in the second component, the polyether polyol can be polyether polyol N330, etc.

[0047] Further, in the second component, the polymerization inhibitor can include di-t-butyl-p-cresol, etc.

[0048] Further, in the second component, the nanosilica can be Cabot M50 hydrophilic fumed silica, Desheng PM20 hydrophobic fumed silica, Zaisheng KS150 hydrophobic fumed silica, and Wacker H18 hydrophobic fumed silica.

[0049] In some embodiments of the present application, the first component is prepared by mixing and uniformly mixing the components.

[0050] In some embodiments of the present application, the second component is prepared by mixing the components.

[0051] In some embodiments of the present application, the volume ratio of the first component to the second component is 1:0.95-1.05. According to a specific aspect of the present application, the first component and the second component are mixed in a volume ratio of 1:1.

[0052] In some embodiments of the present application, the viscosity of the first component and the viscosity of the second component are independently 500-3000 mPa·s.

[0053] In some embodiments of the present application, the viscosity of the first component and the viscosity of the second component are within 10% of each other, further within 5% of each other, and more further within 2% of each other.

[0054] According to some specific aspects of the present application, the viscosity of the first component and the viscosity of the second component are within 1% of each other, or equal.

[0055] The present application provides still another technical solution: a construction method of the two-component polyurethane grouting material described above, the construction method comprising: The first component and the second component are pumped out from their respective pipelines, mixed in a mixer according to a preset volume ratio, and then the obtained mixed slurry is injected into the crack to be repaired.

[0056] In some embodiments of the present application, the preset volume ratio is 1:0.95-1.05.

[0057] In some embodiments of the present application, during the injection of the mixed slurry, the grouting output pressure (0.5-5 MPa adjustable) and the grouting speed (200-800 mL / min).

[0058] The present application provides still another technical solution: a preparation method of a two-component polyurethane grouting material, the preparation method comprising: Preparation of the first component: water, modified nanosilicate, thermosetting phenolic emulsion, thermosetting urea-formaldehyde emulsion, and thermosetting acrylic emulsion are sequentially added to a mixing container in a predetermined ratio, and are mixed uniformly under low-speed stirring (for example, 300-500 rpm), and finally a composite catalyst is added and stirred; Preparation of the second component: multi-methylene multi-phenyl polyisocyanate is preheated (for example, 35-45℃), and then hydroxylated castor oil, polyether polyol, and optionally diisocyanate are added, and are fully stirred, and finally optional nanosilica and optional polymerization inhibitor are added, and are dispersed uniformly under high-speed shearing (for example, 1000-2000 rpm).

[0059] Further, the first component and the second component are mixed and grouted during construction.

[0060] The application further provides another technical scheme: a catalyst for a two-component polyurethane grouting material, raw materials of the catalyst include reaction monomers, dibutyltin dilaurate, p-toluenesulfonic acid and polyol amine, the reaction monomers include diisocyanate and polyol; The feeding molar ratio of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyol amine is (4-8):(1-5):(0.2-4); The adding amount of the reaction monomers is 60%-100% of the total adding amount of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyol amine; In the reaction monomers, the feeding mass ratio of the diisocyanate to the polyol is 1:(0.8-1.2).

[0061] In the application, most of the catalysts in the composite catalyst can be in a capsule shape, i.e. the dibutyltin dilaurate and the p-toluenesulfonic acid are used as core materials, and the polyurethane formed after the reaction of the reaction monomers is used as wall material, of course, the dibutyltin dilaurate and the p-toluenesulfonic acid can be used as core materials respectively or be combined together as core materials. At the same time, the polyol amine can participate in the formation process of the polyurethane, and then be firmly fixed on the molecular structure of the polyurethane and not be easy to migrate or be lost; or be doped in the dibutyltin dilaurate and / or the p-toluenesulfonic acid as core materials. The application can occur interface polymerization through the way that the reaction monomers and the catalysts are mixed and reacted together, and then form a composite catalyst with a similar coating structure or a capsule shape. On the one hand, through the formation of the polyurethane wall material, the dispersion uniformity of the catalyst in the first component or in the grouting slurry after being mixed with the second component can be improved. On the other hand, the polyurethane wall material can gradually dissolve in the grouting slurry through the similar compatibility principle, and then release the internal core materials, so that the coated and uniformly dispersed state can be achieved during storage, and the catalytic effect can be released after being mixed and grouted. Especially, the application uses three kinds of catalysts for combination, which can play a role in different reactions and different stages, so that the polyurethane grouting material of the application can realize the synergy of multiple curing mechanisms. Specifically, the p-toluenesulfonic acid can catalyze the reaction between amino and hydroxyl groups, the re-polymerization of thermosetting acrylic emulsion, etc., the dibutyltin dilaurate can catalyze the curing reaction of isocyanate, the polyol amine can also catalyze the curing reaction of isocyanate, etc. According to the different catalytic efficiencies and the activities of the reaction groups, the curing reaction can occur rapidly at the initial stage to realize rapid initial setting, form an initial network and obtain a certain strength, avoid the grouting from being washed away in a dynamic environment, and with the progress of the curing reaction, the main curing is formed in the middle stage to realize the large strength of the grouting, and finally the slow reaction can realize the late enhancement under the action of the catalyst, so as to achieve the purpose of structural filling and enhancement.

[0062] In addition, by controlling the amount of catalyst added, active control of the gel time can be achieved, for example, the gel time can be controlled to be 30 minutes to 2 hours, facilitating construction operation while improving the resistance to scouring.

[0063] Due to the above technical solutions, the present application has the following advantages compared with the prior art: The modified two-component polyurethane grouting material of the present application solves the engineering pain points of "not sticking, not fastening, and not controlling" in the dynamic water grouting process. Specifically, the two-component polyurethane grouting material of the present application has the following advantages: 1. Excellent adaptability to dynamic water environment and high retention rate: Traditional materials are easily washed away in dynamic water, leading to grouting failure. By adjusting the formula system, the present application not only realizes the functions of increasing viscosity and stabilizing foam, but also realizes the synergistic effect of multiple curing mechanisms, achieving high resistance to dispersion in dynamic water.

[0064] 2. Ultra-strong underwater bonding strength and interfacial bonding force: Through the deep penetration and chemical bonding effect of silane-modified nanosilicate and the composite system of multi-element thermosetting resin emulsion, the problem of weak underwater bonding is improved, and the material has excellent hydrophilicity and wet surface wettability, can quickly spread on the concrete surface and form a firm bond.

[0065] 3. Wide range of adjustable gel time and excellent workability: The composite catalyst realizes the active regulation of the curing process, solving the contradiction between "running grout" and "pipe blockage". The present application can accurately control the gel time. It is convenient for construction and also improves the initial strength and the guarantee of later strength, thereby improving the resistance to scouring.

[0066] 4. Excellent environmental performance: Using water as the dispersion medium, the content of volatile organic compounds (VOC) is greatly reduced. The VOC content of the product of the present application is <15g / L, which is much lower than that of traditional oil-based polyurethane materials (>100g / L), and is more friendly to the construction environment and operating personnel.

[0067] 5. Excellent durability and dimensional stability: The multiple curing of the present application can form an interpenetrating network structure, thereby forming a dense and strong consolidated body, and the aging resistance and anti-shrinkage performance are significantly improved.

[0068] In summary, the present application provides a new type of grouting material with high strength, excellent dynamic water adaptability, excellent durability, good environmental performance, and convenient and reliable construction, which can fundamentally solve the problem of organic-inorganic compatibility and overcome at least one problem in the prior art. DETAILED DESCRIPTION

[0069] The above scheme is further described below in conjunction with specific examples. It should be understood that these examples are used to illustrate the basic principles, main features and advantages of the present application, and the present application is not limited in scope by the following examples. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not specified in the examples are generally the conditions in conventional experiments.

[0070] In the following examples, all raw materials are commercially available or prepared by conventional methods in the art, unless otherwise specified.

[0071] In the following examples, the silane-modified nanosilicate is prepared as follows: nanosilicate (specifically, nanometer kaolin powder, purchased from Zhejiang Haoyang New Material Technology Co., Ltd., model HY80) is dried at 120°C for 4h (the moisture content is about 0.3%), and then the surface hydroxyl groups are activated in a plasma treatment instrument (Pdca-002, USA harrick). Under nitrogen protection, the silane coupling agent (specifically, KH550, purchased from Hubei Wuda Silicone Co., Ltd.) is reacted at room temperature, and the grafting rate is controlled at about 6%, to obtain the silane-modified nanosilicate.

[0072] In the following examples, the composite catalyst is prepared as follows: dibutyltin dilaurate (DBTL), p-toluenesulfonic acid (PTSA) and triethanolamine (TEOA) are mixed uniformly at room temperature in a molar ratio of 5:3:2. The above-mentioned compounded catalyst is used as the core material, and is reacted with isophorone diisocyanate (IPDI) and ethylene glycol as the reaction monomers by mixing and stirring (the reaction temperature is 60°C) to prepare the composite catalyst; wherein the mass ratio of isophorone diisocyanate (IPDI) and ethylene glycol is 1:1, and the mass of the reaction monomers accounts for 80% of the mass of the compounded catalyst.

[0073] In the following examples, the hydroxylated castor oil is prepared as follows: castor oil and glycerol are added to a reaction kettle in a molar ratio of 1:0.6, and reacted at 220°C under nitrogen protection for 3 hours to form a monoglyceride; the above-mentioned product is cooled to 60°C, and a peroxymethane acid solution generated by pre-reaction of hydrogen peroxide (provided by adding hydrogen peroxide) and formic acid in a molar ratio of 1.8-2.2:1 is slowly added, and the reaction temperature is controlled at 60-65°C, and the reaction is carried out for 6 hours. After the reaction is completed, the modified castor oil is washed with alkaline water and separated to obtain the modified castor oil. The modified castor oil is reacted with maleic anhydride at 80°C for 4h in a mass ratio of 10:1; an appropriate amount of ethanol is added to terminate the reaction, and the hydroxylated castor oil is obtained after washing and drying.

[0074] The thermosetting phenolic emulsion was purchased from Baidefu Chemical Industry, with the brand 520, and the solid content was 50%. The thermosetting urea-formaldehyde emulsion was purchased from Jiangsu Jiantuo Chemical Industry, with the brand 502, and the solid content was 55%. The thermosetting acrylic emulsion was purchased from Wanhua Chemical, with the brand 8060, and the solid content was 50%. The polymeric methylene diphenyl diisocyanate (polymeric MDI) was purchased from Wanhua Chemical, with the brand PM200. The polyether polyol N330 was purchased from Lansen East, with the brand 330N. The nano-silica was PM20 hydrophobic silica from Deshan. The polymerization inhibitor was di-tert-butyl-p-cresol, purchased from BASF Chemical, with the brand BHT. Example 1

[0075] The present example provides a two-component polyurethane grouting material and a preparation method thereof, which comprises a first component and a second component. The first component comprises, in parts by weight, 35 parts of silane-modified nanosilicate, 18 parts of thermosetting phenolic emulsion, 12 parts of thermosetting urea-formaldehyde emulsion, 10 parts of thermosetting acrylic emulsion, 2.5 parts of composite catalyst, and 22.5 parts of water. The second component comprises 45 parts of polymeric methylene diphenyl diisocyanate (PM-200), 22 parts of hydroxylated castor oil, 18 parts of polyether polyol N330, 4 parts of nano-silica, and 0.2 parts of polymerization inhibitor.

[0076] The preparation method of the two-component polyurethane grouting material comprises: Preparation of the first component: according to the proportion, water, modified nanosilicate, thermosetting phenolic emulsion, thermosetting urea-formaldehyde emulsion, and thermosetting acrylic emulsion are sequentially added to a mixing container and mixed uniformly under low-speed stirring (400 rpm). Finally, the composite catalyst is added and stirred to obtain the first component. Preparation of the second component: according to the proportion, the polymeric methylene diphenyl diisocyanate is preheated to 40°C. The hydroxylated castor oil and the polyether polyol are added and stirred thoroughly. Finally, the nano-silica and the polymerization inhibitor are added and dispersed uniformly under high-speed shearing (1500 rpm) to obtain the second component.

[0077] Further, during construction, the first component and the second component are mixed and grouted in a volume ratio of 1:1 at 25°C. Example 2

[0078] The present example provides a two-component polyurethane grouting material and a preparation method thereof, which comprises a first component and a second component. The first component comprises, in parts by weight, 40 parts of silane-modified nanosilicate, 17 parts of thermosetting phenolic emulsion, 10 parts of thermosetting urea-formaldehyde emulsion, 8 parts of thermosetting acrylic emulsion, 2.8 parts of composite catalyst, and 22.2 parts of water. The second component and the preparation method are the same as those in Example 1. Example 3:

[0079] The present example provides a two-component polyurethane grouting material and a preparation method thereof, the two-component polyurethane grouting material comprising a first component and a second component; wherein, in terms of parts by weight, the first component comprises silane-modified nanosilicate 32 parts, thermosetting phenolic emulsion 15 parts, thermosetting urea-formaldehyde emulsion 15 parts, thermosetting acrylic emulsion 8 parts, composite catalyst 3.5 parts, and water 26.5 parts; The other second component, preparation method, and the like are the same as those in Example 1. Example 4:

[0080] The present example provides a two-component polyurethane grouting material and a preparation method thereof, the two-component polyurethane grouting material comprising a first component and a second component; wherein, in terms of parts by weight, the first component comprises silane-modified nanosilicate 30 parts, thermosetting phenolic emulsion 15 parts, thermosetting urea-formaldehyde emulsion 10 parts, thermosetting acrylic emulsion 15 parts, composite catalyst 2.0 parts, and water 28 parts; The second component comprises polymeric MDI (PM-200) 40 parts, hydroxylated castor oil 20 parts, polyether polyol N330 25 parts, nanosilica 4 parts, and polymerization inhibitor 0.2 part.

[0081] The other preparation method of the two-component polyurethane grouting material and the like is the same as that in Example 1. Example 5:

[0082] The present example provides a two-component polyurethane grouting material and a preparation method thereof, the two-component polyurethane grouting material comprising a first component and a second component; wherein, in terms of parts by weight, the first component comprises silane-modified nanosilicate 35 parts, thermosetting phenolic emulsion 18 parts, thermosetting urea-formaldehyde emulsion 12 parts, thermosetting acrylic emulsion 10 parts, composite catalyst 3.2 parts, low-temperature activity promoter (specifically DMCHA, purchased from Arkema Chemical, trade name DMCHA 99%) 5 parts, and water 16.8 parts; The other second component, preparation method, and the like are the same as those in Example 1. Comparative Example 1: Traditional polyurethane material

[0083] The present example provides a two-component polyurethane grouting material and a preparation method thereof, wherein: The first component: ordinary cement slurry (water-cement ratio 0.4), 120 parts; The second component: pure polymeric MDI (PM-200) 100 parts.

[0084] The other components are the same as those in Example 1. Comparative Example 2:

[0085] This example provides a two-component polyurethane grouting material and a preparation method thereof, wherein: The first component: water 40 parts, thermosetting phenolic emulsion 20 parts, thermosetting urea-formaldehyde emulsion 15 parts, thermosetting acrylic emulsion 10 parts, dibutyltin dilaurate 2.5 parts.

[0086] The others are the same as Example 1. Comparative Example 3:

[0087] This example provides a two-component polyurethane grouting material and a preparation method thereof, wherein: The first component: silane-modified nanosilicate 35 parts, thermosetting urea-formaldehyde emulsion 40 parts, composite catalyst 2.5 parts, water 22.5 parts.

[0088] The others are the same as Example 1. Comparative Example 4:

[0089] This example provides a two-component polyurethane grouting material and a preparation method thereof, wherein: The first component: modified nanosilicate solution 35 parts, thermosetting phenolic emulsion 18 parts, thermosetting urea-formaldehyde emulsion 12 parts, thermosetting acrylic emulsion 10 parts, dibutyltin dilaurate 2.5 parts, water 22.5 parts.

[0090] The others are the same as Example 1. Performance test:

[0091] According to the standards T / CECS 10313-2023 Non-water reaction type two-component polyurethane grouting material, JC / T 2037-2018 Acrylate grouting material, GB / T 30693-2014 Measurement of water contact angle of plastic film, the test is carried out. The specific test results are shown in Table 1. All data are measured under standard test conditions.

[0092]

[0093] Dynamic water retention rate test: a transparent inclined water tank (~ 45°) is built, and the circulating control flow rate of the water pump is 1.5 m / s (calibrated by flowmeter). After weighing, the slurry (M1) is coated on the bottom of the tank, and the residual solidified body is collected and weighed (M2) after 60 seconds of flushing. Retention rate = (M2 / M1) × 100%. Repeat 3 times and take the average value.

[0094] The retention rate of the two-component polyurethane grouting material of the present application is up to 95% or more, while the retention rate of the traditional polyurethane material (comparative example 1) is only 35%, proving its excellent water dilution resistance and scouring resistance. At the same time, the underwater bonding strength, controllable curing, environmental protection and durability and other key performance indicators are significantly improved, meeting the harsh requirements of concrete structure leakage treatment in complex dynamic water environment, having great engineering application value and market prospect.

[0095] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application shall be covered within the protection scope of the present application.

[0096] The endpoints of the ranges and any values in the ranges disclosed herein are not limited to the precise values. The ranges should be interpreted as being approximate, and the endpoints are to be understood to be open-ended. The ranges are understood to include values near the endpoints. For ranges having a minimum and maximum value, the minimum and maximum values are included in the range. For ranges having a minimum value but no maximum value, the minimum value is included in the range. For ranges having a maximum value but no minimum value, the maximum value is included in the range. For ranges having no minimum or maximum value, the range is understood to include values near the endpoints.

Claims

1. A two-component polyurethane grouting material, characterized in that, The two-component polyurethane grouting material comprises a first component and a second component; The first component comprises silane-modified nanosilicate, thermosetting phenolic emulsion, thermosetting urea-formaldehyde emulsion, thermosetting acrylic emulsion, composite catalyst and water; the composite catalyst is prepared by mixing and reacting diisocyanate and polyol as reaction monomers, dibutyltin dilaurate, p-toluenesulfonic acid and polyhydric alcohol amine; The second component comprises polymethylene polyphenyl polyisocyanate, optional diisocyanate, hydroxylated castor oil and polyether polyol.

2. Two-component polyurethane grouting material according to claim 1, characterized in that The silane-modified nanosilicate is prepared by drying nanosilicate, activating surface hydroxyl groups and then reacting the activated nanosilicate with silane coupling agent; Further, the nanosilicate comprises nanosodium silicate and / or nanoclay; Further, the average particle size of the nanosilicate is 50-100 nm; Further, the surface hydroxyl groups of the nanosilicate are activated by using a plasma treatment instrument; Further, the grafting rate of the silane coupling agent in the silane-modified nanosilicate is controlled to be 5%-8%.

3. The two-component polyurethane grouting material according to claim 1, characterized in that In the preparation of the composite catalyst, the molar ratio of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine is (4-8):(1-5):(0.2-4).

4. Two-component polyurethane grouting material according to claim 3, characterized in that The molar amounts of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine are sequentially decreased; or the molar ratio of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine is (4-6):(2.5-3.5):(1-2.4).

5. The two-component polyurethane grouting material according to claim 1, characterized in that In the preparation of the composite catalyst, the addition amount of the reaction monomers is 60%-100% of the total addition amount of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine in terms of mass percentage; and / or, in the reaction monomers, the mass ratio of diisocyanate to polyhydric alcohol is 1:(0.8-1.2); and / or, in the preparation of the composite catalyst, the temperature of the mixing reaction is controlled to be 55-65℃; and / or, in the preparation of the composite catalyst, the mixing reaction is carried out under stirring; and / or, the polyhydric alcohol amine comprises triethanolamine; and / or, in the preparation of the composite catalyst, the diisocyanate comprises isophorone diisocyanate; and / or, in the preparation of the composite catalyst, the polyhydric alcohol comprises ethylene glycol.

6. The two-component polyurethane grouting material according to claim 1, characterized in that The hydroxylated castor oil is prepared by: reacting castor oil with glycerol to obtain a first intermediate; then mixing and reacting the first intermediate with performic acid to obtain a second intermediate; reacting the second intermediate with maleic anhydride to obtain the hydroxylated castor oil; Further, in the preparation of the first intermediate, the molar ratio of the castor oil to the glycerol is controlled to be 1:0.5-0.7; Further, in the preparation of the first intermediate, the temperature of the reaction is controlled to be 210-230℃; and / or, the reaction is carried out under protection of a protective gas. Further, the reaction temperature is controlled to be 60-65℃ during the preparation of the second intermediate; Further, the peroxycarboxylic acid is generated from hydrogen peroxide and formic acid in a molar ratio of 1.8-2.2:1 during the preparation of the second intermediate; Further, the epoxy value of the second intermediate is controlled to be greater than or equal to 0.35 mol / 100g; Further, the mass ratio of the second intermediate to maleic anhydride is controlled to be 9-11:1, and the reaction temperature of the two is 70-90℃.

7. The two-component polyurethane grouting material according to claim 1, characterized in that In the first component, the silane-modified nanosilicate, the thermosetting phenolic emulsion, the thermosetting urea-formaldehyde emulsion, the thermosetting acrylic emulsion, the composite catalyst, the low-temperature activity promoter and the water are 30-40 parts, 10-20 parts, 5-15 parts, 5-20 parts, 0.5-5 parts, 0-8 parts and 10-40 parts respectively by weight, and further, the low-temperature activity promoter comprises N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine or triethylenediamine; and / or, The solid content of the thermosetting phenolic emulsion is 45%-55%; and / or, The solid content of the thermosetting urea-formaldehyde emulsion is 50%-60%; and / or, The solid content of the thermosetting acrylic emulsion is 45%-55%; and / or, In the second component, the polymethylene polyphenyl polyisocyanate, the diisocyanate, the hydroxylated castor oil, the polyether polyol, the nanosilica and the polymerization inhibitor are 40-50 parts, 0-20 parts, 10-35 parts, 10-25 parts, 0-6 parts and 0-1 part respectively by weight; and / or, The first component is prepared by mixing the components uniformly; and / or, The second component is prepared by mixing the components uniformly.

8. The two-component polyurethane grouting material according to claim 1, characterized in that The volume ratio of the first component to the second component is 1:0.95-1.05; and / or, the viscosity of the first component, the viscosity of the second component are independently 500-3000 mPa·s; and / or, the difference between the viscosity of the first component and the viscosity of the second component is within 10%, further within 5%, and more further within 2%.

9. A method of applying a two-component polyurethane grouting material as claimed in any one of claims 1 to 8, characterized in that, The construction method comprises: The first component and the second component are pumped out from the respective pipelines, mixed in a mixer according to a preset volume ratio, and then the obtained mixed slurry is injected into the crack to be repaired.

10. A catalyst for two-component polyurethane grouting material, characterized by, The raw materials of the catalyst comprise reaction monomers, dibutyltin dilaurate, p-toluenesulfonic acid and polyhydric alcohol amine, and the reaction monomers comprise diisocyanate and polyhydric alcohol; The molar ratio of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine is (4-8):(1-5):(0.2-4); The addition amount of the reaction monomers is 60%-100% of the total addition amount of the dibutyltin dilaurate, the p-toluenesulfonic acid and the polyhydric alcohol amine; In the reaction monomers, the mass ratio of diisocyanate to polyhydric alcohol is 1:(0.8-1.2).

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