A method for repairing damaged concrete surface

Abstract

The present invention discloses a method for repairing a damaged concrete surface, comprising the following steps: S1: cleaning the damaged concrete surface by roughening and fully wetting; S2: pouring water and a reinforcement repair material into a mixer at a mass ratio of 0.06-0.1:1 and fully stirring for 10-20 minutes to obtain a reinforcement repair wet material; S3: injecting the reinforcement repair wet material into the wetted damaged concrete surface, and evenly applying the concrete surface with a trowel and a scraper to ensure that the reinforcement repair wet material fully fills the damaged concrete surface. The present invention can effectively improve the combination effect of the concrete repair material and the damaged concrete surface through the reasonable design of materials and processes, effectively avoid cracking and falling off of the repair layer, and improve the durability and safety of the structure.

Description

Technical Field

[0001] The invention relates to the technical field of building repair, and in particular to a method for repairing a damaged concrete surface. Background Art

[0002] In recent years, with the rapid development of my country's infrastructure, engineering construction has developed towards larger, longer, more stable and more durable directions, which has put forward higher requirements for the use of concrete materials. Engineering practice shows that repairing and reinforcing damaged concrete structures is one of the most effective means to restore their use functions and meet service design requirements.

[0003] In the existing repair process of damaged concrete surfaces, due to the uneven temperature distribution inside the concrete repair material and the poor interface bonding effect with the damaged concrete surface, the repair layer is prone to cracking and falling off, which significantly reduces the durability and safety of the structure. Summary of the invention

[0004] In order to solve the problems in the prior art, the present invention provides a method for repairing damaged concrete surfaces. Through the reasonable design of materials and processes, the bonding effect between concrete repair materials and damaged concrete surfaces can be effectively improved, and cracking and falling off of the repair layer can be effectively avoided.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0006] The present invention provides a method for repairing a damaged concrete surface, comprising the following steps:

[0007] S1: Chisel and clean the damaged surface of the concrete and moisten it thoroughly;

[0008] S2: Pour water and reinforcement repair materials into a mixer at a mass ratio of 0.06-0.1:1 and stir thoroughly for 10-20 minutes to obtain reinforcement repair wet material;

[0009] S3: Inject the reinforcement and repair wet material into the moistened damaged concrete surface, and use a trowel and scraper to evenly spread the concrete surface to ensure that the reinforcement and repair wet material fully fills the damaged concrete surface.

[0010] Furthermore, the components of the reinforcement and repair material include, by weight: 30-40 parts of silicate cement, 3-18 parts of silica fume, 6-15 parts of fly ash, 3-10 parts of metakaolin, 11-56 parts of sand, 1-3 parts of UHPC hydration temperature rise inhibitor as a network structure component, and 1-3 parts of fiber.

[0011] Furthermore, the preparation method of the reinforcement repair material comprises the following steps:

[0012] Portland cement, silica fume, fly ash, metakaolin and sand are weighed by weighing scales and transported to a mixer for stirring for 10-15 minutes;

[0013] Add the network structure component UHPC hydration temperature rise inhibitor into the mixer and continue stirring for 15-20 minutes;

[0014] The fibers are added into a blender and stirred for 15-20 minutes to obtain a reinforcement repair material.

[0015] Further, the silicate cement is selected from any one or more combinations of P·O 42.5, P·O 52.5, P·I 42.5, and P·I 52.5;

[0016] The fiber is any one or more combinations of steel fiber, polyvinyl alcohol fiber, polypropylene fiber, and polyoxymethylene fiber;

[0017] The sand is standard sand, and the screening mesh number is 20-70 mesh.

[0018] Furthermore, the molecular structure of the UHPC hydration temperature rise inhibitor of the network structure component is as follows:

[0019]

[0020] Among them, the structural formula of R is:

[0021]

[0022] Among them, R 2 The structural formula is:

[0023]

[0024] In the above formula, a, b, c, x, y, z, and n are integers representing the number of repeating units of each part in the polymer, a is in the range of 5-10, b is in the range of 10-15, c is in the range of 10-25, x is in the range of 5-10, y is in the range of 5-15, z is in the range of 10-25, and n is in the range of 10-150; R 1 CH 2 CH 2 CH 2 , R 3 H or Na, R 4 CH 2 , CH 2 CH 2 or O(CH 2 CH 2 O) 2 .

[0025] Furthermore, the preparation method of the network structure component UHPC hydration temperature rise inhibitor is: prepare the carboxyl-terminal β-CD by substitution modification of β-CD and halogenated acid, then react with amino POSS and polysaccharide oxides in sequence to obtain polysaccharide network structure macromolecules, and then react with halogenated compounds, unsaturated carboxylate small monomers, unsaturated sulfonic acid small monomers and polyether macromonomers to undergo substitution-ATRP reaction to obtain the network structure component UHPC hydration temperature rise inhibitor.

[0026] Furthermore, the preparation method of the network structure component UHPC hydration temperature rise inhibitor specifically comprises the following steps:

[0027] Step 1, preparation of carboxyl-terminal β-CD: β-CD and an alkaline solvent with a mass fraction of 10-50% are mixed evenly and added to a reactor, and stirred and dissolved at 20-30°C for 0.5-3 hours, and then a halogenated acid is added, and the temperature is raised to 40-80°C for substitution reaction. After reacting for 1-10 hours, the pH value is adjusted to 6-9 with an acidic solvent with a mass fraction of 20-100%, and the precipitate is filtered out after washing with the solvent for 1-6 times, and vacuum dried for 24-48 hours to obtain carboxyl-terminal β-CD;

[0028] Step 2, preparation of a network structure macromolecule: dissolve the carboxyl-terminal β-CD obtained in step 1 in water and add an activator, stir and activate at 0-10°C for 0.1-1 hour, then add amino POSS, heat to 20-60°C for amidation reaction, react for 3-10 hours, use a dialysis bag for 48-72 hours to remove unreacted solvent and small molecules, and vacuum dry for 24-48 hours to obtain a network structure macromolecule;

[0029] Step 3, preparation of polysaccharide oxides: adding 20-40% by mass of starch milk into a reactor, adjusting the pH value to 8-12 with 10-50% by mass of an alkaline solvent, adding an oxidant, heating to 20-60°C for oxidation reaction, reacting for 0.5-7 hours, adjusting the pH value to 6-9 with 20-100% by mass of an acidic solvent, and adding a reducing agent to terminate the reaction, filtering out the precipitate after washing with the solvent for 1-6 times, and vacuum drying for 24-48 hours to obtain polysaccharide oxides;

[0030] Step 4, preparation of polysaccharide network structure macromolecules: dissolve the polysaccharide oxide product obtained in step 3 in water and add an activator, stir and activate at 0-10°C for 0.1-1 hour, then add the network structure macromolecule obtained in step 2, heat to 30-80°C for amidation reaction, react for 3-10 hours, use a dialysis bag for 48-72 hours to remove unreacted solvent and molecules, and vacuum dry for 24-48 hours to obtain polysaccharide network structure macromolecules;

[0031] Step 5, preparation of a network structure component UHPC hydration temperature rise inhibitor: the product obtained in step 4, the polysaccharide network structure macromolecule and the solvent are evenly mixed and added to the reactor, and then a halogenated compound is added to carry out a substitution reaction at 0-40°C. After reacting for 12-48 hours, a transition metal halide, a ligand, an unsaturated carboxylate small monomer, an unsaturated sulfonic acid small monomer and a polyether large monomer are added, and the temperature is continuously raised to 50-100°C under nitrogen protection for ATRP reaction. The reaction is carried out for 5-60 hours, and the organic solvent and by-products are removed by desalination and reduced pressure distillation to obtain a network structure component UHPC hydration temperature rise inhibitor.

[0032] Furthermore, the base in the alkaline solvent in step 1 is one or more combinations of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide, and the molar ratio of the base in the alkaline solvent to β-CD is 2-4:1;

[0033] In step 1, the halogenated acid is chloroacetic acid, bromoacetic acid, iodoacetic acid, 2-chloropropionic acid, 2-bromopropionic acid or 2-iodopropionic acid, and the molar ratio of the halogenated acid to β-CD is 2-4:1;

[0034] The acidic solvent in step 1 is concentrated hydrochloric acid or concentrated sulfuric acid; the molar ratio of the acid in the acidic solvent to the base in the alkaline solvent is 0.6-2.5:1;

[0035] In step 1, the solvent is methanol or acetone, and the mass ratio of the solvent to β-CD is 2-10:1;

[0036] The water in step 2 is deionized water, and the mass ratio of the deionized water to the carboxyl-terminal β-CD is 5-20:1;

[0037] In step 2, the activator is 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, the molar ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide to N-hydroxysuccinimide is 0.5-2:1, and the molar ratio of the activator to the carboxyl-terminal β-CD is 2-4:1;

[0038] The amino POSS in step 2 is octaaminopropyl POSS, and the molar ratio of the amino POSS to the carboxyl-terminal β-CD is 2-4:1.

[0039] Furthermore, the alkali in the alkaline solvent in step 3 is one or more combinations of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide, and the mass ratio of the alkali in the alkaline solvent to the starch milk is 0.1-0.5:1;

[0040] In step 3, the oxidant is sodium hypochlorite, hydrogen peroxide, potassium permanganate, potassium persulfate, peroxy acid or periodic acid, and the mass ratio of the oxidant to starch milk is 0.06-0.14:1;

[0041] The acidic solvent in step 3 is concentrated hydrochloric acid or concentrated sulfuric acid, and the molar ratio of the acid in the acidic solvent to the base in the alkaline solvent is 0.6-2.5:1;

[0042] In step 3, the reducing agent is sodium bisulfite, sodium thiosulfate, sodium sulfite or manganese sulfate, and the mass ratio of the reducing agent to starch milk is 0.06-0.18:1;

[0043] The water in step 4 is deionized water, and the mass ratio of the deionized water to the polysaccharide oxide is 5-20:1;

[0044] In step 4, the activator is 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, the molar ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide to N-hydroxysuccinimide is 0.5-2:1, and the molar ratio of the activator to the polysaccharide oxide is 0.5-1:1;

[0045] In step 4, the molar ratio of the network structure macromolecule to the polysaccharide oxide is 2.5-3.75:1.

[0046] Furthermore, the solvent in step 5 is selected from one or more combinations of dichloromethane, dichloropropane, chloroform, and trichloroethane, and the mass ratio of the solvent to the polysaccharide network structure macromolecule is 5-20:1;

[0047] The halogenated compound is 2-bromoisobutyryl bromide or 2-chloroisobutyryl chloride, and the molar ratio of the halogenated compound to the polysaccharide network structure macromolecule is 40-100:1;

[0048] The transition metal halide is one or more combinations of cuprous bromide, ferrous bromide, cuprous chloride, ferrous bromide, and ferrous chloride, and the molar ratio of the transition metal halide to the polysaccharide network structure macromolecule is 30-100:1;

[0049] The ligand is one or more combinations of N,N,N,N,N-pentamethyldivinyltriamine, 2,2-bipyridine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, N,N,N,N-tetra[(2-pyridyl)methyl]ethylenediamine, and tri[2-(dimethylamino)ethyl]amine, and the molar ratio of the ligand to the polysaccharide network structure macromolecule is 30-100:1;

[0050] The unsaturated carboxylate small monomer is selected from sodium acrylate, sodium methacrylate, potassium acrylate or potassium methacrylate, and the molar ratio of the unsaturated carboxylate small monomer to the polysaccharide network structure macromolecule is 200-1000:1;

[0051] The unsaturated sulfonic acid small monomer is 2-acrylamide-2-methylpropanesulfonic acid or 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid sodium salt, and the molar ratio of the unsaturated sulfonic acid small monomer to the polysaccharide network structure macromolecule is 200-1500:1;

[0052] The polyether macromolecule is methyl allyl polyoxyethylene ether, isopentanol polyoxyethylene ether or butanediol monovinyl polyoxyethylene ether with a molecular weight of 2000-5000 g / mol, and the molar ratio of the polyether macromolecule to the polysaccharide network structure macromolecule is 400-2500:1;

[0053] The salt removed in the desalting process of step 5 is one or more of cuprous bromide, cupric chloride, cupric bromide, ferric bromide, cuprous chloride, ferric chloride, ferrous bromide or ferrous chloride.

[0054] The beneficial effects of the present invention are as follows:

[0055] 1) Through the reasonable design of materials and processes, the present invention can effectively improve the bonding effect between concrete repair materials and damaged concrete surfaces, effectively avoid cracking and falling off of the repair layer, and improve the durability and safety of the structure.

[0056] 2) The present invention cleans and roughens the damaged surface of concrete and fully wets it to improve the adhesion and bonding between the reinforcement and repair wet material and the damaged surface of concrete.

[0057] 3) The network structure component UHPC hydration temperature rise inhibitor in the reinforcement and repair material of the present invention is modified by substitution of β-CD and halogenated acid to prepare carboxyl-terminated β-CD, and then undergoes amidation reaction with amino POSS and polysaccharide oxides in sequence to obtain polysaccharide network structure macromolecules, and then functionalized by substitution + ATRP reaction to obtain a long side chain "network" structure UHPC hydration temperature rise inhibitor, whose macromolecular POSS structure and β-CD and polysaccharide oxides contain a large number of Si-O skeletons and hydroxyl groups respectively, and the synergistic effect of the two can greatly improve the early mechanical properties of UHPC, reduce hydration heat and inhibit shrinkage, thereby avoiding uneven temperature distribution inside the concrete repair material and cracking and shedding of the repair layer caused by solidification shrinkage. In addition, the multi-carboxyl monomers and long side chain polyether monomers introduced into the molecular structure can significantly improve the working performance of UHPC and enhance the durability and safety of the structure.

[0058] 4) The "net-like" structure hydration temperature rise inhibitor synthesized independently by the present invention is formulated into a concrete damaged surface repair material, which has good abilities of reducing hydration heat, inhibiting shrinkage, improving early strength and repairing. It is applied to the repair of damaged concrete and can meet the requirements of long-term service life. In addition, biomass materials are introduced to reduce the use of petroleum-based monomers, which significantly reduces the preparation cost of hydration temperature rise inhibitor and repair materials. The raw materials are green, environmentally friendly, non-toxic and harmless, showing significant economic benefits, performance advantages and application prospects.

[0059] 5) The "net-like" structure UHPC hydration temperature rise inhibitor designed and synthesized by the present invention has excellent effects in reducing hydration heat, inhibiting shrinkage and resisting mud, and can significantly improve the early mechanical properties and working performance of concrete. First, β-CD and starch structures contain a large number of hydroxyl groups, which react with Ca in cement. 2+ It interacts with the surface of cement particles, inhibits the growth of hydration products, and thus reduces heat release and temperature rise; secondly, the POSS structure has a macromolecular effect, and its size is much larger than the distance between clay layers, which prevents the intercalation adsorption of the long side chains of the hydration temperature rise inhibitor between clay layers; in addition, the Si-O skeleton contained in the POSS structure has a significant nucleation effect on the calcium silicate formed by cement hydration, which effectively improves the early strength of concrete; finally, the multiple adsorption groups and long polyether side chains introduced into the structure can produce strong adsorption and steric hindrance, effectively disperse the cement particles, and make the prepared network structure component UHPC hydration temperature rise inhibitor have excellent water-reducing and dispersion effects.

[0060] 6) Different from the current mainstream direction of reducing the hydration heat of UHPC, the present invention makes full use of the characteristics of chemical admixtures with large structural design flexibility and strong performance control capabilities. Based on molecular structure design, it innovatively introduces independently synthesized polymers with unique molecular structures, and uses substitution, amidation, oxidation, and ATRP reaction methods to form a unique "network" structure, which increases the spatial effect of the polymer and the types and contents of functional groups. The overall adaptability and energy efficiency of the hydration temperature rise inhibitor in ultra-high performance large-volume concrete are improved, the hydration heat and shrinkage rate of UHPC are reduced on a macro scale, its early strength and working performance are improved, and the repair layer is effectively prevented from cracking, falling off, etc., and the durability and safety of the repair layer are improved. It has significant performance advantages and application prospects. DETAILED DESCRIPTION

[0061] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0062] This embodiment provides a method for repairing a damaged concrete surface, comprising the following steps:

[0063] S1: Chisel and clean the damaged surface of concrete and fully moisten it to improve the adhesion and bonding between the reinforcement and repair wet material and the damaged surface of concrete;

[0064] S2: Pour water and reinforcement repair materials into a mixer at a mass ratio of 0.06-0.1:1 and stir thoroughly for 10-20 minutes to obtain reinforcement repair wet material;

[0065] The reinforcement and repair material comprises 30-40 parts of silicate cement, 3-18 parts of silica fume, 6-15 parts of fly ash, 3-10 parts of metakaolin, 11-56 parts of sand, 1-3 parts of UHPC hydration temperature rise inhibitor as a network structure component, and 1-3 parts of fiber. The preparation method of the reinforcement and repair material comprises the following steps:

[0066] The silicate cement, silica fume, fly ash, metakaolin and sand are measured by a weighing scale and transported to a mixer for stirring for 10-15 minutes; the network structure component UHPC hydration temperature rise inhibitor is added to the mixer and stirring is continued for 15-20 minutes; the fiber is added to the mixer and stirred for 15-20 minutes to obtain a reinforcement repair material.

[0067] S3: Inject the reinforcement and repair wet material into the moistened damaged concrete surface, and use a trowel and scraper to evenly spread the concrete surface to ensure that the reinforcement and repair wet material fully fills the damaged concrete surface.

[0068] The molecular structure of the above-mentioned network structure component UHPC hydration temperature rise inhibitor is as follows:

[0069]

[0070] Among them, the structural formula of R is:

[0071]

[0072] Among them, R 2 The structural formula is:

[0073]

[0074] In the above formula, a, b, c, x, y, z, and n are integers representing the number of repeating units of each part in the polymer, a is in the range of 5-10, b is in the range of 10-15, c is in the range of 10-25, x is in the range of 5-10, y is in the range of 5-15, z is in the range of 10-25, and n is in the range of 10-150; R 1 CH 2 CH 2 CH 2 , R 3 H or Na, R 4 CH 2 , CH 2 CH 2 or O(CH 2 CH 2 O) 2 .

[0075] The preparation method of the UHPC hydration temperature rise inhibitor with a network structure component specifically comprises the following steps:

[0076] Step 1, preparation of carboxyl-terminal β-CD: β-CD and 10-50% by mass of alkaline solvent are uniformly mixed and added to a reactor, stirred and dissolved at 20-30°C for 0.5-3 hours, and then a halogenated acid is added, and the temperature is raised to 40-80°C for substitution reaction. After reacting for 1-10 hours, the pH value is adjusted to 6-9 with 20-100% by mass of acidic solvent, and the precipitate is filtered out after washing with the solvent for 1-6 times, and vacuum dried for 24-48 hours to obtain carboxyl-terminal β-CD. The alkali in the alkaline solvent is one or more combinations of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide, and the molar ratio of the alkali in the alkaline solvent to β-CD is 2-4:1; the halogenated acid is chloroacetic acid, bromoacetic acid, iodoacetic acid, 2-chloropropionic acid, 2-bromopropionic acid or 2-iodopropionic acid, and the molar ratio of the halogenated acid to β-CD is 2-4:1; the acidic solvent is concentrated hydrochloric acid or concentrated sulfuric acid; the molar ratio of the acid in the acidic solvent to the alkali in the alkaline solvent is 0.6-2.5:1; the solvent is methanol or acetone, and the mass ratio of the solvent to β-CD is 2-10:1.

[0077] Step 2, preparation of network structure macromolecules: dissolve the carboxyl-terminal β-CD obtained in step 1 in water and add an activator, stir and activate at 0-10°C for 0.1-1 hour, then add amino POSS, heat to 20-60°C for amidation reaction, react for 3-10 hours, use a dialysis bag for 48-72 hours to remove unreacted solvent and small molecules, and vacuum dry for 24-48 hours to obtain a network structure macromolecule. The water is deionized water, and the mass ratio of deionized water to carboxyl-terminal β-CD is 5-20:1; the activator is 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, and the molar ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 0.5-2:1, and the molar ratio of the activator to the carboxyl-terminal β-CD is 2-4:1; the amino POSS is octaaminopropyl POSS, and the molar ratio of the amino POSS to the carboxyl-terminal β-CD is 2-4:1.

[0078] Step 3, preparation of polysaccharide oxides: add 20-40% by mass of starch milk into a reactor, adjust the pH value to 8-12 with 10-50% by mass of an alkaline solvent, add an oxidant, heat to 20-60 ° C for oxidation reaction, react for 0.5-7 hours, adjust the pH value to 6-9 with 20-100% by mass of an acidic solvent, add a reducing agent to terminate the reaction, filter out the precipitate after washing with the solvent for 1-6 times, and vacuum dry for 24-48 hours to obtain polysaccharide oxides. Among them, the alkali in the alkaline solvent is one or more combinations of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide, and the mass ratio of the alkali in the alkaline solvent to the starch milk is 0.1-0.5:1; the oxidant is sodium hypochlorite, hydrogen peroxide, potassium permanganate, potassium persulfate, peroxy acid or periodic acid, and the mass ratio of the oxidant to the starch milk is 0.06-0.14:1; the acidic solvent is concentrated hydrochloric acid or concentrated sulfuric acid, and the molar ratio of the acid in the acidic solvent to the alkali in the alkaline solvent is 0.6-2.5:1; the reducing agent is sodium bisulfite, sodium thiosulfate, sodium sulfite or manganese sulfate, and the mass ratio of the reducing agent to the starch milk is 0.06-0.18:1.

[0079] Step 4, preparation of polysaccharide network structure macromolecules: dissolve the polysaccharide oxide product obtained in step 3 in water and add an activator, stir and activate at 0-10°C for 0.1-1 hour, then add the network structure macromolecule obtained in step 2, raise the temperature to 30-80°C for amidation reaction, after reacting for 3-10 hours, use a dialysis bag to dialyze for 48-72 hours to remove unreacted solvent and molecules, and vacuum dry for 24-48 hours to obtain polysaccharide network structure macromolecules. The water is deionized water, and the mass ratio of deionized water to polysaccharide oxide is 5-20:1; the activator is 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, and the molar ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 0.5-2:1, and the molar ratio of the activator to polysaccharide oxide is 0.5-1:1; the molar ratio of the network structure macromolecule to the polysaccharide oxide is 2.5-3.75:1.

[0080] Step 5, preparation of a UHPC hydration temperature rise inhibitor as a network structure component: the product obtained in step 4, the polysaccharide network structure macromolecule, and the solvent are evenly mixed and added to the reactor, and then a halogenated compound is added to carry out a substitution reaction at 0-40°C. After the reaction for 12-48 hours, a transition metal halide, a ligand, an unsaturated carboxylate small monomer, an unsaturated sulfonic acid small monomer and a polyether large monomer are added, and the mixture is sealed under nitrogen protection and the temperature is continuously raised to 50-100°C for ATRP reaction. The reaction is carried out for 5-60 hours, and the salt removed is desalted (the salt removed is one or more of cuprous bromide, cupric chloride, cupric bromide, ferric bromide, cuprous chloride, ferric chloride, ferrous bromide or ferrous chloride) and the organic solvent and by-products are removed by reduced pressure distillation to obtain a UHPC hydration temperature rise inhibitor as a network structure component. The solvent is selected from one or more combinations of dichloromethane, dichloropropane, chloroform and trichloroethane, and the mass ratio of the solvent to the polysaccharide network structure macromolecule is 5-20:1; the halogenated compound is 2-bromoisobutyryl bromide or 2-chloroisobutyryl chloride, and the molar ratio of the halogenated compound to the polysaccharide network structure macromolecule is 40-100:1; the transition metal halide is one or more combinations of cuprous bromide, ferrous bromide, cuprous chloride, ferrous bromide and ferrous chloride, and the molar ratio of the transition metal halide to the polysaccharide network structure macromolecule is 30-100:1; the ligand is N,N,N,N,N-pentamethyldiethylenetriamine, 2,2-bipyridine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, N,N,N,N- One or more combinations of tetra[(2-pyridyl)methyl]ethylenediamine, tri[2-(dimethylamino)ethyl]amine, the molar ratio of the ligand to the polysaccharide network structure macromolecule is 30-100:1; the unsaturated carboxylate small monomer is selected from sodium acrylate, sodium methacrylate, potassium acrylate or potassium methacrylate, the molar ratio of the unsaturated carboxylate small monomer to the polysaccharide network structure macromolecule is 200-1000:1; the unsaturated sulfonic acid small monomer is 2-acrylamide-2-methylpropanesulfonic acid or 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid sodium salt, the molar ratio of the unsaturated sulfonic acid small monomer to the polysaccharide network structure macromolecule is 200-1500:1; the polyether large monomer is a molecular weight of 2000-5000 g / mol of methyl allyl polyoxyethylene ether, isopentanol polyethoxyethylene ether or butanediol monovinyl polyoxyethylene ether, and the molar ratio of polyether macromolecules to polysaccharide network structure macromolecules is 400-2500:1.

[0081] Example 1

[0082] In this embodiment, the reinforcement and repair material ratio is: 30 parts of P·O 42.5 silicate cement, 3 parts of silica fume, 6 parts of fly ash, 3 parts of metakaolin, 56 parts of sand, 1 part of UHPC hydration temperature rise inhibitor of the network structure component, and 1 part of polypropylene fiber. The reinforcement and repair material and water are mixed at a mass ratio of 0.06-0.1:1.

[0083] The preparation method of the UHPC hydration temperature rise inhibitor with a network structure component is as follows:

[0084] (1) Preparation of carboxyl-terminated β-CD: First, 20 g of β-CD and 1.41 g of 10% potassium hydroxide solution were mixed evenly and added to a reactor. The mixture was stirred and dissolved at 20°C for 0.5 hour. Then, 4.90 g of bromoacetic acid was added and the temperature was raised to 40°C for substitution reaction. After reacting for 1 hour, the pH value was adjusted to 9 with 0.15 g of 80% concentrated sulfuric acid. The precipitate was washed once with 40 g of acetone and filtered out. The precipitate was vacuum dried for 24 hours to obtain carboxyl-terminated β-CD.

[0085] (2) Preparation of network structure macromolecules: 20 g of carboxyl-terminated β-CD was dissolved in 100 g of water and 4.96 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 3.68 g of N-hydroxysuccinimide were added. The mixture was stirred and activated at 6 °C for 0.1 h. Then 24.84 g of octaaminopropyl POSS was added and the temperature was raised to 20 °C for amidation reaction. After 3 hours of reaction, the unreacted solvent and small molecules were removed by dialyzing with a dialysis bag for 48 hours. The mixture was then vacuum dried for 24 hours to obtain a network structure macromolecule.

[0086] (3) Preparation of polysaccharide oxides: 200 g of 20% starch milk was added into the reactor, and the pH value was adjusted to 8 with 4 g of 10% potassium hydroxide solution, and then 2.4 g of hydrogen peroxide was added. The temperature was raised to 20 °C for oxidation reaction. The reaction lasted for 0.5 h, and the pH value was adjusted to 9 with 0.59 g of 80% concentrated sulfuric acid. 2.4 g of sodium thiosulfate was added to terminate the reaction. After washing with solvent once, the precipitate was filtered out and vacuum dried for 24 h to obtain polysaccharide oxides.

[0087] (4) Preparation of polysaccharide network macromolecules: 20 g of polysaccharide oxide was dissolved in 100 g of water and 0.048 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.029 g of N-hydroxysuccinimide were added. The mixture was stirred and activated at 8 °C for 0.1 hour. Then 18.78 g of network macromolecules was added. The mixture was heated to 30 °C for amidation reaction. After 3 hours of reaction, the mixture was dialyzed for 48 hours using a dialysis bag to remove unreacted solvent and molecules. The mixture was vacuum dried for 24 hours to obtain polysaccharide network macromolecules.

[0088] (5) Preparation of UHPC hydration temperature rise inhibitor with network structure component: 2 g of polysaccharide network structure macromolecule and 10 g of dichloropropane were mixed evenly and added to the reactor, and then 0.035 g of 2-chloroisobutyryl chloride was added to carry out substitution reaction at 20 °C. After 12 hours of reaction, 0.32 g of ferrous bromide, 0.24 g of 2,2-bipyridine, 1.48 g of sodium methacrylate, 2.31 g of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid sodium salt and 40 g of isopentanol polyethoxylated ether were added. The mixture was sealed under nitrogen protection and the temperature was continued to rise to 50 °C for ATRP reaction. The reaction was carried out for 5 hours, and the organic solvent and by-products were removed by desalination and reduced pressure distillation. Finally, 177.4 g of water was added to obtain a 20% network structure component UHPC hydration temperature rise inhibitor.

[0089] Example 2

[0090] In this embodiment, the reinforcement and repair material ratio is: 40 parts of P·I 52.5 silicate cement, 18 parts of silica fume, 15 parts of fly ash, 10 parts of metakaolin, 11 parts of sand, 3 parts of UHPC hydration temperature rise inhibitor of the network structure component, and 3 parts of steel fiber. The reinforcement and repair material and water are mixed at a mass ratio of 0.06-0.1:1.

[0091] (1) Preparation of carboxyl-terminated β-CD: First, 20 g of β-CD and 2.47 g of 50% ammonium hydroxide solution were mixed evenly and added to a reactor. The mixture was stirred and dissolved at 30°C for 3 hours. Then, 9.83 g of iodoacetic acid was added and the temperature was raised to 80°C for substitution reaction. After reacting for 10 hours, the pH value was adjusted to 8 with 3.21 g of 30% concentrated hydrochloric acid. The precipitate was washed with 200 g of acetone for 4 times and filtered out. The precipitate was vacuum dried for 40 hours to obtain carboxyl-terminated β-CD.

[0092] (2) Preparation of network structure macromolecules: 20 g of carboxyl-terminated β-CD was dissolved in 400 g of water and 8.41 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 2.53 g of N-hydroxysuccinimide were added. The mixture was stirred and activated at 10 °C for 0.5 h, and then 34.06 g of octaaminopropyl POSS was added. The mixture was heated to 60 °C for amidation reaction. After 10 h of reaction, the unreacted solvent and small molecules were removed by dialyzing with a dialysis bag for 60 h, and vacuum dried for 30 h to obtain a network structure macromolecule.

[0093] (3) Preparation of polysaccharide oxides: 200 g of 20% starch milk was added into the reactor, and the pH value was adjusted to 10 with 20 g of 10% ammonium hydroxide solution, and then 4 g of potassium persulfate was added. The temperature was raised to 60 °C for oxidation reaction. The reaction was carried out for 7 hours, and the pH value was adjusted to 8 with 3.74 g of 30% concentrated hydrochloric acid, and 4 g of sodium sulfite was added to terminate the reaction. After washing with solvent three times, the precipitate was filtered out and vacuum dried for 32 hours to obtain polysaccharide oxides.

[0094] (4) Preparation of polysaccharide network macromolecules: 20 g of polysaccharide oxide was dissolved in 400 g of water and 0.058 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.017 g of N-hydroxysuccinimide were added. The mixture was stirred and activated at 10 °C for 0.5 h. Then 25.08 g of network macromolecules was added. The mixture was heated to 80 °C for amidation reaction. After 10 h of reaction, the mixture was dialyzed for 62 h using a dialysis bag to remove unreacted solvent and molecules. The mixture was vacuum dried for 30 h to obtain polysaccharide network macromolecules.

[0095] (5) Preparation of UHPC hydration temperature rise inhibitor with network structure component: 2 g of polysaccharide network structure macromolecule and 40 g of chloroform were mixed evenly and added to the reactor, and then 0.87 g of 2-bromo-2-methylpropionyl bromide was added to carry out substitution reaction at 40 °C. After reacting for 24 hours, 0.38 g of cuprous chloride, 0.86 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, 4.94 g of potassium acrylate, 13.18 g of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid sodium salt and 76 g of butanediol monovinyl polyoxyethylene ether were added. The mixture was sealed under nitrogen protection and the temperature was continued to rise to 80 °C for ATRP reaction. The reaction was carried out for 30 hours, and the organic solvent and by-products were removed by desalination and reduced pressure distillation. Finally, 222.51 g of water was added to obtain a 30% network structure component UHPC hydration temperature rise inhibitor.

[0096] Example 3

[0097] In this embodiment, the reinforcement and repair material ratio is: 40 parts of P·O 52.5 silicate cement, 5 parts of silica fume, 15 parts of fly ash, 5 parts of metakaolin, 30 parts of sand, 3 parts of UHPC hydration temperature rise inhibitor of network structure component, and 2 parts of polyvinyl alcohol fiber. The reinforcement and repair material and water are mixed at a mass ratio of 0.06-0.1:1.

[0098] (1) Preparation of carboxyl-terminated β-CD: First, 20 g of β-CD and 2.82 g of 30% sodium hydroxide solution were mixed evenly and added to a reactor. The mixture was stirred and dissolved at 25°C for 2 hours. Then, 6.66 g of chloroacetic acid was added and the temperature was raised to 60°C for substitution reaction. After 6 hours of reaction, the pH value was adjusted to 6 with 1.93 g of 50% concentrated hydrochloric acid. The precipitate was washed with 160 g of methanol for 6 times and filtered out. The precipitate was vacuum dried for 48 hours to obtain carboxyl-terminated β-CD.

[0099] (2) Preparation of network structure macromolecules: 20 g of carboxyl-terminated β-CD was dissolved in 300 g of water and 11.12 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 13.58 g of N-hydroxysuccinimide were added. The mixture was stirred and activated at 0 °C for 1 hour. Then 45.05 g of octaaminopropyl POSS was added and the temperature was raised to 50 °C for amidation reaction. After 6 hours of reaction, the unreacted solvent and small molecules were removed by dialyzing with a dialysis bag for 72 hours. The mixture was then vacuum dried for 48 hours to obtain a network structure macromolecule.

[0100] (3) Preparation of polysaccharide oxides: 200 g of 40% starch milk was added to a reactor, and the pH value was adjusted to 12 with 40 g of 50% sodium hydroxide solution, and then 11.2 g of sodium hypochlorite was added. The temperature was raised to 50 °C for oxidation reaction. The reaction was carried out for 5 hours, and the pH value was adjusted to 6 with 45.63 g of 50% concentrated hydrochloric acid. 14.4 g of sodium bisulfite was added to terminate the reaction. After washing with solvent for 6 times, the precipitate was filtered out and vacuum dried for 48 hours to obtain polysaccharide oxides.

[0101] (4) Preparation of polysaccharide network macromolecules: 20 g of polysaccharide oxide was dissolved in 300 g of water and 0.063 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.076 g of N-hydroxysuccinimide were added. The mixture was stirred and activated at 0 °C for 1 hour. Then 37.13 g of network macromolecules was added. The mixture was heated to 60 °C for amidation reaction. After 6 hours of reaction, the mixture was dialyzed for 72 hours using a dialysis bag to remove unreacted solvent and molecules. The mixture was vacuum dried for 48 hours to obtain polysaccharide network macromolecules.

[0102] (5) Preparation of UHPC hydration temperature rise inhibitor with network structure component: 2 g of polysaccharide network structure macromolecule and 30 g of dichloromethane were mixed evenly and added to the reactor, and then 0.61 g of 2-bromoisobutyryl bromide was added to carry out substitution reaction at 0 °C. After 48 hours of reaction, 0.38 g of cuprous bromide, 0.46 g of N,N,N,N,N-pentamethyldivinyltriamine, 1.90 g of sodium acrylate, 6.84 g of 2-acrylamide-2-methylpropanesulfonic acid and 198 g of methyl allyl polyoxyethylene ether were added. The mixture was sealed under nitrogen protection and the temperature was continued to rise to 60 °C for ATRP reaction. The reaction was carried out for 48 hours, and the organic solvent and by-products were removed by desalination and reduced pressure distillation. Finally, 311.37 g of water was added to obtain a UHPC hydration temperature rise inhibitor with a concentration of 20%.

[0103] Comparative Example 1

[0104] The UHPC hydration temperature rise inhibitor, which is a network structure component in the reinforcement and repair material of Example 1, is replaced with a commercially available urea hydration temperature rise inhibitor as Comparative Example 1.

[0105] Comparative Example 2

[0106] The UHPC hydration temperature rise inhibitor, a network structure component in the reinforcement and repair material of Example 1, was replaced with a commercially available starch dextrin hydration temperature rise inhibitor as Comparative Example 2.

[0107] Comparative Example 3

[0108] A commercially available ultra-high performance mass concrete with low hydration heat was used as comparative example 3.

[0109] Performance Testing

[0110] 1. Dispersion performance of UHPC reinforcement and repair materials

[0111] In order to investigate the working performance of the UHPC hydration temperature rise inhibitor prepared by the "net-like" structure component of the present invention, the slump, expansion and slump / expansion loss over time of the materials of different embodiments and comparative examples were tested according to GB / T 8076-2008. The test results are shown in Table 1.

[0112] Table 1 Slump and expansion test results of UHPC reinforcement and repair materials

[0113]

[0114] As can be seen from Table 1, the reinforcement and repair materials mixed with the UHPC hydration temperature rise inhibitor synthesized by the method of the present invention show excellent dispersion ability, collapse protection ability and cement adaptability in concrete. The reinforcement and repair materials can be fully combined with the damaged surface of concrete, improve the bonding force between the original repair layer and the damaged surface of concrete, and avoid the shedding of the repair layer.

[0115] 2. Mechanical properties of UHPC reinforcement and repair materials

[0116] In order to investigate the effect of the hydration temperature rise inhibitor of the "net-like" structural component synthesized in the present invention on the early strength development of UHPC reinforcement and repair materials, the test specimens were molded according to GB / T 50081-2019, and the surface was covered with a waterproof film immediately after molding, and then cured at 25 ℃ for 24 hours. After demolding, the compressive strength of the specimens was tested for 1 day, and the remaining specimens continued to be cured at 25 ℃ to the specified age, and the compressive strength of the specimens was tested for 3 days and 28 days respectively. The test results are shown in Table 2.

[0117] Table 2 Compressive strength test results of UHPC reinforcement and repair materials / MPa

[0118]

[0119] As can be seen from Table 2, the addition of the "net-like" structural component UHPC hydration temperature rise inhibitor synthesized by the method of the present invention significantly improves the early and late strength of the reinforcement and repair materials, indicating that the prepared "net-like" structural component UHPC hydration temperature rise inhibitor can promote the development of the early strength of UHPC reinforcement and repair materials, which is beneficial to restore the use function of damaged concrete and meet the service design requirements.

[0120] 3. Thermal insulation temperature rise and shrinkage of UHPC reinforcement and repair materials

[0121] In order to investigate the effect of the UHPC hydration temperature rise inhibitor of the "net-like" structure component synthesized by the present invention on the thermal insulation temperature rise and shrinkage of the UHPC reinforcement and repair material, the proportions of the various components of the concrete were controlled to be the same, and the thermal insulation temperature rise, autogenous shrinkage and drying shrinkage of the concretes added with different embodiments and comparative examples were tested. The test results are shown in Table 3.

[0122] Table 3 Results of thermal insulation temperature rise and shrinkage test of UHPC reinforcement and repair materials

[0123]

[0124] As can be seen from Table 3, the UHPC hydration temperature rise inhibitor with a "net-like" structural component synthesized by the method of the present invention can delay the hydration exothermic process, reduce the adiabatic temperature rise, and significantly improve the temperature rise and shrinkage inhibition effects of the UHPC reinforcement and repair materials. This shows that the prepared UHPC hydration temperature rise inhibitor with a "net-like" structural component can promote the reinforcement and repair of damaged concrete by reinforcement and repair materials, inhibit the shrinkage and cracking of concrete, and further extend the service life of the concrete structure.

[0125] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for repairing a damaged concrete surface, characterized in that: The steps include: S1: Chisel and clean the damaged surface of the concrete and moisten it thoroughly; S2: Pour water and reinforcement repair materials into a mixer at a mass ratio of 0.06-0.1:1 and stir thoroughly for 10-20 minutes to obtain reinforcement repair wet material; S3: Inject the reinforcement and repair wet material into the damaged concrete surface after moistening, and evenly spread it on the concrete surface with a trowel and scraper to ensure that the reinforcement and repair wet material fully fills the damaged concrete surface; The components of the reinforcement and repair material include, by weight: 30-40 parts of silicate cement, 3-18 parts of silica fume, 6-15 parts of fly ash, 3-10 parts of metakaolin, 11-56 parts of sand, 1-3 parts of UHPC hydration temperature rise inhibitor as a network structure component, and 1-3 parts of fiber; The preparation method of the network structure component UHPC hydration temperature rise inhibitor is as follows: prepare carboxyl terminal β-CD by substitution modification of β-CD and halogenated acid, then sequentially react with amino POSS and polysaccharide oxide to obtain polysaccharide network structure macromolecules, and then react with halogenated compounds, unsaturated carboxylate small monomers, unsaturated sulfonic acid small monomers and polyether macromonomers to undergo substitution-ATRP reaction to obtain the network structure component UHPC hydration temperature rise inhibitor; The halogenated compound is 2-bromoisobutyryl bromide or 2-chloroisobutyryl chloride.

2. The method for repairing a damaged concrete surface according to claim 1, characterized in that: The preparation method of the reinforcement repair material comprises the following steps: Portland cement, silica fume, fly ash, metakaolin and sand are weighed by weighing scales and transported to a mixer for stirring for 10-15 minutes; Add the network structure component UHPC hydration temperature rise inhibitor into the mixer and continue stirring for 15-20 minutes; The fibers are added into a blender and stirred for 15-20 minutes to obtain a reinforcement repair material.

3. The method for repairing a damaged concrete surface according to claim 1, characterized in that: The silicate cement is selected from any one or more combinations of P·O 42.5, P·O 52.5, P·I 42.5, and P·I 52.5; The fiber is any one or more combinations of steel fiber, polyvinyl alcohol fiber, polypropylene fiber, and polyoxymethylene fiber; The sand is standard sand, and the screening mesh number is 20-70 mesh.

4. The method for repairing a damaged concrete surface according to claim 1, characterized in that: The molecular structure of the UHPC hydration temperature rise inhibitor of the network structure component is as follows: Among them, the structural formula of R is: Among them, the structural formula of R2 is: In the above formula, a, b, c, x, y, z, and n are integers representing the number of repeating units of each part in the polymer, a ranges from 5 to 10, b ranges from 10 to 15, c ranges from 10 to 25, x ranges from 5 to 10, y ranges from 5 to 15, z ranges from 10 to 25, and n ranges from 10 to 150; R1 is CH2CH2CH2, R3 is H or Na, and R4 is CH2, CH2CH2, or O(CH2CH2O)2.

5. The method for repairing a damaged concrete surface according to claim 1, characterized in that: The preparation method of the network structure component UHPC hydration temperature rise inhibitor specifically comprises the following steps: Step 1, preparation of carboxyl-terminal β-CD: β-CD and an alkaline solvent with a mass fraction of 10-50% are mixed evenly and added to a reactor, and stirred and dissolved at 20-30°C for 0.5-3 hours, and then a halogenated acid is added, and the temperature is raised to 40-80°C for substitution reaction. After reacting for 1-10 hours, the pH value is adjusted to 6-9 with an acidic solvent with a mass fraction of 20-100%, and the precipitate is filtered out after washing with the solvent for 1-6 times, and vacuum dried for 24-48 hours to obtain carboxyl-terminal β-CD; Step 2, preparation of a network structure macromolecule: dissolve the carboxyl-terminal β-CD obtained in step 1 in water and add an activator, stir and activate at 0-10°C for 0.1-1 hour, then add amino POSS, heat to 20-60°C for amidation reaction, react for 3-10 hours, use a dialysis bag for 48-72 hours to remove unreacted solvent and small molecules, and vacuum dry for 24-48 hours to obtain a network structure macromolecule; Step 3, preparation of polysaccharide oxides: adding 20-40% by mass of starch milk into a reactor, adjusting the pH value to 8-12 with 10-50% by mass of an alkaline solvent, adding an oxidant, heating to 20-60°C for oxidation reaction, reacting for 0.5-7 hours, adjusting the pH value to 6-9 with 20-100% by mass of an acidic solvent, and adding a reducing agent to terminate the reaction, filtering out the precipitate after washing with the solvent for 1-6 times, and vacuum drying for 24-48 hours to obtain polysaccharide oxides; Step 4, preparation of polysaccharide network structure macromolecules: dissolve the polysaccharide oxide product obtained in step 3 in water and add an activator, stir and activate at 0-10°C for 0.1-1 hour, then add the network structure macromolecule obtained in step 2, heat to 30-80°C for amidation reaction, react for 3-10 hours, use a dialysis bag for 48-72 hours to remove unreacted solvent and molecules, and vacuum dry for 24-48 hours to obtain polysaccharide network structure macromolecules; Step 5, preparation of a UHPC hydration temperature rise inhibitor as a network structure component: the polysaccharide network structure macromolecule obtained in step 4 and the solvent are evenly mixed and added to a reactor, and then a halogenated compound is added to carry out a substitution reaction at 0-40°C. After reacting for 12-48 hours, a transition metal halide, a ligand, an unsaturated carboxylate small monomer, an unsaturated sulfonic acid small monomer and a polyether large monomer are added, and the mixture is sealed under nitrogen protection and the temperature is continuously raised to 50-100°C for ATRP reaction. The reaction is carried out for 5-60 hours, and the organic solvent and by-products are removed by desalination and reduced pressure distillation to obtain a UHPC hydration temperature rise inhibitor as a network structure component.

6. The method for repairing a damaged concrete surface according to claim 5, characterized in that: The alkali in the alkaline solvent in step 1 is one or more combinations of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide, and the molar ratio of the alkali in the alkaline solvent to β-CD is 2-4:1; In step 1, the halogenated acid is chloroacetic acid, bromoacetic acid, iodoacetic acid, 2-chloropropionic acid, 2-bromopropionic acid or 2-iodopropionic acid, and the molar ratio of the halogenated acid to β-CD is 2-4:1; The acidic solvent in step 1 is concentrated hydrochloric acid or concentrated sulfuric acid; the molar ratio of the acid in the acidic solvent to the base in the alkaline solvent is 0.6-2.5:1; In step 1, the solvent is methanol or acetone, and the mass ratio of the solvent to β-CD is 2-10:1; The water in step 2 is deionized water, and the mass ratio of the deionized water to the carboxyl-terminal β-CD is 5-20:1; In step 2, the activator is 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, the molar ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide to N-hydroxysuccinimide is 0.5-2:1, and the molar ratio of the activator to the carboxyl-terminal β-CD is 2-4:1; The amino POSS in step 2 is octaaminopropyl POSS, and the molar ratio of the amino POSS to the carboxyl-terminal β-CD is 2-4:

1.

7. The method for repairing a damaged concrete surface according to claim 5, characterized in that: The alkali in the alkaline solvent in step 3 is one or more combinations of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide, and the mass ratio of the alkali in the alkaline solvent to the starch milk is 0.1-0.5:1; In step 3, the oxidant is sodium hypochlorite, hydrogen peroxide, potassium permanganate, potassium persulfate, peroxy acid or periodic acid, and the mass ratio of the oxidant to starch milk is 0.06-0.14:1; The acidic solvent in step 3 is concentrated hydrochloric acid or concentrated sulfuric acid, and the molar ratio of the acid in the acidic solvent to the base in the alkaline solvent is 0.6-2.5:1; In step 3, the reducing agent is sodium bisulfite, sodium thiosulfate, sodium sulfite or manganese sulfate, and the mass ratio of the reducing agent to starch milk is 0.06-0.18:1; The water in step 4 is deionized water, and the mass ratio of the deionized water to the polysaccharide oxide is 5-20:1; In step 4, the activator is 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, the molar ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide to N-hydroxysuccinimide is 0.5-2:1, and the molar ratio of the activator to the polysaccharide oxide is 0.5-1:1; In step 4, the molar ratio of the network structure macromolecule to the polysaccharide oxide is 2.5-3.75:

1.

8. The method for repairing a damaged concrete surface according to claim 5, characterized in that: The solvent in step 5 is selected from one or more combinations of dichloromethane, dichloropropane, chloroform, and trichloroethane, and the mass ratio of the solvent to the polysaccharide network structure macromolecule is 5-20:1; The molar ratio of the halogenated compound to the polysaccharide network structure macromolecule is 40-100:1; The transition metal halide is one or more combinations of cuprous bromide, ferrous bromide, cuprous chloride, and ferrous chloride, and the molar ratio of the transition metal halide to the polysaccharide network structure macromolecule is 30-100:1; The ligand is one or more combinations of N,N,N,N,N-pentamethyldivinyltriamine, 2,2-bipyridine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, N,N,N,N-tetra[(2-pyridyl)methyl]ethylenediamine, and tri[2-(dimethylamino)ethyl]amine, and the molar ratio of the ligand to the polysaccharide network structure macromolecule is 30-100:1; The unsaturated carboxylate small monomer is selected from sodium acrylate, sodium methacrylate, potassium acrylate or potassium methacrylate, and the molar ratio of the unsaturated carboxylate small monomer to the polysaccharide network structure macromolecule is 200-1000:1; The unsaturated sulfonic acid small monomer is 2-acrylamide-2-methylpropanesulfonic acid or 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid sodium salt, and the molar ratio of the unsaturated sulfonic acid small monomer to the polysaccharide network structure macromolecule is 200-1500:1; The polyether macromolecule is methyl allyl polyoxyethylene ether, isopentanol polyoxyethylene ether or butanediol monovinyl polyoxyethylene ether with a molecular weight of 2000-5000 g / mol, and the molar ratio of the polyether macromolecule to the polysaccharide network structure macromolecule is 400-2500:1; The salt removed in the desalting process of step 5 is one or more of cuprous bromide, cupric chloride, cupric bromide, ferric bromide, cuprous chloride, ferric chloride, ferrous bromide or ferrous chloride.

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