Intelligent response type multi-element nano crystal nucleus early strength agent as well as preparation method and application thereof

Abstract

The invention discloses an intelligent response type multi-element nanocrystal nucleus early strength agent as well as a preparation method and application thereof, and belongs to the technical field of concrete early strength agents. The method comprises the following steps: adding a compound into a dispersing agent for ultrasonic dispersion, and centrifuging, washing, drying and grinding the obtained suspension to obtain the powdery intelligent response type multi-element nanocrystal nucleus early strength agent, wherein the compound is one or more of a hydrated calcium silicate and intelligent response type hyperbranched polymer compound, a calcium hydroxide and intelligent response type hyperbranched polymer compound and a hydrated calcium sulphoaluminate and intelligent response type hyperbranched polymer compound; the preparation method comprises the following steps: carrying out an etherification reaction on a phenol monomer and an enol monomer, carrying out a sulfonation reaction with sulfuric acid to obtain sulfonic acid aryl alkenyl ether, and carrying out free radical polymerization on the sulfonic acid aryl alkenyl ether and monomers such as polyol and a polyoxyethylene ether compound under the action of an initiator to obtain the intelligent response type hyperbranched polymer. The obtained early strength agent can generate intelligent response in a cement pore solution environment, the workability of cement mortar is remarkably improved, the super-early mechanical property of a cement-based material is improved, and the early strength agent has unique technical advantages and wide application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of concrete early-strength agents, and particularly relates to an intelligent-responsive multi-component nano-crystal nucleus early-strength agent and its preparation method and application. Background Art

[0002] Cement-based materials have become the most widely used artificial building materials in engineering construction due to their low raw material prices, strong moldability, and excellent mechanical properties after hardening. With the increasing demand for shortening the formwork removal time, improving production efficiency, accelerating construction speed, and simplifying the construction process in construction projects, the requirement for the early strength of cement-based materials has also increased accordingly.

[0003] As an important type of concrete admixture, early-strength agents can significantly improve the early strength of concrete, adapt to construction in low-temperature environments, and improve the durability of concrete. Early-strength agents accelerate the cement hydration reaction, shorten the setting time, and increase the 1-day and 3-day strengths, thereby accelerating the construction progress. In winter or emergency repair projects, early-strength agents can effectively reduce the impact of low temperature on the hardening of concrete, prevent frost damage, and ensure the project progress. In addition, early-strength agents can also reduce the porosity of concrete, enhance the compactness, improve the impermeability, frost resistance, and chemical erosion resistance, and extend the service life of concrete.

[0004] Currently, the research and development of concrete early-strength agents are moving towards environmental protection, compounding, and intelligence. Its core value lies in balancing construction efficiency, structural performance, and sustainable development needs. With the deepening of green building policies and the innovation of material technologies, the role of early-strength agents in infrastructure construction, prefabricated buildings, and other fields is becoming increasingly crucial. Early-strength agents can not only reduce the emissions of harmful substances such as chloride ions and sulfates, meet the requirements of low-carbon building policies, but also improve the utilization rate of industrial waste (such as slag and fly ash), further reducing resource consumption and environmental pollution.

[0005] However, existing early-strength agents often have an adverse impact on the later strength of concrete while improving the early strength, and have limited improvement on the workability of cement-based materials. Therefore, developing an intelligent-responsive early-strength agent that can not only significantly improve the early strength but also maintain or improve the later strength while improving the workability of cement-based materials has important practical significance and application value. Summary of the Invention

[0006] The present invention proposes an intelligent-responsive multi-component nano-crystal nucleus early-strength agent and its preparation method and application, aiming to prepare a multi-component nano-crystal nucleus early-strength agent by innovating the molecular structure design and monomer design and introducing an intelligent-responsive hyperbranched polymer, so as to solve the deficiencies of existing early-strength agents in improving early strength, workability, and maintaining later strength, and promote the further development of concrete early-strength agent technology.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] One of the objects of the present invention is to provide a preparation method of an intelligent response type multi-component nanocrystalline nucleus early strength agent, comprising the following steps: adding a composite into a dispersant for ultrasonic dispersion, and centrifuging, washing, drying and grinding the obtained suspension to obtain a powdery intelligent response type multi-component nanocrystalline nucleus early strength agent;

[0009] Wherein, the composite is one or several of a calcium silicate hydrate and an intelligent response type hyperbranched polymer composite, calcium hydroxide and an intelligent response type hyperbranched polymer composite, and calcium sulfoaluminate hydrate and an intelligent response type hyperbranched polymer composite;

[0010] The reaction principle of the polymer with calcium silicate hydrate is that the sulfonate groups on the main chain are complexed and adsorbed on the surface through calcium ions, and the side chains are intercalated into the interlayer of calcium silicate hydrate; the reaction principle of the polymer with calcium hydroxide is that the sulfonate groups on the main chain are electrostatically adsorbed on the surface of calcium hydroxide, and the ether bonds on the side chains are hydrogen-bonded to the surface of calcium hydroxide; the reaction principle of the polymer with calcium sulfoaluminate hydrate is that the sulfonate groups on the main chain are electrostatically adsorbed on the positively charged sites on the surface of calcium sulfoaluminate hydrate.

[0011] The specific preparation steps of the intelligent response type hyperbranched polymer include:

[0012] Mixing a phenolic monomer, an enol monomer and a catalyst, heating and stirring, and obtaining an aryl vinyl ether monomer through neutralization, extraction, liquid separation and vacuum distillation;

[0013] Mixing the aryl vinyl ether monomer with an acid, heating and stirring, and obtaining an intelligent response type monomer through neutralization, extraction, liquid separation and vacuum distillation;

[0014] Mixing a polyoxyethylene ether monomer, a polyol monomer, a cerium tetravalent salt, an oxidant and water, heating and stirring, and then dropping a mixed aqueous solution of the intelligent response type monomer, a chain transfer agent and a reducing agent into the above solution, and keeping warm and stirring after dropping to obtain an intelligent response type hyperbranched polymer.

[0015] Through innovative monomer design, the phenolic monomers introduced in the present invention first undergo etherification with enol monomers and then sulfonation reaction with sulfuric acid or fuming sulfuric acid to obtain functional monomers with intelligent response characteristics. These functional monomers are connected with polyoxyethylene ether monomers through a free radical polymerization reaction initiated by cerium(IV) ions and polyols to obtain a polymer with intelligent response characteristic groups. The adsorption groups contained in its main chain can adsorb on the surface of seed particles to control their nucleation and growth. At the same time, the polymer adsorbed on the surface of the seeds can achieve intelligent response in the cement pore solution environment and desorb through the hydrolysis of aryl ether bonds. The desorbed macromolecules can significantly improve the workability of fresh cement paste, and have the effects of dispersing both nano-crystals and cement particles. The prepared powder nano-crystal nucleating accelerator can improve the workability of fresh cement paste compared with the existing nano-crystal nucleating accelerators on the market, which is an innovation in the multi-functional direction of nano-crystal nucleating accelerators, and opens up ideas and directions for the subsequent in-depth development of new varieties of nano-crystal nucleating accelerator materials.

[0016] Through innovative molecular structure design, the present invention introduces an initiation system of cerium(IV) ions and polyols, and develops a polymer with a hyperbranched topological structure. Its hyperbranched structure can control the particle size of seed particles from multiple dimensions and significantly improve the particle morphology, greatly enhancing the early mechanical properties of cement-based materials. The prepared powder nano-crystal nucleating accelerator has a more significant early strength enhancing effect compared with the existing nano-crystal nucleating accelerators on the market, which is a breakthrough in the design, preparation and performance upgrade directions of nano-crystal nucleating accelerators, and expands the paths and directions for the subsequent further development of high-performance nano-crystal nucleating accelerator materials.

[0017] The present invention realizes innovation on the basis of traditional calcium silicate hydrate nano-crystal nucleating accelerator and ettringite nano-crystal nucleating accelerator. By respectively preparing a variety of organic-inorganic composite nano-particles with compositions and structures similar to those of cement hydration products and compounding them to obtain a multi-component nano-crystal nucleating accelerator, it realizes the synchronous nucleation and growth of multiple hydration products during cement hydration, promotes the formation of a relatively complete microstructure in hardened cement-based materials at an earlier age, further improves the early mechanical properties of cement-based materials on the basis of traditional nano-crystal nucleating accelerators, and also provides a new technical approach for developing corresponding nano-early strength enhancers for multi-component building material systems.

[0018] Furthermore, by mass percentage, the content ratios of the raw materials in the suspension are as follows: 0-25% of the complex of calcium silicate hydrate and intelligent response type hyperbranched polymer, 0-25% of the complex of calcium hydroxide and intelligent response type hyperbranched polymer, 0-25% of the complex of calcium sulfoaluminate and intelligent response type hyperbranched polymer, and the balance is a dispersant; among them, the contents of the complex of calcium silicate hydrate and intelligent response type hyperbranched polymer, the complex of calcium hydroxide and intelligent response type hyperbranched polymer, and the complex of calcium sulfoaluminate and intelligent response type hyperbranched polymer are not all 0 at the same time.

[0019] Furthermore, the molecular structural formula of the intelligent responsive hyperbranched polymer is as follows:

[0020]

[0021] Wherein,

[0022] The structural formula of R is

[0023] The structural formula of R' is

[0024] R" is H or

[0025] a, b and n are the number of repeating units of each part in the polymer, which are integers, 10 < a < 160, 5 < b < 40, 10 < n < 150;

[0026] R1 is H or CH3;

[0027] R2 is CH2, CH2CH2, OCH2CH2 or O(CH2CH2)2;

[0028] R3 is H, CH3 or CH2CH3;

[0029] R4 is H or CH3;

[0030] R5 is H or CH3;

[0031] R6 is CH2OH or CH2CHOH;

[0032] R7 is

[0033] R8 is

[0034] Furthermore, in the process of preparing the intelligent responsive hyperbranched polymer:

[0035] The molar ratio of the phenolic monomer to the enol monomer is 1∶(1 - 2); and / or

[0036] The molar ratio of the catalyst to the total amount of the phenolic monomer and the enol monomer is (0.5 - 1.5)∶1; and / or

[0037] The phenolic monomer is phenol, 2 - methylphenol, 2,6 - dimethylphenol, 2 - ethyl - 6 - methylphenol, 2,6 - diethylphenol or β - naphthol; and / or

[0038] The enol monomers are allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, cis-2-buten-1-ol, crotyl alcohol, 2-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 4-penten-1-ol, 4-penten-2-ol, 1-penten-3-ol, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 3-penten-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol or 3-methyl-3-buten-2-ol; except for these listed enol monomers, other potential enol monomers are all feasible and can achieve similar effects, and the present invention will not list them all.

[0039] The catalyst is concentrated sulfuric acid or concentrated phosphoric acid; and / or

[0040] In the process of preparing aryl vinyl ether monomers, the conditions of heating and stirring are: stirring and reacting at 5 - 80 °C for 1 - 24 h; and / or

[0041] The acid is sulfuric acid or fuming sulfuric acid; when the acid is sulfuric acid, the molar ratio of aryl vinyl ether monomer to sulfuric acid is 1∶(1 - 1.2); when the acid is fuming sulfuric acid, the mass ratio of aryl vinyl ether monomer to fuming sulfuric acid is 1∶(0.8 - 1.5);

[0042] In the process of preparing smart-responsive monomers, the conditions of heating and stirring are: stirring and reacting at 45 - 165 °C for 0.5 - 6 h; and / or

[0043] The molar ratio of the polyol monomer to the cerium(IV) salt is 1∶(3 - 4.5); and / or

[0044] The molar ratio of the polyoxyethylene ether monomer, polyol monomer, oxidant, smart-responsive monomer, chain transfer agent and reducing agent is 1∶(0.01 - 0.05)∶(0.05 - 0.4)∶(1 - 6)∶(0.05 - 0.5)∶(0 - 0.08); and / or

[0045] The polyoxyethylene ether monomers are allyl alcohol polyoxyethylene ether, methallyl polyoxyethylene ether, isopentenol polyoxyethylene ether, ethylene glycol mono vinyl polyoxyethylene ether or butanediol mono vinyl polyoxyethylene ether; and / or

[0046] The polyol monomers are 2-hydroxymethyl-1,3-propanediol, pentaerythritol or 3-hydroxymethyl-1,5-pentanediol; and / or

[0047] The cerium(IV) salts are cerium nitrate, ammonium cerium nitrate, cerium sulfate, ammonium cerium sulfate or cerium fluoride; and / or

[0048] The oxidants are ammonium persulfate, potassium persulfate or hydrogen peroxide with a concentration of 20 - 30%; and / or

[0049] The chain transfer agent is thioglycolic acid, 3-mercaptopropionic acid or sodium methallylsulfonate; and / or

[0050] The reducing agent is ascorbic acid or Rongalite; and / or

[0051] The conditions for heat preservation and stirring are: heat preservation and stirring reaction at 20 - 70 °C for 0.5 - 2.5 h.

[0052] Furthermore, the specific preparation steps of the calcium silicate hydrate and the intelligent response type hyperbranched polymer composite include: adding the intelligent response type hyperbranched polymer into water to obtain an intelligent response type hyperbranched polymer aqueous solution, adjusting the pH to alkaline, heating, then dropping in an aqueous metal salt solution and an aqueous silicate solution, and stirring and reacting after dropping is completed. The obtained suspension is centrifuged, washed, dried and ground to obtain a powdery calcium silicate hydrate and intelligent response type hyperbranched polymer composite.

[0053] The compounding principle of the intelligent response type hyperbranched polymer and calcium silicate hydrate is that the sulfonic acid groups existing in its main chain are deprotonated under alkaline conditions to form negatively charged sulfonate groups, which are adsorbed on the surface of calcium silicate hydrate by means of calcium ion complexation. The polyether side chains of the intelligent response type hyperbranched polymer can enter the interlayer position of calcium silicate hydrate and combine with calcium silicate hydrate in an intercalation manner.

[0054] Even further, in the process of preparing the calcium silicate hydrate and the intelligent response type hyperbranched polymer composite:

[0055] The concentration of the intelligent response type hyperbranched polymer aqueous solution is 1 - 30 wt%;

[0056] The dosage of the intelligent response type hyperbranched polymer is 5 - 30% of the total mass of the solid raw materials (the total mass of the solid raw materials refers to the mass of all solid raw materials in the preparation process of the calcium silicate hydrate and the intelligent response type hyperbranched polymer composite, the same below);

[0057] The metal salt is one or more of soluble aluminum salts, soluble iron salts and soluble calcium salts; among them, the soluble aluminum salt is one or more of aluminum chloride and aluminum nitrate; the soluble iron salt is one or more of ferric chloride and ferric nitrate; the soluble calcium salt is one or more of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate and calcium dihydrogen phosphate;

[0058] The silicate is soluble silicate, which is one or more of lithium silicate, sodium silicate and potassium silicate;

[0059] The molar ratio of the soluble aluminum salt, soluble iron salt, soluble calcium salt and silicate is (0 - 0.5)∶(0 - 0.3)∶(0.8 - 2)∶1;

[0060] The concentration of the soluble aluminum salt aqueous solution is 0 - 3.0 mol / L, the concentration of the soluble iron salt aqueous solution is 0 - 7.5 mol / L, the concentration of the soluble calcium salt aqueous solution is 0.5 mol / L - 5.8 mol / L, and the concentration of the soluble silicate aqueous solution is 0.5 mol / L - 2.9 mol / L;

[0061] The acid solution used to adjust the pH is hydrochloric acid or nitric acid with a concentration of 1 - 10 wt%; all the alkali solutions are lithium hydroxide solution, sodium hydroxide solution or potassium hydroxide solution with a concentration of 1 - 10 wt%;

[0062] The empirical formula of the inorganic component of the obtained calcium silicate hydrate and the intelligent responsive hyperbranched polymer composite is aCaO·SiO2·bAl2O3·cFe2O3·dH2O, where 0.8 < a < 2.0, 0 < b < 0.5, 0 < c < 0.3, and 1 < d < 6.

[0063] Furthermore, the specific preparation steps of the calcium hydroxide and the intelligent responsive hyperbranched polymer composite include: adding the intelligent responsive hyperbranched polymer into water to obtain an intelligent responsive hyperbranched polymer aqueous solution, adjusting the pH to alkaline, heating, then dropping in the calcium salt aqueous solution and the alkali solution, and after the dropping is completed, stirring and reacting. The obtained suspension is centrifuged, washed, dried and ground to obtain a powdery calcium hydroxide and intelligent responsive hyperbranched polymer composite.

[0064] The compounding principle of the intelligent responsive hyperbranched polymer and calcium hydroxide is that the sulfonic acid groups existing in its main chain are deprotonated under alkaline conditions to form negatively charged sulfonate groups, which are adsorbed on the surface of calcium hydroxide by electrostatic adsorption, and the polyether side chains of the intelligent responsive hyperbranched polymer form hydrogen bonds with the hydroxyl groups on the surface of calcium hydroxide and bind to the surface of calcium hydroxide.

[0065] Even further, in the process of preparing the calcium hydroxide and the intelligent responsive hyperbranched polymer composite:

[0066] The concentration of the intelligent responsive hyperbranched polymer composite aqueous solution is 1 - 40 wt%;

[0067] The dosage of the intelligent responsive hyperbranched polymer is 1 - 40% of the total mass of the solid raw materials;

[0068] The alkali solution is an aqueous solution of lithium hydroxide, sodium hydroxide or potassium hydroxide, with a concentration of 10 - 40 wt%;

[0069] The calcium salt is a soluble calcium salt, which is one or more of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate and calcium dihydrogen phosphate;

[0070] The alkali is a soluble alkali, which is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;

[0071] The molar ratio of the calcium salt to the base is (1 - 2)∶1;

[0072] The concentration of the aqueous calcium salt solution is 0.5 - 6.5 mol / L, and the concentration of the base solution is 0.5 - 4.5 mol / L.

[0073] Furthermore, the specific preparation steps of the calcium sulfoaluminate and the intelligent response type hyperbranched polymer composite include: adding the intelligent response type hyperbranched polymer into water to obtain an intelligent response type hyperbranched polymer aqueous solution, adjusting the pH to alkaline, heating, and then dropping into the aqueous solutions of the calcium salt, the base, the aluminate / aluminum salt and the sulfate. After the dropping is completed, stir and react. The obtained suspension is centrifuged, washed, dried and ground to obtain a powdery calcium sulfoaluminate and intelligent response type hyperbranched polymer composite.

[0074] The composite principle of the intelligent response type hyperbranched polymer and calcium sulfoaluminate is that the sulfonic acid groups existing in its main chain are deprotonated under alkaline conditions to form negatively charged sulfonate groups, and are adsorbed on the positively charged sites on the surface of calcium sulfoaluminate through electrostatic interaction.

[0075] Even further, in the process of preparing the calcium sulfoaluminate and intelligent response type hyperbranched polymer composite:

[0076] The concentration of the intelligent response type hyperbranched polymer composite aqueous solution is 1 - 20 wt%;

[0077] The dosage of the intelligent response type hyperbranched polymer is 5 - 25% of the total mass of the solid raw materials;

[0078] The base solution is an aqueous solution of lithium hydroxide, sodium hydroxide or potassium hydroxide, and the concentration is 10 - 40 wt%;

[0079] The calcium salt is a soluble calcium salt, which is one or more of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate and calcium dihydrogen phosphate;

[0080] The base is a soluble base, which is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;

[0081] The aluminate is a soluble aluminate, which is sodium aluminate;

[0082] The sulfate is a soluble sulfate, which is one or more of sodium sulfate, potassium sulfate, potassium alum and aluminum sulfate;

[0083] The aluminate is a soluble aluminate, which is sodium aluminate;

[0084] The concentration of the soluble calcium salt aqueous solution is 0.5 - 5.8 mol / L;

[0085] The concentration of the soluble alkali aqueous solution is 0.5 - 4.5 mol / L;

[0086] The concentration of the soluble aluminum salt / aluminate aqueous solution is 0.1 - 5.5 mol / L;

[0087] The concentration of the soluble sulfate aqueous solution is 0.1 - 3.0 mol / L;

[0088] The molar ratio of the calcium salt to the alkali is 1∶(1 - 2);

[0089] The molar ratio of calcium element, sulfur element and aluminum element in the calcium salt, aluminum salt / aluminate and sulfate is (4 - 6)∶(1 - 3)∶2;

[0090] The acid solution used to adjust the pH is hydrochloric acid or nitric acid with a concentration of 1 - 10 wt%; all alkali solutions are lithium hydroxide solution, sodium hydroxide solution or potassium hydroxide solution with a concentration of 1 - 10 wt%;

[0091] The empirical formula of the inorganic component of the calcium sulfoaluminate and the intelligent responsive hyperbranched polymer composite obtained is 3CaO·Al2O3·aCaSO4·bH2O, where 1 < a < 3 and 12 < b < 32.

[0092] The second object of the present invention is to provide an intelligent responsive multi - component nano - crystal nucleus early - strength agent prepared by the above - mentioned preparation method.

[0093] The third object of the present invention is to provide a concrete, using the intelligent responsive multi - component nano - crystal nucleus early - strength agent as an external admixture, and the dosage is 0.1 - 5 wt% of the mass of the cementitious material in the cement - based material.

[0094] The fourth object of the present invention is to provide the application of the intelligent responsive multi - component nano - crystal nucleus early - strength agent in the fields of fresh neat paste, mortar and concrete.

[0095] The fifth object of the present invention is to provide the application of the intelligent responsive multi - component nano - crystal nucleus early - strength agent in the cementitious system containing a large amount of supplementary cementitious materials and the solid - waste - based cementitious material system.

[0096] The intelligent response type multi - component nano - crystal nucleating early - strength agent designed and prepared by the present invention is not only applicable to Portland cement, but also can be applied to cementitious systems containing large amounts of supplementary cementitious materials and solid - waste - based cementitious material systems. The proportion of the multi - component nano - crystal nucleating early - strength agent can be accurately regulated according to the chemical and mineral compositions of different cementitious systems and the types and proportions of hydration products, so as to maximize the improvement of the early mechanical properties of different cementitious systems, providing a feasible solution for further enhancing the early strength of cement - based materials. At the same time, it also promotes the breakthrough development of building functional materials, significantly enhancing the application potential and commercial value, and becoming a new material favored by the market.

[0097] Compared with the prior art, the present invention has the following advantages and technical effects:

[0098] The intelligent response type multi - component nano - crystal nucleating early - strength agent designed and prepared by the present invention can rapidly improve the early strength of cement - based materials in different cementitious systems, greatly improving the quality of construction projects. This intelligent response type multi - component nano - crystal nucleating early - strength agent can be applied to various fresh neat pastes, mortars and concretes, and also specifically promotes the engineering applications of cementitious systems containing large amounts of supplementary cementitious materials and solid - waste - based cementitious material systems, solves the problem of low early strength of various building materials, significantly enhances the environmental, economic and social benefits, and has great market potential and application value. Detailed implementation manners

[0099] Now, the various exemplary implementation manners of the present invention will be described in detail. This detailed description should not be regarded as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and implementation schemes of the present invention.

[0100] It should be understood that the terms described in the present invention are only for describing particular implementation manners and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0101] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes the preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0102] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the description of the present invention, which are obvious to those skilled in the art. Other embodiments obtained from the description of the present invention are obvious to those skilled in the art. The description and examples of the present invention are merely exemplary.

[0103] Regarding the use of "comprising", "including", "having", "containing", etc. in this article, they are all open-ended terms, meaning including but not limited to.

[0104] In the present invention, first, an etherification reaction occurs between a phenolic monomer and an enol monomer, and then a sulfonation reaction occurs with sulfuric acid to obtain a sulfonic acid aromatic vinyl ether. Under the action of an initiator, a free radical polymerization occurs with monomers such as polyols and polyoxyethylene ether compounds to obtain an intelligent response type hyperbranched polymer. Using soluble calcium salts, silicates, aluminum salts or aluminates and sulfates as solid raw materials, nano-calcium silicate hydrate, nano-calcium hydroxide and nano-calcium sulfoaluminate hydrate are respectively prepared with the intelligent response type hyperbranched polymer. Through centrifugal washing, vacuum drying and grinding, and then compounding nano-calcium silicate hydrate, nano-calcium hydroxide and nano-calcium sulfoaluminate hydrate in a specific ratio, an intelligent response type multi-nano crystal nucleus early strength agent can be obtained, which can have an intelligent response in the cement pore solution environment, significantly improve the workability of cement mortar, and enhance the ultra-early mechanical properties of cement-based materials, having unique technical advantages and broad application prospects.

[0105] The preparation method of the intelligent response type multi-nano crystal nucleus early strength agent provided by the embodiment of the present invention includes the following steps: adding the composite into a dispersant, stirring at a speed of 10 - 1500 rpm for 1 - 30 min to obtain a mixed solution; placing the obtained mixed solution in a water bath ultrasonic instrument, and performing ultrasonic dispersion at a temperature of 5 - 60 °C, a frequency of 25 - 100 kHz, and an ultrasonic power of 5 - 300 W for 1 - 30 min to obtain a suspension, and centrifuging, washing, drying and grinding the obtained suspension to obtain a powdery intelligent response type multi-nano crystal nucleus early strength agent;

[0106] Among them, the composite is one or several of a calcium silicate hydrate and an intelligent response type hyperbranched polymer composite, a calcium hydroxide and an intelligent response type hyperbranched polymer composite, and a calcium sulfoaluminate hydrate and an intelligent response type hyperbranched polymer composite. In some alternative embodiments, when the composite is added to the dispersant, the stirring speed can be selected as 500 rpm, 1000 rpm or 1500 rpm, and the stirring time can be selected as 5 min or 5 min.

[0107] In some alternative embodiments, the parameters of the ultrasound can be selected as follows: temperature of 15 °C, 20 °C or 30 °C, frequency of 80 kHz or 100 kHz, power of 30 W, 60 W or 100 W, and ultrasound time of 5 min, 20 min or 30 min.

[0108] In some alternative embodiments, by mass percentage, the content ratios of the raw materials in the suspension are as follows: 0 - 25% of the calcium silicate hydrate and smart-responsive hyperbranched polymer complex, 0 - 25% of the calcium hydroxide and smart-responsive hyperbranched polymer complex, 0 - 25% of the calcium sulfoaluminate hydrate and smart-responsive hyperbranched polymer complex, and the balance is the dispersant; wherein, the contents of the calcium silicate hydrate and smart-responsive hyperbranched polymer complex, the calcium hydroxide and smart-responsive hyperbranched polymer complex, and the calcium sulfoaluminate hydrate and smart-responsive hyperbranched polymer complex are not all 0 at the same time. In alternative embodiments of the present invention, the mass ratios of the calcium silicate hydrate and smart-responsive hyperbranched polymer complex, the calcium hydroxide and smart-responsive hyperbranched polymer complex, the calcium sulfoaluminate hydrate and smart-responsive hyperbranched polymer complex, and the dispersant can be selected as 1∶3∶6∶40, 1.5∶1∶18 or 6.9∶2.1∶1∶90.

[0109] In some alternative embodiments, the dispersant is one or more of water, ethanol, ethylene glycol and isopropanol. Exemplarily, the dispersant can be selected as isopropanol, ethanol.

[0110] In some alternative embodiments, the molecular structural formula of the smart-responsive hyperbranched polymer is as follows:

[0111]

[0112] Wherein,

[0113] The structural formula of R is The structural formula of R' is R" is H or a, b and n are the number of repeating units of each part in the polymer, which are integers, 10 < a < 160, 5 < b < 40, 10 < n < 150;

[0114] R1 is H or CH3;

[0115] R2 is CH2, CH2CH2, OCH2CH2 or O(CH2CH2)2;

[0116] R3 is H, CH3 or CH2CH3;

[0117] R4 is H or CH3;

[0118] R5 is H or CH3;

[0119] R6 is CH2OH or CH2CHOH;

[0120] R7 is

[0121] R8 is

[0122] The specific preparation steps of the intelligent responsive hyperbranched polymer include:

[0123] (1) Preparation of aryl vinyl ether monomer: Mix a phenolic monomer, an enol monomer and a catalyst, and stir and react at 5 - 80 °C for 1 - 24 h. After neutralization, extraction, liquid separation and vacuum distillation, the aryl vinyl ether monomer is obtained; optionally, the stirring temperature can be selected as 65 °C and the stirring time can be selected as 8 h;

[0124] (2) Preparation of intelligent responsive monomer: Mix the aryl vinyl ether monomer with an acid and stir and react at 45 - 165 °C for 0.5 - 6 h. After neutralization, extraction, liquid separation and vacuum distillation, the intelligent responsive monomer is obtained; optionally, the stirring temperature can be selected as 80 °C and the stirring time can be selected as 1 h;

[0125] (3) Preparation of intelligent responsive hyperbranched polymer complex: Add a polyoxyethylene ether monomer, a polyol monomer, a cerium(IV) salt, an oxidant and water into a reactor, stir and keep the temperature at 20 - 70 °C (the temperature can be selected as 45 °C and the heat preservation time can be selected as 30 min), then uniformly drop the mixed aqueous solution of the intelligent responsive monomer, a chain transfer agent and a reducing agent into the reactor within 1 - 4 h (4 h can be selected). After the dropping is completed, keep stirring and reacting at 20 - 70 °C for 0.5 - 2.5 h to obtain the intelligent responsive hyperbranched polymer. Preferably, the heat preservation temperature can be selected as 45 °C and the reaction time can be selected as 1 h.

[0126] In step (1), the molar ratio of the phenolic monomer to the enol monomer is 1∶(1 - 2); in the following examples of the present invention, the molar ratio of the phenolic monomer to the enol monomer can be selected as 1∶1.3, 1∶1.4 or 1∶1.8;

[0127] The molar ratio of the catalyst to the total amount of the phenolic monomer and the enol monomer is (0.5 - 1.5)∶1; in the following examples of the present invention, the molar ratio of the optional catalyst to the total amount of the phenolic monomer and the enol monomer can be selected as 0.8∶1, 1.1∶1 or 1.2∶1;

[0128] The phenolic monomer is phenol, 2-methylphenol, 2,6-xylenol, 2-ethyl-6-methylphenol, 2,6-diethylphenol or β-naphthol; exemplarily, in the following examples of the present invention, the phenolic monomer can be selected from phenol, β-naphthol or 2-ethyl-6-methylphenol;

[0129] The enol monomer is allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, cis-2-buten-1-ol, crotyl alcohol, 2-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 4-penten-1-ol, 4-penten-2-ol, 1-penten-3-ol, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 3-penten-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol or 3-methyl-3-buten-2-ol; exemplarily, in the following examples of the present invention, the enol monomer can be selected from allyl alcohol, 4-penten-1-ol or 3-buten-2-ol.

[0130] The catalyst is concentrated sulfuric acid or concentrated phosphoric acid.

[0131] In step (2), the molar ratio of the aryl vinyl ether monomer to the acid is 1:(0.8 - 1.5); when the acid is sulfuric acid, the molar ratio of the aryl vinyl ether monomer to sulfuric acid is 1:(1 - 1.2); when the acid is fuming sulfuric acid, the mass ratio of the aryl vinyl ether monomer to fuming sulfuric acid is 1:(0.8 - 1.5); exemplarily, in the following examples of the present invention, the molar ratio of the aryl vinyl ether monomer to the acid can be selected from 1:1, 1:1.1 or 1:1.2.

[0132] The acid is sulfuric acid or fuming sulfuric acid; the mass concentration of free sulfur trioxide in the fuming sulfuric acid is 20 - 70%; exemplarily, in the following examples of the present invention, the mass concentration of free sulfur trioxide in the fuming sulfuric acid can be selected as 65%, that is, the mass concentration of the fuming sulfuric acid can be selected as 65%.

[0133] In step (3), the molar ratio of the polyol monomer to the cerium(IV) salt is 1:(3 - 4.5); exemplarily, in the following examples of the present invention, the molar ratio of the polyol monomer to the cerium(IV) salt can be selected from 1:3.0, 1:4.0 or 1:3.5.

[0134] The molar ratio of the polyoxyethylene ether monomer, polyol monomer, oxidant, intelligent responsive monomer, chain transfer agent and reducing agent is 1∶(0.01 - 0.05)∶(0.05 - 0.4)∶(1 - 6)∶(0.05 - 0.5)∶(0 - 0.08) (i.e., the reducing agent may not be added); Exemplarily, in the following examples of the present invention, the molar ratio of the polyoxyethylene ether monomer, polyol monomer, oxidant, intelligent responsive monomer, chain transfer agent and reducing agent can be selected as 1∶0.02∶0.3∶4.0∶0.1∶0.06, 1∶0.01∶0.28∶2.0∶0.2∶0 or 1∶0.04∶0.18∶5.0∶0.09∶0.02.

[0135] The polyoxyethylene ether monomer is allyl alcohol polyoxyethylene ether, methyl allyl polyoxyethylene ether, isopentenol polyoxyethylene ether, ethylene glycol mono vinyl polyoxyethylene ether or butanediol mono vinyl polyoxyethylene ether; Exemplarily, in the following examples of the present invention, the polyoxyethylene ether monomer can be selected as isopentenol polyoxyethylene ether, methyl allyl polyoxyethylene ether or butanediol mono vinyl polyoxyethylene ether.

[0136] The polyol monomer is 2 - hydroxymethyl - 1,3 - propanediol, pentaerythritol or 3 - hydroxymethyl - 1,5 - pentanediol; Exemplarily, in the following examples of the present invention, the polyol monomer can be selected as 2 - hydroxymethyl - 1,3 - propanediol, pentaerythritol or 3 - hydroxymethyl - 1,5 - pentanediol.

[0137] The tetravalent cerium salt is cerium nitrate, ammonium cerium nitrate, cerium sulfate, ammonium cerium sulfate or cerium fluoride; Exemplarily, in the following examples of the present invention, the tetravalent cerium salt can be selected as cerium sulfate, ammonium cerium nitrate or ammonium cerium sulfate.

[0138] The oxidant is ammonium persulfate, potassium persulfate or hydrogen peroxide with a concentration of 20 - 30 wt%; Exemplarily, in the following examples of the present invention, the oxidant can be selected as hydrogen peroxide or ammonium persulfate.

[0139] The chain transfer agent is mercaptoacetic acid, mercaptopropionic acid or sodium methallyl sulfonate; Exemplarily, in the following examples of the present invention, the chain transfer agent can be selected as mercaptopropionic acid or mercaptoacetic acid.

[0140] The reducing agent is ascorbic acid or sodium formaldehyde sulfoxylate.

[0141] In some alternative embodiments, the specific preparation steps of the calcium silicate hydrate and intelligent responsive hyperbranched polymer composite include:

[0142] S1. Add the intelligent responsive hyperbranched polymer into water to obtain an aqueous solution of the intelligent responsive hyperbranched polymer. Put this solution into a reactor, adjust the pH value of the system to 10.5 - 11.5 with an alkali solution under stirring conditions, and set the temperature to 20 - 75 °C; optionally, the pH value can be adjusted to 11.0 or 11.2, and the temperature can be set to 20 °C, 25 °C or 60 °C;

[0143] S2. Slowly and uniformly add an aqueous solution of metal salt and an aqueous solution of silicate into the reactor within 1 - 24 h (such as 6 h). During the dropping process, use an acid solution and an alkali solution to keep the pH value of the system stable at 10.5 - 11.5 (such as 11.0 or 11.2). After the dropping is completed, stir and react at 20 - 75 °C (such as 20 °C, 25 °C or 60 °C) for 0 - 2 h (such as 1 h or 2 h). During the reaction process, continuously stir at a speed of 300 - 1700 rpm (such as 600 rpm, 750 rpm or 800 rpm) to obtain a suspension of calcium silicate hydrate and intelligent responsive hyperbranched polymer composite;

[0144] S3. Centrifuge, wash, dry and grind the obtained suspension to obtain a powdery calcium silicate hydrate and intelligent responsive hyperbranched polymer composite.

[0145] In step S1, the concentration of the aqueous solution of the intelligent responsive hyperbranched polymer is 1 - 30 wt%;

[0146] The dosage of the intelligent responsive hyperbranched polymer is 5 - 30% of the total mass of the solid raw materials;

[0147] In step S2, the metal salt is one or more of soluble aluminum salts, soluble iron salts and soluble calcium salts; among them, the soluble aluminum salt is one or more of aluminum chloride and aluminum nitrate; the soluble iron salt is one or more of ferric chloride and ferric nitrate; the soluble calcium salt is one or more of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate and calcium dihydrogen phosphate; optionally, in the following examples of the present invention, the metal salt can be a mixture of aluminum nitrate nonahydrate and calcium nitrate tetrahydrate, anhydrous calcium chloride, a mixture of calcium nitrate tetrahydrate and ferric nitrate nonahydrate;

[0148] The silicate is soluble silicate, which is one or more of lithium silicate, sodium silicate and potassium silicate; optionally, in the following examples of the present invention, the silicate can be sodium silicate nonahydrate;

[0149] The molar ratio of the soluble aluminum salt, soluble iron salt, soluble calcium salt, and silicate is (0 - 0.5)∶(0 - 0.3)∶(0.8 - 2)∶1; optionally, in the following examples of the present invention, the molar ratio of the soluble aluminum salt, soluble iron salt, soluble calcium salt, and silicate is 0.1∶0∶1.0∶1, 0∶0∶1.7∶1, or 0∶0.2∶1.5∶1;

[0150] The concentration of the soluble aluminum salt aqueous solution is 0 - 3.0 mol / L, such as 0 mol / L, 0.2 mol / L; the concentration of the soluble iron salt aqueous solution is 0 - 7.5 mol / L, such as 0 mol / L or 0.2 mol / L; the concentration of the soluble calcium salt aqueous solution is 0.5 - 5.8 mol / L, such as 1.4 mol / L, 1.5 mol / L, or 2.3 mol / L; the concentration of the soluble silicate aqueous solution is 0.5 - 2.9 mol / L, such as 0.8 mol / L or 1.5 mol / L;

[0151] The acid solution used to adjust the pH is hydrochloric acid or nitric acid with a concentration of 1 - 10 wt%; all the base solutions are lithium hydroxide solution, sodium hydroxide solution, or potassium hydroxide solution with a concentration of 1 - 40 wt%, such as sodium hydroxide solution with a concentration of 40 wt%;

[0152] The empirical formula of the inorganic component of the obtained calcium silicate hydrate and the intelligent responsive hyperbranched polymer composite is aCaO·SiO2·bAl2O3·cFe2O3·dH2O, where 0.8 < a < 2.0, 0 ≤ b < 0.5, 0 ≤ c < 0.3, 1 < d < 6. Exemplarily, the empirical formula can be CaO·SiO2·0.05Al2O3·0Fe2O3·2.1H2O, 1.7CaO·SiO2·0Al2O3·0Fe2O3·0.8H2O, or 1.5CaO·SiO2·0Al2O3·0.08Fe2O3·1.9H2O.

[0153] In some optional embodiments, the specific preparation steps of the calcium hydroxide and intelligent responsive hyperbranched polymer composite include:

[0154] A. Add the intelligent responsive hyperbranched polymer into water to obtain an intelligent responsive hyperbranched polymer aqueous solution, add this solution into a reactor, adjust the pH value of the system to 11.0 - 12.0 with a base solution under stirring conditions, and set the temperature to 30 - 60°C; optionally, the pH can be adjusted to 11.0, 11.5, or 12.0; the temperature can be set to 30°C, 40°C, or 60°C;

[0155] B. adding the calcium salt aqueous solution and the alkaline solution to the reactor at a uniform speed within 1-6 hours (such as 1 hour, 3 hours or 5 hours), respectively, and keeping the reaction at 30-60° C. (such as 30° C., 40° C. or 60° C.) for 0-3 hours (such as 1 hour or 2 hours) after the addition is completed, and stirring at a speed of 500-1500 rpm (such as 700 rpm, 800 rpm or 1000 rpm) during the reaction to obtain a suspension of calcium hydroxide and a smart responsive hyperbranched polymer composite;

[0156] C. The obtained suspension is centrifuged, washed, dried and ground to obtain a powdered calcium hydroxide and smart responsive hyperbranched polymer composite.

[0157] In step A, the concentration of the intelligent responsive hyperbranched polymer complex aqueous solution is 1-40 wt %.

[0158] The amount of the intelligent response type hyperbranched polymer used is 1-40% of the total mass of the solid raw material.

[0159] The alkaline solution is an aqueous solution of lithium hydroxide, sodium hydroxide or potassium hydroxide with a concentration of 10-40wt%; such as a potassium hydroxide solution with a concentration of 40wt% or a sodium hydroxide solution with a concentration of 30wt%.

[0160] In step B, the calcium salt is a soluble calcium salt, which is one or more of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate and calcium dihydrogen phosphate; illustratively, in the following embodiments of the present invention, the calcium salt can be selected from calcium nitrate tetrahydrate or anhydrous calcium chloride.

[0161] The alkali is a soluble alkali, which is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; illustratively, in the following embodiments of the present invention, the alkali can be selected from sodium hydroxide or potassium hydroxide.

[0162] The molar ratio of the calcium salt to the base (the base is only the base in step B, excluding the base in step A and the base used to adjust the pH) is (1-2):1; illustratively, in the following embodiments of the present invention, the molar ratio of the calcium salt to the base can be selected from 2:1, 1.25:1 or 1:1.

[0163] The concentration of the calcium salt aqueous solution is 0.5-6.5 mol / L, such as 2.3 mol / L, 3.6 mol / L or 4.0 mol / L; the concentration of the alkali solution is 0.5-4.5 mol / L, such as 4.0 mol / L or 4.5 mol / L.

[0164] In some optional embodiments, the specific preparation steps of the composite of calcium sulphoaluminate hydrate and smart responsive hyperbranched polymer include:

[0165] Step 1: Add the intelligent responsive hyperbranched polymer into water to obtain an intelligent responsive hyperbranched polymer aqueous solution. Add this solution into a reactor, and under stirring conditions, adjust the pH value of the system to 10.5 - 11.7 with an alkali solution, and set the temperature to 25 - 60°C; Optionally, the pH can be adjusted to 11.0; the temperature can be set to 25°C;

[0166] Step 2: Respectively and uniformly dropwise add aqueous solutions of calcium salt, alkali, aluminum salt / aluminate, and sulfate into the reactor within 1 - 12 h (such as 5 h). During the dropping process, adjust the pH of the system to be stable at 10.5 - 11.7 (such as 11.0) with an acid solution and an alkali solution. After the dropping is completed, keep the temperature at 25 - 60°C (such as 25°C) and carry out a holding reaction for 0 - 2 h (such as 1 h). During the reaction process, continuously stir at a speed of 600 - 2000 rpm (such as 1500 rpm or 1800 rpm) to obtain a suspension of calcium sulfoaluminate and intelligent responsive hyperbranched polymer complex (in this step, the " / " in "aluminum salt / aluminate" means "or", that is, calcium salt, alkali, aluminum salt, and sulfate can be selected simultaneously, or calcium salt, alkali, aluminate, and sulfate can be selected simultaneously);

[0167] Step 3: Centrifuge, wash, dry, and grind the obtained suspension to obtain a powdery calcium sulfoaluminate and intelligent responsive hyperbranched polymer complex.

[0168] In Step 1, the concentration of the intelligent responsive hyperbranched polymer aqueous solution is 1 - 20 wt%.

[0169] The dosage of the intelligent responsive hyperbranched polymer is 5 - 25% of the total mass of the solid raw materials.

[0170] The alkali solution is an aqueous solution of lithium hydroxide, sodium hydroxide, or potassium hydroxide, and the concentration is 10 - 40 wt%; such as a sodium hydroxide solution with a concentration of 30 wt%.

[0171] In Step 2, the calcium salt is a soluble calcium salt, which is one or more of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate, and calcium dihydrogen phosphate; Exemplarily, in the following examples of the present invention, the calcium salt can be selected as calcium nitrate tetrahydrate.

[0172] The alkali is a soluble alkali, which is one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide; Exemplarily, in the following examples of the present invention, the alkali can be selected as sodium hydroxide or potassium hydroxide.

[0173] The aluminum salt is a soluble aluminum salt, which is one or more of aluminum nitrate, aluminum chloride, potassium alum, and aluminum sulfate; Exemplarily, in the following examples of the present invention, the aluminum salt can be selected as aluminum sulfate octadecahydrate or aluminum nitrate nonahydrate.

[0174] The aluminate is a soluble aluminate, specifically sodium metaaluminate.

[0175] The sulfate is a soluble sulfate, which is one or more of sodium sulfate, potassium sulfate, potassium alum, and aluminum sulfate; for example, in the following examples of the present invention, the aluminum sulfate or sodium sulfate.

[0176] The concentration of the aqueous solution of the soluble calcium salt is 0.5 - 5.8 mol / L, such as 2.3 mol / L.

[0177] The concentration of the aqueous solution of the soluble base is 0.5 - 4.5 mol / L, such as 4.5 mol / L.

[0178] The concentration of the aqueous solution of the soluble aluminum salt / aluminate is 0.1 - 5.5 mol / L, such as 0.4 mol / L or 0.8 mol / L.

[0179] The concentration of the aqueous solution of the soluble sulfate is 0.1 - 3.0 mol / L, such as 0.4 mol / L or 0.8 mol / L.

[0180] The molar ratio of the calcium salt to the base is 1∶(1 - 2); for example, in the following examples of the present invention, the molar ratio of the calcium salt to the base is 1∶2.

[0181] The molar ratio of calcium, sulfur, and aluminum elements in the calcium salt, aluminum salt / aluminate, and sulfate is (4 - 6)∶(1 - 3)∶2; for example, in the following examples of the present invention, the molar ratio of calcium, sulfur, and aluminum elements in the calcium salt, aluminum salt / aluminate, and sulfate is 6∶3∶2 or 4∶1∶2.

[0182] The acid solution used to adjust the pH is hydrochloric acid or nitric acid with a concentration of 1 - 10 wt%; all the base solutions are lithium hydroxide solution, sodium hydroxide solution, or potassium hydroxide solution with a concentration of 1 - 10 wt%.

[0183] The empirical formula of the inorganic component of the calcium sulfoaluminate and the intelligent response - type hyperbranched polymer composite obtained in step three is 3CaO·Al2O3·aCaSO4·bH2O, where 1 < a < 3 and 12 < b < 32. For example, in the following examples of the present invention, the empirical formula of the inorganic component can be 3CaO·Al2O3·3CaSO4·32H2O or 3CaO·Al2O3·CaSO4·12H2O.

[0184] Using the above - mentioned preparation method, an intelligent response - type multi - component nano - crystal nucleus early - strength agent can be prepared.

[0185] An embodiment of the present invention also provides a kind of concrete, using the intelligent response type multi - nano crystal nucleus early - strength agent as an external admixture, and the dosage is 0.1 - 5wt% of the mass of the cementitious material in the cement - based material.

[0186] The intelligent response type multi - nano crystal nucleus early - strength agent can be applied to the fields of fresh neat cement paste, mortar and concrete.

[0187] The intelligent response type multi - nano crystal nucleus early - strength agent can be applied to the cementitious system containing a large amount of supplementary cementitious materials and the solid - waste - based cementitious material system.

[0188] All raw materials used in the present invention are obtained by purchasing in the market.

[0189] The technical solution of the present invention is further described below through examples.

[0190] In the following examples of the present invention:

[0191] The specific operations of neutralization, extraction, liquid - liquid separation and vacuum distillation are as follows: after the reaction is completed, add a sodium hydroxide, sodium carbonate or sodium bicarbonate solution with a mass concentration of 5 - 40% to the reaction mixture until the pH value of the solution reaches 7 - 8; add the mixture to a separating funnel and let it stand for layering, and obtain the organic phase by liquid - liquid separation; through vacuum distillation, the required product is separated from the organic phase. The parameters in this process do not affect the final performance of the product, and all tests maintain unified operations. These parameters are not discussed as creative factors of the present invention.

[0192] The specific operations of centrifugation, washing, drying and grinding are as follows: the rotation speed of centrifugation is preferably 4000 - 15000r / min, more preferably 8000 - 10000r / min; the number of washing times is preferably 0 - 6 times, more preferably 0 - 2 times; the temperature of vacuum drying is preferably 20 - 80°C, more preferably 25 - 40°C; the time of vacuum drying is preferably 12 - 48h, more preferably 24 - 36h; the particle size of the complex obtained by grinding is preferably 50 - 900nm, more preferably 200 - 800nm. The parameters in this process do not affect the final performance of the product, and all tests maintain unified operations. These parameters are not discussed as creative factors of the present invention.

[0193] Example 1

[0194] A preparation method of an intelligent response type multi - nano crystal nucleus early - strength agent, comprising the following steps:

[0195] (1) Preparation of aryl vinyl ether monomer: Add 41.0g of phenol, 32.7g of allyl alcohol and 75.5g of concentrated sulfuric acid (mass concentration of 98.0%) into a reactor, stir and react at a constant temperature of 65°C for 8h, and obtain the aryl vinyl ether monomer through neutralization, extraction, liquid - liquid separation and vacuum distillation;

[0196] (2) Preparation of intelligent responsive monomer: Add 52.5 g of the aryl vinyl ether monomer obtained in step (1) and 39.2 g of sulfuric acid (mass concentration 98.0%) into a reactor, stir and react at a constant temperature of 80 °C for 1 h, and obtain the intelligent responsive monomer through neutralization, extraction, liquid separation and vacuum distillation;

[0197] (3) Preparation of intelligent responsive hyperbranched polymer: Add 0.05 g of 2-hydroxymethyl-1,3-propanediol, 60 g of isopentenyl alcohol polyoxyethylene ether, 0.5 g of cerium sulfate, 0.9 g of 30 wt% hydrogen peroxide and 65 g of water into a reactor, stir at 45 °C for 30 min. Dissolve 70.4 g of the intelligent responsive monomer obtained in step (2) in 105 g of water, and dissolve 0.9 g of mercaptopropionic acid and 0.9 g of ascorbic acid in 30.4 g of water to obtain solution A; Under the condition of constant temperature stirring at 45 °C, drop the intelligent responsive monomer aqueous solution and solution A into the reactor uniformly within 4 h, and after the dropping is completed, keep stirring and reacting at 45 °C for 1 h to obtain an intelligent responsive hyperbranched polymer solution;

[0198] The structural formula of the intelligent responsive hyperbranched polymer is:

[0199]

[0200] where a∶b = 4∶1, n = 53;

[0201] (4) Preparation of calcium silicate hydrate and intelligent responsive hyperbranched polymer composite: Dissolve 51.9 g of sodium silicate nonahydrate in 92.1 g of water, dissolve 43.1 g of calcium nitrate tetrahydrate and 6.8 g of aluminum nitrate nonahydrate in 105.6 g of water. Add 47.2 g of the intelligent responsive hyperbranched polymer solution obtained in step (3) and 153.3 g of water into a reactor, adjust the pH value to 11.2 with 40 wt% sodium hydroxide solution and set the temperature to 25 °C. Under the stirring speed of 600 rpm, drop the sodium silicate aqueous solution and the aqueous solution of calcium nitrate and aluminum nitrate into the reactor uniformly within 6 h. After the dropping is completed, keep reacting at 25 °C for 1 h. Centrifuge the suspension, wash the precipitate to neutral, dry to constant weight and grind to obtain a calcium silicate hydrate and intelligent responsive hyperbranched polymer composite with an average particle size of 343 nm;

[0202] (5) Preparation of calcium hydroxide and intelligent response type hyperbranched polymer composite: Dissolve 25 g of sodium hydroxide and 73.8 g of calcium nitrate tetrahydrate in 138.9 g and 116.4 g of water respectively. Add 59.3 g of the intelligent response type hyperbranched polymer solution obtained in step (3) and 86.6 g of water into the reactor, adjust the pH value to 11.0 with 40 wt% sodium hydroxide solution and set the temperature to 30 °C. Dropwise add the sodium hydroxide aqueous solution and calcium nitrate aqueous solution into the reactor at a constant speed within 1 h under a stirring speed of 700 rpm. After the dropping is completed, immediately centrifuge the suspension, wash the precipitate to neutral, dry it to constant weight and grind it to obtain a composite of calcium hydroxide and intelligent response type hyperbranched polymer with an average particle size of 495 nm;

[0203] (6) Preparation of calcium sulfoaluminate and intelligent response type hyperbranched polymer composite: Dissolve 20.4 g of sodium hydroxide, 60.3 g of calcium nitrate tetrahydrate and 28.4 g of aluminum sulfate octadecahydrate (in this process, aluminum sulfate octadecahydrate is counted as both aluminum salt and sulfate at the same time. When using aluminum sulfate, no additional aluminum salt needs to be added. The molar ratio of aluminum salt to sulfate needs to ensure that the molar ratio of aluminum element to sulfur element is 2:1 - 3, and this condition can be met only by using aluminum sulfate, so no additional aluminum salt or sulfate needs to be added) in 113.5 g, 95.1 g and 99.7 g of water respectively. Add 32.7 g of the intelligent response type hyperbranched polymer solution obtained in step (3) and 49.8 g of water into the reactor, adjust the pH value to 11.0 with 30 wt% sodium hydroxide solution and set the temperature to 25 °C. Dropwise add the sodium hydroxide solution, calcium nitrate solution and aluminum sulfate solution into the reactor at a constant speed within 5 h under a stirring speed of 1800 rpm. After the dropping is completed, keep the temperature at 25 °C for 1 h for reaction. Centrifuge the suspension, wash the precipitate to neutral, dry it to constant weight and grind it to obtain a composite of calcium sulfoaluminate and intelligent response type hyperbranched polymer with an average particle size of 201 nm;

[0204] (7) Preparation of intelligent response type multi - component nano - crystal nucleus early strength agent: Add the composite obtained in step (4), the composite obtained in step (5), the composite obtained in step (6) and isopropyl alcohol (purity is AR, mass concentration is 99.7%) into a container, stir at a speed of 1500 rpm for 15 min, place the container in a water - bath ultrasonic instrument, and ultrasonicate at a power of 30 W and a frequency of 80 kHz at 15 °C for 20 min. After centrifugation, washing, drying and grinding, obtain a powdery intelligent response type multi - component nano - crystal nucleus early strength agent. (The mass ratio of isopropyl alcohol, the composite obtained in step (5), the composite obtained in step (6) and the composite obtained in step (4) is 40:3:6:1).

[0205] Example 2

[0206] Preparation method of intelligent response type multi-component nanocrystalline nucleus early strength agent, comprising the following steps:

[0207] (1) Preparation of aryl vinyl ether monomer: Add 21.6 g of β-naphthol, 18.1 g of 4-penten-1-ol and 38.8 g of concentrated phosphoric acid (mass concentration 85.0%) into a reactor, stir and react at a constant temperature of 70 °C for 4 h, and obtain the aryl vinyl ether monomer through neutralization, extraction, liquid separation and vacuum distillation;

[0208] (2) Preparation of intelligent response type monomer: Add 21.2 g of the aryl vinyl ether monomer obtained in step (1) and 23.4 g of 65% oleum into a reactor, stir and react at a constant temperature of 160 °C for 1 h, and obtain the intelligent response type monomer through neutralization, extraction, liquid separation and vacuum distillation;

[0209] (3) Preparation of intelligent response type hyperbranched polymer: Add 0.05 g of pentaerythritol, 80 g of methyl allyl polyoxyethylene ether, 0.9 g of ammonium cerium nitrate, 2.1 g of ammonium persulfate and 70 g of water into a reactor, stir at 65 °C for 30 min, dissolve 19.5 g of the intelligent response type monomer obtained in step (2) in 90 g of water, dissolve 0.6 g of mercaptoacetic acid in 31.6 g of water, and uniformly add the intelligent response type monomer aqueous solution and mercaptoacetic acid aqueous solution into the reactor within 3 h under the condition of constant temperature stirring at 65 °C. After the dropping is completed, keep stirring and reacting at 65 °C for 2 h to obtain an intelligent response type hyperbranched polymer solution;

[0210] The structural formula of the intelligent response type hyperbranched polymer is:

[0211]

[0212] where a∶b = 2∶1 and n = 53;

[0213] (4) Preparation of the complex of calcium silicate hydrate and intelligent response type hyperbranched polymer: Dissolve 33.1 g of sodium silicate nonahydrate and 22.0 g of anhydrous calcium chloride in 126.8 g and 145.7 g of water respectively. Add 39.4 g of the intelligent response type hyperbranched polymer solution obtained in step (3) and 133.0 g of water into a reactor, adjust the pH value to 11.0 with 40 wt% sodium hydroxide solution and set the temperature to 60 °C. Under the stirring speed of 750 rpm, uniformly drop the sodium silicate aqueous solution and calcium nitrate aqueous solution into the reactor within 12 h. After the dropping is completed, keep reacting at 60 °C for 2 h. Centrifuge, wash, dry and grind the suspension to obtain a complex of calcium silicate hydrate and intelligent response type hyperbranched polymer with an average particle size of 265 nm;

[0214] (5) Preparation of calcium hydroxide and intelligent responsive hyperbranched polymer composite: Dissolve 20.1 g of potassium hydroxide and 67.7 g of calcium nitrate tetrahydrate in 79.6 g and 59.0 g of water respectively. Add 20.1 g of the intelligent responsive hyperbranched polymer solution obtained in step (3) and 253.6 g of water into the reactor, adjust the pH value to 11.5 with 40 wt% potassium hydroxide solution and set the temperature to 60 °C. Dropwise add the potassium hydroxide aqueous solution and calcium nitrate aqueous solution into the reactor at a uniform speed within 3 h under a stirring speed of 1000 rpm. After the dropping is completed, keep stirring and reacting at 60 °C for 1 h. The suspension is centrifuged, washed, dried and ground to obtain a composite of calcium hydroxide and intelligent responsive hyperbranched polymer with an average particle size of 759 nm;

[0215] (6) Preparation of intelligent responsive multi-nanocrystalline nucleus early strength agent: Add the composite obtained in step (4), the composite obtained in step (5) and ethanol (purity AR, mass concentration 99.5%) into a container, stir at a speed of 1000 rpm for 5 min, place the container in a water bath ultrasonic instrument, and ultrasonicate at 30 °C with a power of 100 W and a frequency of 100 kHz for 5 min. After centrifugation, washing, drying and grinding, a powdery intelligent responsive multi-nanocrystalline nucleus early strength agent is obtained. (The mass ratio of ethanol, the composite obtained in step (4) and the composite obtained in step (5) is 18:1.5:1).

[0216] Example 3

[0217] Preparation method of intelligent responsive multi-nanocrystalline nucleus early strength agent, comprising the following steps:

[0218] (1) Preparation of aryl vinyl ether monomer: Add 47.7 g of 2-ethyl-6-methylphenol, 45.4 g of 3-buten-2-ol and 120.1 g of concentrated sulfuric acid into the reactor, keep stirring and reacting at 40 °C for 20 h, and obtain the aryl vinyl ether monomer through neutralization, extraction, liquid separation and vacuum distillation.

[0219] (2) Preparation of intelligent responsive monomer: Add 57.1 g of the aryl vinyl ether monomer obtained in step (1) and 33.8 g of concentrated sulfuric acid into the reactor, keep stirring and reacting at 50 °C for 5 h, and obtain the intelligent responsive monomer through neutralization, extraction, liquid separation and vacuum distillation.

[0220] (3) Preparation of intelligent response hyperbranched polymer: Add 0.3 g of 3-hydroxymethyl-1,5-pentanediol, 60 g of butanediol mono vinyl polyoxyethylene ether, 3.6 g of ammonium cerium(IV) sulfate, 1.1 g of 27.5% hydrogen peroxide and 65 g of water into a reactor, stir at 25 °C for 30 min. Dissolve 67.6 g of the intelligent response monomer obtained in step (2) in 110 g of water. Dissolve 0.5 g of mercaptopropionic acid and 0.2 g of Rongalite in 23.5 g of water to obtain solution A. Under the condition of constant temperature stirring at 25 °C, add the aqueous solution of the intelligent response monomer and solution A into the reactor uniformly within 1 h. After the dropping is completed, keep stirring at 25 °C for 0.5 h to obtain an intelligent response hyperbranched polymer solution.

[0221] The structural formula of the intelligent response hyperbranched polymer is:

[0222]

[0223] where a∶b = 5∶1 and n = 24;

[0224] (4) Preparation of calcium silicate hydrate and intelligent response hyperbranched polymer composite: Dissolve 39.2 g of sodium silicate nonahydrate in 69.5 g of water. Dissolve 48.8 g of calcium nitrate tetrahydrate and 8.3 g of ferric nitrate nonahydrate in 73.6 g of water. Add 48.2 g of the intelligent response hyperbranched polymer solution obtained in step (3) and 212.3 g of water into the reactor, adjust the pH value to 11.0 with 40 wt% sodium hydroxide solution and set the temperature to 20 °C. Under the stirring speed of 800 rpm, add the aqueous solution of sodium silicate and the aqueous solution of calcium nitrate and aluminum nitrate into the reactor uniformly within 24 h. Centrifuge, wash, dry and grind the suspension to obtain a composite of calcium silicate hydrate and intelligent response hyperbranched polymer with an average particle size of 253 nm.

[0225] (5) Preparation of calcium hydroxide and intelligent response hyperbranched polymer composite: Dissolve 23.7 g of sodium hydroxide and 65.6 g of anhydrous calcium chloride in 138.9 g and 116.4 g of water respectively. Add 59.3 g of the intelligent response hyperbranched polymer solution obtained in step (3) and 86.6 g of water into the reactor, adjust the pH value to 12.0 with 30 wt% sodium hydroxide solution and set the temperature to 40 °C. Under the stirring speed of 800 rpm, add the aqueous solution of sodium hydroxide and the aqueous solution of calcium nitrate into the reactor uniformly within 5 h. After the dropping is completed, keep stirring at 40 °C for 2 h. Centrifuge, wash, dry and grind the suspension to obtain a composite of calcium hydroxide and intelligent response hyperbranched polymer with an average particle size of 637 nm.

[0226] (6) Preparation of calcium sulfoaluminate hydrate and intelligent response hyperbranched polymer composite: Dissolve 23.2 g of potassium hydroxide, 48.8 g of calcium nitrate tetrahydrate, 38.7 g of aluminum nitrate nonahydrate, and 9.0 g of sodium sulfate in 91.8 g, 76.9 g, 38.3 g, and 91.8 g of water respectively. Add 29.9 g of the intelligent response hyperbranched polymer solution obtained in step (3) and 51.7 g of water into a reactor, adjust the pH value to 11.0 with 30% potassium hydroxide solution, and set the temperature to 25°C. Under the stirring speed of 1500 rpm, dropwise add sodium hydroxide solution, calcium nitrate solution, aluminum nitrate solution, and sodium sulfate solution into the reactor at a uniform speed within 10 h. After the dropping is completed, keep the reaction at 25°C for 1 h. Centrifuge, wash, dry, and grind the suspension to obtain a composite of calcium sulfoaluminate hydrate and intelligent response hyperbranched polymer with an average particle size of 309 nm.

[0227] (7) Preparation of intelligent response multi-nano crystal nucleus early strength agent: Add the composite obtained in step (4), the composite obtained in step (5), the composite obtained in step (6), and ethanol into a container, stir at a speed of 500 rpm for 15 min, place the container in a water bath ultrasonic device, and ultrasonicate at 20°C with a power of 60 W and a frequency of 100 kHz for 30 min. After centrifugation, washing, drying, and grinding, obtain a powdery intelligent response multi-nano crystal nucleus early strength agent. (The mass ratio of ethanol, the composite obtained in step (4), the composite obtained in step (5), and the composite obtained in step (6) is 90∶6.9∶2.1∶1).

[0228] Comparative Example 1

[0229] Add the powder with an average particle size of 288 nm obtained by centrifuging, washing, drying, and grinding the suspension of the commercially available nano crystal nucleus early strength agent (BASF Chemical Building Materials Co., Ltd.) and ethanol (mass concentration of 99.5%) into a container, stir at a speed of 1500 rpm for 20 min, place the container in a water bath ultrasonic device, and ultrasonicate at 20°C with a power of 50 kW and a frequency of 80 kHz for 30 min. After centrifugation, washing, drying, and grinding, obtain a powdery nano crystal nucleus early strength agent (the mass ratio of ethanol to the powder obtained by centrifuging, washing, drying, and grinding the suspension is 9∶1).

[0230] Performance test:

[0231] 1. Workability of cement mortar

[0232] To investigate the effect of the intelligent response type multi - nano - crystal nucleus early - strength agent of the present invention on the workability of cement mortar, under the same dosage and water - binder ratio, the initial fluidity and fluidity with time of cement mortar mixed with Examples 1 - 3 and Comparative Example 1 were tested according to GB / T2419. In the experiment, W / C (water - cement ratio, the same below) = 0.5∶1, and the dosage of the intelligent response type multi - nano - crystal nucleus early - strength agent was 0.5% of the cement mass. The cement mortar used in the examples was the one mixed with the intelligent response type multi - nano - crystal nucleus early - strength agent prepared in Examples 1 - 3 of the present invention, the cement mortar used in the comparative example was the one mixed with the nano - crystal nucleus early - strength agent of Comparative Example 1, and the blank used was the cement mortar without adding nano - crystal nucleus early - strength agent. The test results of the initial fluidity and fluidity with time of the cement mortar are shown in Table 1.

[0233] Table 1 Test results of the fluidity of cement mortar

[0234]

[0235] As can be seen from Table 1, the initial fluidities of the cement mortar mixed with Examples 1 - 3 and Comparative Example 1 both reached the same level as that of the blank. The fluidity with time of the cement mortar mixed with Examples 1 - 3 after 1 h could still reach the same level as that of the blank, and was significantly higher than the fluidity of the cement mortar mixed with Comparative Example 1. This shows that the intelligent response type multi - nano - crystal nucleus early - strength agent can significantly improve the workability retention ability of cement mortar.

[0236] 2. Mechanical properties of cement mortar

[0237] To investigate the effect of the intelligent response type multi - nano - crystal nucleus early - strength agent of the present invention on the early mechanical properties of cement mortar, under the same dosage and water - binder ratio, the 6 - h and 1 - d compressive strengths of cement mortar mixed with Examples 1 - 3 and Comparative Example 1 were tested according to GB / T17671. In the experiment, W / C = 0.35∶1, and the dosage of the nano - crystal nucleus early - strength agent was 0.5% of the cement mass. The specimens of cement mortar used in the examples were those mixed with the intelligent response type multi - nano - crystal nucleus early - strength agent prepared in Examples 1 - 3 of the present invention, the specimens of cement mortar used in the comparative example were those mixed with the nano - crystal nucleus early - strength agent of Comparative Example 1, and the blank specimens used were the cement mortar specimens without adding nano - crystal nucleus early - strength agent. The test results of the compressive strength of the cement mortar are shown in Table 2.

[0238] Table 2 Test results of the compressive strength of cement mortar

[0239]

[0240] As can be seen from Table 2, compared with Comparative Example 1, the intelligent response type multi - nano - crystal nucleus early - strength agent prepared in Examples 1 - 3 can significantly improve the early mechanical properties of cement mortar, indicating that the intelligent response type multi - nano - crystal nucleus early - strength agent has excellent early - strength ability.

[0241] 3. Mechanical Properties of Concrete

[0242] In this experiment, concrete with a strength grade of C30 was selected, and its mix proportion is shown in Table 3. Among them, the cement used was P·O42.5 cement provided by Chengde Jinyu Cement Co., Ltd., the gravel was 5-25mm continuously graded gravel provided by Baotong Mining Co., Ltd. in Chengde, Hebei, the natural sand was continuously graded medium sand in Zone II from Heishanju Town, Fengning Manchu Autonomous County, Chengde City, Hebei Province, the manufactured sand was continuously graded medium sand in Zone II provided by Baotong Mining Co., Ltd. in Chengde, Hebei, the dosage of the nano-crystal nucleus early-strength agent was 0.5% of the mass of the cementitious material, and the forming and curing of the concrete specimens were carried out according to GB / T50081. The concrete used in the examples was the concrete doped with the intelligent response type multi-nano-crystal nucleus early-strength agent prepared in Examples 1-3 of the present invention, the concrete used in the comparative example was the concrete doped with the nano-crystal nucleus early-strength agent in Comparative Example 1, and the blank was the concrete without the addition of the nano-crystal nucleus early-strength agent.

[0243] Table 3 Mix Proportion of C30 Concrete (kg / m 3 )

[0244] Cement Fly ash Ground granulated blast-furnace slag Natural sand Manufactured sand Crushed stone Water 346 81 81 359.5 493.25 923 104.45

[0245] In order to investigate the effect of the intelligent response type multi-nano-crystal nucleus early-strength agent synthesized by the present invention on the compressive strength of concrete, the proportions of each component of the concrete were controlled to be the same. According to GB / T50081, immediately after molding, the surface was covered with an impermeable film and cured for 24h. After demolding, the compressive strength of the concrete specimens at 1d was tested, and the remaining concrete specimens were continuously cured until the age of 28d, and the compressive strength of the concrete specimens was tested. The test results are shown in Table 4.

[0246] Table 4 Test Results of Concrete Compressive Strength

[0247]

[0248] It can be seen from Table 4 that the compressive strength of the concrete specimens doped with Examples 1-3 at the age of 1d was significantly higher than that of the concrete specimens doped with Comparative Example 1. The early strength of the concrete was significantly improved and the later strength did not decrease, indicating that the intelligent response type multi-nano-crystal nucleus early-strength agent prepared by the present invention can promote the development of the early strength of concrete and does not reduce the later strength.

[0249] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed in the present application should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for preparing an intelligent responsive multi-element nanocrystalline core early strength agent, characterized in that: The following steps are involved: The composite is added into a dispersant for ultrasonic dispersion, and the obtained suspension is centrifuged, washed, dried and ground to obtain a powdered intelligent responsive multi-element nano-crystal core early strength agent; Wherein, the composite is one or more of a composite of calcium silicate hydrate and a smart response type hyperbranched polymer, a composite of calcium hydroxide and a smart response type hyperbranched polymer, and a composite of calcium sulphoaluminate hydrate and a smart response type hyperbranched polymer; The specific preparation steps of the smart responsive hyperbranched polymer include: The phenol monomer, the enol monomer and the catalyst are mixed and heated and stirred, and the aryl enyl ether monomer is obtained by neutralization, extraction, liquid separation and reduced pressure distillation; The aryl alkenyl ether monomer is mixed with an acid and heated and stirred, and then neutralized, extracted, separated and distilled under reduced pressure to obtain an intelligent responsive monomer; The polyoxyethylene ether monomer, polyol monomer, tetravalent cerium salt, oxidant and water are mixed and heated and stirred to obtain a solution, and then the mixed aqueous solution of the smart response monomer, chain transfer agent and reducing agent is dripped into the above solution, and after the dripping is completed, the solution is kept warm and stirred to obtain the smart response hyperbranched polymer.

2. The method for preparing the intelligent response type multi-element nanocrystalline core early strengthening agent according to claim 1, characterized in that: According to the mass percentage, the content of each raw material in the suspension is as follows: 0-25% of calcium silicate hydrate and smart response type hyperbranched polymer composite, 0-25% of calcium hydroxide and smart response type hyperbranched polymer composite, 0-25% of calcium sulfoaluminate hydrate and smart response type hyperbranched polymer composite, and the rest of dispersant; Wherein, the contents of the composite of calcium silicate hydrate and smart response type hyperbranched polymer, the composite of calcium hydroxide and smart response type hyperbranched polymer, and the composite of calcium sulphoaluminate hydrate and smart response type hyperbranched polymer are not all 0 at the same time.

3. The method for preparing the intelligent response type multi-element nanocrystalline core early strengthening agent according to claim 1, characterized in that: The molecular structure of the intelligent responsive hyperbranched polymer is as follows: in, The structural formula of R is The structural formula of R' is R" is H or a, b and n are the number of repeating units in each part of the polymer, which are integers, 10 <a<160,5<b<40,10<n<150; R1 is H or CH3; R2 is CH2, CH2CH2, OCH2CH2 or O(CH2CH2)2; R3 is H, CH3 or CH2CH3; R4 is H or CH3; R5 is H or CH3; R6 is CH2OH or CH2CHOH; R7 is R8 is 4. The method for preparing the intelligent responsive multi-element nanocrystalline core early strengthening agent according to claim 1, characterized in that: The specific preparation steps of the calcium silicate hydrate and smart responsive hyperbranched polymer composite include: The smart responsive hyperbranched polymer is added into water to obtain a smart responsive hyperbranched polymer aqueous solution, the pH is adjusted to alkaline, heated, and then a metal salt aqueous solution and a silicate aqueous solution are dripped into the water. After the dripping is completed, the solution is stirred for reaction, and the obtained suspension is centrifuged, washed, dried and ground to obtain a powdery calcium silicate hydrate and smart responsive hyperbranched polymer composite.

5. The method for preparing the intelligent response type multi-element nanocrystalline core early strengthening agent according to claim 1, characterized in that: The specific preparation steps of the calcium hydroxide and intelligent responsive hyperbranched polymer composite include: The smart responsive hyperbranched polymer is added into water to obtain a smart responsive hyperbranched polymer aqueous solution, the pH is adjusted to alkaline, heated, and then a calcium salt aqueous solution and an alkali solution are dripped into the water. After the dripping is completed, the solution is stirred for reaction, and the obtained suspension is centrifuged, washed, dried and ground to obtain a powdered calcium hydroxide and smart responsive hyperbranched polymer composite.

6. The method for preparing the intelligent responsive multi-element nanocrystalline core early strengthening agent according to claim 1, characterized in that: The specific preparation steps of the calcium sulphoaluminate hydrate and the intelligent responsive hyperbranched polymer composite include: The smart responsive hyperbranched polymer is added into water to obtain a smart responsive hyperbranched polymer aqueous solution, the pH is adjusted to alkaline, heated, and then aqueous solutions of calcium salt, alkali, aluminum salt / aluminate and sulfate are dripped into water, stirred for reaction after the dripping is completed, and the obtained suspension is centrifuged, washed, dried and ground to obtain a powdery calcium sulfoaluminate hydrate and smart responsive hyperbranched polymer composite.

7. An intelligent responsive multi-element nanocrystalline core early strengthening agent prepared by the preparation method according to any one of claims 1 to 6.

8. A concrete, characterized in that: The intelligent response type multi-element nanocrystalline core early strength agent according to claim 7 is used as an admixture, and the admixture amount is 0.1-5wt% of the mass of the cementitious material in the cement-based material.

9. Application of the intelligent responsive multi-element nanocrystalline core early strength agent as claimed in claim 7 in the fields of freshly mixed paste, mortar and concrete.

10. Use of the intelligent responsive multi-element nanocrystalline core early strength agent as claimed in claim 7 in a gelling system and a solid waste-based gelling material system.

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