CN113979661B - Preparation method of nano calcium silicate suspension with high stability and good early strength effect - Google Patents

Preparation method of nano calcium silicate suspension with high stability and good early strength effect Download PDF

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CN113979661B
CN113979661B CN202111443936.8A CN202111443936A CN113979661B CN 113979661 B CN113979661 B CN 113979661B CN 202111443936 A CN202111443936 A CN 202111443936A CN 113979661 B CN113979661 B CN 113979661B
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dropping
dropping liquid
liquid
water
calcium silicate
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CN113979661A (en
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范士敏
张磊
刘江
牟忠江
王国锋
王碧涛
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Jiangsu Jinmutu Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/08—Allyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid

Abstract

The invention discloses a preparation method of a nano calcium silicate suspension with high stability and good early strength effect, which takes a polyether macromonomer, unsaturated alcohol, water and an oxidant as raw materials to prepare a base solution A; preparing dropping liquid A by using unsaturated carboxylic acid, unsaturated amide and water as raw materials; preparing a dropping liquid B by using a reducing agent, a chain transfer agent and water as raw materials; preparing the dropping liquid A, the dropping liquid B and the primer liquid A into a special dispersant finished product; and (3) taking a special dispersant aqueous solution as a primer B, taking a soluble calcium aqueous solution as a dropping liquid C, taking a soluble silicate aqueous solution as a dropping liquid D, and preparing the dropping liquid C, the dropping liquid D and the primer B into a nano calcium silicate suspension. According to the invention, unsaturated alcohol, unsaturated amide and the like are used as comonomers, hydroxyl and amido are introduced into the molecular structure of the dispersing agent, and hydroxyl hydrogen or amido hydrogen can form hydrogen bonds with silicon atoms, so that the stability of the nano calcium silicate suspension is improved.

Description

Preparation method of nano calcium silicate suspension with high stability and good early strength effect
Technical Field
The invention relates to a preparation method of a nano calcium silicate suspension, in particular to a preparation method of a nano calcium silicate suspension with high stability and good early strength effect, belonging to the field of application of concrete admixtures.
Background
Precast concrete products such as precast components, tubular piles and the like have the advantages of convenience in construction, reduction in dust pollution and the like, and are widely popularized and applied in the field of public or civil buildings such as high-rise buildings, high-speed rails, highways, bridges and the like. The demoulding time of the precast concrete products after the concrete is formed is short, the requirement on the early strength of the concrete is high, the requirement on the demoulding time of the precast concrete products cannot be met by additives with early strength effects such as inorganic salt early strength agents, early strength water reducing agents and the like, and production enterprises generally transfer the precast concrete products after being formed into a steam curing tank for high-temperature curing, so that the hydration rate of cement and other glue materials is accelerated, and the demoulding time of the precast concrete products is shortened.
With the improvement of the requirements of energy conservation and emission reduction by domestic industrial policies and the price improvement of power energy sources such as coal, electric power, fuel oil and the like, the industry of precast concrete products urgently needs to develop a production process without steam curing, and nano calcium silicate (also called C-S-H gel) is one of breakthroughs for solving the curing technology of concrete products.
Zhangyang et al (influence of nano C-S-H on cement hydration, hardened slurry pore structure and concrete strength [ J ],2019,47(5), 585-.
Patent CN110330257B reports a preparation method of C-S-H gel nano crystal nucleus early strength agent, tricalcium silicate, sodium carbonate, polycarboxylic acid water reducing agent, sodium polyacrylate and water are used as raw materials to prepare suspension, the mixing amount is 2% -4% of the glue material, and the 1d compressive strength is increased by 170% -300%.
Patent CN107311504A reports a preparation method of an additive for improving the strength of a cement-based material, nano-silica and acrylic monomer polymer, soluble calcium salt, soluble silicate and the like are used as dropping liquid components, the dropping liquid components are respectively dropped into a reaction system for synthesis, nano-silica is used as a carrier, hydrated nano-calcium silicate gel is loaded, the hydrated calcium silicate-nano-silica type composite cement additive is obtained, and the early and later compressive strengths of the cement material are obviously improved.
Patent CN112830710A reports a preparation method of a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent, which takes soluble calcium salt, soluble silicon salt, a dispersing agent and a coupling agent as raw materials to synthesize a hydrated C-S-H gel suspension with the mass fraction of 5-30%. It has the functions of promoting cement hydration, shortening setting time and raising early strength of concrete.
The synthesis process of the nano calcium silicate reported in the patent and the literature generally adopts a polycarboxylic acid water reducing agent as a dispersing agent, and the prepared nano calcium silicate suspension is applied to a cement-based material as an early strength agent, so that the hydration of cement can be remarkably promoted, and the early strength of the cement-based material is improved. However, research on how to prevent the nano calcium silicate from aggregating and precipitating from the suspension is less, and mainly sodium polyacrylate, coupling agent or the like is used as a stabilizer of the suspension, so that problems of retardation and high cost exist, and the production process of the nano calcium silicate is complicated.
Disclosure of Invention
The invention aims to specially develop a preparation method of a dispersing agent capable of effectively dispersing and ensuring the stability of a suspension, and apply the method to the synthesis of a nano calcium silicate suspension, simplify the synthesis process of the nano calcium silicate suspension and ensure the early strength effect of the nano calcium silicate.
The invention realizes the aim through the following technical scheme, and the preparation method of the nano calcium silicate suspension with high stability and good early strength effect comprises the following steps,
s1, synthesis of special dispersant: preparing a base solution A by using a polyether macromonomer, unsaturated alcohol, water and an oxidant as raw materials; preparing dropping liquid A by using unsaturated carboxylic acid, unsaturated amide and water as raw materials; preparing a dropping liquid B by using a reducing agent, a chain transfer agent and water as raw materials; setting the dropping time of the dropping liquid A and the dropping liquid B, respectively dropping the dropping liquid A and the dropping liquid B into the base solution A under the conditions of stirring and normal pressure, after the dropping is finished, carrying out heat preservation reaction for 30min, and neutralizing by using liquid alkali to obtain a special dispersant finished product;
s2, synthesis of nano calcium silicate suspension: preparing the special dispersing agent prepared in the step S1 and water as raw materials into a base solution B, adjusting the pH to a specified value by using 32% liquid alkali, preparing a dropping liquid C by using soluble calcium salt and water as raw materials, preparing a dropping liquid D by using soluble silicate and water as raw materials, setting the dropping time of the dropping liquid C and the dropping time of the dropping liquid D, respectively dropping the dropping liquid C and the dropping liquid D into the base solution B under the conditions of stirring and normal pressure, and obtaining light blue suspension liquid after the dropping is finished, namely the nano calcium silicate suspension liquid.
Preferably, the mass ratio of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide in the step S1 is 100: (1-3): (10-15): (2-4), the amount of an oxidant in the base solution A preparation process is 0.3-0.8% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide, the amount of a reducing agent in the dropping liquid B preparation process is 0.1-0.2% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide, and the amount of a chain transfer agent in the dropping liquid B preparation process is 0.2-0.7% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide.
Preferably, the dropping liquid A is an aqueous solution with a concentration of 80-90% compounded by unsaturated carboxylic acid, unsaturated amide and water, the unsaturated carboxylic acid is one of acrylic acid, methacrylic acid, itaconic acid and maleic acid, and the unsaturated amide is one of acrylamide, methacrylamide, N-methylolacrylamide, N-methacrylamide and N-hydroxyethyl acrylamide.
Preferably, the priming solution A is an aqueous solution with a concentration of 40% -50% and formed by compounding a polyether macromonomer, an unsaturated alcohol and water, the polyether macromonomer has a number average molecular weight of 5000-8000, is one of HPEG, IPEG, EPEG or VPEG, and belongs to a commercially available polyether macromonomer product, the unsaturated alcohol is one of allyl alcohol, methallyl alcohol, 3-isopentenol, ethylene glycol vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, isopulegol and 7-octen-1-ol, and the oxidant is one of 30% hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
Preferably, the dropping liquid B is an aqueous solution with the concentration of 2% -5% compounded by a reducing agent, a chain transfer agent and water, the reducing agent is one of L-ascorbic acid, sodium formaldehyde sulfoxylate, E51, sodium thiosulfate and sodium sulfite, and the chain transfer agent is one of thioglycolic acid, mercaptoethanol and mercaptopropionic acid.
Preferably, the reaction condition in the step S1 is a polymerization reaction under normal temperature and pressure, the dropping time of the dropping solution a is 60min to 180min, and the dropping time of the dropping solution B is 10min to 30min longer than that of the dropping solution a.
Preferably, 32% liquid caustic soda is adopted for neutralization in the step S1, and the pH value of the reaction system is neutralized to 7-8, so that a finished product of the special dispersant is obtained.
Preferably, the mass ratio of the special dispersant, the soluble calcium salt and the soluble silicate in the step S2 is 1: (1.2-2.4): (1.0-2.0), the primer solution B in the step S2 is an aqueous solution with the concentration of 5% -10% prepared from a special dispersant and water, the pH value is adjusted to 9-11 by using 32% liquid alkali, the dropping liquid C is an aqueous solution with the concentration of 25% prepared from soluble calcium salt and water, and the dropping liquid D is an aqueous solution with the concentration of 25% prepared from soluble silicate and water.
Preferably, the soluble calcium salt is one of calcium nitrate tetrahydrate, calcium nitrate tetrahydrate and calcium formate, and the soluble silicate is one of anhydrous sodium silicate, sodium silicate pentahydrate and sodium silicate nonahydrate.
Preferably, the dropping time of the dropping liquid C and the dropping time of the dropping liquid D in the step S2 are the same, the dropping time is between 30min and 100min, the solid content of the nano calcium silicate suspension is between 8 percent and 20 percent, and the mixing amount is 1 percent to 4 percent of the mass of the cement and other glue materials.
The invention has the beneficial effects that: the preparation method of the nano calcium silicate suspension with high stability and good early strength effect disclosed by the invention has obvious advantages in the following aspects:
1. according to the invention, unsaturated alcohol, unsaturated amide and the like are used as comonomers, hydroxyl and amido are introduced into the molecular structure of the dispersing agent, and hydroxyl hydrogen or amido hydrogen can form hydrogen bonds with silicon atoms, so that the stability of the nano calcium silicate suspension is improved.
2. According to the invention, the polyether macromonomer with large molecular weight is used, the acid-ether ratio of the dispersing agent is improved, namely the density of carboxylic acid adsorption groups on the main chain of the dispersing agent is increased, the adsorption and dispersion effects of anionic groups on calcium silicate are facilitated, and the stability of the nano calcium silicate suspension is improved. Meanwhile, the dispersant synthesized by the polyether macromonomer with large molecular weight has better early strength effect, and can further improve the early strength performance of the nano calcium silicate.
3. According to the preparation method of the nano calcium silicate suspension provided by the invention, the molecular structure of the dispersing agent is designed and optimized, so that the stability of the nano calcium silicate suspension is improved, the addition of extra components such as sodium polyacrylate, a coupling agent and the like is avoided, the preparation process of the nano calcium silicate suspension is simplified, and the production time of the nano calcium silicate suspension is obviously shortened.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art will be able to make variations within the scope of the invention based on the disclosure herein, in reagents, catalysts and reaction process conditions. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
In the examples of the present invention, the molecular weight and molecular weight distribution of the dispersant were measured by Wyatttechnology corporation gel permeation chromatography.
The gel column comprises ShodexSB806+8032 chromatographic columns which are connected in series; the eluent is tetrahydrofuran; the speed of the mobile phase is 1 ml/min; the sample injection amount is 20 mu l; the sample preparation concentration is 0.5% (sample g/mobile phase g);
a detector, a ShodexRI-71 type differential refraction detector;
polyethylene glycol GPC;
standard sample preparation: Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232.
In the application examples of the invention, unless otherwise specified, the parts are specifically parts by mass, and the addition amounts of other materials are converted into parts by mass.
A preparation method of a nano calcium silicate suspension with high stability and good early strength effect comprises the following steps,
s1, synthesis of special dispersant: preparing a base solution A by using a polyether macromonomer, unsaturated alcohol, water and an oxidant as raw materials; preparing dropping liquid A by using unsaturated carboxylic acid, unsaturated amide and water as raw materials; preparing a dropping liquid B by using a reducing agent, a chain transfer agent and water as raw materials; setting the dropping time of the dropping liquid A and the dropping liquid B, respectively dropping the dropping liquid A and the dropping liquid B into the base solution A under the conditions of stirring and normal pressure, after the dropping is finished, carrying out heat preservation reaction for 30min, and neutralizing by using liquid alkali to obtain a special dispersant finished product;
in the step S1, the mass ratio of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide is 100: (1-3): (10-15): (2-4), the amount of the oxidant in the base solution A preparation process is 0.3-0.8% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide, the amount of the reducing agent in the dropping liquid B preparation process is 0.1-0.2% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide, and the amount of the chain transfer agent in the dropping liquid B preparation process is 0.2-0.7% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide.
The dropping liquid A is an aqueous solution with the concentration of 80-90% compounded by unsaturated carboxylic acid, unsaturated amide and water, the unsaturated carboxylic acid is one of acrylic acid, methacrylic acid, itaconic acid and maleic acid, and the unsaturated amide is one of acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-methacrylamide and N-hydroxyethyl acrylamide.
The base solution A is an aqueous solution which is prepared by compounding a polyether macromonomer, unsaturated alcohol and water and has the concentration of 40-50%, the number average molecular weight of the polyether macromonomer is 5000-8000, the polyether macromonomer is one of HPEG, IPEG, EPEG or VPEG, the base solution belongs to a commercially available polyether macromonomer product, the unsaturated alcohol is one of allyl alcohol, methallyl alcohol, 3-isopentenol, ethylene glycol vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, isopulegol and 7-octene-1-ol, and the oxidant is one of 30% hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
The dropping liquid B is a 2-5% aqueous solution compounded by a reducing agent, a chain transfer agent and water, the reducing agent is one of L-ascorbic acid, sodium formaldehyde sulfoxylate, E51, sodium thiosulfate and sodium sulfite, and the chain transfer agent is one of thioglycolic acid, mercaptoethanol and mercaptopropionic acid.
The reaction conditions in the step S1 are polymerization reaction under normal temperature and normal pressure, the dropping time of the dropping liquid A is 60-180 min, and the dropping time of the dropping liquid B is 10-30 min longer than that of the dropping liquid A.
And in the step S1, neutralizing by using 32% liquid caustic soda, and neutralizing the pH value of the reaction system to 7-8 to obtain a finished product of the special dispersant.
S2, synthesis of nano calcium silicate suspension: preparing the special dispersing agent prepared in the step S1 and water as raw materials into a base solution B, adjusting the pH to a specified value by using 32% liquid alkali, preparing a dropping liquid C by using soluble calcium salt and water as raw materials, preparing a dropping liquid D by using soluble silicate and water as raw materials, setting the dropping time of the dropping liquid C and the dropping time of the dropping liquid D, respectively dropping the dropping liquid C and the dropping liquid D into the base solution B under the conditions of stirring and normal pressure, and obtaining light blue suspension liquid after the dropping is finished, namely the nano calcium silicate suspension liquid.
The mass ratio of the special dispersant, the soluble calcium salt and the soluble silicate in the step S2 is 1: (1.2-2.4): (1.0-2.0), the primer solution B in the step S2 is an aqueous solution with the concentration of 5% -10% prepared from a special dispersant and water, the pH value is adjusted to 9-11 by using 32% liquid alkali, the dropping liquid C is an aqueous solution with the concentration of 25% prepared from soluble calcium salt and water, and the dropping liquid D is an aqueous solution with the concentration of 25% prepared from soluble silicate and water.
The soluble calcium salt is one of calcium nitrate tetrahydrate, calcium nitrate tetrahydrate and calcium formate, and the soluble silicate is one of anhydrous sodium silicate, sodium silicate pentahydrate and sodium silicate nonahydrate.
The dropping time of the dropping liquid C and the dropping time of the dropping liquid D in the step S2 are the same, the dropping time is 30-100 min, the solid content of the nano calcium silicate suspension is 8-20%, the doping amount is 1-4% of the mass of the cement and other glue materials, the influence on the fluidity is small, and the early strength performance is excellent.
Example 1
Weighing 100.0 parts of HPEG-5000(Mw is 5000) polyether macromonomer, 1.0 part of allyl alcohol and 0.35 part of 30% hydrogen peroxide in a reaction device, adding water to dilute the mixture to a water solution with the mass concentration of 40%, starting a machine to stir, fully mixing and dissolving the mixture uniformly, and preparing the primer solution. Weighing 15.0 parts of acrylic acid and 2.0 parts of acrylamide, and adding water to prepare an aqueous solution with the mass concentration of 80%, namely a dropping liquid A; 0.12 part of L-ascorbic acid and 0.24 part of mercaptopropionic acid are weighed, and water is added to prepare an aqueous solution with the mass concentration of 2 percent, namely the dropping liquid B. Dropping the dropping liquid A and the dropping liquid B into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid A is 60min, and the dropping time of the dropping liquid B is 70 min. After the dropwise addition is finished, the reaction is carried out for 30min under the condition of heat preservation, 32% of liquid alkali is used for neutralizing the reaction liquid until the pH value is 7, and a finished product of the dispersing agent is obtained and is marked as PCE-1. The weight average molecular weight (hereinafter abbreviated as Mw) was 52897 and the molecular weight distribution (hereinafter abbreviated as PDI) was 1.92 as measured by GPC.
In the same way, under the same reaction conditions, the following dispersing agent for preparing the nano calcium silicate suspension is prepared
Dispersing agent PCE-2: base liquid beating: IPEG-6000100.0 parts, methallyl alcohol 3.0 parts, ammonium persulfate 0.98 parts, and water are added to dilute the mixture to obtain a 60% aqueous solution by mass fraction; dropping liquid A: 15.0 parts of methacrylic acid and 4.0 parts of methacrylamide, and adding water to dilute the mixture to obtain an aqueous solution with the mass concentration of 90%; dropping liquid B: 0.49 part of sodium formaldehyde sulfoxylate and 0.85 part of thioglycolic acid, and adding water to dilute the mixture to a water solution with the mass fraction of 5%; the dropping time of the dropping liquid A is 180min, and the dropping time of the dropping liquid B is 210 min. Mw was 49128 and PDI was 1.87 by GPC.
Dispersing agent PCE-3: base liquid beating: EPEG-7000100.0 parts, 3-isopentenol 2.0 parts, ammonium persulfate 0.59 parts, and water is added to dilute the mixture to 50% aqueous solution by mass fraction; dropping liquid A: 13.0 parts of itaconic acid and 3.0 parts of methacrylamide, and water is added to dilute the mixture to obtain an aqueous solution with the mass concentration of 90%; dropping liquid B: 0.18 part of sodium thiosulfate and 0.59 part of mercaptoethanol, and water is added to dilute the mixture to a water solution with the mass fraction of 3%; the dropping time of the dropping liquid A is 80min, and the dropping time of the dropping liquid B is 100 min. Mw was 49752 and PDI was 1.89 by GPC.
Dispersing agent PCE-4: base liquid beating: VPEG-8000100.0 parts, ethylene glycol vinyl ether 2.5 parts and sodium persulfate 0.72 part, and adding water to dilute the mixture to obtain a 45 mass percent aqueous solution; dropping liquid A: 14.0 parts of maleic acid and 3.5 parts of N-hydroxymethyl acrylamide, and adding water to dilute the mixture to an aqueous solution with the mass concentration of 80%; dropping liquid B: 0.20 part of sodium sulfite and 0.48 part of mercaptoethanol, and water is added to dilute the mixture to obtain a 4% aqueous solution; the dropping time of the dropping liquid A is 120min, and the dropping time of the dropping liquid B is 130 min. Mw was 50917 and PDI was 1.81 by GPC.
Dispersing agent PCE-5: base liquid beating: EPEG-7000100.0 parts, diethylene glycol monovinyl ether 1.5 parts, potassium persulfate 0.46 parts, water diluted to 55% water solution by mass; dropping liquid A: 11.0 parts of acrylic acid and 3.0 parts of N-hydroxyethyl acrylamide, and adding water to dilute the mixture to form an aqueous solution with the mass concentration of 85%; dropping liquid B: e510.21 parts and 0.81 part of mercaptopropionic acid, and adding water to dilute the mixture to obtain a 2 mass percent aqueous solution; the dropping time of the dropping liquid A is 150min, and the dropping time of the dropping liquid B is 170 min. Mw was 53019 and PDI was 1.95 by GPC.
Dispersing agent PCE-6: base liquid beating: IPEG-7000100.0 parts, isopulegol 2.0 parts, 30% hydrogen peroxide 0.60 parts, adding water to dilute to 55% water solution by mass; dropping liquid A: 14.0 parts of acrylic acid and 4.0 parts of N-methacrylamide, and adding water to dilute the mixture to an aqueous solution with the mass concentration of 80%; dropping liquid B: 0.18 part of L-ascorbic acid, 0.75 part of thioglycollic acid and water are added for dilution to obtain a water solution with the mass fraction of 4%; the dropping time of the dropping liquid A is 80min, and the dropping time of the dropping liquid B is 90 min. Mw was 50368 and PDI was 1.92 by GPC.
Example 2
Weighing and adding 1100 parts of dispersing agent PCE-1100 into a reaction device, adding water to dilute the mixture to 5% aqueous solution by mass, adjusting the pH value of the solution to 9 by using 32% liquid alkali, and preparing the primer solution. Weighing 120 parts of calcium nitrate tetrahydrate, adding water to dilute the calcium nitrate tetrahydrate to obtain an aqueous solution with the mass fraction of 25%, and dripping liquid C to prepare the calcium nitrate. Weighing 100 parts of anhydrous sodium silicate, adding water to dilute the anhydrous sodium silicate to obtain an aqueous solution with the mass fraction of 25%, and dripping liquid D to prepare the solution. Dropping the dropping liquid C and the dropping liquid D into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid C and the dropping liquid D is 30 min. After the dropwise addition, water is added to dilute the suspension until the mass fraction is 10%, and a light blue nano calcium silicate suspension is obtained and is marked as NJH-1.
Example 3
Weighing and adding 2100 parts of dispersing agent PCE-2100 into a reaction device, adding water to dilute the mixture to obtain 10% aqueous solution by mass fraction, adjusting the pH value of the solution to 11 by using 32% liquid alkali, and preparing the primer solution. Weighing 240 parts of calcium nitrate tetrahydrate, adding water to dilute the calcium nitrate tetrahydrate to obtain an aqueous solution with the mass fraction of 25%, and dripping liquid C to prepare the calcium nitrate solution. Weighing 200 parts of sodium silicate pentahydrate, adding water to dilute the sodium silicate pentahydrate into an aqueous solution with the mass fraction of 25%, and dripping liquid D to prepare the solution. Dropping the dropping liquid C and the dropping liquid D into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid C and the dropping liquid D is 100 min. After the dropwise addition, water is added to dilute the suspension until the mass fraction is 20%, and a light blue nano calcium silicate suspension is obtained and is marked as NJH-2.
Example 4
Weighing PCE-3100 parts of dispersing agent, adding the dispersing agent into a reaction device, adding water to dilute the dispersing agent into 8% aqueous solution by mass fraction, adjusting the pH value of the solution to 10 by using 32% liquid alkali, and preparing the bottoming solution. Weighing 180 parts of calcium formate, adding water to dilute the calcium formate into 25 mass percent of water solution, and dripping liquid C to prepare the calcium formate. Weighing 180 parts of sodium silicate pentahydrate, adding water to dilute the sodium silicate pentahydrate into an aqueous solution with the mass fraction of 25%, and dripping liquid D to prepare the solution. Dropping the dropping liquid C and the dropping liquid D into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid C and the dropping liquid D is 60 min. After the dropwise addition is finished, water is added to dilute the suspension until the mass fraction is 15%, and light blue nano calcium silicate suspension is obtained and is recorded as NJH-3.
Example 5
Weighing 4100 parts of dispersing agent PCE-4100, adding water to dilute the solution into a reaction device until the mass fraction of the solution is 6%, adjusting the pH value of the solution to 9 by using 32% liquid alkali, and preparing the primer solution. Weighing 150 parts of calcium formate, adding water to dilute the calcium formate into an aqueous solution with the mass fraction of 25%, and dripping liquid C to prepare the calcium formate. Weighing 160 parts of sodium silicate pentahydrate, adding water to dilute the sodium silicate pentahydrate into an aqueous solution with the mass fraction of 25%, and dripping liquid D to prepare the solution. Dropping the dropping liquid C and the dropping liquid D into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid C and the dropping liquid D is 80 min. After the dropwise addition, water is added to dilute the suspension until the mass fraction is 10%, and a light blue nano calcium silicate suspension is obtained and is marked as NJH-4.
Example 6
And (3) weighing 0 part of dispersing agent PCE-5100, adding water to dilute the mixture into a reaction device until the mass fraction of the mixture is 9% of water solution, adjusting the pH value of the solution to 10 by using 32% of liquid alkali, and preparing the primer solution. Weighing 140 parts of calcium nitrate tetrahydrate, adding water to dilute the calcium nitrate tetrahydrate to obtain an aqueous solution with the mass fraction of 25%, and dripping liquid C to prepare the calcium nitrate. Weighing 150 parts of sodium silicate nonahydrate, adding water to dilute the sodium silicate nonahydrate into an aqueous solution with the mass fraction of 25%, and dripping liquid D to prepare the solution. Dropping the dropping liquid C and the dropping liquid D into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid C and the dropping liquid D is 60 min. After the dropwise addition, water is added to dilute the suspension until the mass fraction is 20%, and a light blue nano calcium silicate suspension is obtained and is marked as NJH-5.
Example 7
And (3) weighing PCE-6100 parts of dispersant, adding water to dilute the mixture into a reaction device to obtain a 7% aqueous solution, adjusting the pH value of the aqueous solution to 11 by using 32% liquid alkali, and preparing the primer solution. Weighing 220 parts of calcium nitrate tetrahydrate, adding water to dilute the calcium nitrate tetrahydrate to obtain an aqueous solution with the mass fraction of 25%, and dripping liquid C to prepare the calcium nitrate. Weighing 190 parts of sodium silicate nonahydrate, adding water to dilute the sodium silicate nonahydrate into an aqueous solution with the mass fraction of 25%, and dripping liquid D to prepare the solution. Dropping the dropping liquid C and the dropping liquid D into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid C and the dropping liquid D is 90 min. After the dropwise addition, water is added to dilute the suspension until the mass fraction is 15%, and a light blue nano calcium silicate suspension is obtained and is marked as NJH-6.
Comparative example 1
Weighing 100.0 parts of HPEG-2400(Mw is 2400) polyether macromonomer and 0.54 part of 30% hydrogen peroxide in a reaction device, adding water to dilute the mixture to 50% aqueous solution, starting mechanical stirring, fully mixing and dissolving the mixture uniformly, and preparing the primer solution. Weighing 15.0 parts of acrylic acid, and adding water to prepare an aqueous solution with the mass concentration of 80%, namely a dropping liquid A; 0.17 part of L-ascorbic acid and 0.48 part of mercaptopropionic acid are weighed, and water is added to prepare an aqueous solution with the mass concentration of 4 percent, namely the dropping liquid B. Dropping the dropping liquid A and the dropping liquid B into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid A is 180min, and the dropping time of the dropping liquid B is 200 min. After the dropwise addition is finished, the reaction is carried out for 30min under the condition of heat preservation, 32% of liquid alkali is used for neutralizing the reaction liquid until the pH value is 7, and a finished product of the dispersing agent is obtained and is marked as PCE-7. The weight average molecular weight (Mw) was 29147 and the molecular weight distribution (PDI) was 1.78 as determined by GPC.
And weighing PCE-7100 parts of dispersing agent, adding the dispersing agent into a reaction device, adding water to dilute the dispersing agent into a 7% aqueous solution by mass fraction, adjusting the pH value of the solution to 10 by using 32% liquid alkali, and preparing the priming solution. Weighing 300 parts of calcium formate, adding water to dilute the calcium formate into an aqueous solution with the mass fraction of 25%, and dripping liquid C to prepare the calcium formate. Weighing 240 parts of sodium silicate pentahydrate, adding water to dilute the sodium silicate pentahydrate into an aqueous solution with the mass fraction of 25%, and dripping liquid D to prepare the solution. Dropping the dropping liquid C and the dropping liquid D into the polymerization reactor under the conditions of mechanical stirring and normal temperature and pressure, wherein the dropping time of the dropping liquid C and the dropping liquid D is 300 min. After the dropwise addition, water is added to dilute the suspension until the mass fraction is 15%, and a light blue nano calcium silicate suspension, which is recorded as NJH-7, is obtained.
Comparative example 2
Weighing 5 parts of dispersing agent PCE-7100 and sodium polyacrylate (Mw is 3000, 50% of solid content), adding the dispersing agent PCE-7100 and the sodium polyacrylate into a reaction device, adding water to dilute the mixture to a 7% aqueous solution by mass fraction, adjusting the pH value of the solution to 10 by using 32% liquid alkali, and preparing the priming solution. Weighing 180 parts of tetrahydrate calcium nitrate, adding water to dilute the tetrahydrate calcium nitrate until the mass fraction of the tetrahydrate calcium nitrate is 25% of water solution, and dripping liquid C to prepare the calcium nitrate. Weighing 240 parts of anhydrous sodium silicate, adding water to dilute the anhydrous sodium silicate to obtain an aqueous solution with the mass fraction of 25%, and dripping liquid D to prepare the solution. And (3) dropwise adding the dropping liquid C and the dropping liquid D into the polymerization reactor under the conditions of mechanical stirring and normal temperature and normal pressure, wherein the dropwise adding time of the dropping liquids C and D is 300 min. After the dropwise addition, water is added to dilute the suspension until the mass fraction is 25%, and a light blue nano calcium silicate suspension is obtained and is marked as NJH-8.
Application example 1
The pH value, the nano-particle size, the storage stability and the like of the nano calcium silicate suspension are tested. The PH value test is carried out by using a pH meter, and the particle size test is carried out by using a dynamic light scattering method (DLS) introduced in the methods of the reference report method of the nano particle size of nano calcium silicate (Zhangyang et al, the influence of nano C-S-H on the cement hydration, the hardened slurry pore structure and the concrete strength [ J ],47(5) and 585-; storage stability the suspensions were observed for sedimentation at 10d, 30d and 60d by standing storage. The test results are shown in table 1.
Table 1 nano calcium silicate suspension pH, nano particle size and storage stability testing
Figure BDA0003384440150000171
As can be seen from the data in table 1, the median particle size of the suspension of nano calcium silicate prepared by the method for preparing a suspension of nano calcium silicate according to the present invention is significantly smaller than that of the suspension of nano calcium silicate prepared by using a conventional water reducing agent as a dispersant. Furthermore, the nano calcium silicate synthesized by the preparation method of the nano calcium silicate suspension has higher storage stability.
Application example 2
The early strength performance of the nano calcium silicate suspension is evaluated by using a cement mortar test. The cement used was ordinary portland cement (p.o42.5) and the sand used was 1350 g/bag of standard sand, unless otherwise specified.
The test method is as follows: the mixing amount of a commercially available water reducing agent is 0.12 percent of the mass of the glue material, the bending and fixing mixing amount of the nano calcium silicate suspension is 0.4 percent of the mass of the glue material, 450g of sea snail 425 cement, 1350g of standard sand and 0.4 of water-glue ratio. And after the mixing of the mortar is finished, filling the mortar into a mold twice for molding, wherein the vibration time is 60s each time. And (3) removing the mold after the standard sample is subjected to 20 hours at the temperature of 20 ℃, continuously maintaining under the same condition, and respectively testing the strength development conditions of the mortar for 6 hours, 12 hours, 1d and 3d, wherein the test results are shown in table 2.
Table 2 cement mortar strength testing of nano calcium silicate suspensions
Figure BDA0003384440150000181
The data in table 2 show that the suspension of nano calcium silicate synthesized by the preparation method of nano calcium silicate suspension of the invention has good early strength effect, the strength of the cement mortar test block in 6 hours is improved by 200-300%, the strength in 12 hours is improved by 80-100%, the strength in 1d is improved by more than 10%, and the strength in 3d is still higher than that of the cement mortar test block without nano calcium silicate suspension. The strength of the nano calcium silicate suspension synthesized by adopting the existing documents and patent reports is 30-50% in 6h, the strength is improved by 40-50% in 12h, and the strength of 1d and 3d is basically the same as that of a cement mortar test block without the nano calcium silicate suspension.
In conclusion, the nano calcium silicate suspension prepared by the preparation method of the nano calcium silicate suspension has the obvious advantage of early strength.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (10)

1. A preparation method of a nano calcium silicate suspension with high stability and good early strength effect is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, synthesis of special dispersant: preparing a base solution A by using a polyether macromonomer, unsaturated alcohol, water and an oxidant as raw materials; preparing dropping liquid A by using unsaturated carboxylic acid, unsaturated amide and water as raw materials; preparing a dropping liquid B by using a reducing agent, a chain transfer agent and water as raw materials; setting the dropping time of the dropping liquid A and the dropping liquid B, respectively dropping the dropping liquid A and the dropping liquid B into the base solution A under the conditions of stirring and normal pressure, after the dropping is finished, carrying out heat preservation reaction for 30min, and neutralizing by using liquid alkali to obtain a special dispersant finished product;
s2, synthesis of nano calcium silicate suspension: preparing the special dispersing agent prepared in the step S1 and water as raw materials into a base solution B, adjusting the pH to a specified value by using 32% liquid alkali, preparing a dropping liquid C by using soluble calcium salt and water as raw materials, preparing a dropping liquid D by using soluble silicate and water as raw materials, setting the dropping time of the dropping liquid C and the dropping time of the dropping liquid D, respectively dropping the dropping liquid C and the dropping liquid D into the base solution B under the conditions of stirring and normal pressure, and obtaining light blue suspension liquid after the dropping is finished, namely the nano calcium silicate suspension liquid.
2. The preparation method of the nano calcium silicate suspension with high stability and good early strength effect according to claim 1, characterized in that: in the step S1, the mass ratio of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide is 100: (1-3): (10-15): (2-4), the amount of an oxidant in the base solution A preparation process is 0.3-0.8% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide, the amount of a reducing agent in the dropping liquid B preparation process is 0.1-0.2% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide, and the amount of a chain transfer agent in the dropping liquid B preparation process is 0.2-0.7% of the mass of the polyether macromonomer, the unsaturated alcohol, the unsaturated carboxylic acid and the unsaturated amide.
3. The preparation method of the nano calcium silicate suspension with high stability and good early strength effect according to claim 1, characterized in that: the dropping liquid A is an aqueous solution with the concentration of 80-90% compounded by unsaturated carboxylic acid, unsaturated amide and water, the unsaturated carboxylic acid is one of acrylic acid, methacrylic acid, itaconic acid and maleic acid, and the unsaturated amide is one of acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-methacrylamide and N-hydroxyethyl acrylamide.
4. The method for preparing a suspension of nano calcium silicate with high stability and good early strength effect as claimed in claim 1 or claim 2, wherein: the base solution A is an aqueous solution which is prepared by compounding a polyether macromonomer, unsaturated alcohol and water and has the concentration of 40-50%, the number average molecular weight of the polyether macromonomer is 5000-8000, the polyether macromonomer is one of HPEG, IPEG, EPEG or VPEG, the base solution belongs to a commercially available polyether macromonomer product, the unsaturated alcohol is one of allyl alcohol, methallyl alcohol, 3-isopentenol, ethylene glycol vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, isopulegol and 7-octene-1-ol, and the oxidant is one of 30% hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
5. The method for preparing a suspension of nano calcium silicate with high stability and good early strength effect as claimed in claim 1 or claim 2, wherein: the dropping liquid B is a 2-5% aqueous solution compounded by a reducing agent, a chain transfer agent and water, the reducing agent is one of L-ascorbic acid, sodium formaldehyde sulfoxylate, E51, sodium thiosulfate and sodium sulfite, and the chain transfer agent is one of thioglycolic acid, mercaptoethanol and mercaptopropionic acid.
6. The preparation method of the nano calcium silicate suspension with high stability and good early strength effect according to claim 1, characterized in that: the reaction conditions in the step S1 are polymerization reaction under normal temperature and normal pressure, the dropping time of the dropping liquid A is 60-180 min, and the dropping time of the dropping liquid B is 10-30 min longer than that of the dropping liquid A.
7. The preparation method of the nano calcium silicate suspension with high stability and good early strength effect according to claim 1, characterized in that: and step S1, neutralizing with 32% liquid alkali to a pH value of 7-8 to obtain a special dispersant finished product.
8. The preparation method of the nano calcium silicate suspension with high stability and good early strength effect according to claim 1, characterized in that: the mass ratio of the special dispersant, the soluble calcium salt and the soluble silicate in the step S2 is 1: (1.2-2.4): (1.0-2.0), the primer B in the step S2 is an aqueous solution with the concentration of 5% -10% prepared from a special dispersant and water, the pH value is adjusted to be 9-11 by using 32% liquid caustic soda, the dropping liquid C is an aqueous solution with the concentration of 25% prepared from soluble calcium salt and water, and the dropping liquid D is an aqueous solution with the concentration of 25% prepared from soluble silicate and water.
9. The method for preparing a nano calcium silicate suspension with high stability and good early strength effect according to claim 1 or claim 8, wherein the method comprises the following steps: the soluble calcium salt is one of calcium nitrate tetrahydrate, calcium nitrate tetrahydrate and calcium formate, and the soluble silicate is one of anhydrous sodium silicate, sodium silicate pentahydrate and sodium silicate nonahydrate.
10. The preparation method of the nano calcium silicate suspension with high stability and good early strength effect according to claim 1, characterized in that: the dropping time of the dropping liquid C and the dropping liquid D in the step S2 is the same, the dropping time is between 30min and 100min, the solid content of the nano calcium silicate suspension is between 8 percent and 20 percent, and the mixing amount is 1 percent to 4 percent of the mass of the cement and other glue materials.
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