A high-efficiency liquid alkali-free quick-setting agent and its preparation method and application

Abstract

The invention discloses a high-efficiency liquid alkali-free quick-setting agent and a preparation method and application thereof. The quick-setting agent is prepared from a polyacrylate urea-propionamide macromolecular functional component, an aluminum-containing functional component, a fluorine-containing functional component, a dispersant functional component and a thickener functional component. Among them, the poly (acrylate urea / propionamide) macromolecular functional component involved in the invention is prepared from acrylamide monomer, acrylate urea monomer and acrylic acid monomer through aqueous phase free radical polymerization, and the invention mainly utilizes the urea group, amide group and carboxyl group and other functional groups in the designed and prepared poly (acrylate urea / propionamide) macromolecular structure to effectively solubilize and complex aluminum ions to improve the storage stability of the quick-setting agent, and further improves the flowability and construction performance of the quick-setting agent through auxiliary dispersing and thickening functional components. Therefore, the new high-efficiency liquid alkali-free quick-setting agent is stable in storage, does not stratify after long-term storage, has significant quick-setting efficiency, and has broad application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of concrete admixtures, and specifically relates to a novel high-efficiency liquid alkali-free quick-setting agent and a preparation method and application thereof. Background Art

[0002] As one of the most commonly used materials in the construction industry, cement concrete is widely used in various construction projects, including various building structures such as house structures, bridges, tunnels and factory facilities; in addition, it is also widely used in infrastructure construction such as roads, railways, and water conservancy. Among them, with the increasing number of underground rail transit, tunnels, culverts and various underground engineering projects in my country's cities in recent years, the requirements for rapid setting and rapid construction of cement concrete have become higher and higher, and thus the demand for accelerated setting agents for concrete has also increased. However, the traditional accelerated setting agents currently have a series of problems due to the excessive alkali content, such as alkali-aggregate reaction, serious loss of concrete strength in the later stage, pollution to the environment, and serious damage to construction workers.

[0003] Accelerator is a kind of concrete setting regulator, which can accelerate the solidification and hardening of concrete, thus becoming an indispensable admixture in major projects such as tunnels, railways, and bridges. According to the alkali content (equivalent content of NaO2), accelerators are divided into high-alkali accelerators (alkali content>5.0%), low-alkali accelerators (alkali content 1.0%~5.0%) and alkali-free accelerators (alkali content ≤1.0%). Compared with alkali accelerators, liquid alkali-free accelerators have the advantages of low alkali content and high late strength. They cause less corrosion damage to construction workers during the construction process, and can greatly improve the late strength of shotcrete, which is beneficial to the construction of the project. Therefore, liquid alkali-free accelerators are receiving more and more attention.

[0004] At present, the construction of highways and high-speed railways in my country is developing rapidly, and there are many tunnel projects. The demand for liquid quick-setting agents, especially high-performance liquid alkali-free quick-setting agents, is also increasing. At present, the mainstream liquid alkali-free quick-setting agents all use aluminum sulfate as the main accelerating component. However, aluminum sulfate has a low solubility in aqueous solution, and the product has a short storage time. Stratification, precipitation or crystallization may occur in a short time, thereby affecting the performance of the liquid alkali-free quick-setting agent. Therefore, the present invention aims at the problems existing in the current liquid alkali-free quick-setting agent, starts with the design and preparation of polymer molecules, combines the organic / inorganic composite concept, prepares a functional poly (acrylate urea / propionamide) macromolecule through polymer structure design, and then supplements it with aluminum-containing functional components, fluorine-containing functional components, dispersant functional components and thickener functional components to obtain a new type of high-efficiency liquid alkali-free quick-setting agent. The new type of high-efficiency liquid alkali-free quick-setting agent is stable in storage, does not stratify after long-term storage, and has significant quick-setting efficiency, and has broad application prospects. Summary of the invention

[0005] The object of the present invention is to provide a novel high-efficiency liquid alkali-free quick-setting agent. Starting from organic / inorganic composite, the present invention prepares a functional poly (acrylate urea / propionamide) macromolecule through polymer structure design, and then supplements with aluminum-containing functional components, fluorine-containing functional components, dispersant functional components and thickener functional components to obtain a novel high-efficiency liquid alkali-free quick-setting agent. The novel high-efficiency liquid alkali-free quick-setting agent is stable in storage, does not delaminate after long-term storage, has significant quick-setting performance, and has broad application prospects.

[0006] In order to achieve the above technical objectives, the technical solution adopted by the present invention is:

[0007] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 10-30 parts of polyacrylate urea-propionamide macromolecular functional components, 20-50 parts of aluminum-containing functional components, 5-15 parts of fluorine-containing functional components, 1-3 parts of dispersant functional components, 1-3 parts of thickener functional components, and 20-40 parts of deionized water.

[0008] Preferably, the high-efficiency liquid alkali-free accelerating setting agent is prepared from the following raw materials in parts by weight: 15-25 parts of polyacrylate urea-propionamide macromolecular functional component, 30-45 parts of aluminum-containing functional component, 5-15 parts of fluorine-containing functional component, 1-3 parts of dispersant functional component, 1-3 parts of thickener functional component, and 25-35 parts of deionized water.

[0009] Preferably, the polyacrylate urea-propionamide macromolecular functional component is prepared by the following method:

[0010] S1: acrylamide monomer, acrylate urea monomer and acrylic acid monomer are mixed in a mass ratio and dissolved in deionized water to prepare an acrylate monomer solution; the mass ratio of the deionized water to the acrylate monomer mixture is 1:1.1-1.2.

[0011] S2: dissolving the initiator in deionized water to prepare an initiator solution with a mass concentration of 1.1%; the amount of the initiator used is 0.5% of the total mass of the acrylate monomer mixture;

[0012] S3: Add appropriate amount of deionized water to the polymerization kettle, stir and heat to 80°C, then simultaneously add the acrylate monomer solution obtained in S1 and the initiator solution obtained in S2 to the reactor, control the dropping time to be 3h, raise the temperature to 90°C after the dropping is completed, keep the temperature for reaction for 1h and then cool to room temperature, add appropriate amount of organic amine to adjust the pH to 7-8, and obtain polyacrylate urea-propionamide macromolecular functional components; the mass ratio of deionized water: acrylate monomer solution: initiator solution is 4:13:3.

[0013] Preferably, the mass ratio of acrylamide monomer: acrylate urea monomer: acrylic acid monomer in the acrylate monomer mixture is 20-30:2-10:1-5; the acrylate urea monomer is one of a urea-based wet adhesion monomer (WAM-E, Solvay) and a double-bond-containing urea heterocyclic compound (V-50M, Shanghai Zhongcheng Fine Chemicals).

[0014] Preferably, the organic amine is 2-amino-2-methyl-1-propanol; and the initiator is potassium persulfate.

[0015] Preferably, the aluminum-containing functional component is one or a combination of aluminum sulfate, polyaluminum sulfate, aluminum chloride, aluminum nitrate, and sodium aluminate.

[0016] More preferably, the aluminum-containing functional component is one of aluminum sulfate and polyaluminum sulfate.

[0017] Preferably, the fluorine-containing functional component is one or a combination of hydrofluoric acid, trifluoroacetic acid, trifluorobutyric acid, fluorosilicic acid, sodium fluoride, sodium fluorosilicate, magnesium fluorosilicate, and lithium fluorosilicate.

[0018] More preferably, the fluorine-containing functional component is one or a combination of trifluorobutyric acid, sodium fluorosilicate, magnesium fluorosilicate, and lithium fluorosilicate.

[0019] Preferably, the dispersant functional component is one or a combination of polycarboxylate water reducer, melamine water reducer, naphthalene water reducer and aminosulfonate water reducer.

[0020] More preferably, the dispersant functional component is one of a polycarboxylate water reducer and a melamine water reducer.

[0021] Preferably, the thickener functional component is one or a combination of alkali-swellable associative thickeners (L-344, Akzo Nobel, COADIS615, Gaotai), polyurethane thickeners (Cryminal 662, 990, Xupu).

[0022] More preferably, the thickener functional component is an alkali-swellable associative thickener.

[0023] A preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent comprises the following steps: firstly, deionized water is added into a homogenizing kettle, then a dispersant functional component, an aluminum-containing functional component and a fluorine-containing functional component are added in sequence, stirred to fully dissolve them, then a polyacrylate urea-propionamide macromolecular functional component is added dropwise, and the dropping time is controlled to be 0.5h, and finally a thickener functional component is added to adjust the viscosity of the system, so as to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0024] The application of a high-efficiency liquid alkali-free quick-setting agent mainly involves the fields related to shotcrete building materials for engineering projects such as tunnel and mine reinforcement, urban road and waterproof facility repair and reinforcement.

[0025] The high-efficiency liquid alkali-free quick-setting agent prepared by the present invention has the following advantages and beneficial effects:

[0026] (1) The present invention starts with the design and preparation of polymer molecules, combines the concept of organic / inorganic composite, prepares a functional polyacrylate urea / propionamide macromolecule through polymer structure design, and utilizes the urea group, amide group and carboxyl group and other functional groups of the polyacrylate urea / propionamide macromolecule to effectively solubilize and complex aluminum ions to improve the storage stability of the accelerator. At the same time, the auxiliary dispersing and thickening functional components are used to effectively improve the flow properties of the liquid accelerator while maintaining a certain viscosity, which further improves the construction performance of the liquid accelerator. Therefore, the new high-efficiency liquid alkali-free accelerator is stable in storage, does not stratify after long-term storage, has significant quick-setting efficiency, and has broad application prospects.

[0027] (2) The novel high-efficiency liquid alkali-free quick-setting agent designed and prepared by the present invention can also meet the setting needs of different building materials fields by optimizing and regulating the ratio and composition of the raw materials, so the application prospects are broader. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described below in conjunction with specific embodiments, but is not limited thereto.

[0029] Preparation Example 1

[0030] Preparation of functional polyacrylate urea / propionamide macromolecular functional components: 27.0 kg acrylamide, 5.0 kg acrylate urea monomer (WAM-E, Solvay), and 3.0 kg acrylic acid were dissolved in 30.0 kg deionized water to prepare an acrylate monomer solution, and then 0.17 kg potassium persulfate was dissolved in 14.83 kg deionized water to prepare an initiator solution. Finally, 20.0 kg of deionized water was added to the polymerization kettle, stirred and heated to 80°C, and the acrylate monomer solution and the initiator solution were added dropwise at the same time. The dropping time was controlled to 3 hours. After the dropping was completed, the temperature was raised to 90°C, and the reaction was kept warm for 1 hour and then cooled to room temperature. The organic amine was neutralized to a pH of 7-8 to obtain the polyacrylate urea-propionamide macromolecular functional component.

[0031] Preparation Example 2

[0032] Preparation of functional polyacrylate urea / propionamide macromolecular functional components: 24.0 kg acrylamide, 8.0 kg acrylate urea monomer (WAM-E, Solvay), and 3.0 kg acrylic acid were dissolved in 30.0 kg deionized water to prepare an acrylate monomer solution, and then 0.17 kg potassium persulfate was dissolved in 14.83 kg deionized water to prepare an initiator solution. Finally, 20.0 kg of deionized water was added to the polymerization kettle, stirred and heated to 80°C, and the acrylate monomer solution and the initiator solution were added dropwise at the same time. The dropping time was controlled to 3 hours. After the dropping was completed, the temperature was raised to 90°C, and the reaction was kept warm for 1 hour and then cooled to room temperature. The organic amine was neutralized to a pH of 7-8 to obtain the polyacrylate urea-propionamide macromolecular functional component.

[0033] Preparation Example 3

[0034] Preparation of functional polyacrylate urea / propionamide macromolecular functional components: 22.0 kg acrylamide, 10.0 kg acrylate urea monomer (WAM-E, Solvay), and 3.0 kg acrylic acid were dissolved in 30.0 kg deionized water to prepare an acrylate monomer solution, and then 0.17 kg potassium persulfate was dissolved in 14.83 kg deionized water to prepare an initiator solution. Finally, 20.0 kg of deionized water was added to the polymerization kettle, stirred and heated to 80°C, and the acrylate monomer solution and the initiator solution were added dropwise at the same time. The dropping time was controlled to 3 hours. After the dropping was completed, the temperature was raised to 90°C, and the reaction was kept warm for 1 hour and then cooled to room temperature. The organic amine was neutralized to a pH of 7-8 to obtain the polyacrylate urea-propionamide macromolecular functional component.

[0035] Preparation Example 4

[0036] Preparation of functional polyacrylate urea / propionamide macromolecular functional components: 27.0 kg acrylamide, 5.0 kg acrylate urea monomer (V50M, Shanghai Zhongcheng Fine Chemicals), and 3.0 kg acrylic acid were dissolved in 30.0 kg deionized water to prepare an acrylate monomer solution, and then 0.17 kg potassium persulfate was dissolved in 14.83 kg deionized water to prepare an initiator solution. Finally, 20.0 kg of deionized water was added to the polymerization kettle, stirred and heated to 80°C, and the acrylate monomer solution and the initiator solution were added dropwise at the same time. The dropping time was controlled to 3 hours. After the dropping was completed, the temperature was raised to 90°C, and the reaction was kept warm for 1 hour and then cooled to room temperature. The organic amine was neutralized to a pH of 7-8 to obtain the polyacrylate urea-propionamide macromolecular functional component.

[0037] Preparation Example 5

[0038] Preparation of functional polyacrylate urea / propionamide macromolecular functional components: 24.0 kg acrylamide, 8.0 kg acrylate urea monomer (V50M, Shanghai Zhongcheng Fine Chemicals), and 3.0 kg acrylic acid were dissolved in 30.0 kg deionized water to prepare an acrylate monomer solution, and then 0.17 kg potassium persulfate was dissolved in 14.83 kg deionized water to prepare an initiator solution. Finally, 20.0 kg of deionized water was added to the polymerization kettle, stirred and heated to 80°C, and the acrylate monomer solution and the initiator solution were added dropwise at the same time. The dropping time was controlled to 3 hours. After the dropping was completed, the temperature was raised to 90°C, and the reaction was kept warm for 1 hour and then cooled to room temperature. The organic amine was neutralized to a pH of 7-8 to obtain the polyacrylate urea-propionamide macromolecular functional component.

[0039] Preparation Example 6

[0040] Preparation of functional polyacrylate urea / propionamide macromolecular functional components: 22.0 kg acrylamide, 10.0 kg acrylate urea monomer (V50M, Shanghai Zhongcheng Fine Chemicals), and 3.0 kg acrylic acid were dissolved in 30.0 kg deionized water to prepare an acrylate monomer solution, and then 0.17 kg potassium persulfate was dissolved in 14.83 kg deionized water to prepare an initiator solution. Finally, 20.0 kg of deionized water was added to the polymerization kettle, stirred and heated to 80°C, and the acrylate monomer solution and the initiator solution were added dropwise at the same time. The dropping time was controlled to 3 hours. After the dropping was completed, the temperature was raised to 90°C, and the reaction was kept warm for 1 hour and then cooled to room temperature. The organic amine was neutralized to a pH of 7-8 to obtain the polyacrylate urea-propionamide macromolecular functional component.

[0041] Example 1

[0042] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 10 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 1, 20 kg of an aluminum-containing functional component (aluminum sulfate), 5 kg of a fluorine-containing functional component (magnesium fluorosilicate), 1 kg of a dispersant functional component (polycarboxylic acid water-reducing agent), 1.2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 20 kg of deionized water.

[0043] The preparation method of the above-mentioned high-efficiency liquid alkali-free accelerating setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequentially adding a polycarboxylic acid water-reducing agent, aluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 1, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free accelerating setting agent.

[0044] Example 2

[0045] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 20 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 2, 40 kg of an aluminum-containing functional component (aluminum sulfate), 10 kg of a fluorine-containing functional component (magnesium fluorosilicate), 2 kg of a dispersant functional component (melamine water reducer), 2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 30 kg of deionized water.

[0046] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, and then melamine water reducer, aluminum sulfate and magnesium fluorosilicate are added in sequence, stirred to fully dissolve, and then the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 2 is added dropwise, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0047] Example 3

[0048] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 30 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 3, 50 kg of an aluminum-containing functional component (polyaluminum sulfate), 15 kg of a fluorine-containing functional component (magnesium fluorosilicate), 3 kg of a dispersant functional component (polycarboxylic acid water reducer), 3 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 40 kg of deionized water.

[0049] The preparation method of the new high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequentially adding polycarboxylic acid water-reducing agent, polyaluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 3, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0050] Example 4

[0051] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 20 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 4, 45 kg of an aluminum-containing functional component (aluminum sulfate), 5 kg of a fluorine-containing functional component (magnesium fluorosilicate), 2 kg of a dispersant functional component (melamine water reducer), 1.2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 25 kg of deionized water.

[0052] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequential addition of melamine water reducer, aluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 4, preferably controlling the dropping time to 0.5h, and finally adding 1.2kg of alkali-swellable associative thickener to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0053] Example 5

[0054] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 20 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 5, 45 kg of an aluminum-containing functional component (polyaluminum sulfate), 5 kg of a fluorine-containing functional component (magnesium fluorosilicate), 2 kg of a dispersant functional component (polycarboxylic acid water-reducing agent), 1.2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 25 kg of deionized water.

[0055] The preparation method of the above-mentioned high-efficiency liquid alkali-free accelerating setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequentially adding polycarboxylic acid water-reducing agent, polyaluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 5, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free accelerating setting agent.

[0056] Example 6

[0057] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 20 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 6, 45 kg of an aluminum-containing functional component (polyaluminum sulfate), 5 kg of a fluorine-containing functional component (magnesium fluorosilicate), 2 kg of a dispersant functional component (polycarboxylic acid water-reducing agent), 1.2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 25 kg of deionized water.

[0058] The preparation method of the above-mentioned high-efficiency liquid alkali-free accelerating setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequentially adding polycarboxylic acid water-reducing agent, polyaluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 6, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free accelerating setting agent.

[0059] Example 7

[0060] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 25 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 2, 45 kg of an aluminum-containing functional component (aluminum sulfate), 5 kg of a fluorine-containing functional component (sodium fluorosilicate), 2 kg of a dispersant functional component (melamine water reducer), 1.2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 20 kg of deionized water.

[0061] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, and then melamine water reducer, aluminum sulfate and sodium fluorosilicate are added in sequence, stirred to fully dissolve, and then the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 2 is added dropwise, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0062] Example 8

[0063] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 15 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 2, 35 kg of an aluminum-containing functional component (aluminum sulfate), 5 kg of a fluorine-containing functional component (lithium fluorosilicate), 2 kg of a dispersant functional component (polycarboxylic acid water-reducing agent), 1.2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 30 kg of deionized water.

[0064] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequentially adding a polycarboxylic acid water-reducing agent, aluminum sulfate and lithium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 2, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0065] Example 9

[0066] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 20 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 3, 35 kg of an aluminum-containing functional component (aluminum sulfate), 5 kg of a fluorine-containing functional component (3 kg of magnesium fluorosilicate + 2 kg of sodium fluorosilicate), 2.5 kg of a dispersant functional component (polycarboxylic acid water-reducing agent), 2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 30 kg of deionized water.

[0067] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequential addition of polycarboxylic acid water-reducing agent, aluminum sulfate, magnesium fluorosilicate and sodium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 3, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0068] Example 10

[0069] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 25 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 5, 30 kg of an aluminum-containing functional component (polyaluminum sulfate), 10 kg of a fluorine-containing functional component (sodium fluorosilicate), 3 kg of a dispersant functional component (melamine water reducer), 2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 20 kg of deionized water.

[0070] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: 20.0 kg of deionized water is added to a homogenizing kettle, followed by sequentially adding melamine water reducer, polyaluminum sulfate and sodium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 5, and the dropping time is preferably controlled to be 0.5 h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0071] Embodiment 11

[0072] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 15 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 5, 40 kg of an aluminum-containing functional component (aluminum sulfate), 15 kg of a fluorine-containing functional component (lithium fluorosilicate), 1 kg of a dispersant functional component (polycarboxylic acid water-reducing agent), 3 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 30 kg of deionized water.

[0073] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequentially adding a polycarboxylic acid water-reducing agent, aluminum sulfate and lithium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 5, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0074] Example 12

[0075] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 25 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 4, 30 kg of an aluminum-containing functional component (aluminum sulfate), 10 kg of a fluorine-containing functional component (magnesium fluorosilicate), 1 kg of a dispersant functional component (melamine water reducer), 2 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 20 kg of deionized water.

[0076] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, and then melamine water reducer, aluminum sulfate and magnesium fluorosilicate are added in sequence, stirred to fully dissolve, and then the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 4 is added dropwise, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0077] Example 13

[0078] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 10 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 6, 30 kg of an aluminum-containing functional component (polyaluminum sulfate), 5 kg of a fluorine-containing functional component (4.0 kg of trifluorobutyric acid + 1.0 kg of lithium fluorosilicate), 3 kg of a dispersant functional component (polycarboxylic acid water-reducing agent), 1 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 30 kg of deionized water.

[0079] The preparation method of the above-mentioned high-efficiency liquid alkali-free quick-setting agent is as follows: deionized water is added to a homogenizing kettle, and then polycarboxylic acid water-reducing agent, aluminum sulfate, trifluorobutyric acid and lithium fluorosilicate are added in sequence, stirred to fully dissolve, and then the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 6 is added dropwise, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

[0080] Embodiment 14

[0081] A high-efficiency liquid alkali-free quick-setting agent is prepared from the following raw materials in parts by weight: 20 kg of the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 6, 40 kg of an aluminum-containing functional component (polyaluminum sulfate), 15 kg of a fluorine-containing functional component (magnesium fluorosilicate), 1 kg of a dispersant functional component (polycarboxylic acid water-reducing agent), 3 kg of a thickener functional component (alkali-swellable associative thickener L-344), and 30 kg of deionized water.

[0082] The preparation method of the above-mentioned high-efficiency liquid alkali-free accelerating setting agent is as follows: deionized water is added to a homogenizing kettle, followed by sequentially adding polycarboxylic acid water-reducing agent, polyaluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and then dropwise adding the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 6, and the dropping time is preferably controlled to be 0.5h. Finally, an alkali-swellable associative thickener is added to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free accelerating setting agent.

[0083] Comparative Example 1

[0084] A liquid alkali-free quick-setting agent, whose raw material composition is basically the same as that of Example 1, except that it does not contain the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 1.

[0085] The preparation method is as follows: deionized water is added to a homogenizing kettle, followed by sequential addition of polycarboxylate water reducer, aluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and finally adding an alkali-swellable associative thickener to adjust the viscosity of the system to obtain a liquid alkali-free accelerating setting agent.

[0086] Comparative Example 2

[0087] A liquid alkali-free quick-setting agent, whose raw material composition is basically the same as that of Example 2, except that it does not contain the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 2.

[0088] The preparation method is as follows: deionized water is added to a homogenizing kettle, followed by sequential addition of polycarboxylate water reducer, aluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and finally adding an alkali-swellable associative thickener to adjust the viscosity of the system to obtain a liquid alkali-free accelerating setting agent.

[0089] Comparative Example 3

[0090] A liquid alkali-free quick-setting agent, whose raw material composition is basically the same as that of Example 3, except that it does not contain the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 3.

[0091] The preparation method is as follows: deionized water is added to a homogenizing kettle, followed by sequential addition of polycarboxylate water reducer, aluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and finally adding an alkali-swellable associative thickener to adjust the viscosity of the system to obtain a liquid alkali-free accelerating setting agent.

[0092] Comparative Example 4

[0093] A liquid alkali-free quick-setting agent, whose raw material composition is basically the same as that of Example 4, the only difference is that it does not contain the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 4.

[0094] The preparation method is as follows: deionized water is added to a homogenizing kettle, followed by sequential addition of polycarboxylate water reducer, aluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and finally adding an alkali-swellable associative thickener to adjust the viscosity of the system to obtain a liquid alkali-free accelerating setting agent.

[0095] Comparative Example 5

[0096] A liquid alkali-free quick-setting agent, whose raw material composition is basically the same as that of Example 5, the only difference being that it does not contain the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 5.

[0097] The preparation method is as follows: deionized water is added to a homogenizing kettle, followed by sequential addition of polycarboxylate water reducer, aluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and finally adding an alkali-swellable associative thickener to adjust the viscosity of the system to obtain a liquid alkali-free accelerating setting agent.

[0098] Comparative Example 6

[0099] A liquid alkali-free quick-setting agent, whose raw material composition is basically the same as that of Example 6, the only difference being that it does not contain the polyacrylate urea-propionamide macromolecular functional component obtained in Preparation Example 6.

[0100] The preparation method is as follows: deionized water is added to a homogenizing kettle, followed by sequential addition of polycarboxylate water reducer, aluminum sulfate and magnesium fluorosilicate, stirring to fully dissolve them, and finally adding an alkali-swellable associative thickener to adjust the viscosity of the system to obtain a liquid alkali-free accelerating setting agent.

[0101] Performance Testing

[0102] At present, stability and quick-setting effect are the two most important indicators for measuring and evaluating liquid performance. Therefore, the stability test method of the new high-efficiency liquid alkali-free quick-setting agent designed and prepared by the present invention is as follows: after the quick-setting agent sample is fully shaken, it is placed in a beaker, and then transferred to a 100mL measuring cylinder and the cylinder stopper is tightly covered. When the quick-setting agent in the measuring cylinder is precipitated, crystallized, or the supernatant is ≥5mL, the quick-setting agent is judged to have poor stability. At the same time, the quick-setting effect of the new high-efficiency liquid alkali-free quick-setting agent designed and prepared by the present invention is measured with reference to the setting time of the net slurry mixed with liquid quick-setting agent in GB / T 35159-2017 "Quick-setting Agent for Shotcrete". In addition, the strength of the cement mortar mixed with the new high-efficiency liquid alkali-free quick-setting agent designed and prepared by the present invention is measured and evaluated in accordance with GB / T 35159-2017 "Quick-setting Agent for Shotcrete", and the specific results are shown in Table 1.

[0103] Table 1 Performance test results

[0104]

[0105] The results show that compared with the commercially available liquid alkali-free quick-setting agent (LSN1) and comparative examples 1-6, the present invention starts with the design and preparation of polymer molecules, combines the concept of organic / inorganic composite, and prepares a functional poly (acrylate urea / propionamide) macromolecule through polymer structure design. The urea group, amide group and carboxyl group of the poly (acrylate urea / propionamide) macromolecule are used to effectively solubilize and complex aluminum ions to improve the storage stability of the new high-efficiency liquid alkali-free quick-setting agent. The auxiliary dispersing and thickening functional components effectively improve the flow properties of the liquid quick-setting agent while maintaining a certain viscosity, which further improves the construction performance of the liquid quick-setting agent. Therefore, the new high-efficiency liquid alkali-free quick-setting agent is stable in storage, does not stratify for a long time, and has significant quick-setting efficiency, and has broad application prospects. In addition, for the new high-efficiency liquid alkali-free quick-setting agent designed and prepared by the present invention, the setting needs of different building materials fields can be met by optimizing and regulating the ratio and composition of the raw materials, so the application prospects are even broader.

[0106] It should be noted that the above embodiments are only partial embodiments of the preferred methods of implementing the present invention, rather than all embodiments. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

Claims

1. A high-efficiency liquid alkali-free quick-setting agent, characterized in that: The invention is prepared from the following raw materials in parts by weight: 10-30 parts of polyacrylate urea-propionamide macromolecular functional component, 20-50 parts of aluminum-containing functional component, 5-15 parts of fluorine-containing functional component, 1-3 parts of dispersant functional component, 1-3 parts of thickener functional component, and 20-40 parts of deionized water; The polyacrylate urea-propionamide macromolecular functional component is prepared by the following method: S1: mixing acrylamide monomer, acrylate urea monomer and acrylic acid monomer according to a mass ratio and dissolving them in deionized water to prepare an acrylate monomer solution; the mass ratio of the deionized water to the acrylate monomer mixture is 1:1.1-1.2; S2: dissolving the initiator in deionized water to prepare an initiator solution with a mass concentration of 1.1%; the amount of the initiator used is 0.5% of the total mass of the acrylate monomer mixture; S3: Add appropriate amount of deionized water to the polymerization kettle, stir and heat to 80°C, then simultaneously add the acrylate monomer solution obtained in S1 and the initiator solution obtained in S2 to the reactor, control the dropping time to be 3h, raise the temperature to 90°C after the dropping is completed, keep the temperature for reaction for 1h and then cool to room temperature, add appropriate amount of organic amine to adjust the pH to 7-8, and obtain polyacrylate urea-propionamide macromolecular functional components; the mass ratio of deionized water: acrylate monomer solution: initiator solution is 4:13:

3.

2. The high-efficiency liquid alkali-free quick-setting agent according to claim 1, characterized in that: The mass ratio of acrylamide monomer: acrylate urea monomer: acrylic acid monomer in the acrylate monomer mixture is 20-30: 2-10: 1-5; the acrylate urea monomer is a urea-based wet adhesion monomer, a urea heterocyclic compound containing a double bond.

3. The high-efficiency liquid alkali-free quick-setting agent according to claim 1, characterized in that: The organic amine is 2-amino-2-methyl-1-propanol; and the initiator is potassium persulfate.

4. The high-efficiency liquid alkali-free quick-setting agent according to claim 1, characterized in that: The aluminum-containing functional component is one of aluminum sulfate and polyaluminum sulfate.

5. The high-efficiency liquid alkali-free quick-setting agent according to claim 1, characterized in that: The fluorine-containing functional component is one or a combination of trifluorobutyric acid, sodium fluorosilicate, magnesium fluorosilicate and lithium fluorosilicate.

6. The high-efficiency liquid alkali-free quick-setting agent according to claim 1, characterized in that: The dispersant functional component is one of a polycarboxylate water reducer and a melamine water reducer.

7. The high-efficiency liquid alkali-free quick-setting agent according to claim 1, characterized in that: The thickener functional component is an alkali swelling associative thickener.

8. A method for preparing a high-efficiency liquid alkali-free quick-setting agent according to any one of claims 1 to 7, characterized in that: The following steps are involved: First, add deionized water into the homogenizing kettle, then add the dispersant functional component, the aluminum-containing functional component and the fluorine-containing functional component in turn, stir to fully dissolve them, then dropwise add the polyacrylate urea-propionamide macromolecular functional component, control the dropping time to 0.5h, and finally add the thickener functional component to adjust the viscosity of the system to obtain a new high-efficiency liquid alkali-free quick-setting agent.

9. Use of a high-efficiency liquid alkali-free quick-setting agent according to any one of claims 1 to 7, characterized in that: Application in shotcrete.

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