A low-temperature antifreeze type early-strength alkali-free quick-setting agent composition, quick-setting agent, preparation method and application thereof

Abstract

The invention relates to the field of building materials, and discloses a low-temperature antifreeze type early-strength alkali-free quick-setting agent composition, an accelerator, and a preparation method and application thereof. The low-temperature antifreeze type early-strength alkali-free quick-setting agent composition contains aluminum sulfate, triethanolamine, a composite antifreeze agent, an alcohol compound, a stabilizer, and a pH regulator; the composite antifreeze agent is a product obtained by a method comprising the following steps: in the presence of water I, calcium nitrate, diethanol monoisopropanolamine, acrylamide, ethylene glycol and ursolic acid are contacted and reacted. The low-temperature antifreeze type early-strength alkali-free quick-setting agent prepared by the method provided by the invention has high early strength, good stability, and good antifreeze effect on concrete.

Description

Technical Field

[0001] The invention relates to the field of building materials, and in particular to a low-temperature antifreeze type early-strength alkali-free quick-setting agent composition, an quick-setting agent, and a preparation method and application thereof. Background Art

[0002] With the continuous development of my country's railways, building more, longer, larger and deeper tunnels in high-altitude and high-latitude cold regions has become a development trend of tunnel engineering. However, with the continuous construction of tunnels in cold regions, frost damage inside the tunnel has become one of the main difficulties in tunnel construction. More than 50% of the cold-region tunnels in the country have frost damage problems to varying degrees. Some tunnels cannot be used normally for nearly half a year a year, and some have even been scrapped. For example, lining leakage and ice hanging caused by freeze-thaw damage, ice accumulation and frost heaving of surrounding rocks, and lining concrete cracking, crumbling, and spalling have seriously affected the structural safety and stable operation of the tunnel, and increased the cost of disease remediation and maintenance.

[0003] At present, the main methods to affect the frost resistance of concrete include adding rubber particles, fibers, air entraining agents and antifreeze agents. However, these methods are not compatible with the construction industry of shotcrete spraying, and cannot truly improve the waterproof and anti-seepage properties of cement concrete. In traditional tunnel construction, alkaline accelerators are highly corrosive, causing great harm to construction workers, and have disadvantages such as large construction rebound and serious loss of strength in the later stage. Therefore, alkali-free accelerators are the most important admixtures in the process of shotcrete forming. The alkali-free accelerator first proposed by a Japanese company uses aluminum sulfate as the main accelerating component, and is combined with other early strength components such as triethanolamine to act as an early strength accelerating component for shotcrete. However, alkali-free accelerators also have problems such as low early strength, poor stability, and the presence of harmful substances.

[0004] At the same time, underground construction in cold areas at high altitudes and high latitudes requires higher antifreeze properties for quick-setting agent products, and aluminum salt materials are very easy to precipitate crystals in low temperature environments. Therefore, how to lower the freezing point of aluminum salt materials at low temperatures to improve the antifreeze properties of quick-setting agent products is also a major difficulty.

[0005] In the prior art, CN115849759A discloses a low-temperature resistant early-strength alkali-free liquid accelerator. Although the accelerator can meet the requirements of alkali-free early strength, the fluorosilicic acid used therein will affect the strength of concrete and easily cause physical harm to production and construction personnel.

[0006] Therefore, it is very important for the development of tunnel engineering to provide an alkali-free liquid quick-setting agent with high early strength, good stability, no harmful substances, and excellent antifreeze performance. Summary of the invention

[0007] The purpose of the invention is to overcome the problems of low early strength, poor stability, harmful substances and low antifreeze performance of the quick-setting agent in the prior art.

[0008] In order to achieve the above object, the first aspect of the present invention provides a low-temperature antifreeze type early-strength alkali-free quick-setting agent composition, which contains the following components which are stored separately or in combination:

[0009] Aluminum sulfate, triethanolamine, composite antifreeze agent, alcohol compound, stabilizer, pH regulator; the alcohol compound is ethylene glycol and / or glycerol; based on the total weight of the low-temperature antifreeze type early strength alkali-free quick-setting agent composition, the content of aluminum sulfate is 73.4-87.1wt%, the content of triethanolamine is 2.8-10.5wt%, the content of the composite antifreeze agent is 4.2-9.6wt%, the content of the alcohol compound is 1.4-4.2wt%, the content of the stabilizer is 2.0-4.2wt%, and the content of the pH regulator is 1.0-2.5wt%;

[0010] The composite antifreeze agent is a product obtained by a method comprising the following steps:

[0011] In the presence of water I, calcium nitrate, diethanol monoisopropanolamine, acrylamide, ethylene glycol and ursolic acid are contacted and reacted.

[0012] The second aspect of the present invention provides a method for preparing a low-temperature antifreeze type early-strength alkali-free quick-setting agent, which is carried out using the components in the composition described in the first aspect, comprising:

[0013] S1. In the presence of water II, aluminum sulfate, a pH regulator and an alcohol compound are first mixed to obtain a mixture A;

[0014] S2, mixing the mixture A with triethanolamine and a stabilizer for a second time to obtain a pre-mother solution;

[0015] S3, mixing the pre-mother solution with the composite antifreeze agent for the third time to obtain a low-temperature antifreeze type early-strength alkali-free quick-setting agent;

[0016] Wherein, the alcohol compound is ethylene glycol and / or glycerol; based on the total weight of the low-temperature antifreeze type early-strength alkali-free quick-setting agent, the amount of aluminum sulfate is 51-56wt%, the amount of triethanolamine is 2-6wt%, the amount of the composite antifreeze agent is 3-6wt%, the amount of the alcohol compound is 0.9--2.5wt%, the amount of the stabilizer is 0.8-2.5wt%, the amount of the pH regulator is 0.8-1.5wt%, and the amount of water II is 25.5-34.7wt%;

[0017] The composite antifreeze agent is a product obtained by a method comprising the following steps:

[0018] In the presence of water I, calcium nitrate, diethanol monoisopropanolamine, acrylamide, ethylene glycol and ursolic acid are contacted and reacted.

[0019] The third aspect of the present invention provides a low-temperature antifreeze type early-strength alkali-free quick-setting agent prepared by the method described in the second aspect.

[0020] The fourth aspect of the present invention provides the use of the low-temperature antifreeze-type early-strength alkali-free quick-setting agent described in the third aspect in the field of building materials.

[0021] Compared with the prior art, the low-temperature antifreeze-type early-strength alkali-free quick-setting agent prepared by the method provided by the present invention has high early strength, good stability, and good antifreeze effect on concrete, and can meet the requirements of national standard GB / T35159-2017 and railway standard Q / CR 807-2020 for rapid setting, early strength and stability, and can improve the antifreeze performance of cement concrete in a curing environment of -5°C to -15°C. DETAILED DESCRIPTION

[0022] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0023] As mentioned above, the first aspect of the present invention provides a low-temperature antifreeze type early-strength alkali-free quick-setting agent composition, which contains the following components which are stored separately or in combination:

[0024] Aluminum sulfate, triethanolamine, composite antifreeze agent, alcohol compound, stabilizer, pH regulator; the alcohol compound is ethylene glycol and / or glycerol; based on the total weight of the low-temperature antifreeze type early strength alkali-free quick-setting agent composition, the content of aluminum sulfate is 73.4-87.1wt%, the content of triethanolamine is 2.8-10.5wt%, the content of the composite antifreeze agent is 4.2-9.6wt%, the content of the alcohol compound is 1.4-4.2wt%, the content of the stabilizer is 2.0-4.2wt%, and the content of the pH regulator is 1.0-2.5wt%;

[0025] The composite antifreeze agent is a product obtained by a method comprising the following steps:

[0026] In the presence of water I, calcium nitrate, diethanol monoisopropanolamine, acrylamide, ethylene glycol and ursolic acid are contacted and reacted.

[0027] Preferably, the contact reaction operation comprises: at 40-60°C,

[0028] (1) in the presence of the water I, the calcium nitrate, the diethanol monoisopropanolamine and the acrylamide are first contacted to obtain a mixture I;

[0029] (2) contacting the mixture I with the ethylene glycol and the ursolic acid for a second time to obtain the composite antifreeze agent.

[0030] The inventors have found that the above preferred conditions can make the low-temperature antifreeze type early-strength alkali-free quick-setting agent prepared from the low-temperature antifreeze type early-strength alkali-free quick-setting agent composition have better stability.

[0031] According to a preferred embodiment, the temperatures of the first contacting and the second contacting are independently 40-60°C.

[0032] Preferably, in the contact reaction, the weight ratio of the calcium nitrate, the water I, the diethanol monoisopropanolamine, the acrylamide, the ethylene glycol and the ursolic acid is 1-4: 1: 1-2: 1-3: 0.2-1: 0.01-0.05. The inventors found that in this preferred case, the low-temperature antifreeze type early strength alkali-free quick-setting agent prepared from the antifreeze agent has higher low-temperature antifreeze performance.

[0033] Preferably, in step (1), the first contact is carried out under stirring conditions and at least meets the following conditions: a rotation speed of 300-400 rpm and a time of 30-60 min.

[0034] Preferably, in step (2), the second contact is carried out under stirring conditions and at least meets the following conditions: a rotation speed of 300-400 rpm and a time of 25-45 min.

[0035] Preferably, the stabilizer is pseudo-boehmite and / or sepiolite.

[0036] Preferably, the pH adjuster is formic acid and / or acrylic acid.

[0037] Preferably, the aluminum sulfate meets the requirements of HG / T 2225-2018 "Industrial Aluminum Sulfate".

[0038] Preferably, the triethanolamine meets the requirements of HG / T 3268-2002 "Triethanolamine for Industrial Use".

[0039] As mentioned above, the second aspect of the present invention provides a method for preparing a low-temperature antifreeze type early-strength alkali-free quick-setting agent, which is carried out using the components in the composition described in the first aspect, comprising:

[0040] S1. In the presence of water II, aluminum sulfate, a pH regulator and an alcohol compound are first mixed to obtain a mixture A;

[0041] S2, mixing the mixture A with triethanolamine and a stabilizer for a second time to obtain a pre-mother solution;

[0042] S3, mixing the pre-mother solution with the composite antifreeze agent for the third time to obtain a low-temperature antifreeze type early-strength alkali-free quick-setting agent;

[0043] Wherein, the alcohol compound is ethylene glycol and / or glycerol; based on the total weight of the low-temperature antifreeze type early-strength alkali-free quick-setting agent, the amount of aluminum sulfate is 51-56wt%, the amount of triethanolamine is 2-6wt%, the amount of the composite antifreeze agent is 3-6wt%, the amount of the alcohol compound is 0.9-2.5wt%, the amount of the stabilizer is 0.8-2.5wt%, the amount of the pH regulator is 0.8-1.5wt%, and the amount of water II is 25.5-34.7wt%;

[0044] The composite antifreeze agent is a product obtained by a method comprising the following steps:

[0045] In the presence of water I, calcium nitrate, diethanol monoisopropanolamine, acrylamide, ethylene glycol and ursolic acid are contacted and reacted.

[0046] It should be noted that, in the present invention, there is no limitation on the reactors for the first mixing, the second mixing, and the third mixing, and they can be performed in a reactor, for example.

[0047] It should be noted that, in the present invention, the water I and the water II are both water, but are added in different steps.

[0048] According to a preferred embodiment, the method of the present invention further includes: before the aluminum sulfate is mixed with the pH regulator and the alcohol compound for the first time, the aluminum sulfate is first mixed and dissolved with the water II to obtain dissolved aluminum sulfate, and then the dissolved aluminum sulfate is mixed with the pH regulator and the alcohol compound for the first time.

[0049] Preferably, the mixed dissolution is carried out at a rotation speed of 50-250 rpm, and further comprises:

[0050] SS1, dissolving 2 / 3 of the weight of the aluminum sulfate and all of the water II for 25-35 minutes at 60-75° C. to obtain a dissolved product I;

[0051] SS2, at 60-75° C., dissolving the solute I and the remaining 1 / 3 weight of the aluminum sulfate for a second time for 15-25 min to obtain solute II;

[0052] SS3. Stir the dissolved substance II at 50-60° C. for 15-25 min to obtain dissolved aluminum sulfate.

[0053] More preferably, in the dissolution, the temperature of the first dissolution is 4-10° C. higher than the temperature of the second dissolution. The inventors found that the low-temperature antifreeze type early-strengthening alkali-free quick-setting agent prepared under this preferred condition has better early-strengthening performance.

[0054] Preferably, in step S1, the first mixing is performed under stirring conditions and at least meets the following conditions: temperature is 60-80°C, rotation speed is 50-250rpm, and time is 30-120min.

[0055] Preferably, in step S2, the second mixing is performed under stirring conditions and at least meets the following conditions: 40-70°C, a rotation speed of 50-150 rpm, and a time of 60-120 min.

[0056] Preferably, in step S3, the third mixing is performed under stirring conditions and at least meets the following conditions: 40-60°C, a rotation speed of 50-150 rpm, and a time of 45-100 min.

[0057] More preferably, the rotation speed of the first mixing is 15-30 rpm higher than the rotation speeds of the second mixing and the third mixing.

[0058] Preferably, the method of the present invention further comprises: before the first mixing, mixing and dissolving the aluminum sulfate and the water II, and then mixing the obtained product with the pH regulator and the alcohol compound in the first mixing.

[0059] According to a preferred embodiment, the method of the present invention comprises the following steps:

[0060] Preparation of composite antifreeze:

[0061] (1) in the presence of the water I, the calcium nitrate, the diethanol monoisopropanolamine and the acrylamide are first contacted to obtain a mixture I;

[0062] (2) contacting the mixture I with the ethylene glycol and the ursolic acid for a second time to obtain the composite antifreeze agent;

[0063] Preparation of low temperature antifreeze type early strength alkali-free accelerating setting agent:

[0064] S1. In the presence of water II, aluminum sulfate, a pH regulator and an alcohol compound are first mixed to obtain a mixture A;

[0065] S2, mixing the mixture A with triethanolamine and a stabilizer for a second time to obtain a pre-mother solution;

[0066] S3, mixing the pre-mother solution with the composite antifreeze agent for the third time to obtain a low-temperature antifreeze type early-strength alkali-free quick-setting agent.

[0067] Preferably, in the second mixing, the triethanolamine and / or the stabilizer are added to the mixture A in a dropwise manner to perform the second mixing, wherein the dropping speed is 80-150 mL / min for each 1 L of the mixture A. The inventors have found that the low-temperature antifreeze type early-strength alkali-free quick-setting agent prepared under this preferred condition has better stability.

[0068] As mentioned above, the third aspect of the present invention provides a low-temperature antifreeze type early-strength alkali-free quick-setting agent prepared by the method described in the second aspect.

[0069] As mentioned above, the fourth aspect of the present invention provides the use of the low-temperature antifreeze-type early-strength alkali-free quick-setting agent described in the third aspect in the field of building materials.

[0070] The present invention is described in detail below by way of examples. Unless otherwise specified, the raw materials used are common commercial products of analytical grade.

[0071] Aluminum sulfate: industrial aluminum sulfate with a purity of 80wt%, meeting HG / T 2225-2018 "Industrial aluminum sulfate", purchased from Zibo Juying Aluminum Co., Ltd.;

[0072] Triethanolamine: industrial triethanolamine, meeting HG / T 3268-2002 "Industrial Triethanolamine", purchased from Zibo Sangfei Economic and Trade Co., Ltd.;

[0073] Alcohol compounds:

[0074] Alcohol compound I: ethylene glycol;

[0075] Alcohol compound II: glycerol;

[0076] Stabilizer: pseudo-boehmite, purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., model number DW3422;

[0077] pH adjuster: formic acid;

[0078] Antifreeze I: Calcium nitrate;

[0079] Antifreeze II: The preparation method of antifreeze in CN115849759A is adopted, comprising:

[0080] Add 15 g of diethylene glycol to 40 g of an aqueous solution of oxalic acid (50 wt%) at 70° C. and heat to react for 1 h. After the reaction is completed, add 50 g of an aqueous solution of urea (35 wt%) and stir evenly to obtain antifreeze II.

[0081] Preparation Example A-1

[0082] The composite antifreeze agent I was prepared by the following method and with reference to the parameters in Table 1:

[0083] (1) at 60° C. and a rotation speed of 350 rpm, in the presence of water I, calcium nitrate, diethanol monoisopropanolamine and acrylamide are first contacted for 45 minutes to obtain a mixture I;

[0084] (2) The mixture I is brought into second contact with the ethylene glycol and ursolic acid at 40° C. and a rotation speed of 300 rpm for 30 minutes to obtain a composite antifreeze agent I.

[0085] Preparation Example A-2

[0086] This preparation example is carried out by a method similar to that of Preparation Example A-1, except that the amount of substances used and the condition parameters are changed. For details, refer to Table 1, and finally a composite antifreeze agent II is obtained.

[0087] Preparation Example A-3

[0088] This preparation example is carried out by a method similar to that of Preparation Example A-1, except that the amount of ursolic acid used is 0 g, and finally a composite antifreeze agent III is obtained.

[0089] Preparation Example A-4

[0090] This preparation example is carried out by a method similar to that of Preparation Example A-1, except that an equal mass (5 g) of propylene glycol is used instead of ethylene glycol for the second contact, and finally a composite antifreeze agent IV is obtained.

[0091] Preparation Example 1

[0092] This preparation example is used to illustrate a preferred method for preparing a low-temperature antifreeze type early-strength alkali-free quick-setting agent provided by the present invention, and is carried out with reference to the parameters in Table 2, specifically including:

[0093] SS1, dissolving 2 / 3 of the weight of the aluminum sulfate and all of the water II for 30 minutes at 60° C. and 200 rpm to obtain a dissolved product I;

[0094] SS2, dissolving the solute I and the remaining 1 / 3 weight of the aluminum sulfate for a second time at 60° C. and 220 rpm for 20 min to obtain solute II;

[0095] SS3. Stir the dissolved substance II at 55° C. and 220 rpm for 20 min to obtain dissolved aluminum sulfate.

[0096] S1. Mixing the dissolved aluminum sulfate, the pH regulator and the alcohol compound for a first time for 40 minutes at 75° C. and a rotation speed of 150 rpm to obtain a mixture A;

[0097] S2, at 70°C and a rotation speed of 125 rpm, triethanolamine and a stabilizer are added dropwise to the mixture A to perform a second mixing for 60 min to obtain a pre-mother solution; wherein the rate of each dropwise addition is 90 mL / min for each 1 L of the mixture A;

[0098] S3. The pre-mother solution and the composite antifreeze agent I were mixed for a third time at 50° C. and a rotation speed of 125 rpm for 60 min to obtain a low-temperature antifreeze type early-strength alkali-free quick-setting agent, named P1.

[0099] Preparation Example 2

[0100] This preparation example is carried out by a method similar to that of Preparation Example 1, except that the composite antifreeze used is composite antifreeze II, and the substance type, dosage and condition parameters are changed. For specific parameters, see Table 2. Finally, a low-temperature antifreeze type early-strength alkali-free quick-setting agent is obtained, which is named P2.

[0101] Comparative Example 1

[0102] This comparative example was prepared by a method similar to that of Preparation Example 1, except that the composite antifreeze agent used was composite antifreeze agent III, and an accelerated setting agent was finally obtained, which was named DP1.

[0103] Comparative Example 2

[0104] This comparative example was prepared by a method similar to that of Preparation Example 1, except that the composite antifreeze agent used was composite antifreeze agent IV, and an accelerated setting agent was finally obtained, which was named DP2.

[0105] Comparative Example 3

[0106] This comparative example was prepared by a method similar to that of Preparation Example 1, except that the same mass (50 g) of antifreeze I (calcium nitrate) was used instead of the composite antifreeze, and an accelerated setting agent was finally obtained, which was named DP3.

[0107] Comparative Example 4

[0108] This comparative example was prepared by a method similar to that of Preparation Example 1, except that the same mass (50 g) of antifreeze II was used instead of the composite antifreeze I, and an accelerated setting agent was finally obtained, which was named DP4.

[0109] Comparative Example 5

[0110] This comparative example was prepared by a method similar to that of Preparation Example 1, except that the amount of the composite antifreeze agent was reduced to 20 g, and an accelerated setting agent was finally obtained, which was named DP5.

[0111] Test Example 1

[0112] The accelerator density, pH value, solid content, stability, chloride ion content and alkali content of the products obtained in the above examples were tested in accordance with the provisions of GB / T 35159-2017 "Accelerators for Shotcrete";

[0113] Test the corresponding fluoride ion content according to the fluoride ion content test method specified in Q / CR 807-2020 "Liquid alkali-free accelerator for tunnel shotcrete";

[0114] According to the test methods specified in the national standards GB / T 35159-2017 "Accelerators for Shotcrete" and JC475-2004 "Antifreeze Agents for Concrete", PI42.5 standard silicate cement and standard sand produced by Xiamen AIS were used to test the setting time of the mortar, the compressive strength of the mortar, the air content and the freeze-thaw strength loss during low-temperature curing at -15°C.

[0115] Please see Table 3 for the test results.

[0116] Table 1

[0117] Components Preparation Example A-1 Preparation Example A-2 Calcium Nitrate Dosage / g 35 45 Diethanol Monoisopropanolamine Dosage / g 15 20 Acrylamide Dosage / g 25 20 Ethylene glycol Dosage / g 5 10 Ursolic acid Dosage / g 0.3 0.5 Water I Dosage / g 10 12 Conditional parameters First Contact Temperature / ℃ 60 55 Time / min 45 50 Speed / rpm 350 400 Second Contact Temperature / ℃ 40 45 Time / min 30 25 Speed / rpm 300 350

[0118] Table 2

[0119] substance Preparation Example 1 Preparation Example 2 Aluminum sulfate Dosage / g 530 530 Water II Dosage / g 345 340 pH Adjusters Dosage / g 8 10 Alcohol compounds name Alcohol Compound I Alcohol Compound II Alcohol compounds Dosage / g 9 10 Triethanolamine Dosage / g 50 45 Stabilizer Dosage / g 8 10 Composite antifreeze name Composite antifreeze I Composite antifreeze II Composite antifreeze Dosage / g 50 55 Conditional parameters First Mix Temperature / ℃ 75 80 Time / min 40 30 Speed / rpm 150 125 Second Mix Temperature / ℃ 70 65 Time / min 60 85 Speed / rpm 125 150 Third Mix Temperature / ℃ 50 60 Time / min 60 45 Speed / rpm 125 150

[0120] Table 3

[0121]

[0122]

[0123] From the above results, it can be seen that the low-temperature antifreeze type early-strength alkali-free quick-setting agent prepared by the method provided by the present invention has high early strength, good stability and good antifreeze effect on concrete, can meet the requirements of national standard GB / T35159-2017 and railway standard Q / CR807-2020 for rapid setting, early strength and stability, and can significantly improve the antifreeze performance of cement concrete in a curing environment of -5°C to -15°C.

[0124] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A low-temperature antifreeze type early-strength alkali-free quick-setting agent composition, characterized in that: The low-temperature antifreeze type early-strength alkali-free quick-setting agent composition contains the following components which are stored independently or in combination: Aluminum sulfate, triethanolamine, composite antifreeze agent, alcohol compound, stabilizer, pH regulator; the alcohol compound is ethylene glycol and / or glycerol; based on the total weight of the low-temperature antifreeze type early strength alkali-free quick-setting agent composition, the content of aluminum sulfate is 73.4-87.1wt%, the content of triethanolamine is 2.8-10.5wt%, the content of the composite antifreeze agent is 4.2-9.6wt%, the content of the alcohol compound is 1.4-4.2wt%, the content of the stabilizer is 2.0-4.2wt%, and the content of the pH regulator is 1.0-2.5wt%; The composite antifreeze agent is a product obtained by a method comprising the following steps: In the presence of water I, calcium nitrate, diethanol monoisopropanolamine, acrylamide, ethylene glycol and ursolic acid are contacted and reacted; In the contact reaction, the weight ratio of the calcium nitrate, the water I, the diethanol monoisopropanolamine, the acrylamide, the ethylene glycol and the ursolic acid is 1-4:1:1-2:1-3:0.2-1:0.01-0.

05.

2. The composition according to claim 1, wherein The contact reaction operation includes: at 40-60°C, (1) in the presence of the water I, the calcium nitrate, the diethanol monoisopropanolamine and the acrylamide are first contacted to obtain a mixture I; (2) contacting the mixture I with the ethylene glycol and the ursolic acid for a second time to obtain the composite antifreeze agent.

3. The composition according to claim 2, wherein In step (1), the first contact is carried out under stirring conditions and at least meets the following conditions: a rotation speed of 300-400 rpm and a time of 30-60 min; and / or In step (2), the second contact is carried out under stirring conditions and at least meets the following conditions: a rotation speed of 300-400 rpm and a time of 25-45 min.

4. The composition according to claim 1 or 2, wherein The stabilizer is pseudo-boehmite and / or sepiolite; and / or The pH adjuster is formic acid and / or acrylic acid.

5. A method for preparing a low-temperature antifreeze type early-strength alkali-free quick-setting agent, characterized in that: The method is carried out using the components in the composition according to any one of claims 1 to 4, comprising: S1. In the presence of water II, aluminum sulfate, a pH regulator and an alcohol compound are first mixed to obtain a mixture A; S2, mixing the mixture A with triethanolamine and a stabilizer for a second time to obtain a pre-mother solution; S3, mixing the pre-mother solution with the composite antifreeze agent for the third time to obtain a low-temperature antifreeze type early-strength alkali-free quick-setting agent; Wherein, the alcohol compound is ethylene glycol and / or glycerol; based on the total weight of the low-temperature antifreeze type early-strength alkali-free quick-setting agent, the amount of aluminum sulfate is 51-56wt%, the amount of triethanolamine is 2-6wt%, the amount of the composite antifreeze agent is 3-6wt%, the amount of the alcohol compound is 0.9--2.5wt%, the amount of the stabilizer is 0.8-2.5wt%, the amount of the pH regulator is 0.8-1.5wt%, and the amount of water II is 25.5-34.7wt%; The composite antifreeze agent is a product obtained by a method comprising the following steps: In the presence of water I, calcium nitrate, diethanol monoisopropanolamine, acrylamide, ethylene glycol and ursolic acid are contacted and reacted; In the contact reaction, the weight ratio of the calcium nitrate, the water I, the diethanol monoisopropanolamine, the acrylamide, the ethylene glycol and the ursolic acid is 1-4:1:1-2:1-3:0.2-1:0.01-0.

05.

6. The method according to claim 5, wherein: In step S1, the first mixing is performed under stirring conditions and at least meets the following conditions: 60-80°C, a rotation speed of 50-250 rpm, and a time of 30-120 min; and / or In step S2, the second mixing is performed under stirring conditions and at least meets the following conditions: 40-70° C., a rotation speed of 50-150 rpm, and a time of 60-120 min; and / or In step S3, the third mixing is performed under stirring conditions and at least meets the following conditions: 40-60°C, a rotation speed of 50-150 rpm, and a time of 45-100 min.

7. The method according to claim 5 or 6, wherein: The method further includes: before performing the first mixing, first mixing and dissolving the aluminum sulfate with the water II, and then performing the first mixing of the dissolved aluminum sulfate with the pH regulator and the alcohol compound.

8. A low-temperature antifreeze type early-strength alkali-free accelerating setting agent prepared by the method described in any one of claims 5 to 7.

9. Use of the low-temperature antifreeze type early-strength alkali-free quick-setting agent described in claim 8 in the field of building materials.

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