Self-thickening asphalt emulsifier as well as preparation method therefor and use thereof

Abstract

The present invention relates to a self-thickening asphalt emulsifier as well as a preparation method therefor and the use thereof. The emulsifier is prepared by condensing maleated rosin or fumarated rosin and a polyamine to generate a plurality of amide structures, and then the amides and an acrylate undergoing an addition reaction to generate a plurality of zwitterionic hydrophilic clusters. Emulsified asphalt prepared by using the emulsifier of the present invention has high consistency itself, no additional thickening agent such as cellulose ether is needed in the formula of the emulsified asphalt, and the emulsified asphalt has good stability against divalent metal ions such as calcium and magnesium ions and has good mechanical stability; and asphalt-based coatings prepared by means of using the emulsified asphalt have the characteristics of low water absorption rate, good water-induced yellowing resistance and good acid corrosion resistance.

Description

A self-thickening asphalt emulsifier and its preparation method and application

[0001] This application claims the benefit of Chinese patent application No. 2023115975785, filed on November 28, 2023. This application incorporates the entirety of the aforementioned Chinese patent application. Technical Field

[0002] The present invention relates to the technical field of asphalt emulsifiers, in particular to a self-thickening asphalt emulsifier and a preparation method and application thereof. Background Art

[0003] As a byproduct of petroleum refining, asphalt has been widely used in road construction and building waterproofing due to its low cost, excellent hydrophobicity, and waterproofing properties. In the field of building waterproofing, asphalt is mainly used in the form of modified asphalt waterproofing membranes. During construction, it needs to be heated and laid on-site with open flames. The production and construction process consumes a lot of energy, and open flame construction poses safety hazards. At the same time, due to differences in construction personnel's operation, it is difficult to completely avoid local hollowing in the waterproofing membrane after construction. Once the hollowing area is damaged, water will seep down from the membrane on a large scale, causing leakage and failure of the waterproofing layer. With the upgrading of industry standards in the field of building waterproofing, water-based asphalt-based liquid membranes that can be constructed at room temperature and do not contain harmful solvents are being used in more and more projects. However, the quality of the emulsified asphalt currently available on the market specifically for liquid membranes is uneven, and there are even fewer types of asphalt emulsifiers specifically for liquid membranes.

[0004] In order to increase the construction thickness of asphalt-based waterproof coatings, a certain proportion of fillers and thickeners (such as heavy calcium powder, etc.) need to be added. Heavy calcium powder will ionize into positively charged calcium ions or magnesium ions when it comes into contact with water. Emulsified asphalt used for waterproofing is generally produced using anionic emulsifiers. When anionic emulsifiers come into contact with positively charged calcium ions under high-speed dispersion conditions, flocculated particles are easily generated, and even emulsion demulsification occurs. At present, domestic waterproof coatings use emulsified asphalt and asphalt emulsifiers. In order to improve the mixing stability of anionic emulsified asphalt and heavy calcium carbonate, a mixture of weakly charged lignin sulfonates and a large amount of non-ionic surfactants is generally used, or conventional zwitterionic surfactants are used. This zwitterionic surfactant is obtained by reacting long-chain alkyl tertiary amines with chloroacetic acid or sodium chloroacetate. The emulsifier contains 5%-9% of inorganic salt by-products such as sodium chloride. The removal process of inorganic salts is complicated and costly. The emulsified asphalt made with it has poor storage stability and requires the addition of thickeners such as cellulose ether. However, the thickening efficiency of the coating is low, the amount of thickener used is large, and it is easy to separate water from the surface after long-term storage. After the coating dries and forms a film, non-ionic surfactants and inorganic salts such as lignin sulfonates and sodium chloride remain in the dried coating film, resulting in poor water-resistant yellowing effect of the coating film, high water absorption rate, and reduced bonding strength, which weakens the waterproof effect of the asphalt-based waterproof coating and reduces the service life of the asphalt-based waterproof coating.

[0005] Patent CN 113214159 A discloses a method for preparing an imidazoline-type zwitterionic emulsifier. The method uses a synthesized alkyl imidazoline intermediate to directly react with acrylic acid to produce a zwitterionic emulsifier, which is then adjusted to alkalinity with sodium hydroxide. However, direct contact between imidazoline and acrylic acid as an organic base and an organic acid will produce an acid-base neutralization reaction, which competes with the addition reaction and results in low conversion efficiency. In addition, the imidazoline structure will hydrolyze when stored in alkaline aqueous solution for a long time. Therefore, the emulsifier's emulsification ability is relatively weak, the asphalt emulsion has low viscosity and unsatisfactory storage stability, and the addition of a cellulose ether thickening stabilizer is required. Cellulose ether has the characteristics of water absorption and water retention, which reduces the water resistance of the waterproof coating. In addition, the emulsified asphalt produced has a short storage period.

[0006] Patent CN 114539556 A discloses a method for preparing a cold-mix high-viscosity asphalt emulsifier. The method uses the addition reaction of rosin acid and acrylic acid to generate two moles of carboxyl groups per mole of intermediate. The carboxyl groups react with polyamines to form amides or imidazolines. The amides or imidazolines are then neutralized with organic acids to form salts to produce a cationic asphalt emulsifier. This method belongs to the field of road materials. During construction, the emulsified asphalt can be directly mixed with gravel or spread on the road surface. However, it cannot be stored as a coating for a long time. In the field of building waterproofing, the emulsified asphalt needs to be mixed and dispersed evenly with modified emulsions and fillers (such as heavy calcium powder) and can be stably stored in a container for more than six months. However, the modified emulsions (such as acrylic emulsions), wetting agents, dispersants, and thickeners (such as alkali-swellable thickeners) used to make asphalt-based coatings are all anionic. The use of cationic emulsified asphalt with these anions will cause the emulsion to break and clump, making it unusable.

[0007] Patent EP1721938A2 discloses a compound of a rosin derivative and a mineral component for use as an emulsifier in the production of emulsified asphalt for waterproofing or road paving. The structural groups of the rosin derivative are simple carboxyl groups, making it suitable for spray application on low-grade roads or for waterproofing. However, the asphalt material has poor high and low temperature performance. When used in combination with an anionic acrylic emulsion designed to improve high and low temperature performance and a large dose of filler, it is very prone to flocculation and even demulsification, resulting in a limited range of applications.

[0008] Summary of the Invention

[0009] The purpose of the present invention is to provide a self-thickening asphalt emulsifier to solve the above problems. The emulsifier is prepared by condensing rosin fumarate or rosin maleate with a polyamine to form three amide structures, which are then added with acrylate to form multiple zwitterionic hydrophilic clusters.

[0010] The purpose of the present invention is achieved through the following technical solutions:

[0011] A self-thickening asphalt emulsifier, comprising the following general structural formula:

[0012] In Formula I,

[0013] X represents a fumaric acid rosin or maleic acid rosin structure;

[0014] R1 to R9 are each independently selected from CH2CH2COO - , CH2CH2NH2, CH2CH2OH, H, and at least one of R1 to R9 is CH2CH2COO - .

[0015] As a preferred technical solution of the present invention, R1 to R9 contain 2 to 7 CH2CH2COO - .

[0016] As a more preferred technical solution of the present invention, R1 to R9 contain 3-5 CH2CH2COO - , for example, 3, 4, 5 CH2CH2COO - .

[0017] A preparation method of a self-thickening asphalt emulsifier comprises the following steps: condensing fumaric acid rosin or maleic acid rosin with a polyamine to generate an emulsifier containing three amide structures, and then reacting the emulsifier with acrylate to generate an emulsifier containing one or more zwitterionic hydrophilic clusters.

[0018] As a preferred technical solution of the present invention, the preparation method specifically comprises the following steps:

[0019] (1) Adding rosin fumarate or rosin maleate to a reaction vessel and heating it, then adding polyamine dropwise under stirring, raising the temperature to the reaction temperature after the addition is complete, and keeping the temperature to react. After the reaction is complete, vacuuming to remove excess polyamine, and cooling to obtain an intermediate containing three amide structures;

[0020] (2) adding acrylate dropwise to the intermediate of step (1) under stirring, heating to the reaction temperature under stirring after the addition is completed, keeping the temperature for reaction, and cooling to room temperature after the reaction is completed to obtain the product.

[0021] As a preferred technical solution of the present invention, the emulsifier comprises the following raw material components in parts by weight: the emulsifier comprises the following raw material components in a molar ratio of rosin fumarate or rosin maleate: polyamine: acrylate of 1: (3-5): (1-9). Preferably, the emulsifier comprises the following raw material components in a molar ratio of rosin fumarate or rosin maleate: polyamine: acrylate of 1: (4-5): (2-7).

[0022] More preferably, the emulsifier comprises raw material components in the following molar ratio: rosin fumarate or rosin maleate: polyamine: acrylate is 1: (4-5): (3-5).

[0023] Preferably, for example, in a specific embodiment, the ratio of the fumaric acid rosin or maleic acid rosin: polyamine: acrylate is 1:4:4.

[0024] As a preferred technical solution of the present invention, the fumaric acid rosin is selected from M115, M130, and M120 fumaric acid rosin produced by Deqing Jiyuan Synthetic Resin Co., Ltd.

[0025] As a preferred technical solution of the present invention, for example, the maleic acid rosin is selected from 103#, 105#, 107#, and 115# maleic rosin produced by Sanming Senke New Materials Co., Ltd.

[0026] As a preferred technical solution of the present invention, the polyamine is selected from one or more of ethylenediamine, hydroxyethylethylenediamine, and diethylenetriamine;

[0027] And / or, in step (1), fumaric acid rosin or maleic acid rosin is added to a reaction vessel and then heated to 90-120° C., preferably 100-110° C.;

[0028] And / or, the reaction temperature in step (1) is 150-200°C, preferably 175-185°C, and the insulation reaction time is 120-300 min, preferably 150-200 min;

[0029] And / or, after the reaction in step (1) is completed, the temperature is lowered to 50-100° C., preferably 80-100° C.;

[0030] And / or, when the polyamine is added dropwise in step (1), the addition time is 30-240 min, preferably 150-210 min.

[0031] As a preferred technical solution of the present invention, the acrylate in step (2) is obtained by reacting acrylic acid with a neutralizing base, specifically by mixing the acrylic acid and the neutralizing base uniformly at a temperature of 30-90° C. for 20-120 minutes;

[0032] Preferably, the acrylic acid and the neutralizing base are mixed uniformly at a temperature of 35-45° C. for 50-70 minutes;

[0033] Preferably, the neutralizing base is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia, triethylamine, and triethanolamine. More preferably, the neutralizing base is selected from sodium hydroxide, and preferably, a 30% concentration sodium hydroxide aqueous solution is used;

[0034] Preferably, the molar ratio of the acrylic acid to the neutralizing base is 1:1-1.5, more preferably, the molar ratio of the acrylic acid to the neutralizing base is 1:1-1.2.

[0035] As a preferred technical solution of the present invention, when the acrylate is added dropwise in step (2), the stirring speed is controlled to be 30-150 rpm; preferably 60-80 rpm;

[0036] And / or, the acrylate is added dropwise within 20-40 minutes;

[0037] And / or, the reaction temperature is 60-100° C., preferably 80-90° C., and the insulation reaction time is 60-180 min, preferably 100-140 min.

[0038] Application of a self-thickening asphalt emulsifier, which is used to prepare emulsified asphalt;

[0039] Preferably, the emulsifier is mixed with water and heated to prepare an emulsifier aqueous solution, which is then mixed evenly with the base asphalt to obtain a self-thickening emulsified asphalt;

[0040] Preferably, the self-thickening emulsified asphalt is prepared by the following method: the emulsifier and water are mixed in a mass ratio of 1.5-2:40-50, heated to 50-60°C, and an emulsifier aqueous solution is prepared; the emulsifier aqueous solution is mixed with the base asphalt in a mass ratio of 45-50:50-60, the base asphalt is heated to 130-140°C, sheared together with the emulsifier aqueous solution through a colloid mill, and cooled to below 50°C to obtain the self-thickening emulsified asphalt;

[0041] The self-thickening emulsified asphalt is used to prepare an asphalt-based waterproof coating. Preferably, the self-thickening emulsified asphalt is fully mixed and dispersed evenly with an emulsion, a dispersant, an NXZ defoamer, heavy calcium powder, AMP-95, a thickener, and water to obtain an asphalt-based waterproof coating.

[0042] The asphalt emulsifier of the present invention has a modified rosin-based structure and has significant hydrophobicity. Each emulsifier molecule contains three groups of zwitterionic clusters, which can improve the water solubility of the rosin-based emulsifier itself. Moreover, the three groups of hydrophilic groups are all amphoteric structures, which have a good calcium soap dispersing effect. The emulsified asphalt prepared under alkaline conditions is an anionic emulsion and can be mixed with other anionic emulsions and additives. At the same time, the stability and mechanical stability of the emulsified asphalt mixed with divalent metal ions such as calcium ions and magnesium ions can be improved. The emulsification production process and the coating dispersion production process can be directly produced using tap water, simplifying the production process and reducing production costs. The obtained coating is uniformly dispersed, free of particles, has high viscosity, and is stable in storage. The polycyclic ring structure of the rosin group has a good hydrophobic effect, can improve the water resistance of the coating after drying and film formation, and improve the water-resistant yellowing effect of the coating after film formation.

[0043] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0044] 1. The emulsified asphalt and asphalt-based coatings prepared using the emulsifier of the present invention have high consistency and self-thickening, and do not require the addition of thickeners such as cellulose ether. They improve the anti-sagging effect of the vertical surface of the asphalt-based waterproof coating, increase the thickness of a single construction, and reduce the construction process.

[0045] 2. The anionic emulsified asphalt produced using the emulsifier of the present invention has multiple zwitterionic clusters, good stability to divalent metal ions such as calcium and magnesium ions, and mechanical stability. When mixed and dispersed with fillers such as heavy calcium powder, it is not easy to produce flocculated particles or demulsification. The emulsified asphalt can be produced directly with tap water without the need for deionized water.

[0046] 3. The rosin group introduced in the present invention has a large hydrophobic group structure, which can improve the water-resistant yellowing effect of the coating film and improve the bonding strength and peeling strength of the water-based asphalt waterproof coating.

[0047] 4. The zwitterionic surfactant of the present invention does not contain halide inorganic salts, can reduce the water absorption rate of the coating, extend the service life of the waterproof layer, and reduce the corrosion of the halide ion coating on the building.

[0048] 5. The amide structure in the structure of the present invention has a corrosion inhibition effect and can improve the asphalt coating's resistance to low-concentration sulfuric acid corrosion. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 is a comparison of the effects of emulsified asphalt stored at 50°C for 7 days;

[0050] Figure 2 shows a photo of asphalt waterproof coating made from emulsified asphalt stored at 50°C for 7 days;

[0051] Figure 3 is a photo of the yellowing resistance of the dry film of asphalt waterproof coating after being immersed in 23°C water for 1 hour;

[0052] Figure 4 is a photograph of the appearance of the asphalt waterproof coating after it was dried and soaked in a 5% sulfuric acid solution for 7 days and then taken out and wiped dry. DETAILED DESCRIPTION

[0053] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0054] The present invention aims to solve the problems of weak emulsification ability of existing asphalt emulsifiers, low viscosity of asphalt emulsions, poor storage stability, and incompatibility with other components, and proposes an improved emulsifier solution.

[0055] After in-depth research, the inventors found that rosin acid can be used as an asphalt emulsifier to produce emulsified asphalt, and the asphalt emulsion produced has a thickening effect. However, rosin acid has only one carboxyl structure and is very sensitive to calcium ions and magnesium ions in fillers and water. During the coating dispersion process, particles are very likely to appear, and even emulsion demulsification occurs. The effect of using it in combination with non-ionic surfactants is also not good. While surfactants with zwitterionic structures have anionic properties under alkaline conditions and have good calcium soap dispersibility, conventional amphoteric surfactants have low viscosity and poor emulsion stability in emulsified asphalt, and there are also relatively The excessive amount of impurities such as chloride inorganic salts affects the water resistance of the coating; the lipophilic group of rosin acid is relatively large and its dissolution rate in aqueous solution is slow, so maleic rosin or fumaric acid rosin with more hydrophilic groups is selected to convert it into multiple zwitterionic clusters, which have better calcium soap dispersion effect. The amine group is grafted with acrylate instead of chloroacetate to avoid the introduction of by-product chloride inorganic salts. After testing, it was found that the emulsified asphalt made with it has self-thickening and good emulsified asphalt stability, and the coating has better water resistance and a certain ability to resist low-concentration sulfuric acid corrosion.

[0056] Based on the above findings, the present invention provides a self-viscosifying and thickening asphalt emulsifier and a preparation method thereof.

[0057] The preparation method of the self-thickening asphalt emulsifier comprises the following steps:

[0058] (1) Add rosin fumarate or rosin maleate to a reaction vessel, heat to 90-120°C, then dropwise add polyamine while stirring, keep warm for 120-300 minutes, vacuum to remove the remaining polyamine, and cool to 50-100°C to obtain a first intermediate containing an amide structure;

[0059] (2) slowly mixing acrylic acid and a neutralizing base (sodium hydroxide, potassium hydroxide, ammonia water, triethylamine, triethanolamine, etc.) under temperature-controlled conditions for 20-120 minutes at a mixing temperature of 30-90° C. to obtain a second intermediate, i.e., acrylate;

[0060] (3) The second intermediate is slowly added dropwise to the first intermediate under stirring. After the addition is completed, the temperature is raised to 60-100° C. under stirring and kept warm for 60-180 minutes. After the insulation is completed, the mixture is cooled to room temperature.

[0061] The above technical solution is illustrated below by means of more specific embodiments.

[0062] Example 1

[0063] A method for preparing a self-thickening asphalt emulsifier comprises the following steps:

[0064] S1. Weigh the following raw materials: 0.5 mol of 115# maleic rosin (Sanming Senke New Materials Co., Ltd.), 2 mol of ethylenediamine, 2 mol of acrylic acid, and 2.1 mol of sodium hydroxide (prepared into a 30% aqueous solution) and set aside.

[0065] S2, heating the 115# maleic rosin weighed in S1 to 110°C, then adding the ethylenediamine weighed in S1 dropwise under stirring for 180 min. After the addition, heating to 180°C, keeping the temperature for 180 min, vacuuming to remove the remaining polyamine, and cooling to 90°C to obtain the first intermediate;

[0066] S3. Slowly mix the acrylic acid weighed in S1 and sodium hydroxide under temperature-controlled conditions for 60 min at a mixing temperature of 40° C. to obtain a second intermediate;

[0067] S4. Slowly add the second intermediate obtained in S3 to the first intermediate under stirring, with a stirring speed of 70 rpm and an addition time of 30 min. After the addition is completed, heat the mixture to 85°C under stirring and keep warm for 120 min. After the addition is completed, cool the mixture to room temperature to obtain the asphalt emulsifier.

[0068] Application Example 1

[0069] 1.8 g of the emulsifier prepared in Example 1 was added to 45 g of tap water and heated to 55°C to prepare an emulsifier aqueous solution. 55 g of Donghai-70# asphalt was weighed, heated to 136°C, and sheared together with the emulsifier aqueous solution through a colloid mill for 45 seconds. The outlet was cooled to below 50°C through a heat exchanger to produce a self-thickening emulsified asphalt, which was the emulsified asphalt sample of Application Example 1.

[0070] 30 g of the emulsified asphalt sample of Application Example 1 cooled to room temperature was thoroughly mixed and dispersed evenly with 30 g of BLJ-6098 emulsion (Shanghai Baoliga New Materials), 0.2 g of 5040 dispersant (Nopco), 0.2 g of NXZ defoamer (Nopco), 30 g of 800 mesh heavy calcium powder, 0.1 g of AMP-95 and 0.1 g of TT-935 thickener (Rohm and Haas Company) and 10 g of tap water to obtain the coating sample of Application Example 1.

[0071] Example 2

[0072] A method for preparing a self-thickening asphalt emulsifier comprises the following steps:

[0073] S1. Weigh the following raw materials: 0.5 mol of M130 fumarate rosin (Deqing Jiyuan Synthetic Resin Co., Ltd.), 2.5 mol of ethylenediamine, 2.5 mol of acrylic acid, and 2.7 mol of sodium hydroxide (prepared into a 30% aqueous solution) and set aside.

[0074] S2, heating the M130 fumarate rosin weighed in S1 to 120°C, then adding the ethylenediamine weighed in S1 dropwise under stirring for 185 min. After the addition, heating to 180°C, keeping the temperature for 180 min, evacuating the remaining polyamine, and cooling to 80°C to obtain a first intermediate;

[0075] S3. Slowly mix the acrylic acid weighed in S1 and sodium hydroxide under temperature-controlled conditions for 70 min at a mixing temperature of 40° C. to obtain a second intermediate;

[0076] S4. Slowly add the second intermediate obtained in S3 to the first intermediate under stirring, with a stirring speed of 70 rpm and an addition time of 30 min. After the addition is completed, heat the mixture to 85°C under stirring and keep warm for 120 min. After the addition is completed, cool the mixture to room temperature to obtain the asphalt emulsifier.

[0077] Application Example 2

[0078] The emulsified asphalt sample in Application Example 1 was replaced with the emulsifier sample prepared in Example 2, and the other raw materials and conditions remained unchanged. The emulsified asphalt sample in Application Example 2 and the coating sample in Application Example 2 were prepared accordingly.

[0079] Example 3

[0080] A method for preparing a self-thickening asphalt emulsifier comprises the following steps:

[0081] S1. Weigh the following raw materials: 0.5 mol of 115# maleic rosin (Sanming Senke New Materials Co., Ltd.), 2 mol of hydroxyethylethylenediamine, 2 mol of acrylic acid, and 2.1 mol of sodium hydroxide (prepared into a 30% aqueous solution) and set aside.

[0082] S2, heating the 115# maleic rosin weighed in S1 to 110°C, then adding the hydroxyethylethylenediamine weighed in S1 dropwise under stirring for 180 min. After the addition, heating to 180°C, keeping the temperature for 180 min, vacuuming to remove the remaining polyamine, and cooling to 90°C to obtain the first intermediate;

[0083] S3. Slowly mix the acrylic acid weighed in S1 and sodium hydroxide under temperature-controlled conditions for 60 min at a mixing temperature of 40° C. to obtain a second intermediate;

[0084] S4. Slowly add the second intermediate obtained in S3 to the first intermediate under stirring, with a stirring speed of 70 rpm and an addition time of 30 min. After the addition is completed, heat the mixture to 85°C under stirring and keep warm for 120 min. After the addition is completed, cool the mixture to room temperature to obtain the asphalt emulsifier.

[0085] Application Example 3

[0086] The emulsifier sample in Application Example 1 was replaced with the emulsifier sample prepared in Example 3, and the other raw materials and conditions remained unchanged. The emulsified asphalt sample of Application Example 3 and the coating sample of Application Example 3 were prepared accordingly.

[0087] Example 4

[0088] A method for preparing a self-thickening asphalt emulsifier comprises the following steps:

[0089] S1. Weigh the following raw materials: 0.5 mol of M130 fumarate rosin (Deqing Jiyuan Synthetic Resin Co., Ltd.), 2.5 mol of diethylenetriamine, 2.5 mol of acrylic acid, and 2.7 mol of sodium hydroxide (prepared into a 30% aqueous solution) and set aside.

[0090] S2, heating the M130 fumarate rosin weighed in S1 to 120°C, then adding the diethylenetriamine weighed in S1 dropwise under stirring for 185 min. After the addition, heating to 180°C, keeping the temperature for 180 min, evacuating to remove the remaining polyamine, and cooling to 80°C to obtain a first intermediate;

[0091] S3. Slowly mix the acrylic acid weighed in S1 and sodium hydroxide under temperature-controlled conditions for 70 min at a mixing temperature of 40° C. to obtain a second intermediate;

[0092] S4. Slowly add the second intermediate obtained in S3 to the first intermediate under stirring, with a stirring speed of 70 rpm and an addition time of 30 min. After the addition is completed, heat the mixture to 85° C. under stirring and keep warm for 120 min. After the addition is completed, cool the mixture to room temperature to obtain an asphalt emulsifier.

[0093] Application Example 4

[0094] The emulsifier sample in Application Example 1 was replaced with the emulsifier sample prepared in Example 4, and the other raw materials and conditions remained unchanged. The emulsified asphalt sample of Application Example 4 and the coating sample of Application Example 4 were prepared accordingly.

[0095] Comparative Example 1

[0096] Commercially available anionic waterproof asphalt emulsifier (lignin and non-ionic surfactant compound).

[0097] Comparative Application Example 1

[0098] The emulsifier sample in Application Example 1 was replaced with the commercially available anionic waterproof asphalt emulsifier in Comparative Example 1. The emulsified asphalt sample and the coating sample were prepared according to the same raw material dosage and process as the sample in Application Example 1, which is the sample in Comparative Example 1.

[0099] Comparative Example 2

[0100] Commercially available anionic waterproof asphalt emulsifier (betaine type zwitterionic surfactant type).

[0101] Application Comparative Example 2

[0102] The emulsifier sample in Application Example 1 was replaced with the commercially available anionic waterproof asphalt emulsifier in Comparative Example 2. The emulsified asphalt sample and the coating sample were prepared according to the same raw material dosage and process as the sample in Application Example 1, which is the sample in Comparative Example 2.

[0103] Comparative Example 3

[0104] Commercially available sodium rosinate (CAS No. 14351-66-7).

[0105] Application Comparative Example 3

[0106] The emulsifier sample in Application Example 1 was replaced with the commercially available rosin acid emulsifier in Comparative Example 3. The emulsified asphalt sample and the coating sample were prepared according to the same raw material dosage and process as the sample in Application Example 1, which is the sample in Comparative Example 3.

[0107] Comparative Example 4

[0108] Commercially available cationic rosin acid amide asphalt emulsifier.

[0109] Comparative Application Example 4

[0110] The emulsifier sample in Application Example 1 was replaced with the commercially available cationic rosin acid amide asphalt emulsifier in Comparative Example 4. The emulsified asphalt sample and the coating sample were prepared using the same raw material dosage and process as the sample in Application Example 1, which is the sample in Comparative Example 4.

[0111]

Performance test

[0112] The performance tests of the emulsified asphalt samples obtained in the above examples / comparative examples were carried out, specifically including:

[0113] Solid content: 5.5 in JC / T 408-2005;

[0114] Brookfield viscosity of emulsified asphalt: BROOKFIELD viscometer, 2#, 60rpm;

[0115] 50℃, 7-day thermal storage stability: Place 200ml of the emulsion in a sealed transparent container and place it in a 50℃ constant temperature box for 7 days. Observe the state of the emulsified asphalt. If there is no stratification or demulsification, it is qualified.

[0116] Beating stability: Emulsified asphalt is evenly mixed and dispersed with other raw materials in waterproof coating, without demulsification and obvious particles.

[0117] The performance tests of the coating samples of the above application examples and comparative examples were conducted with reference to the group standard T / SZWA 006-2021 "Technical Specifications for the Application of High-Viscosity and Anti-Skidding Rubber Asphalt Waterproof Coatings", specifically including:

[0118] Water absorption: refer to 7.12 in JC / T 1017-2020;

[0119] Coating KU viscosity: GB / T 9269;

[0120] Concrete block bond strength: GB / T 16777 7.1B method;

[0121] Peel strength: 5.8 in JC / T 1069-2008;

[0122] Retention rate of peel strength after 7 days of immersion in water: after the specimen is immersed in water for 7 days, it shall be in accordance with 5.8 in JC / T1069-2008;

[0123] The specific test results are shown in Table 1 and Table 2.

[0124] Table 1 Asphalt emulsifier performance test results

[0125] Table 2 Coating sample performance test results

[0126] As can be seen from Tables 1 and 2, the test results of the embodiments of the present invention are significantly better than those of the comparative examples, especially in terms of the viscosity of the emulsified asphalt and the bonding strength of the coating, where various performance indicators are significantly improved.

[0127] Figure 1 is a comparison photo of the effects of emulsified asphalt prepared with an emulsifier and stored at 50°C for 7 days. It can be seen that after the emulsified asphalt of Examples 1-4 was stored in a constant temperature box at 50°C for 7 days, there was no obvious stratification on the surface, while there was an obvious water layer on the upper part of Comparative Example 1 and Comparative Example 2, and a small amount of slight water layer was present in Comparative Example 3 and Comparative Example 4.

[0128] Figure 2 shows a photo of asphalt waterproof coating made of emulsified asphalt stored at 50°C for 7 days. It can be seen that when the asphalt-based coating made of emulsified asphalt was stored in a constant temperature box at 50°C for 7 days and then taken out, there was no obvious stratification in Examples 1-4, but there was a water layer on the upper part of Comparative Example 1 and the coating was segregated, there was a water layer on the upper part of Comparative Example 2, and Comparative Examples 3 and 4 were demulsified.

[0129] Figure 3 is a photograph of the apparent effect of water-resistant yellowing of the dry film of the asphalt waterproof coating after being immersed in water at 23°C for 1 hour. It can be seen that after the dry film of the coating is immersed in water at room temperature for 1 hour, Examples 1-4 still maintain black color, with the color slightly lighter, while Comparative Examples 1-2 are obviously yellow.

[0130] Figure 4 is a photograph of the apparent state of the asphalt waterproof coating after it was dried and immersed in a 5% sulfuric acid solution for 7 days and then taken out and wiped dry. It can be seen that the dry film of the coating was immersed in a 5% concentration sulfuric acid solution for 7 days, taken out and wiped dry. The surface of the embodiment has a small amount of corrosion marks but no bubbles, while the surfaces of comparative examples 1 and 2 both have dense bubbles bulging.

[0131] The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. Improvements and modifications made by those skilled in the art based on the disclosure of the present invention, without departing from the scope of the present invention, should be within the scope of protection of the present invention.

Claims

1. A self-thickening asphalt emulsifier, characterized in that: The emulsifier comprises the following general structural formula: In Formula I, X represents a fumaric acid rosin or a maleic acid rosin structure; R1 to R9 are each independently selected from CH2CH2COO - , CH2CH2NH2, CH2CH2OH, H, and at least one of R1 to R9 is CH2CH2COO - .

2. A self-thickening asphalt emulsifier according to claim 1, characterized in that: R1~R9 contain 2-7 CH2CH2COO - .

3. A self-thickening asphalt emulsifier according to claim 1, characterized in that: R1~R9 contain 3-5 CH2CH2COO - .

4. The method for preparing a self-thickening asphalt emulsifier according to claim 1, characterized in that: Fumaric acid rosin or maleic acid rosin is condensed with polyamine to generate an emulsifier containing three amide structures, which is then reacted with acrylate to generate an emulsifier containing one or more zwitterionic hydrophilic clusters.

5. The method for preparing a self-thickening asphalt emulsifier according to claim 4, characterized in that: The following steps are involved: (1) adding rosin fumarate or rosin maleate to a reaction vessel and heating it, then dropping a polyamine under stirring, raising the temperature to the reaction temperature after the dropping is complete, keeping the temperature for reaction, vacuuming to remove excess polyamine after the reaction is complete, and cooling to obtain an intermediate containing three amide structures; (2) Adding acrylate dropwise to the intermediate of step (1) under stirring, heating to the reaction temperature under stirring after the addition is completed, keeping the temperature for reaction, and cooling to room temperature after the reaction is completed to obtain the product.

6. The method for preparing a self-thickening asphalt emulsifier according to claim 5, characterized in that: The emulsifier comprises raw material components in the following molar ratio: fumaric acid rosin or maleic acid rosin: polyamine: acrylate is 1: (3-5): (1-9).

7. The method for preparing a self-thickening asphalt emulsifier according to claim 5, characterized in that: The polyamine is selected from one or more of ethylenediamine, hydroxyethylethylenediamine, and diethylenetriamine; And / or, in step (1), fumaric acid rosin or maleic acid rosin is added into a reaction vessel and then heated to 90-120° C., preferably 100-110° C., And / or, the reaction temperature in step (1) is 150-200°C, preferably 175-185°C, and the insulation reaction time is 120-300 min, preferably 150-200 min; And / or, after the reaction in step (1) is completed, the temperature is lowered to 50-100° C., preferably 80-100° C.; And / or, when the polyamine is added dropwise in step (1), the adding time is 30-240 min, preferably 150-210 min.

8. The method for preparing a self-thickening asphalt emulsifier according to claim 5, characterized in that: The acrylate in step (2) is obtained by reacting acrylic acid with a neutralizing base, and the specific method is: mixing the acrylic acid and the neutralizing base uniformly under a temperature control condition of 30-90° C. for a mixing time of 20-120 min; Preferably, the acrylic acid and the neutralizing base are mixed uniformly at a temperature of 35-45° C. for 50-70 minutes; Preferably, the neutralizing base is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia water, triethylamine, and triethanolamine. More preferably, the neutralizing base is selected from sodium hydroxide.

9. The method for preparing a self-thickening asphalt emulsifier according to claim 5, characterized in that: When the acrylic acid salt is added dropwise in step (2), the stirring speed is controlled to be 30-150 rpm, preferably 60-80 rpm; And / or, the acrylate is added dropwise within 20-40 minutes; And / or, the reaction temperature is 60-100° C., preferably 80-90° C., and the insulation reaction time is 60-180 min, preferably 100-140 min.

10. The use of a self-thickening asphalt emulsifier according to claim 1, characterized in that: The emulsifier is used to make emulsified asphalt; The emulsifier is mixed with water and heated to prepare an emulsifier aqueous solution, which is evenly mixed with the base asphalt to obtain a self-thickening emulsified asphalt; And / or, the self-thickening emulsified asphalt is used to prepare an asphalt-based waterproof coating: the self-thickening emulsified asphalt is fully mixed and dispersed evenly with an emulsion, a dispersant, a NXZ defoamer, heavy calcium powder, AMP-95, a thickener, and water to obtain an asphalt-based waterproof coating.

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