Cationic anti-sticking waterproof asphalt emulsion for roads and bridges and preparation method of cationic anti-sticking waterproof asphalt emulsion

Abstract

The invention discloses a cationic anti-sticking waterproof asphalt emulsion for roads and bridges and a preparation method of the cationic anti-sticking waterproof asphalt emulsion, and relates to the technical field of road and bridge engineering waterproof materials.The papermaking industry waste lignin is adopted as a main base material of a rosin-lignin composite cationic emulsifier, and resource utilization of waste is achieved through chemical modification; meanwhile, waste rubber powder obtained by crushing waste tires at normal temperature is used in the emulsion, so that the raw material cost is further reduced, compared with a traditional cationic road and bridge waterproof emulsion, the raw material cost is reduced by 30% or above, and the preparation process is simple, efficient, suitable for large-scale industrial production and suitable for industrial production. And the method has remarkable economic benefits and social benefits.

Description

Technical Field

[0001] This invention relates to the field of waterproof materials technology for road and bridge engineering, specifically to a cationic anti-adhesive waterproof asphalt emulsion for road and bridge applications and its preparation method. Background Technology

[0002] With the rapid development of transportation infrastructure construction, road and bridge engineering, as an important link connecting various places, has its quality and durability directly related to traffic safety and efficiency. In road and bridge construction, the application of waterproof materials is crucial, as it can not only effectively prevent water penetration and damage to the road and bridge structure, but also extend the service life of the road and bridge.

[0003] Traditional waterproofing materials for roads and bridges, such as ordinary waterproof membranes or coatings, while meeting the waterproofing needs of roads and bridges to a certain extent, still have many shortcomings in practical applications. First, these materials have limited bonding strength and elongation, making it difficult to adapt to the slight deformations of road and bridge structures caused by factors such as temperature changes and vehicle loads, which can easily lead to cracking or peeling of the waterproof layer. Second, traditional waterproofing materials have poor aging resistance, especially under strong ultraviolet radiation or extreme weather conditions, where they are prone to powdering and cracking, seriously affecting the waterproofing effect and service life. In addition, the manufacturing process of traditional waterproofing materials is complex and costly, and some materials are difficult to recycle as waste, putting pressure on the environment.

[0004] In view of the problems of insufficient bonding strength and elongation, poor aging resistance, and complex preparation process and high cost of traditional road and bridge waterproof materials, this invention proposes a cationic anti-adhesive waterproof asphalt emulsion for road and bridge use and its preparation method, which is of particular importance. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a cationic anti-adhesive waterproof asphalt emulsion for road and bridge applications and its preparation method. By optimizing the raw material formulation and preparation process, it can significantly improve the physical properties and durability of waterproof materials, especially in terms of self-healing ability and resistance to ultraviolet aging. At the same time, this invention also makes full use of waste resources such as waste lignin from the paper industry and waste tire rubber powder, realizing the recycling of resources, reducing raw material costs, and is of great significance to environmental protection and sustainable development.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications, which is made from the following raw materials in parts by weight:

[0007] The modified asphalt contains 40-50%, rosin-lignin composite cationic emulsifier 3-5%, modified hydrogenated castor oil 6-10%, hydroxyl alkyd resin 4-8%, viscosity reducer 2-4%, waste rubber powder 3-7%, methyl acrylate 3-5%, chloroprene rubber 1-3%, tackifier 2-4%, acetylsalicylic acid 1-3%, polydimethylsiloxane 2-4%, UV stabilizer 1-3%, cement affinity agent 1-3%, and pentaerythritol 1-3%.

[0008] The rosin-lignin composite cationic emulsifier is synthesized using waste lignin from the papermaking industry as a base material through a grafting reaction of rosin derivatives and diethylenetriamine.

[0009] The performance indicators of the emulsion meet the following requirements: solid content 39-41%, viscosity <100cp, particle size <100nm, pH value 2-5, bonding strength 0.61-0.75MPa, elongation 136-154mm, self-healing rate ≥90% at room temperature for 2 hours, UV aging resistance ≥300 hours, stability error <0.4% after 5 days of storage, and the raw material cost is more than 30% lower than that of traditional cationic road and bridge waterproof emulsions.

[0010] Furthermore, the modified asphalt is SBS modified asphalt or rubber modified asphalt, and the modified asphalt has a softening point ≥55℃, a penetration of 40-60, and a ductility ≥20cm.

[0011] Furthermore, in the raw materials for synthesizing the rosin-lignin composite cationic emulsifier, the mass ratio of purified waste lignin to rosin derivatives is 1:0.8-1.2, and the mass ratio of lignin-rosin complex to diethylenetriamine is 1:2-3.

[0012] Furthermore, the waste rubber powder has a particle size of 80-120 mesh and is derived from the room temperature crushing and processing of waste tires, wherein the rubber hydrocarbon content is ≥55%, the ash content is ≤8%, and the moisture content is ≤1%; the UV stabilizer is a benzotriazole UV stabilizer or a hindered amine UV stabilizer.

[0013] Furthermore, the test conditions for the stability error of <0.4% after 5 days of storage are: static storage at 25℃±2℃ in a sealed and light-proof environment, and centrifugal separation method is used for testing. The difference in solid content between the upper and lower layers is the stability error.

[0014] Furthermore, the test method for achieving a self-healing rate of ≥90% at room temperature for 2 hours is as follows: Microcracks with a width of 0.2 mm and a depth of 0.1 mm are artificially created on the surface of the coating after emulsion film formation. The coating is then left to stand for 2 hours at 25℃±1℃ and relative humidity of 60%±5%. The degree of crack closure is observed under a microscope. The self-healing rate is calculated as (initial crack width - residual crack width) / initial crack width × 100%. The test standard for UV resistance aging time ≥300 hours is as follows: A xenon lamp aging test is conducted with an irradiation intensity of 0.71 W / m²@340 nm and a black standard temperature of 63℃±3℃. After aging, the coating shows no chalking or cracking, and the adhesion strength retention rate is ≥80%.

[0015] Furthermore, the rosin derivative is rosin glycerol ester or hydrogenated rosin, and the rosin derivative has an oleophilic value of 3-5, an acid value ≤10mgKOH / g, and a softening point ≥80℃.

[0016] Furthermore, the viscosity reducer is a polyether-type viscosity reducer or an ester-type viscosity reducer; the viscosity modifier is a petroleum resin-based viscosity modifier or a rosin resin-based viscosity modifier, and the softening point of the viscosity modifier is 90-110℃.

[0017] Furthermore, the cement affinity agent is an aminosilane affinity agent or an epoxysilane affinity agent, and the effective component content of the cement affinity agent is ≥98%; the pentaerythritol is industrial grade pentaerythritol with a purity of ≥95% and a hydroxyl value of ≥47%.

[0018] On the other hand, a method for preparing a cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications is characterized by comprising the following steps:

[0019] S1. Pre-synthesis of rosin-lignin composite cationic emulsifier: Lignin pretreatment: Take waste lignin from the paper industry, add 5-8% NaOH solution (liquid-solid ratio 5:1-8:1), stir at 80-90℃ for 1-1.5 hours until completely dissolved, adjust pH to 2-3 with 3-5% hydrochloric acid to precipitate lignin, wash repeatedly with deionized water until neutral, dry at 105-110℃ for 2-3 hours, pulverize and pass through 100- Purified lignin was obtained by sieving through a 120-mesh sieve. Lipophilic group grafting: The purified lignin and rosin derivative were added to a reaction vessel, heated to 120-140℃, and stirred at 200-250 rpm for 2-3 hours to form a lignin-rosin complex. Hydrophilic group introduction: Diethylenetriamine was added to the reaction vessel, the temperature was lowered to 80-100℃, and the mixture was stirred and kept at this temperature for 1.5-2.5 hours. The mixture was then cooled to room temperature to obtain a rosin-lignin composite cationic emulsifier.

[0020] S2. Raw material preparation: Weigh each raw material according to the weight percentage, and remove impurities from the waste rubber powder by 80-120 mesh screening.

[0021] S3. Preliminary mixing: Heat the modified asphalt to 120-130℃ to melt it, add rosin-lignin composite cationic emulsifier, modified hydrogenated castor oil, and hydroxyl alkyd resin, and stir at 300-400 rpm for 10-20 minutes to form a uniform paste mixture.

[0022] S4. Add auxiliary components: Add viscosity reducer, waste rubber powder, methyl acrylate and chloroprene rubber in sequence while stirring. Control the system temperature ≤80℃ and continue stirring for 25-35 minutes until completely dispersed.

[0023] S5. Ultrasonic treatment: Transfer the mixture to an ultrasonic treatment device, set the frequency to 12kHz, the temperature to 60-70℃, and the treatment time to 8-12 minutes to obtain a fine and uniform dispersion system.

[0024] S6. Add functional additives: Add thickener, acetylsalicylic acid, polydimethylsiloxane, UV stabilizer, cement affinity agent, and pentaerythritol to the dispersion system, and continue stirring at 300-400 rpm for 35-45 minutes to ensure that all components are fully dissolved and dispersed.

[0025] S7. Finished product preparation: The above mixture is filtered through a 200-300 mesh filter to remove impurities, thus obtaining a cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications.

[0026] Compared with existing technologies, this cationic anti-adhesion and waterproof asphalt emulsion for road and bridge applications and its preparation method have the following advantages:

[0027] I. This invention uses waste lignin from the paper industry as the main base material of the rosin-lignin composite cationic emulsifier. Through chemical modification, the waste is utilized as a resource, reducing environmental pollution. At the same time, the emulsion uses waste rubber powder obtained by room temperature crushing of waste tires, further reducing raw material costs. Compared with traditional cationic road and bridge waterproof emulsions, the raw material cost of this invention is reduced by more than 30%, and the preparation process is simple and efficient, suitable for large-scale industrial production, with significant economic and social benefits.

[0028] II. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications of the present invention has excellent physical properties, including high solids content, low viscosity, small particle size, and good bonding strength and elongation. In particular, the self-healing rate of this emulsion can reach more than 90% within 2 hours at room temperature, effectively repairing micro-cracks and preventing water penetration. At the same time, its resistance to ultraviolet aging exceeds 300 hours, ensuring long-term use under harsh climatic conditions without powdering or cracking. The bonding strength retention rate is as high as 80% or more, significantly extending the service life of road and bridge applications.

[0029] Other advantages, objectives and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination or study, or may be learned from the practice of the invention. Attached Figure Description

[0030] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.

[0031] Figure 1 This is a flowchart of a cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications and its preparation method. Detailed Implementation

[0032] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with the accompanying drawings and preferred embodiments, is provided below.

[0033] Examples one to three only varied the content of the rosin-lignin composite cationic emulsifier. Example 1

[0034] The modified asphalt used was SBS modified asphalt, with an addition amount of 45%; the rosin-lignin composite cationic emulsifier was self-made, with an addition amount of 3%, the mass ratio of purified waste lignin to rosin glycerol ester was 1:1, and the mass ratio of lignin-rosin complex to diethylenetriamine was 1:2.5; modified hydrogenated castor oil 6%; hydroxyl alkyd resin 6%; polyether-type viscosity reducer 3%; 100-mesh waste rubber powder 5%, derived from waste tires crushed at room temperature, with a rubber hydrocarbon content of 58%, ash content of 6%, and moisture content of 0.8%; methyl acrylate 4%; chloroprene rubber 2%; petroleum resin tackifier 3%; acetylsalicylic acid 2%; polydimethylsiloxane 3%; benzotriazole UV stabilizer 2%; aminosilane cementitious agent 2%; and industrial-grade pentaerythritol 3%.

[0035] Pre-synthesis of rosin-lignin composite cationic emulsifier: Waste lignin from the paper industry was taken and added to a 6% (w / w) NaOH solution. The mixture was stirred at 85°C and 200 rpm for 1.2 hours until dissolved. The pH was adjusted to 2.5 with 4% hydrochloric acid, and the precipitate was washed with water until neutral. The precipitate was dried at 108°C for 2.5 hours and then pulverized through a 110-mesh sieve to obtain purified lignin. The purified lignin and rosin glycerol ester were added to a reaction vessel and stirred at 130°C and 220 rpm for 2.5 hours to form a complex. Diethylenetriamine was added, and the mixture was cooled to 90°C and stirred for 2 hours. After cooling, the emulsifier was obtained.

[0036] Raw material preparation: Weigh each raw material according to the formula, and remove impurities by passing the waste rubber powder through a 100-mesh sieve.

[0037] Preliminary mixing: Heat SBS modified bitumen to 125℃ to melt, add emulsifier, modified hydrogenated castor oil and hydroxyl alkyd resin, stir at 350 rpm for 15 minutes to form a uniform paste mixture.

[0038] Add auxiliary components: Add viscosity reducer, waste rubber powder, methyl acrylate and chloroprene rubber in sequence while stirring continuously. Control the temperature at 75℃ and stir for 30 minutes until completely dispersed.

[0039] Ultrasonic treatment: The mixture is transferred to an ultrasonic device and treated at 12 kHz and 65°C for 10 minutes to obtain a finely dispersed system.

[0040] Add functional additives: Add thickener, acetylsalicylic acid and other additives, and stir at 350 rpm for 40 minutes until fully dispersed.

[0041] Finished product preparation: Filter through a 250-mesh filter to remove impurities and obtain the finished product.

[0042] Results: Storage stability: After 5 days of sealed and light-proof storage at 25℃±2℃, the stability error measured by centrifugation was 0.38%, which meets the requirement of <0.4%. A small amount of flocculent matter appeared at the bottom in the later stage of storage, which could be restored to homogeneity by slight stirring.

[0043] Self-healing performance: When the coating creates a 0.2mm×0.1mm microcrack, and is left to stand for 2 hours at 25℃±1℃ and 60%±5% relative humidity, the remaining crack width is 0.02mm, and the self-healing rate is (0.2-0.02) / 0.2×100%=90%, which meets the standard of ≥90%.

[0044] UV aging resistance: After 300 hours of xenon lamp aging test, the coating showed no obvious chalking, only very slight discoloration in some areas, and the adhesion strength retention rate was 81%, meeting the requirement of ≥80%.

[0045] Other key properties: 1.2MPa bond strength with cementitious substrate; no flow at 60℃ but slightly softened edges; no cracking at -10℃; 0.5g / m² of sand adhering during construction, which can be manually cleaned without residue. Example 2

[0046] The modified asphalt used was SBS modified asphalt, with an addition amount of 45%, a softening point of 58℃, a penetration of 50, and a ductility of 25cm. The rosin-lignin composite cationic emulsifier was self-made, with an addition amount of 4.5%. The mass ratio of purified waste lignin to rosin glycerol ester was 1:1, and the mass ratio of lignin-rosin complex to diethylenetriamine was 1:2.5. Modified hydrogenated castor oil 6%; hydroxyl alkyd resin 6%; polyether-type viscosity reducer 3%; 100-mesh waste rubber powder 5%, derived from waste tires crushed at room temperature, with a rubber hydrocarbon content of 58%, ash content of 6%, and moisture content of 0.8%; methyl acrylate 4%; chloroprene rubber 2%; petroleum resin tackifier 3%; acetylsalicylic acid 2%; polydimethylsiloxane 3%; benzotriazole UV stabilizer 2%; aminosilane cementitious agent 2%; and industrial-grade pentaerythritol 3%.

[0047] Pre-synthesis of rosin-lignin composite cationic emulsifier: Waste lignin from the paper industry was taken and added to a 6% (w / w) NaOH solution. The mixture was stirred at 85°C and 200 rpm for 1.2 hours until dissolved. The pH was adjusted to 2.5 with 4% hydrochloric acid, and the precipitate was washed with water until neutral. The precipitate was dried at 108°C for 2.5 hours and then pulverized through a 110-mesh sieve to obtain purified lignin. The purified lignin and rosin glycerol ester were added to a reaction vessel and stirred at 130°C and 220 rpm for 2.5 hours to form a complex. Diethylenetriamine was added, and the mixture was cooled to 90°C and stirred for 2 hours. After cooling, the emulsifier was obtained.

[0048] Raw material preparation: Weigh each raw material according to the formula, and remove impurities by passing the waste rubber powder through a 100-mesh sieve.

[0049] Preliminary mixing: Heat SBS modified bitumen to 125℃ to melt, add emulsifier, modified hydrogenated castor oil and hydroxyl alkyd resin, stir at 350 rpm for 15 minutes to form a uniform paste mixture.

[0050] Add auxiliary components: Add viscosity reducer, waste rubber powder, methyl acrylate and chloroprene rubber in sequence while stirring continuously. Control the temperature at 75℃ and stir for 30 minutes until completely dispersed.

[0051] Ultrasonic treatment: The mixture is transferred to an ultrasonic device and treated at 12 kHz and 65°C for 10 minutes to obtain a finely dispersed system.

[0052] Add functional additives: Add thickener, acetylsalicylic acid and other additives, and stir at 350 rpm for 40 minutes until fully dispersed.

[0053] Finished product preparation: Filter through a 250-mesh filter to remove impurities and obtain the finished product.

[0054] Results: Storage stability: After 5 days of storage at 25℃±2℃ in a sealed, light-protected environment, the stability error measured by centrifugation was 0.25%, which is far below the requirement of <0.4%. During storage, the emulsion was uniformly milky white, with no stratification, precipitation, or flocculent matter.

[0055] Self-healing performance: When the coating creates a 0.2mm×0.1mm microcrack and is left to stand for 2 hours at 25℃±1℃ and 60%±5% relative humidity, the residual crack width is 0.014mm, and the self-healing rate is (0.2-0.014) / 0.2×100%=93%, which is better than the standard of ≥90%.

[0056] UV aging resistance: After 300 hours of xenon lamp aging test, the coating has a uniform color without powdering or cracking, and the adhesion strength retention rate is 86%, which is higher than the requirement of ≥80%.

[0057] Other key performance characteristics: 1.4MPa bond strength with cement substrate; no flow or deformation after 24 hours at 60℃; no cracks or embrittlement after being frozen at -10℃ for 24 hours and then restored to normal temperature; 0.3g / m² of sand adhering during construction, and can be easily detached by slight vibration. Example 3

[0058] The modified asphalt used was SBS modified asphalt, with an addition amount of 45%, a softening point of 58℃, a penetration of 50, and a ductility of 25cm. The rosin-lignin composite cationic emulsifier was self-made, with an addition amount of 5%. The mass ratio of purified waste lignin to rosin glycerol ester was 1:1, and the mass ratio of lignin-rosin complex to diethylenetriamine was 1:2.5. Modified hydrogenated castor oil was 6%; hydroxyl alkyd resin was 6%; polyether-type viscosity reducer was 3%; 100-mesh waste rubber powder was 5%, derived from waste tires crushed at room temperature, with a rubber hydrocarbon content of 58%, ash content of 6%, and moisture content of 0.8%; methyl acrylate was 4%; chloroprene rubber was 2%; petroleum resin tackifier was 3%; acetylsalicylic acid was 2%; polydimethylsiloxane was 3%; benzotriazole UV stabilizer was 2%; aminosilane cementitious agent was 2%; and industrial-grade pentaerythritol was 3%.

[0059] Pre-synthesis of rosin-lignin composite cationic emulsifier: Waste lignin from the paper industry was taken and added to a 6% (w / w) NaOH solution. The mixture was stirred at 85°C and 200 rpm for 1.2 hours until dissolved. The pH was adjusted to 2.5 with 4% hydrochloric acid, and the precipitate was washed with water until neutral. The precipitate was dried at 108°C for 2.5 hours and then pulverized through a 110-mesh sieve to obtain purified lignin. The purified lignin and rosin glycerol ester were added to a reaction vessel and stirred at 130°C and 220 rpm for 2.5 hours to form a complex. Diethylenetriamine was added, and the mixture was cooled to 90°C and stirred for 2 hours. After cooling, the emulsifier was obtained.

[0060] Raw material preparation: Weigh each raw material according to the formula, and remove impurities by passing the waste rubber powder through a 100-mesh sieve.

[0061] Preliminary mixing: Heat SBS modified bitumen to 125℃ to melt, add emulsifier, modified hydrogenated castor oil and hydroxyl alkyd resin, stir at 350 rpm for 15 minutes to form a uniform paste mixture.

[0062] Add auxiliary components: Add viscosity reducer, waste rubber powder, methyl acrylate and chloroprene rubber in sequence while stirring continuously. Control the temperature at 75℃ and stir for 30 minutes until completely dispersed.

[0063] Ultrasonic treatment: The mixture is transferred to an ultrasonic device and treated at 12 kHz and 65°C for 10 minutes to obtain a finely dispersed system.

[0064] Add functional additives: Add thickener, acetylsalicylic acid and other additives, and stir at 350 rpm for 40 minutes until fully dispersed.

[0065] Finished product preparation: Filter through a 250-mesh filter to remove impurities and obtain the finished product.

[0066] Results: Storage stability: After 5 days of storage at 25℃±2℃ in a sealed, light-protected environment, the stability error measured by centrifugation was 0.2%, which is far below the requirement of <0.4%. After 7 days of storage, the emulsion still maintained a homogeneous state and there was no significant change in fluidity.

[0067] Self-healing performance: When the coating creates a 0.2mm×0.1mm microcrack and is left to stand for 2 hours at 25℃±1℃ and 60%±5% relative humidity, the residual crack width is 0.012mm, and the self-healing rate is (0.2-0.012) / 0.2×100%=94%, which is significantly better than the standard of ≥90%.

[0068] UV aging resistance: After 300 hours of xenon lamp aging test, the coating remained intact without chalking, cracking, or discoloration, and the adhesion strength retention rate was 88%, which is higher than the requirement of ≥80%.

[0069] Other key properties: 1.5MPa bond strength with cementitious substrate; no flow or softening after 48 hours at 60℃; stable coating performance without damage after being frozen at -15℃ for 24 hours and then restored to normal temperature; excellent anti-adhesion effect with 0.25g / m² sand adhesion during construction.

[0070] Examples four through six only varied the content of the viscosity reducer. Example 4

[0071] The modified asphalt used was SBS modified asphalt, with an addition amount of 45%, a softening point of 58℃, a penetration of 50, and a ductility of 25cm. The rosin-lignin composite cationic emulsifier was self-made, with an addition amount of 4%. The mass ratio of purified waste lignin to rosin glycerol ester was 1:1, and the mass ratio of lignin-rosin complex to diethylenetriamine was 1:2.5. Modified hydrogenated castor oil was 6%; hydroxyl alkyd resin was 6%; polyether-type viscosity reducer was 2%; 100-mesh waste rubber powder was 5%, derived from waste tires crushed at room temperature, with a rubber hydrocarbon content of 58%, ash content of 6%, and moisture content of 0.8%; methyl acrylate was 4%; chloroprene rubber was 2%; petroleum resin tackifier was 3%; acetylsalicylic acid was 2%; polydimethylsiloxane was 3%; benzotriazole UV stabilizer was 2%; aminosilane cementitious agent was 2%; and industrial-grade pentaerythritol was 3%.

[0072] Pre-synthesis of rosin-lignin composite cationic emulsifier: Waste lignin from the paper industry was taken and added to a 6% (w / w) NaOH solution. The mixture was stirred at 85°C and 200 rpm for 1.2 hours until completely dissolved. The pH was adjusted to 2.5 with 4% (w / w) hydrochloric acid. After precipitation, the precipitate was washed with water until neutral, dried at 108°C for 2.5 hours, and pulverized through a 110-mesh sieve to obtain purified lignin. The purified lignin and rosin glycerol ester were added to a reaction vessel and stirred at 130°C and 220 rpm for 2.5 hours to form a complex. Diethylenetriamine was added, and the mixture was cooled to 90°C and stirred for 2 hours. After cooling, the emulsifier was obtained.

[0073] Raw material preparation: Weigh each raw material according to the formula, and remove impurities by passing the waste rubber powder through a 100-mesh sieve.

[0074] Preliminary mixing: Heat SBS modified bitumen to 125℃ to melt, add emulsifier, modified hydrogenated castor oil and hydroxyl alkyd resin, stir at 350 rpm for 15 minutes to form a uniform paste mixture.

[0075] Add auxiliary components: Add 2% polyether-type viscosity reducer, sieved waste rubber powder, methyl acrylate, and chloroprene rubber in sequence while continuously stirring. Control the temperature at 75℃ and stir for 30 minutes until completely dispersed.

[0076] Ultrasonic treatment: The mixture is transferred to an ultrasonic device and treated at 12 kHz and 65°C for 10 minutes to obtain a finely dispersed system.

[0077] Add functional additives: Add thickener, acetylsalicylic acid and other additives, and stir at 350 rpm for 40 minutes until fully dispersed.

[0078] Finished product preparation: Filter through a 250-mesh filter to remove impurities and obtain the finished product.

[0079] Results: Storage stability: After 5 days of sealed and light-proof storage at 25℃±2℃, the stability error measured by centrifugation was 0.37%, which meets the requirement of <0.4%. The emulsion viscosity is relatively high, and there are trace amounts of fine particles precipitated at the bottom. It can be evenly dispersed after stirring.

[0080] Self-healing performance: When the coating creates a 0.2mm×0.1mm microcrack, and is left to stand for 2 hours at 25℃±1℃ and 60%±5% relative humidity, the residual crack width is 0.018mm, and the self-healing rate is (0.2-0.018) / 0.2×100%=91%, which meets the standard of ≥90%.

[0081] UV aging resistance: After 300 hours of xenon lamp aging test, the coating showed no chalking or cracking, and the adhesion strength retention rate was 82%, meeting the requirement of ≥80%.

[0082] Other key properties: bonding strength with cementitious substrate is 1.2 MPa; no flow or softening at 60℃; no cracking at -10℃; emulsion application viscosity is 85 s, requiring slightly increased brushing pressure during application; good anti-sticking properties; sand adhesion is 0.45 g / m². Example 5

[0083] The modified asphalt used was SBS modified asphalt, with an addition amount of 45%, a softening point of 58℃, a penetration of 50, and a ductility of 25cm. The rosin-lignin composite cationic emulsifier was self-made, with an addition amount of 4%. The mass ratio of purified waste lignin to rosin glycerol ester was 1:1, and the mass ratio of lignin-rosin complex to diethylenetriamine was 1:2.5. Modified hydrogenated castor oil was 6%; hydroxyl alkyd resin was 6%; polyether-type viscosity reducer was 4%; 100-mesh waste rubber powder was 5%, derived from waste tires crushed at room temperature, with a rubber hydrocarbon content of 58%, ash content of 6%, and moisture content of 0.8%; methyl acrylate was 4%; chloroprene rubber was 2%; petroleum resin tackifier was 3%; acetylsalicylic acid was 2%; polydimethylsiloxane was 3%; benzotriazole UV stabilizer was 2%; aminosilane cementitious agent was 2%; and industrial-grade pentaerythritol was 3%.

[0084] Pre-synthesis of rosin-lignin composite cationic emulsifier: Waste lignin from the paper industry was taken and added to a 6% (w / w) NaOH solution. The mixture was stirred at 85°C and 200 rpm for 1.2 hours until dissolved. The pH was adjusted to 2.5 with 4% hydrochloric acid, and the precipitate was washed with water until neutral. The precipitate was dried at 108°C for 2.5 hours and then pulverized through a 110-mesh sieve to obtain purified lignin. The purified lignin and rosin glycerol ester were added to a reaction vessel and stirred at 130°C and 220 rpm for 2.5 hours to form a complex. Diethylenetriamine was added, and the mixture was cooled to 90°C and stirred for 2 hours. After cooling, the emulsifier was obtained.

[0085] Raw material preparation: Weigh each raw material according to the formula, and remove impurities by passing the waste rubber powder through a 100-mesh sieve.

[0086] Preliminary mixing: Heat SBS modified bitumen to 125℃ to melt, add emulsifier, modified hydrogenated castor oil and hydroxyl alkyd resin, stir at 350 rpm for 15 minutes to form a uniform paste mixture.

[0087] Add auxiliary components: Add viscosity reducer, waste rubber powder, methyl acrylate and chloroprene rubber in sequence while stirring continuously. Control the temperature at 75℃ and stir for 30 minutes until completely dispersed.

[0088] Ultrasonic treatment: The mixture is transferred to an ultrasonic device and treated at 12 kHz and 65°C for 10 minutes to obtain a finely dispersed system.

[0089] Add functional additives: Add thickener, acetylsalicylic acid and other additives, and stir at 350 rpm for 40 minutes until fully dispersed.

[0090] Finished product preparation: Filter through a 250-mesh filter to remove impurities and obtain the finished product.

[0091] Results: Storage stability: After 5 days of sealed storage at 25℃±2℃ and protected from light, the stability error measured by centrifugation was 0.28%, which is far below the requirement of <0.4%. The emulsion was uniform and fine, without layering, sedimentation or particle feel. There was no significant change in performance after 7 days of storage.

[0092] Self-healing performance: When the coating creates a 0.2mm×0.1mm microcrack and is left to stand for 2 hours at 25℃±1℃ and 60%±5% relative humidity, the residual crack width is 0.013mm, and the self-healing rate is (0.2-0.013) / 0.2×100%=93.5%, which is better than the standard of ≥90%.

[0093] UV aging resistance: After 300 hours of xenon lamp aging test, the coating has a bright color without chalking or cracking, and the adhesion strength retention rate is 87%, which is higher than the requirement of ≥80%.

[0094] Other key properties: 1.4MPa bond strength with cement substrate; no flow or deformation after 24 hours at 60℃; good elasticity and no cracks after being frozen at -10℃ for 24 hours and then restored to room temperature; emulsion application viscosity of 52s, good fluidity, smooth application, excellent anti-sticking properties, and sand adhesion of 0.3g / m². Example 6

[0095] The modified asphalt used was SBS modified asphalt, with an addition amount of 45%, a softening point of 58℃, a penetration of 50, and a ductility of 25cm. The rosin-lignin composite cationic emulsifier was self-made, with an addition amount of 4%. The mass ratio of purified waste lignin to rosin glycerol ester was 1:1, and the mass ratio of lignin-rosin complex to diethylenetriamine was 1:2.5. Modified hydrogenated castor oil was 6%; hydroxyl alkyd resin was 6%; polyether-type viscosity reducer was 5%; 100-mesh waste rubber powder was 5%, derived from waste tires crushed at room temperature, with a rubber hydrocarbon content of 58%, ash content of 6%, and moisture content of 0.8%; methyl acrylate was 4%; chloroprene rubber was 2%; petroleum resin tackifier was 3%; acetylsalicylic acid was 2%; polydimethylsiloxane was 3%; benzotriazole UV stabilizer was 2%; aminosilane cementitious agent was 2%; and industrial-grade pentaerythritol was 3%.

[0096] Pre-synthesis of rosin-lignin composite cationic emulsifier: Waste lignin from the paper industry was taken and added to a 6% (w / w) NaOH solution. The mixture was stirred at 85°C and 200 rpm for 1.2 hours until dissolved. The pH was adjusted to 2.5 with 4% hydrochloric acid, and the precipitate was washed with water until neutral. The precipitate was dried at 108°C for 2.5 hours and then pulverized through a 110-mesh sieve to obtain purified lignin. The purified lignin and rosin glycerol ester were added to a reaction vessel and stirred at 130°C and 220 rpm for 2.5 hours to form a complex. Diethylenetriamine was added, and the mixture was cooled to 90°C and stirred for 2 hours. After cooling, the emulsifier was obtained.

[0097] Raw material preparation: Weigh each raw material according to the formula, and remove impurities by passing the waste rubber powder through a 100-mesh sieve.

[0098] Preliminary mixing: Heat SBS modified bitumen to 125℃ to melt, add emulsifier, modified hydrogenated castor oil and hydroxyl alkyd resin, stir at 350 rpm for 15 minutes to form a uniform paste mixture.

[0099] Add auxiliary components: Add viscosity reducer, waste rubber powder, methyl acrylate and chloroprene rubber in sequence while stirring continuously. Control the temperature at 75℃ and stir for 30 minutes until completely dispersed.

[0100] Ultrasonic treatment: The mixture is transferred to an ultrasonic device and treated at 12 kHz and 65°C for 10 minutes to obtain a finely dispersed system.

[0101] Add functional additives: Add thickener, acetylsalicylic acid and other additives, and stir at 350 rpm for 40 minutes until fully dispersed.

[0102] Finished product preparation: Filter through a 250-mesh filter to remove impurities and obtain the finished product.

[0103] Results: Storage stability: After 5 days of sealed storage in the dark at 25℃±2℃, the stability error measured by centrifugation was 0.22%, which is far below the requirement of <0.4%. The emulsion has extremely strong fluidity, is thin emulsion, and has no stratification or sedimentation. However, after standing for 10 days, a very thin floating oil layer appears on the surface, which can be restored to homogeneity after stirring.

[0104] Self-healing performance: When the coating creates a 0.2mm×0.1mm microcrack and is left to stand for 2 hours at 25℃±1℃ and 60%±5% relative humidity, the residual crack width is 0.011mm, and the self-healing rate is (0.2-0.011) / 0.2×100%=94.5%, which is significantly better than the standard of ≥90%.

[0105] UV aging resistance: After 300 hours of xenon lamp aging test, the coating showed no chalking or cracking, and the adhesion strength retention rate was 86%, which is higher than the requirement of ≥80%.

[0106] Other key properties: Bond strength to cement substrate is 1.3 MPa; slight flow appears at the coating edge after 12 hours at 60℃, and the flow reaches 0.3 mm after 24 hours; no cracking at -15℃; emulsion application viscosity is 38s, which is too fluid and requires control of the coating thickness; good anti-sticking properties; sand particle adhesion is 0.28 g / m².

[0107] The specific content is shown in the table below:

[0108] As shown in the table above, Examples 1 to 3 clearly demonstrate the influence of rosin-lignin composite cationic emulsifier content on the performance of asphalt emulsions by only changing the content of the emulsifier: as the emulsifier content increases from 3% to 5%, the overall performance of the product shows a gradient optimization trend. Regarding storage stability, the stability error decreased from 0.38% to 0.2%, and the emulsion homogeneity retention ability was significantly enhanced. At low content, trace amounts of flocculent matter were prone to appear in the later stages of storage, while at high content, the stable storage period could be extended. Self-healing performance gradually improved with increasing emulsifier content, with the self-healing rate increasing from 90% to 94%, accelerating the closure speed of microcracks, and improving damage repair ability. UV aging resistance improved simultaneously, with the bond strength retention rate increasing from 81% to 88%, making the coating's weather resistance more suitable for long-term outdoor road and bridge use. The bond strength with cementitious substrate increased from 1.2 MPa to 1.5 MPa, and high and low temperature stability and anti-adhesion performance were also optimized with increasing emulsifier content. From a cost-performance perspective, when the emulsifier content is 3%, the product only meets the basic performance requirements and is suitable for cost-sensitive temporary road and bridge maintenance; when it is 4.5%, the performance is balanced and the cost is controllable, making it suitable for conventional road and bridge waterproofing projects; when it is 5%, the performance is optimal and it can be used in key road and bridge projects under harsh environments such as high temperature and strong ultraviolet radiation, providing a clear basis for product selection under different working conditions.

[0109] Examples four through six only varied the content of the polyether-type viscosity reducer. These three examples clearly demonstrate the dual impact of viscosity reducer dosage on the performance of asphalt emulsions, showing an overall trend of initial improvement followed by subsequent deterioration. Regarding application and dispersion performance, as the viscosity reducer content increased from 2% to 5%, the emulsion application viscosity decreased from 85s to 38s, with fluidity gradually improving. At 2%, application was difficult; at 4%, fluidity was optimal and application was smooth; at 5%, the low viscosity increased the difficulty of controlling application thickness. In terms of storage stability, increasing the content resulted in more uniform dispersion, reducing the stability error from 0.37% to 0.22%. However, at 5%, oil floating occurred, and stability continued to decline. Among the core functional properties, the self-healing rate increased from 91% to 94.5% with increasing content; the bond strength reached a peak of 1.4MPa at 4%, and slightly decreased at 5%; UV resistance... All contents met the requirements with no significant differences; however, high-temperature stability decreased with higher contents, with high-temperature flow occurring at 5%, while 2% and 4% showed stability. Overall, when the polyether-type viscosity reducer content was 4%, the emulsion achieved the optimal balance in terms of construction fluidity, storage stability, bond strength, and high and low temperature resistance, making it suitable for most road and bridge waterproofing scenarios; a 2% content was suitable for special working conditions with extremely high requirements for high-temperature stability but low requirements for construction efficiency; and due to its high-temperature performance defects, a 5% content could only be used cautiously in temporary maintenance projects with low temperature and short construction time. This conclusion provides a precise basis for selecting the amount of viscosity reducer under different construction needs.

[0110] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications, characterized in that, Made from the following raw materials in parts by weight: The modified asphalt contains 40-50%, rosin-lignin composite cationic emulsifier 3-5%, modified hydrogenated castor oil 6-10%, hydroxyl alkyd resin 4-8%, viscosity reducer 2-4%, waste rubber powder 3-7%, methyl acrylate 3-5%, chloroprene rubber 1-3%, tackifier 2-4%, acetylsalicylic acid 1-3%, polydimethylsiloxane 2-4%, UV stabilizer 1-3%, cement affinity agent 1-3%, and pentaerythritol 1-3%. The rosin-lignin composite cationic emulsifier is synthesized using waste lignin from the papermaking industry as a base material through a grafting reaction of rosin derivatives and diethylenetriamine.

2. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications according to claim 1, characterized in that, The modified asphalt is SBS modified asphalt or rubber modified asphalt, and the softening point of the modified asphalt is ≥55℃, the penetration is 40-60, and the ductility is ≥20cm.

3. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications according to claim 1, characterized in that, In the raw materials for synthesizing the rosin-lignin composite cationic emulsifier, the mass ratio of purified waste lignin to rosin derivatives is 1:0.8-1.2, and the mass ratio of lignin-rosin complex to diethylenetriamine is 1:2-3.

4. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge construction according to claim 1, characterized in that, The waste rubber powder has a particle size of 80-120 mesh and is derived from the room temperature crushing and processing of waste tires. The rubber hydrocarbon content is ≥55%, the ash content is ≤8%, and the moisture content is ≤1%. The UV stabilizer is a benzotriazole UV stabilizer or a hindered amine UV stabilizer.

5. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications according to claim 1, characterized in that, The test conditions for a 5-day stability error of <0.4% are: static storage at 25℃±2℃ in a sealed, light-proof environment, and centrifugal separation method is used for testing. The difference in solid content between the upper and lower layers is the stability error.

6. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge construction according to claim 1, characterized in that, The test method for a self-healing rate of ≥90% at room temperature for 2 hours is as follows: microcracks with a width of 0.2 mm and a depth of 0.1 mm are artificially created on the surface of the coating after the emulsion film is formed. The coating is left to stand for 2 hours at 25℃±1℃ and relative humidity of 60%±5%, and the degree of crack closure is observed under a microscope. The test standard for UV resistance aging time of ≥300 hours is as follows: a xenon lamp aging test is conducted with an irradiation intensity of 0.71 W / m²@340 nm and a black standard temperature of 63℃±3℃. After aging, the coating shows no chalking or cracking, and the adhesion strength retention rate is ≥80%.

7. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge construction according to claim 1, characterized in that, The rosin derivative is rosin glycerol ester or hydrogenated rosin, and the rosin derivative has an oleophilic value of 3-5, an acid value ≤10mgKOH / g, and a softening point ≥80℃.

8. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge construction according to claim 1, characterized in that, The viscosity reducer is a polyether-type viscosity reducer or an ester-type viscosity reducer; the viscosity modifier is a petroleum resin-based viscosity modifier or a rosin resin-based viscosity modifier, and the softening point of the viscosity modifier is 90-110℃.

9. The cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications according to claim 1, characterized in that, The cement affinity agent is an aminosilane affinity agent or an epoxysilane affinity agent, and the effective component content of the cement affinity agent is ≥98%; the pentaerythritol is industrial grade pentaerythritol with a purity of ≥95% and a hydroxyl value of ≥47%.

10. A method for preparing a cationic anti-adhesion and waterproof asphalt emulsion for road and bridge applications, used to prepare the cationic anti-adhesion and waterproof asphalt emulsion for road and bridge applications as described in any one of claims 1-9, characterized in that, Includes the following steps: S1. Pre-synthesis of rosin-lignin composite cationic emulsifier: Lignin pretreatment: Take waste lignin from the paper industry, add 5-8% NaOH solution (liquid-solid ratio 5:1-8:1), stir at 80-90℃ for 1-1.5 hours until completely dissolved, adjust pH to 2-3 with 3-5% hydrochloric acid to precipitate lignin, wash repeatedly with deionized water until neutral, dry at 105-110℃ for 2-3 hours, pulverize and pass through 100- Purified lignin was obtained by sieving through a 120-mesh sieve. Lipophilic group grafting: The purified lignin and rosin derivative were added to a reaction vessel, heated to 120-140℃, and stirred at 200-250 rpm for 2-3 hours to form a lignin-rosin complex. Hydrophilic group introduction: Diethylenetriamine was added to the reaction vessel, the temperature was lowered to 80-100℃, and the mixture was stirred and kept at this temperature for 1.5-2.5 hours. The mixture was then cooled to room temperature to obtain a rosin-lignin composite cationic emulsifier. S2. Raw material preparation: Weigh each raw material according to the weight percentage, and remove impurities from the waste rubber powder by 80-120 mesh screening. S3. Preliminary mixing: Heat the modified asphalt to 120-130℃ to melt it, add rosin-lignin composite cationic emulsifier, modified hydrogenated castor oil, and hydroxyl alkyd resin, and stir at 300-400 rpm for 10-20 minutes to form a uniform paste mixture. S4. Add auxiliary components: Add viscosity reducer, waste rubber powder, methyl acrylate and chloroprene rubber in sequence while stirring. Control the system temperature ≤80℃ and continue stirring for 25-35 minutes until completely dispersed. S5. Ultrasonic treatment: Transfer the mixture to an ultrasonic treatment device, set the frequency to 12kHz, the temperature to 60-70℃, and the treatment time to 8-12 minutes to obtain a fine and uniform dispersion system. S6. Add functional additives: Add thickener, acetylsalicylic acid, polydimethylsiloxane, UV stabilizer, cement affinity agent, and pentaerythritol to the dispersion system, and continue stirring at 300-400 rpm for 35-45 minutes to ensure that all components are fully dissolved and dispersed. S7. Finished product preparation: The above mixture is filtered through a 200-300 mesh filter to remove impurities, thus obtaining a cationic anti-adhesive and waterproof asphalt emulsion for road and bridge applications.

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