A styrene-butadiene latex composite adhesive and its preparation process

Abstract

This invention relates to the field of adhesive technology, specifically to a styrene-butadiene latex composite adhesive and its preparation process. The preparation process includes the following steps: preparing a styrene-butadiene latex emulsion; preparing a sulfonated phenolic resin; preparing a sulfonated resin / styrene-butadiene latex emulsion; preparing a polyaniline-copper complex; and preparing the styrene-butadiene latex composite adhesive. This invention uses a sulfur trioxide-pyridine complex to sulfonate the phenolic resin, forming sulfonic acid groups. These sulfonic acid groups can form hydrogen bonds or ionic bonds with substrates such as metals, concrete, and fibers, significantly improving adhesion. Furthermore, the sulfur trioxide-pyridine complex can also form sulfate ester bonds and phenolic hydroxyl bonds during the sulfonation of the phenolic resin. After the sulfonated resin is added to the styrene-butadiene latex, it can improve the adhesive strength of the styrene-butadiene latex. This higher adhesive strength, when added to asphalt, provides better ductility and aging resistance, extending the service life of the asphalt.

Description

Technical Field

[0001] This invention relates to the field of adhesive technology, specifically to a styrene-butadiene latex composite adhesive and its preparation process. Background Technology

[0002] Styrene-butadiene latex composite adhesive is a high-performance adhesive prepared by adding other components to styrene-butadiene latex. Styrene-butadiene latex is a synthetic rubber latex formed by emulsion polymerization of butadiene and styrene monomers. It has high bonding strength and can firmly bond with a variety of materials. At the same time, styrene-butadiene latex is also a commonly used emulsified asphalt modifier, which is widely used in the construction and maintenance of elastomeric modified asphalt, i.e., road asphalt. It can improve the low-temperature crack resistance and waterproof performance of elastomeric modified asphalt and extend the service life of elastomeric modified asphalt.

[0003] However, although styrene-butadiene rubber latex can improve the low-temperature crack resistance of elastomer-modified asphalt, its high carbon-carbon double bond content in its molecular chain results in inferior aging resistance compared to some high-performance modified materials. Furthermore, its performance degrades significantly after thermo-oxidative aging. Additionally, the large difference in molecular weight between styrene-butadiene rubber and asphalt makes modified asphalt prone to segregation and stratification during hot storage. Therefore, while it improves the low-temperature crack resistance of pavement, its impact on the aging resistance of elastomer-modified asphalt is relatively small at room temperature (15-25℃). A composite binder prepared using styrene-butadiene rubber latex can solve the problem of segregation and stratification in modified asphalt after its addition. The binder's adhesive properties bind different layers of modified asphalt together, while also improving the asphalt's ductility and aging resistance. Therefore, this invention provides a styrene-butadiene rubber latex composite binder and its preparation process. The prepared styrene-butadiene rubber latex composite binder simultaneously possesses the aforementioned effects of improving the ductility and aging resistance of modified asphalt. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a styrene-butadiene latex composite adhesive and its preparation process.

[0005] A preparation process for a styrene-butadiene latex composite adhesive includes the following steps:

[0006] S1: Preparation of styrene-butadiene rubber latex emulsion

[0007] The compound surfactant solution was stirred and heated, and styrene, butadiene and initiator ammonium persulfate solution were added to react and obtain a pre-reaction solution. The pre-reaction solution and polybutadiene were added dropwise to the compound surfactant solution and heated to react and obtain styrene-butadiene latex emulsion.

[0008] S2: Preparation of sulfonated phenolic resin

[0009] Weigh dichloromethane, stir and heat it, add phenolic resin, stir, then add nano-iron tetroxide and sulfur trioxide-pyridine complex, react, filter, wash and dry to obtain sulfonated phenolic resin.

[0010] S3: Preparation of sulfonated resin / styrene-butadiene latex emulsion

[0011] Sulfonated phenolic resin was mixed with deionized water to obtain a suspension, which was then added dropwise to styrene-butadiene rubber latex emulsion. The mixture was stirred and degassed under vacuum to obtain sulfonated resin / styrene-butadiene rubber latex emulsion.

[0012] S4: Preparation of polyaniline-copper complex

[0013] Aniline monomer was dissolved in hydrochloric acid solution to obtain aniline solution. Ammonium persulfate solution was added dropwise to aniline solution and stirred. Then copper sulfate solution was added, the temperature was raised and the reaction was carried out. The filtrate was removed by suction filtration, washed and dried to obtain polyaniline-copper complex powder.

[0014] S5: Preparation of styrene-butadiene latex composite adhesive

[0015] Polyaniline-copper complex powder was added to deionized water and stirred until a dispersion was obtained. Sulfonated resin / styrene-butadiene latex emulsion was added to an ethanol solution, and the dispersion was added while stirring. Subsequently, vacuum degassing was performed to prepare a styrene-butadiene latex composite adhesive.

[0016] Further, step S1, preparing the styrene-butadiene rubber latex emulsion, includes the following steps:

[0017] 10-15 parts by weight of the compound surfactant solution are heated to 65-70℃ under stirring at 200-250 r / min. During stirring, 5-10 parts by weight of styrene, 5-8 parts by weight of butadiene, and 1-3 parts by weight of initiator ammonium persulfate solution are added. The temperature is maintained for 1-1.5 h after heating to obtain a pre-reaction solution. 1-5 parts by weight of the pre-reaction solution and 1-5 parts by weight of polybutadiene are added dropwise to 10-12 parts by weight of the compound surfactant solution, with the addition time controlled at 1-2 h. At the same time, the temperature is heated to 60-70℃ and reacted for another 2-3 h to obtain styrene-butadiene latex emulsion.

[0018] Further, step S2 prepares sulfonated phenolic resin, including the following steps:

[0019] Weigh 9-12 parts by mass of dichloromethane into a single-necked flask and stir at 100-150 r / min while controlling the temperature at 30-35℃. Then add 1-3 parts by mass of phenolic resin and continue stirring at 100-150 r / min. Next, add 0.5-1 parts by mass of nano-ferric oxide and adjust the temperature to 5-10℃. Mix and stir at 550-600 r / min for 30-35 min. Then, add 0.5-1 parts by mass of sulfur trioxide-pyridine complex, keep stirring and react for 20-30 min. Filter, wash and dry to obtain sulfonated phenolic resin.

[0020] Further, step S3, preparing the sulfonated resin / styrene-butadiene latex emulsion, includes the following steps:

[0021] Mix 5-8 parts by weight of sulfonated phenolic resin with 100-110 parts by weight of deionized water and stir for 5-10 minutes to obtain a suspension. Then, add the suspension dropwise to the styrene-butadiene rubber latex emulsion while stirring at a speed of 600-650 r / min. After the addition is complete, adjust the speed to 1200-1300 r / min and stir for 20-25 minutes. Then, degas under vacuum for 10-15 minutes to obtain the sulfonated resin / styrene-butadiene rubber latex emulsion.

[0022] Further, step S4 prepares the polyaniline-copper complex, including the following steps:

[0023] Dissolve 1-3 parts by weight of aniline monomer in 100-105 parts by weight of 1-1.5M hydrochloric acid solution, cool to 0-5℃ in an ice bath to obtain aniline solution, slowly add ammonium persulfate solution dropwise to aniline solution while maintaining the temperature at 0-5℃, stir at 60-100 r / min for 1 h, then add copper sulfate solution, heat to 25-30℃, react for 2-2.5 h, filter to remove filtrate, wash the product 3 times with deionized water, and then vacuum dry at 60-65℃ for 5-6 h to obtain polyaniline-copper complex powder.

[0024] Further, step S5, preparing the styrene-butadiene latex composite adhesive, includes the following steps:

[0025] Add 2-3 parts by weight of polyaniline-copper complex powder to 100-105 parts by weight of deionized water and stir until uniform to obtain a dispersion. Add 20-25 parts by weight of styrene-butadiene latex to 40-50 parts by weight of ethanol solution and stir at 200-250 r / min for 30-35 min. Then increase the speed to 400-500 r / min and add 10-15 parts by weight of dispersion while stirring. Then stir at 1000-1100 r / min for 30-35 min. Degas under vacuum for 5-10 min, and then remove ethanol by rotary evaporation to adjust the viscosity to obtain styrene-butadiene latex composite adhesive.

[0026] Furthermore, the compound surfactant solution is prepared by mixing sodium styrene sulfonate and sodium dodecyl sulfate in a mass ratio of 1:(1-2).

[0027] Furthermore, the concentration of the ammonium persulfate solution is 8-12 wt%.

[0028] Furthermore, the concentration of the copper sulfate solution is 0.4-0.8 wt%.

[0029] A styrene-butadiene latex composite adhesive is prepared by a styrene-butadiene latex composite adhesive preparation process.

[0030] Compared with the prior art, the present invention has at least the following beneficial effects:

[0031] 1. This invention uses a sulfur trioxide-pyridine complex to react with phenolic resin. The sulfur trioxide-pyridine complex acts as a strong electrophilic agent and stabilizer in the reaction, reducing the intensity of the reaction. Furthermore, the groups released by the sulfur trioxide-pyridine complex can react with the phenolic resin to form sulfonic acid groups. These sulfonic acid groups can form chemical bonds with substrates such as metals, concrete, and fibers, significantly improving adhesion. In addition, the sulfur trioxide-pyridine complex can also form sulfate ester bonds and phenolic hydroxyl bonds during the sulfonation of phenolic resin. After the sulfonated resin is added to styrene-butadiene latex, it can improve the adhesion of the styrene-butadiene latex. The higher adhesion can bring better ductility and aging resistance to asphalt after the styrene-butadiene latex composite adhesive is added to asphalt, extending the service life of the asphalt. Moreover, the phenolic hydroxyl bonds and ester bonds in the sulfonated phenolic resin can also bring reversible recombination characteristics to the styrene-butadiene latex. When the adhesive prepared from styrene-butadiene latex is added to asphalt, a reversible reaction can occur at high temperatures, realizing the self-repair of microcracks and further improving the aging resistance.

[0032] 2. This invention involves complexing aniline monomers with copper sulfate and reacting to generate a polymer. The resulting polymer is then added to styrene-butadiene latex. After the copper sulfate complexes with polyaniline, it forms additional electron transport channels, thereby increasing the conductivity of the polymer. Simultaneously, copper ions can coordinate with the groups of styrene-butadiene latex to form crosslinking points, thereby increasing the elastic modulus of the styrene-butadiene latex. This results in a styrene-butadiene latex composite binder with certain electrical conductivity and ductility. When this styrene-butadiene latex composite binder is added to asphalt, it can bring a certain degree of conductivity to the asphalt, thereby improving the adhesion between the asphalt and aggregates, reducing spalling and water damage, and thus improving the ductility and anti-aging ability of the asphalt. Attached Figure Description

[0033] The accompanying drawings, which are incorporated herein and form part of the specification, illustrate embodiments of the present disclosure and, together with the specification, further serve to explain the principles of the present disclosure and enable those skilled in the art to implement and use the present disclosure.

[0034] Figure 1 This is a process flow diagram of the preparation process of a styrene-butadiene latex composite adhesive used in an embodiment of the present invention. Detailed Implementation

[0035] The following describes in detail a styrene-butadiene latex composite adhesive and its preparation process provided by the present invention, with reference to the accompanying drawings and specific embodiments. It should be noted that, to make the embodiments more detailed, the following embodiments are the best and preferred embodiments; those skilled in the art can also use other alternative methods to implement some known technologies; and the accompanying drawings are only for more specific description of the embodiments and are not intended to specifically limit the present invention.

[0036] Example 1:

[0037] A preparation process for a styrene-butadiene latex composite adhesive, such as... Figure 1 As shown, it includes the following steps:

[0038] S1: Preparation of styrene-butadiene rubber latex emulsion

[0039] Ten parts by mass of the compound surfactant solution were heated to 65°C under stirring at 200 r / min. During stirring, five parts by mass of styrene, five parts by mass of butadiene, and one part by mass of ammonium persulfate initiator solution were added. The temperature was maintained for 1 hour after heating to obtain a pre-reaction solution. One part by mass of the pre-reaction solution and one part by mass of polybutadiene were added dropwise to ten parts by mass of the compound surfactant solution, and the addition time was controlled to be 1 hour. At the same time, the temperature was heated to 60°C and reacted for another 2 hours to obtain styrene-butadiene latex emulsion.

[0040] The compound surfactant solution was prepared by mixing sodium styrene sulfonate and sodium dodecyl sulfate in a 1:1 mass ratio.

[0041] S2: Preparation of sulfonated phenolic resin

[0042] Weigh 9 parts by mass of dichloromethane and place it in a single-necked flask. Stir at 100 r / min while controlling the temperature at 30°C. Then add 1 part by mass of phenolic resin and continue stirring at 100 r / min. Next, add 0.5 parts by mass of nano-ferric oxide and adjust the temperature to 5°C. Mix and stir at 550 r / min for 30 min. Then, add 0.5 parts by mass of sulfur trioxide-pyridine complex, keep stirring and react for 20 min. Filter, wash and dry to obtain sulfonated phenolic resin.

[0043] S3: Preparation of sulfonated resin / styrene-butadiene latex emulsion

[0044] Five parts by weight of sulfonated phenolic resin were mixed with 100 parts by weight of deionized water and stirred for 5 minutes to obtain a suspension. The suspension was then added dropwise to styrene-butadiene rubber latex while stirring at 600 r / min. After the addition was completed, the stirring speed was adjusted to 1200 r / min and stirred for 20 minutes. Then, vacuum degassing was performed for 10 minutes to obtain sulfonated resin / styrene-butadiene rubber latex emulsion.

[0045] S4: Preparation of polyaniline-copper complex

[0046] One part by mass of aniline monomer was dissolved in 100 parts by mass of 1M hydrochloric acid solution, and the solution was cooled to 0°C in an ice bath to obtain an aniline solution. An 8 wt% ammonium persulfate solution was slowly added dropwise to the aniline solution while maintaining the temperature at 0°C and stirring at 60 r / min for 1 h. Then, a 0.4 wt% copper sulfate solution was added, the temperature was raised to 25°C, and the reaction was carried out for 2 h. The filtrate was removed by suction filtration, and the product was washed three times with deionized water and then dried under vacuum at 60°C for 5 h to obtain polyaniline-copper complex powder.

[0047] S5: Preparation of styrene-butadiene latex composite adhesive

[0048] Two parts by mass of polyaniline-copper complex powder were added to 100 parts by mass of deionized water and stirred until a dispersion was obtained. 20 parts by mass of sulfonated resin / styrene-butadiene latex emulsion were added to 40 parts by mass of ethanol solution and stirred at 200 r / min for 30 min. The stirring speed was then increased to 400 r / min, and 10 parts by mass of the dispersion were added during stirring. The mixture was then stirred at 1000 r / min for 30 min, and vacuum degassing was performed for 5 min. The ethanol was then removed by rotary evaporation to adjust the viscosity, and the styrene-butadiene latex composite adhesive was obtained.

[0049] Example 2:

[0050] A preparation process for a styrene-butadiene latex composite adhesive, such as... Figure 1 As shown, it includes the following steps:

[0051] S1: Preparation of styrene-butadiene rubber latex emulsion

[0052] 15 parts by mass of the compound surfactant solution were heated to 65°C under stirring at 200 r / min. During stirring, 10 parts by mass of styrene, 8 parts by mass of butadiene, and 3 parts by mass of ammonium persulfate initiator solution were added. The temperature was maintained for 1 hour after heating to obtain a pre-reaction solution. 5 parts by mass of the pre-reaction solution and 5 parts by mass of polybutadiene were added dropwise to 12 parts by mass of the compound surfactant solution, with the addition time controlled at 1 hour. The mixture was heated to 60°C and reacted for another 2 hours to obtain styrene-butadiene latex emulsion.

[0053] The compound surfactant solution was prepared by mixing sodium styrene sulfonate and sodium dodecyl sulfate in a mass ratio of 1:2.

[0054] S2: Preparation of sulfonated phenolic resin

[0055] Weigh 12 parts by mass of dichloromethane and place it in a single-necked flask. Stir at 100 r / min while controlling the temperature at 30°C. Then add 3 parts by mass of phenolic resin and continue stirring at 100 r / min. Next, add 1 part by mass of nano-ferric oxide and adjust the temperature to 5°C. Mix and stir at 550 r / min for 30 min. Then, add 1 part by mass of sulfur trioxide-pyridine complex, keep stirring and react for 20 min. Filter, wash and dry to obtain sulfonated phenolic resin.

[0056] S3: Preparation of sulfonated resin / styrene-butadiene latex emulsion

[0057] Eight parts by weight of sulfonated phenolic resin were mixed with 110 parts by weight of deionized water and stirred for 5 minutes to obtain a suspension. The suspension was then added dropwise to styrene-butadiene rubber latex while stirring at 600 r / min. After the addition was completed, the stirring speed was adjusted to 1200 r / min and stirred for 20 minutes. Then, vacuum degassing was performed for 10 minutes to obtain sulfonated resin / styrene-butadiene rubber latex emulsion.

[0058] S4: Preparation of polyaniline-copper complex

[0059] Three parts by mass of aniline monomer were dissolved in 100 parts by mass of 1M hydrochloric acid solution, and the solution was cooled to 0°C in an ice bath to obtain an aniline solution. An 8 wt% ammonium persulfate solution was slowly added dropwise to the aniline solution while maintaining the temperature at 0°C and stirring at 60 r / min for 1 h. Then, a 0.4 wt% copper sulfate solution was added, the temperature was raised to 25°C, and the reaction was carried out for 2 h. The filtrate was removed by suction filtration, and the product was washed three times with deionized water and then dried under vacuum at 60°C for 5 h to obtain polyaniline-copper complex powder.

[0060] S5: Preparation of styrene-butadiene latex composite adhesive

[0061] Three parts by mass of polyaniline-copper complex powder were added to 105 parts by mass of deionized water and stirred until a dispersion was obtained. 25 parts by mass of sulfonated resin / styrene-butadiene latex emulsion were added to 50 parts by mass of ethanol solution and stirred at 200 r / min for 30 min. The stirring speed was then increased to 400 r / min, and 15 parts by mass of the dispersion were added during stirring. The mixture was then stirred at 1000 r / min for 30 min, vacuum degassing was performed for 5 min, and then the ethanol was removed by rotary evaporation to adjust the viscosity, thus obtaining the styrene-butadiene latex composite adhesive.

[0062] Example 3:

[0063] A preparation process for a styrene-butadiene latex composite adhesive, such as... Figure 1 As shown, it includes the following steps:

[0064] S1: Preparation of styrene-butadiene rubber latex emulsion

[0065] Ten parts by mass of the compound surfactant solution were heated to 70°C under stirring at 250 r / min. During stirring, five parts by mass of styrene, five parts by mass of butadiene, and one part by mass of ammonium persulfate initiator solution were added. The temperature was maintained for 1.5 h after heating to obtain a pre-reaction solution. One part by mass of the pre-reaction solution and one part by mass of polybutadiene were added dropwise to ten parts by mass of the compound surfactant solution, and the addition time was controlled to be 2 h. At the same time, the temperature was heated to 70°C and reacted for another 3 h to obtain styrene-butadiene latex emulsion.

[0066] The compound surfactant solution was prepared by mixing sodium styrene sulfonate and sodium dodecyl sulfate in a 1:1 mass ratio.

[0067] S2: Preparation of sulfonated phenolic resin

[0068] Weigh 9 parts by mass of dichloromethane and place it in a single-necked flask. Stir at 150 r / min while controlling the temperature at 35°C. Then add 1 part by mass of phenolic resin and continue stirring at 150 r / min. Next, add 0.5 parts by mass of nano-ferric oxide and adjust the temperature to 10°C. Mix and stir at 600 r / min for 35 min. Then, add 0.5 parts by mass of sulfur trioxide-pyridine complex, keep stirring and react for 30 min. Filter, wash and dry to obtain sulfonated phenolic resin.

[0069] S3: Preparation of sulfonated resin / styrene-butadiene latex emulsion

[0070] Five parts by weight of sulfonated phenolic resin were mixed with 100 parts by weight of deionized water and stirred for 10 minutes to obtain a suspension. The suspension was then added dropwise to styrene-butadiene rubber latex while stirring at 650 r / min. After the addition was completed, the stirring speed was adjusted to 1200 r / min and stirred for 25 minutes. Then, vacuum degassing was performed for 15 minutes to obtain the sulfonated resin / styrene-butadiene rubber latex emulsion.

[0071] S4: Preparation of polyaniline-copper complex

[0072] One part by mass of aniline monomer was dissolved in 100 parts by mass of 1M hydrochloric acid solution, and the solution was cooled to 0°C in an ice bath to obtain an aniline solution. A 12 wt% ammonium persulfate solution was slowly added dropwise to the aniline solution while maintaining the temperature at 0°C and stirring at 60 r / min for 1 h. Then, a 0.8 wt% copper sulfate solution was added, the temperature was raised to 30°C, and the reaction was carried out for 2.5 h. The filtrate was removed by suction filtration, and the product was washed three times with deionized water and then dried under vacuum at 60°C for 5 h to obtain polyaniline-copper complex powder.

[0073] S5: Preparation of styrene-butadiene latex composite adhesive

[0074] Two parts by mass of polyaniline-copper complex powder were added to 100 parts by mass of deionized water and stirred until a dispersion was obtained. 20 parts by mass of sulfonated resin / styrene-butadiene latex emulsion were added to 40 parts by mass of ethanol solution and stirred at 250 r / min for 35 min. The stirring speed was then increased to 500 r / min, and 10 parts by mass of the dispersion were added during stirring. The mixture was then stirred at 1100 r / min for 35 min, vacuum degassing was performed for 10 min, and then the ethanol was removed by rotary evaporation to adjust the viscosity, thus obtaining the styrene-butadiene latex composite adhesive.

[0075] Comparative Example 1:

[0076] Compared with Example 1, the difference of Comparative Example 1 is that sulfonated phenolic resin is not added in step S3, but phenolic resin is used instead of sulfonated phenolic resin. Specifically, "S3: 5 parts by mass of phenolic resin and 100 parts by mass of deionized water are mixed and stirred for 5 minutes to obtain a suspension, which is then dropped into styrene-butadiene latex emulsion. While dropping, the mixture is stirred at a speed of 600 r / min. After the dropping is completed, the speed is adjusted to 1200 r / min and stirred for 20 minutes. Then, vacuum degassing is performed for 10 minutes to obtain phenolic resin / styrene-butadiene latex emulsion." In subsequent steps, phenolic resin / styrene-butadiene latex emulsion is used instead of sulfonated resin / styrene-butadiene latex emulsion, and the other steps remain unchanged. The prepared styrene-butadiene latex composite adhesive is referred to as Comparative Example 1.

[0077] Comparative Example 2:

[0078] Compared with Example 1, Comparative Example 2 differs in that phenolic resin is not added in step S2, but epoxy resin is used instead. Specifically, "S2: Weigh 9 parts by mass of dichloromethane and place it in a single-necked flask, stir at 100 r / min and heat to 30°C, then add 1 part by mass of epoxy resin, continue stirring at 100 r / min, then add 0.5 parts by mass of nano-ferric oxide, adjust the temperature to 5°C, mix and stir at 550 r / min for 30 min, then add 0.5 parts by mass of sulfur trioxide-pyridine complex, keep stirring and react for 20 min, filter, wash and dry to obtain sulfonated epoxy resin." In subsequent steps, sulfonated epoxy resin is used instead of sulfonated phenolic resin, and the other steps remain unchanged. The prepared styrene-butadiene latex composite adhesive is designated as Comparative Example 2.

[0079] Comparative Example 3:

[0080] Compared with Example 1, the difference of Comparative Example 3 is that in step S5, polyaniline-copper complex powder is not added, but polyaniline powder is used instead of polyaniline-copper complex powder. Specifically, "S5: 2 parts by mass of polyaniline powder are added to 100 parts by mass of deionized water and stirred evenly to obtain a dispersion. 20 parts by mass of sulfonated resin / styrene-butadiene latex emulsion are added to 40 parts by mass of ethanol solution and stirred at 200 r / min for 30 min. Then the speed is increased to 400 r / min, and 10 parts by mass of dispersion are added during stirring. Then the mixture is stirred at 1000 r / min for 30 min, vacuum degassing is performed for 5 min, and then the ethanol is removed by rotary evaporation to adjust the viscosity, thus obtaining styrene-butadiene latex composite adhesive." The remaining steps are unchanged, and the prepared styrene-butadiene latex composite adhesive is referred to as Comparative Example 3.

[0081] Comparative Example 4:

[0082] Comparative Example 4 is a commercially available styrene-butadiene latex adhesive.

[0083] The styrene-butadiene latex composite binders of Examples 1-3 and Comparative Examples 1-4 were added to road asphalt. The specific steps were as follows: the road asphalt was heated to 150°C until it was completely fluid. Then, the styrene-butadiene latex composite binders of Examples 1-3 and Comparative Examples 1-4 were added to the road asphalt at a dosage of 5 wt%. Stirring was then started at a speed of 600 r / min for 3 h to obtain styrene-butadiene latex composite asphalt. The aging resistance of the styrene-butadiene latex composite asphalt was tested. According to the "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" (JTGE20-2011), the ductility at 15°C of Examples 1-3 and Comparative Examples 1-4 was tested. Then, an aging test was conducted: 40 g of styrene-butadiene latex composite asphalt was aged in a rotating thin film oven for 100 min. The ductility retention rate after aging was measured. The ductility retention rate = (ductility at 15°C after aging / ductility at 15°C before aging) * 100%. The test results are shown in Table 1.

[0084] Table 1

[0085]

[0086] As shown in Table 1, the ductility of Examples 1-3 before aging at 15℃ was above 59 cm, and the ductility retention rate was above 90%, both higher than the comparative examples. Furthermore, Comparative Example 4, being a commercially available product, had a ductility of 56 cm and a ductility retention rate of 87% before aging at 15℃, both lower than the examples. The ductility of asphalt refers to the length at which a standard figure-eight shaped specimen is stretched at 5 cm / min to break. The ductility of road asphalt is generally tested at 15℃. Higher ductility indicates better flexibility and extensibility, reducing the possibility of road surface cracking. A higher ductility retention rate indicates better retention of extensibility during aging and stronger anti-aging properties. Therefore, the styrene-butadiene latex composite binder prepared from the raw material combinations of Examples 1-3 exhibits better flexibility and anti-aging properties after being added to road asphalt.

[0087] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A process for the preparation of styrene butadiene latex composite binder, characterized by, Comprising the following steps: S1: preparing styrene-butadiene latex emulsion The complex surfactant solution is stirred and heated, and styrene, butadiene and initiator ammonium persulfate solution are added, and the pre-reaction liquid is obtained by reaction. The pre-reaction liquid and polybutadiene are added to the complex surfactant solution, heated and reacted to obtain the styrene-butadiene latex emulsion; S2: preparing sulfonated phenolic resin The dichloromethane is weighed and stirred and heated, the phenolic resin is added, and after stirring, the nano ferric oxide and sulfur trioxide-pyridine complex are added, reacted, filtered, washed and dried to obtain the sulfonated phenolic resin; S3: preparing sulfonated resin / styrene-butadiene latex emulsion The sulfonated phenolic resin is mixed with deionized water to obtain a suspension, which is then added dropwise into the styrene-butadiene latex emulsion, stirred and vacuum degassed to obtain the sulfonated resin / styrene-butadiene latex emulsion; S4: preparing polyaniline-copper complex The aniline monomer is dissolved in hydrochloric acid solution to obtain an aniline solution, the ammonium persulfate solution is added dropwise into the aniline solution, stirred, and then the copper sulfate solution is added, heated and reacted, the filtrate is removed by suction filtration, washed and dried to obtain the polyaniline-copper complex powder; S5: preparing styrene-butadiene latex composite adhesive The polyaniline-copper complex powder is added to deionized water, stirred uniformly to obtain a dispersion, the sulfonated resin / styrene-butadiene latex emulsion is added to an ethanol solution, the dispersion is added under stirring, and then vacuum degassing is performed to prepare the styrene-butadiene latex composite adhesive.

2. A process for the preparation of a styrene butadiene latex composite binder as claimed in claim 1, wherein, Step S1: preparing styrene-butadiene latex emulsion, comprising the following steps: The 10-15 mass parts of complex surfactant solution is heated to 65-70℃ under stirring at 200-250r / min, and 5-10 mass parts of styrene, 5-8 mass parts of butadiene and 1-3 mass parts of initiator ammonium persulfate solution are added during stirring, and the temperature is maintained after heating for 1-1.5h to obtain the pre-reaction liquid. 1-5 mass parts of pre-reaction liquid and 1-5 mass parts of polybutadiene are added to 10-12 mass parts of complex surfactant solution, the dropping time is controlled for 1-2h, and at the same time, heating is performed to 60-70℃, and then reaction is performed for 2-3h to obtain the styrene-butadiene latex emulsion.

3. A process for the preparation of a styrene butadiene latex composite binder as claimed in claim 2, wherein, Step S2: preparing sulfonated phenolic resin, comprising the following steps: 9-12 mass parts of dichloromethane is weighed in a single-necked flask and stirred at a speed of 100-150r / min while controlling the temperature at 30-35℃, then 1-3 mass parts of phenolic resin is added, and stirring is continued at a speed of 100-150r / min, then 0.5-1 mass parts of nano ferric oxide is added, and the temperature is adjusted to 5-10℃, and mixing and stirring is performed at a speed of 550-600r / min for 30-35min, then 0.5-1 mass parts of sulfur trioxide-pyridine complex is added, stirring is maintained and reaction is performed for 20-30min, and the sulfonated phenolic resin is obtained by filtration, washing and drying.

4. A process for the preparation of a styrene butadiene latex composite binder as claimed in claim 3, wherein, Step S3: preparing sulfonated resin / styrene-butadiene latex emulsion, comprising the following steps: Mix 5-8 parts by mass of sulfonated phenolic resin with 100-110 parts by mass of deionized water and stir for 5-10 min to obtain a suspension, then drop into the styrene-butadiene latex emulsion, and stir at a speed of 600-650 r / min while dropping, after the dropping is completed, adjust the speed to 1200-1300 r / min and stir for 20-25 min, then vacuum degassing for 10-15 min to obtain a sulfonated resin / styrene-butadiene latex emulsion.

5. A process for the preparation of a styrene butadiene latex composite binder as claimed in claim 1, wherein, The step S4 for preparing the polyaniline-copper complex includes the following steps: Dissolve 1-3 parts by mass of aniline monomer in 100-105 parts by mass of 1-1.5 M hydrochloric acid solution, cool to 0-5°C in an ice bath to obtain an aniline solution, slowly drop the ammonium persulfate solution into the aniline solution while keeping the temperature at 0-5°C, and stir at a speed of 60-100 r / min for 1 h, then add the copper sulfate solution, warm to 25-30°C, and react for 2-2.5 h, remove the filtrate by suction filtration, wash the product with deionized water 3 times, then vacuum dry at 60-65°C for 5-6 h to obtain polyaniline-copper complex powder.

6. A process for the preparation of a styrene butadiene latex composite binder as claimed in claim 4, wherein, The step S5 for preparing the styrene-butadiene latex composite binder includes the following steps: Add 2-3 parts by mass of polyaniline-copper complex powder to 100-105 parts by mass of deionized water and stir uniformly to obtain a dispersion, add 20-25 parts by mass of styrene-butadiene latex to 40-50 parts by mass of ethanol solution and stir at a speed of 200-250 r / min for 30-35 min, then increase the speed to 400-500 r / min and add 10-15 parts by mass of the dispersion while stirring, then stir at a speed of 1000-1100 r / min for 30-35 min, vacuum degassing for 5-10 min, then remove the ethanol by rotary evaporation to adjust the viscosity, and obtain the styrene-butadiene latex composite binder.

7. A process for the preparation of a styrene butadiene latex composite binder as claimed in claim 2, wherein, The compounded surfactant solution is prepared by mixing sodium p-styrenesulfonate and sodium dodecyl sulfate at a mass ratio of 1:(1-2).

8. A process for the preparation of a styrene butadiene latex composite binder as claimed in claim 4, wherein, The concentration of the ammonium persulfate solution is 8-12 wt%.

9. A process for the preparation of a styrene butadiene latex composite binder as claimed in claim 4, wherein, The concentration of the copper sulfate solution is 0.4-0.8 wt%.

10. A styrene butadiene latex composite binder characterized by, It is prepared by the preparation process of the styrene-butadiene latex composite binder of any one of the above claims 1-9. It is prepared by the preparation process of the styrene-butadiene latex composite binder of any one of the above claims 1-9.

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