SBS modifier and its preparation method, use, asphalt coating composition and its preparation method, waterproof coiled material

Abstract

The present application discloses an SBS modifier and its preparation method, uses, an asphalt coating composition and its preparation method, and a waterproof coiled material. The preparation method of the SBS modifier includes: dissolving SBS in a first solvent to obtain an SBS solution; adding a mercapto compound to the SBS solution and carrying out solution graft polymerization at 50°C to 90°C to obtain a graft-modified SBS grafted with a mercapto group containing an alkyl group having any one of a hydroxyl group and a carboxyl group, or grafted with a mercapto group and an alkyl group substituted or unsubstituted by a hydroxyl group grafted through the mercapto group; adding a biomass carbon aerogel and the graft-modified SBS to a second solvent according to a mass ratio of 1:(0.5 to 1.5) to obtain a first mixture; adding concentrated sulfuric acid and sodium hypophosphite to the first mixture and carrying out a reaction under a temperature condition of 120°C to 130°C to obtain the SBS modifier. The preparation method of the SBS modifier changes the polarity of SBS by grafting through a mercapto group, that is, making it closer to the polarity of asphalt; the graft-modified SBS reacts with the biomass carbon aerogel to form a macromolecular compound, preventing the performance attenuation during the aging process of the coiled material.

Description

Technical Field

[0001] This application belongs to the technical field of waterproof materials, and particularly relates to an SBS modifier and its preparation method, uses, asphalt coating composition and its preparation method, and waterproof coiled material. Background Art

[0002] Currently, the thermoplastic elastomer styrene-butadiene-styrene triblock copolymer (SBS) is the most commonly used asphalt modifier in asphalt waterproof coiled materials, which can significantly improve the high-temperature aging resistance and low-temperature bending resistance of asphalt. However, there are differences in structure, molecular weight, polarity, etc. between matrix asphalt and SBS, resulting in phase separation between the SBS modifier and asphalt during long-term storage of SBS-modified asphalt, leading to the problem that the performance does not meet the standards after 3 months or longer. Moreover, SBS has double bonds in the polybutadiene segment (PB segment), so the presence of unsaturated bonds will cause it to easily react with oxygen during long-term aging, and the aging resistance drops sharply. In view of this, researchers have proposed technical solutions for chemically modifying SBS to improve the aging resistance of asphalt. Common methods for chemically modifying SBS include catalytic hydrogenation, grafting modification, epoxidation modification, sulfonation modification, halogenation modification, thiol-ene click reaction, etc.

[0003] The existing preparation method of SBS-modified asphalt discloses that a stabilizer is prepared by the esterification reaction of styrene-maleic anhydride copolymer and long-chain alcohol under acid catalysis, and then the stabilizer is physically adsorbed on the polystyrene and asphaltene macromolecules of SBS through physical action to enhance the dispersion effect of light components in asphalt on SBS and asphaltene, so that SBS-modified asphalt has long-term thermal storage stability. Although this method achieves the effect of modifying asphalt, it does not have long-term stability compared with the structure formed by chemical reactions during long-term storage of asphalt. The prior art also discloses an asphalt modifier, using vinyltrimethoxysilane as a crosslinking agent and dibenzoyl peroxide as an initiator to crosslink SBS polymer, maleic anhydride and methyl methacrylate to prepare modified SBS. Although this method makes the adhesion effect of SBS polymer better and improves the binding force between the SBS modifier and asphalt, the preparation process is relatively cumbersome. Summary of the Invention

[0004] The embodiments of this application provide an SBS modifier and its preparation method, which change the polarity of SBS by thiol grafting to make it closer to the polarity of asphalt, and then react with biomass carbon aerogel to generate a macromolecular compound with relatively stable structure, preventing the performance of asphalt waterproof coiled materials containing the SBS modifier from significantly deteriorating during long-term aging.

[0005] In a first aspect, the present application provides a method for preparing an SBS modifier, comprising: dissolving SBS in a first solvent to obtain an SBS solution; adding a mercapto compound to the SBS solution, and performing solution graft polymerization at a temperature of 50°C to 90°C to obtain graft-modified SBS, wherein the graft-modified SBS is grafted with a mercapto group to an alkyl group containing at least one of a hydroxyl group and a carboxyl group, or is grafted with a mercapto group and an alkyl group substituted or unsubstituted by a hydroxyl group through the mercapto group; adding biomass carbon aerogel and graft-modified SBS to a second solvent according to a mass ratio of 1:(0.5 to 1.5) to obtain a first mixture; adding concentrated sulfuric acid and sodium hypophosphite to the first mixture, and reacting at a temperature of 120°C to 130°C to obtain the SBS modifier.

[0006] According to an embodiment of the first aspect of the present application, SBS has a linear structure, and the weight-average molecular weight of SBS (ethylene-butadiene-styrene triblock copolymer) is 100,000 to 450,000.

[0007] According to an embodiment of the first aspect of the present application, the weight-average molecular weight of SBS is 150,000 to 300,000.

[0008] According to an embodiment of the first aspect of the present application, the content of the styrene segment in SBS is 20% to 30%; the melt flow rate is 0 g / 10 min to 1 g / 10 min.

[0009] According to an embodiment of the first aspect, the first solvent is selected from at least one of toluene, cyclohexane, CCl 4 、CHCl 3 and the like.

[0010] According to an embodiment of the first aspect of the present application, during the process of dissolving SBS in the first solvent, the temperature of the first solvent is raised to 30°C to 50°C to accelerate the dissolution rate of SBS.

[0011] According to an embodiment of the first aspect of the present application, a mercapto compound is added to the SBS solution, and solution graft polymerization is carried out using an initiator at a temperature of 50°C to 90°C.

[0012] According to an embodiment of the first aspect, the addition amount of the initiator is 0.5 wt% to 3 wt% of the mass of SBS. The initiator is azobisisobutyronitrile. Optionally, the addition amount of azobisisobutyronitrile is 0.5 wt% to 2 wt% of the mass of SBS.

[0013] According to an embodiment of the first aspect, the graft-modified SBS is prepared through the following steps: dissolving SBS in a first solvent under the protection of an inert atmosphere to obtain an SBS solution; adding a mercapto compound and an initiator to the SBS solution, and raising the temperature to 50°C to 90°C for solution graft polymerization to obtain the graft-modified SBS.

[0014] According to an embodiment of the first aspect, a mercapto compound and an initiator are added to an SBS solution, and the temperature is raised to 50°C to 90°C for solution graft polymerization to obtain a modified SBS mixture.

[0015] According to an embodiment of the first aspect of the present application, the steps of preparing the graft-modified SBS further include: dropping the modified SBS mixture into methanol for purification treatment to prepare the graft-modified SBS.

[0016] According to an embodiment of the first aspect, the mass ratio of SBS to the mercapto compound is 20:(5 - 15).

[0017] According to an embodiment of the first aspect, the mercapto compound is selected from at least one of mercaptoethanol, n-dodecyl mercaptan, and mercaptopropionic acid.

[0018] According to an embodiment of the first aspect of the present application, the biomass carbon aerogel and the graft-modified SBS are added to a second solvent at a mass ratio of 1:(0.5 - 1.5), and the temperature is raised to 50°C to 90°C.

[0019] According to an embodiment of the first aspect, the second solvent is selected from dimethyl sulfoxide (DMSO) and dimethylformamide (DMF).

[0020] According to an embodiment of the first aspect of the present application, concentrated sulfuric acid and sodium hypophosphite are added to the first mixture, and the reaction is carried out at a temperature of 120°C to 130°C, and heat preservation treatment is carried out under an inert atmosphere to obtain an SBS modifier.

[0021] According to an embodiment of the first aspect of the present application, the process parameters that need to be satisfied when concentrated sulfuric acid and sodium hypophosphite are added to the first mixture, the reaction is carried out at a temperature of 120°C to 130°C, and heat preservation treatment is carried out under an inert atmosphere are: the pressure is -80 KPa to -50 KPa, an inert atmosphere is introduced, and the heat preservation treatment time is 2.5 hours to 4 hours.

[0022] According to an embodiment of the first aspect of the present application, the biomass carbon aerogel in the step of obtaining the first mixture is prepared through the following steps: mixing wood materials and water according to a preset ratio for hydrothermal treatment to obtain a first product; washing and freezing the first product to obtain a frozen product; freeze-drying the frozen product to obtain the biomass carbon aerogel.

[0023] According to an embodiment of the first aspect of the present application, the wood materials are selected from the sawdust of at least one of eucalyptus, pine, poplar, elm, willow, apricot, birch, maple, camphor, and shrubs.

[0024] According to an embodiment of the first aspect, the preset ratio of the wood materials to water is 1:(5 - 10).

[0025] According to the embodiments of the first aspect of the present application, the process parameters for the hydrothermal treatment of wood materials and water need to satisfy: reacting at 200°C to 350°C for 10 hours to 15 hours.

[0026] According to the embodiments of the first aspect, the freezing temperature for freezing the first product is -40°C to -10°C, and the freezing time is 15 hours to 30 hours.

[0027] According to the embodiments of the first aspect, the above-mentioned inert atmosphere is formed by at least one selected from nitrogen, argon, and neon.

[0028] In the second aspect, the present application provides an SBS modifier, which is prepared according to the above-mentioned preparation method of the SBS modifier.

[0029] In the third aspect, the present application provides an asphalt coating composition, including raw materials with the following rubber addition percentages: asphalt, 100 PHR; asphalt softening oil, 5 PHR to 10 PHR; SBS modifier, 3 PHR to 5 PHR; the SBS modifier is the SBS modifier prepared according to the above-mentioned preparation method of the SBS modifier; SBR modifier, 2 PHR to 4 PHR; rubber powder, 30 PHR to 50 PHR; powder, 50 PHR to 70 PHR.

[0030] According to the embodiments of the third aspect, the asphalt is selected from 70# asphalt, 90# asphalt or a combination thereof.

[0031] According to the embodiments of the third aspect, the asphalt softening oil is at least one of naphthenic oil, soybean oil, and aromatic oil.

[0032] According to the embodiments of the third aspect, the rubber powder is 60-mesh to 80-mesh tire rubber powder, with a rubber content of 30% to 50% and an ash content of 10% to 30%.

[0033] According to the embodiments of the third aspect, the powder is selected from heavy calcium powder and talc powder, with a particle size of 200 mesh to 400 mesh.

[0034] In the fourth aspect, the present application provides a preparation method of an asphalt coating composition, including: mixing asphalt and asphalt softening oil according to the ratio of the asphalt coating composition to obtain a first mixture; heating the first mixture to completely melt the asphalt, adding the SBS modifier and the SBR modifier to the first mixture for dispersion to obtain a second mixture; adding rubber powder to the second mixture for dispersion to obtain a third mixture; adding powder to the third mixture for dispersion to obtain the asphalt coating composition.

[0035] According to the embodiments of the fourth aspect, the first mixture is heated to 130°C to 150°C to completely melt the asphalt.

[0036] According to an embodiment of the fourth aspect, rubber powder is added to the second mixture and the temperature is raised to 180°C to 190°C for dispersion.

[0037] According to an embodiment of the fourth aspect, powder is added to the third mixture and dispersion is carried out at 180°C to 190°C.

[0038] In a fifth aspect, the present application provides a waterproof coiled material, comprising: a main substrate; an asphalt coating layer provided on at least one surface of the main substrate, and the asphalt coating layer is formed by coating the above-mentioned asphalt coating composition on at least one surface of the main substrate.

[0039] According to an embodiment of the fifth aspect, the waterproof coiled material further comprises an isolation and protection layer covering the asphalt coating layer.

[0040] According to an embodiment of the fifth aspect, the main substrate is selected from a polyester tire, a fiberglass tire or a polyester-fiberglass tire.

[0041] According to an embodiment of the fifth aspect, the isolation and protection layer is a single-sided release film made of transparent PET material.

[0042] In the preparation method of the SBS modifier according to the embodiment of the present application, SBS is grafted through a mercapto group to change the polarity of SBS, and grafted modified SBS is obtained, making the grafted modified SBS closer to the polarity of asphalt; the grafted modified SBS then reacts with biomass carbon aerogel to generate a macromolecular compound with a relatively stable structure, that is, the SBS modifier, to prevent the performance of the asphalt waterproof coiled material containing the SBS modifier from significantly deteriorating during long-term aging. Description of the Drawings

[0043] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings required to be used in the embodiments of the present application. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative efforts.

[0044] Figure 1 is a schematic flow chart of the preparation method of the SBS modifier provided by the embodiment of the present application;

[0045] Figure 2 is a schematic flow chart of the preparation method of the asphalt coating composition provided by the present application;

[0046] Figure 3 is a schematic structural diagram of the waterproof coiled material provided by the embodiment of the present application.

[0047] Explanation of the reference numerals: 1, main substrate; 2, asphalt coating layer; 3, release protection layer. Detailed Embodiments

[0048] The features and exemplary embodiments of various aspects of the present application will be described in detail below. To make the objectives, technical solutions, and advantages of the present application clearer and more understandable, the present application will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only intended to explain the present application and not to limit the present application. For those skilled in the art, the present application can be implemented without some of these specific details. The following description of the embodiments is only to provide a better understanding of the present application by showing examples of the present application.

[0049] It should be noted that in this document, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device. Without further limitation, elements defined by the statement "including..." do not exclude the existence of additional identical elements in the process, method, article or device including the said elements.

[0050] As a commonly used asphalt modifier, SBS can significantly improve the high-temperature aging resistance and low-temperature bending resistance of asphalt. However, due to the differences in structure, molecular weight, and polarity between SBS and asphalt, SBS and asphalt undergo phase separation during long-term storage of SBS-modified asphalt, resulting in the problem that the performance does not meet the standards after 3 months or longer. The double bonds contained in asphalt are easily reacted with oxygen, causing the aging resistance of asphalt waterproofing membranes to drop sharply.

[0051] The inventors of the present application found that compared with the aforementioned several other methods, the thiol-ene click reaction is simple and easy to perform, has high selectivity, and produces no by-products.

[0052] To solve the problems of the prior art, the embodiments of the present application provide an SBS modifier and its preparation method, use, asphalt coating composition and its preparation method, and waterproofing membrane. First, the SBS modifier and its preparation method provided by the embodiments of the present application will be introduced below.

[0053] First, prepare biomass carbon aerogel as the raw material for preparing the SBS modifier.

[0054] Preparation of Biomass Carbon Aerogel

[0055] The preparation of biomass carbon aerogel includes:

[0056] B1. Mix the wood material and water according to a preset ratio and perform hydrothermal treatment to obtain a first product.

[0057] B2. Wash and freeze the first product to obtain a frozen product.

[0058] B3. Perform freeze-drying treatment on the frozen product to obtain a biomass carbon aerogel.

[0059] The morphology of the biomass carbon aerogel prepared in the embodiments of the present application is solid powder.

[0060] In some embodiments of the present application, the wood material is selected from the chips of at least one of eucalyptus, pine, poplar, elm, willow, apricot, birch, maple, camphor, and shrubs. Among them, the shrubs are selected from shrubs with woody fibers in their branches or roots.

[0061] In the embodiments of the present application, mixing the wood material and water according to a preset ratio and performing hydrothermal treatment includes: mixing the wood material and water according to a preset ratio to obtain a first mixture; adjusting the pH value of the first mixture to 8-12 and adding a cross-linking agent for dispersion, and reacting at 180°C-200°C for 8-12 hours to obtain a black carbon aerogel crude product, that is, the first product. It should be noted that the water used to obtain the first mixture is distilled water.

[0062] In some embodiments of the present application, the preset ratio of the wood material to water is 1:(5-10). Exemplarily, the preset ratio of the wood material to water is 1:5.1, 1:5.15, 1:5.2, 1:5.5, 1:5.8, 1:6.0, 1:6.5, 1:6.8, 1:6.9, 1:7.0, 1:7.2, 1:7.5, 1:7.8, 1:8.0, 1:8.5, 1:8.8, 1:9.0, 1:9.3, 1:9.5, 1:9.8, 1:9.9.

[0063] In the embodiments of the present application, the cross-linking agent is epichlorohydrin or ethylene oxide. In addition to the epoxy group in the cross-linking agent forming covalent bonds with the hydroxyl, amine, and carboxyl active groups in the wood material, the chloropropyl group in the cross-linking agent will undergo a substitution reaction with the nucleophilic substances or nucleophilic groups in the wood material to generate a new compound with a cross-linked structure, thereby forming a macromolecular compound. The ethylene oxide in the cross-linking agent forms covalent bonds with the hydroxyl, amine, and carboxyl active groups in the wood material and can also form a macromolecular compound with a certain molecular weight.

[0064] In some embodiments, the mass ratio of the crosslinking agent to the wood material is 1:(1.2 - 2). Exemplarily, the mass ratio of the crosslinking agent to the wood material is 1:1.25, 1:1.3, 1:1.35, 1:1.5, 1:1.6, 1:1.7, 1:1.75, 1:1.8, 1:1.9, 1:1.95.

[0065] In the embodiments of the present application, the pH value of the first mixture can be adjusted to 8 - 12 by adding an alkaline compound to the first mixture. The alkaline compound is selected from alkali metal hydroxides or ammonia water. Exemplarily, sodium hydroxide, potassium hydroxide, or ammonia water can be added to adjust the pH value of the first mixture to 8, 8.5, 9, 9.7, 10, 10.5, 11, 11.5, 12.

[0066] In the embodiments of the present application, washing the first product includes: successively performing multiple cleaning treatments on the first product using distilled water, ethanol, or isopropanol. That is, first wash the first product multiple times with distilled water, then use ethanol, or use ethanol and isopropanol, or use isopropanol to wash multiple times to remove the excess alkali solution and solvent on the crude carbon aerogel product.

[0067] In some embodiments of the present application, the freezing temperature for freezing the washed first product is -40°C to -10°C, and the freezing duration is 15 hours to 30 hours.

[0068] In the embodiments of the present application, the first product after washing treatment can maintain the original structure in the wood material after freezing treatment. Freeze-drying the frozen product rapidly vaporizes the water in the woody material. During the freeze-drying process, it is not affected by surface tension, so that the internal structure in the wood material can be well preserved, especially for materials with porous and easily collapsible structures, thereby enabling the preparation of biomass carbon aerogels with a large specific surface area.

[0069] Exemplarily, the preparation of biomass carbon aerogel includes: placing 6 g to 10 g of wood material, namely dry pine powder, in a 100 ml beaker, adding 10 ml to 12 ml of deionized water to obtain a first mixture; adding 5 ml to 8 ml of a NaOH solution with a mass fraction of 2% to 5% to the first mixture, adjusting the pH value to 8 to 12, adding epichlorohydrin under magnetic stirring and stirring until evenly mixed, the mass ratio of epichlorohydrin to wood material is 1:(1.2 to 2), transferring the obtained homogeneous mixture to a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 180°C to 200°C for 8 to 12 h to obtain a black carbon aerogel crude product, namely the first product; washing the first product with distilled water and ethanol three times each in sequence and then performing a freezing treatment, the freezing temperature is -20°C to -10°C, the freezing time is 20 hours to 25 hours to obtain a frozen product; placing the frozen product in a freeze dryer for freeze-drying treatment to obtain the biomass carbon aerogel.

[0070] Figure 1 The flowchart showing the preparation method of the SBS modifier provided by the embodiment of the present application is shown.

[0071] Preparation of SBS modifier

[0072] The preparation method of the SBS modifier includes:

[0073] S1. Dissolve SBS in a first solvent to obtain an SBS solution;

[0074] S2. Add a mercapto compound to the SBS solution, perform solution graft polymerization under the temperature condition of 50°C to 90°C to obtain graft-modified SBS, and the graft-modified SBS is grafted with an alkyl group containing any one of a hydroxyl group and a carboxyl group through a mercapto group, or grafted with a mercapto group and an alkyl group substituted or unsubstituted by a hydroxyl group through a mercapto group;

[0075] S3. Add the biomass carbon aerogel and the graft-modified SBS to a second solvent according to a mass ratio of 1:(0.5 to 1.5) to obtain a first mixed solution;

[0076] S4. Add concentrated sulfuric acid and sodium hypophosphite to the first mixed solution and react under the temperature condition of 120°C to 130°C to obtain the SBS modifier.

[0077] The preparation method of the SBS modifier in the embodiment of the present application makes SBS change its polarity through mercapto grafting to obtain graft-modified SBS, making the graft-modified SBS closer to the polarity of asphalt; the graft-modified SBS reacts with the biomass carbon aerogel to generate a macromolecular compound with a relatively stable structure, that is, an SBS modifier with stable performance and good durability is prepared, preventing the performance of the waterproof coiled material containing the SBS modifier from significantly deteriorating during long-term aging.

[0078] In some embodiments of the present application, SBS has a linear structure, and the weight-average molecular weight of SBS (ethylene-butadiene-styrene triblock copolymer) is 100,000 to 450,000.

[0079] In some embodiments of the present application, the weight-average molecular weight of SBS is preferably 150,000 to 300,000.

[0080] In some embodiments of the present application, the content of the styrene block in SBS is 20% to 30%, and the melt flow rate is 0 g / 10 min to 1 g / 10 min.

[0081] In some embodiments, the first solvent is selected from at least one of toluene, cyclohexane, CCl 4 , CHCl 3 and the like.

[0082] In some embodiments of the present application, during the process of dissolving SBS in the first solvent, the temperature of the first solvent is raised to 30°C to 50°C to accelerate the dissolution rate of SBS. Optionally, the dissolution of SBS in the first solvent is carried out under the protection of an inert atmosphere. Among them, the inert atmosphere is formed by at least one selected from nitrogen, argon, and neon. For example, the inert atmosphere is formed by nitrogen alone.

[0083] In some embodiments of the present application, a mercapto compound is added to the SBS solution, and solution graft polymerization is carried out using an initiator under the temperature condition of 50°C to 90°C.

[0084] In the embodiments of the present application, the addition amount of the initiator is 0.5 wt% to 3 wt% of the mass of SBS.

[0085] In some embodiments of the present application, the initiator is azobisisobutyronitrile (AIBN). Optionally, the addition amount of azobisisobutyronitrile (AIBN) is 0.5 wt% to 2 wt% of the mass of SBS.

[0086] In some embodiments of the present application, the process parameters required for the solution graft polymerization of the SBS solution and the mercapto compound are: rotation speed 250 rpm to 350 rpm, and the time of solution graft polymerization is 1 hour to 2 hours.

[0087] In some embodiments of the present application, a mercapto compound and an initiator are added to the SBS solution, and the temperature is raised to 50°C to 90°C for solution graft polymerization to obtain a modified SBS mixture.

[0088] In some embodiments of the present application, the mercapto compound is selected from at least one of mercaptoethanol, n-dodecyl mercaptan, and mercaptopropionic acid. Among them, mercaptopropionic acid is selected from 2-mercaptopropionic acid, 3-mercaptopropionic acid or a combination thereof. After mercaptopropionic acid is grafted onto SBS by reacting with the vinyl double bond of SBS through mercapto grafting, the mercapto (-SH) and carboxyl (-COOH) groups contained in the graft-modified SBS can undergo an esterification reaction with the carboxyl (-COOH) and hydroxyl (-OH) groups contained in the biomass carbon aerogel to generate a macromolecular compound, thereby improving the stability of the asphalt coating material and waterproof coiled material containing the SBS modifier.

[0089] In some embodiments of the present application, the mass ratio of SBS to the mercapto compound is 20:(5 - 15). That is, the mass ratio of SBS to mercaptoethanol is 20:(5 - 15). Or, the mass ratio of SBS to mercaptoethanol and n-dodecyl mercaptan is 20:(5 - 15). Or, the mass ratio of SBS to n-dodecyl mercaptan is 20:(5 - 15). Or, the mass ratio of SBS to mercaptopropionic acid is 20:(5 - 15). Exemplarily, the mass ratio of SBS to mercaptoethanol, the mass ratio of SBS to mercaptoethanol and n-dodecyl mercaptan, the mass ratio of SBS to n-dodecyl mercaptan, and the mass ratio of SBS to mercaptopropionic acid can all be 20:5.5, 20:6, 20:7.2, 20:7.5, 20:7.8, 20:8, 20:9, 20:10, 20:12, 20:13.5, 20:14, 20:15.

[0090] In some embodiments of the present application, the preparation method of the graft-modified SBS further includes a purification treatment of the modified SBS mixture, including: dropping the modified SBS mixture into methanol for purification treatment to obtain a graft-modified SBS with a higher purity.

[0091] In some embodiments of the present application, dropping the modified SBS mixture into methanol for purification treatment includes: dropping the modified SBS mixture into methanol for precipitation, filtration, and drying, dissolving the dried product with a first solvent and repeating the steps of precipitation, filtration, and drying in methanol multiple times, and drying the obtained target product to a constant weight to obtain the graft-modified SBS.

[0092] Exemplarily, under nitrogen protection, 20 g of SBS was dissolved in 200 ml of toluene, and the toluene was heated to 50 °C to completely dissolve SBS, obtaining an SBS solution; 5 g to 15 g of mercaptoethanol and AIBN accounting for 0.1 wt.% to 2 wt.% of the mass of SBS were added to the SBS solution, and the SBS solution added with mercaptoethanol and AIBN was heated to 80 °C for reaction, and solution graft polymerization was carried out at 80 °C and 250 rpm for 1 hour to 2 hours to obtain a modified SBS mixture; the modified SBS mixture was dropped into methanol for precipitation and filtration, and the filtered sample was vacuum dried at 70 °C for 12 hours to 15 hours; the dried sample was dissolved in toluene, and then successively precipitated, filtered, and vacuum dried in methanol, and the drying product was dissolved and the above steps of precipitation, filtration, and vacuum drying were repeated 3 times, and the obtained product was placed in an oven at 70 °C and dried to constant weight to obtain graft-modified SBS. The mercaptoethanol therein can also be replaced by mercaptopropionic acid, n-dodecyl mercaptan, or replaced by a mixture of mercaptoethanol and n-dodecyl mercaptan, or a mixture of mercaptopropionic acid and n-dodecyl mercaptan. Optionally, in some embodiments, the content of mercaptopropionic acid can be partially in excess to avoid the reduction of mercaptopropionic acid caused by the self-polymerization of mercaptopropionic acid, or the polymerization of mercaptopropionic acid with mercaptoethanol, or the polymerization of mercaptopropionic acid with n-dodecyl mercaptan.

[0093] In the embodiments of the present application, SBS is mixed with mercaptoethanol, so that SBS grafts corresponding functional groups through mercapto groups, and graft-modified SBS grafted with an alkyl group containing a hydroxyl group through mercapto groups, or grafted with a mercapto group and an alkyl group substituted by a hydroxyl group through mercapto groups is prepared. Furthermore, the hydroxyl group or mercapto group in the molecular structure of the graft-modified SBS can undergo an esterification reaction with the carboxyl group in the biomass carbon aerogel to form a macromolecular compound, that is, an SBS modifier, so that the performance of the asphalt coating composition containing the SBS modifier is more stable. Exemplarily, SBS reacts with mercaptoethanol to form a compound with the following structural formula:

[0094]

[0095] In Formula (1) and Formula (2), both represent the SBS main chain skeleton. In some embodiments of the present application, mercaptoethanol is used as a modifier for SBS. SBS and mercaptoethanol react to form graft-modified SBS grafted with an alkyl group containing a hydroxyl group through mercapto groups, or form graft-modified SBS containing a mercapto group and an alkyl group substituted by a hydroxyl group through mercapto groups. Thus, the graft-modified SBS can undergo an esterification reaction with the carboxyl group in the biomass carbon aerogel through the hydroxyl group or mercapto group on its side chain to prepare a compound with a macromolecular structure, that is, an SBS modifier.

[0096] In addition, similar reactions can occur between SBS and mercaptoethanol and dodecyl mercaptan, or between SBS and dodecyl mercaptan. Through grafting with mercapto groups, graft-modified SBS close to the polarity of asphalt can be obtained from SBS, which further reacts with the biomass carbon aerogel to form a macromolecular compound connected by covalent bonds, making the performance of the asphalt coating material containing the SBS modifier more stable. It should be noted that since dodecyl mercaptan contains a mercapto group, after it is connected to the butadiene double bond of SBS through the mercapto group, the resulting product is an alkyl group grafted through the mercapto group, or graft-modified SBS grafted with a mercapto group and an alkyl group grafted through the mercapto group. It can be understood that mercaptoethanol, mercaptoethanol and dodecyl mercaptan, and dodecyl mercaptan can all be replaced by other alcohol compounds containing mercapto groups. The activities of the mercapto group and the alcohol hydroxyl group are relatively high. The double bond of the vinyl group in SBS reacts with the mercapto group under the action of an initiator and is grafted onto the SBS molecular chain, and the alcohol hydroxyl group reacts with the carboxyl group of the biomass carbon aerogel to obtain a macromolecular compound.

[0097] In some other embodiments of the present application, the mercapto compound can also be selected from at least one of 4-mercaptobutyric acid, 1-propanethiol, 1-butanethiol, phenylthiol, 1-pentanethiol, 1-hexanethiol, 2-phenylethylthiol, 2-bromobenzenethiol, 4-bromobenzenethiol, and 4-hydroxybenzenethiol. That is, mercaptoethanol can also be replaced by a combination of one or more of these mercapto compounds.

[0098] In the embodiments of the present application, in the step of adding concentrated sulfuric acid and sodium hypophosphite to the first mixture, concentrated sulfuric acid acts as a catalyst to catalyze the reaction between the biomass carbon aerogel and the graft-modified SBS. The dosage of concentrated sulfuric acid is 0.2% - 0.8% of the total mass of the biomass carbon aerogel and the graft-modified SBS, and the mass concentration of concentrated sulfuric acid is 98% or more. Sodium hypophosphite is used to maintain the appearance of the graft-modified SBS, and the dosage is 0.05 wt.% - 0.1 wt.% of the mass of the graft-modified SBS. Among them, the carboxyl group (-COOH) contained in the biomass carbon aerogel can undergo an esterification reaction with the hydroxyl group (-OH) or mercapto group (-SH) of the graft-modified SBS to form a macromolecular compound with a relatively stable structure, preventing the performance of the waterproof coil containing the SBS modifier from significantly deteriorating during long-term aging.

[0099] In some embodiments of the present application, the biomass carbon aerogel and the graft-modified SBS are added to the second solvent at a mass ratio of 1:(0.5 - 1.5) and heated to 50°C - 90°C to promote the dissolution and dispersion of the graft-modified SBS.

[0100] In some embodiments, the second solvent is selected from dimethyl sulfoxide (DMSO) and dimethylformamide (DMF).

[0101] In some embodiments, concentrated sulfuric acid and sodium hypophosphite are added to the first mixed solution, and the reaction is carried out at a temperature of 120°C to 130°C, and heat preservation treatment is carried out under an inert atmosphere to obtain an SBS modifier.

[0102] In some embodiments, the process parameters that need to be satisfied for heat preservation treatment under an inert atmosphere are: the pressure is -80 KPa to -50 KPa, an inert atmosphere is introduced, and the heat preservation treatment time is 2.5 hours to 4 hours. Among them, the inert atmosphere is formed by at least one selected from nitrogen, argon, and neon. For example, the inert atmosphere is formed by nitrogen.

[0103] In some embodiments of the present application, the preparation method of the SBS modifier further includes: dropping the first mixed solution added with concentrated sulfuric acid and sodium hypophosphite and subjected to heat preservation treatment into methanol for precipitation, filtration, and drying, redissolving the product obtained by the first purification with a second solvent and repeating the steps of precipitation, filtration, and drying multiple times, and drying the obtained target product to a constant weight to obtain the SBS modifier. Among them, the first mixed solution is in a liquid state after heat preservation treatment, and the product after heat preservation treatment also needs to be purified.

[0104] The preparation method of the SBS modifier in the embodiments of the present application reacts graft-modified SBS with biomass carbon aerogel to generate a macromolecular compound with a relatively stable structure, that is, the SBS modifier, to prevent the performance of the waterproof coiled material containing the SBS modifier from significantly deteriorating during long-term aging. Among them, the macromolecular compound is more stable in structure and is not prone to phase separation in the formulation of the asphalt coating composition.

[0105] The SBS modifier in the embodiments of the present application can reduce its own polarity and be compatible with asphalt molecules through the ethylidene or dodecylidene part grafted with a mercapto group, preventing phase separation due to different polarities of the components of the asphalt coating composition; the biomass carbon aerogel part can improve the anti-aging performance of the waterproof coiled material while utilizing its own characteristics of good heat resistance and heat insulation, and increase the physical entanglement with asphalt molecules by using its own powdery structure, increasing the resistance to phase separation and preventing phase separation of the waterproof coiled material.

[0106] SBS modifier

[0107] The SBS modifier in the embodiments of the present application is prepared according to the above preparation method of the SBS modifier. The SBS modifier in the embodiments of the present application reacts graft-modified SBS with biomass carbon aerogel to generate a macromolecular compound with a relatively stable structure, that is, an SBS modifier with stable performance and good durability, to prevent the performance of the waterproof coiled material containing the SBS modifier from significantly deteriorating during long-term aging.

[0108] In the embodiments of the present application, the SBS modifier prepared by reacting biomass carbon aerogel in the form of solid powder with graft-modified SBS remains in the form of solid powder.

[0109] Use of SBS modifier

[0110] In some embodiments of the present application, there is provided a use of an SBS modifier for modifying asphalt, so that the asphalt has good stability and prevents phase separation.

[0111] Asphalt coating composition

[0112] The embodiments of the present application also provide an asphalt coating composition, comprising raw materials with the following rubber addition percentage by weight (PHR): asphalt, 100 PHR; asphalt softening oil, 5 PHR to 10 PHR; SBS modifier, 3 PHR to 5 PHR; the SBS modifier is the SBS modifier prepared according to the above-mentioned SBS modifier preparation method; SBR modifier, 2 PHR to 4 PHR; rubber powder, 30 PHR to 50 PHR; powder, 50 PHR to 70 PHR.

[0113] In some embodiments of the present application, the asphalt is selected from 70# asphalt, 90# asphalt or a combination thereof.

[0114] In some embodiments, the asphalt softening oil is selected from at least one of naphthenic oil, soybean oil, and aromatic oil.

[0115] In some embodiments of the present application, the rubber powder is 60-mesh to 80-mesh tire rubber powder, with a rubber content of 30% to 50% and an ash content of 10% to 30%.

[0116] In some embodiments, the powder is selected from heavy calcium powder and talc powder, with a particle size of 200 mesh to 400 mesh.

[0117] Preparation method of asphalt coating composition

[0118] Figure 2 The flow diagram showing the preparation method of the asphalt coating composition provided by the embodiments of the present application is shown.

[0119] A preparation method of an asphalt coating composition, comprising:

[0120] C1. Mix asphalt and asphalt softening oil according to the ratio of the asphalt coating composition to obtain a first mixture;

[0121] C2. Heat the first mixture until all the asphalt is melted, and add the SBS modifier and the SBR modifier to the first mixture for dispersion to obtain a second mixture;

[0122] C3. Add rubber powder to the second mixture for dispersion to obtain a third mixture;

[0123] C4. Add powder to the third mixture for dispersion to obtain an asphalt coating composition.

[0124] In some embodiments, the mixture of asphalt and asphalt softening oil is heated to 130°C to 150°C to completely melt the 70# asphalt.

[0125] In some embodiments of the present application, when adding SBS modifier and SBR modifier to the first mixture for dispersion, the temperature can be raised to 160°C to 180°C and kept warm for 1 hour to 1.5 hours.

[0126] In some embodiments, add rubber powder to the second mixture and heat it to 180°C to 190°C for dispersion.

[0127] In some embodiments of the present application, add rubber powder to the second mixture, heat it to 180°C to 190°C, and disperse it at 500 rpm to 800 rpm for 3 hours to 4 hours.

[0128] In some embodiments, add powder to the third mixture and disperse it at 180°C to 190°C.

[0129] In some embodiments of the present application, add powder to the third mixture, disperse it at 180°C to 190°C and 800 rpm to 1000 rpm for 1 hour to 2 hours.

[0130] Waterproof coiled material

[0131] As Figure 3 shown, the embodiments of the present application further provide a waterproof coiled material, including a main substrate; and an asphalt coating layer provided on at least one surface of the main substrate, and the asphalt coating layer is formed by coating the above-mentioned asphalt coating composition on at least one surface of the main substrate.

[0132] In some embodiments, the waterproof coiled material further includes an isolation and protection layer covering the asphalt coating layer.

[0133] In some embodiments, the main substrate is made of a reinforcing material. The main substrate is selected from polyester tire, fiberglass tire or polyester fiberglass tire. The isolation and protection layer is a single-sided release film made of transparent PET material, with a thickness of 0.001 mm to 0.035 mm, which is coated with solvent-free silicone oil, and the release force is 0.1 N / 25 mm to 0.5 N / 25 mm.

[0134] In the embodiments of the present application, the SBS modifier improves the stability of the waterproof coiled material during long-term storage. On the one hand, after SBS is modified, the SBS modifier is obtained and stably exists in the asphalt coating composition, making the SBS modifier compatible with the asphalt component and preventing the occurrence of phase separation. On the other hand, biomass carbon aerogel is an anti-aging material that is resistant to high and low temperatures and has relatively stable properties. When the SBS modifier and biomass carbon aerogel are jointly applied to the asphalt coating composition, it can effectively prevent the performance attenuation of the waterproof coiled material containing the asphalt coating composition in a short time.

[0135] Test part

[0136] The following are the grades / models or available sources of some raw materials and reagents: SBS, grade 411, manufacturer is Yueyang Baling Petrochemical. SBR modifier, grade 095, manufacturer is Yueyang Baling Petrochemical. Asphalt softening oil, naphthenic oil, soybean oil, aromatic oil; rubber powder, 60-mesh to 80-mesh tire rubber powder, in which the mass content of rubber is 30% to 50%, and the ash content is 10% to 30%, manufacturer is Sanming Hongyuan; mercaptoethanol, purchased from Sinopharm Chemical Reagent Co., Ltd.; azobisisobutyronitrile (AIBN), purchased from Shandong Huayu Chemical Technology Co., Ltd.

[0137] Preparation of biomass carbon aerogel

[0138] Mix 10 g of wood materials (dry pine powder and eucalyptus powder with a mass ratio of 1:1) and distilled water according to a mass ratio of 10:12 to obtain a first mixture; add a NaOH solution with a mass fraction of 2.5% to the first mixture, adjust the pH value of the first mixture to 9, add 6.66 g of epichlorohydrin under magnetic stirring and stir until evenly mixed, transfer the obtained homogeneous mixture to a stainless steel reaction kettle with a polytetrafluoroethylene inner liner, completely seal it, and place the stainless steel reaction kettle in an electrothermal blast drying oven for hydrothermal treatment at 200 °C. The reaction time for hydrothermal treatment is 12 hours, and then it is naturally cooled to room temperature to obtain a first product.

[0139] Wash the first product with distilled water and ethanol successively 3 times each, then put it in the refrigerator and freeze it at -15 °C for 24 hours to obtain a frozen product as a sample; dry the frozen sample in a freeze dryer to prepare biomass carbon aerogel.

[0140] Preparation of graft-modified SBS

[0141] Preparation of graft-modified SBS (N1): Under nitrogen protection, 20 g of SBS was dissolved in 200 ml of toluene, and the temperature was raised to 50 °C to completely dissolve SBS, obtaining an SBS solution; 5 g of mercaptoethanol and 1.0% AIBN based on the mass of SBS were added to the SBS solution, and the SBS solution added with mercaptoethanol and AIBN was heated to 80 °C for reaction, and solution graft polymerization was carried out at 80 °C and 250 rpm for 1 hour to obtain a modified SBS mixture; the modified SBS mixture was dropped into methanol for precipitation and filtration, and the filtered sample was vacuum dried at 70 °C for 12 hours; the dried sample was dissolved in toluene, and then precipitation, filtration, and vacuum drying were carried out in sequence, and the above steps of precipitation, filtration, and vacuum drying were repeated 3 times, and the obtained product was placed in an oven at 70 °C and dried to a constant weight to obtain graft-modified SBS, and the graft-modified SBS was grafted with mercapto groups, denoted as N1.

[0142] Preparation of graft-modified SBS (N2): Under nitrogen protection, 20 g of SBS was dissolved in 200 ml of toluene, and the temperature was raised to 50 °C to completely dissolve SBS, obtaining an SBS solution; 10 g of mercaptoethanol and 1.0% AIBN based on the mass of SBS were added to the SBS solution, and the SBS solution added with mercaptoethanol and AIBN was heated to 80 °C for reaction, and solution graft polymerization was carried out at 80 °C and 250 rpm for 1 hour to obtain a modified SBS mixture; the modified SBS mixture was dropped into methanol for precipitation and filtration, and the filtered sample was vacuum dried at 70 °C for 12 hours; the dried sample was dissolved in toluene, and then precipitation, filtration, and vacuum drying were carried out in sequence, and the above steps of precipitation, filtration, and vacuum drying were repeated 3 times, and the obtained product was placed in an oven at 70 °C and dried to a constant weight to obtain graft-modified SBS, and the graft-modified SBS was grafted with mercapto groups, denoted as N2.

[0143] Preparation of graft-modified SBS (N3): Under nitrogen protection, 20 g of SBS was dissolved in 200 ml of toluene, and the temperature was raised to 50 °C to completely dissolve SBS, obtaining an SBS solution; 15 g of mercaptoethanol and 1.0% AIBN based on the mass of SBS were added to the SBS solution, and the SBS solution added with mercaptoethanol and AIBN was heated to 80 °C for reaction, and solution graft polymerization was carried out at 80 °C and 250 rpm for 1 hour to obtain a modified SBS mixture; the modified SBS mixture was dropped into methanol for precipitation and filtration, and the filtered sample was vacuum dried at 70 °C for 12 hours; the dried sample was dissolved in toluene, and then precipitation, filtration, and vacuum drying were carried out in sequence, and the above steps of precipitation, filtration, and vacuum drying were repeated 3 times, and the obtained product was placed in an oven at 70 °C and dried to a constant weight to obtain graft-modified SBS, and the graft-modified SBS was grafted with mercapto groups, denoted as N3.

[0144] Preparation of SBS modifier

[0145] Weigh the graft-modified SBS labeled N1, N2, and N3 respectively, and add them to dimethyl sulfoxide at a mass ratio of 1:1 with the biomass carbon aerogel prepared above. Heat to 50°C and stir until there is no solid matter to obtain the first mixed solution respectively; slowly add the same amount of concentrated sulfuric acid and sodium hypophosphite to each first mixed solution, continue to heat to 120°C - 125°C, and introduce nitrogen under a vacuum of -80 KPa to keep warm for 2.5 hours. After the reaction is completed, obtain the mixed solution of the SBS modifier respectively; perform precipitation and filtration on the mixed solution of the SBS modifier respectively, and dry the filtered product to obtain the SBS modifier, denoted as W1, W2, and W3 respectively.

[0146] Example 1

[0147] A waterproof coiled material includes: a main substrate, an asphalt coating layer provided on at least one surface of the main substrate, and an isolation and protection layer covering the asphalt coating layer. The asphalt coating layer is formed by coating the above asphalt coating composition (containing W1) on one surface of the main substrate. Among them, the asphalt coating composition is made of raw materials with the following rubber addition percentage by weight (PHR): 70# asphalt, 100 PHR; asphalt softening oil, 5 PHR; SBS modifier (W1), 3 PHR; SBR modifier, 4 PHR; rubber powder, 30 PHR; heavy calcium, 70 PHR.

[0148] The preparation method of the asphalt coating composition includes: mixing 70# asphalt and asphalt softening oil at a speed of 1000 rpm according to the ratio of the asphalt coating composition, and heating to 140°C - 145°C and then keeping warm for 1.5 hours to completely melt the 70# asphalt to obtain the first mixture; adding the SBS modifier (W1) and SBR modifier to the first mixture and heating to 170°C - 180°C for dispersion, and keeping warm for 1.5 hours to obtain the second mixture; adding rubber powder to the second mixture and heating to 180°C - 190°C to perform shear dispersion at a speed of 800 rpm for 2.5 hours to obtain the third mixture; adding powder to the third mixture and performing shear dispersion at a speed of 1000 rpm at 180°C - 185°C for 1.5 hours to obtain the asphalt coating composition.

[0149] Example 2

[0150] A waterproof coiled material, comprising: a main substrate, an asphalt coating layer provided on at least one surface of the main substrate, and an isolation and protection layer covering the asphalt coating layer. The asphalt coating layer is formed by coating the above-mentioned asphalt coating composition (containing W2) on one surface of the main substrate. Among them, the asphalt coating composition is made of raw materials with the following rubber addition percentage content (PHR): 70# asphalt, 100 PHR; asphalt softening oil, 5 PHR; SBS modifier (W2), 3 PHR; SBR modifier, 4 PHR; rubber powder, 30 PHR; heavy calcium, 70 PHR.

[0151] A preparation method of an asphalt coating composition, comprising: mixing 70# asphalt and asphalt softening oil at a rotation speed of 1000 rpm according to the ratio of the asphalt coating composition, and heating to 140°C - 145°C, then insulating for 1.5 hours to completely melt the 70# asphalt to obtain a first mixture; adding SBS modifier (W2) and SBR modifier to the first mixture, heating to 170°C - 180°C for dispersion, and insulating for 1.5 hours to obtain a second mixture; adding rubber powder to the second mixture, heating to 180°C - 190°C, and shearing and dispersing at a rotation speed of 800 rpm for 2.5 hours to obtain a third mixture; adding powder to the third mixture, and shearing and dispersing at a rotation speed of 1000 rpm at 180°C - 185°C for 1.5 hours to obtain the asphalt coating composition.

[0152] Example 3

[0153] A waterproof coiled material, comprising: a main substrate, an asphalt coating layer provided on at least one surface of the main substrate, and an isolation and protection layer covering the asphalt coating layer. The asphalt coating layer is formed by coating the above-mentioned asphalt coating composition (containing W3) on one surface of the main substrate. Among them, the asphalt coating composition is made of raw materials with the following rubber addition percentage content (PHR): 70# asphalt, 100 PHR; asphalt softening oil, 5 PHR; SBS modifier (W3), 3 PHR; SBR modifier, 4 PHR; rubber powder, 30 PHR; heavy calcium, 70 PHR.

[0154] Preparation method of asphalt coating composition, comprising: mixing 70# asphalt and asphalt softening oil at a rotation speed of 1000 rpm according to the proportion of the asphalt coating composition, heating to 140°C - 145°C, and then keeping warm for 1.5 hours to completely melt the 70# asphalt to obtain a first mixture; adding SBS modifier (W3) and SBR modifier to the first mixture, heating to 170°C - 180°C for dispersion, and keeping warm for 1.5 hours to obtain a second mixture; adding rubber powder to the second mixture, heating to 180°C - 190°C, and performing shear dispersion at a rotation speed of 800 rpm for 2.5 hours to obtain a third mixture; adding powder to the third mixture, and performing shear dispersion at a rotation speed of 1000 rpm at 180°C - 185°C for 1.5 hours to obtain the asphalt coating composition.

[0155] Example 4

[0156] A waterproof coiled material, comprising: a main substrate, an asphalt coating layer provided on at least one surface of the main substrate, and an isolation and protection layer covering the asphalt coating layer. The asphalt coating layer is formed by coating the above-mentioned asphalt coating composition (containing W3) on one surface of the main substrate. Among them, the asphalt coating composition is made of raw materials with the following rubber addition percentage content (PHR): 70# asphalt, 100 PHR; asphalt softening oil, 5 PHR; SBS modifier (W3), 4 PHR; SBR modifier, 4 PHR; rubber powder, 30 PHR; heavy calcium, 70 PHR.

[0157] Preparation method of asphalt coating composition, comprising: mixing 70# asphalt and asphalt softening oil at a rotation speed of 1000 rpm according to the proportion of the asphalt coating composition, heating to 140°C - 145°C, and then keeping warm for 1.5 hours to completely melt the 70# asphalt to obtain a first mixture; adding SBS modifier (W3) and SBR modifier to the first mixture, heating to 170°C - 180°C for dispersion, and keeping warm for 1.5 hours to obtain a second mixture; adding rubber powder to the second mixture, heating to 180°C - 190°C, and performing shear dispersion at a rotation speed of 800 rpm for 2.5 hours to obtain a third mixture; adding powder to the third mixture, and performing shear dispersion at a rotation speed of 1000 rpm at 180°C - 185°C for 1.5 hours to obtain the asphalt coating composition.

[0158] Example 5

[0159] A waterproof coiled material, comprising: a main substrate, an asphalt coating layer provided on at least one surface of the main substrate, and an isolation and protection layer covering the asphalt coating layer. The asphalt coating layer is formed by coating the above-mentioned asphalt coating composition (containing W3) on one surface of the main substrate. Among them, the asphalt coating composition is made of raw materials with the following rubber addition percentages (PHR): 70# asphalt, 100 PHR; asphalt softening oil, 5 PHR; SBS modifier (W3), 5 PHR; SBR modifier, 4 PHR; rubber powder, 30 PHR; heavy calcium carbonate, 70 PHR.

[0160] A preparation method of the asphalt coating composition, comprising: mixing 70# asphalt and asphalt softening oil at a rotation speed of 1000 rpm according to the ratio of the asphalt coating composition, and heating to 140°C - 145°C, then insulating for 1.5 hours to completely melt the 70# asphalt to obtain a first mixture; adding the SBS modifier (W3) and SBR modifier to the first mixture, heating to 170°C - 180°C for dispersion, and insulating for 1.5 hours to obtain a second mixture; adding rubber powder to the second mixture, heating to 180°C - 190°C, and performing shear dispersion at a rotation speed of 800 rpm for 2.5 hours to obtain a third mixture; adding powder to the third mixture, and performing shear dispersion at a rotation speed of 1000 rpm at 180°C - 185°C for 1.5 hours to obtain the asphalt coating composition.

[0161] Comparative Example 1

[0162] A waterproof coiled material, comprising: a main substrate, an asphalt coating layer provided on at least one surface of the main substrate, and an isolation and protection layer covering the asphalt coating layer. The asphalt coating layer is formed by coating the above-mentioned asphalt coating composition on one surface of the main substrate. Among them, the asphalt coating composition is made of raw materials with the following rubber addition percentages (PHR): 70# asphalt, 100 PHR; asphalt softening oil, 5 PHR; SBS, 5 PHR; wherein, the SBS is not subjected to modification treatment; SBR modifier, 4 PHR; rubber powder, 30 PHR; heavy calcium carbonate, 70 PHR.

[0163] Preparation method of bitumen coating composition, comprising: mixing 70# bitumen and bitumen softening oil at a rotation speed of 1000 rpm according to the proportion of the bitumen coating composition, heating to 140°C - 145°C, and then insulating for 1.5 hours to completely melt the 70# bitumen, obtaining a first mixture; adding SBS and SBR modifiers to the first mixture, heating to 170°C - 180°C for dispersion, and insulating for 1.5 hours to obtain a second mixture; adding rubber powder to the second mixture, heating to 180°C - 190°C, and performing shear dispersion at a rotation speed of 800 rpm for 2.5 hours to obtain a third mixture; adding powder to the third mixture, and performing shear dispersion at a rotation speed of 1000 rpm at 180°C - 185°C for 1.5 hours to obtain the bitumen coating composition.

[0164] Comparative Example 2

[0165] A waterproof coiled material, comprising: a main substrate, a bitumen coating layer provided on at least one surface of the main substrate, and an isolation and protection layer covering the bitumen coating layer. The bitumen coating layer is formed by coating the above-mentioned bitumen coating composition on one surface of the main substrate. Among them, the bitumen coating composition is made of raw materials with the following rubber addition percentage by weight (PHR): 70# bitumen, 100 PHR; bitumen softening oil, 5 PHR; graft-modified SBS (N1), 5 PHR; SBR, 4 PHR; rubber powder, 30 PHR; heavy calcium, 70 PHR.

[0166] Preparation method of bitumen coating composition, comprising: mixing 70# bitumen and bitumen softening oil at a rotation speed of 1000 rpm according to the proportion of the bitumen coating composition, heating to 140°C - 145°C, and then insulating for 1.5 hours to completely melt the 70# bitumen, obtaining a first mixture; adding graft-modified SBS (N1) and SBR modifiers to the first mixture, heating to 170°C - 180°C for dispersion, and insulating for 1.5 hours to obtain a second mixture; adding rubber powder to the second mixture, heating to 180°C - 190°C, and performing shear dispersion at a rotation speed of 800 rpm for 2.5 hours to obtain a third mixture; adding powder to the third mixture, and performing shear dispersion at a rotation speed of 1000 rpm at 180°C - 185°C for 1.5 hours to obtain the bitumen coating composition.

[0167] Performance test

[0168] Perform the following performance tests on the waterproof coiled materials of Examples 1 - 5 and Comparative Examples 1 - 2, and record the test data in Table 1:

[0169] 1. Low-temperature flexibility test before and after aging

[0170] The aging conditions for the waterproof coiled material are as follows: The forced-air oven is aged at a temperature of 70°C for 7 days and 14 days. The test method for the low-temperature flexibility of the waterproof coiled material is carried out according to Part 14 of the national standard GB / T 328-2007 "Test Methods for Building Waterproof Coiled Materials". Among them, the low-temperature flexibility limit tests are respectively carried out on the waterproof coiled materials after 7 days and 14 days of aging treatment. It should be noted that the low-temperature limit can characterize the durability of the waterproof coiled material containing SBS modifier. The lower the low-temperature limit temperature, the better the durability of the waterproof coiled material.

[0171] 2. Test of the aluminum plate peel strength of the waterproof coiled material

[0172] The sample preparation and the test of the aluminum plate peel strength are carried out according to the national standard GB 23442-2009 "Self-adhesive Polymer Modified Bitumen Waterproof Coiled Materials". Among them, the maximum value of the aluminum plate peel strength is taken.

[0173] Table 1

[0174]

[0175] Combining the component compositions of Examples 1-5 and Comparative Examples 1-2, it can be seen from the test data of the low-temperature flexibility and peel strength of the waterproof coiled materials in the examples and comparative examples that:

[0176] The asphalt coating composition of the waterproof coiled material in Comparative Example 1 contains unmodified SBS. The limit low temperature of the low-temperature flexibility of the waterproof coiled material before aging is -26°C, and the peel strength is 2.09 N / mm; the limit low temperature after 7 days of aging is -17°C, and the peel strength is 1.53 N / mm. The attenuation amplitude of the limit low temperature after 7 days of aging is 34.62%, and the reduction amplitude of the peel strength is 26.79%. The limit low temperature after 14 days of aging is -14°C, the attenuation amplitude of the limit low temperature is 46.51%, the peel strength after 14 days of aging is still 1.53 N / mm, and the reduction amplitude of the peel strength is still 26.79%. The above test data show that the peel strength and aging strength of the waterproof coiled material before and after 7 days and 14 days of aging are not linearly related, but the limit low-temperature performance of the waterproof coiled material is significantly affected by the aging strength.

[0177] In the bitumen coating composition of the waterproof coiled material of Comparative Example 2, graft-modified SBS is contained. The ultimate low temperature of the low temperature flexibility before the aging of the waterproof coiled material is -27°C, and the peel strength is 1.98 N / mm. After aging for 7 days, the ultimate low temperature is -22°C, and the peel strength is 1.87 N / mm. The attenuation amplitude of the ultimate low temperature after aging for 7 days is 18.52%, and the reduction amplitude of the peel strength is 5.56%. After aging for 14 days, the ultimate low temperature is -18°C, the attenuation amplitude of the ultimate low temperature is 33.33%, the peel strength after aging for 14 days is 1.74 N / mm, and the reduction amplitude of the peel strength is 12.12%. The above test data show that the peel strength and aging strength of the waterproof coiled material before and after aging for 7 days and 14 days are not linearly related, but the ultimate low temperature performance of the waterproof coiled material is significantly affected by the aging strength.

[0178] The ultimate low temperature flexibility performance, peel strength and attenuation amplitude of the waterproof coiled material obtained by grafting mercapto modification on SBS in Comparative Example 2 are better than the ultimate low temperature flexibility, peel strength and attenuation amplitude of the waterproof coiled material in Comparative Example 1 without modifying SBS. The ultimate low temperature flexibility performance, peel strength performance and their attenuation amplitude of the waterproof coiled material containing SBS modifier in Example 5 are better than the ultimate low temperature flexibility, peel strength and their respective performance attenuation amplitude of the waterproof coiled material in Comparative Example 2 only grafting mercapto modification on SBS. The test results of Example 5, Comparative Example 1 and Comparative Example 2 show that the ultimate low temperature flexibility, peel strength and their respective performance attenuation amplitude of the waterproof coiled material prepared by grafting mercapto modification on SBS and reacting with biomass carbon aerogel to form SBS modifier are better than the ultimate low temperature flexibility and peel strength of the waterproof coiled material only grafting mercapto modification on SBS, and have a lower performance attenuation amplitude.

[0179] By comparing the waterproof coiled materials of Comparative Examples 1-3, it can be obtained that with the increase of the structural unit corresponding to mercaptoethanol in the SBS modifier, the attenuation amplitude of the low temperature flexibility of the waterproof coiled material decreases, and the peel strength of the waterproof coiled material increases. With the relative increase of the dosage of the SBS modifier containing the highest content of mercaptoethanol structural unit in Examples 4 and 5, the attenuation amplitude of the low temperature flexibility of the waterproof coiled materials in Examples 4 and 5 decreases significantly, and the ultimate low temperature remains at -24°C to -27°C, and the reduction amplitude of the peel strength of the waterproof coiled material also gradually decreases. It shows that increasing the dosage of the SBS modifier in the examples of the present application can effectively enhance the aging resistance performance of the waterproof coiled material and improve the problem of phase separation.

[0180] Before aging, the low temperature flexibility limit low temperature of the waterproof coiled material of Example 5 was -28°C. After 7 days of aging treatment, the low temperature flexibility limit low temperature was -27°C, and the attenuation amplitude of the low temperature performance was only 3.57%. After 14 days of aging treatment, the low temperature flexibility limit temperature was -25°C, and the attenuation amplitude of the low temperature performance was only 10.71%. Moreover, the peel strength attenuation after 7 days and 14 days of aging was the smallest, both being 3.32%. This shows that the waterproof coiled material with the asphalt coating composition matching Example 5 has good aging resistance, thus having a long-lasting low temperature flexibility attenuation performance and a low peel strength reduction rate, enabling the waterproof coiled material to be stored, transported, and served more stably.

[0181] The asphalt coating composition of the waterproof coiled materials in Examples 1 - 5 of this application contains an SBS modifier treated by the reaction of biomass carbon aerogel and graft-modified SBS. Before aging, the low temperature flexibility limit low temperature of the waterproof coiled material was at most -26°C, at least -28°C, and the minimum peel strength was 1.89 N / mm. After 7 days of aging, the limit low temperature was at most -19°C, and the minimum peel strength was 1.69 N / mm. After 7 days of aging, the maximum attenuation amplitude of the limit low temperature was 26.92%, and the maximum reduction amplitude of the peel strength was 10.58%. After 14 days of aging, the limit low temperature was at most -14°C, the attenuation amplitude of the limit low temperature was 46.51%, the minimum peel strength after 14 days of aging was 1.58 N / mm, and the maximum reduction amplitude of the peel strength was 16.58%. That is, the maximum attenuation amplitude of the limit low temperature performance of the waterproof coiled material after 14 days of aging in Examples 1 - 5 was 46.51%. The peel strength of the waterproof coiled material after 14 days of aging was also stronger than that of the waterproof coiled material in Comparative Example 1 as a whole. The maximum reduction amplitude of the peel strength was 16.58%, which was significantly smaller than the limit low temperature attenuation amplitude and peel strength attenuation amplitude of the waterproof coiled material in Comparative Example 1 that did not modify SBS. Only the low temperature performance attenuation amplitude of the waterproof coiled material after 14 days of aging in Examples 1 and 2 was higher than that of the waterproof coiled material after 14 days of aging in Comparative Example 2, and only the peel strength attenuation amplitude of the waterproof coiled material after 14 days of aging in Examples 1 and 2 was higher than that of the waterproof coiled material in Comparative Example 2 that only graft-modified SBS. The above test data show that the peel strength and aging strength of the waterproof coiled material before and after 7 days and 14 days of aging are not linearly related, but the limit low temperature performance of the waterproof coiled material is significantly affected by the aging strength.

[0182] The above data test results of the waterproof coiled materials in Examples 1-5 can prove that the overall low-temperature flexibility of the waterproof coiled materials prepared in the embodiments of the present application containing SBS modifiers is better than that of the existing waterproof coiled materials. The attenuation amplitude of the ultimate low-temperature performance is relatively low after 7 days and 14 days of aging treatment, the peel strength is relatively high, and the reduction amplitude of the peel strength is also relatively small as a whole. Therefore, the test results of the ultimate low-temperature performance and the aging peel strength show that, overall, the asphalt coating composition containing SBS modifiers in the present application can prevent the performance of the waterproof coiled materials from significantly deteriorating during long-term aging.

[0183] The inventors of the present application found that asphalt itself has extremely low polarity, which is quite different from that of SBS. Initially, it was simply physically and mechanically mixed. After being placed for a period of time, phase separation would occur between asphalt and SBS, resulting in the coiled materials not achieving long-term stability. However, by using the SBS modifier obtained by the reaction of biomass carbon aerogel and graft-modified SBS in the present application, the polarity of SBS is changed, and the compatibility between asphalt and the SBS modifier is increased, and high product performance can be maintained during the processes of production, transportation, storage, and service.

[0184] On the one hand, the SBS modifier of the present application can stably exist in the asphalt coating composition after being modified. On the other hand, biomass carbon aerogel is an anti-aging material that is resistant to high and low temperatures and has relatively stable performance. The two raw materials are stably combined and applied to the asphalt coating composition to prevent the performance attenuation of the asphalt coating in a short time, thereby preventing the waterproof coiled materials from occurring phase separation and solving the problem of a sharp decline in anti-aging performance.

[0185] The above is only the specific implementation manner of the present application. Those skilled in the art can clearly understand that for the convenience and brevity of description, the specific working process described above can refer to the corresponding process in the foregoing method embodiments and will not be repeated here. It should be understood that the protection scope of the present application is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present application can easily think of various equivalent modifications or substitutions, and these modifications or substitutions should all be covered within the protection scope of the present application.

Claims

1. A method for preparing a SBS modifier, characterized in that: include: dissolving SBS in a first solvent to obtain an SBS solution; Adding a thiol compound to the SBS solution, performing solution graft polymerization at a temperature of 50° C. to 90° C., to obtain a graft-modified SBS; the mass ratio of the SBS to the thiol compound is 20:(5-15), and the thiol compound is selected from at least one of mercaptoethanol, n-dodecyl mercaptan, and mercaptopropionic acid; The biomass carbon aerogel and the grafted modified SBS are added to the second solvent in a mass ratio of 1: (0.5-1.5) to obtain a first mixed solution; in the step of obtaining the first mixed solution, the biomass carbon aerogel is prepared by the following steps: mixing wood material and water in a preset ratio and performing hydrothermal treatment to obtain a first product; The method of mixing the wood material and water according to a preset ratio for hydrothermal treatment includes: mixing the wood material and water according to a preset ratio, wherein the preset ratio of the wood material and water is (6g-10g): (10ml-12ml), obtaining a first mixture, adjusting the pH value of the first mixture to 8-12, adding a cross-linking agent to disperse the mixture, and reacting the mixture at 180°C-200°C to obtain a first product; wherein the cross-linking agent is epichlorohydrin or ethylene oxide, and the mass ratio of the cross-linking agent to the wood material is 1: (1.2-2); washing and freezing the first product to obtain a frozen product; and freeze-drying the frozen product to obtain a biomass carbon aerogel; Concentrated sulfuric acid and sodium hypophosphite are added to the first mixed solution, and the mixture is reacted at a temperature of 120° C. to 130° C. to obtain an SBS modifier.

2. The method for preparing the SBS modifier according to claim 1, characterized in that: Meet at least one of the following requirements: The SBS has a linear structure, and the weight average molecular weight of the SBS is 100,000 to 450,000; The first solvent is selected from at least one of toluene, cyclohexane, CCl4, and CHCl3; Dissolving the SBS in the first solvent under the protection of an inert atmosphere; In the process of dissolving the SBS in the first solvent, the temperature of the first solvent is raised to 30° C. to 50° C. to accelerate the dissolution of the SBS; The thiol compound is added to the SBS solution, and solution graft polymerization is performed using an initiator at a temperature of 50° C. to 90° C.; Add the biomass carbon aerogel and the grafted modified SBS in a mass ratio of 1: (0.5-1.5) into a second solvent and heat it to 50° C.-90° C.; The second solvent is selected from dimethyl sulfoxide and dimethylformamide; The concentrated sulfuric acid and sodium hypophosphite are added to the first mixed solution to react at a temperature of 120° C. to 130° C., and the mixture is heat-insulated in an inert atmosphere to obtain an SBS modifier.

3. The preparation method of the SBS modifier according to claim 2, characterized in that, Meet at least one of the following requirements: The weight average molecular weight of the SBS is 150,000 to 300,000; The content of styrene segments in the SBS is 20% to 30%; the melt flow rate is 0 g / 10min to 1 g / 10min; The amount of the initiator added is 0.5wt% to 3wt% of the mass of the SBS; The initiator is azobisisobutyronitrile; The inert atmosphere is formed by at least one selected from nitrogen, argon and neon; The process parameters that need to be met for the heat preservation treatment under an inert atmosphere are: a pressure of -80KPa to -50KPa, an inert atmosphere, and a heat preservation treatment time of 2.5 hours to 4 hours.

4. The method for preparing the SBS modifier according to claim 1, characterized in that: The wood material is selected from at least one of eucalyptus, pine, poplar, elm, willow, apricot, birch, maple, camphor and shrub chips.

5. A SBS modifier, characterized in that: The SBS modifier is prepared according to the preparation method of any one of claims 1 to 4.

6. Use of the SBS modifier as claimed in claim 5 for asphalt modification.

7. An asphalt coating composition, characterized in that: Including the following raw materials with rubber addition percentage: Asphalt, 100PHR; Asphalt softening oil, 5PHR~10PHR; SBS modifier, 3PHR to 5PHR, wherein the SBS modifier is the SBS modifier according to claim 5; SBR modifier, 2PHR~4PHR; Rubber powder, 30PHR~50PHR; Powder, 50PHR~70PHR.

8. The asphalt coating composition according to claim 7, characterized in that: Meet at least one of the following requirements: The asphalt is selected from 70# asphalt, 90# asphalt or a combination thereof; The asphalt softening oil is at least one of naphthenic oil, soybean oil and aromatic oil; The rubber powder is 60-80 mesh tire rubber powder, with a rubber content of 30%-50% and an ash content of 10%-30%; The powder is selected from heavy calcium powder and talcum powder, and the particle size is 200-400 meshes.

9. A method for preparing the asphalt coating composition according to claim 7 or 8, characterized in that: include: The asphalt and asphalt softening oil are mixed according to the ratio of the asphalt coating material composition to obtain a first mixture; The first mixture is heated until the asphalt is completely melted, and the SBS modifier and the SBR modifier are added to the first mixture for dispersion to obtain a second mixture; adding the rubber powder to the second mixed material for dispersion to obtain a third mixed material; The powder is added to the third mixture for dispersion to obtain an asphalt coating material composition.

10. The method for preparing the asphalt coating composition according to claim 9, characterized in that: Meet at least one of the following requirements: Heating the first mixture to 130° C. to 150° C. to melt all the asphalt; The SBS modifier and the SBR modifier are added to the first mixed material for dispersion and the temperature can be raised to 160° C. to 180° C.; adding the rubber powder into the second mixture and heating it to 180° C. to 190° C. for dispersion; The powder is added to the third mixed material and dispersed at 180° C. to 190° C.

11. A waterproof roll material, characterized in that: include: Main substrate; And an asphalt coating layer is arranged on at least one side of the surface of the main substrate, and the asphalt coating layer is formed by applying the asphalt coating composition according to claim 7 or 8 on at least one side of the surface of the main substrate.

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