SBS asphalt modifier and preparation method thereof, self-adhesive modified asphalt and preparation method thereof, and self-adhesive modified asphalt waterproof coiled material

Abstract

The invention provides an SBS asphalt modifier and a preparation method thereof, self-adhesive modified asphalt and a preparation method thereof, and a self-adhesive modified asphalt waterproof coiled material, and belongs to the technical field of waterproof materials. The preparation method of the SBS asphalt modifier comprises the following steps: adding SBS into naphthenic oil, heating to a dissolution temperature, and stirring until the SBS is completely dissolved to obtain an SBS solution; adding a polymerizable monomer containing C10-C30 linear alkyl into the SBS solution, and uniformly mixing to obtain a mixed solution; adding a free radical polymerization initiator into the mixed solution, and carrying out a free radical grafting reaction in an inert atmosphere; and adding a terminating agent to terminate the reaction to obtain the SBS asphalt modifier.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of waterproof materials, and particularly relates to an SBS asphalt modifier, a preparation method thereof, a self-adhesive modified asphalt, and a preparation method and self-adhesive modified asphalt waterproof coiled material. BACKGROUND

[0002] Traditional styrene-butadiene-styrene block copolymer (SBS) modified asphalt has obvious defects in a low-temperature environment: on the one hand, the material is prone to embrittlement, and the adhesion performance is significantly reduced; on the other hand, the material needs to be heated to soften during construction, which not only has high energy consumption, but also has insufficient adhesion under low-temperature conditions, directly affecting the sealing reliability of the waterproof coiled material or road joint filling material.

[0003] Although the existing self-adhesive asphalt improves the construction convenience by adding tackifying resin or plasticizer, such a formula has unavoidable problems: the weather resistance is weak, and the material is prone to aging due to environmental influence during long-term use; the tackifying resin or plasticizer is prone to migration and precipitation, resulting in performance degradation of the material; meanwhile, the low-temperature flexibility of the material is still not ideal, and the adaptability under low-temperature conditions is still insufficient. SUMMARY

[0004] In view of the above technical problems, the present application provides an SBS asphalt modifier, a preparation method thereof, a self-adhesive modified asphalt, and a preparation method and self-adhesive modified asphalt waterproof coiled material, so as to at least partially solve the above technical problems, and thus the specific technical solutions provided by the present application are as follows.

[0005] As a first aspect of the present application, a preparation method of an SBS asphalt modifier is provided, which comprises: adding SBS into naphthenic oil, heating to a dissolution temperature and stirring until complete dissolution to obtain an SBS solution; adding a C 10 -C 30 adding a polymerizable monomer of a linear alkyl group into the SBS solution and uniformly mixing to obtain a mixed solution; adding a free radical polymerization initiator into the mixed solution and performing a free radical grafting reaction under an inert atmosphere; adding a termination agent to terminate the reaction to obtain the SBS asphalt modifier.

[0006] As a second aspect of the present application, an SBS asphalt modifier is provided, which is prepared by the above preparation method of the SBS asphalt modifier.

[0007] As a third aspect of the present application, a self-adhesive modified asphalt is provided, which comprises the following raw materials in parts by weight:

[0008] 100 parts of base asphalt;

[0009] 5-20 parts of the above SBS asphalt modifier;

[0010] SBR and / or SSBR modifier, 10-25 parts;

[0011] Functional aid, 1-15 parts.

[0012] As a fourth aspect of the present application, a preparation method of the self-adhesive modified asphalt is provided, comprising: mixing the base asphalt, the SBS asphalt modifier, the SBR and / or SSBR modifier, and carrying out the first shearing development, then adding the functional aid and the inorganic filler, mixing and carrying out the second shearing development, to obtain the self-adhesive modified asphalt; wherein the temperature of the first shearing and the second shearing is independently 160-180℃, and the time of the first shearing and the second shearing is independently 1-2h.

[0013] As a fifth aspect of the present application, a self-adhesive modified asphalt waterproofing membrane is provided, which is prepared from the self-adhesive modified asphalt.

[0014] Based on the above technical solutions, the SBS asphalt modifier and the preparation method, the self-adhesive modified asphalt and the preparation method, and the self-adhesive modified asphalt waterproofing membrane provided by the present application at least have one of the following beneficial effects.

[0015] In the embodiments of the present application, a preparation method of the SBS asphalt modifier is provided, which dissolves the SBS by using naphthenic oil and introduces a long-chain alkyl monomer (i.e., a polymerizable monomer containing C 10 -C 30 straight-chain alkyl group) to perform a free radical grafting reaction, so as to realize the functional modification of the SBS molecular chain in a chemical bonding manner. The use of the naphthenic oil improves the dissolution and dispersion efficiency of the SBS, and avoids the toxicity problem of the traditional solvent; the free radical grafting reaction has high controllability, and can ensure that the long-chain alkyl group (i.e., the C 10 -C 30 straight-chain alkyl group) is uniformly grafted to the SBS molecular chain, effectively solving the component separation problem caused by physical blending. The obtained SBS asphalt modifier has excellent compatibility with asphalt and other aids, lays a foundation for subsequent preparation of high-performance self-adhesive modified asphalt, and has a simple process and is easy to industrialize, being suitable for large-scale production.

[0016] In the embodiments of the present application, the SBS asphalt modifier is provided, which grafts a long-chain alkyl group to the SBS molecular chain and contains a naphthenic oil carrier, and has excellent low-temperature fluidity and interface affinity. The long-chain alkyl group gives the molecular chain good flexibility, and the naphthenic oil enhances the compatibility with asphalt, so that the SBS asphalt modifier is uniformly dispersed in the asphalt, can effectively improve the low-temperature toughness and self-adhesion of the asphalt, and overcomes the defects of easy separation and short-term effect of the traditional modifier, providing a stable and reliable modification basis for improving the performance of asphalt.

[0017] In the embodiment of the present application, the present application provides a self-adhesive modified asphalt, by compounding SBS asphalt modifier and SBR / SSBR modifier in a specific ratio, the synergistic effect between components is achieved. The long-chain alkyl grafted by SBS cooperates with the rubber phase of SBR / SSBR, which significantly improves the low-temperature flexibility and persistent self-adhesion of the system, and still maintains good workability below-10℃; the functional additives further optimize the aging resistance, fatigue resistance and other properties. It can be cold-applied without high-temperature heating, which reduces energy consumption and safety risks, and the comprehensive performance is better than that of traditional products, and is suitable for waterproofing and road engineering in harsh environments such as cold regions.

[0018] In the embodiment of the present application, the present application provides a preparation method of self-adhesive modified asphalt, which adopts a step-by-step shearing development process. First, high-temperature shearing is used to promote the uniform dispersion of SBS asphalt modifier and SBR / SSBR modifier in the base asphalt, forming a stable network structure; then, functional additives and inorganic fillers are added for secondary shearing to ensure the full combination of each component. By controlling the shearing temperature and time, the full compatibility of each component is ensured and over-aging is avoided. The process is stable and controllable, and can efficiently prepare self-adhesive modified asphalt with uniform performance, which is suitable for industrial continuous production.

[0019] In the embodiment of the present application, the self-adhesive modified asphalt waterproofing membrane prepared from the above self-adhesive modified asphalt inherits the excellent performance of self-adhesive modified asphalt, which is flexible and does not crack at low temperature, has persistent self-adhesion, and is convenient to construct and reliable in sealing. Its weather resistance and fatigue resistance can meet the long-term use requirements, and can effectively prevent leakage, providing high-quality waterproofing protection for building, road and other engineering projects, and is especially suitable for cold regions and special engineering scenarios. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below with specific examples.

[0021] In the process of implementing the concept of the present application, it is found that the traditional SBS modified asphalt relies on physical blending to introduce tackifying or toughening components, which is prone to cause problems such as low-temperature embrittlement, adhesion decay and component migration due to insufficient compatibility, especially in environments below-10℃, the workability and sealing effect are significantly reduced. At the same time, the tackifying resin used in the existing self-adhesive asphalt has poor weather resistance, and is prone to precipitation and failure during long-term use. Based on this, the present application provides a SBS asphalt modifier and a preparation method thereof, a self-adhesive modified asphalt and a preparation method thereof, and a self-adhesive modified asphalt waterproofing membrane, by chemically grafting long-chain alkyl groups into the SBS molecular chain, the interfacial interaction with asphalt and the molecular flexibility can be enhanced, and the low-temperature compatibility of naphthenic oil and the elastic synergy of the rubber phase can be combined, which can break through the performance bottleneck and improve the comprehensive performance of self-adhesive asphalt through chemical bonding and compounding synergy.

[0022] As a first aspect of the present application, a preparation method of SBS asphalt modifier is provided, comprising: adding SBS into naphthenic oil, heating to a dissolution temperature and stirring until completely dissolved to obtain a SBS solution; adding a polymerizable monomer containing a linear alkyl into the SBS solution and mixing uniformly to obtain a mixed solution; adding a free radical polymerization initiator into the mixed solution to perform a free radical grafting reaction under an inert atmosphere; and adding a terminating agent to terminate the reaction to obtain the SBS asphalt modifier. 10 -C 30 The polymerizable monomer containing a linear alkyl is added into the SBS solution and mixed uniformly to obtain a mixed solution; the free radical polymerization initiator is added into the mixed solution to perform a free radical grafting reaction under an inert atmosphere; the terminating agent is added to terminate the reaction to obtain the SBS asphalt modifier.

[0023] In the embodiments of the present application, the low-temperature performance of SBS modified asphalt and the efficiency of the preparation process are significantly improved by the following method: long-chain alkyl groups are introduced into the SBS molecular chain to form a SBS asphalt modifier with a low-temperature plasticizing function. The SBS asphalt modifier improves the low-temperature flexibility of asphalt through three mechanisms: flexible chain segment effect (grafted long-chain alkyl groups increase the intermolecular distance of polymer chains, improve the free volume, enhance the chain segment movement ability, and reduce the T g g), internal plasticizing effect (flexible long-chain alkyl groups can reduce the intermolecular van der Waals force and promote chain segment sliding), and inhibition of crystallization (grafted long-chain alkyl groups can inhibit the crystallization of the main chain and maintain the amorphous structure). Secondly, naphthenic oil is used as a solvent to prepare the SBS asphalt modifier. This solvent has the advantages of excellent compatibility (good compatibility with both the polybutadiene segment and the polystyrene segment in SBS, ensuring uniform grafting reaction), plasticizing effect (no need to completely remove after the reaction, directly remaining in the product to reduce the melt viscosity), chemical inertness (high saturation, does not interfere with the grafting reaction), high boiling point (allows high-temperature reaction, reduces solvent volatilization loss), low cost, and easy availability (widely used in industry). The above advantages not only simplify the process flow and avoid the high energy consumption and environmental pressure caused by solvent replacement, but also make the final product performance more uniform and highly matched with the target application scenario.

[0024] According to the embodiments of the present application, the polymerizable monomer containing a linear alkyl includes any one of a linear alpha-olefin, a linear alkyl mercaptan, a linear alkyl acrylate, and a linear alkyl amine. 10 -C 30 The polymerizable monomer containing a linear alkyl includes any one of a linear alpha-olefin, a linear alkyl mercaptan, a linear alkyl acrylate, and a linear alkyl amine.

[0025] In the embodiments of the present application, the polymerizable monomer containing a linear alkyl includes any one of a linear alpha-olefin, a linear alkyl mercaptan, a linear alkyl acrylate, and a linear alkyl amine. 10 -C 30 The polymerizable monomer containing a linear alkyl (linear alpha-olefin, etc.) can precisely introduce long-chain alkyl groups (i.e., C 10 -C30 The linear alkyl ensures that the low-temperature plasticizing mechanism efficiently works; the naphthenic oil (such as KN4010, T15, etc.) has excellent compatibility with each section of SBS, ensures uniformity of the grafting reaction and has a plasticizing function; the dicumyl peroxide initiator can controllably start the free radical reaction, and the hydroquinone can efficiently terminate the reaction to avoid generation of by-products. The synergistic effect of the above raw materials makes the SBS asphalt modifier have high grafting efficiency and stable performance, and the raw materials are low in cost and easy to obtain, further improving the process feasibility and product practicability, and providing a reliable material basis for breaking through the low-temperature performance of modified asphalt.

[0026] According to the embodiment of the present application, the dissolving temperature is 120-160℃. The reaction temperature of the free radical grafting reaction is 150-170℃, and the reaction time of the free radical grafting reaction is 2-4h. Inert gas is continuously introduced during the free radical grafting reaction. The inert gas includes nitrogen (N2), argon (Ar) and the like, which can be selected according to the actual situation, and the present application is not limited thereto. Further, the inert gas is introduced during the process of dissolving SBS in naphthenic oil, which can isolate oxygen to avoid oxidation degradation of SBS molecular chains (especially polybutadiene section) due to high temperature, and reduce the generation of bubbles in the dissolving system, so as to ensure that SBS is uniformly dispersed in naphthenic oil, provide a stable and uniform reaction matrix for the subsequent free radical grafting reaction, and ensure the preparation effect of the SBS asphalt modifier.

[0027] In the embodiment of the present application, the dissolving temperature (120-160℃) set by the present application can ensure that SBS is efficiently dissolved in naphthenic oil and avoid excessive thermal aging, and provide a uniformly dispersed system for the subsequent grafting reaction; the grafting reaction temperature of 150-170℃ and the reaction time of 2-4h match the activity of the initiator, which can promote the long-chain alkyl monomer to graft to the SBS molecular chain sufficiently, and ensure the grafting density and efficiency; the continuous introduction of inert gas in the reaction can isolate the quenching effect of oxygen on free radicals and reduce side reactions. The synergistic optimization of the above process parameters makes the grafting reaction have strong controllability and the product has stable performance, which endows the modifier with excellent low-temperature plasticizing and dispersing ability, and the process conditions are mild and easy to control in industry.

[0028] According to the embodiment of the present application, the mass ratio of SBS to naphthenic oil in the SBS solution is 1:4-9. The content of the long-chain alkyl monomer in the SBS solution is 5-20% of the mass of SBS. 10 The content of the initiator is 0.2-1% of the mass of the long-chain alkyl monomer. 30 The content of the initiator is 0.2-1% of the mass of the long-chain alkyl monomer. 10 The content of the initiator is 0.2-1% of the mass of the long-chain alkyl monomer. 30 The content of the initiator is 0.2-1% of the mass of the long-chain alkyl monomer. 10 The content of the initiator is 0.2-1% of the mass of the long-chain alkyl monomer. 30 The content of the initiator is 0.2-1% of the mass of the long-chain alkyl monomer.

[0029] In the embodiments of the present application, the SBS forms a stable system uniformly dispersed in naphthenic oil by optimizing the proportion of each component, which provides a suitable concentration environment for the grafting reaction and ensures the content of C 10 -C 30 The polymerizable monomer of linear alkyl is in full contact with the SBS molecular chain. The content of C 10 -C 30 The content of the polymerizable monomer of linear alkyl forms a reasonable proportion with SBS, which ensures the grafting density to fully exert the low-temperature plasticizing effect and avoids the performance fluctuation caused by excessive monomers not participating in the reaction. The content of the initiator and the terminator is accurately matched with the reaction demand, which can efficiently start the grafting reaction and timely terminate the reaction to control the product structure and reduce the generation of by-products. The synergistic regulation of the proportion of each component makes the modified grafting efficient and stable in performance, which further improves the compatibility with the subsequent asphalt system and provides a reliable guarantee for the optimization of the low-temperature performance of modified asphalt.

[0030] Specifically, the grafting rate of long-chain alkyl can be realized by adjusting the reaction temperature, time, initiator content and the proportion of monomer and SBS: increasing the reaction temperature or prolonging the reaction time can promote the generation of free radicals and the grafting of monomers, and increase the grafting rate; increasing the content of initiator can accelerate the reaction process and moderately increase the grafting rate, but excessive amount can easily cause side reactions; increasing the proportion of monomers can also increase the grafting rate, but excessive monomers should be avoided. The grafting rate has a significant impact on performance: if the grafting rate is too low, the introduction of long-chain alkyl is insufficient, which makes it difficult to exert the low-temperature plasticizing effect, interface affinity and other effects, and the low-temperature toughness and viscosity of the material are limited; if the grafting rate is too high, the molecular chain will be more entangled, which will affect the chain segment mobility, or the compatibility with asphalt will be reduced due to excessive accumulation of branched chains. Therefore, adjusting the appropriate grafting rate is the key to balancing the low-temperature performance, viscosity and compatibility of the material.

[0031] As a second aspect of the present application, an SBS asphalt modifier is provided, which is prepared by the preparation method of the SBS asphalt modifier.

[0032] In the embodiments of the present application, the SBS asphalt modifier provided has excellent low-temperature fluidity and interface affinity due to the grafting of long-chain alkyl on the SBS molecular chain and the presence of naphthenic oil carrier. The long-chain alkyl makes the molecular chain have good flexibility, and the naphthenic oil enhances the compatibility with asphalt, which enables the SBS asphalt modifier to be uniformly dispersed in asphalt, thereby effectively improving the low-temperature toughness and self-adhesion of asphalt, and solves the problems of separation and short-term modification effect of traditional modifiers, laying a stable and reliable modification foundation for the improvement of asphalt performance.

[0033] As a third aspect of the present application, a self-adhesive modified asphalt is provided, which comprises the following raw materials in parts by weight:

[0034] Base asphalt, 100 parts;

[0035] SBS asphalt modifier, 5-20 parts;

[0036] SBR and / or SSBR modifier, 10-25 parts;

[0037] Functional additive, 1-15 parts.

[0038] In the embodiments of the present application, the self-adhesive modified asphalt is prepared by compounding SBS asphalt modifier and SBR / SSBR modifier in a specific ratio, so as to realize the synergistic effect among the components. The long-chain alkyl groups grafted on the SBS molecular chain and the rubber phase of SBR / SSBR cooperate with each other, which can significantly enhance the low-temperature flexibility and durable self-adhesion of the system, and the system still maintains good construction performance even below-10℃. The addition of the functional additive further optimizes the aging resistance, fatigue resistance and other properties of the material. The self-adhesive modified asphalt can realize cold construction without high-temperature heating, which reduces the energy consumption and safety risk, and the comprehensive performance is better than that of the traditional products, and is suitable for waterproofing and road engineering in harsh environments such as cold regions.

[0039] According to the embodiments of the present application, the base asphalt includes at least one of 70# asphalt and 90# asphalt. The functional additive includes at least one of an antioxidant, an ultraviolet absorber, a root inhibitor, a tackifying resin, and a crosslinking agent. Further, the optional antioxidant includes a phenolic antioxidant (such as 2,6-di-tert-butyl-p-cresol), an amine antioxidant (such as N,N'-diphenyl-p-phenylenediamine), and a phosphite auxiliary antioxidant (such as tris(2,4-di-tert-butylphenyl) phosphite), etc.; the optional ultraviolet absorber includes a benzotriazole ultraviolet absorber (such as 2-(2'-hydroxy-5'-methylphenyl) benzotriazole), a benzophenone ultraviolet absorber (such as 2-hydroxy-4-methoxybenzophenone), a salicylate ultraviolet absorber (such as phenyl salicylate), etc.; the optional root inhibitor includes an organic root inhibitor (such as trifluralin, pendimethalin) and an inorganic root inhibitor (such as copper sulfate, zinc sulfate), etc.; the optional tackifying resin includes a rosin resin (such as rosin glycerin ester), a petroleum resin (such as C5 / C9 petroleum resin), a terpene resin, etc.; and the available crosslinking agent includes an organic peroxide crosslinking agent (such as dicumyl peroxide), an isocyanate crosslinking agent (such as diphenylmethane diisocyanate), etc.

[0040] In the embodiments of the present application, the 70# and 90# base bitumen selected by the present application has suitable viscosity and compatibility, provides a stable base material for self-adhesive modified bitumen, and has excellent performance and matching with modifiers and rubber, which can ensure uniform dispersion of the system. In the functional additives, the antioxidant and the ultraviolet absorber synergistically improve the weather resistance of the material and delay aging; the root inhibitor gives the waterproofing membrane the ability to resist penetration by plant roots; the tackifying resin enhances the interfacial adhesion; and the crosslinking agent promotes the formation of a three-dimensional network structure to optimize the mechanical properties. The synergistic effect of the above-mentioned raw materials makes the self-adhesive modified bitumen have low-temperature construction performance, long-lasting adhesion and environmental resistance, meets the engineering needs of different scenes, and further broadens the application range.

[0041] According to the embodiments of the present application, the raw materials of the self-adhesive modified bitumen further include: 0.1-40 parts of inorganic fillers. The inorganic fillers include at least one of calcium carbonate, talc, aluminum hydroxide, graphite, and carbon fiber.

[0042] In the embodiments of the present application, the introduction of inorganic fillers (such as calcium carbonate, talc, etc.) in the self-adhesive modified bitumen can optimize the performance in the following ways: filling the gaps between the system to improve the density of the self-adhesive modified bitumen, enhance the mechanical strength and anti-deformation ability; aluminum hydroxide and the like have flame-retardant effect, which improves the safety in use; graphite and carbon fiber can improve the thermal conductivity and electrical conductivity, and expand the functional scenarios. The fillers and the organic phase realize synergy through interfacial action, while ensuring low-temperature flexibility and self-adhesion, the cost is reduced, the amount of organic components is reduced, the dimensional stability and weather resistance are improved, so that the self-adhesive modified bitumen has significantly improved comprehensive performance and environmental adaptability on the basis of maintaining the core performance, and meets the diversified engineering needs.

[0043] As a fourth aspect of the present application, a preparation method of the above-mentioned self-adhesive modified bitumen is provided, which comprises: mixing the base bitumen, the SBS bitumen modifier, the SBR and / or SSBR modifier, and then performing first shearing development, then adding functional additives and inorganic fillers and mixing, and then performing second shearing development to obtain the self-adhesive modified bitumen; wherein the temperature of the first shearing and the second shearing is independently 160-180℃, and the time of the first shearing and the second shearing is independently 1-2h.

[0044] In the embodiments of the present application, the preparation method of the self-adhesive modified bitumen provided adopts a step-by-step shearing development process: in the first step, high-temperature shearing is performed to promote the uniform dispersion of the SBS bitumen modifier and the SBR / SSBR modifier in the base bitumen, and to form a stable network structure; in the second step, functional additives and inorganic fillers are added for secondary shearing to ensure that the components are fully combined. Through precise control of the shearing temperature and time, it can not only ensure that the components are fully compatible, but also avoid over-aging of the material. This process is stable and controllable, and can efficiently prepare self-adhesive modified bitumen with uniform performance, which is suitable for industrialized continuous production.

[0045] As a fifth aspect of the present application, a self-adhesive modified asphalt waterproofing membrane is provided, which is prepared from the self-adhesive modified asphalt described above.

[0046] In the embodiments of the present application, the self-adhesive modified asphalt waterproofing membrane prepared from the self-adhesive modified asphalt described above retains the excellent properties of the self-adhesive modified asphalt. The membrane remains flexible at low temperatures without brittle fracture, has durable and stable self-adhesive properties, and is convenient and efficient to use and reliable in sealing effect. At the same time, it has good weather resistance and fatigue resistance, can meet the needs of long-term use, and can effectively prevent leakage, providing high-quality waterproof protection for various engineering projects such as buildings and roads, and has significant applicability in cold regions and special engineering scenarios.

[0047] For example, when preparing the self-adhesive modified asphalt waterproofing membrane, the prepared self-adhesive modified asphalt is coated on the surface of the base film (the base film can be selected from cross-laminated film, polyethylene terephthalate (PET) film, etc.) at a temperature of 160-180°C, and then a release film (such as a polyethylene (PE) silicon-coated release film, a PET silicon-coated release film, a polypropylene (PP) silicon-coated release film, etc.) is applied, and the self-adhesive modified asphalt waterproofing membrane is prepared through this process.

[0048] The present application is further illustrated by the following examples and related test experiments. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the present application. However, it will be apparent to one of ordinary skill in the art that one or more embodiments can be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail since it would be apparent to one of ordinary skill in the art that one or more embodiments can be practiced without or with these specific details. Moreover, the details in each of the following examples can be combined in any combination for other possible examples.

[0049] Example 1

[0050] In this example 1, 1-octadecene is grafted to modify SBS to prepare an SBS asphalt modifier, and a self-adhesive modified asphalt waterproofing membrane is further prepared. The specific preparation process is as follows.

[0051] 20g of SBS 7301 particles were dissolved in 90g of naphthenic oil KN4010, heated to 160°C and stirred until completely dissolved under nitrogen protection. 2g of 1-octadecene was added, stirred for 10 minutes to mix evenly, and cooled to 110°C.

[0052] 0.02g of initiator BPO was dissolved in 10g of naphthenic oil KN4010, and was added to the SBS 7301 solution at a uniform speed, and the dropping was completed within 1 minute. The temperature was raised to 160°C, and the reaction was carried out for 2 hours under constant temperature and continuous nitrogen protection. 0.11g of hydroquinone was added to terminate the reaction, and finally a yellow SBS asphalt modifier was obtained.

[0053] Take 55 g SBS asphalt modifier into the mixed solution of 30 g SBR and 440 g 70# asphalt, shear development for 1 h at 170 ℃, add 22 g C9 tackifying resin, stir for 15 min, add 100 g talcum powder, stir for 30 min, to get self-adhesive modified asphalt. The self-adhesive modified asphalt is coated on a polyethylene terephthalate (PET) film base and covered with a PET silicon-coated release film to obtain a 1-octadecene grafted SBS self-adhesive modified asphalt waterproofing membrane.

[0054] Example 2

[0055] This example 2 uses octadecyl methacrylate grafted SBS to prepare SBS asphalt modifier, and further prepares a self-adhesive modified asphalt waterproofing membrane. The specific preparation process is described as follows.

[0056] Dissolve 20 g SBS 7301 particles in 90 g naphthenic oil KN4010, heat to 160 ℃ and stir until completely dissolved under nitrogen protection. Add 2 g octadecyl methacrylate, stir for 10 min to mix evenly, and cool to 110 ℃.

[0057] Dissolve 0.02 g of initiator BPO in 10 g of naphthenic oil KN4010, and add it to the SBS 7301 solution at a uniform speed, dropwise adding within 1 min, heat to 160 ℃, and react for 2 h at constant temperature, continuously passing nitrogen gas, and finally obtain yellow SBS asphalt modifier.

[0058] Take 55 g SBS asphalt modifier into the mixed solution of 30 g SBR and 440 g 70# asphalt, shear development for 1 h at 170 ℃, add 22 g C9 tackifying resin, stir for 15 min, add 100 g talcum powder, stir for 30 min, to get self-adhesive modified asphalt. The self-adhesive modified asphalt is coated on a polyethylene terephthalate (PET) film base and covered with a PET silicon-coated release film to obtain a 1-octadecene grafted SBS self-adhesive modified asphalt waterproofing membrane.

[0059] Comparative Example 1

[0060] This comparative example 1 uses ungrafted SBS asphalt modifier to prepare a self-adhesive modified asphalt waterproofing membrane. The specific preparation process is described as follows.

[0061] 10g SBS7301 and 30g SBR were dissolved in a mixed solution of 45g naphthenic oil KN4010 and 440g 70# base asphalt, sheared at 170℃ for 1h, 22g C9 tackifying resin was added, stirred for 15min, 100g talcum powder was added, stirred for 30min, to obtain a self-adhesive modified asphalt. The self-adhesive modified asphalt was coated on a polyethylene terephthalate (PET) film base and covered with a PET silicon-coated release film to obtain a self-adhesive modified asphalt waterproofing membrane prepared from the ungrafted modified SBS asphalt modifier.

[0062] Further, the grafting rate, glass transition temperature, initial tack force at 0℃ and -5℃ of the SBS asphalt modifier in Examples 1-2 and Comparative Example 1, and the peel strength at 0℃ and -5℃ of the self-adhesive modified asphalt waterproofing membrane in Examples 1-2 and Comparative Example 1 were tested. The grafting rate test method was Soxhlet extraction. The test process was: (1) the SBS asphalt modifier was precipitated with methanol, and the modified SBS solid was separated. (2) After repeated washing, the SBS solid was extracted with toluene in a Soxhlet extractor to remove unreacted monomers and homopolymers. (3) The modified SBS after extraction was dried to constant weight. The grafting rate calculation: grafting rate (%) = [(W g -W0) / W0]x100%. Wherein, W g is the mass of the purified modified SBS, and W0 is the mass of the pure SBS input. The test method for glass transition temperature was differential scanning calorimetry (DSC). The test method for initial tack force was probe peeling. The test method for peel strength was GB / T328.20-2007, self-adhesive adhesive bonding. The test results are shown in Table 1.

[0063] Table 1 Test results of grafting rate, glass transition temperature, initial tack force and peel strength

[0064]

[0065] As shown in Table 1, the grafting rates of Examples 1 and 2 were 8% and 10%, respectively, indicating that the process of the examples could achieve effective grafting. The glass transition temperatures (T g ) of Examples 1 and 2 were -16℃ and -18℃, respectively, which were much lower than the 8℃ of Comparative Example 1, reflecting good low-temperature flexibility. In terms of initial tack force and peel strength, Examples 1 and 2 both had good performance at 0℃ and -5℃, while Comparative Example 1 had 0, indicating that the low-temperature tackiness and interfacial bonding force of the materials of Examples 1 and 2 were superior. In summary, the performance of the self-adhesive modified asphalt of Examples 1 and 2 was superior to that of Comparative Example 1, and the grafting process had a significant effect on performance improvement.

[0066] In summary, the development of low-temperature bonding type self-adhesive modified asphalt can effectively overcome the problems of traditional self-adhesive asphalt, such as difficult construction in cold environment, easy failure of bonding. Specifically, first, it breaks the limitation of low-temperature construction, so that the construction season can be extended; second, it ensures that the waterproof layer is firmly bonded and sealed during low-temperature construction; third, it meets the waterproof requirements of high-cold regions and special low-temperature scenarios; fourth, it enhances the environmental adaptability and market competitiveness of self-adhesive membranes. This achievement conforms to the trend of building waterproof materials towards high performance, all-weather application, and convenient construction, and is an inevitable product of industry development.

[0067] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing an SBS asphalt modifier, characterized in that: include: Add SBS to naphthenic oil, heat to dissolution temperature and stir until completely dissolved to obtain SBS solution; Contains C 10 -C 30 Adding a polymerizable monomer having a linear alkyl group to the SBS solution and mixing them uniformly to obtain a mixed solution; adding a free radical polymerization initiator to the mixed solution to carry out a free radical grafting reaction under an inert atmosphere; A terminator is added to terminate the reaction to obtain SBS asphalt modifier.

2. The preparation method according to claim 1, characterized in that The C-containing 10 -C 30 The linear alkyl polymerizable monomer includes any one of linear α-olefins, linear alkyl mercaptans, linear alkyl acrylates, and linear alkyl amines; The naphthenic oil includes at least one of KN4010, KN4020, T9, T15, T19, NYTEX 4700, NYTEX 810, and NYTEX 820; The free radical polymerization initiator includes any one of dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile; The terminator includes hydroquinone.

3. The preparation method according to claim 2, characterized in that The dissolution temperature is 120-160°C; The reaction temperature of the free radical grafting reaction is 150-170° C., and the reaction time of the free radical grafting reaction is 2-4 hours; Inert gas is continuously introduced during the free radical grafting reaction.

4. The preparation method according to claim 1, characterized in that The mass ratio of SBS to naphthenic oil in the SBS solution is 1:4-9; The C-containing 10 -C 30 The amount of the linear alkyl polymerizable monomer added is 5-20% of the mass of SBS; The amount of initiator added is C 10 -C 30 0.2-1% by mass of the polymerizable monomer of linear alkyl group; The amount of the terminator added is 10 -C 30 0.1-0.5% by mass of the linear alkyl polymerizable monomer.

5. An SBS asphalt modifier, characterized in that: Prepared by the preparation method according to any one of claims 1 to 4.

6. A self-adhesive modified asphalt, characterized in that: The composition comprises the following raw materials in parts by weight: Base asphalt, 100 parts; 5-20 parts of the SBS asphalt modifier according to claim 5; SBR and / or SSBR modifier, 10-25 parts; Functional additives, 1-15 parts.

7. The self-adhesive modified asphalt according to claim 6, characterized in that The matrix asphalt includes at least one of 70# asphalt and 90# asphalt; The functional additives include at least one of an antioxidant, an ultraviolet absorber, a root inhibitor, a tackifying resin, and a cross-linking agent.

8. The self-adhesive modified asphalt according to claim 7, characterized in that: The raw materials of the self-adhesive modified asphalt also include: 0.1-40 parts of inorganic filler; Wherein, the inorganic filler includes at least one of calcium carbonate, talc, aluminum hydroxide, graphite, and carbon fiber.

9. A method for preparing a self-adhesive modified asphalt according to any one of claims 6 to 8, characterized in that: include: After mixing the base asphalt, SBS asphalt modifier, SBR and / or SSBR modifier and performing a first shear development, the functional additive and inorganic filler are added, mixed and performed a second shear development to obtain a self-adhesive modified asphalt; The temperatures of the first shearing and the second shearing are independently 160-180° C., and the times of the first shearing and the second shearing are independently 1-2 hours.

10. A self-adhesive modified asphalt waterproof membrane, characterized in that: Prepared from the self-adhesive modified asphalt as described in any one of claims 6 to 8.

Images