Non-cured asphalt-based waterproof coating and preparation method thereof

Abstract

The invention provides a non-cured asphalt-based waterproof coating and a preparation method thereof. Wherein the non-cured asphalt-based waterproof coating comprises the following raw material components in parts by weight: 45-70 parts of asphalt; 10 to 20 parts of a compatilizer; 3-10 parts of a thermoplastic elastomer; 3-5 parts of styrene butadiene rubber; 3-5 parts of resin; 2-5 parts of wax powder; 5 to 20 parts of modified graphene oxide; 12-25 parts of an inorganic filler; 0.2 to 0.8 part of a dispersant; wherein the modified graphene oxide is alkylamine modified graphene oxide. According to the non-cured asphalt-based waterproof coating provided by the invention, alkylamine modified graphene oxide is introduced into the waterproof coating, has better compatibility with other components, and forms more heat conduction routes in the non-cured asphalt-based waterproof coating, so that the heat conductivity coefficient of the waterproof coating is effectively improved, and the heating time and heating temperature of coating construction are reduced; no smoke is generated during construction, the environmental protection property is high, and fire of the non-curing coating caused by high-temperature heating can be effectively reduced.

Description

Technical Field

[0001] This application belongs to the technical field of waterproof coatings, and particularly relates to a non-curing asphalt-based waterproof coating and a preparation method thereof. Background Art

[0002] The non-curing asphalt-based waterproof coating has the characteristics of good creep performance, strong self-healing ability and excellent bonding performance. It is widely used in various waterproof projects and has become one of the waterproof materials with rapid development in the waterproof industry.

[0003] However, during the construction heating process of the non-curing asphalt-based waterproof coating, uneven heating is likely to occur, resulting in a large amount of smoke emission, which affects the health of workers and pollutes the environment. It is also easy to have local overheating during heating, causing the material to be ignited and easily leading to fires. Summary of the Invention

[0004] In view of this, this application provides a non-curing asphalt-based waterproof coating and a preparation method thereof, which can effectively improve the thermal conductivity coefficient of the waterproof coating, reduce the construction heating time and heating temperature of the coating, produce no smoke during construction, have strong environmental protection, and can effectively reduce the ignition of the non-curing coating caused by high-temperature heating.

[0005] In the first aspect, an embodiment of this application provides a non-curing asphalt-based waterproof coating, which includes the following raw material components in parts by weight: asphalt, 45 - 70 parts; compatibilizer, 10 - 20 parts; thermoplastic elastomer, 3 - 10 parts; styrene-butadiene rubber, 3 - 5 parts; resin, 3 - 5 parts; wax powder, 2 - 5 parts; modified graphene oxide, 5 - 20 parts; inorganic filler, 12 - 25 parts; dispersant, 0.2 - 0.8 parts; wherein, the modified graphene oxide is alkylamine-modified graphene oxide, and the number of carbon atoms in the alkyl chain of the alkylamine-modified graphene oxide is 10 - 20.

[0006] According to the embodiment of the first aspect of this application, the grafting rate of alkylamine in the modified graphene oxide is 20% - 35%.

[0007] According to the embodiment of the first aspect of this application, the inorganic filler includes magnesium hydroxide and auxiliary filler, and the auxiliary filler includes one or more of talc powder, heavy calcium, barium sulfate, titanium dioxide, mica powder, talc powder, kaolin.

[0008] According to the embodiment of the first aspect of this application, the mass ratio of magnesium hydroxide to the auxiliary filler is 1:(1.2 - 1.5).

[0009] According to the embodiment of the first aspect of this application, the thermoplastic elastomer is an SBS elastomer, and the molar ratio of butadiene to styrene in the SBS elastomer is 1:2.3 - 2.5, and the degree of hydrogenation is 3 - 8%.

[0010] According to an embodiment of the first aspect of the present application, the penetration of the asphalt is 130-200.

[0011] According to an embodiment of the first aspect of the present application, the compatibilizer includes one or more of cashew shell oil, aromatic oil, extraction oil, residue oil, bio-oil, base oil, and rubber oil.

[0012] According to an embodiment of the first aspect of the present application, the resin includes one or more of C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymerized petroleum resin, terpene resin, and alicyclic epoxy resin.

[0013] According to an embodiment of the first aspect of the present application, the dispersant is a hyperdispersant, and the molecular weight of the hyperdispersant is 2000-6000.

[0014] According to an embodiment of the first aspect of the present application, the average particle size of the modified graphene oxide is 800 mesh to 1500 mesh.

[0015] According to an embodiment of the first aspect of the present application, the average particle size of the inorganic filler is 800 mesh to 1500 mesh.

[0016] In a second aspect, an embodiment of the present application provides a method for preparing a non-curing asphalt-based waterproof coating, including the following steps: providing raw materials according to the components and component contents included in the non-curing asphalt-based waterproof coating of the first aspect of the present application; mixing the asphalt with the compatibilizer to obtain a first slurry; adding a thermoplastic elastomer, styrene-butadiene rubber, and resin to the first slurry for mixing to obtain a second slurry; adding modified graphene oxide, wax powder, inorganic filler, and hyperdispersant to the second slurry for mixing to obtain a non-curing asphalt-based waterproof coating.

[0017] According to an embodiment of the second aspect of the present application, the method further includes: preparing modified graphene oxide by the following method: dissolving alkylamine in an alcohol solvent to obtain an alkylamine solution; adding graphene oxide to the alkylamine solution, removing the unreacted alkylamine after the reaction, and drying to obtain a parent powder; dissolving the parent powder in deionized water to obtain a parent powder solution, adding a reducing agent, and drying after the reaction to obtain modified graphene oxide.

[0018] Compared with the prior art, the present application has at least the following beneficial effects:

[0019] The non-curing asphalt-based waterproof coating provided by this application introduces long-chain alkylamine modified graphene oxide into the waterproof coating. Due to the grafting of long alkyl chains, the graphene modified by alkylamine has better compatibility with other components in the waterproof coating. At the same time, the introduction of amino groups in the alkylamine modified graphene oxide can reduce the agglomeration of substances such as asphalt and powder, forming more heat conduction routes in the non-curing asphalt-based waterproof coating, thereby effectively increasing the thermal conductivity of the waterproof coating, reducing the construction heating time and heating temperature of the coating, generating no flue gas during construction, having strong environmental protection, and effectively reducing the risk of the non-curing coating catching fire caused by high-temperature heating; and by comprehensively adjusting the weight parts between various components, the adhesion and long-term storage stability of the non-curing asphalt-based waterproof coating can be significantly improved, and when applied to non-curing asphalt-based waterproof coiled materials, etc., it can effectively improve the adhesion to the cement concrete base surface, and improve the aging resistance and anti-channeling water performance of the asphalt coiled material. Detailed Embodiments

[0020] In order to make the application purpose, technical solution and beneficial technical effects of this application clearer, the following further details this application with reference to embodiments. It should be understood that the embodiments described in this specification are only for explaining this application and not for limiting this application.

[0021] For simplicity, this application only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form a range not explicitly recorded; and any lower limit can be combined with other lower limits to form a range not explicitly recorded, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recorded. In addition, although not explicitly recorded, each point or single value between the range endpoints is included in this range. Thus, each point or single value can be used as its own lower or upper limit and combined with any other point or single value or combined with other lower or upper limits to form a range not explicitly recorded.

[0022] In the description of this application, it should be noted that unless otherwise specified, "above" and "below" include this number, and "multiple" in "one or more" means two or more.

[0023] Currently, non-curing rubber-modified asphalt-based waterproof coatings are prepared from raw materials such as asphalt, SBS, SBR, compatibilizers, fillers, modified rubber powder / rubber powder, etc. Non-curing rubber-modified asphalt-based waterproof coatings have characteristics such as good creep performance, strong self-healing ability, and excellent adhesion performance, and are widely used in various waterproof projects, becoming one of the waterproof materials with relatively fast development in the waterproof industry; however, in the prior art, the general construction heating time is too long, and heating unevenness is likely to occur during the construction heating process, resulting in a large amount of harmful flue gas emerging, affecting the health of workers and polluting the environment, and it is also easy to have local overheating during heating, causing the material to be ignited, easily triggering a fire, and at the same time the material fails.

[0024] In view of the above problems, the present application provides a non-curing asphalt-based waterproof coating with easy heating, aging resistance, and good adhesion performance, and a preparation method thereof.

[0025] Non-curing asphalt-based waterproof coating

[0026] In a first aspect, an embodiment of the present application provides a non-curing asphalt-based waterproof coating, which includes the following raw material components in parts by weight: asphalt, 45-70 parts; compatibilizer, 10-20 parts; thermoplastic elastomer, 3-10 parts; styrene-butadiene rubber, 3-5 parts; resin, 3-5 parts; wax powder, 2-5 parts; modified graphene oxide, 5-20 parts; inorganic filler, 12-25 parts; super dispersant, 0.2-0.8 part; wherein, the modified graphene oxide is alkylamine-modified graphene oxide, and the number of carbon atoms in the alkyl chain of the alkylamine-modified graphene oxide is 10-20.

[0027] In order to ensure the non-curing property of the non-curing asphalt-based waterproof coating and maintain a non-curing state at normal temperature. Exemplarily, the asphalt includes one or a mixture of two of asphalt with a grade of 160# (160#) and above. The above grades of asphalt have excellent comprehensive properties such as anti-slip, heat resistance, and viscosity. Among them, 160# represents the grade of asphalt, and each grade of asphalt corresponds to a specific composition, and its specific physical and chemical property parameters are not exactly the same. It can be understood that as the asphalt grade increases, its penetration increases and its low-temperature performance is better; but as the asphalt grade decreases, its softening point increases and its heat resistance improves. Exemplarily, the weight of the asphalt is 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts.

[0028] The addition of the thermoplastic elastomer makes the non-curing asphalt-based waterproof coating have better stability at high temperatures, reducing the flow and deformation of the asphalt at high temperatures. For example, in hot summer, ordinary asphalt-based waterproof coatings may flow due to too high temperature, resulting in uneven thickness of the waterproof layer and affecting the waterproof effect. After adding the thermoplastic elastomer, this situation can be effectively avoided, and the coating can still maintain good waterproof performance in a high-temperature environment.

[0029] Meanwhile, the thermoplastic elastomer has a certain elasticity, which can significantly improve the flexibility and elasticity of the waterproof coating, making the coating not easily break when subjected to external force stretching, bending or base layer deformation, and effectively adapting to changes such as the expansion and contraction, cracking of the base layer. The addition of the thermoplastic elastomer significantly improves the low-temperature flexibility of the asphalt-based waterproof coating, making it not easily brittle at low temperatures. In cold winters, the unmodified asphalt-based waterproof coating may become hard and brittle and prone to cracks, while the presence of the thermoplastic elastomer can keep the coating elastic at low temperatures, adapt to the deformation and contraction of the base layer, and thus effectively prevent the generation of cracks and ensure the integrity of the waterproof layer. Exemplarily, the weight parts of the thermoplastic elastomer are 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts or 20 parts.

[0030] Styrene-butadiene rubber has good heat resistance. In the non-curing asphalt-based waterproof coating, it can form a stable cross-linked structure with asphalt, making the asphalt not easily flow and deform at high temperatures, thereby improving the service performance of the coating in high-temperature environments and ensuring good waterproof effects of the waterproof layer under high-temperature conditions such as hot summers; the flexible chain segments in the molecular structure of styrene-butadiene rubber can increase the flexibility of asphalt, reduce its brittle point, make the non-curing asphalt-based waterproof coating not easily brittle at low temperatures, improve the low-temperature flexibility of the coating, enable it to adapt to the climatic conditions in cold regions, and reduce problems such as cracking of the waterproof layer caused by low temperatures. Exemplarily, the weight parts of styrene-butadiene rubber are 3 parts, 4 parts or 5 parts.

[0031] The wax powder can improve the heat resistance of the non-curing asphalt-based waterproof coating. When the temperature drops below the melting point of the wax powder, the wax powder will crystallize and precipitate with some saturated components adsorbed and dissolved by it to form a stable network lattice structure, hindering the movement of asphalt molecules, thereby significantly enhancing the heat resistance of the asphalt-based waterproof coating and reducing the occurrence of phenomena such as flowing and deformation of the coating in high-temperature environments. Exemplarily, the weight parts of the wax powder are 2 parts, 3 parts, 4 parts or 5 parts.

[0032] Preferably, the wax powder is oxidized polyethylene wax powder. The oxidized polyethylene wax powder has a coupling effect, can improve the bonding force between the resin and the inorganic filler, enhance the mechanical properties and comprehensive quality of the non-curing asphalt-based waterproof coating, and strengthen the durability and reliability of the non-curing asphalt-based waterproof coating.

[0033] The resin can improve the heat resistance of the non-curing asphalt-based waterproof coating. After adding the resin, the softening point of the non-curing asphalt-based waterproof coating can be increased, enabling it to still maintain good stability and waterproof performance in high-temperature environments; the resin can adjust the viscosity of the asphalt-based waterproof coating, making it easier to operate during construction processes such as brushing and spraying, and being able to better control the thickness and uniformity of the coating. For example, terpenes, coumarone and rosin glyceride can temporarily increase the viscosity of asphalt. Exemplarily, the weight parts of the resin are 3 parts, 4 parts or 5 parts.

[0034] The non-curing asphalt-based waterproof coating includes multiple components, which have significant differences in terms of polarity, molecular weight, chemical structure, etc. The non-curing asphalt-based waterproof coating of the embodiments of the present application can reduce the interfacial tension between different components by adding a compatibilizer, making it easier for them to disperse and mix with each other, forming a stable system, and avoiding phenomena such as phase separation, precipitation, and delamination, thereby improving the quality and performance stability of the non-curing asphalt-based waterproof coating. Exemplarily, the weight parts of the compatibilizer are 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, or 20 parts.

[0035] Graphene modified with alkylamine has a grafted alkyl chain. Alkylamine can form an organic molecular layer on the surface of graphene oxide, having better compatibility with the non-curing asphalt-based waterproof coating. At the same time, the introduction of amino groups in the alkylamine-modified graphene oxide can reduce the agglomeration of substances such as asphalt and powder. The alkylamine-modified graphene oxide has an ultra-high in-plane thermal conductivity. In the non-curing asphalt-based waterproof coating, when the addition amount of the alkylamine-modified graphene oxide is sufficient and evenly dispersed, its flaky structure can be interconnected to form a thermal conduction network, and heat can be rapidly transferred inside the coating through this network, thereby effectively improving the overall thermal conductivity of the coating. Since the alkylamine-modified graphene oxide improves the thermal conductivity of the coating, it helps to evenly distribute the heat during the heating process of the coating, reducing the occurrence of local overheating phenomena, thereby inhibiting the thermal stress generated due to rapid temperature changes. Therefore, it can reduce the construction heating time and heating temperature of the coating, with no flue gas generated during construction, strong environmental protection, and can effectively reduce the ignition of the non-curing coating caused by high-temperature heating. At the same time, when the coating is applied to the surface of an object, it can more rapidly conduct the heat on the surface of the object to the surface of the coating and dissipate it to the surrounding environment. For some devices or structures that require heat dissipation, such as the roofs and walls of buildings and the outer shells of industrial equipment, it can effectively reduce their surface temperature, reduce heat accumulation, and prevent problems such as material aging and deformation caused by overheating. Exemplarily, the weight parts of the alkylamine-modified graphene oxide are 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, or 20 parts.

[0036] In the embodiments of the present application, the number of carbon atoms in the alkyl chain of the alkylamine-modified graphene oxide is 10 - 20. Exemplarily, the number of carbon atoms in the alkyl chain is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0037] Inorganic fillers can enhance the strength of non-curing asphalt-based waterproof coatings. Inorganic fillers have a relatively high hardness. When added to the waterproof coating, they can significantly improve the hardness and wear resistance of the waterproof coating, making the coating film less likely to be damaged when subjected to external forces, thereby enhancing the durability of the waterproof layer. Exemplarily, the weight parts of the inorganic filler are 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts or 25 parts.

[0038] The dispersant is used to evenly disperse each component in the coating system to prevent particle agglomeration. Uniformly dispersed particles can better exert their respective properties. Exemplarily, the weight parts of the dispersant are 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts or 20 parts. Exemplarily, the dispersant includes one or more of sodium hexametaphosphate, sodium tripolyphosphate, oleic acid, stearic acid, triethanolamine, sodium polyacrylate, polyether-based polymer dispersants and polyurethane-based dispersants.

[0039] The non-curing asphalt-based waterproof coating provided by this application introduces alkylamine-modified graphene oxide into the waterproof coating. Due to the grafting of alkyl chains, the graphene modified by alkylamine has better compatibility with other components in the waterproof coating. At the same time, the introduction of amino groups in the alkylamine-modified graphene oxide can reduce the agglomeration of substances such as asphalt and powder, forming more heat conduction paths in the non-curing asphalt-based waterproof coating, thereby effectively increasing the thermal conductivity of the waterproof coating, reducing the coating construction heating time and heating temperature, generating no flue gas during construction, having strong environmental protection, and being able to effectively reduce the ignition of non-curing coatings caused by high-temperature heating; and by comprehensively adjusting the weight parts between each component, it can significantly improve the adhesion and long-term storage stability of the non-curing asphalt-based waterproof coating, and can effectively improve the adhesion to the cement concrete base surface when applied to non-curing asphalt-based waterproof rolls, etc., and improve the aging resistance and anti-channeling water performance of asphalt rolls.

[0040] In some embodiments, the grafting rate of alkylamine in the modified graphene oxide is 20% - 35%.

[0041] In the embodiments of this application, the grafting rate refers to the ratio of the mass of alkylamine grafted onto graphene oxide to the mass of graphene oxide in the grafting reaction. Exemplarily, through energy dispersive X-ray spectroscopy (EDS) characterization, the atomic percentages and weight percentages of C, O, and N are obtained, and then the grafting rate of alkylamine is calculated.

[0042] The inventors of the present application noticed in experiments that a good thermal conductivity can be achieved when the grafting rate of alkylamine in modified graphene oxide is within this range. This may be because alkylamine can form an organic molecular layer on the surface of graphene oxide, increasing the steric hindrance between the graphene oxide sheets, reducing the interaction between the sheets, thus effectively preventing their agglomeration and enabling them to disperse more uniformly in the waterproof coating. With better thermal conductivity, the heating time and temperature during coating construction can be reduced. There is no smoke generated during construction, and it has strong environmental protection, effectively reducing the risk of non-curing coating ignition caused by high-temperature heating. Exemplarily, the grafting rate is 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34% or 35%.

[0043] In some embodiments, the inorganic filler includes magnesium hydroxide and auxiliary fillers, and the auxiliary fillers include one or more of talc powder, heavy calcium carbonate, barium sulfate, titanium dioxide, mica powder, talc powder, kaolin.

[0044] Magnesium hydroxide and auxiliary fillers can make the non-curing asphalt-based waterproof coating more durable during use, enhancing wear resistance, scratch resistance and impact resistance; moreover, the fine particle structure of magnesium hydroxide also makes the non-curing asphalt-based waterproof coating more uniform and stable, not prone to precipitation and stratification phenomena, thus improving the overall quality of the non-curing asphalt-based waterproof coating; in addition, magnesium hydroxide is an endothermic material that can absorb a large amount of heat, assisting the non-curing asphalt-based waterproof coating system to conduct heat faster. When combined with modified graphene oxide, it can effectively improve the thermal conductivity of the waterproof coating, reduce the heating time and temperature during coating construction, generate no smoke during construction, have strong environmental protection, and effectively reduce the ignition of non-curing coatings caused by high-temperature heating.

[0045] Considering that magnesium hydroxide is an alkaline substance, adding an excessive amount will cause the non-curing asphalt-based waterproof coating system to be prone to cracking during use, and when adding an excessive amount, due to excessive heat absorption by itself, the heating time will be longer instead. Therefore, in some embodiments, the mass ratio of magnesium hydroxide to auxiliary fillers is 1:(1.2 - 1.5). Exemplarily, the mass ratio of magnesium hydroxide to auxiliary fillers is 1:1.2, 1:1.3, 1:1.4 or 1:1.5.

[0046] In some embodiments, the thermoplastic elastomer is an SBS elastomer, and the molar ratio of butadiene to styrene in the SBS elastomer is 1:2.3 - 2.5, and the degree of hydrogenation is 3 - 8%.

[0047] Within this range of SBS hydrogenation degree, the low-temperature performance and adhesion performance are better. Excessive hydrogenation makes the material hard and the elasticity decreases, making it difficult to dissolve in the system and not easily forming a non-curing state, with poor adhesion.

[0048] In some embodiments, the penetration of the asphalt is 130-200. The penetration of the asphalt within this range can ensure the non-curing property of the non-curing asphalt-based waterproof coating, and it can also maintain a non-curing state at room temperature.

[0049] In the embodiments of the present application, the penetration of the asphalt refers to a standard needle with a total load of 100 grams. At a temperature of 25 °C, the depth at which the standard needle vertically penetrates the asphalt specimen within 5 seconds is the penetration of the asphalt, and the unit is 1 / 10 mm.

[0050] In some embodiments, the compatibilizer includes one or more of cashew shell oil, aromatic oil, extraction oil, residual oil, bio-oil, base oil, and rubber oil.

[0051] In some embodiments, the resin includes one or more of C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymerized petroleum resin, terpene resin, and alicyclic epoxy resin.

[0052] Preferably, in the embodiments of the present application, the dispersant is a hyperdispersant. By introducing a hyperdispersant into the non-curing asphalt-based waterproof coating, the molecular structure of the hyperdispersant contains an anchoring group and a solvation chain. The anchoring group can tightly adsorb on the particle surfaces of the modified graphene oxide and the filler, and the solvation chain forms a steric hindrance around the particles, effectively preventing the particles from aggregating due to van der Waals forces, electrostatic attraction, etc., so that the modified graphene oxide and the filler can be uniformly dispersed in the non-curing asphalt-based waterproof coating with a smaller particle size.

[0053] In some embodiments, the molecular weight of the hyperdispersant is 2000-6000.

[0054] For a hyperdispersant with a moderate molecular weight, its solvation chain segment can form a protective layer with sufficient thickness on the particle surface, generating an effective steric hindrance effect to prevent the particles from approaching and aggregating with each other, thereby improving the stability of the dispersion system. If the molecular weight is too small, the solvation chain segment is too short, and the steric effect is not obvious, unable to provide sufficient steric hindrance; while if the molecular weight is too large, it may lead to too long chain segments and too high affinity for the medium, which will not only cause the hyperdispersant to desorb from the particle surface, but may also cause the reverse folding of the chain segments, compressing the steric hindrance or causing entanglement with adjacent molecules, ultimately resulting in the re-aggregation or flocculation of the filler particles. Exemplarily, the molecular weight of the hyperdispersant is 2000-3000, 3000-4000, 4000-5000, 5000-6000, 2000-4000, 2000-5000, 3000-5000, 3000-6000, or 4000-6000.

[0055] Exemplarily, the hyperdispersant includes at least one of polyester-based hyperdispersants, polyether-based hyperdispersants, polyacrylate-based hyperdispersants, and polyolefin-based hyperdispersants.

[0056] Exemplarily, the solvation chains of polyester-based hyperdispersants are prepared by polycondensation of hydroxy acids or ring-opening reactions of lactone compounds. For example, using 12-hydroxystearic acid and ε-caprolactone as raw materials, and fatty acids or resins as end-capping agents to obtain carboxyl-terminated polyesters.

[0057] The solvation chains of polyether-based hyperdispersants are mainly homopolymers and copolymers of substances such as ethylene oxide, propylene oxide, and tetrahydrofuran, such as copolymers of ethylene oxide and propylene oxide. It can be prepared by using an anchoring group as an initiator through ring-opening reactions of cyclic ether substances, and has good dispersion effects on inorganic pigments in strongly polar media such as alcohols and ethers.

[0058] The selection range of acrylate monomers in polyacrylate-based hyperdispersants is wide, and the polarity and solubility parameters of the solvation chains can be adjusted by changing the feeding ratio of copolymer monomers. Generally, mercapto acids, mercapto alcohols, etc. are selected as chain transfer agents to obtain monofunctionalized solvation chains, and the subsequent reactions of carboxyl-terminated or hydroxyl-terminated polyacrylates are similar to those of polyester-based ones.

[0059] Exemplarily, terminal polyisobutene in polyolefin-based hyperdispersants is an important representative, which has excellent dispersion effects in hydrocarbon media, can make the volume fraction of solid particles in the dispersion system reach a relatively high level, while the dispersion still maintains a moderate operating viscosity.

[0060] In some embodiments, the average particle size of the modified graphene oxide is 800 mesh to 1500 mesh.

[0061] A suitable particle size helps the modified graphene oxide to form a more perfect thermal conduction network in the matrix material. When the particle size is small, the number of graphene oxide sheets increases, the specific surface area increases, the contact points and contact areas between them increase, and a continuous thermal conduction path can be constructed more effectively, enabling heat to be transferred more quickly inside the material, thereby improving the thermal conductivity of the composite material.

[0062] In some embodiments, the average particle size of the inorganic filler is 800 mesh to 1500 mesh.

[0063] The average particle size of the inorganic filler within the above range can make the coating more dense. At the same time, it can make the surface of the coating smoother during use, improving the gloss; fillers with too large a particle size may cause an increase in the surface roughness of the coating during use and affect the adhesion performance, while fillers with too small a particle size have poor dispersibility.

[0064] Preparation method of non-curing asphalt-based waterproof coating

[0065] In a second aspect, the embodiments of the present application provide a preparation method for a non-curing asphalt-based waterproof coating, including the following steps:

[0066] S1 Provide raw materials according to the components and component contents of the non-curing asphalt-based waterproof coating of the first aspect of the present application; mix asphalt and compatibilizer to obtain a first slurry;

[0067] S2 Add thermoplastic elastomer, styrene-butadiene rubber and resin to the first slurry for mixing to obtain a second slurry;

[0068] S3 Add modified graphene oxide, wax powder, inorganic filler, and super-dispersant to the second slurry for mixing to obtain a non-curing asphalt-based waterproof coating.

[0069] The present application does not limit the mixing method, as long as the requirement of uniform mixing can be met. Exemplarily, a high-speed mixer can be used for mixing, and the rotation speed and mixing time of the high-speed mixer can be set according to the types and addition amounts of the components to ensure that all components can be fully mixed.

[0070] Exemplarily, in S1, weigh asphalt and compatibilizer according to weight fraction, add them to a reaction kettle, heat up and stir at a low speed for 15 - 20 min to obtain a first slurry; in S2, add thermoplastic elastomer, styrene-butadiene rubber and resin to the stirred reaction kettle, raise the temperature to 170 - 182 °C, and the stirring speed is 1400 r / min, and keep reacting for 2 - 3 h to obtain a second slurry; in S3, add modified graphene oxide, oxidized polyethylene wax powder, inorganic filler, and super-dispersant to the second slurry, the stirring speed is 1500 r / min, the reaction temperature is 175 - 180 °C, and the reaction time is not less than 45 min to obtain a non-curing asphalt-based waterproof coating.

[0071] In some embodiments, modified graphene oxide is prepared by the following method:

[0072] S31 Dissolve alkylamine in an alcohol solvent to obtain an alkylamine solution;

[0073] S32 Add graphene oxide to the alkylamine solution, remove the un-grafted alkylamine after reaction, and obtain a parent powder after drying;

[0074] S33 Dissolve the parent powder in deionized water to obtain a parent powder solution, add a reducing agent, and obtain modified graphene oxide after reaction and drying.

[0075] In the embodiments of the present application, the number of carbon atoms in the alkyl chain of the alkylamine is 10 - 20. Exemplarily, the number of carbon atoms in the alkyl chain is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0076] Exemplarily, in S31, stearylamine is taken and dissolved in anhydrous ethanol at room temperature to obtain a stearylamine solution; in S32, a dispersion solution of modified graphene oxide is added to the solution, and the mixture is stirred at room temperature for 12 h. The solution is filtered by suction with anhydrous ethanol and deionized water to remove the excess stearylamine, and the stearylamine-modified matrix powder is obtained after freeze-drying; in S33, it is dissolved in deionized water to prepare an aqueous solution, an appropriate amount of ascorbic acid is added, and the mixture is stirred and reacted at 80 °C for 12 hours, washed repeatedly with deionized water, and the reduced modified graphene oxide is obtained after freeze-drying.

[0077] Exemplarily, the present application provides a method for preparing graphene oxide: concentrated sulfuric acid is added in an ice-water bath, flake graphite and sodium nitrate are added, and then potassium permanganate is slowly added, controlling the temperature not to exceed 10 °C, and stirring and reacting for at least 40 minutes; then the reaction solution is transferred to a warm water bath, the temperature is controlled at about 35 °C, and stirring and reacting continue for 2 hours; deionized water is added, the temperature is maintained between 70-100 °C, hydrogen peroxide is added after the reaction to reduce the residual oxidant, and the solution turns bright yellow; 5% hydrochloric acid solution is used to remove metal ions. The obtained golden-yellow mixed solution is centrifuged and washed repeatedly with deionized water until the pH value of the solution is 6-7, and then low-frequency ultrasonic treatment is carried out for 2 h to obtain a graphene oxide dispersion solution.

[0078] Examples

[0079] The following examples more specifically describe the content disclosed in the present invention. These examples are only for illustrative purposes, because various modifications and changes within the scope of the present invention are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are all commercially available.

[0080] The sources of some raw materials used in the following examples are as follows:

[0081] Asphalt: Sinopec asphalt

[0082] Graphene: natural flake graphite, purchased from Qingdao Xincheng New Materials Co., Ltd.

[0083] Stearylamine: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0084] Hyperdispersant D-8001: purchased from Foshan Guiteng New Materials Technology Co., Ltd., with a molecular weight of 2000-6000

[0085] Aromatic oil: Cangzhou Nandagang Management Area Ruite Petroleum Products Co., Ltd.

[0086] Residual oil: Chongqing Longchong New Materials Co., Ltd.

[0087] SBS: Purchased from Baling Petrochemical

[0088] SBR: Shandong Qianyu New Materials Co., Ltd.

[0089] C5 petroleum resin: Henghe Material Technology Co., Ltd.

[0090] Styrene-modified terpene resin: Jining Tangyi Chemical Co., Ltd.

[0091] Example 1

[0092] The non-curing asphalt-based waterproof coating of this example includes the following raw material components in parts by weight:

[0093] 160# asphalt 52 parts

[0094] Compatibilizer 10 parts

[0095] SBS 3.5 parts

[0096] SBR 4 parts

[0097] Resin 5 parts

[0098] Oxidized polyethylene wax powder 2 parts

[0099] Modified graphene oxide 10 parts

[0100] Inorganic filler 13.1 parts

[0101] Hyperdispersant D-8001 0.4 parts

[0102] Among them, the compatibilizer is aromatic oil and residual oil, and the ratio is 1:0.2;

[0103] SBS is hydrogenated SBS with butadiene:styrene = 1:2.5 and a hydrogenation degree of 4%;

[0104] SBR is emulsion-polymerized styrene-butadiene rubber particles with an effective content > 92%.

[0105] The resin is a mixed resin of C5 petroleum resin and styrene-modified terpene resin with a mass ratio of 1:0.8;

[0106] The modified graphene oxide is reduced octadecylamine-modified graphene oxide with a grafting rate of 25% and an average particle size of 1000 mesh;

[0107] The inorganic filler is magnesium hydroxide:talc powder = 1:1.4;

[0108] Its preparation method includes the following steps:

[0109] Step 1: Weigh asphalt and compatibilizer according to weight fraction and add them into the reaction kettle. Heat up and stir at a low speed for 15 - 20 min to obtain the first slurry.

[0110] Step 2: Add SBS, SBR, and resin into the stirred reaction kettle. Raise the temperature to 175 °C and the stirring speed to 1400 r / min. Keep reacting for 2.5 h to obtain the second slurry.

[0111] Step 3: Add modified graphene oxide, inorganic filler, and dispersant into the second slurry. The stirring speed is 1500 r / min, the reaction temperature is 175 °C, and the reaction time is 1 h to obtain the non-curing asphalt-based waterproof coating.

[0112] Example 2

[0113] The difference from Example 1 is that the addition amount of reduced octadecylamine-modified graphene oxide powder is 15 parts, and the inorganic filler is 8.1 parts.

[0114] Example 3

[0115] The difference from Example 1 is that the addition amount of reduced octadecylamine-modified reduced graphene powder is 6 parts, and the inorganic filler is 17.1 parts

[0116] Example 4

[0117] The difference from Example 1 is that the compatibilizer is rubber oil: cashew shell oil = 1:0.3, and the oxidized polyethylene wax powder is 3.5 parts.

[0118] Example 5

[0119] The difference from Example 1 is that the grafting rate of octadecylamine in the modified graphene oxide is 15%.

[0120] Example 6

[0121] The difference from Example 1 is that the average particle size of the modified graphene oxide is 100 mesh.

[0122] Example 7

[0123] The difference from Example 1 is that the inorganic filler is magnesium hydroxide: talc powder = 1:1.

[0124] Example 8

[0125] The difference from Example 1 is that the inorganic filler is talc powder.

[0126] Example 9

[0127] The difference from Example 1 is that the inorganic filler is talc powder and the SBS is linear SBS.

[0128] Example 10

[0129] Different from Example 1, the modified graphene oxide is reduced hexadecylamine modified graphene oxide powder.

[0130] Example 11

[0131] Different from Example 1, the modified graphene oxide is reduced tetradecylamine modified graphene oxide powder.

[0132] Example 12

[0133] Different from Example 1, the modified graphene oxide is reduced dodecylamine modified graphene oxide powder.

[0134] Example 13

[0135] Different from Example 1, oleic acid is used as the dispersant instead of the hyperdispersant.

[0136] Comparative Example 1

[0137] Different from Example 1, graphene oxide is added instead of modified graphene oxide.

[0138] Comparative Example 2

[0139] Different from Example 1, the addition amount of reduced octadecylamine modified reduced graphene powder is 4 parts, and the inorganic filler is 19.1 parts.

[0140] Comparative Example 3

[0141] Different from Example 1, the modified graphene oxide is reduced n-hexylamine modified graphene oxide powder.

[0142] Testing section

[0143] Perform relevant performance tests on the non-curing asphalt-based waterproof coatings prepared in Examples 1 to 13 and Comparative Examples 1 to 3. The performance test results are shown in Table 1:

[0144] Table 1

[0145]

[0146]

[0147]

[0148] According to the above performance test results, it can be seen that the non-curing asphalt-based waterproof coating provided by this application has excellent heat resistance and high thermal conductivity, and the construction heating time is significantly reduced and there is no flue gas, with strong environmental protection, and it can effectively reduce the fire of the non-curing coating caused by high-temperature heating.

[0149] As can be seen from Examples 1-3, different addition amounts of reduced octadecylamine-modified graphene oxide powder will affect the thermal conductivity. When the addition amount of reduced octadecylamine-modified graphene oxide powder is 15 parts, the thermal conductivity is the highest; in Example 4, appropriately increasing the content of oxidized polyethylene wax powder can also increase the thermal conductivity; from Examples 1, 5 and 6, it can be seen that too little grafting rate and mesh number have a greater impact on the thermal conductivity and bonding performance. Too low grafting rate will lead to too low thermal conductivity; too large mesh number will lead to uneven dispersion, unqualified bonding performance, and lower thermal conductivity, resulting in an extended non-curing heating time; in Example 7, the inorganic filler is magnesium hydroxide: talc powder = 1:1, and the non-curing asphalt-based waterproof coating also has a relatively high thermal conductivity; when the inorganic filler is only talc powder in Example 8, the thermal conductivity is lower than that in Example 1, resulting in an extended non-curing heating time; in Example 9, the inorganic filler is talc powder and the SBS is linear SBS. The thermal conductivity is lower than that in Example 1, resulting in an extended non-curing heating time, and the bonding performance with the wet base surface is reduced. It may be that partially hydrogenated SBS has good solubility, blending performance and excellent oil filling properties. In the non-curing asphalt coating, it can be better mixed with asphalt and other components to form a more stable structure, thereby enhancing the bonding force between the coating and the substrate, enabling the coating to adhere more firmly to the substrate surface, improving the waterproof effect, and effectively preventing the occurrence of waterproof layer peeling and water channeling phenomena; as can be seen from Examples 10-12, different alkane-modified graphene oxides also have an impact on the thermal conductivity; as can be seen from Example 13, when the dispersant is xylene, the thermal conductivity is lower than that in Example 1, and other properties also decline.

[0150] In Comparative Example 1, graphene oxide was not grafted, and the thermal conductivity was low; in Comparative Example 2, the amount of modified graphene oxide used was small, and the thermal conductivity was also low; Comparative Example 3 was reduced n-hexylamine-modified graphene oxide powder, and the thermal conductivity was also relatively low compared to the examples of the present application.

[0151] As described above, the above are only specific embodiments of the present application, but 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. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A non-curing asphalt-based waterproof coating, characterized in that, It includes the following raw material components in parts by weight: Asphalt, 45 - 70 parts; Compatibilizer, 10 - 20 parts; Thermoplastic elastomer, 3 - 10 parts; Styrene - butadiene rubber, 3 - 5 parts; Resin, 3 - 5 parts; Wax powder, 2 - 5 parts; Modified graphene oxide, 5 - 20 parts; Inorganic filler, 12 - 25 parts; Dispersant, 0.2 - 0.8 part; Among them, the modified graphene oxide is alkylamine - modified graphene oxide, and the number of carbon atoms in the alkyl chain of the alkylamine - modified graphene oxide is 10 - 20.

2. The non-curing asphalt-based waterproof coating according to claim 1, characterized in that, The grafting rate of alkylamine in the modified graphene oxide is 20% - 35%.

3. The non-curing asphalt-based waterproof coating according to claim 1, characterized in that, The inorganic filler includes magnesium hydroxide and auxiliary fillers, and the auxiliary fillers include one or more of talc powder, heavy calcium carbonate, barium sulfate, titanium dioxide, mica powder, talc powder, kaolin.

4. The non-curing asphalt-based waterproof coating according to claim 3, wherein, The mass ratio of the magnesium hydroxide to the auxiliary filler is 1:(1.2 - 1.5).

5. The non-curing asphalt-based waterproof coating according to claim 1, characterized in that, The thermoplastic elastomer is SBS elastomer, and the molar ratio of butadiene to styrene in the SBS elastomer is 1:2.3 - 2.5, and the degree of hydrogenation is 3 - 8%.

6. The non-curing asphalt-based waterproof coating according to claim 1, characterized in that The penetration of the asphalt is 130 - 200; and / or, The compatibilizer includes one or more of cashew shell oil, aromatic oil, extraction oil, residual oil, bio - oil, base oil, rubber oil; and / or, The resin includes one or more of C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymerized petroleum resin, terpene resin, and alicyclic epoxy resin.

7. The non-curing asphalt-based waterproof coating according to claim 1, characterized in that The dispersant is a hyper - dispersant, and the molecular weight of the hyper - dispersant is 2000 - 6000.

8. The non-curing asphalt-based waterproof coating according to claim 1, characterized in that The average particle size of the modified graphene oxide is 800 mesh - 1500 mesh; and / or, The average particle size of the inorganic filler is 800 mesh - 1500 mesh.

9. A preparation method of a non-curing asphalt-based waterproof coating, characterized in that, It includes the following steps: Provide raw materials according to the components and component contents of the non - curing asphalt - based waterproof coating described in any one of claims 1 to 8; Mix the asphalt with the compatibilizer to obtain a first slurry; Add the thermoplastic elastomer, styrene - butadiene rubber, and resin to the first slurry and mix to obtain a second slurry; Add the modified graphene oxide, wax powder, inorganic filler, and hyper - dispersant to the second slurry and mix to obtain the non - curing asphalt - based waterproof coating.

10. The preparation method of the non-curing asphalt-based waterproof coating according to claim 9, characterized in that, The method also includes preparing the modified graphene oxide by the following method: Dissolve alkylamine in an alcohol solvent to obtain an alkylamine solution; Add graphene oxide to the alkylamine solution, remove the ungrafted alkylamine after reaction, and obtain a mother powder after drying; Dissolve the mother powder in water to obtain a mother powder solution, add a reducing agent, and obtain the modified graphene oxide after reaction and drying.

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