Modified palygorskite, method for preparing same, composition for asphalt waterproof coating, asphalt waterproof coating, and method for preparing same
By combining modified attapulgite with modifiers and employing chemical bonding and dynamic vulcanization processes, the adhesion and anti-slip properties of asphalt waterproof coatings have been improved, solving the problems of poor adhesion and shear resistance in existing technologies and achieving high heat resistance and excellent thermal insulation effects.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-21
- Publication Date
- 2026-07-24
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention relates to the field of building waterproofing technology, specifically to a modified attapulgite soil and its preparation method, a composition for asphalt waterproof coatings, and an asphalt waterproof coating and its preparation method. Background Technology
[0002] In the construction industry, waterproofing is crucial to structural safety and lifespan. Early rigid waterproofing relied on the density of concrete, but as building scale increased and waterproofing requirements rose, concrete's defects became increasingly apparent. Its numerous internal pores and capillaries make it prone to cracking under the influence of temperature, settlement, and stress, thus facilitating water penetration.
[0003] Traditional waterproofing membranes and coatings are the mainstays of waterproofing in the construction industry. Membrane membranes rely on laying to form a physical barrier, while coatings rely on the density of their coating for waterproofing. However, membrane application requires a high-quality substrate, joints are prone to leakage, and they age and deform quickly, significantly reducing their waterproofing performance. Coatings are used because of their ease of application and adaptability to complex substrate shapes. However, most current waterproofing coatings are based on bitumen or polymer-modified emulsions. While they possess some waterproofing and flexibility, their physicochemical adhesion to the substrate is insufficient, and their cohesive strength and shear resistance are poor. This leads to sagging and slippage when applied to vertical surfaces or pitched roofs, preventing the formation of a uniform coating thickness. Furthermore, with subsequent structural settlement or temperature-induced deformation, the coating is prone to peeling off from the substrate, resulting in waterproofing leaks.
[0004] Common methods for improving adhesion and shear resistance include physical blending modification (such as adding SBS, SBR and other rubbers to improve elasticity), inorganic filler reinforcement (such as adding nano calcium carbonate and talc to improve strength), and chemical crosslinking technology. For example, adding vulcanizing agents such as sulfur can make rubber molecules form a network structure, or introducing reactive components such as epoxy resin can enhance the cohesion of the coating.
[0005] The above-mentioned technologies have the following drawbacks: limited modification effect and insufficient long-term stability. Physically blended materials are prone to phase separation and aging. Excessive addition of inorganic fillers will sacrifice the flexibility and creep performance of the material. Conventional chemical vulcanization processes are difficult to precisely control the crosslinking density and speed in the complex organic system of asphalt, which can easily lead to excessive crosslinking and brittleness or insufficient crosslinking and poor performance. They cannot simultaneously achieve the creep characteristics of "never curing" and the mechanical properties of "high viscosity and anti-slip".
[0006] Therefore, there is an urgent need to develop a new type of high-performance waterproof coating that can inherit the advantages of traditional non-curing coatings, such as never curing and strong self-healing properties, while overcoming their bottlenecks of weak adhesion and poor shear resistance. This coating can achieve ultimate adhesion between the coating and the substrate and high anti-slip capability, so as to meet the stringent requirements of modern buildings for the reliability, durability and safety of waterproofing systems. Summary of the Invention
[0007] The purpose of this invention is to solve the problems of poor adhesion, shear resistance, and anti-slip performance of existing asphalt waterproof coatings.
[0008] To achieve the above objectives, a first aspect of the present invention provides a method for preparing modified attapulgite, the method comprising:
[0009] Attapulgite, a modification solution, and aliphatic diglycidyl ether are mixed to obtain the modified attapulgite; the modification solution contains 3-5 wt% silane coupling agent and 2-3 wt% intercalating agent.
[0010] The aliphatic diglycidyl ether is selected from at least one of polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, and 1,6-hexanediol diglycidyl ether.
[0011] The mass ratio of the attapulgite clay to the modified solution is 1:3-8;
[0012] The mass ratio of the attapulgite clay to the aliphatic diglycidyl ether is 100:0.5-3.
[0013] A second aspect of the invention provides modified attapulgite prepared by the method described in the first aspect.
[0014] A third aspect of the present invention provides a composition for an asphalt waterproof coating, the composition comprising a main agent and an auxiliary agent; the main agent comprising asphalt, aromatic oil, modifier, tackifying resin, and modified attapulgite.
[0015] Based on the total mass of the composition, the content of the asphalt is 40-60 wt%, the content of the aromatic oil is 10-20 wt%, the content of the modifier is 6-12 wt%, the content of the tackifying resin is 2-5 wt%, the content of the modified attapulgite is 5-10 wt%, and the content of the additives is 0.5-2 wt%.
[0016] The modifier is a combination of carboxylated modified styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer, and polyurethane prepolymer in a content-to-mass ratio of 1:1-3:0.5-2.
[0017] The modified attapulgite is the modified attapulgite described in the second aspect.
[0018] A fourth aspect of the present invention provides a method for preparing an asphalt waterproof coating, the method being carried out using the composition described in the third aspect of the invention, comprising mixing and reacting a mixture containing the asphalt waterproof coating and the components of the composition to obtain the asphalt waterproof coating.
[0019] The fifth aspect of the present invention provides an asphalt waterproof coating prepared by the method described in the fourth aspect.
[0020] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects:
[0021] (1) The modified attapulgite in the composition for asphalt waterproof coating provided by the present invention can chemically bond with the modifier provided by the present invention and work synergistically to improve the non-curing bonding performance of the asphalt waterproof coating.
[0022] (2) The dynamic vulcanization process of this invention enables the modifier to act as an "anchor pile" on the surface of asphalt and modified attapulgite soil, which enhances the bonding ability between the components and thus improves the anti-slip performance after construction.
[0023] (3) The asphalt waterproof coating provided by the present invention has high heat resistance and excellent heat insulation effect. Detailed Implementation
[0024] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0025] As previously stated, a first aspect of the present invention provides a method for preparing modified attapulgite, the method comprising:
[0026] Attapulgite, a modification solution, and aliphatic diglycidyl ether are mixed to obtain the modified attapulgite; the modification solution contains 3-5 wt% silane coupling agent and 2-3 wt% intercalating agent.
[0027] The aliphatic diglycidyl ether is selected from at least one of polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, and 1,6-hexanediol diglycidyl ether.
[0028] The mass ratio of the attapulgite clay to the modified solution is 1:3-8;
[0029] The mass ratio of the attapulgite clay to the aliphatic diglycidyl ether is 100:0.5-3.
[0030] Preferably, the mass ratio of the attapulgite clay to the modified solution is 1:4-6.
[0031] In some embodiments, the solvent in the modified solution is anhydrous ethanol.
[0032] Preferably, the mass ratio of the attapulgite clay to the aliphatic diglycidyl ether is 100:1-2.
[0033] According to a preferred embodiment, the mixing operation method includes:
[0034] SI. Premix attapulgite with the modified solution to obtain intermediate material;
[0035] SII. Reaction of aliphatic diglycidyl ether with the intermediate material yields the modified attapulgite.
[0036] The premixing conditions include: a temperature of 60-70℃ and a time of 1-2 hours;
[0037] The reaction conditions include a temperature of 75-90℃ and a time of 1-3 hours.
[0038] Preferably, the intercalating agent is selected from one or more of alkyltrimethylammonium halides and dialkyldimethylammonium halides with a carbon chain length of C12 to C18. For example, hexadecyltrimethylammonium bromide and dioctadecyldimethylammonium chloride.
[0039] It should be noted that the method for preparing the modified attapulgite includes conventional pretreatment and posttreatment steps. For example, the attapulgite is calcined before modification; and the obtained modified attapulgite is washed, dried, and then pulverized to a particle size with an average diameter of no more than 15 micrometers.
[0040] As previously stated, a second aspect of the present invention provides modified attapulgite prepared by the method described in the first aspect.
[0041] As described above, a third aspect of the present invention provides a composition for asphalt waterproof coating, the composition comprising a main agent and an additive; the main agent comprising asphalt, aromatic oil, modifier, tackifying resin, and modified attapulgite.
[0042] Based on the total mass of the composition, the content of the asphalt is 40-60 wt%, the content of the aromatic oil is 10-20 wt%, the content of the modifier is 6-12 wt%, the content of the tackifying resin is 2-5 wt%, the content of the modified attapulgite is 5-10 wt%, and the content of the additives is 0.5-2 wt%.
[0043] The modifier is a combination of carboxylated modified styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer, and polyurethane prepolymer in a content-to-mass ratio of 1:1-3:0.5-2.
[0044] The modified attapulgite soil is the modified attapulgite soil described in the second aspect above.
[0045] Preferably, the modifier is a combination of carboxylated styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer, and polyurethane prepolymer in a mass ratio of 1:1.5-2:0.8-1. The inventors have found that, under this preferred embodiment, the obtained asphalt waterproof coating exhibits superior adhesion and shear resistance.
[0046] According to a preferred embodiment, the asphalt is selected from at least one of 70# asphalt, 90# asphalt and 100# asphalt.
[0047] Preferably, the tackifying resin is selected from C5 petroleum resin and / or C9 petroleum resin.
[0048] Preferably, the grafting rate of maleic anhydride in the maleic anhydride-grafted styrene-butadiene-styrene block copolymer is 1.5-2.5 wt%. The inventors have found that, under this preferred embodiment, this grafting rate achieves the best balance between modification effect and process stability; when the grafting rate is below 1.5%, the polarity improvement is insufficient, and the improvement in compatibility and adhesion performance is limited; when it is above 2.5%, the product viscosity increases, the dispersion and solubility in asphalt deteriorates, and excessive cross-linking affects the creep performance of the product; within this preferred grafting rate range, excellent adhesion performance, excellent high-temperature anti-slip properties, and stable non-curing characteristics can be achieved simultaneously.
[0049] It should be noted that the maleic anhydride-grafted styrene-butadiene-styrene block copolymer described in this invention can be commercially available (domestic manufacturers: Hunan Yueyang Baling Petrochemical, Beijing Yanshan Petrochemical, etc.; model example: TME series produced by Baling Petrochemical or commercially available maleic anhydride-grafted styrene-butadiene-styrene block copolymers with a grafting rate of 1.5-2.5%), or it can be prepared using conventional methods in the art. For example, the maleic anhydride-grafted styrene-butadiene-styrene block copolymer with a grafting rate of 1.5-2.5 wt% provided by this invention is prepared using a method including the following steps:
[0050] 100 parts by weight of styrene-butadiene-styrene block copolymer (such as Yuehua 791-H), 1.5-3.5 parts by weight of maleic anhydride and 0.1-0.3 parts by weight of dicumyl peroxide (DCP) are premixed evenly in a high-speed mixer. Then, the mixture is melt-grafted at 160-190℃ through a twin-screw extruder. After water cooling, pelletizing and drying, a maleic anhydride-grafted styrene-butadiene-styrene block copolymer with a grafting rate of 1.5-2.5 wt% is obtained.
[0051] It should be noted that, in this invention, the grafting rate of maleic anhydride in the maleic anhydride-grafted styrene-butadiene-styrene block copolymer is determined by acid-base titration: m grams of the sample are accurately weighed, dissolved in toluene, and titrated to the endpoint with a C mol / L potassium hydroxide-ethanol standard solution using phenolphthalein as an indicator, consuming V ml. The grafting rate (GD%) is calculated using the formula GD% = (V × C × 0.049 / m) × 100%.
[0052] Preferably, the carboxyl content in the carboxylated styrene-butadiene rubber is 1.2-1.8 wt%.
[0053] It should be noted that the method for obtaining carboxylated modified styrene-butadiene rubber provided by this invention can be purchased externally (manufacturers: Jiangsu BASF, Shandong Qilu Petrochemical, Zhejiang Weitai, etc. Example models: BASF Styrofan® SD500N series or carboxylated styrene-butadiene latex with a carboxyl content of 1.2-1.8%, which is usually sold in emulsion form (carboxylated styrene-butadiene latex) and needs to be prepared into solid dry rubber through "demulsification, washing, and drying" steps before use). Alternatively, it can be prepared using conventional methods in the art, as long as the carboxyl content is 1.2-1.8 wt% as specified in this invention. Exemplarily, the carboxylated modified styrene-butadiene rubber with a carboxyl content of 1.2-1.8 wt% provided by this invention is prepared using a method including the following steps:
[0054] A pre-emulsion was prepared by mixing 60-70 parts butadiene, 28-38 parts styrene, 1.5-2.5 parts acrylic acid and / or methacrylic acid, 1.0-3.5 parts emulsifier, 0.1-0.5 parts molecular weight regulator, and 0.1-1 parts electrolyte with 100-200 parts water. Under nitrogen protection, 0.2-0.5 parts initiator were added to initiate the polymerization reaction at 60±2℃ for 6-8 hours. After the reaction, the mixture was demulsified, washed, and vacuum dried to obtain carboxyl-modified styrene-butadiene rubber. The carboxyl content was determined to be 1.2-1.8 wt% by titration.
[0055] It should be noted that the carboxyl content in this invention is determined by potentiometric titration. Specifically, the purified and dried sample is dissolved in a toluene-ethanol mixed solvent, and titrated with a potassium hydroxide ethanol standard solution. The titration endpoint is determined by the change in potential. Carboxyl content (%) = [(V-V0)×C×45.02×100] / m, where V is the volume of alkali solution consumed by the sample, V0 is the volume consumed by the blank, C is the concentration of the alkali solution (mol / L), and m is the mass of the sample.
[0056] Preferably, the isocyanate group content in the polyurethane prepolymer is 4-8 wt%.
[0057] It should be noted that the polyurethane prepolymer provided by this invention can be obtained externally or by self-production. If purchased externally, examples of manufacturers include Covestro (Germany), Huntsman (USA), Wanhua Chemical, and Yantai Huada Chemical, etc., and examples of models include Covestro Desmodur E series or aromatic or aliphatic polyurethane prepolymers with an NCO content of 4-8%. If self-produced, an exemplary method is as follows:
[0058] Under dry nitrogen protection, add 100 parts by weight of polyether polyol (such as PPG-2000) to the reactor, heat to 110-120℃ and dehydrate under vacuum for 2 hours, then cool to 40-60℃, control the -NCO / -OH molar ratio (R value) between 1.5-2.5, add the measured amount of diisocyanate, then heat to 70-90℃ and keep the reaction at this temperature for 2-3 hours until the NCO content in the system reaches the theoretical value (4-8wt%), cool down and discharge the material, then seal and store it.
[0059] It should be noted that the content of isocyanate groups in the polyurethane prepolymer of this invention is determined by di-n-butylamine titration; the specific steps are exemplarily as follows:
[0060] Weigh the sample and dissolve it in anhydrous toluene. Add excess di-n-butylamine-toluene solution and react at room temperature for 15-20 minutes. Using bromocresol green as an indicator, titrate the remaining di-n-butylamine with standard hydrochloric acid solution and determine the concentration using the formula NCO%=[(V0-V2)×C]. HCl The value is calculated as [×4.202] / m; where V0 is the volume of hydrochloric acid standard solution consumed in the blank test, in milliliters (mL); V2 is the volume of hydrochloric acid standard solution consumed in the sample test, in milliliters (mL); C HCl ρ represents the accurate concentration of the hydrochloric acid standard solution, in moles per liter (mol / L); m represents the mass of the sample, in grams (g); 4.202 is a calculation constant.
[0061] Preferably, based on the total mass of the composition, the additive contains 0.3-0.8 wt% of antioxidant and 0.5-1.2 wt% of vulcanizing agent.
[0062] More preferably, the vulcanizing agent is selected from a composite granulation of sulfur and zinc stearate in a mass ratio of 1:0.2-0.4.
[0063] As previously stated, a fourth aspect of the present invention provides a method for preparing an asphalt waterproof coating, the method being carried out using the composition described in the third aspect, comprising mixing and reacting a mixture containing the asphalt waterproof coating with the components of the composition to obtain the asphalt waterproof coating.
[0064] Preferably, the step of carrying out the mixing reaction includes:
[0065] (1) The maleic anhydride-grafted styrene-butadiene-styrene block copolymer is mixed with aromatic oil to obtain the first material;
[0066] (2) The asphalt is mixed with the first material in a second mixing process to obtain the second material;
[0067] (3) The carboxylated styrene-butadiene rubber, part of the tackifying resin, modified attapulgite clay and the second material are mixed in a third mixture to obtain the third material;
[0068] (4) The polyurethane prepolymer, the remaining tackifying resin and the third material are mixed in a fourth mixture to obtain the fourth material;
[0069] (5) The fourth material is subjected to dynamic vulcanization treatment in the presence of a vulcanizing agent, and then mixed with an antioxidant in a fifth process.
[0070] Preferably, the conditions for the first mixing include: a temperature of 160-170°C and a time of 1-4 hours.
[0071] Preferably, the second mixing is carried out under stirring conditions, which include: a temperature of 170-180°C, a stirring speed of 2500-3500 rpm, and a time of 20-40 min.
[0072] Preferably, the third mixing is carried out under stirring conditions, which include: a temperature of 170-180℃, a stirring speed of 2500-3500 rpm, and a time of 0.5-2h.
[0073] Preferably, the fourth mixing is carried out under stirring conditions, which include: a temperature of 160-165℃, a stirring speed of 1000-2000 rpm, and a time of 0.5-1h.
[0074] Preferably, the fifth mixing is carried out under stirring conditions, which include: a temperature of 100-130℃, a stirring speed of 500-800 rpm, and a time of 15-20 min.
[0075] Preferably, in step (5), the operation method for performing the dynamic vulcanization treatment includes:
[0076] SI-1. In the presence of nitrogen, the fourth material is subjected to a first vulcanization treatment with 10-30 wt% of vulcanizing agent to obtain the first vulcanized material.
[0077] SI-2, In the presence of nitrogen gas with an oxygen content of 2-5% by volume, 10-30 wt% of vulcanizing agent is subjected to a second vulcanization treatment with the first vulcanizing material to obtain a second vulcanizing material;
[0078] SI-3. In the presence of oxygen, 10-30 wt% of the vulcanizing agent is subjected to a third vulcanization treatment with the second vulcanizing material to obtain the third vulcanized material.
[0079] SI-4. In the presence of nitrogen, 10-30 wt% of a vulcanizing agent is subjected to a fourth vulcanization treatment with the third material. The inventors have discovered that, under this preferred embodiment, the asphalt waterproof coating obtained by the present invention exhibits superior adhesion and anti-slip properties.
[0080] More preferably, the conditions for the first vulcanization treatment include: a temperature of 160-170°C, a time of 20-40 min, and a rotation speed of 1500-2500 rpm;
[0081] The conditions for the second vulcanization treatment include: a temperature of 170-180℃ and a time of 20-40 min;
[0082] The conditions for the third vulcanization treatment include: a temperature of 170-180℃ and a time of 20-40 min;
[0083] The conditions for the fourth vulcanization treatment include: a temperature of 180-185℃, a time of 20-40 min, and a rotation speed of 1500-2500 rpm.
[0084] More preferably, the second vulcanization treatment and the third vulcanization treatment are each carried out independently under variable frequency pulse shearing conditions, the variable frequency pulse shearing conditions including: alternating between holding at a speed of 1500-2500 rpm for 20-40 seconds and holding at a speed of 600-1000 rpm for 5-15 seconds.
[0085] As previously stated, the fifth aspect of the present invention provides an asphalt waterproof coating prepared by the method described in the fourth aspect.
[0086] The present invention will be described in detail below through examples.
[0087] Unless otherwise specified, all reagents and raw materials used in the following examples are commercially available products, and all reagents are analytical grade products.
[0088] raw material:
[0089] Base asphalt: 70# petroleum asphalt from China Petroleum & Chemical Corporation
[0090] Aromatic oil: Sinopec D-AE100 aromatic oil
[0091] Preparation Example 1
[0092] A styrene-butadiene-styrene block copolymer grafted with maleic anhydride at a grafting rate of 1.5 wt% was prepared.
[0093] Raw materials and equipment:
[0094] Raw materials: SBS (YH-791, Hunan Yueyang Baling Petrochemical), maleic anhydride (MAH), initiator (dicumyl peroxide, DCP), antioxidant (BHT);
[0095] Equipment: Twin-screw extruder (melt process). This formulation is a mild grafting method, designed to introduce an appropriate amount of polar groups while maximizing the preservation of the original mechanical properties of SBS.
[0096] The grafting rate is controlled by the amount of maleic anhydride (MAH) and initiator (DCP). The higher the amount of MAH and DCP, the higher the grafting rate. However, it should be noted that excessive DCP will lead to SBS degradation and crosslinking, affecting performance.
[0097] Raw material ratio:
[0098] SBS: 100 parts by weight;
[0099] Maleic anhydride (MAH): 1.8 parts by weight;
[0100] Initiator (DCP): 0.15 parts by weight;
[0101] Antioxidant (BHT): 0.2 parts by weight;
[0102] Preparation process:
[0103] Premixing: SBS granules, MAH powder, DCP and antioxidant BHT are thoroughly mixed in a high-speed mixer for 8 minutes to ensure uniform dispersion of each component;
[0104] Melt reaction extrusion: The mixed material is fed into a twin-screw extruder (temperature setting: from the feed port to the die head, the zone temperature is set to: 160℃-175℃-185℃-180℃-170℃; screw speed: 120 rpm; feeding speed: matched with the screw speed to ensure that the material residence time in the extruder is 2.5 minutes).
[0105] Vacuum devolatilization: After the reaction section, the vacuum is turned on to remove unreacted MAH monomers and byproducts (vacuum degree -0.08MPa to -0.098MPa, devolatilization time 2 minutes).
[0106] Extrusion, cooling and granulation: The strip extruded from the die is cooled in a water bath and then cut into uniform particles by a pelletizer to obtain the maleic anhydride-grafted styrene-butadiene-styrene block copolymer product with a grafting rate of 1.5 wt%.
[0107] Preparation Example 2
[0108] A styrene-butadiene-styrene block copolymer grafted with maleic anhydride at a grafting rate of 2.5 wt% was prepared.
[0109] This preparation example uses a similar process to Preparation Example 1, except that the raw material ratios and process conditions are different. The raw material ratios for this preparation example are as follows:
[0110] SBS: 100 parts by weight;
[0111] Maleic anhydride (MAH): 3.2 parts by weight;
[0112] Initiator (DCP): 0.25 parts by weight;
[0113] Antioxidant (BHT): 0.3 parts by weight;
[0114] Process conditions:
[0115] Premixing: Same as preparation example 1;
[0116] Melt reaction extrusion: (Temperature settings: From the feed port to the die head, the zoned temperature settings are: 165℃-180℃-190℃-185℃-175℃; Screw speed: 150 rpm; Feeding speed: Matched to the screw speed to ensure that the material residence time in the extruder is 2 minutes).
[0117] Vacuum devouring: vacuum degree -0.09MPa to -0.098MPa, devouring time 3 minutes);
[0118] Extrusion, cooling and granulation: Same as in preparation example 1.
[0119] The procedures and conditions not listed are the same as those in Preparation Example 1.
[0120] Preparation Example 3
[0121] A styrene-butadiene-styrene block copolymer grafted with maleic anhydride at a grafting rate of 5.0 wt% was prepared.
[0122] This preparation example uses a similar process to Preparation Example 1, except that the raw material ratios and process conditions are different. The raw material ratios for this preparation example are as follows:
[0123] SBS: 100 parts by weight;
[0124] Maleic anhydride (MAH): 6.5 parts by weight;
[0125] Initiator (DCP): 0.45 parts by weight;
[0126] Antioxidant (BHT): 0.5 parts by weight;
[0127] Process conditions:
[0128] Premixing: Same as preparation example 1;
[0129] Melt reaction extrusion: (Temperature settings: from the feed port to the die head, zone temperature settings are: 170℃-185℃-195℃-190℃-180℃; Screw speed: 180 rpm; Feeding speed: matched with the screw speed to ensure that the material residence time in the extruder is 1.5 minutes).
[0130] Vacuum devolatilization: vacuum degree -0.095MPa to -0.098MPa, devolatilization time 4 minutes).
[0131] Extrusion, cooling and granulation: Same as in preparation example 1;
[0132] The procedures and conditions not listed are the same as those in Preparation Example 1.
[0133] Preparation Example 4
[0134] This preparation example provides a carboxylated styrene-butadiene rubber with a carboxyl content of 1.2 wt%.
[0135] Preparation principle: Through an emulsion polymerization system, butadiene, styrene (St) and a third monomer containing carboxyl groups (such as acrylic acid) are copolymerized in an aqueous phase to generate carboxylated styrene-butadiene rubber with carboxyl groups located on the polymer backbone. The solid product is then obtained through coagulation, washing and drying.
[0136] raw material:
[0137] Polymer monomers: butadiene, styrene, and acrylic acid;
[0138] Emulsifier: Sodium dodecyl sulfate;
[0139] Initiator: Potassium persulfate;
[0140] Molecular weight regulator: tert-dodecyl mercaptan;
[0141] Electrolyte: Sodium phosphate;
[0142] Terminator: Sodium dimethyl dithiocarbamate;
[0143] Medium: Water;
[0144] Equipment: High-pressure polymerization reactor;
[0145] Raw material ratio:
[0146] Polymer monomers: 65 wt% butadiene, 33.5 wt% styrene and 1.5 wt% acrylic acid;
[0147] For every 100 parts by weight of the polymerizable monomer, the amount of water is 150 parts by weight, the amount of emulsifier is 3 parts by weight, the amount of initiator is 0.3 parts by weight, the amount of molecular weight regulator is 0.2 parts by weight, the amount of electrolyte is 0.4 parts by weight, and the amount of terminator is 0.5 parts by weight.
[0148] Preparation process:
[0149] Water, emulsifier, electrolyte, styrene, acrylic acid and molecular weight regulator were added to a pre-emulsification tank and stirred at high speed (2000 rpm, 15 min) to form a stable pre-emulsion; then butadiene was added to the pre-emulsion and stirring was continued (1200 rpm, 30 min) to obtain a mixture.
[0150] The mixture is pressed into a high-pressure polymerization reactor, an initiator is added, and nitrogen is introduced to replace the air in the reactor three times to make the oxygen content lower than 500 ppm. Then the temperature is raised to 60°C and the polymerization reaction is carried out for 12 hours (500 rpm). During the reaction, the reaction temperature is controlled by cooling with a jacket.
[0151] When the conversion rate of the polymer monomer reaches 95% (determined by gas chromatography), a terminator is added to the reactor (stirring continues for 30 min) to terminate the reaction. The resulting latex is discharged into a pressure relief tank. The latex undergoes coagulation (adding calcium chloride-hydrochloric acid solution), washing, dehydration, and drying steps to obtain a carboxylated modified styrene-butadiene rubber product with a solid carboxyl group content of 1.2 wt%.
[0152] Preparation Example 5
[0153] This preparation example provides a carboxylated styrene-butadiene rubber with a carboxyl content of 1.8 wt%.
[0154] This preparation example uses a similar process to Preparation Example 4, except that the proportions of the reactants are different. Specifically:
[0155] Polymer monomers: 64.5 wt% butadiene, 33.2 wt% styrene and 2.3 wt% acrylic acid;
[0156] For every 100 parts by weight of the polymerizable monomer, the amount of water is 150 parts by weight, the amount of emulsifier is 3.2 parts by weight, the amount of initiator is 0.3 parts by weight, the amount of molecular weight regulator is 0.2 parts by weight, the amount of electrolyte is 0.4 parts by weight, and the amount of terminator is 0.5 parts by weight.
[0157] The remaining unlisted procedures are the same as those in Preparation Example 4.
[0158] Preparation Example 6
[0159] This preparation example provides a carboxylated styrene-butadiene rubber with a carboxyl content of 0.8 wt%.
[0160] This preparation example uses a similar process to Preparation Example 4, except that the proportions of the reactants are different. Specifically:
[0161] Polymer monomers: 68 wt% butadiene, 30.7 wt% styrene and 1.3 wt% acrylic acid;
[0162] For every 100 parts by weight of the polymerized monomer, the amount of water is 150 parts by weight, the amount of emulsifier is 2.8 parts by weight, the amount of initiator is 0.3 parts by weight, the amount of molecular weight regulator is 0.15 parts by weight, the amount of electrolyte is 0.4 parts by weight, and the amount of terminator is 0.5 parts by weight.
[0163] The remaining unlisted procedures are the same as those in Preparation Example 4.
[0164] Preparation Example 7
[0165] This preparation example is used to prepare a polyurethane prepolymer with an isocyanate group content of 4 wt%.
[0166] It is prepared in-house using the following method:
[0167] Preparation principle: Polyurethane prepolymer is a compound with terminal isocyanate groups generated by the reaction of excess diisocyanate with oligomeric polyol;
[0168] Raw material ratio:
[0169] Polyether polyol (PPG, Mn=2000, functionality=2): 100 parts by weight;
[0170] Toluene diisocyanate (TDI-80, NCO content = 48.3%): 16.5 parts by weight;
[0171] Catalyst: Dibutyltin dilaurate (DBTDL): 30 ppm (based on the total mass of raw materials used);
[0172] Preparation process:
[0173] Under dry nitrogen protection, 100 parts by weight of polyether polyol (such as PPG-2000) were added to the reactor, heated to 115°C, and vacuum dehydrated for 2 hours. The temperature was then lowered to 55°C, and a measured amount of TDI was added. The mixture was stirred at 150 rpm for 15 minutes. The catalyst was then added, and the temperature was raised to 75°C and maintained for 2.5 hours. Samples were taken periodically during this period, and the NCO content was determined by di-n-butylamine titration. When the measured NCO content was 4.0 wt%, the reaction was stopped. The temperature was lowered to below 40°C, the product was discharged, and the mixture was sealed, protected from light, and stored in a dry place.
[0174] Preparation Example 8
[0175] This preparation example is used to prepare a polyurethane prepolymer with an isocyanate group content of 8 wt%.
[0176] Raw material ratio:
[0177] Polyether polyol (PPG, Mn=2000, functionality=2): 100 parts by weight;
[0178] Toluene diisocyanate (TDI-80, NCO content = 48.3%): 55 parts by weight;
[0179] Catalyst: Dibutyltin dilaurate (DBTDL): 30 ppm (based on the total mass of raw materials used);
[0180] Preparation process:
[0181] Under dry nitrogen protection, 100 parts by weight of polyether polyol (such as PPG-2000) were added to the reactor, heated to 115°C, and vacuum dehydrated for 2 hours. The temperature was then lowered to 55°C, and a measured amount of TDI was added. The mixture was stirred at 150 rpm for 15 minutes. The catalyst was then added, and the temperature was raised to 80°C and maintained for 3.5 hours. Samples were taken periodically during this period, and the NCO content was determined by di-n-butylamine titration. When the measured NCO content was 8.0 wt%, the reaction was stopped. The temperature was lowered to below 40°C, the product was discharged, and the mixture was sealed, protected from light, and stored in a dry place.
[0182] Preparation Example 9
[0183] This preparation example is used to prepare a polyurethane prepolymer with an isocyanate group content of 10 wt%.
[0184] Raw material ratio:
[0185] Polyether polyol (PPG, Mn=2000, functionality=2): 100 parts by weight;
[0186] Toluene diisocyanate (TDI-80, NCO content = 48.3%): 135 parts by weight;
[0187] Catalyst: Dibutyltin dilaurate (DBTDL): 30 ppm (based on the total mass of raw materials used);
[0188] Solvent (anhydrous xylene): 15 parts by weight (for controlling high viscosity systems);
[0189] Preparation process:
[0190] Under dry nitrogen protection, 100 parts by weight of polyether polyol (such as PPG-2000) were added to the reactor, heated to 115°C, and vacuum dehydrated for 2 hours. The temperature was then lowered to 55°C, and a measured amount of TDI was added. The mixture was stirred at 150 rpm for 15 minutes. Anhydrous xylene was added, and the mixture was stirred at 150 rpm for 15 minutes. Then, the catalyst was added, and the temperature was raised to 80°C and maintained for 3.5 hours. Samples were taken periodically during this period, and the NCO content was determined by di-n-butylamine titration. When the measured NCO content was 10.0 wt%, the reaction was stopped. The temperature was lowered to below 40°C, the product was discharged, and stored in a sealed, light-protected, and dry place.
[0191] Attapulgite: Purchased from Anhui Mingmei Mineral Chemical Co., Ltd.
[0192] Preparation Example 10
[0193] This preparation example is used to prepare the modified attapulgite provided by the present invention. The preparation method is as follows: attapulgite is calcined at 500°C for 3 hours.
[0194] S1. Premix attapulgite with the modification solution to obtain intermediate material; the modification solution is an ethanol solution containing 3 wt% silane coupling agent and 2 wt% hexadecyltrimethylammonium bromide.
[0195] The premixing conditions are: temperature 65℃, ultrasonic frequency 40KHz, and time 1.5h.
[0196] The mass ratio of the attapulgite clay to the modified solution is 1:5;
[0197] SII. The polyethylene glycol diglycidyl ether is reacted with the intermediate material, and then the mixture is washed, dried and pulverized in sequence until the modified attapulgite Z1 has an average particle diameter of no more than 15 μm; the mass ratio of the attapulgite to the polyethylene glycol diglycidyl ether is 100:1.5.
[0198] The reaction conditions include a temperature of 80°C and a time of 2 hours.
[0199] Preparation Example 11
[0200] This preparation example is used to prepare the modified attapulgite provided by the present invention. The preparation method is as follows: attapulgite is calcined at 500°C for 3 hours.
[0201] S1. Premix attapulgite with the modification solution to obtain intermediate material; the modification solution is an ethanol solution containing 5 wt% silane coupling agent and 3 wt% hexadecyltrimethylammonium bromide.
[0202] The premixing conditions are: temperature 65℃, ultrasonic frequency 40KHz, and time 1.5h.
[0203] The mass ratio of the attapulgite clay to the modified solution is 1:8;
[0204] SII. The polyethylene glycol diglycidyl ether is reacted with the intermediate material, and then the material is washed, dried and pulverized in sequence until the modified attapulgite Z2 has an average particle diameter of no more than 15 μm; the mass ratio of the attapulgite to the polyethylene glycol diglycidyl ether is 100:3.
[0205] The reaction conditions include a temperature of 80°C and a time of 2 hours.
[0206] Example 1
[0207] Maleic anhydride-grafted styrene-butadiene-styrene block copolymer: maleic anhydride grafting rate of 1.5 wt%;
[0208] Carboxyl-modified styrene-butadiene rubber: the carboxyl content is 1.2 wt%;
[0209] Polyurethane prepolymer: isocyanate group content is 4 wt%;
[0210] Modifier: A combination of carboxylated modified styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer and polyurethane prepolymer in a mass ratio of 1:1.5:0.8;
[0211] Modified attapulgite: Z1 obtained in Preparation Example 10;
[0212] Tackifying resin: C5 petroleum resin;
[0213] Vulcanizing agent: a composite granulation of sulfur and zinc stearate in a mass ratio of 1:0.3;
[0214] Antioxidants: Hindered phenols (such as antioxidant 1010) and phosphites (such as antioxidant 168) are compounded in a 1:1 mass ratio;
[0215] (1) Maleic anhydride-grafted styrene-butadiene-styrene block copolymer is mixed with aromatic oil to obtain a first material; the conditions for the first mixing include: temperature of 160°C and time of 2h.
[0216] (2) Mix 70# asphalt with the first material to obtain the second material; the conditions for the second mixing include: temperature of 178℃, stirring speed of 3000rpm, and time of 30min.
[0217] (3) The carboxylated styrene-butadiene rubber, two-thirds of the total amount of tackifying resin, modified attapulgite clay and the second material are mixed in a third mixture to obtain the third material; the conditions for the third mixing include: temperature of 175°C, stirring speed of 2500 rpm and time of 1.5 h.
[0218] (4) The polyurethane prepolymer, the remaining tackifying resin and the third material are mixed in a fourth mixture to obtain a fourth material; the conditions for the fourth mixing include: a temperature of 162°C, a stirring speed of 1500 rpm and a time of 40 min.
[0219] (5) The fourth material is subjected to dynamic vulcanization treatment in the presence of a vulcanizing agent, and then mixed with an antioxidant in a fifth mixture; the conditions for the fifth mixture include: temperature of 130°C, stirring speed of 700 rpm, and time of 20 min; to obtain the asphalt waterproof coating S1;
[0220] The operation method for performing the dynamic vulcanization treatment includes:
[0221] SI-1. In the presence of nitrogen, the fourth material is subjected to a first vulcanization treatment with 20 wt% vulcanizing agent to obtain a first vulcanized material; the conditions of the first vulcanization treatment include: temperature of 162°C, time of 30 min, and rotation speed of 2000 rpm.
[0222] SI-2. In the presence of nitrogen with an oxygen content of 4% by volume, 30wt% of vulcanizing agent is subjected to a second vulcanization treatment with the first vulcanizing material to obtain a second vulcanizing material. The conditions of the second vulcanization treatment include: a temperature of 177°C, a time of 30min, and a frequency-controlled pulse shearing process that alternates between maintaining a speed of 2000rpm for 30s and maintaining a speed of 800rpm for 10s.
[0223] SI-3. In the presence of oxygen, 30 wt% of the vulcanizing agent and the second vulcanizing material are subjected to a third vulcanization treatment to obtain the third vulcanized material. The conditions for the third vulcanization treatment include: a temperature of 177°C, a time of 30 min, and a frequency-controlled pulse shearing process that alternates between maintaining a speed of 2000 rpm for 30 s and maintaining a speed of 800 rpm for 10 s.
[0224] SI-4. In the presence of nitrogen, 20 wt% of the vulcanizing agent and the third material are subjected to a fourth vulcanization treatment. The conditions for the fourth vulcanization treatment include: a temperature of 180°C, a time of 30 min, and a rotation speed of 1500 rpm.
[0225] Based on the total mass (10 kg) of the composition, the amount of the asphalt is 60 wt%, the amount of the aromatic oil is 16 wt%, the amount of the modifier is 10 wt%, the amount of the tackifying resin is 4 wt%, the amount of the modified attapulgite is 9 wt%, the amount of the vulcanizing agent is 0.5 wt%, and the amount of the antioxidant is 0.5 wt%.
[0226] Example 2
[0227] Maleic anhydride-grafted styrene-butadiene-styrene block copolymer: maleic anhydride grafting rate of 2.5 wt%;
[0228] Carboxyl-modified styrene-butadiene rubber: the carboxyl content is 1.8 wt%;
[0229] Polyurethane prepolymer: isocyanate group content is 8 wt%;
[0230] Modifier: A combination of carboxylated styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer and polyurethane prepolymer in a mass ratio of 1:2:1;
[0231] Modified attapulgite: Z2 obtained in Preparation Example 11;
[0232] Tackifying resin: C9 petroleum resin;
[0233] Vulcanizing agent: a composite granulation of sulfur and zinc stearate in a mass ratio of 1:0.3;
[0234] Antioxidants: Hindered phenols (such as antioxidant 1010) and phosphites (such as antioxidant 168) are compounded in a 1:1 mass ratio;
[0235] (1) Maleic anhydride-grafted styrene-butadiene-styrene block copolymer is mixed with aromatic oil to obtain a first material; the conditions for the first mixing include: temperature of 165°C and time of 3h.
[0236] (2) Mix 70# asphalt with the first material to obtain the second material; the conditions for the second mixing include: temperature of 175℃, stirring speed of 2500rpm, and time of 40min.
[0237] (3) The carboxylated styrene-butadiene rubber, two-thirds of the total amount of tackifying resin, modified attapulgite clay and the second material are mixed in a third mixture to obtain the third material; the conditions for the third mixing include: temperature of 175°C, stirring speed of 2500 rpm and time of 1.5 h.
[0238] (4) The polyurethane prepolymer, the remaining tackifying resin and the third material are mixed in a fourth mixture to obtain a fourth material; the conditions for the fourth mixing include: a temperature of 165°C, a stirring speed of 2000 rpm and a time of 40 min.
[0239] (5) The fourth material is subjected to dynamic vulcanization treatment in the presence of a vulcanizing agent, and then mixed with an antioxidant in a fifth mixture; the conditions for the fifth mixture include: temperature of 130°C, stirring speed of 700 rpm, and time of 20 min; to obtain the asphalt waterproof coating S2;
[0240] The operation method for performing the dynamic vulcanization treatment includes:
[0241] SI-1. In the presence of nitrogen, the fourth material is subjected to a first vulcanization treatment with 20 wt% vulcanizing agent to obtain a first vulcanized material; the conditions of the first vulcanization treatment include: temperature of 162°C, time of 30 min, and rotation speed of 2000 rpm.
[0242] SI-2. In the presence of nitrogen with an oxygen content of 4% by volume, 30wt% of vulcanizing agent is subjected to a second vulcanization treatment with the first vulcanizing material to obtain a second vulcanizing material. The conditions of the second vulcanization treatment include: a temperature of 177°C, a time of 30min, and a frequency-controlled pulse shearing process that alternates between maintaining a speed of 2000rpm for 30s and maintaining a speed of 800rpm for 10s.
[0243] SI-3. In the presence of oxygen, 30 wt% of the vulcanizing agent and the second vulcanizing material are subjected to a third vulcanization treatment to obtain the third vulcanized material. The conditions for the third vulcanization treatment include: a temperature of 177°C, a time of 30 min, and a frequency-controlled pulse shearing process that alternates between maintaining a speed of 2000 rpm for 30 s and maintaining a speed of 800 rpm for 10 s.
[0244] SI-4. In the presence of nitrogen, 20 wt% of the vulcanizing agent and the third material are subjected to a fourth vulcanization treatment; the conditions for the fourth vulcanization treatment include: a temperature of 180°C, a time of 30 min, and a rotation speed of 1500 rpm.
[0245] Based on the total mass of the composition (10 kg), the amount of the asphalt is 54.5 wt%, the amount of the aromatic oil is 20 wt%, the amount of the modifier is 12 wt%, the amount of the tackifying resin is 5 wt%, the amount of the modified attapulgite is 7.5 wt%, the content of the vulcanizing agent is 0.5 wt%, and the content of the antioxidant is 0.5 wt%.
[0246] Example 3
[0247] This embodiment follows a similar process to Example 1. The difference is that the amount of modifier used is controlled in the same way as in Example 1, but the modifier is a combination of carboxylated modified styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer, and polyurethane prepolymer in a mass ratio of 1:3:0.8.
[0248] The remaining preparation steps are the same as in Example 1.
[0249] Asphalt waterproof coating S3 was prepared.
[0250] Example 4
[0251] This embodiment follows a similar process to Example 1. The difference is that the amount of modifier used is controlled in the same way as in Example 1, but the modifier is a combination of carboxylated styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer, and polyurethane prepolymer in a mass ratio of 1:1.5:2.
[0252] The remaining preparation steps are the same as in Example 1.
[0253] Asphalt waterproof coating S4 was prepared.
[0254] Example 5
[0255] This embodiment follows a similar process to Example 1, except that in this embodiment, the grafting rate of maleic anhydride in the maleic anhydride-grafted styrene-butadiene-styrene block copolymer is 5 wt%.
[0256] The remaining preparation steps are the same as in Example 1.
[0257] Asphalt waterproof coating S5 was prepared.
[0258] Example 6
[0259] This embodiment follows a similar process to Example 1, except that the preparation method is not entirely the same as in Example 1. Specifically:
[0260] The oxygen concentration control and pulse shearing in the dynamic vulcanization process are eliminated, and replaced with conventional single-temperature, continuous shear vulcanization; the specific steps are as follows:
[0261] Under the conditions of the fourth material obtained in Example 1, the fourth material is subjected to dynamic vulcanization treatment in the presence of a vulcanizing agent; the operation method for performing dynamic vulcanization treatment includes:
[0262] Under nitrogen protection, the entire amount of vulcanizing agent was added to the fourth material at once, and continuously sheared at 1500 rpm for 120 minutes at 175°C. After the reaction was completed, it was mixed with an antioxidant in a fifth mixing process; the conditions for the fifth mixing were: temperature of 130°C, stirring speed of 700 rpm, and time of 20 minutes; thus obtaining the asphalt waterproof coating S6.
[0263] Example 7
[0264] This embodiment follows a similar process to Example 1. The difference is that the amount of modifier is controlled in the same way as in Example 1. However, the carboxyl content of the carboxylated styrene-butadiene rubber is 0.8 wt%, and the NCO content of the polyurethane prepolymer is 10 wt%.
[0265] The remaining preparation steps are the same as in Example 1.
[0266] Asphalt waterproof coating S7 was prepared.
[0267] Comparative Example 1
[0268] This comparative example follows a similar process to Example 1, except that unmodified attapulgite is used instead of the modified attapulgite in Example 1.
[0269] The remaining preparation steps are the same as in Example 1.
[0270] The asphalt waterproof coating DS1 was prepared.
[0271] Comparative Example 2
[0272] This comparative example follows a similar procedure to Example 1, except that the modified attapulgite clay is prepared using the following method:
[0273] a. Pass the attapulgite clay through a 325-mesh sieve (remove the sieve material), calcine it at 500℃ for 3 hours, and then cool it for later use;
[0274] b. Mix attapulgite clay with an anhydrous ethanol solution of 3wt% silane coupling agent KH-570 at a mass ratio of 1:5, and sonicate at 65℃ for 1.5 hours.
[0275] c. After centrifugation, washing with ethanol, and air drying, the modified attapulgite is obtained.
[0276] The remaining preparation steps are the same as in Example 1.
[0277] The asphalt waterproof coating DS2 was prepared.
[0278] Comparative Example 3
[0279] This comparative example follows a similar process to Example 1, except that polyurethane prepolymer is not used; instead, an equal mass of epoxy resin E-51 is used.
[0280] The remaining preparation steps are the same as in Example 1.
[0281] The asphalt waterproof coating DS3 was prepared.
[0282] Comparative Example 4
[0283] This comparative example follows a similar process to Example 1. The difference is that the amount of modifier used in this comparative example is controlled in the same way as in Example 1. However, the modifier is a combination of styrene-butadiene rubber, styrene-butadiene-styrene block copolymer and polyurethane prepolymer in a mass ratio of 1:1.5:0.8 (wherein, the raw material sources of styrene-butadiene rubber, styrene-butadiene-styrene block copolymer and polyurethane prepolymer are the same as in Example 1).
[0284] The remaining preparation steps are the same as in Example 1.
[0285] The asphalt waterproof coating DS4 was prepared.
[0286] Test case
[0287] The performance of the asphalt waterproof coatings obtained in the above embodiments and comparative examples was tested.
[0288] Test method for adhesion performance (standard): Chapter 7 "Test method for adhesion strength" "Method A" of GB / T 16777-2008 "Test methods for waterproof coatings for buildings";
[0289] Shear resistance test method (standard): A self-designed inclined plane shear resistance test was used. The coating was hot-melted to 130℃ and applied to a concrete slab with a coating area of 100×50mm. The concrete slab dimensions were 120×70×5mm. The coating was cured for 24 hours under standard curing conditions and then kept at a constant temperature of 90℃ and a 45° inclination angle for 24 hours. The maximum non-slip coating thickness (mm) was measured. The greater the thickness, the better the shear resistance. Three events were tested in each group.
[0290] Test method for anti-slip performance (standard): Test method for anti-slip performance of composite with roll material: Heat the sample to melt and scrape it onto a qualified concrete slab. The coating area is (150×120) mm, the thickness is (2±0.2) mm, and the concrete slab size is 200×150×5 mm. After coating, cure under standard curing conditions for 2 hours ± 5 minutes. Take a prepared 4 mm thick SBS bitumen-based waterproof roll material, remove the surface PE release film by hot melting, and stick it on the coating. The roll material size is (125×100) mm. Roll it back and forth three times with a 2 kg roller to ensure complete adhesion between the roll material and the sample. Place it under standard conditions for 24 hours. Draw a horizontal line on the upper edge of the roll material, with both ends of the line extending beyond the coating width. Place the specimen vertically into an electric heating drying oven that has been kept at a constant temperature to the specified temperature, with the distance between the specimen and the drying oven wall not less than 50 mm. After processing the specimens for 2 hours ± 2 minutes, remove them and observe and measure the vertical slippage distance between the upper edge of the specimen and the marked line. A slippage distance not exceeding 2 mm is considered as no slippage of the roll material. A total of 3 specimens were tested.
[0291] Test method for heat resistance (standard): The test method for heat resistance refers to JC / T 2428-2017, and the test temperature is 90℃;
[0292] Test method for thermal insulation performance (standard): Refer to GB / T 10295-2008, test the thermal conductivity of the coating (W / (m×k)), the lower the value, the better the thermal insulation performance;
[0293] The test results are shown in Table 1.
[0294] Table 1
[0295]
[0296] As can be seen from the results in Table 1, the asphalt waterproof coating provided by the present invention has excellent shear resistance, anti-slip properties and heat resistance, while also having higher bonding strength and better thermal conductivity.
[0297] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A composition for asphalt waterproof coating, characterized in that, The composition contains a main agent and an auxiliary agent; the main agent includes asphalt, aromatic oil, modifier, tackifying resin, and modified attapulgite. Based on the total mass of the composition, the content of the asphalt is 40-60 wt%, the content of the aromatic oil is 10-20 wt%, the content of the modifier is 6-12 wt%, the content of the tackifying resin is 2-5 wt%, the content of the modified attapulgite is 5-10 wt%, and the content of the additives is 0.5-2 wt%. The modifier is a combination of carboxylated modified styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer, and polyurethane prepolymer in a content-to-mass ratio of 1:1-3:0.5-2. The modified attapulgite clay is prepared using a method comprising the following steps: Attapulgite, a modification solution, and aliphatic diglycidyl ether are mixed to obtain the modified attapulgite; the modification solution contains 3-5 wt% silane coupling agent and 2-3 wt% intercalating agent. The aliphatic diglycidyl ether is selected from at least one of polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, and 1,6-hexanediol diglycidyl ether. The mass ratio of the attapulgite clay to the modified solution is 1:3-8; The mass ratio of the attapulgite clay to the aliphatic diglycidyl ether is 100:0.5-3.
2. The composition according to claim 1, characterized in that, The modifier is a combination of carboxylated styrene-butadiene rubber, maleic anhydride-grafted styrene-butadiene-styrene block copolymer, and polyurethane prepolymer in a mass ratio of 1:1.5-2:0.8-1.
3. The composition according to claim 2, characterized in that, The grafting rate of maleic anhydride in the maleic anhydride-grafted styrene-butadiene-styrene block copolymer is 1.5-2.5 wt%. And / or, the carboxyl content in the carboxylated styrene-butadiene rubber is 1.2-1.8 wt%; And / or, the isocyanate group content in the polyurethane prepolymer is 4-8 wt%; And / or, based on the total mass of the composition, the additive contains 0.3-0.8 wt% of antioxidant and 0.5-1.2 wt% of vulcanizing agent.
4. A method for preparing asphalt waterproof coating, characterized in that, The method is carried out using the composition according to any one of claims 1-3, comprising mixing and reacting a mixture containing the asphalt waterproof coating with the components of the composition to obtain the asphalt waterproof coating.
5. The method according to claim 4, characterized in that, The steps for carrying out the mixed reaction include: (1) The maleic anhydride-grafted styrene-butadiene-styrene block copolymer is mixed with aromatic oil to obtain the first material; (2) The asphalt is mixed with the first material in a second mixing process to obtain the second material; (3) The carboxylated styrene-butadiene rubber, a portion of the tackifying resin, the modified attapulgite clay and the second material are mixed in a third mixture to obtain the third material; (4) The polyurethane prepolymer, the remaining tackifying resin and the third material are mixed in a fourth mixture to obtain the fourth material; (5) The fourth material is subjected to dynamic vulcanization treatment in the presence of a vulcanizing agent, and then mixed with an antioxidant in a fifth process.
6. The method according to claim 5, characterized in that, The conditions for the first mixing include: a temperature of 160-170℃ and a time of 1-4 hours; And / or, the second mixing is carried out under stirring conditions, the conditions of which include: a temperature of 170-180°C, a stirring speed of 2500-3500 rpm, and a time of 20-40 min; And / or, the third mixing is carried out under stirring conditions, the conditions of which include: a temperature of 170-180℃, a stirring speed of 2500-3500 rpm, and a time of 0.5-2 h; And / or, the fourth mixing is carried out under stirring conditions, the fourth mixing conditions including: temperature of 160-165℃, stirring speed of 1000-2000rpm, and time of 0.5-1h; And / or, the fifth mixing is carried out under stirring conditions, the fifth mixing conditions including: temperature of 100-130℃, stirring speed of 500-800rpm, and time of 15-20min.
7. The method according to claim 5 or 6, characterized in that, In step (5), the operation method for performing the dynamic vulcanization treatment includes: SI-1. In the presence of nitrogen, the fourth material is subjected to a first vulcanization treatment with 10-30 wt% of vulcanizing agent to obtain the first vulcanized material. SI-2, In the presence of nitrogen gas with an oxygen content of 2-5% by volume, 10-30 wt% of vulcanizing agent is subjected to a second vulcanization treatment with the first vulcanizing material to obtain a second vulcanizing material; SI-3. In the presence of oxygen, 10-30 wt% of the vulcanizing agent is subjected to a third vulcanization treatment with the second vulcanizing material to obtain the third vulcanized material. SI-4. In the presence of nitrogen, 10-30 wt% of the vulcanizing agent is subjected to a fourth vulcanization treatment with the third material.
8. The asphalt waterproof coating prepared by the method according to any one of claims 4-7.
Citation Information
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Attapulgite nano complex iron oxide brown for easily-dispersible water-based paint
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