CN118063784A

CN118063784A - Nano material grafted block copolymer composite modified asphalt and waterproof application

Info

Publication number: CN118063784A
Application number: CN202410192181.6A
Authority: CN
Inventors: 胡彬; 丁永玲; 孙华东; 刘论文; 吴聚明; 王英文; 甘旺
Original assignee: Suzhou Feite Brothers New Material Technology Co ltd
Current assignee: Suzhou Feite Brothers New Material Technology Co ltd
Priority date: 2024-02-21
Filing date: 2024-02-21
Publication date: 2024-05-24

Abstract

The invention discloses a nano material grafted block copolymer composite modified asphalt and waterproof application, and belongs to the technical field of waterproof materials. The composite modifier is prepared from a hydroxylation nano material and a functional block copolymer through a grafting reaction. The composite modifier can be used for preparing modified asphalt, and the structural characteristics of the asphalt material can be changed on the nanometer scale based on the synergistic effect of the nanometer material and the segmented copolymer, so that the macroscopic performance of the asphalt material is greatly optimized, such as high-low temperature performance, temperature sensitivity and ageing resistance are effectively improved. The introduction of the surface functional groups of the composite modifier promotes the compatibility and dispersibility of the modifier and asphalt, and the waterproof coiled material coating material obtained by using the modified asphalt has better adhesion performance with a tire base layer. The invention adopts a one-step addition method, simplifies the preparation process of preparing modified asphalt by two modifiers, and has the advantages of simple and efficient preparation method, low energy consumption, low cost, good comprehensive performance and the like.

Description

Nano material grafted block copolymer composite modified asphalt and waterproof application

Technical Field

The invention belongs to the technical field of waterproof materials, and particularly relates to a nano material grafted block copolymer composite modified asphalt and waterproof application.

Background

With the development of the construction industry and the transportation industry, the demand of waterproof materials is continuously increasing. The main raw material of the asphalt-based waterproof coiled material is waterproof asphalt, and the low temperature resistance of Gao Wen is greatly dependent on the high temperature resistance and the low temperature resistance of the waterproof asphalt. Due to the influences of thermal aging, photo-thermal coupling aging and the like, the traditional asphalt-based waterproof material has the problems of easy flowing at high temperature, easy brittle fracture at low temperature, poor ductility and the like in the use process, has a short effective period and has great use limitation. At present, most of the traditional waterproof asphalt matrix is modified by adding high molecular materials such as copolymer, rubber powder, polypropylene and the like as a modifier and functional filler, and then the modified asphalt is further coated on the matrix to prepare the waterproof coiled material, so that the comprehensive performance of the waterproof coiled material is improved. The high molecular modifier is mainly a modified material with a high molecular polymer as a main component. The nano material is used as a functional filler modifier, and can be added into asphalt to improve various performances of the asphalt, reduce temperature sensitivity of asphalt-based materials and improve high-temperature performance and ageing resistance of the asphalt. However, compatibility and dispersibility of the modifier and asphalt are important preconditions for the modifying effect, and therefore, the modifier should have good melt dispersibility in asphalt. However, due to extremely high specific surface area and van der Waals force, the functional nanomaterial is easy to agglomerate, and the agglomerated nanomaterial not only is difficult to exert the advantages of the shape, the size and the performance of the nanomaterial, but also can cause large performance discreteness of the asphalt-based composite material, and even has adverse effects on mechanical properties. Therefore, good dispersibility is a precondition for preparing the nano modified asphalt-based composite material. The compatibility between the nano material and asphalt is one of key factors for improving the performance of the nano modified asphalt composite material. When the polymer modifier is added into the matrix asphalt, the compatibility of the modifier and the petroleum asphalt determines the stability of a modified asphalt compatible system, the asphalt has a large chemical structure difference with the polymer, and the molecular weight and the solubility parameter have a large difference, so that a thermodynamic compatible system is difficult to form between the asphalt and the polymer, the stability is poor, and the system segregation is easy to generate, thereby influencing the storage and the use of the rubber asphalt. Therefore, a modifier with good dispersibility and compatibility is developed, and the modifier has important significance for preparing high-temperature-resistant and anti-aging modified waterproof asphalt and applying the modified asphalt to waterproof coiled materials.

Disclosure of Invention

The invention provides a preparation method of a hydroxylation nanomaterial grafted functionalized block copolymer composite modifier, which comprises the following steps:

(1) Functional modification

Dissolving the segmented copolymer in an organic solvent, adding a polymer, a phase transfer agent and an oxidant, and reacting at constant temperature; after the reaction is finished, regulating the pH value to be neutral, adding a protective agent, heating and stirring, and recovering the organic solvent; after the reaction system is cooled, adding water for precipitation, and drying the solid precipitate to obtain an epoxidized block copolymer;

(2) Hydroxylation modification

Adding the nano material and the dispersing agent into a dispersing solvent, performing ultrasonic dispersion, then adding a hydroxyl modifier, and performing reflux reaction; after the reaction is finished, cooling, filtering, and drying the solid reactant to obtain the hydroxylation nanomaterial;

(3) Grafting reaction

Dissolving the epoxidized block copolymer in an organic solvent, adding a hydroxylated nano material, adjusting the pH to be alkaline, and stirring for reaction; and after the reaction is finished, cooling, and drying the solid precipitate to obtain the hydroxylation nanomaterial grafted epoxidized block copolymer composite modifier.

In the preparation method of the composite modifier, in the step (1), the mass ratio of the block copolymer, the organic solvent, the polymer, the phase transfer agent, the oxidant and the protective agent is selected from 1:10-20:0.02-0.5:0.001-0.1:0.1-5:0.002-0.1.

In the preparation method of the composite modifier, in the step (2), the mass ratio of the nanomaterial to the dispersant to the hydroxyl modifier to the dispersion solvent is selected from 1:0.1-2:10-50.

In the preparation method of the composite modifier, in the step (3), the mass ratio of the epoxidized block copolymer to the hydroxylated nanomaterial to the organic solvent is selected from 1:0.5 to 3:10 to 30.

In the preparation method of the composite modifier, in the step (1), the block copolymer is selected from one or more of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene-propylene (SEP), styrene-ethylene-butylene-styrene (SEBS) and styrene-ethylene-propylene-styrene (SEPS); the polymer is one or more selected from polyacrylic acid, poly (pyromellitic dianhydride-co-4, 4' diaminodiphenyl ether) amic acid, polymaleic acid, polyethylene aspartic acid and polymethacrylic acid; the phase transfer agent is selected from any one of trioctyl methyl ammonium chloride, tetrabutyl ammonium bromide, polyethylene glycol monomethyl ether, polyethylene glycol (the molecular weight is 200-4000), tetrabutyl ammonium chloride, vinyl benzyl mercaptan, dodecyl mercaptan, chain polyethylene glycol dialkyl ether, benzyl triethyl ammonium chloride, tetrabutyl ammonium bisulfate, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, quaternary ammonium salt and pyridine; the oxidant is at least one selected from potassium persulfate, ammonium persulfate, hydrogen peroxide, sodium persulfate and potassium persulfate, wherein the concentration of the hydrogen peroxide is 30-50%; the protective agent is selected from one or more of pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy hydrocinnamate), pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, tris (2, 4-di-tert-butylphenyl) phosphite, N' - (hexane-1, 6-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ]; the organic solvent is one or more selected from cyclohexane, acetone, butanone, cyclohexanone, methanol, toluene, xylene, benzene, methyl ethyl ketone, ethyl acetate and dichloroethane.

In the preparation method of the composite modifier, in the step (2), the nanomaterial is selected from zero-dimensional, one-dimensional or two-dimensional nanomaterial; wherein the zero-dimensional nano material comprises one or more of nano calcium carbonate, nano silicon dioxide, nano kaolin, nano aluminum oxide, nano titanium oxide and nano zinc oxide, the particle size of the zero-dimensional nano material is 10 nm-1 mu m, and the appearance is one or more of spherical, ellipsoidal, flower-shaped, regular polyhedral and irregular polyhedral; the length-diameter ratio of the one-dimensional nano material is more than 10, the diameter is 1-200 nm, and the one-dimensional nano material comprises at least one of carbon nano tubes, nano carbon fibers, polyacrylonitrile, polyvinylpyrrolidone, polyaniline and organic nano fibers formed by polyurethane, and a metal compound with the appearance of nano wires, nano rods or whiskers formed by one or more of calcium, silicon, aluminum, titanium and zinc; the two-dimensional nanomaterial comprises at least one of graphene, graphene oxide, nano montmorillonite, graphite phase carbon nitride, molybdenum disulfide, titanium disulfide and titanium diselenide; the dispersing agent is one or more selected from Polyvinylpyrrolidone (PEI), sodium Dodecyl Sulfate (SDS), cetyltrimethylammonium bromide (CTAB), polysulfonic acid and ethanol; the hydroxyl modifier is selected from polyalcohol, saccharide, phenols and polyhydroxy macromolecular compounds, the polyalcohol is selected from at least one of 2-amino-2-methoxy-1, 3-propanediol, glycerol, 1, 2-propanediol, 2-methyl-2, 3-butanediol, 2-methyl-2, 4, 5-pentanetriol, 1, 3-propanediol, 1, 4-butanediol, pentaerythritol, neopentyl glycol, butyl tetraol, ribitol, n-hexanol, dipropylene glycol, arabitol, 4-hydroxybenzyl alcohol (p-hydroxybenzyl alcohol), pentanediol, xylitol, diethylene glycol, sorbitol, mannitol, dulcitol, trimethylolpropane, perfluoropolyether polyol, cis (trans) -1, 2-cyclopentanediol, cis (trans) -1, 2-cycloheptanediol, cis (trans) -1, 2-cyclohexanediol; the saccharide is at least one of glucose, mannose, starch, sorbose, sucrose, lactose, maltose, alpha-D-furanose galactose, beta-D-furanose, beta-L-furanose, alpha-L-barking furanrhamnose, beta-L-barking furanose, alpha-D-barking furanose; the phenols are selected from at least one of catechol, 3-nitrocatechol, 4-nitrocatechol, 3, 5-dinitrocatechol and 3, 4-dihydroxybenzoic acid; the polyhydroxy macromolecular compound is at least one selected from polyvinyl alcohol, cellulose, polyethylene glycol, gelatin, agar, chondroitin sulfate and sodium hyaluronate; the dispersion solvent is at least one of water, ethanol, methylene dichloride and chloroform.

In the preparation method of the composite modifier, in the step (3), the organic solvent is one or more selected from cyclohexane, toluene, dimethyl sulfoxide, methyl ethyl ketone, ethyl acetate and dichloroethane; the alkaline solution is one or more selected from sodium hydroxide, potassium carbonate, potassium hydroxide, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide, potassium ethoxide, sodium hydroxide, potassium phosphate and potassium fluoride.

In the preparation method of the composite modifier, in the steps (1) and (3), alkali solution is adopted to adjust the pH, and the alkali solution is prepared from one or more of potassium phosphate, sodium hydroxide, potassium carbonate, sodium methoxide, potassium hydroxide, potassium ethoxide, sodium carbonate or sodium bicarbonate, and the concentration is 0.1-1 mol/L; wherein the pH in step (1) is adjusted to neutral; the pH in the step (3) is adjusted to be alkaline, and the pH is between 8 and 10.

In the preparation method of the composite modifier, in the step (1), the conditions of the constant temperature reaction are selected from the group consisting of: reacting for 100-180 min in an oil bath with constant temperature of 50-80 ℃; the conditions of heating and stirring are selected from the following: heating to 80-100 ℃ and stirring for 1-3 h; in the step (2), the condition of the reflux reaction is selected from the group consisting of: condensing and refluxing for 18-24 h under the oil bath at 100-120 ℃; in the step (3), the condition of stirring reaction is selected from the group consisting of: stirring and reacting for 30-40 min at 100-120 ℃.

In the above-described composite modifier preparation method, the drying conditions in each step are selected from: vacuum drying at 40-80 deg.c to constant weight.

The invention provides the hydroxylation nano material grafted functional block copolymer composite modifier prepared by the method.

The invention provides a preparation method of composite modifier modified asphalt, which comprises the following steps:

mixing the hydroxylated nano material grafted functionalized block copolymer composite modifier with a dispersion solvent, and stirring at a high temperature to obtain a composite modifier solution; then, heating the matrix asphalt to a molten state at a high temperature, gradually adding the composite modifier solution, shearing at a high temperature, and stirring at a low speed to obtain the composite modifier modified asphalt.

In the preparation method of the composite modifier modified asphalt, the matrix asphalt is selected from 70# or 90# petroleum asphalt; the dispersion solvent is selected from one of furfural oil, rubber oil, maleic anhydride and dibutyl phthalate; the mass ratio of the matrix asphalt to the composite modifier to the dispersing agent is selected from 1:0.03-0.06:0.05-0.5; the temperature is Wen Xuanzi ℃ to 150 ℃ in the high-temperature stirring and high-temperature conditions; the high temperature shear is selected from the following conditions: shearing at the temperature of 170-190 ℃ for 30-60 min at 2000-3000 r/min, and shearing at the temperature of 4000-6000 r/min for 30-40 min; the conditions of low speed stirring are selected from: stirring at a low speed of 200-500 r/min for 1-2 h at 140-160 ℃.

The invention provides the composite modifier modified asphalt prepared by the method.

The invention provides application of the hydroxylation nanomaterial grafted functionalized block copolymer composite modifier or composite modifier modified asphalt in waterproof coating; preferably for preparing the waterproof coiled material coating material.

The invention provides a waterproof coiled material coating material, which consists of the composite modifier modified asphalt, functional filler and base oil; wherein the mass ratio of the composite modifier modified asphalt to the functional filler to the base oil is selected from 1:0.3-0.6:0.6-1.0.

The functional filler is selected from one of talcum powder, fly ash, limestone powder, organic montmorillonite and slate powder; the base oil is selected from vegetable oil, mineral oil or light oil; the vegetable oil is selected from one of soybean oil, corn oil and kitchen waste grease, the mineral oil is selected from one of extracted oil, lubricating oil, engine oil and heavy oil, and the light oil is selected from one of naphtha, gasoline, diesel oil and kerosene.

The waterproof coiled material coating material can be preferably prepared by the following method: and mixing and heating the modified asphalt, the functional filler and the base oil to 130-150 ℃, and shearing for 0.5-4 h in a shearing machine with the rotating speed of 3000-5000 rpm to obtain the waterproof coiled material coating material.

The beneficial effects of the invention are as follows:

1. According to the invention, the modifier is prepared by grafting and compounding the nano material and the block copolymer, and the functional modification of the block copolymer and the crosslinking of the nano material and the block copolymer are carried out by the organic polymer, so that the problems of particle agglomeration and low dispersity caused by the independent doping of the nano material are avoided, the problems of poor compatibility of the nano material, the block copolymer, asphalt and the like, difficult modification and the like are effectively solved, and the wide application of the nano material in the field of modified asphalt is promoted. The composite modifier increases the crosslinking force of the asphalt material and each component, and the whole system forms a stable three-dimensional network structure, so that molecules are tightly combined, and the ageing resistance, high-temperature stability, crack resistance, low-temperature toughness and compatibility of the modified asphalt are improved.

2. The invention can change the structural characteristics of the asphalt material on the nanometer scale based on the synergistic effect of the nanometer material and the segmented copolymer, thereby realizing the great optimization of the macroscopic performance of the asphalt material, such as the high-low temperature performance, the temperature sensitivity and the ageing resistance, and effectively improving. The one-step addition method simplifies the preparation process of the modified asphalt prepared by the two modifiers, and has the advantages of simple and efficient preparation method, low energy consumption, low cost and the like.

3. The hydroxylated nano material grafted epoxy functional modified segmented copolymer is used as a modifier and has physical modification and chemical modification in the process of compounding modified asphalt, on one hand, the functional group modification can improve the compatibility of the segmented copolymer and asphalt molecules, on the other hand, the functional groups such as hydroxyl functional groups and carboxyl groups of asphalt molecules are used for realizing effective adsorption through hydrogen bonds existing among the functional groups, and more asphalt is attached to the surfaces of the nano particles due to the characteristic of large self surface area of the nano particles, so that a layer of diffusion solvent film with a certain thickness can be formed, and the higher the content of the modified asphalt is used as structural asphalt, the better the performance of the asphalt is, and the more stable the performance of the compounded modified asphalt is.

4. The epoxidation modification of the segmented copolymer is carried out by adding a small amount of phase transfer catalyst into the reaction system, thereby improving the epoxidation degree of the segmented copolymer, improving the utilization ratio of the organic acid polymer and the oxidant, improving the mass fraction of the epoxy group and reducing the occurrence of side reaction. Meanwhile, the organic solvent is distilled off by azeotropically using water and the organic solvent, and the organic solvent is recovered and reused based on the immiscible characteristic of the water and the organic solvent. The invention avoids the problems of high cost, complex process, environmental pollution and the like caused by using alcohol solvents in the sedimentation and washing processes, and reduces the cost and the pollution degree to the environment, thereby being suitable for the requirement of industrial production.

5. The invention adopts epoxy groups and hydroxyl groups to modify the surface functional groups of the segmented copolymer and the nano material respectively, so that the epoxidized segmented copolymer and the polyhydroxy modified nano material are formed, and the functional groups can promote the compatibility of the modifier and asphalt, so that no additional compatilizer is needed to be added in the modification process. The waterproof coiled material coating material obtained by using the modified asphalt has better adhesion performance with the tire base layer.

6. The invention selectively oxidizes the carbon-carbon double bond of the middle soft segment of the segmented copolymer to become an epoxy segmented copolymer, the double bond in the epoxy segmented copolymer is epoxidized, the polarity is stronger, the cohesive strength is higher, and simultaneously, an epoxy group is introduced, so that a novel reaction center is provided, and a functional group is provided for further chemical modification and application.

7. The nanometer material composite block copolymer is grafted onto the surface of the rigid nanometer material to make the interface modulus lower than that of the matrix asphalt and the nanometer material. The composite modifier with reinforced rigid-flexible combination can form a low-modulus flexible interface layer, is favorable for buffering external load and absorbing energy, thereby resisting creep deformation of the material at low temperature and rutting resistance at high temperature, finally realizing the effect of reinforcing and toughening modified asphalt and improving the problem of uneven dispersion of nano materials in an asphalt matrix.

Drawings

FIG. 1 is a FT-IR spectrum of nano calcium carbonate and hydroxylated nano calcium carbonate;

FIG. 2 is an SEM image of nano calcium carbonate (a) and hydroxylated nano calcium carbonate (b);

FIG. 3 is a schematic representation of the reaction of an epoxidized block copolymer with a hydroxylated calcium carbonate;

FIG. 4 is a FT-IR spectrum of pristine carbon nanofibers (a) and hydroxylated carbon nanofibers (b);

FIG. 5 is a photograph showing the original carbon nanofiber (a) and the hydroxylated carbon nanofiber grafted epoxidized styrene-ethylene-propylene-styrene composite modifier (b) dispersed in dichloroethane and allowed to stand for various times;

FIG. 6 is a contact angle of nano titanium disulfide (a) and hydroxylated nano titanium disulfide grafted epoxidized styrene-ethylene-butylene-styrene (b);

FIG. 7 shows the complex shear modulus (G) change for various modified asphalt;

FIG. 8 is a graph showing the change in phase angle (delta) for various modified asphalt;

FIG. 9 is a graph of various modified asphalt rut factor variations;

FIG. 10 is a fluorescence microscope image of the modified asphalt of comparative example 4 (a) and example 1 (b);

FIG. 11 is a BBR test result for various modified asphalt;

FIG. 12 is a graph of the residual softening point increase for a spin film oven test (RTFOT) and Pressure Aging (PAV) for various modified asphalt;

FIG. 13 is a graph of low temperature flexibility of various modified asphalt;

FIG. 14 shows peel strength of various modified asphalts.

Detailed Description

The asphalt used in the following embodiments of the present invention is 70-base asphalt manufactured by zilupetrifaction corporation, and the parameters thereof are shown in table 1 below.

TABLE 1

Other materials used in the present invention, such as those not specifically stated, are available through commercial sources. Other terms used herein, unless otherwise indicated, generally have meanings commonly understood by those of ordinary skill in the art. The invention will be described in further detail below in connection with specific embodiments and with reference to the data. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.

Example 1

The embodiment relates to preparation of a hydroxylated nano calcium carbonate grafted functionalized styrene-isoprene-styrene composite modifier, modified asphalt and waterproof coiled material coating material.

1. Hydroxylated nano calcium carbonate grafted functional styrene-isoprene-styrene composite modifier

The preparation method comprises the following steps:

(1) Preparation of epoxidized styrene-isoprene-styrene

5G of a styrene-isoprene-styrene (SIS) block copolymer was added to 60g of cyclohexane, heated to 60℃and stirred so that the styrene-isoprene-styrene (SIS) was completely dissolved; 0.2g of polyacrylic acid and 0.05g of chain polyethylene glycol dialkyl ether and 1g of potassium persulfate were added and reacted in an oil bath at a constant temperature of 55℃for 120 minutes. After the reaction is finished, adding 0.2mol/L potassium ethoxide to adjust the pH value of the solution to be neutral, adding 0.05g of pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy hydrocinnamate), heating the solution to 85 ℃, stirring for 1.5h, recovering the organic solvent, cooling the solution, pouring the solution into a beaker, adding distilled water for precipitation, repeatedly washing to obtain a solid precipitate, transferring the solid precipitate to an infrared lamp for drying, placing the solid precipitate in a vacuum oven at 70 ℃, and drying the solid precipitate in a constant quantity to obtain the epoxidized styrene-isoprene-styrene.

The mass fraction of epoxy groups of the obtained epoxidized styrene-isoprene-styrene elastomer was determined by the tetraethylammonium bromide method according to the GB/T4612-1984 standard and was 15.5%.

(2) Hydroxylation modification of nano calcium carbonate

Taking 5g of nano calcium carbonate with the particle size of 50nm and 1g of Polyvinylpyrrolidone (PEI), adding into 100g of ethanol, performing ultrasonic dispersion for 30min, adding 1g of glycerol, magnetically stirring, condensing and refluxing for 18h under the oil bath at the temperature of 100 ℃, cooling, performing suction filtration, flushing with ethanol, placing in a drying oven with the constant temperature of 70 ℃ after filtration, and drying for 8h to constant volume to obtain the hydroxylated modified nano calcium carbonate.

(3) Preparation of hydroxylated nano calcium carbonate grafted epoxidized styrene-isoprene-styrene

5G of epoxy styrene-isoprene-styrene is added into 60g of cyclohexane, heated to 100 ℃ until the epoxy styrene-isoprene-styrene is completely dissolved, 4g of hydroxyl modified nano calcium carbonate is added, the pH value is adjusted to 8 through 0.2mol/L sodium hydroxide solution, the mixture is stirred and reacted for 30min at 100 ℃, then the mixture is kept stand for 40min, the solid precipitate is taken out after cooling, the solid precipitate is transferred to an infrared lamp for drying to remove the solvent, the product is placed into a vacuum oven at 45 ℃ for drying after being odorless, and the hydroxyl modified nano calcium carbonate grafted epoxy styrene-isoprene-styrene composite modifier is obtained after the product is kept constant.

2. Modified asphalt

The preparation method comprises the following steps:

Mixing 4g of hydroxylated nano calcium carbonate grafted epoxidized styrene-isoprene-styrene composite modifier with 10g of dibutyl phthalate, and mixing and stirring for 1h at 135 ℃ to obtain a composite modifier solution; heating 100g of asphalt to a molten state at 145 ℃, gradually adding a composite modifier solution, shearing at 2500r/min for 40min at 180 ℃ by a high-speed shearing machine, shearing at 5000r/min for 30min, and finally stirring at 300r/min for 1h at 150 ℃ at a low speed to obtain the composite modifier modified asphalt.

3. Waterproof coiled material coating material

The preparation method comprises the following steps:

5g of modified asphalt of the composite modifier, 1.5g of fly ash and 4g of naphtha are mixed and heated to 130 ℃, and sheared for 2 hours in a shearing machine with the rotating speed of 3000rpm, so as to obtain the waterproof coiled material coating material.

In the present invention, fig. 1 shows infrared spectra of nano calcium carbonate (a) and hydroxylated nano calcium carbonate (b). As can be seen from FIG. 1, the characteristic peak vibration of the hydroxylated nano calcium carbonate at 3442cm ^-1 is most obvious compared with that of the unmodified nano calcium carbonate, and is due to the fact that the surface of the functionalized nano calcium carbonate contains more hydroxyl groups, the characteristic peak fluctuation amplitude at 2495, 1775, 1004, 818 and 702cm ^-1 is smaller, and the asymmetric stretching vibration peak of CO ₃ ^2- is mainly 1475cm ^-1 due to the fact that the in-plane and bending vibration of bonds such as-CH ₂, C-H and the like and C-C skeleton vibration are generated. The surface of the functionalized nano calcium carbonate is shown to contain abundant hydroxyl functional groups and few other functional groups. The above results indicate that nano calcium carbonate has successfully modified hydroxyl functional groups.

In the present invention, fig. 2 shows SEM images of nano calcium carbonate (a) and hydroxylated nano calcium carbonate (b). Under the condition of the same magnification, the dispersion degree of nano calcium carbonate in deionized water before and after modification is observed, the particle size of the non-functionalized nano calcium carbonate is about 50nm as shown in fig. 2 (a), and the nano calcium carbonate is in a calcite structure, and untreated calcium carbonate powder has the tendency of agglomeration. As shown in the figure 2 (b), the nano calcium carbonate modified by hydroxyl has obviously reduced agglomeration of powder and more uniform dispersion, and most particles are in a monodisperse state, so that the nano calcium carbonate is in a more ideal distribution state. The dispersibility of the nano particles is obviously improved, which indicates that the hydroxyl modifier can reduce the surface energy of nano calcium carbonate and reduce agglomeration, thus being beneficial to the dispersion of nano fillers in asphalt matrix and improving filling and modifying effects. Meanwhile, the appearance of the calcium carbonate particles is not changed by introducing the hydroxyl modifier, which indicates that the hydroxyl modifier is dispersed on the surface of the nano calcium carbonate in a single molecule form. It can be inferred that the hydroxyl modified nanoparticles have better dispersion effect than the unmodified nanoparticles when applied to the polymer.

In the present invention, FIG. 3 shows a schematic reaction diagram of an epoxidized block copolymer and hydroxylated calcium carbonate.

Example 2

The embodiment relates to preparation of a hydroxylated nano calcium carbonate grafted functionalized styrene-isoprene-styrene composite modifier, modified asphalt and waterproof coiled material coating material. The preparation method is as shown in the above example 1; unlike example 1, in the preparation step of the modified asphalt, the amount of the hydroxylated nano calcium carbonate grafted epoxidized styrene-isoprene-styrene composite modifier used was 5g.

Example 3

The embodiment relates to preparation of a hydroxylated nano calcium carbonate grafted functionalized styrene-isoprene-styrene composite modifier, modified asphalt and waterproof coiled material coating material. The preparation method is as shown in the above example 1; unlike example 1, in the preparation step of the modified asphalt, the amount of the hydroxylated nano calcium carbonate grafted epoxidized styrene-isoprene-styrene composite modifier used was 6g.

Example 4

The embodiment relates to preparation of a hydroxylated carbon nanofiber grafted functionalized styrene-ethylene-propylene-styrene composite modifier, modified asphalt and waterproof coiled material coating material.

1. Hydroxylated carbon nanofiber grafted functionalized styrene-ethylene-propylene-styrene composite modifier

The preparation method comprises the following steps:

(1) Preparation of epoxidized styrene-ethylene-propylene-styrene

5G of styrene-ethylene-propylene-styrene (SEPS) block copolymer was added to 70g of toluene, heated to 70℃and stirred so that styrene-ethylene-propylene-styrene (SEPS) was completely dissolved; 0.3g of poly (pyromellitic dianhydride-co-4, 4' -diaminodiphenyl ether) amic acid, 0.1g of vinylbenzyl mercaptan and 1.5g of ammonium persulfate were added and reacted in an oil bath at a constant temperature of 65℃for 140 minutes. After the reaction, adding sodium bicarbonate to adjust the pH value of the solution to be neutral, adding 0.1g of N, N' - (hexane-1, 6-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ], heating the solution to 90 ℃, stirring for 2 hours, recovering the organic solvent, cooling the solution, pouring the solution into a beaker, adding distilled water for precipitation, repeatedly washing to obtain a solid precipitate, transferring the solid precipitate to an infrared lamp for drying, and placing the solid precipitate in a vacuum oven at 75 ℃ for drying, thus obtaining the epoxidized styrene-ethylene-propylene-styrene after constant quantity.

(2) Hydroxylation modification of carbon nanofibers

Adding 5g of carbon nanofiber (with the diameter of 100-150 nm, the length-diameter ratio of 70 and the length of 10-20 mu m) and 2g of Sodium Dodecyl Sulfate (SDS) into 150g of dichloromethane, performing ultrasonic dispersion for 20min, adding 2g of beta-L-furanose, performing magnetic stirring, condensing and refluxing for 20h under the oil bath at the temperature of 110 ℃, cooling, performing suction filtration, washing with ethanol, placing in a drying oven with the constant temperature of 75 ℃ after filtration, and drying for 9h to constant quantity to obtain the hydroxylated modified carbon nanotube.

(3) Preparation of hydroxylated carbon nanofiber grafted epoxidized styrene-ethylene-propylene-styrene composite modifier

Adding 5g of epoxy styrene-ethylene-propylene-styrene into 70g of dichloroethane, heating to 110 ℃ until the epoxy styrene-ethylene-propylene-styrene is completely dissolved, adding 3g of hydroxylated carbon nanofiber, regulating the pH to 9 through a 0.5mol/L potassium hydroxide solution, stirring and reacting for 35min at 110 ℃, standing for 35min, cooling, taking out a solid precipitate, transferring to an infrared lamp for drying to remove a solvent, placing the product into a vacuum oven at 50 ℃ for drying after the product is odorless, and obtaining the hydroxylated carbon nanofiber grafted epoxy styrene-ethylene-propylene-styrene composite modifier after the product is constant.

2. Modified asphalt

The preparation method comprises the following steps:

Mixing 6g of hydroxylated carbon nanofiber grafted epoxidized styrene-ethylene-propylene-styrene composite modifier with 20g of maleic anhydride, and mixing and stirring for 1.5h at 130 ℃ to obtain a composite modifier solution; heating 100g of asphalt to a molten state at 140 ℃, gradually adding a composite modifier solution, shearing for 50min at 2000r/min at 185 ℃ by a high-speed shearing machine, shearing for 35min at 5500r/min, and finally stirring for 1.5h at 400r/min at 155 ℃ at low speed to obtain the composite modifier modified asphalt.

3. Waterproof coiled material coating material

The preparation method comprises the following steps:

5g of composite modifier modified asphalt, 2g of slate powder and 3g of soybean oil are mixed and heated to 140 ℃, and sheared for 2.5 hours in a shearing machine with the rotating speed of 4000rpm, so as to obtain the waterproof coiled material coating material.

In the present invention, fig. 4 shows infrared spectra of the carbon nanofibers (a) and the hydroxylated carbon nanofibers (b). As can be seen from fig. 4, there is a strong absorption peak at 1648cm ^-1, which is due to the stretching vibration of c=c, and is considered as a characteristic peak of the original carbon nanotube. The absorption band at 3538cm ^-1 is due to the presence of-OH groups, which are generated by oxidation of the carbon nanotubes during purification. The graph b represents the hydroxylated carbon nanofibers. The strong and broad absorption peak at 3435cm ^-1 is due to the stretching vibration of the-OH group. The absorption peak of C-O appears at 1180cm ^-1, and the appearance of the absorption peak of hydroxyl and the absorption peak of C-O compared with the curve of the original carbon nanofiber show successful modification of the hydroxyl group on the carbon nanofiber.

In the present invention, fig. 5 is a photograph of carbon nanofiber (a) and hydroxylated carbon nanofiber grafted epoxidized styrene-ethylene-propylene-styrene composite modifier (b) dispersed in dichloroethane and left to stand for different times. From fig. 5 it can be seen that the original carbon fibers begin to settle immediately upon completion of the ultrasonic vibration in dichloroethane, as is evident at 10 minutes. When the carbon fiber is left to stand for 30min, it is clear from fig. 5 that the carbon fiber has almost settled completely, the composite modifier has not changed, and the dispersion is relatively uniform. When the composite modifier is kept stand for 24 hours, all the carbon fibers are settled at the bottom of the dichloroethane solvent, and the composite modifier shows good dispersibility without obvious settlement. The comparison shows that the hydroxylated carbon nanofiber grafted epoxidized styrene-ethylene-propylene-styrene can fully improve the dispersibility of the modifier in polar solvents, and further proves that the composite modifier has good compatibility with organic solvents such as dichloroethane and the like and can effectively prevent agglomeration of the carbon nanofibers. Effectively ensures the dispersion stability of the composite catalyst in the asphalt matrix.

Example 5

This example relates to the preparation of hydroxylated titanium disulfide grafted functionalized styrene-ethylene-butylene-styrene composite modifier, modified asphalt, and waterproof roll coating.

1. Hydroxylation titanium disulfide grafted functionalized styrene-ethylene-butylene-styrene composite modifier

The preparation method comprises the following steps:

(1) Preparation of epoxidized styrene-ethylene-butene-styrene

5G of styrene-ethylene-butylene-styrene (SEBS) was added to 80g of dichloroethane, heated to 70℃and stirred so that styrene-ethylene-butylene-styrene (SEBS) was completely dissolved; 0.5g of polymaleic acid, 0.2g of trioctyl methyl ammonium chloride and 2g of potassium hydrogen persulfate were added and reacted in an oil bath at a constant temperature of 70℃for 150 minutes. After the reaction is finished, adding a potassium ethoxide solution to adjust the pH value of the solution to be neutral, adding 0.2g of N, N' - (hexane-1, 6-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ], heating the solution to 100 ℃, stirring for 2.5 hours, recovering the organic solvent, cooling the solution, pouring the solution into a beaker, adding distilled water for precipitation, repeatedly washing to obtain a solid precipitate, transferring the solid precipitate to an infrared lamp for drying, placing the solid precipitate in a vacuum oven at 80 ℃ for drying, and obtaining the epoxidized styrene-ethylene-butylene-styrene after constant quantity.

(2) Hydroxylation modification of nano titanium disulfide

Adding 5g of nano titanium disulfide and 3g of Cetyl Trimethyl Ammonium Bromide (CTAB) into 200g of chloroform, performing ultrasonic dispersion for 30min, adding 3g of 3-nitrocatechol, performing magnetic stirring, condensing and refluxing for 22h under an oil bath at 120 ℃, cooling, performing suction filtration, flushing with ethanol, placing the mixture in a drying oven at a constant temperature of 80 ℃ after filtration, and drying for 10h to constant quantity to obtain the hydroxylated modified nano titanium disulfide.

(3) Preparation of hydroxylated nano titanium disulfide grafted epoxy styrene-ethylene-butylene-styrene

Adding 5g of epoxy styrene-ethylene-butylene-styrene into 80g of dichloroethane, heating to 120 ℃ until the epoxy styrene-ethylene-butylene-styrene is completely dissolved, adding 5g of hydroxyl nano titanium disulfide, regulating the pH to 10 through 1mol/L potassium ethoxide solution, stirring and reacting for 40min at 120 ℃, standing for 30min, cooling, taking out solid precipitate, transferring to an infrared lamp for drying to remove solvent, placing the product into a vacuum oven at 60 ℃ for drying after the product is odorless, and obtaining the hydroxyl nano titanium disulfide grafted epoxy styrene-ethylene-butylene-styrene composite modifier after the product is constant.

2. Modified asphalt

The preparation method comprises the following steps:

Mixing 6g of hydroxylated nano titanium disulfide grafted epoxidized styrene-ethylene-butylene-styrene composite modifier with 30g of furfural oil, and mixing and stirring for 2 hours at 150 ℃ to obtain a composite modifier solution; heating 100g of asphalt to a molten state at 150 ℃, gradually adding a composite modifier solution, shearing for 60min at 3000r/min at 190 ℃ by a high-speed shearing machine, shearing for 40min at 6000r/min, and finally stirring for 2h at 500r/min at 160 ℃ at a low speed to obtain the composite modifier modified asphalt.

3. Waterproof coiled material coating material

The preparation method comprises the following steps:

5g of composite modifier modified asphalt, 3g of talcum powder and 5g of soybean oil are mixed and heated to 150 ℃, and sheared for 4 hours in a shearing machine with the rotating speed of 5000rpm, so that the waterproof coiled material coating material is obtained.

In the present invention, fig. 6 shows contact angles of nano titanium disulfide (a) and hydroxylated nano titanium disulfide grafted epoxidized styrene-ethylene-butylene-styrene (b). As shown in fig. 6, the contact angle of nano titanium disulfide is 53.2 °, the contact angle of hydroxylated nano titanium disulfide grafted epoxidized styrene-ethylene-butylene-styrene is 116.4 °, and the lipophilicity is significantly enhanced. The method is characterized in that the organic modification of the epoxy styrene-ethylene-butylene-styrene reduces hydrophilic groups on the surface of the nano titanium disulfide, and the introduction of the organic groups greatly improves the oleophylic and hydrophobic properties of the nano titanium disulfide, thereby being beneficial to the compatibility and dispersibility of the composite modifier and the asphalt matrix.

Comparative example 1

This comparative example provides the unmodified No. 70 base asphalt produced by ziluting corporation, the relevant index of which is shown in table 1 above.

Comparative example 2

This comparative example relates to the preparation of epoxidized styrene-isoprene-styrene modified asphalt and waterproof roll coating materials. The preparation method is as shown in the above example 1; unlike example 1, in this comparative example, the amount of nano calcium carbonate used was 0g.

1. Epoxidized styrene-isoprene-styrene

The preparation method comprises the following steps:

2. Epoxidized styrene-isoprene-styrene modified asphalt

The preparation method comprises the following steps:

4g of an epoxidized styrene-isoprene-styrene (SIS) composite modifier and 10g of dibutyl phthalate are mixed and stirred for 1h at 135 ℃ to obtain a composite modifier solution; heating 100g of asphalt to a molten state at 145 ℃, gradually adding a composite modifier solution, shearing at 2500r/min for 40min at 180 ℃ by a high-speed shearing machine, shearing at 5000r/min for 30min, and finally stirring at 300r/min for 1h at 150 ℃ at a low speed to obtain the epoxidized styrene-isoprene-styrene modified asphalt.

3. Waterproof coiled material coating material

The preparation method comprises the following steps:

5g of epoxidized styrene-isoprene-styrene modified asphalt, 1.5g of fly ash and 4g of naphtha are mixed and heated to 130 ℃, and sheared for 2 hours in a shearing machine with the rotating speed of 3000rpm, so as to obtain the waterproof coiled material coating material.

Comparative example 3

This comparative example relates to the preparation of hydroxylated nano calcium carbonate modified asphalt and waterproof roll coating materials. The preparation method is as shown in the above example 1; unlike example 1, in this comparative example, the amount of styrene-isoprene-styrene used was 0g.

1. Hydroxylated nano calcium carbonate

The preparation method comprises the following steps:

2. Hydroxylated nano calcium carbonate modified asphalt

The preparation method comprises the following steps:

Mixing 4g of hydroxylated nano calcium carbonate with 10g of dibutyl phthalate, and stirring and mixing for 1h at 135 ℃ to obtain a composite modifier solution; heating 100g of asphalt to a molten state at 145 ℃, gradually adding a composite modifier solution, shearing at 2500r/min for 40min at 180 ℃ by a high-speed shearing machine, shearing at 5000r/min for 30min, and finally stirring at 300r/min for 1h at 150 ℃ at a low speed to obtain the hydroxylated nano calcium carbonate modified asphalt.

3. Waterproof coiled material coating material

The preparation method comprises the following steps:

5g of hydroxylated nano calcium carbonate modified asphalt, 1.5g of fly ash and 4g of naphtha are mixed and heated to 130 ℃, and are sheared for 2 hours in a shearing machine with the rotating speed of 3000rpm, so that the waterproof coiled material coating material is obtained.

Comparative example 4

This comparative example relates to the preparation of hydroxylated nano calcium carbonate/epoxidized styrene-isoprene-styrene modified asphalt and waterproof roll coating. The preparation method is as shown in the above example 1; unlike example 1, in this comparative example, the hydroxylated nano calcium carbonate and the epoxidized styrene-isoprene-styrene (SIS) were not grafted.

1. Epoxidized styrene-isoprene-styrene

The preparation method comprises the following steps:

2. Hydroxylated nano calcium carbonate

The preparation method comprises the following steps:

3. Modified asphalt

The preparation method comprises the following steps:

Mixing 4g of hydroxylated nano calcium carbonate and 4g of epoxidized styrene-isoprene-styrene composite modifier with 10g of dibutyl phthalate, and stirring and mixing for 1h at 135 ℃ to obtain a composite modifier solution; heating 100g of asphalt to a molten state at 145 ℃, gradually adding a composite modifier solution, shearing at 2500r/min for 40min at 180 ℃ by a high-speed shearing machine, shearing at 5000r/min for 30min, and finally stirring at 300r/min for 1h at 150 ℃ at a low speed to obtain the composite modifier modified asphalt.

4. Waterproof coiled material coating material

The preparation method comprises the following steps:

5g of composite modifier modified asphalt, 1.5g of fly ash and 4g of naphtha are mixed and heated to 130 ℃, and sheared for 2 hours in a shearing machine with the rotating speed of 3000rpm, so as to obtain the waterproof coiled material coating material.

1. Modified asphalt performance test

1. Basic performance index

The indexes such as penetration, ductility, softening point and viscosity are basic performance indexes of asphalt, and the influence of the nano material grafted block copolymer modifier on the basic performance indexes of asphalt is examined according to the requirements in the test procedure of highway engineering asphalt and asphalt mixture (JTG E20-2011).

The test results are shown in table 2:

TABLE 2

As can be seen from Table 2, the modified asphalt prepared by the embodiment of the invention meets the requirements of JTGF 40-2004 technical Specification for construction of Highway asphalt pavement on the related index of the modified asphalt. The specific analysis is as follows.

(1) Softening point, ductility and penetration

In asphalt, the softening point is an important property that reflects the cohesiveness and plasticity of asphalt at high temperatures. Asphalt with a low softening point tends to soften at high temperatures, whereas asphalt with a high softening point requires a higher temperature to soften. The softening point can be used for evaluating the performance of asphalt at different temperatures, and the improvement of the softening point indicates that the asphalt has better high-temperature stability due to the addition of the modifier. Penetration indicates the softness and hardness of asphalt and the resistance to shear failure, and the penetration is reduced, which indicates that the addition of the modifier thickens the asphalt and reduces the influence of temperature change on asphalt fluidity. Ductility indicates the plasticity ability of the asphalt, and ductility increases, indicating that the addition of the modifier increases the deformation resistance of the asphalt.

As can be seen from table 2, the test data of the examples and the comparative examples meet the specification requirements. The singly-doped epoxidized SIS block copolymer, singly-doped hydroxylated calcium carbonate nanoparticle and the epoxidized block copolymer of comparative example 2, comparative example 3 and comparative example 4 were doubly-doped with hydroxylated nanoparticles, and the prepared modified asphalt was significantly different from each example in softening point and penetration, and the softening point and penetration of each example were significantly higher than each comparative example, but the ductility was slightly decreased. As is clear from examples 1, 2 and 3, with the increase of the composite modifier of the hydroxylated nanomaterial grafted epoxidized block copolymer, the softening point of the prepared modified asphalt is significantly increased, the penetration is significantly reduced, and the ductility is slightly reduced, wherein when the use amount of the composite modifier is 5g, the softening point and penetration performance index are optimal, the penetration of the modified asphalt is reduced to 43mm, and the softening point is increased to 74.9 ℃.

Therefore, the softening point and penetration of the modified asphalt prepared by the method are effectively improved, and the ductility is slightly reduced, but still meets the specification requirements. This is mainly due to the increase in molecular chain length after grafting the hydroxylated calcium carbonate nanoparticles with the epoxidized SIS block copolymer and the presence of hydroxyl functional groups, which can form intramolecular hydrogen bonds, resulting in an increase in softening point, which means that under the condition of meeting the requirements for ductility in the specifications, the method can be used to increase the two major indexes of asphalt softening point and penetration by properly increasing the use amount of the composite modifier.

(2) Isolation softening Point difference

The segregation softening point difference can be used to characterize the storage stability of asphalt. The smaller the segregation softening point difference, the better the storage stability of the asphalt.

As can be seen from Table 2, the segregation softening point differences of the respective comparative examples and examples satisfy the specification requirements. In comparison to the matrix asphalt, in comparative example 2, SIS was modified with epoxide groups, in which the c—c double bond of the isoprene group in the molecular chain was saturated with epoxide groups, and the active c=c became more polar epoxide groups. The dispersion of the nonpolar polymer in the asphalt can be promoted, the reinforcing and toughening effects can be achieved, meanwhile, the epoxidized SIS and the light components in the asphalt have different compatibility, and a polymer network structure can be formed, so that the epoxidized SIS has better storage stability than that of the matrix asphalt.

The segregation softening point differences of examples 1,2 and 3 are significantly lower than those of comparative examples 2,3 and 4, and compared with comparative example 4, the epoxidized block copolymer and the hydroxylated nanoparticles are respectively added as modifiers to asphalt, so that the modified asphalt system forms a three-phase blending structure, the properties of materials of each phase are different, the compatibility is weakened compared with that of the two-phase system formed by examples 1,2 and 3, and the storage stability is reduced. And it can be seen from examples 1,2 and 3 that the segregation softening point difference of the prepared modified asphalt is reduced with the increase of the epoxidized block copolymer grafted hydroxylated nano composite modifier, wherein the segregation softening point difference is at least 0.71 when the composite modifier is increased to 5g, because the formed modifier has higher polarity due to the grafting of the epoxidized block copolymer and the hydroxylated nano particles, the interaction between polymer molecules and between polymer and asphalt molecules is enhanced, the modified asphalt is easier to form a network structure as a whole, and the composite modifier chemically reacts with polar components such as carboxyl, phenolic hydroxyl and the like in the asphalt, so that the interaction inside the asphalt can be enhanced. Therefore, the compatibility of the modified asphalt prepared by the composite modifier is enhanced, the segregation phenomenon is not obvious, the storage stability of the asphalt is effectively improved, and the storage stability is also improved along with the proper increase of the use amount of the modifier.

2. Complex shear modulus (G) and phase angle (δ)

The complex shear modulus (G) changes for each modified asphalt are shown in fig. 7, and the phase angle (δ) changes for each modified asphalt are shown in fig. 8.

The complex shear modulus (G) characterizes the total resistance of asphalt to deformation, the greater G indicates that asphalt has good resistance to deformation and rutting in high temperature environments. The phase angle (δ) can evaluate the viscoelastic properties of asphalt, with a larger δ indicating better asphalt viscosity properties and a smaller δ indicating better asphalt elastic properties. In high temperature environment, asphalt is not easy to permanently deform and has excellent high temperature rheological property only when a larger complex shear modulus (G) and a smaller phase angle (delta) are needed.

Temperature scanning of the modified asphalt according to DSR test gave the results of fig. 7 and 8. It can be seen that the complex shear modulus (G) of each comparative example and example gradually decreases with increasing temperature, and that G of each example is higher than that of comparative example at each temperature, and that in comparative example 1, i.e., the matrix asphalt, the complex modulus of the modified asphalt is significantly improved compared with that of the matrix asphalt due to the addition of the functional modifier in comparative examples 2, 3 and 4. The order of the complex shear modulus from large to small is that comparative example 4 is larger than comparative example 3 is larger than comparative example 2, and the complex modulus of the asphalt modified by the two modifiers is further improved by a single modifier, which indicates that the composite modifier has excellent deformation resistance under the same condition. This is because the epoxidized SIS is changed in molecular structure compared with SIS, unsaturated double bonds in isoprene are partially substituted, the isoprene content is relatively reduced, the styrene content is relatively increased, and the high-temperature elasticity of the material is further improved, so that the high-temperature deformation resistance of the modified asphalt is improved. The complex shear modulus of examples 1,2 and 3 is greater than that of comparative example, because the modifier formed by grafting the epoxidized block copolymer and the hydroxylated nanoparticles increases the cohesive force of the asphalt due to the enhanced polarity of the modifier molecules and the chemical bonding with the asphalt molecules, and the external force required for the asphalt to deform identically is increased, and the high temperature deformation resistance is further improved. Example 2 has a higher G than examples 1 and 3 at each temperature and a lower delta than examples 1 and 3 at each temperature. It can be seen that complex shear modulus (G) and phase angle (δ) indices are optimal when the amount of the complex modifier used is increased to 5G. Therefore, after the composite modifier grafted by the epoxidized block copolymer and the hydroxylated nano particles is added in a high-temperature environment, the deformation resistance and the viscoelasticity of the asphalt can be effectively improved, and the deformation resistance and the viscoelasticity of the asphalt show a tendency of being improved as the use amount of the modifier is properly increased. Along with the further increase of the temperature, the complex modulus changes of the matrix asphalt and the modified asphalt are gradually gentle, and the complex modulus difference between different asphalt is gradually reduced, which indicates that the increase of the temperature reduces the viscoelastic property difference between different asphalt.

As shown in fig. 8, in the temperature scan test range, the phase angles of different modified asphalts are all increased along with the increase of the scan temperature, the phase angle of the matrix asphalt is obviously reduced by adding the modifier, and compared with the modified asphalts in comparative examples 2, 3 and 4, the phase angles of examples 1, 2 and 3 are still reduced to a certain extent, which indicates that the elastic components in the nano calcium carbonate composite SIS modified asphalt are increased compared with the epoxidized SIS and the nano calcium carbonate modified asphalt, and the possibility of permanent deformation is reduced. The nano calcium carbonate composite SIS improves the medium-high temperature rheological property of asphalt, and the composite modifier formed by grafting the two modifiers has a further improvement effect compared with a single modifier.

3. Rut factor

The various modified asphalt rut factor changes are shown in fig. 9.

Rutting factor (G/sin delta) asphalt can be used for evaluating rutting resistance. The higher the rutting factor, the better the asphalt's resistance to permanent deformation at high temperatures.

As can be seen from the rutting factor test results in fig. 9, the comparative examples and examples generally show a decreasing trend with increasing temperature, and the rutting factors of different modified asphalt are increased to some extent as compared with the matrix asphalt, and the addition of the modifier increases G on the one hand, decreases δ, and increases G/sin δ under the combined action. The results show that the medium-high temperature deformation resistance of different functionalized modified asphalt is improved, wherein G/sin delta is obviously increased compared with the modified asphalt of comparative examples 2, 3 and 4 after the modifier formed by compounding SIS with calcium carbonate of examples 1,2 and 3 is added, and the high-temperature performance of the modified asphalt is superior to that of the modified asphalt of comparative examples, which is mainly because the hard segment proportion in the modifier is increased by epoxidation of SIS, and the modified asphalt has better high-temperature deformation resistance. Compared with comparative example 4, the modified asphalt structure of examples 1-3 has enhanced cohesive force and enough capacity to resist external force, so that the effective combination of the two functional modifiers significantly improves the high-temperature stability of the modified asphalt.

4. Fluorescence microscopy analysis

Fluorescent microscope images of the modified asphalt of comparative example 4 (a) and example 1 (b) are shown in fig. 10. The compatibility and dispersibility of the modifier and the matrix asphalt can be observed through a fluorescence microscope, the phase distribution conditions in different systems of comparative example 4 and example 1 can be observed through the fluorescence microscope, and the yellow-green substance observed under the magnifying glass is taken as the modifier and is taken as a disperse phase; the black material is matrix asphalt and is used as a continuous phase; the disperse phase in the two modified asphalt systems is crosslinked and entangled with the continuous phase to different degrees to form a blending state. Wherein, the ungrafted epoxidized block copolymer and the hydroxylated nano particles are added in the comparative example 4, the dispersion is uneven, the agglomeration phenomenon can occur, and the ungrafted epoxidized block copolymer and the hydroxylated nano particles are dispersed in the matrix asphalt in a flaky and flocculent form; the composite modifier of the epoxidized block copolymer grafted hydroxylated nano particles is added in the embodiment 1, and the modifier is uniformly distributed in the matrix asphalt in a slender linear shape and a strip shape to form a stable space network structure. From this, it can be seen that the importance of grafting the epoxidized block copolymer and the hydroxylated nanoparticles followed by adding the matrix asphalt is significantly better than the ungrafted case in terms of compatibility and dispersibility.

5. Low temperature rheological properties

The BBR test results of various modified asphalt at-12℃are shown in FIG. 11.

Creep stiffness S and creep rate m are used as indicators for evaluating the low temperature crack resistance of asphalt. At the same temperature, the smaller the creep stiffness S of the asphalt, the larger the creep rate m, which means that the asphalt has good low-temperature elasticity and good low-temperature crack resistance.

As shown in FIG. 11, the creep stiffness of the modified asphalt of examples 1-3 was lower than that of the modified asphalt of comparative examples 2-4, and the creep stiffness of the modified asphalt of different functionalized SIS was lower than that of the base asphalt, and the creep rate of the modified asphalt of different functionalized SIS was higher than that of the base asphalt at the same temperature, as shown in the graph of m. The low-temperature performance of different functionalized modified asphalt is improved compared with that of matrix asphalt, and the low-temperature crack resistance of the matrix asphalt added after the epoxidized block copolymer and the hydroxylated nano particles are grafted is obviously better than that of the matrix asphalt which is singly doped and ungrafted. The epoxy segmented copolymer and the hydroxylated nano particles are easy to form a cross-linked network structure after being grafted, which is beneficial to improving the tensile strength skin low-temperature flexibility of the modified asphalt. Styrene in SIS belongs to hard segment, isoprene belongs to soft segment, has better viscoelasticity, the proportion of isoprene segment is higher, SIS property tends to toughness and elasticity in rubber, and the proportion of the whole isoprene segment of epoxy SIS is reduced, so that the low-temperature performance of modified asphalt is reduced. Deformation of the modified asphalt at low temperature is combined by SIS deformation and asphalt deformation, SIS deformation plays a main role, deformation of the modified asphalt is limited by the single-doped nano material, low-temperature flexibility cannot be fully exerted, and low-temperature creep performance of the asphalt of comparative examples 2-4 is reduced. The nano calcium carbonate is compounded with SIS, and the soft polymer SIS high molecular block copolymer is grafted onto the surface of the rigid nano calcium carbonate, so that the interface modulus is lower than that of the matrix asphalt and the calcium carbonate. The composite modifier with the reinforced rigid-flexible combination can form a low-modulus flexible interface layer, is favorable for buffering external load and absorbing energy, thereby resisting creep deformation of the material at low temperature and finally realizing the effect of reinforcing and toughening the modified asphalt.

6. Evaluation of aging resistance

FIG. 12 is a graph of the residual softening point increase for a spin film oven test (RTFOT) and Pressure Aging (PAV) for base asphalt and various modified asphalt.

After the asphalt is aged, the consistency and the hardness of the asphalt are correspondingly improved due to volatilization of light components and the like, so that the softening point is influenced, the softening point is increased compared with that of the original asphalt, and the smaller the increment of the softening point is, the better the ageing resistance of the asphalt is. Therefore, the softening point increment can also be used for representing the aging degree of asphalt and representing the aging resistance of the asphalt.

Pouring different modified asphalt into an aging disc (phi 150mm multiplied by 9.5 mm), placing the aging disc into a thermal aging test box, wherein the temperature of the test box is 163+/-0.5 ℃, the air flow is controlled within the range of 4000+/-200 mL/min, and the aging time of the sample in a sample bottle is not less than 85min.

As shown in fig. 12, after RTFOT aging and PAV aging, the increase in softening point of the composite modified asphalt of comparative examples 2 to 4 and examples 1 to 3 was reduced as compared with that of comparative example 1. With the addition of the hydroxylated nano calcium carbonate grafted epoxidized styrene-isoprene-styrene composite modifier, namely examples 1-3, the softening point increment of RTFOT and PAV are respectively 4 ℃, 2.5 ℃,3 ℃ and 5.2 ℃, 4.1 ℃ and 4.3 ℃, and the softening point increment of the two ageing residues is obviously reduced. This shows that the hydroxylated nano calcium carbonate grafted epoxidized styrene-isoprene-styrene composite modifier obviously improves the thermal aging resistance of the modified asphalt. The nano calcium carbonate blocks heat and oxygen from being conducted and diffused in the asphalt matrix, slows down volatilization of light components (saturated components and aromatic components) in the asphalt, has better dispersibility in the asphalt matrix, has stronger blocking effect on heat, oxygen and light components, and has more remarkable improving effect on ageing resistance of the modified asphalt. The heat aging resistance improving effect of examples 1 to 3 was more remarkable than that of comparative examples 1 to 4.

2. Waterproof coiled material coating material performance test

In a low-temperature environment, the waterproof asphalt coating material is easy to have the problems of reduced toughness, increased brittleness and the like, so that the deformation resistance of the waterproof asphalt coating material is reduced, and the use durability of the waterproof asphalt coating material is directly influenced by the low-temperature flexibility of the waterproof asphalt coating material. In addition, the winter temperature in different areas has extremely large difference, if the low-temperature performance of the waterproof asphalt coating material is poor, the situation that the waterproof bonding layer is cracked or even broken in the use process can be caused, and the waterproof function is greatly reduced. There is therefore a need for low temperature performance testing of engineering application waterproof asphalt coatings.

The low temperature flexibility of the waterproof asphalt coating was tested with reference to GB/T328.14-2007.

FIG. 13 is a graph of low temperature flexibility of different modified asphalt. Compared with comparative example 1, the low-temperature flexibility of different modified asphalt coating materials is obviously improved. Compared with comparative example 1, the low-temperature flexibility of the waterproof asphalt coating material obtained by respectively adopting the epoxidized SIS (comparative example 2), the hydroxylated nano calcium carbonate (comparative example 3) and respectively doping the epoxidized SIS and the hydroxylated calcium carbonate (comparative example 4) is increased from-2 ℃ to-6 ℃,10 ℃ and 14 ℃ below zero, which is probably that the functionalized SIS and the nano calcium carbonate play a role in delaying crack extension in the coating material bending process, the functionalized modified modifier is more uniformly dispersed in the coating material, the breakage caused by stress concentration can be better prevented, and the low-temperature flexibility is better improved. Compared with comparative examples 1-4, the low-temperature flexibility of examples 1-3 is further improved, the nano calcium carbonate grafted SIS composite modifier is added, a layered covalent bonding mesophase structure is formed between the composite modifier and the asphalt matrix, strong interfacial interaction is generated, the movement of a polymer chain segment is inhibited, meanwhile, SIS groups are elastomers, the elastic components of the asphalt matrix are effectively increased, and the low-temperature flexibility of the modified asphalt is improved under the combined action of the two aspects.

FIG. 14 is a graph of peel strength for various modified asphalt. Compared with comparative example 1, the seam peel strength of the modified asphalt waterproof coiled materials is gradually increased along with the addition of different modifiers in comparative examples 2-4 and examples 1-3, and particularly the increase amplitude is more obvious in examples 1-3. This is probably because the nano calcium carbonate and the functionalized SIS dispersed in the coating material respectively have physical enhancement and chemical crosslinking effects, so that the cohesive force of the coating material is increased, the joint peeling strength is improved, the hydroxylated modified nano calcium carbonate grafted epoxidized SIS block copolymer is more uniformly dispersed in the coating material, and the physical and chemical enhancement effects are stronger, therefore, the modified asphalt coating materials of examples 1-3 have more remarkable effect of improving the joint peeling strength

The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. The preparation method of the hydroxylation nanomaterial grafted functionalized block copolymer composite modifier is characterized by comprising the following steps of:

(1) Functional modification

(2) Hydroxylation modification

(3) Grafting reaction

2. The method according to claim 1, wherein in the step (1), the mass ratio of the block copolymer, the organic solvent, the polymer, the phase transfer agent, the oxidizing agent and the protecting agent is selected from 1:10 to 20:0.02 to 0.5:0.001 to 0.1:0.1 to 5:0.002 to 0.1; in the step (2), the mass ratio of the nano material, the dispersing agent, the hydroxyl modifier and the dispersing solvent is selected from 1:0.1-2:10-50; in the step (3), the mass ratio of the epoxidized block copolymer, the hydroxylated nanomaterial and the organic solvent is selected from 1:0.5-3:10-30.

3. The method of manufacturing according to claim 1, characterized in that: in the step (1), the block copolymer is selected from one or more of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene-propylene (SEP), styrene-ethylene-butylene-styrene (SEBS) and styrene-ethylene-propylene-styrene (SEPS); the polymer is one or more selected from polyacrylic acid, poly (pyromellitic dianhydride-co-4, 4' diaminodiphenyl ether) amic acid, polymaleic acid, polyethylene aspartic acid and polymethacrylic acid; the phase transfer agent is selected from any one of trioctyl methyl ammonium chloride, tetrabutyl ammonium bromide, polyethylene glycol monomethyl ether, polyethylene glycol (the molecular weight is 200-4000), tetrabutyl ammonium chloride, vinyl benzyl mercaptan, dodecyl mercaptan, chain polyethylene glycol dialkyl ether, benzyl triethyl ammonium chloride, tetrabutyl ammonium bisulfate, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, quaternary ammonium salt and pyridine; the oxidant is at least one selected from potassium persulfate, ammonium persulfate, hydrogen peroxide, sodium persulfate and potassium persulfate, wherein the concentration of the hydrogen peroxide is 30-50%; the protective agent is selected from one or more of pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy hydrocinnamate), pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, tris (2, 4-di-tert-butylphenyl) phosphite, N' - (hexane-1, 6-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ]; the organic solvent is one or more selected from cyclohexane, acetone, butanone, cyclohexanone, methanol, toluene, xylene, benzene, methyl ethyl ketone, ethyl acetate and dichloroethane;

In the step (2), the nanomaterial is selected from zero-dimensional, one-dimensional or two-dimensional nanomaterial; wherein the zero-dimensional nano material comprises one or more of nano calcium carbonate, nano silicon dioxide, nano kaolin, nano aluminum oxide, nano titanium oxide and nano zinc oxide, the particle size of the zero-dimensional nano material is 10 nm-1 mu m, and the appearance is one or more of spherical, ellipsoidal, flower-shaped, regular polyhedral and irregular polyhedral; the length-diameter ratio of the one-dimensional nano material is more than 10, the diameter is 1-200 nm, and the one-dimensional nano material comprises at least one of carbon nano tubes, nano carbon fibers, polyacrylonitrile, polyvinylpyrrolidone, polyaniline and organic nano fibers formed by polyurethane, and a metal compound with the appearance of nano wires, nano rods or whiskers formed by one or more of calcium, silicon, aluminum, titanium and zinc; the two-dimensional nanomaterial comprises at least one of graphene, graphene oxide, nano montmorillonite, graphite phase carbon nitride, molybdenum disulfide, titanium disulfide and titanium diselenide; the dispersing agent is one or more selected from Polyvinylpyrrolidone (PEI), sodium Dodecyl Sulfate (SDS), cetyltrimethylammonium bromide (CTAB), polysulfonic acid and ethanol; the hydroxyl modifier is selected from polyalcohol, saccharide, phenols and polyhydroxy macromolecular compounds, the polyalcohol is selected from at least one of 2-amino-2-methoxy-1, 3-propanediol, glycerol, 1, 2-propanediol, 2-methyl-2, 3-butanediol, 2-methyl-2, 4, 5-pentanetriol, 1, 3-propanediol, 1, 4-butanediol, pentaerythritol, neopentyl glycol, butyl tetraol, ribitol, n-hexanol, dipropylene glycol, arabitol, 4-hydroxybenzyl alcohol (p-hydroxybenzyl alcohol), pentanediol, xylitol, diethylene glycol, sorbitol, mannitol, dulcitol, trimethylolpropane, perfluoropolyether polyol, cis (trans) -1, 2-cyclopentanediol, cis (trans) -1, 2-cycloheptanediol, cis (trans) -1, 2-cyclohexanediol; the saccharide is at least one of glucose, mannose, starch, sorbose, sucrose, lactose, maltose, alpha-D-furanose galactose, beta-D-furanose, beta-L-furanose, alpha-L-barking furanrhamnose, beta-L-barking furanose, alpha-D-barking furanose; the phenols are selected from at least one of catechol, 3-nitrocatechol, 4-nitrocatechol, 3, 5-dinitrocatechol and 3, 4-dihydroxybenzoic acid; the polyhydroxy macromolecular compound is at least one selected from polyvinyl alcohol, cellulose, polyethylene glycol, gelatin, agar, chondroitin sulfate and sodium hyaluronate; the dispersion solvent is at least one of water, ethanol, methylene dichloride and chloroform;

In the step (3), the organic solvent is one or more selected from cyclohexane, toluene, dimethyl sulfoxide, methyl ethyl ketone, ethyl acetate and dichloroethane; the alkaline solution is one or more selected from sodium hydroxide, potassium carbonate, potassium hydroxide, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide, potassium ethoxide, sodium hydroxide, potassium phosphate and potassium fluoride.

4. The preparation method according to claim 1, wherein in the steps (1) and (3), the pH is adjusted by adopting an alkali solution, and the alkali solution is prepared from one or more of potassium phosphate, sodium hydroxide, potassium carbonate, sodium methoxide, potassium hydroxide, potassium ethoxide, sodium carbonate or sodium bicarbonate, and the concentration is 0.1-1 mol/L; wherein the pH in step (1) is adjusted to neutral; the pH in the step (3) is regulated to be alkaline, and the pH is between 8 and 10;

In the step (1), the conditions of the constant temperature reaction are selected from the group consisting of: reacting for 100-180 min in an oil bath with constant temperature of 50-80 ℃; the conditions of heating and stirring are selected from the following: heating to 80-100 ℃ and stirring for 1-3 h; in the step (2), the condition of the reflux reaction is selected from the group consisting of: condensing and refluxing for 18-24 h under the oil bath at 100-120 ℃; in the step (3), the condition of stirring reaction is selected from the group consisting of: stirring and reacting for 30-40 min at 100-120 ℃.

5. The hydroxylated nanomaterial grafted functionalized block copolymer composite modifier prepared by the method of any one of claims 1 to 4.

6. The preparation method of the composite modifier modified asphalt is characterized by comprising the following steps:

Mixing the hydroxylated nanomaterial grafted functionalized block copolymer composite modifier of claim 5 with a dispersion solvent, and stirring at high temperature to obtain a composite modifier solution; then, heating the matrix asphalt to a molten state at a high temperature, gradually adding the composite modifier solution, shearing at a high temperature, and stirring at a low speed to obtain the composite modifier modified asphalt.

7. The method of claim 6, wherein the base asphalt is selected from 70# or 90# petroleum asphalt; the dispersion solvent is selected from one of furfural oil, rubber oil, maleic anhydride and dibutyl phthalate; the mass ratio of the matrix asphalt to the composite modifier to the dispersing agent is selected from 1:0.03-0.06:0.05-0.5; the temperature is Wen Xuanzi ℃ to 150 ℃ in the high-temperature stirring and high-temperature conditions; the high temperature shear is selected from the following conditions: shearing at the temperature of 170-190 ℃ for 30-60 min at 2000-3000 r/min, and shearing at the temperature of 4000-6000 r/min for 30-40 min; the conditions of low speed stirring are selected from: stirring at a low speed of 200-500 r/min for 1-2 h at 140-160 ℃.

8. The composite modifier modified asphalt prepared by the method of claim 6 or 7.

9. Use of the composite modifier of claim 5 or the composite modifier modified asphalt of claim 8 in coating waterproofing.

10. A waterproof coiled material coating material, which is characterized by comprising the composite modifier modified asphalt, functional filler and base oil according to claim 8; wherein the mass ratio of the composite modifier modified asphalt to the functional filler to the base oil is selected from 1:0.3-0.6:0.6-1.0;