CN112480695B - Preparation method of graphene modified asphalt and product thereof - Google Patents
Preparation method of graphene modified asphalt and product thereof Download PDFInfo
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- CN112480695B CN112480695B CN202011228284.1A CN202011228284A CN112480695B CN 112480695 B CN112480695 B CN 112480695B CN 202011228284 A CN202011228284 A CN 202011228284A CN 112480695 B CN112480695 B CN 112480695B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention relates to the technical field of modified asphalt, in particular to a preparation method of graphene modified asphalt and a product thereof. The preparation method of the graphene modified asphalt comprises the following steps; firstly preparing polyurethane modified graphene from graphene oxide, and then further preparing a polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material; and heating the asphalt to a molten state, adding the prepared polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material, and shearing at a high speed to obtain the graphene modified asphalt. According to the invention, the polyurethane is modified by polyurethane to prepare the polyurethane graphene oxide, so that the dispersion performance of the polyurethane graphene oxide in asphalt is improved, and then the polyethylene glycol and the titanium dioxide are further combined to prepare the composite material, so that the thermal stability of the modified asphalt is further improved, and thus the diseases of rutting, oil flooding, pit and cracking and the like of an asphalt pavement caused by overhigh or overlow environmental temperature are avoided.
Description
Technical Field
The invention relates to the technical field of modified asphalt, in particular to a preparation method of graphene modified asphalt and a product thereof.
Background
Asphalt material is one of the most main basic construction materials, and due to good viscoelasticity of asphalt, the asphalt material is widely applied in the field of construction, especially in road construction engineering, and is mainly used as a surface layer binding material or a flexible base layer binding material, and at present, most roads at home and abroad are asphalt pavements. However, at high temperatures, bitumen melts easily and flows easily. Therefore, the asphalt pavement is easy to have various defects such as ruts, oil flooding, pit grooves and the like due to overhigh temperature of the pavement in high-temperature seasons, and the normal condition of the asphalt pavement is seriously influenced. Therefore, the asphalt is modified to improve and enhance the road performance so as to meet the use requirements under different severe environments and the increasing demand on high-quality road asphalt.
Experiments prove that the addition of the graphene into the asphalt can generate special effects on the physical and chemical properties of the asphalt, thereby comprehensively improving the performance of the asphalt; however, in actual production, graphene cannot be directly added to asphalt: the reason for this is that graphene cannot be uniformly dispersed due to the serious agglomeration problem in the asphalt, so that graphene cannot have a good modification effect on the asphalt. How to solve the problem of aggregation of graphene in asphalt so that the graphene can uniformly enter an asphalt structure and be stably combined with the asphalt is a technical problem to be solved urgently for preparing high-performance graphene modified asphalt.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of graphene modified asphalt and a product thereof. The polyurethane graphene oxide is prepared by performing polyurethane modification on graphene, so that the dispersion performance of the graphene oxide in asphalt is improved, and then the polyethylene glycol and titanium dioxide are further combined to prepare a composite material, so that the thermal stability of the modified asphalt is further improved, and the diseases of rutting, oil flooding, pit and groove cracking and the like caused by overhigh or overlow environmental temperature of an asphalt pavement are avoided.
The technical scheme of the invention is as follows: a preparation method of graphene modified asphalt comprises the following steps:
(1) placing graphene oxide in an organic solvent for uniform dispersion, adding isocyanate in an inert atmosphere, and reacting for 10-15h at 50-60 ℃; adding monohydric alcohol, and continuing to react for 5-8 h; adding hydrazine hydrate to continue reacting for 5-8h, filtering, cleaning, drying and crushing a product to obtain polyurethane modified graphene;
(2) putting polyethylene glycol, tetrabutyl titanate and the polyurethane modified graphene prepared in the step (1) into a solution, fully and uniformly mixing, adjusting the solution to react for 3-5h in an acid environment, adjusting the solution to be alkaline for aging, and drying to obtain a polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material;
(3) and (3) heating the asphalt to a molten state, adding the polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material prepared in the step (2), and shearing at a high speed to obtain the graphene modified asphalt.
Further, in the step (1), the organic solvent is selected from N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, the monohydric alcohol is isobutanol, and the isocyanate is 4, 4-xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or toluene diisocyanate.
Furthermore, the adding proportion of the graphene oxide, the organic solvent, the isocyanate, the monohydric alcohol and the hydrazine hydrate in the step (1) is 10-20g:100-200ml:0.05-0.1mol:0.05-0.1mol:0.05-0.1 mol.
Further, the mixing mass ratio of the polyethylene glycol, the tetrabutyl titanate and the polyurethane modified graphene in the step (2) is (1-2): (0.5-1): (2-5).
Further, in the step (2), the pH value of the acid environment is 3-4, the reaction temperature of the acid environment is 40-50 ℃, the alkaline pH value is 9-10, and the aging time is 16-48 h.
Further, in the step (3), the addition amount of the polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material is 3-5% of the mass of the asphalt.
Further, the high-speed shearing rate in the step (3) is 1500-.
The invention also provides graphene modified asphalt prepared by the preparation method of the graphene modified asphalt.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method, graphene oxide is used as a raw material to prepare the polyurethane modified graphene, the surface of the graphene oxide contains rich oxygen-containing functional groups such as cyano groups, carboxyl groups and epoxy groups, so that modification and modification of the graphene become possible, isocyanate and the graphene oxide are added to react, monohydric alcohol is used for isocyanate group end capping, and finally a reducing agent is used for reduction to obtain the polyurethane modified graphene, wherein a polyurethane unit can remarkably improve the dispersibility of the graphene in asphalt, the problem of agglomeration of the graphene in the asphalt is solved, and the graphene can be uniformly and deeply combined with the asphalt in a stable manner.
(2) The invention also introduces polyethylene glycol, and polyethylene glycol, tetrabutyl titanate and polyurethane modified graphene are mixed to prepare the composite material, wherein the polyethylene glycol is used as a phase change energy storage material, and the tetrabutyl titanate is hydrolyzed under the acidic environment to obtain TiO2As a wall material, the polyurethane modified graphene is used as a heat-conducting filler, so that the material has high phase-change enthalpy, and the thermal stability and crystallization performance of the material are good. Thereby increasing the softening point of the asphalt and improving the high-temperature rheological property. Meanwhile, the titanium dioxide has the capability of absorbing, reflecting and scattering ultraviolet rays, and can reduce the ultraviolet aging of the asphalt.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The graphene oxide used in the following examples of the present invention was prepared by an improved Hummers method.
Example 1
(1) Putting 10g of graphene oxide into 200mL of N, N-dimethylformamide solution, performing ultrasonic dispersion uniformly, heating to 55 ℃, adding 0.05mol of isophorone diisocyanate under the nitrogen atmosphere, reacting for 12h, adding 0.05mol of isobutanol, continuing to react for 8h, adding 0.05mol of hydrazine hydrate, continuing to react for 6h, filtering, washing, drying and crushing the obtained product to obtain polyurethane modified graphene;
(2) placing polyethylene glycol, tetrabutyl titanate and polyurethane modified graphene in an ethanol solution according to a mass ratio of 1:1:3, performing ultrasonic dispersion uniformly, adjusting the pH value of the solution to 4 by using hydrochloric acid, hydrolyzing for 4 hours in a water bath environment at 45 ℃, adjusting the pH value of the solution to 9 by using sodium hydroxide, standing, aging for 24 hours, filtering and drying to obtain a polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material;
(3) heating asphalt to a molten state, slowly adding polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material with the asphalt mass of 4%, and shearing at a high speed of 1800rpm for 30min to obtain the graphene modified asphalt.
Example 2
(1) Placing 15g of graphene oxide in 150mL of N, N-dimethylformamide solution, performing ultrasonic dispersion uniformly, heating to 40 ℃, adding 0.07mol of isophorone diisocyanate under the nitrogen atmosphere, reacting for 12h, adding 0.05mol of isobutanol, continuing to react for 8h, adding 0.7mol of hydrazine hydrate, continuing to react for 6h, filtering, washing, drying and crushing the obtained product to obtain polyurethane modified graphene;
(2) placing polyethylene glycol, tetrabutyl titanate and polyurethane modified graphene in an ethanol solution according to a mass ratio of 1:0.5:5, performing ultrasonic dispersion uniformly, adjusting the pH value of the solution to 5 by using hydrochloric acid, hydrolyzing for 4 hours in a water bath environment at 50 ℃, adjusting the pH value of the solution to 10 by using sodium hydroxide, standing, aging for 48 hours, filtering, and drying to obtain a polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material;
(3) heating asphalt to a molten state, slowly adding polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material with the asphalt mass of 5%, and shearing at a high speed of 1600rpm for 40min to obtain the graphene modified asphalt.
Example 3
(1) Placing 20g of graphene oxide in 200mL of N, N-dimethylformamide solution, performing ultrasonic dispersion uniformly, heating to 50 ℃, adding 0.1mol of isophorone diisocyanate under the nitrogen atmosphere, reacting for 12h, adding 0.05mol of isobutanol, continuing to react for 8h, adding 0.1mol of hydrazine hydrate, continuing to react for 6h, filtering, washing, drying and crushing the obtained product to obtain polyurethane modified graphene;
(2) placing polyethylene glycol, tetrabutyl titanate and polyurethane modified graphene in an ethanol solution according to a mass ratio of 2:1:3, performing ultrasonic dispersion uniformly, adjusting the pH value of the solution to 4 by using hydrochloric acid, hydrolyzing for 4 hours in a water bath environment at 50 ℃, adjusting the pH value of the solution to 9 by using sodium hydroxide, standing, aging for 48 hours, filtering and drying to obtain a polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material;
(3) heating asphalt to a molten state, slowly adding a polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material with the asphalt mass of 3%, and shearing at a high speed of 1700rpm for 40min to obtain the graphene modified asphalt.
Example 4
The difference from example 1 is that step (1) is omitted and step (2) is carried out using graphene oxide as a starting material.
Example 5
The same as example 1 except that tetrabutyl titanate in step (2) was changed to an equivalent amount of titanium dioxide.
Example 6
The difference from example 1 is that the raw tetrabutyl titanate in step (2) is omitted.
Example 7
The difference from example 1 is that the raw polyethylene glycol in step (2) is omitted.
Example 8
The difference from example 1 is that step (2) is omitted.
Example 9
The difference from example 1 is that the polyurethane modified graphene, polyethylene glycol and titanium dioxide are directly added into molten asphalt and high-speed sheared at 1600rpm for 40min to obtain graphene modified asphalt.
The modified asphalt is subjected to penetration, softening point, ductility and ageing resistance tests according to relevant regulations of road engineering asphalt and asphalt mixture test regulations (JTJE20-2011), and specific test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the technical scheme of the present invention can significantly improve the softening point and aging resistance of the graphene-modified asphalt.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. The preparation method of the graphene modified asphalt is characterized by comprising the following steps:
(1) placing graphene oxide in an organic solvent for uniform dispersion, adding isocyanate in an inert atmosphere, and reacting for 10-15h at 50-60 ℃; adding monohydric alcohol, and continuing to react for 5-8 h; adding hydrazine hydrate to continue reacting for 5-8h, filtering, cleaning, drying and crushing a product to obtain polyurethane modified graphene;
(2) putting polyethylene glycol, tetrabutyl titanate and the polyurethane modified graphene prepared in the step (1) into a solution, fully and uniformly mixing, adjusting the solution to react for 3-5h in an acid environment, adjusting the solution to be alkaline for aging, and drying to obtain a polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material;
(3) heating asphalt to a molten state, adding the polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material prepared in the step (2), and shearing at a high speed to obtain graphene modified asphalt;
in the step (1), the adding proportion of the graphene oxide, the organic solvent, the isocyanate, the monohydric alcohol and the hydrazine hydrate is 10-20g: 100-;
in the step (2), the mixing mass ratio of the polyethylene glycol, the tetrabutyl titanate and the polyurethane modified graphene is (1-2) to (0.5-1) to (2-5);
in the step (2), the pH value of the acidic environment is 3-4, the reaction temperature of the acidic environment is 40-50 ℃, the pH value of the alkaline environment is 9-10, and the aging time is 16-48 h;
the addition amount of the polyethylene glycol/titanium dioxide/polyurethane modified graphene composite material in the step (3) is 3-5% of the mass of the asphalt;
the high-speed shearing rate in the step (3) is 1500-1800rpm, and the shearing time is 30-40 min.
2. The method for preparing graphene-modified asphalt according to claim 1, wherein the organic solvent in step (1) is selected from N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, the monohydric alcohol is isobutanol, and the isocyanate is 4, 4-xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or toluene diisocyanate.
3. A graphene-modified asphalt prepared by the method for preparing a graphene-modified asphalt according to any one of claims 1 to 2.
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| CN114316611A (en) * | 2021-10-20 | 2022-04-12 | 鄂尔多斯市路泰公路工程有限责任公司 | Composite modified asphalt based on epoxy resin rubber powder and mixture |
| CN116178970B (en) * | 2021-11-26 | 2024-04-02 | 重庆市智翔铺道技术工程有限公司 | Polyurethane modified asphalt and preparation method thereof |
| CN115093713B (en) * | 2022-07-18 | 2023-02-21 | 华运通达(浙江)交通科技有限公司 | Graphene modified asphalt and preparation method thereof |
| CN117700156B (en) * | 2024-02-04 | 2024-05-10 | 上海龙盼市政建设工程有限公司 | Regenerated asphalt mixture and preparation method thereof |
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| JPH10169385A (en) * | 1996-12-04 | 1998-06-23 | Fumio Morigami | Waterproofing method by accelerating hardening spray rubber asphalt |
| WO2016040612A1 (en) * | 2014-09-11 | 2016-03-17 | Garmor, Inc. | Graphite oxide entrainment in cement and asphalt composite |
| CN106750223A (en) * | 2016-11-10 | 2017-05-31 | 广东科迪新材料科技有限公司 | A kind of polyurethane-modified aqueous alkide resin of Graphene and preparation method thereof |
| CN109233308A (en) * | 2018-08-02 | 2019-01-18 | 河南工业大学 | A kind of nano material composite modified emulsified asphalt of high osmosis SBR- and preparation method thereof |
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