CN114381132A - Copolymer modified asphalt - Google Patents
Copolymer modified asphalt Download PDFInfo
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- CN114381132A CN114381132A CN202210040049.4A CN202210040049A CN114381132A CN 114381132 A CN114381132 A CN 114381132A CN 202210040049 A CN202210040049 A CN 202210040049A CN 114381132 A CN114381132 A CN 114381132A
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- copolymer
- asphalt
- butyl acrylate
- stainless steel
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to copolymer modified asphalt, which is characterized in that the copolymer is octadecyl methacrylate-butyl acrylate copolymer. After the matrix asphalt is modified by the copolymer, the ductility is obviously improved. The modification method has simple process, good effect and important application value.
Description
Technical Field
The invention relates to the field of road materials, in particular to copolymer modified asphalt.
Background
With the rapid development of the traffic industry of China, roads are planned and constructed more and more. Asphalt is a main material for road paving in China. The asphalt pavement has the advantages of smooth surface, no joint, comfortable driving, small vibration, low noise, simple and convenient maintenance and the like, but has some defects, such as poor temperature stability of the asphalt material, easy softening in summer and easy brittle fracture in winter, and particularly the asphalt material becomes brittle at low temperature to cause pavement cracking, which is the main reason for damaging the asphalt pavement.
To avoid low temperature cracking of asphalt, it is desirable to increase ductility of asphalt. Generally, the greater the ductility of the asphalt, the better the low temperature crack resistance of the asphalt. It is common practice to add rubber powder, fibers, etc. to asphalt. For example, the low-temperature deformability of asphalt can be improved by adding styrene-butadiene rubber (SBR rubber), polybutadiene rubber, styrene-butadiene-styrene block copolymer (SBS rubber), etc. to asphalt, but these modified asphalts belong to a multiphase system and often have the problem of rubber powder segregation, which adversely affects the actual construction and engineering quality. Patent applications 202110242532.6, 202110242533.0, 202110242534.5 employ an in-situ polymerization process to obtain a homogeneous copolymer modified asphalt, which is effective in avoiding segregation of the modifier and asphalt. However, the in-situ polymerization in the asphalt results in higher operation cost for asphalt modification.
The invention provides a scheme of copolymer modified asphalt, the compatibility of the copolymer and the asphalt is good, the copolymer modified asphalt formed by mixing the copolymer and the asphalt has greatly improved ductility compared with unmodified matrix asphalt, the product is uniform, the segregation problem does not exist, the preparation method is simple, and the preparation method has great application value.
Disclosure of Invention
The invention relates to copolymer modified asphalt, which is characterized in that the copolymer is octadecyl methacrylate-butyl acrylate copolymer, and the modification method comprises the following steps: the matrix asphalt is weighed into a stainless steel cup, then the octadecyl methacrylate-butyl acrylate copolymer is weighed into the stainless steel cup, then the stainless steel cup is placed on an electric furnace to be heated, the mixed solution is manually stirred for 5min at 165 ℃ by a stainless steel bar, then the mixed solution is sheared for 5min at 1500 rpm by a high-speed shearing machine, after the shearing is finished, the mixed solution is placed in a 160 ℃ oven to be insulated for 1h, and the copolymer modified asphalt is obtained.
The preparation method of the octadecyl methacrylate-butyl acrylate copolymer comprises the following steps: the octadecyl methacrylate, butyl acrylate, azodiisobutyronitrile and cyclohexane are weighed into a three-neck flask, then the three-neck flask is placed in an oil bath pot, a stirrer, a thermometer and a condenser pipe are installed, stirring is carried out, the temperature of the oil bath is raised to 75 ℃, polymerization reaction is carried out for 4 hours at 75 ℃, the cyclohexane is removed by vacuumizing after the reaction is finished, and then the polymerization solution is placed in a vacuum oven at 55 ℃ for drying for one day, so as to obtain the octadecyl methacrylate-butyl acrylate copolymer.
The copolymer has good compatibility with asphalt, and compared with unmodified matrix asphalt, the modified asphalt formed by mixing the copolymer and the asphalt has the advantages of greatly improved ductility, uniform product, no segregation problem, simple preparation method and great application value.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention.
The matrix asphalt used in the experiment was korean shuanglong No. 70 matrix asphalt.
Ductility of asphalt the ductility at 10 ℃ was measured on a low temperature liquid crystal display ductility tester according to the procedure specified in the test procedure for asphalt and asphalt mixtures for road engineering (JTJ 052-2000).
Example 1
Synthesis of a copolymer of stearyl methacrylate and butyl acrylate (9: 1): in a 1000mL three-neck flask, weighing 180.0g of octadecyl methacrylate, 20.0g of butyl acrylate, 1.4g of azobisisobutyronitrile and 240g of cyclohexane, then placing the three-neck flask in an oil bath, installing a stirrer, a thermometer and a condenser tube, stirring, raising the temperature of the oil bath to 75 ℃, reacting for 4 hours at 75 ℃ in a polymerization reaction, vacuumizing to remove the cyclohexane after the reaction is finished, and then placing the polymerization solution in a 55 ℃ vacuum oven for drying for one day to obtain the octadecyl methacrylate-butyl acrylate (9: 1) copolymer.
Example 2
Synthesis of a copolymer of stearyl methacrylate and butyl acrylate (8: 2): 160.0g of stearyl methacrylate, 40.0g of butyl acrylate, 1.4g of azobisisobutyronitrile and 240g of cyclohexane are weighed into a 1000mL three-neck flask, then the three-neck flask is placed in an oil bath pot, a stirrer, a thermometer and a condenser tube are installed for stirring, the temperature of the oil bath is raised to 75 ℃, the polymerization reaction is carried out for 4 hours at 75 ℃, the reaction is finished, the cyclohexane is removed by vacuumizing, and then the polymerization solution is placed in a vacuum oven at 55 ℃ for drying for one day, thus obtaining the stearyl methacrylate-butyl acrylate (8: 2) copolymer.
Example 3
Synthesis of a copolymer of stearyl methacrylate and butyl acrylate (7: 3): 140.0g of stearyl methacrylate, 60.0g of butyl acrylate, 1.4g of azobisisobutyronitrile and 240g of cyclohexane are weighed into a 1000mL three-neck flask, then the three-neck flask is placed in an oil bath pot, a stirrer, a thermometer and a condenser tube are installed for stirring, the temperature of the oil bath is raised to 75 ℃, the polymerization reaction is carried out for 4 hours at 75 ℃, the reaction is finished, the cyclohexane is removed by vacuumizing, and then the polymerization solution is placed in a vacuum oven at 55 ℃ for drying for one day, thus obtaining the stearyl methacrylate-butyl acrylate (7: 3) copolymer.
Example 4
Synthesis of poly (octadecyl methacrylate): 200.0g of stearyl methacrylate, 1.4g of azobisisobutyronitrile and 240g of cyclohexane are weighed into a 1000mL three-neck flask, then the three-neck flask is placed in an oil bath pot, a stirrer, a thermometer and a condenser tube are installed, stirring is carried out, the temperature of the oil bath is raised to 75 ℃, the polymerization reaction is carried out for 4 hours at 75 ℃, the reaction is finished, the cyclohexane is removed by vacuumizing, and then the polymerization solution is placed in a vacuum oven at 55 ℃ for drying for one day, so as to obtain the stearyl methacrylate.
Example 5
200.0g of matrix asphalt is weighed into a 500mL stainless steel cup, then 4.0g of octadecyl methacrylate-butyl acrylate (9: 1) copolymer is weighed into the stainless steel cup, then the stainless steel cup is placed on an electric furnace to be heated, the mixed solution is manually stirred for 5min by a stainless steel bar at 165 ℃, then the mixed solution is sheared for 5min by a high-speed shearing machine at the rotating speed of 1500 revolutions per minute, after the shearing is finished, the mixed solution is placed in a 160 ℃ oven to be insulated for 1h, and the copolymer modified asphalt is obtained. The ductility of the copolymer modified asphalt is tested to be 76.0 cm.
Example 6
200.0g of matrix asphalt is weighed into a 500mL stainless steel cup, then 4.0g of octadecyl methacrylate-butyl acrylate (8: 2) copolymer is weighed into the stainless steel cup, then the stainless steel cup is placed on an electric furnace to be heated, the mixed solution is manually stirred for 5min by a stainless steel bar at 165 ℃, then the mixed solution is sheared for 5min by a high-speed shearing machine at the rotating speed of 1500 revolutions per minute, and after the shearing is finished, the mixed solution is placed in a 160 ℃ oven to be insulated for 1h, so that the copolymer modified asphalt is obtained. The ductility of the copolymer modified asphalt is tested to be 66.0 cm.
Example 7
200.0g of matrix asphalt is weighed into a 500mL stainless steel cup, then 4.0g of octadecyl methacrylate-butyl acrylate (7: 3) copolymer is weighed into the stainless steel cup, then the stainless steel cup is placed on an electric furnace to be heated, the mixed solution is manually stirred for 5min by a stainless steel bar at 165 ℃, then the mixed solution is sheared for 5min by a high-speed shearing machine at the rotating speed of 1500 revolutions per minute, after the shearing is finished, the mixed solution is placed in a 160 ℃ oven to be insulated for 1h, and the copolymer modified asphalt is obtained. The ductility of the copolymer modified asphalt is 42.0cm through testing.
Example 8
200.0g of matrix asphalt is weighed into a 500mL stainless steel cup, then 8.0g of octadecyl methacrylate-butyl acrylate (9: 1) copolymer is weighed into the stainless steel cup, then the stainless steel cup is placed on an electric furnace to be heated, the mixed solution is manually stirred for 5min by a stainless steel bar at 165 ℃, then the mixed solution is sheared for 5min by a high-speed shearing machine at the rotating speed of 1500 revolutions per minute, after the shearing is finished, the mixed solution is placed in a 160 ℃ oven to be insulated for 1h, and the copolymer modified asphalt is obtained. The ductility of the copolymer modified asphalt is more than 100cm through testing.
Example 9
200.0g of matrix asphalt is weighed into a 500mL stainless steel cup, then 8.0g of octadecyl methacrylate-butyl acrylate (8: 2) copolymer is weighed into the stainless steel cup, then the stainless steel cup is placed on an electric furnace to be heated, the mixed solution is manually stirred for 5min by a stainless steel bar at 165 ℃, then the mixed solution is sheared for 5min by a high-speed shearing machine at the rotating speed of 1500 revolutions per minute, and after the shearing is finished, the mixed solution is placed in a 160 ℃ oven to be insulated for 1h, so that the copolymer modified asphalt is obtained. The ductility of the copolymer modified asphalt is more than 100cm through testing.
Example 10
200.0g of matrix asphalt is weighed into a 500mL stainless steel cup, then 8.0g of octadecyl methacrylate-butyl acrylate (7: 3) copolymer is weighed into the stainless steel cup, then the stainless steel cup is placed on an electric furnace to be heated, the mixed solution is manually stirred for 5min by a stainless steel bar at 165 ℃, then the mixed solution is sheared for 5min by a high-speed shearing machine at the rotating speed of 1500 revolutions per minute, and after the shearing is finished, the mixed solution is placed in a 160 ℃ oven to be insulated for 1h, so that the copolymer modified asphalt is obtained. The ductility of the copolymer modified asphalt is more than 100cm through testing.
Comparative example 1
The unmodified base asphalt, tested, has a ductility of 16.0 cm.
Comparative example 2
Weighing 200.0g of matrix asphalt in a 500mL stainless steel cup, then weighing 4.0g of poly octadecyl methacrylate, then placing the mixture on an electric furnace for heating, manually stirring the mixed solution for 5min at 165 ℃ by using a stainless steel bar, then shearing the mixed solution for 5min at a rotating speed of 1500 revolutions per minute by using a high-speed shearing machine, and after the shearing is finished, placing the mixed solution in a 160 ℃ oven for heat preservation for 1h to obtain the modified asphalt. The ductility of the modified asphalt is 50.7cm through testing.
Comparative example 3
Weighing 200.0g of matrix asphalt in a 500mL stainless steel cup, then weighing 8.0g of poly octadecyl methacrylate, then placing the mixture on an electric furnace for heating, manually stirring the mixed solution for 5min at 165 ℃ by using a stainless steel bar, then shearing the mixed solution for 5min at a rotating speed of 1500 rpm by using a high-speed shearing machine, after the shearing is finished, placing the mixed solution in a 160 ℃ oven for heat preservation for 1h to obtain the modified asphalt. The ductility and ductility of the modified asphalt is greater than 100.0cm through testing.
The experimental data for examples 5-10 and comparative examples 1-3 are summarized in the table.
Summary of Table Experimental results
As can be seen from the comparison between examples 5-10 and comparative example 1, the ductility of the asphalt is obviously improved after the base asphalt is modified by the stearyl methacrylate-butyl acrylate copolymer.
As can be seen from a comparison of examples 5-7 and comparative example 2, the relative proportion of stearyl methacrylate and butyl acrylate in the copolymer synthesis has an effect on the ductility of the modified asphalt. Similarly, 2% of copolymer is added into asphalt, and the ductility of the modified asphalt changes from large to small in sequence as follows: octadecyl methacrylate-butyl acrylate (9: 1) copolymer > octadecyl methacrylate-butyl acrylate (8: 2) copolymer > octadecyl polymethacrylate > octadecyl methacrylate-butyl acrylate (7: 3) copolymer > unmodified.
As can be seen from comparison between examples 8-10 and comparative example 3, when the addition amount of the copolymer is 4%, the ductility of all modified asphalt is good and is more than 100, and the detection limit of an instrument is exceeded, which indicates that the modification effect of the copolymer is very obvious, and the addition amount of 4% can greatly improve the ductility of asphalt and improve the low-temperature cracking resistance of asphalt. .
The octadecyl methacrylate contains an octadecyl long chain in a molecule, so that the octadecyl methacrylate-butyl acrylate copolymer has good compatibility with asphalt, the copolymer is easily dissolved in the asphalt, and the modified asphalt is uniform and integrated without segregation.
Claims (2)
1. The copolymer modified asphalt is characterized in that the copolymer is a stearyl methacrylate-butyl acrylate copolymer, and the modification method comprises the following steps: the matrix asphalt is weighed into a stainless steel cup, then the octadecyl methacrylate-butyl acrylate copolymer is weighed into the stainless steel cup, then the stainless steel cup is placed on an electric furnace to be heated, the mixed solution is manually stirred for 5min at 165 ℃ by a stainless steel bar, then the mixed solution is sheared for 5min at 1500 rpm by a high-speed shearing machine, after the shearing is finished, the mixed solution is placed in a 160 ℃ oven to be insulated for 1h, and the copolymer modified asphalt is obtained.
2. The copolymer modified asphalt of claim 1, wherein the copolymer of stearyl methacrylate and butyl acrylate is prepared by the following steps: the octadecyl methacrylate, butyl acrylate, azodiisobutyronitrile and cyclohexane are weighed into a three-neck flask, then the three-neck flask is placed in an oil bath pot, a stirrer, a thermometer and a condenser pipe are installed, stirring is carried out, the temperature of the oil bath is raised to 75 ℃, polymerization reaction is carried out for 4 hours at 75 ℃, the cyclohexane is removed by vacuumizing after the reaction is finished, and then the polymerization solution is placed in a vacuum oven at 55 ℃ for drying for one day, so as to obtain the octadecyl methacrylate-butyl acrylate copolymer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210040049.4A CN114381132B (en) | 2022-01-14 | 2022-01-14 | Copolymer modified asphalt |
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| CN202210040049.4A CN114381132B (en) | 2022-01-14 | 2022-01-14 | Copolymer modified asphalt |
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| CN114381132A true CN114381132A (en) | 2022-04-22 |
| CN114381132B CN114381132B (en) | 2022-12-06 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160809A (en) * | 2022-08-04 | 2022-10-11 | 苏州科技大学 | Anti-stripping modified asphalt and preparation method thereof |
| CN115181430A (en) * | 2022-08-04 | 2022-10-14 | 苏州科技大学 | Preparation method of anti-stripping modified asphalt |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2420082A (en) * | 1943-07-22 | 1947-05-06 | Standard Oil Dev Co | Bituminous composition comprising an asphalt and a polymerized ester of methacrylic acid |
| GB1367315A (en) * | 1970-09-04 | 1974-09-18 | Huels Chemische Werke Ag | Thermoplastic bituminous composition and process for its manufacture |
| EP0400437A1 (en) * | 1989-06-01 | 1990-12-05 | Röhm Gmbh | Bitumen with improved elasticity |
| US5085701A (en) * | 1989-06-01 | 1992-02-04 | Rohm Gmbh Chemische Fabrik | Polymer-modified bitumen (pmb) |
| EP0491265A2 (en) * | 1990-12-15 | 1992-06-24 | Röhm Gmbh | Homogeneous, polyalkyl(meth)acrylat-modified bitumen |
| CA2069376A1 (en) * | 1991-05-31 | 1992-12-01 | Lyle Edwin Moran | Composition and method for improving the storage stability of polymer modified asphalts |
| CA1315438C (en) * | 1987-03-03 | 1993-03-30 | Lyle Edwin Moran | Flow resistant asphalt paving binder |
| US5266615A (en) * | 1991-08-29 | 1993-11-30 | Roehm Gmbh Chemische Fabrik | Alkyl (meth)acrylate-maleic anhydride copolymer-modified bitumen |
| US20060089430A1 (en) * | 2004-10-25 | 2006-04-27 | Kaneka Corporation | Curable composition |
| CN104327435A (en) * | 2014-09-04 | 2015-02-04 | 克拉玛依市新融科技有限公司 | Polycationic granulated gel and its preparation method |
| CN112961295A (en) * | 2021-03-04 | 2021-06-15 | 苏州科技大学 | Methyl methacrylate-butyl acrylate in-situ copolymerization modified asphalt |
-
2022
- 2022-01-14 CN CN202210040049.4A patent/CN114381132B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2420082A (en) * | 1943-07-22 | 1947-05-06 | Standard Oil Dev Co | Bituminous composition comprising an asphalt and a polymerized ester of methacrylic acid |
| GB1367315A (en) * | 1970-09-04 | 1974-09-18 | Huels Chemische Werke Ag | Thermoplastic bituminous composition and process for its manufacture |
| CA1315438C (en) * | 1987-03-03 | 1993-03-30 | Lyle Edwin Moran | Flow resistant asphalt paving binder |
| EP0400437A1 (en) * | 1989-06-01 | 1990-12-05 | Röhm Gmbh | Bitumen with improved elasticity |
| US5085701A (en) * | 1989-06-01 | 1992-02-04 | Rohm Gmbh Chemische Fabrik | Polymer-modified bitumen (pmb) |
| EP0491265A2 (en) * | 1990-12-15 | 1992-06-24 | Röhm Gmbh | Homogeneous, polyalkyl(meth)acrylat-modified bitumen |
| CA2069376A1 (en) * | 1991-05-31 | 1992-12-01 | Lyle Edwin Moran | Composition and method for improving the storage stability of polymer modified asphalts |
| US5266615A (en) * | 1991-08-29 | 1993-11-30 | Roehm Gmbh Chemische Fabrik | Alkyl (meth)acrylate-maleic anhydride copolymer-modified bitumen |
| US20060089430A1 (en) * | 2004-10-25 | 2006-04-27 | Kaneka Corporation | Curable composition |
| CN104327435A (en) * | 2014-09-04 | 2015-02-04 | 克拉玛依市新融科技有限公司 | Polycationic granulated gel and its preparation method |
| CN112961295A (en) * | 2021-03-04 | 2021-06-15 | 苏州科技大学 | Methyl methacrylate-butyl acrylate in-situ copolymerization modified asphalt |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160809A (en) * | 2022-08-04 | 2022-10-11 | 苏州科技大学 | Anti-stripping modified asphalt and preparation method thereof |
| CN115181430A (en) * | 2022-08-04 | 2022-10-14 | 苏州科技大学 | Preparation method of anti-stripping modified asphalt |
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| CN114381132B (en) | 2022-12-06 |
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