CN114507187A - Modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent and preparation method thereof - Google Patents
Modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent and preparation method thereof Download PDFInfo
- Publication number
- CN114507187A CN114507187A CN202011276470.2A CN202011276470A CN114507187A CN 114507187 A CN114507187 A CN 114507187A CN 202011276470 A CN202011276470 A CN 202011276470A CN 114507187 A CN114507187 A CN 114507187A
- Authority
- CN
- China
- Prior art keywords
- warm
- asphalt
- mixing agent
- quaternary ammonium
- ammonium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010426 asphalt Substances 0.000 title claims abstract description 120
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 83
- 238000002156 mixing Methods 0.000 title claims abstract description 79
- -1 Modified imidazoline quaternary ammonium salt Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 129
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 238000010992 reflux Methods 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 22
- 239000003784 tall oil Substances 0.000 claims abstract description 22
- 238000007112 amidation reaction Methods 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 52
- 235000019441 ethanol Nutrition 0.000 claims description 41
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000008096 xylene Substances 0.000 claims description 20
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 7
- 229960001124 trientine Drugs 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 44
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000010025 steaming Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 14
- 238000010276 construction Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000004568 cement Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000005056 compaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000013521 mastic Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000715 Mucilage Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D233/26—Radicals substituted by carbon atoms having three bonds to hetero atoms
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent and a preparation method thereof are disclosed, wherein the following components are weighed according to molar ratio: adding tall oil and organic polyamine with a molar ratio of 1:1-2 into a reactor, adding a water carrying agent accounting for 20-40% of the total mass, stirring, heating for reflux, carrying out an amidation reaction at a reflux temperature of 120-; evaporating the water carrying agent, raising the temperature to 230-250 ℃ under the vacuum degree of 0.09-0.1MPa, and carrying out cyclization reaction for 1-10h to obtain an imidazoline intermediate; preparing 50 mass percent ethanol solution from a quaternization reagent with the molar ratio of 1:1-1.5 to the imidazoline intermediate, slowly dropwise adding the ethanol solution into the imidazoline intermediate, reacting for 4-24 hours at the temperature of 30-60 ℃ under stirring, and then decompressing and steaming out ethanol and unreacted quaternization reagent to obtain the asphalt warm mixing agent. The asphalt warm-mixing agent does not contain water, does not need a catalyst in the reaction process, can be added by an internal doping method and an external doping method, has low addition amount, and can obviously reduce the mixing and compacting temperature of the asphalt mixture by 30-50 ℃.
Description
Technical Field
The invention relates to a preparation method of an asphalt additive for roads, in particular to a modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent and a preparation method thereof.
Background
With the rapid development of the expressway, the asphalt pavement is widely applied to the construction of high-grade highways due to good driving comfort, low noise and rapid open traffic.
However, the hot-mix asphalt mixture technology is widely adopted in the construction period of asphalt pavements in China, and the technology generally has the main problems of high energy consumption, high pollution and the like, so that not only can the surrounding environment be damaged, but also the health of constructors can be influenced. The temperature is kept at about 150 ℃ in the paving and compacting processes, and according to statistics, 2.7mg/m can be released in the production of one ton of hot-mixed asphalt mixture3CO of2，105mg/m3CO of 149mg/m3NO ofxAnd 5.7mg/m3And (4) harmful gases such as asphalt smoke.
Therefore, to solve this problem, domestic and foreign road scholars have conducted extensive research to reduce pollution and energy consumption while maintaining good road performance. Finally, in 1995, European scholars Shell and Kolo-veideeke developed warm-mix asphalt mixtures, and relevant test tests are carried out in the next year, and the results show that the performances of the warm-mix asphalt mixtures are equivalent to those of hot-mix asphalt mixtures, so that the popularization of the warm-mix technology is possible.
The key point of the warm mixing technology is that the warm mixing agent can be roughly divided into three categories [5] according to the action mechanism: surfactant type, organic viscosity reducing agent type and foaming technology type. Among them, the surfactant warm-mix agent is most widely used because of its excellent performance, convenient construction, and has the advantages of remarkably improving asphalt aging, accelerating construction process, etc. However, the warm-mixing agent is expensive, relatively few in types and poor in universality.
In order to solve the problems, a modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent is independently developed, belongs to a surfactant warm-mixing agent, and can be used in road engineering to remarkably reduce energy consumption and harmful gas emission in the road construction process and achieve the purposes of energy conservation and emission reduction. The novel warm mixing agent has the outstanding advantages of low cost, low-temperature construction and the like, and has wide application prospect.
Disclosure of Invention
The invention aims to provide a preparation method of an asphalt warm-mixing agent, wherein the synthesized warm-mixing agent can be added by an internal mixing method and an external mixing method, has low addition amount and can obviously reduce the mixing and compacting temperature of an asphalt mixture by 30-50 ℃. The raw materials required in the synthesis process are low in cost, the cost required by the catalyst is greatly saved, and the effects of energy conservation and emission reduction can be achieved when the catalyst is used in the asphalt pavement construction and maintenance processes.
In order to achieve the purpose, the preparation method of the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent provided by the invention comprises the following steps:
step 1: adding tall oil, organic polyamine and 20-40% of water carrying agent in a molar ratio of 1:1-2 into a reactor, stirring, heating and refluxing to perform amidation reaction to obtain an amide intermediate;
step 2: after the step 1, evaporating out the water carrying agent, vacuumizing, and heating for cyclization reaction to obtain an imidazoline intermediate;
and step 3: and (3) adding the quaternization reagent into absolute ethyl alcohol to prepare a mixed solution with the mass fraction of 50%, stirring and slowly dripping the mixed solution into the imidazoline intermediate in the step (2), carrying out quaternization reaction, and decompressing to evaporate the ethyl alcohol and the unreacted quaternization reagent to obtain the asphalt warm-mixing agent.
The organic polyamine is at least one of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
The water carrying agent is at least one of toluene and xylene.
The reflux temperature of the invention is 120-160 ℃, and the reaction time is 2-10 h.
The vacuum degree of the invention is 0.09-0.1 MPa.
The cyclization reaction temperature of the invention is 230-250 ℃, and the cyclization time is 1-10 h.
The quaternization reagent is methyl acrylate, and the molar ratio of the quaternization reagent to the imidazoline intermediate is 1: 1-1.5.
The quaternization reaction temperature of the invention is 30-60 ℃, and the reaction time is 4-24 h.
The usage amount of the asphalt warm-mixing agent is 2-12 per mill of the mass of the asphalt.
The invention also provides a modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent prepared by the preparation method.
The invention can also be detailed as follows:
a preparation method of a modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent comprises the following components in a molar mass ratio:
tall oil: organic polyamine 1:1-2
20 to 40 percent of water carrying agent
Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 120 ℃ and 160 ℃ for 2-10 h; evaporating the water carrying agent, raising the temperature to 230-250 ℃ under the vacuum degree of 0.09-0.1MPa, and carrying out cyclization reaction for 1-10h to obtain an imidazoline intermediate; preparing 50 mass percent ethanol solution by using a quaternization reagent with the molar ratio of 1:1-1.5 to the imidazoline intermediate, slowly dropwise adding the ethanol solution into the imidazoline intermediate, reacting for 4-24 hours at the temperature of 30-60 ℃ under stirring, and then decompressing and distilling out ethanol and the unreacted quaternization reagent to obtain the asphalt warm-mixing agent.
The invention is further improved in that the organic polyamine is one or more of diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
The invention is further improved in that the water carrying agent is toluene or xylene.
The invention has the further improvement that the following components are weighed according to the molar mass ratio and are prepared from the following raw materials:
tall oil: organic polyamine 1:1-2
20 to 40 percent of water carrying agent
The invention is further improved in that the adding amount of the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent is 2-12 per mill of the mass of the asphalt.
Compared with the prior art, the invention has the following beneficial effects: due to different structures of raw materials, tall oil and organic polyamine are used as raw materials, imidazoline is obtained through amidation and cyclization, and a final warm mixing agent product is obtained through quaternary amination reaction. The method uses tall oil as a raw material, and a warm-mixing agent product is obtained through amidation, cyclization and quaternization reactions, which are not reported before, so that the application of the tall oil is widened, the preparation method of the warm-mixing agent is enriched, the tall oil is simple and easy to obtain and has low cost, and compared with the preparation method using asphalt-based graphene quantum dots as the raw material, the method greatly saves the production cost; meanwhile, compared with the prior art that the raw material needs additional processing, the tall oil does not need additional processing, the reaction steps are simplified, and the production cost is saved. The asphalt warm-mixing agent does not contain water, the required materials are easy to obtain, a catalyst is not needed in the reaction process, the raw material cost is saved, the reaction is carried out in three steps, and the reaction time and the reaction process can be reasonably controlled. In the practical application process, the asphalt can be added by an internal mixing method and an external mixing method, the mixing amount is small, the mixing and compacting temperature of the asphalt mixture can be obviously reduced by 30-50 ℃, the cooling effect is obvious, the warm mixing effect can be realized, and the energy-saving and emission-reducing effects are obvious.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the public unless otherwise specified.
Example 1
Tall oil and diethylenetriamine with the molar ratio of 1:1 are added into a reactor, and a certain amount of water carrying agent toluene accounting for 20 percent of the total mass is added. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 5 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.2, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
Example 2
Tall oil and diethylenetriamine with the molar ratio of 1: 1.2 are added into a reactor, and a certain amount of water carrying agent xylene which accounts for 30 percent of the total mass is added. Stirring, heating and refluxing, and carrying out amidation reaction at reflux temperature of 140 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution with methyl acrylate with the molar ratio of 1: 1.2 to imidazoline intermediate, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours under the condition of stirring at 40 ℃, and after the reaction is finished, evaporating the ethanol and unreacted methyl acrylate under reduced pressure to obtain a product, namely the warm mixing agent product.
Example 3
Tall oil and diethylenetriamine with the molar ratio of 1: 1.4 are added into a reactor, and a certain amount of water carrying agent toluene accounting for 40 percent of the total mass is added. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.2, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
Example 4
Tall oil and triethylene tetramine with the molar ratio of 1: 1.4 are added into a reactor, and a certain amount of water carrying agent xylene is added, which accounts for 20% of the total mass. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.1, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
Example 5
Tall oil and triethylene tetramine with the molar ratio of 1: 1.2 are added into a reactor, and a certain amount of water carrying agent toluene accounting for 30% of the total mass is added. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.2, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
Example 6
Tall oil and tetraethylenepentamine with the molar ratio of 1:1 are added into a reactor, and a certain amount of water carrying agent xylene is added, which accounts for 20 percent of the total mass. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.2, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
In order to verify the beneficial effects of the product of the present invention, the warm mix asphalt prepared in the above examples 1 to 6 was tested according to the following three methods.
1. Surface tension of asphalt
The molecular structure of a surfactant is generally composed of a polar portion (hydrophilic portion) and a non-polar portion (lipophilic portion). When the ionic surfactant aqueous solution is added into asphalt and stirred uniformly, surfactant molecules can be freely arranged on the surface of the asphalt particles, and the lipophilic hydrocarbon chain ends are firmly adhered to the asphalt particles, so that the surface of the asphalt particles is charged. The hydrophilic ion group contacts with water to form a layer of water film on the surface of the asphalt particles, so that the surface tension of the asphalt particles is reduced, the electrostatic repulsion between the particles is generated by the charges on the surface of the asphalt particles, and the asphalt particles are uniformly dispersed in the continuous water phase to form the balance state of the asphalt particles, the surfactant and the water. This equilibrium prevents the asphalt particles from rejoining and spreading into a sheet, reducing the viscosity of the asphalt, which, coupled with the lubricating and foaming effects of the trace amounts of water, can mix with the aggregate at relatively low temperatures. The specific experimental conditions are as follows.
The asphalt adopted in the test is Qin-70 # matrix asphalt, the temperature of the asphalt in the test is 135 ℃, and the yield of the asphalt warm-mixing agent is 5 per mill, 10 per mill and 15 per mill of the mass of the asphalt.
The test results are shown in Table 1.
TABLE 1 contact Angle test results for warm mix asphalt
As can be seen from the test results in Table 1, the products of examples 1-6 of the present invention can significantly reduce the surface tension of the asphalt, achieve warm mixing effect, and the effect is more significant as the amount of the additive is increased.
2. Brookfield viscosity rotational viscosity method for asphalt
The asphalt mastic is used as a binder to bond the aggregates into a whole in the asphalt mixture, and the performance of the asphalt mastic determines the service performance of the asphalt pavement to a great extent. The viscosity of the asphalt cement determines the mixing and compacting temperature of the asphalt mixture, so that the viscosity of the asphalt cement doped with the warm-mixing agent is measured through a Brookfield rotational viscosity test, and a viscosity-temperature curve is drawn, so as to test the beneficial effect of the product. The specific test cases are as follows.
The asphalt adopted in the test is Qin-70 # matrix asphalt, the temperature of the tested asphalt mucilage is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 150 ℃, and the mixing amount of the asphalt warm-mixing agent is 5 per mill, 10 per mill and 15 per mill of the mass of the asphalt. The test instrument was a Brookfield viscometer.
The test method comprises the following steps: firstly, 600g of matrix asphalt is taken, heated to 145 ℃ in an oven, and then a warm-mixing agent is added at 135 ℃ to be mixed and stirred for 30min to prepare asphalt mucilage. The brookfield viscosity of the asphalt cement is measured according to the test method of T0625-2011 in road engineering asphalt and asphalt mixture test regulation issued by the Ministry of transportation (JTG E20-2011).
The test results are shown in tables 2-7.
Table 2 example 1 warm mix asphalt cement viscosity-temperature curve test results
Table 3 example 1 warm mix asphalt cement viscosity temperature curve test results
Table 4 example 1 warm mix asphalt cement viscosity-temperature curve test results
TABLE 5 example 1 viscosity-temperature curve test results of warm mix asphalt cement
TABLE 6 example 1 viscosity-temperature curve test results of warm mix asphalt cement
TABLE 7 example 1 viscosity-temperature curve test results of warm mix asphalt cement
As can be seen from the experimental results in tables 2-7, the products of examples 1-6 of the present invention all reduce the high temperature viscosity of the asphalt mastic, and the more significant the viscosity reduction of the asphalt mastic is with the increase of the blending amount, the better the product effect is.
3. Asphalt mixture method
In order to evaluate the use effect of the APTL-106 high-performance warm mixing agent, an AC-20 asphalt mixture with 4.4 percent of asphalt is adopted for a comparison test, the cooling capacity is measured by Marshall compaction effect, the compaction temperature is determined by taking the porosity as a measurement index, the mixing temperature is determined according to the condition that the mixing temperature is 10-15 ℃ higher than the compaction temperature, and the influence of the warm mixing agent on the performance of the mixture is examined. The specific experimental conditions are as follows.
The test method comprises the following steps: test piece disease tests are respectively formed on the traditional hot plate asphalt mixture and the warm mix asphalt mixture according to the regulations of T0702, T0703, T0706, T0709, T0719 and T0729 in road engineering asphalt and asphalt mixture test procedures issued by the Ministry of transportation (JTG E20-2011).
Experimental equipment: an automatic compaction instrument for asphalt mixture, a Marshall stability instrument, a SYD-0730 type multifunctional asphalt pressure tester and a full-automatic rutting tester.
The asphalt adopted in the test is Qin-70 # matrix asphalt, and the mixing amount of the warm mixing agent is 5 per mill of the mass of the asphalt. The aggregate is limestone, and the optimal oil-stone ratio is 4.5%. According to the requirements of technical Specification for construction of road asphalt pavements (JTG F40-2011), the technical performances of asphalt and aggregate are tested, and the results meet the specification requirements and can be used. The mineral aggregate gradation determined in the laboratory test is shown in Table 8.
TABLE 8 experimentally determined composition of mineral aggregate of type AC-16
Mixing the hot-mixed asphalt mixture and forming the test piece: the aggregate heating temperature is 150 ℃, the asphalt heating temperature is 150 ℃, the mixing set temperature is 150 ℃, and the test piece forming temperature is 140 ℃.
Mixing the warm-mixed asphalt mixture and forming the test piece: the aggregate heating temperature is 135 ℃, the asphalt heating temperature is 135 ℃, the mixing setting temperature is 135 ℃, and the time forming temperature is 125 ℃.
The results of the laboratory tests are shown in Table 9.
TABLE 9 road Performance test results for hot-mix warm mix asphalt mixture
The experimental results in table 9 show that the volume-increasing indexes and road performance indexes of the warm-mixed asphalt mixture and the hot-mixed asphalt mixture can meet technical specification for road asphalt pavement construction (JTG F40-2011), and the warm-mixed asphalt mixture meets the specification requirements on road performance, so that the road performance is good, and the warm-mixed effect is remarkable.
Three test results for verifying the good effect of the invention are comprehensively compared and analyzed, and it can be found that the examples 1 to 6 can obviously reduce the high-temperature viscosity of the asphalt, reduce the construction temperature and achieve the warm mixing effect.
Example 7
Tall oil and tetraethylenepentamine with the molar ratio of 1: 1.2 are added into a reactor, and a certain amount of water carrying agent toluene accounting for 30 percent of the total mass is added. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.2, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
Example 8
Tall oil and diethylenetriamine with the molar ratio of 1: 1.4 are added into a reactor, and a certain amount of water carrying agent xylene which accounts for 40 percent of the total mass is added. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.1, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
Example 9
Tall oil and triethylene tetramine with the molar ratio of 1: 1.1 are added into a reactor, and a certain amount of water carrying agent toluene accounting for 40% of the total mass is added. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.1, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
Example 10
Tall oil and tetraethylenepentamine with the molar ratio of 1: 1.2 are added into a reactor, and a certain amount of water carrying agent xylene is added, which accounts for 20 percent of the total mass. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution with methyl acrylate with the molar ratio of 1: 1.1 to imidazoline intermediate, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours under the condition of stirring at 40 ℃, and after the reaction is finished, evaporating the ethanol and unreacted methyl acrylate under reduced pressure to obtain a product, namely the warm mixing agent product.
Example 11
Tall oil and triethylene tetramine with the molar ratio of 1:1 are added into a reactor, and a certain amount of toluene as a water carrying agent is added, accounting for 30% of the total mass. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.1, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
Example 12
Tall oil and tetraethylenepentamine with the molar ratio of 1:1 are added into a reactor, and a certain amount of water carrying agent toluene accounting for 30 percent of the total mass is added. Stirring, heating and refluxing, and carrying out amidation reaction at the reflux temperature of 150 ℃ for 4 h. And (3) evaporating xylene, vacuumizing until the vacuum degree is 0.095MPa, heating to 240 ℃ and carrying out cyclization reaction for 4 hours to obtain the imidazoline intermediate. Preparing 50 mass percent ethanol solution from methyl acrylate and imidazoline intermediate in a molar ratio of 1: 1.1, slowly dripping the ethanol solution into imidazoline, reacting for 12 hours at 40 ℃ under stirring, and decompressing and distilling out ethanol and unreacted methyl acrylate to obtain a product, namely the warm mixing agent product.
The asphalt warm-mixing agent does not contain water, does not need a catalyst in the reaction process, can be added by an internal doping method and an external doping method, has low addition amount, and can obviously reduce the mixing and compacting temperature of the asphalt mixture by 30-50 ℃. The raw materials required in the synthesis process are low in cost, the cost required by the catalyst is greatly saved, and the effects of energy conservation and emission reduction can be achieved when the catalyst is used in the asphalt pavement construction and maintenance process.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent is characterized by comprising the following steps:
step 1: adding tall oil, organic polyamine and 20-40% of water carrying agent in a molar ratio of 1:1-2 into a reactor, stirring, heating and refluxing to perform amidation reaction to obtain an amide intermediate;
and 2, step: after the step 1, evaporating out the water carrying agent, vacuumizing, and heating for cyclization reaction to obtain an imidazoline intermediate;
and step 3: and (3) adding the quaternization reagent into absolute ethyl alcohol to prepare a mixed solution with the mass fraction of 50%, stirring and slowly dripping the mixed solution into the imidazoline intermediate in the step (2), carrying out quaternization reaction, and decompressing to evaporate the ethyl alcohol and the unreacted quaternization reagent to obtain the asphalt warm-mixing agent.
2. The method for preparing the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent according to claim 1, wherein the organic polyamine is at least one of diethylenetriamine, triethylene tetramine, and tetraethylene pentamine.
3. The method for preparing the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent according to claim 1, wherein the water carrying agent is at least one of toluene and xylene.
4. The method for preparing the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent as claimed in claim 1, wherein the reflux temperature is 120-160 ℃, and the reaction time is 2-10 h.
5. The method for preparing the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent according to claim 1, wherein the vacuum degree is 0.09-0.1 MPa.
6. The method for preparing the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent as claimed in claim 1, wherein the cyclization reaction temperature is 230 ℃ and 250 ℃, and the cyclization time is 1-10 h.
7. The method for preparing the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent as claimed in claim 1, wherein the quaternizing agent is methyl acrylate, and the molar ratio of the quaternizing agent to the imidazoline intermediate is 1: 1-1.5.
8. The method for preparing the modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent according to claim 1, wherein the quaternization reaction temperature is 30-60 ℃, and the reaction time is 4-24 h.
9. The method for preparing the modified imidazoline quaternary ammonium salt type warm asphalt mixing agent according to claim 1, wherein the amount of the warm asphalt mixing agent is 2-12 per mill of asphalt mass.
10. A modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011276470.2A CN114507187B (en) | 2020-11-16 | 2020-11-16 | Modified imidazoline quaternary ammonium salt type asphalt warm mix agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011276470.2A CN114507187B (en) | 2020-11-16 | 2020-11-16 | Modified imidazoline quaternary ammonium salt type asphalt warm mix agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114507187A true CN114507187A (en) | 2022-05-17 |
| CN114507187B CN114507187B (en) | 2024-04-30 |
Family
ID=81546303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011276470.2A Active CN114507187B (en) | 2020-11-16 | 2020-11-16 | Modified imidazoline quaternary ammonium salt type asphalt warm mix agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114507187B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559122A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Cationic-nonionic compound asphalt warm mixing agent and preparation method thereof |
| CN104941509A (en) * | 2015-05-11 | 2015-09-30 | 中国海洋石油总公司 | Micro-surfacing slow cracking and rapid setting asphalt emulsifier and preparation method thereof |
| CN105085402A (en) * | 2015-09-11 | 2015-11-25 | 陕西科技大学 | Rosin-based imidazoline quaternary ammonium salt compound and preparation method thereof |
-
2020
- 2020-11-16 CN CN202011276470.2A patent/CN114507187B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559122A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Cationic-nonionic compound asphalt warm mixing agent and preparation method thereof |
| CN104941509A (en) * | 2015-05-11 | 2015-09-30 | 中国海洋石油总公司 | Micro-surfacing slow cracking and rapid setting asphalt emulsifier and preparation method thereof |
| CN105085402A (en) * | 2015-09-11 | 2015-11-25 | 陕西科技大学 | Rosin-based imidazoline quaternary ammonium salt compound and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114507187B (en) | 2024-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108863172B (en) | Open-graded basalt fiber asphalt mixture and preparation method thereof | |
| CN104761191B (en) | A kind of organic composite Warm-Mix Bitumen Mixture and preparation method thereof | |
| CN106431088A (en) | Preparation method of fiber and cold patch asphalt mixture | |
| CN102234188B (en) | Method for preparing environment-friendly warm mix asphalt | |
| CN102295445A (en) | Microwave heated and cured emulsified asphalt concrete material and preparation method thereof | |
| CN109534724A (en) | A kind of High Modulus Asphalt Mixture and preparation method thereof modified based on high ash content rock asphalt | |
| CN103980499A (en) | Modified hyperbranched polyamide-amine asphalt emulsifier and preparation method and application thereof | |
| CN110643186A (en) | Asphalt warm-mixing agent and application thereof | |
| CN111019362A (en) | Warm mixing agent for asphalt mixture, preparation method and application | |
| CN107236122A (en) | A kind of environmentally-friendly asphalt warm-mixing agent, preparation and application | |
| CN114381132A (en) | Copolymer modified asphalt | |
| CN114507187A (en) | Modified imidazoline quaternary ammonium salt type asphalt warm-mixing agent and preparation method thereof | |
| CN108239302B (en) | asphalt warm-mixing agent, preparation method and application | |
| CN111205658A (en) | Modified asphalt mortar and preparation method and application thereof | |
| CN111072311A (en) | Modifier for improving anti-rutting performance of asphalt concrete and preparation method thereof | |
| CN104609771B (en) | Warm-mixing reclaiming agent and preparation method thereof | |
| CN110540381A (en) | asphalt mixture preparation method based on asphalt cement | |
| CN110028452A (en) | Compound, warm-mixed asphalt, asphalt and its preparation method and application | |
| CN113265156B (en) | High-toughness modified asphalt and preparation method thereof | |
| CN115124280A (en) | High-proportion RAP warm-mix recycled asphalt cement and preparation method thereof | |
| CN101445662A (en) | Method for preparing modified asphalt | |
| CN104559122B (en) | A kind of cation-non-ionic composite asphalt warm-mix agent and preparation method thereof | |
| CN111925155A (en) | In-situ heat-regenerated asphalt mixture, preparation method and long-road-age pavement construction method | |
| CN115490461B (en) | Recycled asphalt concrete and preparation method thereof | |
| CN115044099B (en) | Two-dimensional asphalt warm mix agent suitable for ultralow-temperature construction of hot mix asphalt mixture, warm mix asphalt and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |