CN-121991360-A - Reactive cationic asphalt emulsifier and preparation method and application thereof

Abstract

The invention discloses a reactive cationic asphalt emulsifier and a preparation method and application thereof, belonging to the technical field of road engineering materials, the emulsifier has a three-segment structure of [ A ] - [ B ] - [ C ], wherein [ A ] is an epoxy chain segment, [ B ] is a polyether chain segment (which is a polyether flexible chain segment), and [ C ] is polyamine and a derivative chain segment thereof. The invention can realize the accurate regulation and control of the performance of the emulsifier by regulating and controlling the type of epoxy resin, the type of polyamine and derivatives thereof, the molecular weight of polyether (such as polyethylene glycol diglycidyl ether) and the amine hydrogen/epoxy ratio. The emulsified asphalt prepared by the emulsifier has the advantages of excellent storage stability, outstanding low-temperature ductility, firm interface combination (covalent bond formation with asphalt) and the like, and can be widely applied to road maintenance engineering such as micro-surfacing, slurry sealing, cold regeneration and the like.

Inventors

• LI RUI
• HUANG YUFEI
• ZHU HONGZHOU
• TANG NAIPENG

Assignees

• 重庆交通大学

Dates

Publication Date

20260508

Application Date

20260311

Claims (10)

1. 1. The reactive cationic asphalt emulsifier is characterized by having a three-stage structure of [ A ] - [ B ] - [ C ], wherein [ A ] is an epoxy chain segment, [ B ] is a polyether chain segment, and [ C ] is polyamine and a derivative chain segment thereof.
2. 2. The reactive cationic asphalt emulsifier of claim 1 wherein the epoxy segment is comprised of an epoxy resin selected from at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and cycloaliphatic epoxy resin; The polyether chain segment is selected from at least one of a polyethylene glycol chain segment, a polypropylene glycol chain segment and a polyethylene glycol-polypropylene glycol block copolymer chain segment; the polyamine and derivative chain segments thereof contain nitrogen-containing cationic groups.
3. 3. The reactive cationic asphalt emulsifier of claim 2 wherein the polyether segments have a number average molecular weight of 400 to 4000; The nitrogen-containing cationic group is selected from at least one of primary amine salt, secondary amine salt, tertiary amine salt, quaternary ammonium salt and imidazoline salt.
4. 4. The reactive cationic asphalt emulsifier of claim 1, wherein the reactive cationic asphalt emulsifier has a three-stage structure of [ EP ] - [ PEG ] - [ PA ], wherein [ EP ] is an epoxy segment, [ PEG ] is a polyethylene glycol segment, [ PA ] is a polyamine and derivative segment thereof; The epoxy value of the epoxy resin in the epoxy chain segment is 0.2-0.6 mol/100g, and the number average molecular weight of the polyethylene glycol chain segment is 600-2000.
5. 5. The reactive cationic asphalt emulsifier of claim 4 wherein the polyamine and derivative thereof is selected from one of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
6. 6. The reactive cationic asphalt emulsifier of claim 2 wherein the bisphenol a type epoxy resin is selected from the group consisting of E-44 epoxy resin, E-51 epoxy resin, and E-20 epoxy resin.
7. 7. A method of preparing the reactive cationic asphalt emulsifier of any one of claims 1 to 6, comprising the steps of: (1) Carrying out copolymerization reaction on epoxy resin and a polymer forming a polyether chain segment in an organic solvent, and adding a catalyst for catalysis to obtain an epoxy-polyether copolymer intermediate; (2) Amination reaction is carried out on the epoxy-polyether copolymer intermediate obtained in the step (1) and polyamine and derivatives thereof, and reaction conditions are controlled to ensure that epoxy groups are partially reserved, so that a copolymer containing amino groups is obtained; (3) And (3) carrying out protonation treatment on the copolymer containing amino groups obtained in the step (2) by using a pH regulator, and regulating the pH to 1.5-3.5 to obtain the reactive cationic asphalt emulsifier.
8. 8. The method for preparing a reactive cationic asphalt emulsifier according to claim 7, wherein in the step (1), the temperature of the copolymerization reaction is 50-90 ℃ for 2-6 hours; In the step (1), the organic solvent is at least one selected from absolute ethyl alcohol, isopropanol, isobutyl alcohol and propylene glycol methyl ether; in the step (2), the temperature of the amination reaction is 40-80 ℃ for 1-4 hours, and the amine hydrogen/epoxy molar ratio is controlled to be 0.5:1-1.2:1; In the step (3), the temperature of the protonation treatment is 20-40 ℃ and the time is 0.5-2 hours.
9. 9. The preparation method of the reactive cationic asphalt emulsifier according to claim 7, wherein the catalyst is one selected from triphenylphosphine, triethylamine and N, N-dimethylbenzylamine, and the dosage is 0.1-1% of the mass of the epoxy resin; the pH regulator is selected from hydrochloric acid or phosphoric acid.
10. 10. Use of a reactive cationic asphalt emulsifier according to any one of claims 1-6 for the preparation of emulsified asphalt.

Description

Reactive cationic asphalt emulsifier and preparation method and application thereof Technical Field The invention belongs to the technical field of road engineering materials, and particularly relates to a reactive cationic asphalt emulsifier, and a preparation method and application thereof. Background The emulsified asphalt is a water-in-oil or oil-in-water emulsion formed by dispersing hot melt asphalt in water containing an emulsifier through mechanical shearing, and is widely applied to road maintenance engineering such as micro-surfacing, slurry sealing, cold regeneration and the like. Traditional cationic asphalt emulsifiers are mostly small molecular compounds such as alkylamines, quaternary ammonium salts, imidazolines and the like. The emulsifier can realize emulsification of asphalt, but has the following problems that (1) a small molecular emulsifier is easy to migrate from an asphalt film and influence road performance, (2) the low-temperature ductility of the emulsified asphalt is obviously lower than that of matrix asphalt and is generally reduced by 40-60 percent, (3) the emulsifying capacity of high-viscosity asphalt such as SBS modified asphalt is insufficient, and (4) the storage stability of the emulsified asphalt is poor and layering precipitation is easy. In order to solve the above problems, researchers have developed a polymer emulsifier. CN118580511a discloses a hyperbranched resin polymer asphalt emulsifier which has excellent properties of high strength, high toughness, impact resistance, hydrophobicity, corrosion resistance and the like. CN120757692a discloses a high molecular polymer asphalt emulsifier which has better emulsifying capability. However, these emulsifiers are all non-reactive, only physical adsorption with asphalt exists, the interfacial bonding strength is limited, and the long-term durability is insufficient. In addition, CN 106883379A discloses a preparation method of a waterborne epoxy resin curing agent, which is mainly used for carrying out curing reaction with waterborne epoxy resin, and structurally, both ends of the waterborne epoxy resin curing agent are of polyamine structures, and no process of adding acid for protonation exists, so that the waterborne epoxy resin curing agent has no charge. Therefore, a high-performance emulsifier which has excellent storage stability, outstanding low-temperature performance and can form chemical bonding with asphalt is developed, and has important industrial application value. Disclosure of Invention The invention provides a reactive cationic asphalt emulsifier and a preparation method and application thereof, and aims to solve the problems of insufficient low-temperature performance, weak interfacial binding force and insufficient long-term durability of the existing emulsifier. In order to achieve the above purpose, the present invention provides the following technical solutions: The invention provides a reactive cationic asphalt emulsifier which has a three-segment structure of [ A ] - [ B ] - [ C ], wherein [ A ] is an epoxy chain segment, [ B ] is a polyether chain segment (which is a polyether flexible chain segment), and [ C ] is polyamine and a derivative chain segment thereof. The invention can realize the accurate regulation and control of the performance of the emulsifier by regulating and controlling the type of epoxy resin, the type of polyamine and derivatives thereof, the molecular weight of polyether (such as polyethylene glycol diglycidyl ether) and the amine hydrogen/epoxy ratio, and solves the problems of insufficient low-temperature performance, weak interface binding force and insufficient long-term durability of the existing emulsifier. The conventional asphalt emulsifier is mainly a small molecular emulsifier, the flexibility of asphalt is difficult to improve at low temperature, secondly, migration and enrichment of the conventional asphalt emulsifier to the surface of the asphalt are easy to occur under the action of external moisture, so that the water absorption is increased, the interfacial adhesion of the asphalt is affected, and in addition, under the long-term action of the external moisture, the moisture diffuses into the asphalt, so that the asphalt performance is attenuated, and the long-term durability of the asphalt is affected. The polyether chain segment in the emulsifier has good flexibility, the low-temperature ductility of the emulsifier is improved, the epoxy group has a certain polarity, the interfacial adhesion with aggregates such as mineral aggregates is enhanced, active groups (epoxy group and imine group) in the emulsifier can react with each other or asphalt to form a crosslinked structure, and the durability of the emulsified asphalt is improved. The emulsified asphalt prepared by the emulsifier has the advantages of excellent storage stability, outstanding low-temperature ductility, firm interface combination (covalent bond formation with asphalt) and the like, and c