Novel asphalt emulsifier and preparation method thereof
Technical Field
The invention relates to the technical field of asphalt, in particular to a novel asphalt emulsifier and a preparation method thereof.
Background
The asphalt is a black or dark black solid or semisolid viscous substance consisting of macromolecular hydrocarbons and non-hydrocarbons, has excellent performances of water resistance, moisture resistance, wear resistance, electrical insulation, toughness and the like, and is an indispensable important material for modern road construction. Due to the weather, vehicle overload and other reasons, the defects of pavement subsidence, cracks, reduced flatness and the like often occur on the asphalt pavement, and the defects are easy to further accelerate the overall damage of the asphalt pavement, so that the potential damage is caused to the vehicle running safety.
Because the solid form of the asphalt is poor in liquidity, is a sticky object and is very strong in viscosity, the asphalt cannot be well mixed with other aggregates, and great difficulty is brought to road construction. The current methods of mixing asphalt with aggregate are mainly solvent methods and heat-melting methods. The solvent method adopts a large amount of organic solvent to dissolve the asphalt, thereby increasing the fluidity of the asphalt and achieving the purpose of uniformly mixing the asphalt with aggregate, but because a large amount of organic solvent exists, the organic solvent volatilizes after the pavement is paved, causing air pollution, and the use cost of the organic solvent is very high, thereby increasing the construction cost. The heating and melting method is to heat and melt asphalt to obtain a fluid with good fluidity, and mix the fluid with aggregate while the fluid is hot, but the method consumes a large amount of heat energy and has very high cost. And the molten asphalt can be cooled quickly, so that the stirring time with the aggregate is short, the aggregate and the asphalt cannot be well and uniformly mixed, and the performance of the prepared pavement is unstable.
The problem of the two methods can be well solved by adopting the emulsifier to prepare the emulsified asphalt. Compared with the traditional method for preparing asphalt maintenance pavement, the emulsified asphalt maintenance pavement has the advantages of low construction cost, environmental protection, pollution removal, working hour saving, pavement performance improvement and pavement service life prolonging, and is the most common material for road maintenance at present. The preparation of the emulsified asphalt is to melt the asphalt at a lower melting temperature (much lower than that of a heating and melting method), and the asphalt is mechanically sheared to be in a droplet shape and uniformly dispersed in an emulsifier aqueous solution to form the emulsified asphalt liquid with stable property and good flowing at normal temperature.
The demulsification process of the emulsified asphalt influences the aggregation of the asphalt and the aggregate, and whether a uniform and continuous asphalt film can be formed on the surface of the aggregate. The demulsification is influenced by a variety of factors, such as the type of bitumen employed, the choice of emulsifier, etc. Wherein the emulsifier is selected from the group consisting of the major emulsifiers.
Asphalt emulsifier is a surfactant whose structure and properties are decisive for the properties of the emulsified asphalt. The molecular structure of the asphalt emulsifier consists of hydrophilic polar groups and hydrophobic nonpolar groups, and an asymmetric amphiphilic structure with one end obviously hydrophilic and the other end obviously hydrophobic is formed. The hydrophilic group in the emulsifier is a linear or branched long-chain sintered body with a hydrophobic group provided by a nitrogen-containing group, wherein the hydrophobic group is carbon atoms, and the linear or branched long-chain sintered body mainly comprises a linear base group, a branched base group, a rosin derivative, a phenyl group, a high molecular weight polypropylene oxide group and the like. Common asphalt emulsifiers comprise four major types, namely cationic emulsifiers, anionic emulsifiers, zwitterionic emulsifiers and nonionic emulsifiers. Anionic emulsifiers have poor adhesion to aggregates and have been gradually eliminated. The cationic emulsifier only has cations as hydrophilic groups, is greatly influenced by pH value, has higher requirement on water quality and has unsatisfactory asphalt emulsifying effect. The amphoteric asphalt emulsifier has better emulsifying property, but the cost is higher. Therefore, the synthesized novel asphalt emulsifier with strong emulsifying capacity and stable emulsion storage has wide application prospect.
Disclosure of Invention
The invention aims to provide a novel asphalt emulsifier and a preparation method thereof, which have good anti-aging effect.
The technical scheme of the invention is realized as follows:
the invention provides a novel asphalt emulsifier which has a structure shown as a formula I:
wherein, KGM represents konjac glucomannan molecular chains.
As a further improvement of the invention, the KGM is replaced by a cellulose molecular chain and has a structure shown in a formula II:
wherein cellulose stands for cellulose molecular chains.
The invention further provides a preparation method of the novel asphalt emulsifier, which comprises the following steps:
s1, mixing p-chlorobenzaldehyde, konjac glucomannan and primary alkali for reaction to obtain a reaction intermediate I, wherein the intermediate I is
S2, mixing the intermediate I, 2-oxo-bis-ethylamine and a second base for reaction to obtain the novel asphalt emulsifier.
The invention further provides a preparation method of the novel asphalt emulsifier, which comprises the following steps:
s1, mixing p-chlorobenzaldehyde, cellulose and first alkali for reaction to obtain a reaction intermediate II
S2, mixing the intermediate II, 2-oxo-bis-ethylamine and a second base for reaction to obtain the novel asphalt emulsifier.
As a further improvement of the invention, in step S1, the first base is one or more selected from triethylamine, ethylenediamine, tert-butylamine, isopropylamine, DMAP (4-dimethylaminopyridine) and DABCO (triethylenediamine).
As a further improvement of the invention, in step S2, the second base is one or more selected from NaOH, KOH, barium hydroxide, sodium carbonate and sodium bicarbonate.
As a further improvement of the invention, the mass ratio of the p-chlorobenzaldehyde, the konjac glucomannan and the first alkali in the step S1 is (1.1-1.5) to 1 to (1-3); the mass ratio of the intermediate I, the 2, 2-oxydiethanamine and the second base in the step S2 is 1: 1.1-1.3: 1-3.
As a further improvement of the invention, the mass ratio of the p-chlorobenzaldehyde, the cellulose and the first alkali in the step S1 is (1.3-1.7) to 1 to (2-4); the mass ratio of the intermediate II, the 2, 2-oxydiethanamine and the second base in the step S2 is 1: 1.1-1.3: 1-3.
The invention further protects the application of the novel asphalt emulsifier in preparing the quick-cracking emulsified asphalt.
The invention further protects emulsified asphalt, which is prepared by adding water into the novel asphalt emulsifier with the dosage of 1-3% of the total mass of the prepared emulsified asphalt to prepare aqueous solution, adding hydrochloric acid to adjust the pH value to 1.5-2.5, and heating to 65-75 ℃ to prepare emulsifier soap solution; emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the emulsified asphalt.
The invention has the following beneficial effects:
1. the konjac glucomannan or cellulose is added into the raw materials, so that the asphalt emulsifier prepared by the method has higher hydrophilicity; the primary amine of 2, 2-oxo-bis-ethylamine and the carbonyl of the intermediate I or the intermediate II are subjected to Mannich reaction and are connected in one step to prepare the asphalt emulsifier molecule, and the asphalt emulsifier contains more carboxyl and hydroxyl hydrophilic groups, so that an interface film, a hydration layer and an interface charge layer are correspondingly enhanced, and the stability of the emulsion is improved;
2. the asphalt emulsifier prepared by the method meets the national standard requirements in all indexes, has good emulsifying performance, can emulsify various types of asphalt, and has fine and uniform emulsified asphalt, good aggregate wrapping property and storage stability. The asphalt emulsifier is suitable for spreading road penetrating layer oil or viscous layer oil, is used for chip sealing, stone chip sealing, fog sealing, repairing slight net crack of pavement and the like, and has the characteristic of quick-crack asphalt emulsifier.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Has a structure shown in formula I:
wherein, KGM represents konjac glucomannan molecular chains.
The reaction equation is as follows:
the preparation method comprises the following steps:
s1, adding 1mol of konjac glucomannan (compound B) and 1mol of triethylamine into a reactor, adding 200mL of acetonitrile/water solution (the volume ratio of acetonitrile to water is 1: 1), heating to boil, dropwise adding 1.1mol of dichloromethane solution (compound A) of p-chlorobenzaldehyde (the total volume is 20mL), and mixing for 2h to obtain a reaction intermediate I (compound C);
s2, adding 1mol of the intermediate I (compound C), 1.1mol of 2, 2-oxo-bis-ethylamine (compound D) and 1mol of NaOH into a reactor, adding 250mL of dichloromethane, heating to 40 ℃, and mixing for reaction for 4h to obtain the novel asphalt emulsifier with the yield of 92%.
The prepared novel asphalt emulsifier shown in the formula I is subjected to FTIR detection after separation and purification, and the result is as follows: 3422cm-1Is a stretching vibration of-OH, 3007cm-1Is the stretching vibration of C-H on a benzene ring, and is 2922cm-12831cm for asymmetric stretching vibration of methylene-1Is methylene symmetric telescopic vibration, 1650cm-1Is NH2Bending vibration, 1593cm-1And 1515cm-1The skeleton of the benzene ring vibrates, 1355cm-11319--1Stretching vibration peak of-C-O-C-, 1261cm-1Is subjected to Ar-O-C stretching vibration, and is 1210cm-1Is C-O-H telescopic vibration, 1142cm-11082cm for C-H in-plane bending vibration-1Is C-O and C-N stretching vibration, 1033cm-1Is subjected to Ar-O-C stretching vibration, 851cm-1Out-of-plane bending vibration of isolated hydrogen on benzene ring, 812cm-1645cm for the out-of-plane bending vibration of the adjacent hydrogen on the benzene ring-1is-OH out-of-plane bending vibration. Therefore, the infrared spectrogram is consistent with the chemical structure of the novel asphalt emulsifier shown in the formula I.
Preparing emulsified asphalt: adding water into the novel asphalt emulsifier which is prepared by the embodiment and accounts for 1 percent of the total mass of the prepared emulsified asphalt to prepare an aqueous solution, adding hydrochloric acid to adjust the pH value to 1.5, and heating to 65 ℃ to prepare emulsifier soap solution; emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the emulsified asphalt.
The prepared emulsified asphalt is detected according to the cationic emulsified asphalt industry standard (JTJ052-2000) set by the China department of transportation, and the result is as follows: the emulsified asphalt prepared by the embodiment is uniform and fine, the asphalt content is 59%, the residual quantity on a sieve is 0.012%, and the coating area of the emulsified asphalt and mineral aggregate is greater than 2/3; the mixture is mixed by the mixture, and the mixing time is 3 seconds. The asphalt emulsion prepared by the emulsifier is quick-cracking emulsified asphalt, and the asphalt emulsifier is quick-cracking emulsified asphalt.
Example 2
Has a structure shown in formula I:
wherein, KGM represents konjac glucomannan molecular chains.
The preparation method comprises the following steps:
s1, adding 1mol of konjac glucomannan (compound B) and 3mol of ethylenediamine into a reactor, adding 200mL of acetonitrile/water solution (the volume ratio of acetonitrile to water is 1: 1), heating to boil, dropwise adding 1.5mol of dichloromethane solution (compound A) of p-chlorobenzaldehyde (the total volume is 20mL), and mixing for 4 hours to obtain a reaction intermediate I (compound C);
s2, adding 1mol of the intermediate I (compound C), 1.3mol of 2, 2-oxo-bis-ethylamine (compound D) and 3mol of sodium carbonate into a reactor, adding 250mL of dichloromethane, heating to 40 ℃, and mixing for reaction for 7h to obtain the novel asphalt emulsifier product with the yield of 94%.
The prepared novel asphalt emulsifier shown as the formula I is subjected to FTIR detection after separation and purification, and the result proves that the novel asphalt emulsifier shown as the formula I.
Preparing emulsified asphalt: adding water into the novel asphalt emulsifier which is prepared by the embodiment and accounts for 3 percent of the total mass of the prepared emulsified asphalt to prepare an aqueous solution, adding hydrochloric acid to adjust the pH to 2.5, and heating to 75 ℃ to prepare emulsifier soap solution; emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the emulsified asphalt.
The prepared emulsified asphalt is detected according to the cationic emulsified asphalt industry standard (JTJ052-2000) set by the China department of transportation, and the result is as follows: the emulsified asphalt prepared by the embodiment is uniform and fine, the asphalt content is 62%, the residue on the screen is 0.01%, and the coating area of the emulsified asphalt and mineral aggregate is greater than 2/3; the mixture is mixed by the mixture, and the mixing time is 3 seconds. The asphalt emulsion prepared by the emulsifier is quick-cracking emulsified asphalt, and the asphalt emulsifier is quick-cracking emulsified asphalt.
Example 3
Has a structure shown in formula II:
wherein cellulose stands for cellulose molecular chains.
The reaction equation is as follows:
the preparation method comprises the following steps:
s1, adding 1mol of cellulose (compound E) and 2mol of tert-butylamine into a reactor, adding 200mL of acetonitrile/water solution (the volume ratio of acetonitrile to water is 2: 1), heating to 65 ℃, dropwise adding 1.3mol of dichloromethane solution (compound A) of p-chlorobenzaldehyde (the total volume is 20mL), and mixing for reaction for 3h to obtain a reaction intermediate II (compound F);
s2, adding 1mol of the intermediate II (compound F), 1.1mol of 2, 2-oxo-bis-ethylamine (compound D) and 1-3mol of KOH into a reactor, adding 250mL of dichloromethane, heating to boil, and carrying out mixed reaction for 3h to obtain the novel asphalt emulsifier with the yield of 95%.
The prepared novel asphalt emulsifier shown as the formula II is subjected to FTIR detection after separation and purification, and the result is as follows: 3420cm-1Is a stretching vibration of-OH, 3011cm-12918cm for C-H stretching vibration on benzene ring-12827cm for asymmetric stretching vibration of methylene-11652cm for symmetric stretching vibration of methylene-1Is NH2Bending vibration, 1590cm-1And 1512cm-1Is the skeletal vibration of a benzene ring, 1422cm-1 and 1365cm-1 are respectively the asymmetric and symmetric flexural vibrations of a methyl group, 1352cm-11310-1015cm for-OH in-plane bending vibration-1Stretching vibration peak of-C-O-C-, 1262cm-11211cm for Ar-O-C stretching vibration-1Is C-O-H telescopic vibration, 1140cm-11086cm for C-H in-plane bending vibration-1Is C-O and C-N stretching vibration, 1035cm-1852cm for Ar-O-C stretching vibration-1815cm, which is an isolated hydrogen out-of-plane bending vibration on the benzene ring-1Is out-of-plane bending vibration of adjacent hydrogen on benzene ring, 641cm-1is-OH out-of-plane bending vibration. Therefore, the infrared spectrogram is consistent with the chemical structure of the novel asphalt emulsifier shown as the formula II.
Preparing emulsified asphalt: adding water into the novel asphalt emulsifier which is prepared by the embodiment and has the dosage of 2 percent of the total mass of the prepared emulsified asphalt to prepare an aqueous solution, adding hydrochloric acid to adjust the pH value to 2, and heating to 70 ℃ to prepare emulsifier soap solution; emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the emulsified asphalt.
The prepared emulsified asphalt is detected according to the cationic emulsified asphalt industry standard (JTJ052-2000) set by the China department of transportation, and the result is as follows: the emulsified asphalt prepared by the embodiment is uniform and fine, the asphalt content is 60%, the residual quantity on a sieve is 0.02%, and the coating area of the emulsified asphalt and mineral aggregate is greater than 2/3; the mixture is mixed by the mixture, and the mixing time is 3 seconds. The asphalt emulsion prepared by the emulsifier is quick-cracking emulsified asphalt, and the asphalt emulsifier is quick-cracking emulsified asphalt.
Example 4
Has a structure shown in formula II:
wherein cellulose stands for cellulose molecular chains.
The preparation method comprises the following steps:
s1, adding 1mol of cellulose (compound E) and 4mol of isopropylamine into a reactor, adding 200mL of acetonitrile/water solution (the volume ratio of acetonitrile to water is 2: 1), heating to 75 ℃, dropwise adding 1.7mol of dichloromethane solution (compound A) of p-chlorobenzaldehyde (the total volume is 20mL), and mixing for 4h to obtain a reaction intermediate II (compound F);
s2, adding 1mol of the intermediate II (compound F), 1.3mol of 2, 2-oxo-bis-ethylamine (compound D) and 3mol of NaOH into a reactor, adding 250mL of dichloromethane, heating to boil, and carrying out mixed reaction for 5 hours to obtain a novel asphalt emulsifier product with the yield of 98%.
The prepared novel asphalt emulsifier shown as the formula II is subjected to FTIR detection after separation and purification, and the result proves that the novel asphalt emulsifier shown as the formula II.
Preparing emulsified asphalt: adding water into the novel asphalt emulsifier which is prepared by the embodiment and accounts for 1 percent of the total mass of the prepared emulsified asphalt to prepare an aqueous solution, adding hydrochloric acid to adjust the pH value to 1.5, and heating to 65 ℃ to prepare emulsifier soap solution; emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the emulsified asphalt.
The prepared emulsified asphalt is detected according to the cationic emulsified asphalt industry standard (JTJ052-2000) set by the China department of transportation, and the result is as follows: the emulsified asphalt prepared by the embodiment is uniform and fine, the asphalt content is 60%, the residual quantity on a sieve is 0.025%, and the coating area of the emulsified asphalt and mineral aggregate is greater than 2/3; the mixture is mixed by the mixture, and the mixing time is 5 seconds. The asphalt emulsion prepared by the emulsifier is quick-cracking emulsified asphalt, and the asphalt emulsifier is quick-cracking emulsified asphalt.
Comparative example 1
In contrast to example 4, isopropylamine was not added in step S1. As a result, intermediate II could not be produced.
Comparative example 2
In comparison with example 4, no NaOH was added in step S2. As a result, a novel asphalt emulsifier represented by the formula II cannot be produced.
Comparative example 3
Has a structure shown in formula III:
wherein cellulose stands for cellulose molecular chains.
The reaction equation is as follows:
the preparation method comprises the following steps:
s1, adding 1mol of cellulose (compound E) and 4mol of isopropylamine into a reactor, adding 200mL of acetonitrile/water solution (the volume ratio of acetonitrile to water is 2: 1), heating to 75 ℃, dropwise adding 1.7mol of dichloromethane solution (compound A) of p-chlorobenzaldehyde (the total volume is 20mL), and mixing for 4h to obtain a reaction intermediate II (compound F);
s2, adding 1mol of the intermediate II (compound F), 1.3mol of ethylenediamine and 3mol of NaOH into a reactor, adding 250mL of dichloromethane, heating to boil, and carrying out mixed reaction for 5 hours to obtain a product asphalt emulsifier, wherein the yield is 75%.
The prepared asphalt emulsifier is subjected to FTIR detection after separation and purification, and the result is as follows: 3421cm-1Is a stretching vibration of-OH, 3010cm-12911cm for C-H stretching vibration on benzene ring-12822cm for asymmetric stretching vibration of methylene-1Is methylene symmetric telescopic vibration, 1650cm-1Is NH2Bending vibration, 1587cm-1And 1512cm-11421cm for vibration of benzene ring skeleton-1And 1362cm-1Asymmetric and para, each being methylWeighing flexural vibration, 1350cm-11261cm for-OH in-plane bending vibration-11215cm for Ar-O-C stretching vibration-1Is C-O-H telescopic vibration, 1141cm-11082cm for C-H in-plane bending vibration-1Is C-O and C-N telescopic vibration, 1036cm-1Is subjected to Ar-O-C stretching vibration and 850cm-1Out-of-plane bending vibration of isolated hydrogen on benzene ring, 812cm-1640cm for out-of-plane bending vibration of adjacent hydrogen on benzene ring-1is-OH out-of-plane bending vibration.
Preparing emulsified asphalt: adding water into the novel asphalt emulsifier which is prepared by the embodiment and accounts for 1 percent of the total mass of the prepared emulsified asphalt to prepare an aqueous solution, adding hydrochloric acid to adjust the pH value to 1.5, and heating to 65 ℃ to prepare emulsifier soap solution; emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the emulsified asphalt. As a result: it cannot be emulsified.
Test example 1
The emulsified asphalts prepared in examples 1-4 of the present invention were subjected to performance tests, and the results are shown in tables 1 and 2.
TABLE 1 storage stability at Normal temperature
TABLE 2 general technical Properties of the emulsified bitumens
Emulsified asphalt
|
Viscosity (S)
|
Asphalt content (%)
|
Oversize residue (%)
|
Wrapping property with coarse aggregate
|
Example 1
|
38
|
59
|
0.012
|
>2/3
|
Example 2
|
36
|
62
|
0.01
|
>2/3
|
Example 3
|
40
|
60
|
0.02
|
>2/3
|
Example 4
|
37
|
60
|
0.25
|
>2/3 |
TABLE 3 demulsification speed of each emulsified asphalt
Emulsified asphalt
|
Degree of mixing stability
|
Example 1
|
Quick crack
|
Example 2
|
Quick crack
|
Example 3
|
Quick crack
|
Example 4
|
Quick crack |
From the results, the cellulose polyether quaternary ammonium salt cationic asphalt emulsifier prepared by the invention can emulsify various asphalt with different types, and the prepared emulsified asphalt is fine and uniform, has good storage stability, and has good aggregate wrapping property and storage stability. The quick-cracking asphalt emulsifier is suitable for spreading road penetrating layer oil or viscous layer oil, is used for chip seal, fog seal, repairing slight net crack of pavement and the like, and has the characteristic of a quick-cracking asphalt emulsifier. The properties of the prepared emulsified asphalt can meet the standard of cationic emulsified asphalt (JTJ052-2000) set by the China department of transportation.
Compared with the prior art, the konjac glucomannan or cellulose is added into the raw materials, so that the asphalt emulsifier prepared by the method has higher hydrophilicity; the primary amine of 2, 2-oxo-bis-ethylamine and the carbonyl of the intermediate I or the intermediate II are subjected to Mannich reaction and are connected in one step to prepare the asphalt emulsifier molecule, and the asphalt emulsifier contains more carboxyl and hydroxyl hydrophilic groups, so that an interface film, a hydration layer and an interface charge layer are correspondingly enhanced, and the stability of the emulsion is improved;
the asphalt emulsifier prepared by the method meets the national standard requirements in all indexes, has good emulsifying performance, can emulsify various types of asphalt, and has fine and uniform emulsified asphalt, good aggregate wrapping property and storage stability. The asphalt emulsifier is suitable for spreading road penetrating layer oil or viscous layer oil, is used for chip sealing, stone chip sealing, fog sealing, repairing slight net crack of pavement and the like, and has the characteristic of quick-crack asphalt emulsifier.
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.