CN111320595A - Secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier and preparation method thereof - Google Patents
Secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/15—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C7/00—Coherent pavings made in situ
- E01C7/08—Coherent pavings made in situ made of road-metal and binders
- E01C7/18—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders
- E01C7/26—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders mixed with other materials, e.g. cement, rubber, leather, fibre
- E01C7/265—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders mixed with other materials, e.g. cement, rubber, leather, fibre with rubber or synthetic resin, e.g. with rubber aggregate, with synthetic resin binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
Abstract
The invention discloses a secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier and a preparation method thereof, wherein the asphalt emulsifier is prepared from the following raw materials in molar ratio: the mol ratio of the cocoyl propyl dimethyl tertiary amine to the alcohol solvent to the water to the epichlorohydrin to the aminoethyl piperazine to the acrylic acid is 1 mol: (4.50-10.00) mol: (14.00-18.00) mol: (1.00-1.15) mol: (1.00-1.20) mol: (1.00-1.20) mol. The alcohol solvent is ethanol, methanol or isopropanol. The asphalt emulsifier has the advantages of easily available synthetic raw materials, low production cost, simple process and no need of high-temperature reaction. Can emulsify various types of asphalt, the prepared emulsified asphalt is fine and uniform, has good storage stability, and can be used for preparing cation or anion emulsified asphalt.
Description
Technical Field
The invention relates to a secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier and a preparation method thereof, belonging to the technical field of fine chemical engineering.
Background
The emulsified asphalt is a liquid asphalt emulsion of asphalt and water which form oil in water under the action of an emulsifier. The emulsified asphalt is mainly classified into cationic emulsified asphalt, anionic emulsified asphalt and nonionic emulsified asphalt. The cation emulsified asphalt has many excellent application characteristics of energy conservation and environmental protection, capability of improving construction conditions, strong adhesion with stones, capability of effectively reducing excessive aging of asphalt and the like, and is widely applied to road construction and pavement maintenance.
The micro-surfacing emulsified asphalt is required to be of a slow-breaking quick-setting type, not only is enough time for mixing with aggregate required, but also can be quickly demulsified and formed after being paved, and is used for quickly opening traffic, the most key factor influencing the pavement performance of the emulsified asphalt is the asphalt emulsifier, the micro-surfacing emulsified asphalt provides high technical requirements for the asphalt emulsifier, the main varieties of the current cationic asphalt emulsifier at home and abroad comprise organic amines, quaternary ammonium salts, imidazolines, amides and the like, and the varieties of the asphalt emulsifier are gradually enriched along with the application of the cationic emulsified asphalt.
U.S. Pat. No. 4,4338136 to C12-18The long-carbon-chain fatty acid reacts with diethylenetriamine under certain conditions to prepare the asphalt emulsifier. The inventor finds that the method has the defects that the prepared asphalt emulsifier is expensive, and when the asphalt emulsifier is used for slurry seal construction, the demulsification time is long, the forming time is slow, and the open traffic time is long. Chinese patent CN1096714 utilizes the reaction of naphthenic acid by-product of oil refinery with alkenyl polyamine to prepare asphalt emulsifier. The inventor finds that the method has the defect that the raw material supply of the emulsifier is greatly restricted, and the method is not beneficial to popularization and application. Chinese patent CN1861721A relates to a rosin cation asphalt emulsifier. The rosin cation asphalt emulsifier with excellent performance is prepared by reacting rosin with alkenyl polyamine to obtain a rosin intermediate, and then condensing the rosin intermediate with different types of quaternary ammonium salt intermediates. The inventors have found that this method has disadvantages in that the reaction step is complicated and a high-temperature reaction is required. Chinese patent CN101712625A relates to a method for synthesizing an amphiprotic slow-breaking quick-setting asphalt emulsifier,oleic acid and polyamine are reacted to generate amide polyamine, and chloroacetic acid is added to generate halogenation reaction to prepare the asphalt emulsifier. The disadvantage of this process is that it requires a high temperature reaction for its preparation. Chinese patent CN101745340A relates to a preparation method of a cationic asphalt emulsifier, wherein a main agent is prepared by reacting mixed organic acid with organic amine to obtain an intermediate and then carrying out quaternization, and auxiliary agents are nonionic surfactants and modification aids. The inventor finds that the method has the disadvantages of complicated preparation steps, high cost and high reaction temperature.
The cationic asphalt emulsifier and the preparation method thereof have the following general defects: the raw materials for preparing the emulsifier have high cost and limited sources, and the emulsifier needs high-temperature reaction during preparation and has high requirements on production experimental equipment.
Therefore, it is necessary to develop a new asphalt emulsifier to enrich the kinds of asphalt emulsifiers, so that the asphalt emulsifier has lower cost and simpler process, and meets the application requirements of road construction and pavement maintenance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier which is low in production cost, simple in process and free of high-temperature reaction and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier, which has a molecular structural formula as follows:
the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier is applied to the preparation of emulsified asphalt, in particular to the preparation of slow-breaking quick-setting or quick-breaking cationic emulsified asphalt and/or anionic emulsified asphalt.
The second aspect of the invention provides a preparation method of a secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier, which comprises the following steps:
(1) mixing aminoethyl piperazine, an alcohol solvent and acrylic acid for reaction to obtain a reaction intermediate I, wherein the structural formula of the reaction intermediate I is as follows:
(2) and (2) gradually adding epoxy chloropropane into the reaction intermediate I, and carrying out mixing reaction to obtain a reaction intermediate II, wherein the structural formula of the reaction intermediate II is as follows:
(3) and (3) adding cocoyl propyl dimethyl tertiary amine into the reaction intermediate II gradually, mixing for reaction, adding water, and mixing for reaction to obtain the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier.
In a third aspect of the present invention, a method for preparing cationic emulsified asphalt is provided, which comprises the following steps: the dosage of the asphalt emulsifier is 1.0-3.0% of the total mass of the prepared emulsified asphalt, the asphalt emulsifier is added with water to prepare an aqueous solution, industrial hydrochloric acid is used for adjusting the pH value to 2-3, and the aqueous solution is heated to 60-70 ℃ to prepare a soap solution; and emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the cation emulsified asphalt.
The cation emulsified asphalt prepared by the preparation method.
In a fourth aspect of the present invention, a method for preparing anionic emulsified asphalt is provided, which comprises the following steps: the dosage of the asphalt emulsifier is 1.0-3.0% of the total mass of the prepared emulsified asphalt, the asphalt emulsifier is added with water to prepare an aqueous solution, the pH value is adjusted to 10-11 by sodium hydroxide, and the aqueous solution is heated to 60-70 ℃ to prepare a soap solution; and emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the anionic emulsified asphalt.
The anionic emulsified asphalt prepared by the preparation method.
In a fifth aspect of the present invention, a micro-surfacing construction method is provided, which includes the following steps: mixing and stirring the prepared cation emulsified asphalt with basalt, cement, water and cation SBR latex according to a set proportion, and paving by a micro-surfacing paver to form a pavement maintenance protective layer.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) the raw materials of the invention are added with acrylic acid, so that the asphalt emulsifier prepared by the invention has larger hydrophilicity and anionic chemical structure; the addition of the aminoethyl piperazine, the epichlorohydrin and the cocoyl propyl dimethyl tertiary amine enables the prepared asphalt emulsifier molecule to have a secondary amide cyclic amine quaternary ammonium salt amphoteric chemical structure, and the charge strength of the asphalt emulsifier molecule is enhanced.
The asphalt emulsifier has more hydrophilic groups in the structural formula, and hydroxyl, amino, carboxyl, quaternary ammonium salt and amide groups correspondingly enhance an interfacial film, a hydration layer and an interfacial charge layer, so that the stability of the emulsion is improved.
(2) The invention adopts specific raw materials of acrylic acid, aminoethyl piperazine, epichlorohydrin and cocoyl propyl dimethyl tertiary amine to generate the asphalt emulsifier with a certain HLB value, the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier prepared by the invention has good emulsifying performance, various performance indexes of the prepared emulsified asphalt are excellent, the emulsified asphalt can emulsify various types of asphalt, and the prepared emulsified asphalt is fine and uniform and has good aggregate wrapping property and storage stability. The prepared emulsified asphalt is detected according to the cationic emulsified asphalt industry standard (JTJ052-2000) formulated by the China department of transportation, and the performance meets the standard requirement. The asphalt emulsifier is suitable for spreading road penetrating layer oil or viscous layer oil, is used for rubble seal, stone chip seal, fog seal, repairing slight net crack of pavement and the like, is used for construction of slurry seal, micro-surfacing and the like, and has the characteristics of slow-crack quick-setting type or quick-crack type asphalt emulsifier. The emulsified asphalt prepared by the emulsifier of the invention can make the mixture have better fluidity and permeability, is beneficial to filling and repairing cracks of the pavement and improves the compactness and the waterproofness of the pavement.
(3) The cocoyl propyl dimethyl tertiary amine serving as the raw material of the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier is cheap and has wide sources compared with the raw material used by the conventional cationic asphalt emulsifier, and the production cost of the asphalt emulsifier is low.
(4) In the prior art, the reaction temperature of the amido amine emulsifier is generally controlled at 140-180 ℃, but the preparation method of the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier has simple process, does not need high-temperature reaction, and reduces energy consumption.
(5) The molecular structure of the asphalt emulsifier of the invention simultaneously has anionic groups and cationic groups, the amphoteric asphalt emulsifier can be suitable for different environments, and has the characteristics of cationic asphalt emulsifier in acid solution and anionic asphalt emulsifier in alkaline solution.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The raw materials and reagents used in the embodiment of the invention are all conventional chemical products, and can be purchased in the market.
In order to enrich the variety of asphalt emulsifiers, the invention provides a secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier, the molecular structural formula of which is as follows:
the structure of the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier is analyzed, hydroxyl, amino, carboxyl, quaternary ammonium salt and amido hydrophilic groups are effectively combined in a certain group form, and then an appropriate carbon chain structure and other lipophilic groups are added to form the asphalt emulsifier with the novel structure. Meanwhile, when the structure is designed, a specific structure (such as cocoyl propyl dimethyl tertiary amine and aminoethyl piperazine with a cyclic structure) is adopted to increase the steric hindrance and the charge intensity of the hydrophilic base end, and the adsorption effect of the hydrophilic group and the surface of aggregate is adjusted, so that the mixing time of the emulsifier and the aggregate can be controlled, and the slow-breaking and quick-setting asphalt emulsifier is formed. Tests prove that the mixing time of the aggregate and basalt-grade aggregate is 2 minutes and 10 seconds.
Aiming at the asphalt emulsifier, the invention also provides a preparation method thereof, which comprises the following steps:
(1) mixing aminoethyl piperazine, an alcohol solvent and acrylic acid for reaction to obtain a reaction intermediate I, wherein the structural formula of the reaction intermediate I is as follows:
(2) and (2) gradually adding epoxy chloropropane into the reaction intermediate I, and carrying out mixing reaction to obtain a reaction intermediate II, wherein the structural formula of the reaction intermediate II is as follows:
(3) and (3) adding cocoyl propyl dimethyl tertiary amine into the reaction intermediate II gradually, mixing for reaction, adding water, and mixing for reaction to obtain the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier.
In some preferred technical schemes of the invention, the mole ratio of the cocoyl propyl dimethyl tertiary amine, the alcohol solvent, the water, the epichlorohydrin, the aminoethyl piperazine and the acrylic acid is 1 mol: (4.50-10.00) mol: (14.00-18.00) mol: (1.00-1.15) mol: (1.00-1.20) mol: (1.00-1.20) mol.
Through a large number of experimental verifications and analyses, the raw materials with the molar ratio enable the performance of the amphoteric asphalt emulsifier containing the cyclic amine quaternary ammonium salt of the secondary amide, which is prepared by the invention, to be ideal, and the raw materials with inappropriate proportioning relationship cannot form the amphoteric asphalt emulsifier containing the cyclic amine quaternary ammonium salt of the secondary amide.
In some preferable technical schemes of the invention, the alcohol solvent is ethanol, methanol or isopropanol, a large number of experiments prove and analyze that the asphalt emulsifier prepared by selecting the alcohol solvent has better effect according to the requirement of the amphoteric asphalt emulsifier of secondary amide cyclic amine quaternary ammonium salt prepared by the invention. Moreover, through experimental research, the inventor unexpectedly finds that when the alcohol solvent is ethanol or methanol, the fast-cracking asphalt emulsifier is obtained; when the alcohol solvent is isopropanol, the obtained slow-breaking quick-setting asphalt emulsifier provides possibility of multiple uses.
In some preferred embodiments of the present invention, in step (1), the reaction temperature is 60-80 ℃, preferably 65-75 ℃, and the reaction time is 2-3 h.
In some preferred embodiments of the present invention, in step (2), the reaction temperature is 60-80 ℃, preferably 65-75 ℃, and the reaction time is 2-3 h.
In some preferred technical schemes of the invention, in the step (3), the reaction temperature is 60-80 ℃, preferably 65-75 ℃, and the reaction time after adding water is 3-4 h.
In some preferred technical schemes of the invention, the preparation method of the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier specifically comprises the following steps:
(1) adding aminoethyl piperazine into a reaction container, adding an alcohol solvent, heating, stirring and mixing, adding acrylic acid in batches, and stirring and reacting for 2-3 hours at 60-80 ℃ after the addition is finished to obtain a reaction intermediate I;
(2) gradually adding epoxy chloropropane into the reaction intermediate I, and reacting at 60-80 ℃ for 2-3h to obtain a reaction intermediate II;
(3) and gradually adding the cocoyl propyl dimethyl tertiary amine into the reaction intermediate II, reacting for 0.5h at 60-80 ℃ after the addition is finished, adding water, and reacting for 3-4h at 60-80 ℃ after the water addition is finished to obtain the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier.
The secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier is applied to the preparation of emulsified asphalt, in particular to the preparation of slow-breaking quick-setting or quick-breaking cationic emulsified asphalt and/or anionic emulsified asphalt.
The invention takes acrylic acid as a reaction raw material of the asphalt emulsifier, introduces carboxyl in the molecular structure of the asphalt emulsifier by adding the acrylic acid, and increases the hydrophilicity of the asphalt emulsifier and the compatibility of the emulsifier and asphalt. In addition, the influence of the carbon chain length on the HLB (hydrophilic-lipophilic balance) and CMC (critical micelle concentration) of the asphalt emulsifier is comprehensively considered, and the aminoethyl piperazine, the epichlorohydrin and the cocoyl propyl dimethyl tertiary amine are selected as raw materials for reaction, so that the HLB of the prepared asphalt emulsifier is in the optimal range, and the emulsifying property of the asphalt emulsifier is improved. In particular to the preparation of slow-breaking quick-setting or quick-breaking cationic emulsified asphalt and/or anionic emulsified asphalt, and has wide application prospect in micro-surfacing construction.
In the process of research on new asphalt emulsifiers, a plurality of amine compounds are tested, however, in view of the diversity and complexity of organic compounds and their reactions and uncontrollable nature, not all amine compounds can react with acrylic acid, and even though an amphoteric compound with a specific structure is obtained, the amine compounds can not be used as asphalt emulsifiers, and the type and performance of the asphalt emulsifier can not be predicted, which causes great difficulty in developing a new asphalt emulsifier with better performance.
Aiming at the amphoteric asphalt emulsifier of the secondary amide cyclic amine quaternary ammonium salt, the invention also provides a preparation method of the cationic emulsified asphalt, which comprises the following steps: the dosage of the asphalt emulsifier is 1.0-3.0% of the total mass of the prepared emulsified asphalt, the asphalt emulsifier is added with water to prepare an aqueous solution, industrial hydrochloric acid is used for adjusting the pH value to 2-3, and the aqueous solution is heated to 60-70 ℃ to prepare a soap solution; and emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the cation emulsified asphalt.
The cation emulsified asphalt prepared by the preparation method.
Aiming at the amphoteric asphalt emulsifier of the secondary amide cyclic amine quaternary ammonium salt, the invention also provides a preparation method of the anionic emulsified asphalt, which comprises the following steps: the dosage of the asphalt emulsifier is 1.0-3.0% of the total mass of the prepared emulsified asphalt, the asphalt emulsifier is added with water to prepare an aqueous solution, the pH value is adjusted to 10-11 by sodium hydroxide, and the aqueous solution is heated to 60-70 ℃ to prepare a soap solution; and emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the anionic emulsified asphalt.
The anionic emulsified asphalt prepared by the preparation method.
Aiming at the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier, the invention also provides a micro-surfacing construction method, which comprises the following steps: mixing and stirring the prepared cation emulsified asphalt with basalt, cement, water and cation SBR latex according to a set proportion, and paving by a micro-surfacing paver to form a pavement maintenance protective layer.
In some of the above preferable micro-surfacing construction methods, the mass ratio of basalt, cement, water, cationic emulsified asphalt, and cationic SBR latex is 100: (0.5-4.0): (7.0-15.0): (10.0-17.0): (0.2-3.0).
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific examples and comparative examples.
Example 1
(1) Preparation of secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier:
1) 141.9g of aminoethylpiperazine and 300g of isopropanol were charged into a reactor, and mixed with heating and stirring. Then, 79.3g of acrylic acid was gradually added thereto, and the mixture was stirred at 75 ℃ for 2 hours to react, thereby obtaining a reaction intermediate I.
2) And gradually adding 97.07g of epoxy chloropropane into the reaction intermediate I, and reacting for 2h at 75 ℃ after the addition is finished to obtain a reaction intermediate II.
3) And (3) adding 284.5g of cocoyl propyl dimethyl tertiary amine into the reaction intermediate II, reacting at 75 ℃ for 0.5h after the addition is finished, adding 300g of water, and reacting at 75 ℃ for 3h after the water addition is finished to obtain the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier which is reserved for the test of emulsified asphalt.
The synthesized product is subjected to FTIR detection after recrystallization, separation and purification, and the results are as follows: 3305cm-1Is the stretching vibration absorption peak of O-H, 3075cm-1Is the absorption peak of the stretching vibration of N-H, 2929cm-1Is asymmetric stretching vibration absorption peak of methylene, 2852cm-1Is the symmetric stretching vibration peak of methylene, 1654cm-1Is C ═ O double bond stretching vibration absorption peak of carboxylic acid, 1558cm-1Is a C ═ O double bond stretching vibration absorption peak of secondary amide, 1463cm-1Is asymmetric bending vibration of methylene group, 1387cm-1Asymmetric bending vibration for methyl group, 1172cm-1Is C-N stretching vibration absorption peak, 1048cm-1Is C-O stretching vibration absorption peak, 883cm-1Is the out-of-plane bending vibration absorption peak of C-H, 718cm-1The absorption peak of the oscillating vibration in the methylene plane is shown.
The reaction equation is as follows:
(2) preparing emulsified asphalt:
300g of AH-90# asphalt is taken and heated to 125 ℃, 12.5g of the asphalt emulsifier prepared in the embodiment is added into 200g of water, the pH value is adjusted to 2-3 by industrial hydrochloric acid, and the mixture is heated to 65 ℃ to prepare soap solution. And emulsifying the asphalt and the emulsifier soap solution by a colloid mill to prepare the cationic emulsified asphalt.
(3) And (3) detecting the performance of 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 56%, the residue on the screen is 0.02%, the coating area of the emulsified asphalt and mineral aggregate is larger than 2/3, and the charge is positive ions.
Mixing by adopting a mixture: 100g of basalt-grade stone, 2.0g of cement, 9.0g of water, 13.0g of emulsified asphalt and 0.4g of cationic SBR latex, and the mixing time is 2 minutes and 10 seconds. The asphalt emulsifier can achieve the purpose of rapidly opening traffic within 60min, and shows that the emulsified asphalt prepared by the asphalt emulsifier is slow-cracking and quick-setting type cationic emulsified asphalt, and the asphalt emulsifier is cationic slow-cracking and quick-setting type micro-surfacing asphalt emulsifier.
Example 2
(1) Preparation of secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier:
1) 141.9g of aminoethylpiperazine and 300g of absolute ethanol were charged into a reactor, and the mixture was heated with stirring. Then, 79.3g of acrylic acid was gradually added thereto, and the mixture was stirred at 65 ℃ to react for 3 hours to obtain a reaction intermediate I.
2) And gradually adding 97.07g of epoxy chloropropane into the reaction intermediate I, and reacting for 2h at 75 ℃ after the addition is finished to obtain a reaction intermediate II.
3) And (3) adding 284.5g of cocoyl propyl dimethyl tertiary amine into the reaction intermediate II, reacting at 75 ℃ for 0.5h after the addition is finished, adding 300g of water, and reacting at 75 ℃ for 3h after the water addition is finished to obtain the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier which is reserved for the test of emulsified asphalt.
(2) Preparing emulsified asphalt:
300g of AH-70# asphalt is taken and heated to 125 ℃, 12.5g of the asphalt emulsifier prepared in the embodiment is added into 200g of water, the pH value is adjusted to 2-3 by industrial hydrochloric acid, and the mixture is heated to 65 ℃ to prepare soap solution. And emulsifying the asphalt and the emulsifier soap solution by a colloid mill to prepare the cationic emulsified asphalt.
(3) And (3) detecting the performance of the emulsified asphalt:
the detection method is the same as the example 1, and the detection result is as follows: the emulsified asphalt is uniform and fine, the asphalt content is 59%, the residual quantity on the screen is 0.03%, the coating area of the emulsified asphalt and mineral aggregate is greater than 2/3, and the charge is positive ions.
Mixing by adopting a mixture: 100g of basalt-grade stone, 2.0g of cement, 8.0g of water, 13.0g of emulsified asphalt and 0.4g of cationic SBR latex, and the mixing time is 10 seconds. The emulsified asphalt prepared by the asphalt emulsifier is fast-cracking type cation emulsified asphalt, and the asphalt emulsifier is fast-cracking type cation.
Example 3
(1) Preparation of secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier:
1) 141.9g of aminoethylpiperazine and 300g of methanol were charged into a reactor, and they were mixed with heating and stirring. Then, 79.3g of acrylic acid was gradually added thereto, and the mixture was stirred at 65 ℃ to react for 3 hours to obtain a reaction intermediate I.
2) And gradually adding 97.07g of epoxy chloropropane into the reaction intermediate I, and reacting for 3h at 65 ℃ after the addition is finished to obtain a reaction intermediate II.
3) And (3) adding 284.5g of cocoyl propyl dimethyl tertiary amine into the reaction intermediate II gradually, reacting at 65 ℃ for 0.5h after the addition is finished, adding 300g of water, and reacting at 65 ℃ for 4h after the water addition is finished to obtain the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier which is reserved for the test of emulsified asphalt.
(2) Preparing emulsified asphalt:
300g of AH-90# asphalt is taken and heated to 125 ℃, 12.5g of the asphalt emulsifier prepared in the embodiment is added into 200g of water, the pH value is adjusted to 2-3 by industrial hydrochloric acid, and the mixture is heated to 65 ℃ to prepare soap solution. And emulsifying the asphalt and the emulsifier soap solution by a colloid mill to prepare the cationic emulsified asphalt.
(3) And (3) detecting the performance of the emulsified asphalt:
the detection method is the same as that of example 1, and the results are as follows: the emulsified asphalt prepared by the embodiment is uniform and fine, the asphalt content is 56%, the residue on the screen is 0.04%, the coating area of the emulsified asphalt and mineral aggregate is larger than 2/3, and the charge is positive ions.
Mixing by adopting a mixture: 100g of basalt-grade stone, 2.0g of cement, 8.0g of water, 13.0g of emulsified asphalt and 0.4g of cationic SBR latex, and the mixing time is 8 seconds. The emulsified asphalt prepared by the asphalt emulsifier is fast-cracking type cation emulsified asphalt, and the asphalt emulsifier is fast-cracking type cation.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier is characterized in that the molecular structural formula of the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier is as follows:
2. the method for preparing the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier according to claim 1, which is characterized by comprising the following steps:
(1) mixing aminoethyl piperazine, an alcohol solvent and acrylic acid for reaction to obtain a reaction intermediate I, wherein the structural formula of the reaction intermediate I is shown in the specification
(2) Adding epoxy chloropropane into the reaction intermediate I, and mixing and reacting to obtain a reaction intermediate II, wherein the structural formula of the reaction intermediate II is shown in the specification
(3) Adding cocoyl propyl dimethyl tertiary amine into the reaction intermediate II, mixing for reaction, adding water, and mixing for reaction to obtain the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier.
3. The process according to claim 2, wherein the molar ratio of cocoyl propyl dimethyl tertiary amine, alcohol solvent, water, epichlorohydrin, aminoethyl piperazine, acrylic acid is 1 mol: (4.50-10.00) mol: (14.00-18.00) mol: (1.00-1.15) mol: (1.00-1.20) mol: (1.00-1.20) mol.
4. The process according to claim 3, wherein the alcoholic solvent is ethanol, methanol or isopropanol.
5. The process according to claim 2, wherein in step (1), the reaction temperature is 60 to 80 ℃, preferably 65 to 75 ℃, and the reaction time is 2 to 3 hours;
in the step (2), the reaction temperature is 60-80 ℃, preferably 65-75 ℃, and the reaction time is 2-3 h;
in the step (3), the reaction temperature is 60-80 ℃, preferably 65-75 ℃, and the reaction time after adding water is 3-4 h.
6. The method of claim 2, comprising the steps of:
(1) adding aminoethyl piperazine into a reaction container, adding an alcohol solvent, heating, stirring and mixing, adding acrylic acid in batches, and stirring and reacting for 2-3 hours at 60-80 ℃ after the addition is finished to obtain a reaction intermediate I;
(2) gradually adding epoxy chloropropane into the reaction intermediate I, and reacting at 60-80 ℃ for 2-3h to obtain a reaction intermediate II;
(3) and gradually adding the cocoyl propyl dimethyl tertiary amine into the reaction intermediate II, reacting for 0.5h at 60-80 ℃ after the addition is finished, adding water, and reacting for 3-4h at 60-80 ℃ after the water addition is finished to obtain the secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier.
7. Use of a secondary amide cyclic amine quaternary ammonium salt amphoteric bitumen emulsifier according to claim 1 for preparing slow-breaking quick-setting or quick-breaking cationic emulsified bitumen and/or anionic emulsified bitumen.
8. A preparation method of emulsified asphalt is characterized by comprising a preparation method of cationic emulsified asphalt or a preparation method of anionic emulsified asphalt; the preparation method of the cationic emulsified asphalt comprises the following steps: the dosage of the asphalt emulsifier is 1.0-3.0% of the total mass of the prepared emulsified asphalt, the asphalt emulsifier of claim 1 is added with water to prepare an aqueous solution, the pH value is adjusted to 2-3, and the aqueous solution is heated to 60-70 ℃ to prepare a soap solution; emulsifying the heated asphalt and emulsifier soap solution through a colloid mill to prepare cation emulsified asphalt;
the preparation method of the anionic emulsified asphalt comprises the following steps: the dosage of the asphalt emulsifier is 1.0-3.0% of the total mass of the prepared emulsified asphalt, the asphalt emulsifier of claim 1 is added with water to prepare an aqueous solution, the pH value is adjusted to 10-11, and the aqueous solution is heated to 60-70 ℃ to prepare a soap solution; and emulsifying the heated asphalt and the emulsifier soap solution through a colloid mill to prepare the anionic emulsified asphalt.
9. The use of the slow-breaking quick-setting cationic emulsified asphalt prepared by the method of claim 8 in micro surfacing.
10. A construction method of a micro-surfacing is characterized by comprising the following steps: mixing and stirring the cationic emulsified asphalt prepared by the method of claim 8 with basalt, cement, water and cationic SBR latex according to a set proportion, and paving by a micro-surfacing paver to form a pavement maintenance protective layer;
preferably, the mass ratio of the basalt to the cement to the water to the cationic emulsified asphalt to the cationic SBR latex is 100: (0.5-4.0): (7.0-15.0): (10.0-17.0): (0.2-3.0).
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