CN104941509B - A kind of micro-surface area is with splitting fast solidifying type asphalt emulsifier and preparation method thereof slowly - Google Patents
A kind of micro-surface area is with splitting fast solidifying type asphalt emulsifier and preparation method thereof slowly Download PDFInfo
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Abstract
The invention discloses a kind of micro-surface area with splitting fast solidifying type asphalt emulsifier and preparation method thereof slowly.This prepares the method for asphalt emulsifier, comprises the steps: 1) by organic acid, organic polyamine and solvent mixing carry out amidation process after, carry out cyclization under vacuum, react the solvent in complete removing system and water, obtain intermediate；2) until step 1) after the cooling of gained reaction system, by the ethanol solution of graft modification agent and step 1) gained intermediate carries out additive reaction, react complete and obtain described asphalt emulsifier.This asphalt emulsifier, it is extensive that it prepares raw material sources, and preparation method is simple, and reaction condition is gentle, environmental friendliness, it is easy to industrialized production.This asphalt emulsifier has good emulsifying capacity to different pitches, and the emulsified asphalt storage stability of preparation is good, microgranule uniform and smooth, good with the adaptability that gathers materials, and splits fast solidifying effect slowly obvious, can be used for preparing micro-surface area emulsified asphalt.
Description
Technical field
The invention belongs to petrochemical industry, relate to a kind of micro-surface area with splitting fast solidifying type asphalt emulsifier and preparation side thereof slowly
Method.
Background technology
Micro-surface area be use special mechanical equipment polymer modification emulsified asphalt, thickness to be gathered materials, filler, water and interpolation
Agent etc. are mixed and stirred into slurry mixture pave on former road surface according to design proportionings, and quickly open to traffic there is high antiskid
Laminate structure with endurance quality.Micro zooming, as an important branch of emulsified asphalt technology, was the most both used
In bituminous paving, it is also used for the cover of cement concrete pavement, is mostly used for bituminous paving and cement concrete in China
Bridge floor, tunnel Covered face of Smooth Slide etc. are it is considered to be repairing road rut and other multiple road diseases most effective, most economical
One of means.
Micro-surface area emulsified asphalt requires as splitting fast solidifying type slowly, both required with gather materials have enough can the mixing time, also want
Energy breakdown of emulsion molding rapidly after paving, quick open to traffic, it is real that these performance requirements depend on asphalt emulsifier
Existing.Micro-surface area proposes the highest technology requirement to asphalt emulsifier, its performance quality will directly affect construction quality and
Progress.It is cationic emulsifier that emulsifying agent used by micro-surface area emulsified asphalt requires, in practice it has proved that, by cationic
Emulsified asphalt prepared by asphalt emulsifier is strong with stone surface absorption affinity, and antistrip performance is good, and shaping speed is fast, in early days
Intensity is high, but owing to its hydrophilic group has stronger polarity, therefore de-emulsification speed is fast, cause can the mixing time short,
And micro-surfacing mixture is cold mixing cold-application type compound, in thin pulp state in work progress, it is contemplated that construction workability and
The quickly requirement of open to traffic, it is therefore necessary to control emulsified asphalt with gather materials can the mixing time.
At present micro-surface area asphalt emulsifier generally exists that to split fast solidifying effect slowly bad, to different pitches and the adaptability that gathers materials
Difference, phase separation is difficult to control to, and emulsifying agent preparation process is lengthy and tedious, and formula is complicated, need to add multiple auxiliary agent, cause it
The shortcoming such as raw material sources are restricted and environment friendly is the best.
Summary of the invention
It is an object of the invention to provide a kind of micro-surface area with splitting fast solidifying type asphalt emulsifier and preparation method thereof slowly.
The method preparing asphalt emulsifier that the present invention provides, comprises the steps:
1), after the mixing of organic acid, organic polyamine and solvent being carried out amidation process, it is cyclized under vacuum
Reaction, reacts the solvent in complete removing system and water, obtains intermediate；
2) until step 1) after the cooling of gained reaction system, by the ethanol solution of graft modification agent and step 1) in gained
Mesosome carries out additive reaction, reacts complete and obtains described asphalt emulsifier.
The step 1 of said method) in, described organic acid is selected from capric acid, lauric acid, tetradecylic acid, Palmic acid, tristearin
At least one in acid, oleic acid, aphthenic acids, ready denier oil acid and rosin acid；
At least one in ethylenediamine, diethylenetriamine, triethylene tetramine and TEPA of described organic polyamine；
Described solvent is 90-120 DEG C selected from toluene, meta-xylene, o-Dimethylbenzene, xylol, mixed xylenes and boiling range
In petroleum ether at least one；Wherein, described mixed xylenes is xylol, o-Dimethylbenzene, meta-xylene and ethylbenzene
Mixture；
The molar ratio of organic acid and organic polyamine is 1:1～2, concretely 1:1.1,1:1.2,1:1.3,
1:1.4,1:1.5,1:1.6,1:1.7,1:1.8 or 1:1.9；
The consumption of described solvent is the 20%-50% of the gross weight of described organic acid and organic polyamine, concretely 25-40%,
Can be more specifically 20%, 30%, 40% or 50%；
In described vacuum condition, vacuum is 0.080-0.098MPa, specially 0.092MPa.
Described step 1) in, in described amidation reaction steps, temperature is 140-180 DEG C, concretely 150-165 DEG C,
Can be more specifically 160 DEG C, 170 DEG C；Time is 2 hours-4 hours, concretely 2.5-3.5 hour, more specifically may be used
It it is 2.0 hours, 3 hours；
In described cyclization step, temperature is 220-260 DEG C, concretely 230-250 DEG C, more specifically can be 240 DEG C；
Time is 2 hours-6 hours, and the time is 3-4.5 hour, can be more specifically 4 hours, 5 hours.
Described step 2) in, described graft modification agent selected from acrylic acid methyl ester., ethyl acrylate, 2-(Acryloyloxy)ethanol,
Hydroxypropyl acrylate, butyl acrylate, Isobutyl 2-propenoate, tert-butyl acrylate and at least the one of hy-droxybutyl
Kind.
The molar ratio of described graft modification agent and described intermediate is 1:1-1.5, concretely 1:1.1,1:1.2,1:1.3,
1:1.4；
In the ethanol solution of described graft modification agent, the mass percentage concentration of graft modification agent is 70-90%, concretely
75-85%, can be more specifically 80%；
Described step 2) in cooling step, the final temperature after cooling is 70-90 DEG C, concretely 75-85 DEG C；
In described additive reaction step, temperature is 80-110 DEG C, concretely 90-105 DEG C, more specifically can be 100 DEG C,
Time is 1 hour-3 hours, concretely 1.5-2.5 hour, can be more specifically 2 hours.
It addition, the asphalt emulsifier prepared according to the method described above and the application in asphalt emulsification of this asphalt emulsifier,
Fall within protection scope of the present invention.Wherein, described asphalt emulsification is the asphalt emulsification carried out at micro-surface area.
The innovative point of the present invention is the design of emulsifying agent structure, is with imidazoline structure as matrix, passes through
Modified to it, increase hydrophilic group end spaces steric hindrance, regulation hydrophilic group and the adsorption of surface of aggregate, reach to control
Emulsified asphalt with gather materials can the purpose of mixing time.Modified emulsifying agent, on the premise of not affecting emulsifiability
Its slow fragility can be improved significantly, have with this emulsified asphalt prepared and good split fast solidifying effect slowly, reach micro-table
Locate the requirement of quick open to traffic.
The asphalt emulsifier that the present invention provides, it is extensive that it prepares raw material sources, and preparation method is simple, and reaction condition is gentle,
Environmental friendliness, it is easy to industrialized production.This asphalt emulsifier has good emulsifying capacity to different pitches, preparation
Emulsified asphalt storing good stability, microgranule uniform and smooth, good with the adaptability that gathers materials, split fast solidifying effect slowly obvious, available
In preparing micro-surface area emulsified asphalt.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following example.Institute
Method of stating is conventional method if no special instructions.Described raw material the most all can obtain from open commercial sources
?.
Embodiment 1,
The lauric acid that mol ratio is 1:1.4 is joined there-necked flask with ethylenediamine, and addition accounts for reaction raw materials gross weight
For the o-Dimethylbenzene of 40wt%, stirring is warming up to 160 DEG C, and steady temperature carries out amidation process 2.0 hours, then
(vacuum 0.092MPa) rising temperature of reaction system is to 240 DEG C under vacuum, proceeds cyclization 4.0
Hour, desolvation and the water of generation, obtain intermediate, after temperature is down to 90 DEG C, will be with intermediate mol ratio
The acrylic acid methyl ester. compound of 1:1.3 is formulated as the ethanol solution of 90wt%, and is slowly added dropwise to intermediate, drips
After adding, under the conditions of 100 DEG C, stirring carries out additive reaction 3.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 1.8wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 5.0wt% of asphalt quality (solid content account for), being regulated pH value with acid is 5.0, is heated to 60 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-70 matrix pitch being heated to 130 DEG C
Blue or green content is the emulsified asphalt of 63wt%.
According to " highway engineering Colophonium and Asphalt Mixture Experiment code " (JTG E20--2011), to above-mentioned prepared
Emulsified asphalt carries out performance test: emulsified asphalt is cationic, and volume average particle sizes is 3.0 μm, 1 day and 5 days
Bin stability be respectively 0.6% and 3.0%, on sieve, surplus is 0.01%, and evaporated residue content is 63.0wt%,
Mix and stir as slow breaking with MS-3 type basalt aggregate, can be more than 170s, presetting period 32min the mixing time.
Comparative example 1
The intermediate prepared the amido in its structure not being carried out graft modification in embodiment 1 as asphalt emulsifier,
For preparing emulsified asphalt, prepare the condition of emulsified asphalt with embodiment 1.Many prepared emulsified asphalts carry out performance
Test: emulsified asphalt is cationic, and volume average particle sizes is 3.6 μm, the bin stability of 1 day and 5 days is respectively
Being 0.7% and 4.8%, on sieve, surplus is 0.05%, and evaporated residue content is 64.0wt%, with the MS-3 type Black Warrior
Rock gathers materials and mixes and stirs, and can be 105s the mixing time, presetting period 35min.
Embodiment 2
Capric acid that mol ratio is 1:1 is added in there-necked flask with ethylenediamine, and adds and account for reaction raw materials gross weight and be
The toluene of 20wt%, stirring is warming up to 140 DEG C, and steady temperature carries out amidation process 4.0 hours, then at vacuum bar
Under part, (vacuum 0.092MPa) rising temperature of reaction system is to 220 DEG C, proceeds cyclization 6.0 hours,
Desolvation and the water of generation, obtain intermediate, after temperature is down to 70 DEG C, will be 1:1.0 with intermediate mol ratio
Acrylic acid methyl ester. compound be formulated as the ethanol solution of 70wt%, and be slowly added dropwise to intermediate, after dropping
Under the conditions of 80 DEG C, stirring carries out additive reaction 1.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 3.0wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 3.0wt% of asphalt quality (solid content account for), being regulated pH value with hydrochloric acid is 2.0, is heated to
55 DEG C, by colloid mill and the CNOOC's Suizhong abundant shear-mixed system of 36-1AH-90 matrix pitch being heated to 120 DEG C
It is the emulsified asphalt of 60wt% for going out bitumen content.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
2.1 μm, the bin stability of 1 day and 5 days is respectively 0.4% and 2.3%, and on sieve, surplus is 0.01%, evaporates residual
Staying thing content is 62.4wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can be more than 180s the mixing time,
Presetting period 25min.
Comparative example 2
The intermediate prepared the amido in its structure not being carried out graft modification in embodiment 2 as asphalt emulsifier,
For preparing emulsified asphalt, prepare the condition of emulsified asphalt with embodiment 2.Prepared emulsified asphalt is carried out performance
Test: emulsified asphalt is cationic, and volume average particle sizes is 2.6 μm, the bin stability of 1 day and 5 days is respectively
Being 0.6% and 3.1%, on sieve, surplus is 0.04%, and evaporated residue content is 62.2wt%, with the MS-3 type Black Warrior
Rock gather materials mix and stir into, can be 75s the mixing time, presetting period 29min.
Embodiment 3
Capric acid that mol ratio is 1:1.2 and ethylenediamine are joined there-necked flask, and adds and account for reaction raw materials gross weight and be
The meta-xylene of 30wt%, stirring is warming up to 150 DEG C, and steady temperature carries out amidation process 3.0 hours, then very
Under empty condition, (vacuum 0.092MPa) rising temperature of reaction system is to 230 DEG C, proceeds cyclization 5.0 little
Time, desolvation and the water of generation, obtain intermediate, after temperature is down to 80 DEG C, will be 1 with intermediate mol ratio:
The ethyl acrylate compound of 1.2 is formulated as the ethanol solution of 80wt%, and is slowly added dropwise to intermediate, drips
After Biing, under the conditions of 90 DEG C, stirring carries out additive reaction 2.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 2.0wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 3.5wt% of asphalt quality (solid content account for), being regulated pH value with acid is 3.0, is heated to 70 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-70 matrix pitch being heated to 110 DEG C
Blue or green content is the emulsified asphalt of 65wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
2.4 μm, the bin stability of 1 day and 5 days is respectively 0.4% and 3.2%, and on sieve, surplus is 0.01%, evaporates residual
Staying thing content is 65.0wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can be more than 180s the mixing time,
Presetting period 28min.
Comparative example 3
The imidazoline intermediate prepared the amido in its structure not being carried out graft modification in embodiment 3 is as Colophonium
Emulsifying agent, is used for preparing emulsified asphalt, prepares the condition of emulsified asphalt with embodiment 3.Many prepared emulsified asphalts
Carrying out performance test: emulsified asphalt is cationic, volume average particle sizes is 2.8 μm, and the storage of 1 day and 5 days is steady
Qualitative respectively 0.6% and 3.5%, on sieve, surplus is 0.05%, and evaporated residue content is 64.9wt%, with MS-3
Type basalt aggregate is mixed and stirred, and can be 90s the mixing time, presetting period 35min.
Embodiment 4
Tetradecylic acid that mol ratio is 1:1.6 and diethylenetriamine are joined there-necked flask, and adds that to account for reaction raw materials total
Weight is the o-Dimethylbenzene of 50wt%, and stirring is warming up to 170 DEG C, and steady temperature carries out amidation process 3.0 hours,
(vacuum 0.092MPa) rising temperature of reaction system is to 250 DEG C the most under vacuum, proceeds cyclisation anti-
Answer 3.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 80 DEG C, will rub with intermediate
You are formulated as the ethanol solution of 80wt% than the butyl acrylate compound for 1:1.4, and are slowly added dropwise to intermediate,
After dropping, under the conditions of 90 DEG C, stirring carries out additive reaction 2.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 1.0wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 4.0wt% of asphalt quality (solid content account for), being regulated pH value with acid is 4.0, is heated to 45 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-90 matrix pitch being heated to 140 DEG C
Blue or green content is the emulsified asphalt of 50wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
2.7 μm, the bin stability of 1 day and 5 days is respectively 0.5% and 4.0%, and on sieve, surplus is 0.03%, evaporates residual
Staying thing content is 51.4wt%, with MS-3 type basalt aggregate mix and stir in split type, can be 140s the mixing time, just
Solidifying time 20min.
Comparative example 4
The intermediate prepared the amido in its structure not being carried out graft modification in embodiment 4 as asphalt emulsifier,
For preparing emulsified asphalt, prepare the condition of emulsified asphalt with embodiment 4.Prepared emulsified asphalt is carried out performance
Test: emulsified asphalt is cationic, and volume average particle sizes is 3.0 μm, the bin stability of 1 day and 5 days is respectively
Being 0.7% and 4.5%, on sieve, surplus is 0.1%, and evaporated residue content is 50.1wt%, with the MS-3 type Black Warrior
Rock gathers materials and mixes and stirs, and can be 60s the mixing time, presetting period 25min.
Embodiment 5
The rosin acid that mol ratio is 1:1.3 is joined in there-necked flask with ethylenediamine, and addition accounts for reaction raw materials gross weight
Amount is the petroleum ether (boiling range is 90～120 DEG C) of 20wt%, and stirring is warming up to 150 DEG C, and steady temperature carries out amidatioon
Reacting 3.0 hours, (vacuum 0.092MPa) rising temperature of reaction system is to 230 DEG C the most under vacuum,
Proceed cyclization 5.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 90 DEG C,
The ethanol solution of 90wt% will be formulated as with the hy-droxybutyl compound that intermediate mol ratio is 1:1.3, and slowly
Dropping in intermediate, after dropping, under the conditions of 90 DEG C, stirring carries out additive reaction 2.0 hours, i.e. obtains Colophonium
Emulsifier production.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 1.0wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 3.0wt% of asphalt quality (solid content account for), being regulated pH value with acid is 3.0, is heated to 45 DEG C,
Preparing bitumen content by colloid mill and the abundant shear-mixed of AH-70 matrix pitch being heated to 110 DEG C is 50.0wt%
Emulsified asphalt.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
1.5 μm, the bin stability of 1 day and 5 days is respectively 0.4% and 3.2%, and on sieve, surplus is 0.03%, evaporates residual
Staying thing content is 50.6wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can be 160s the mixing time, just
Solidifying time 26min.
Embodiment 6
The aphthenic acids that mol ratio is 1:1.1 is joined in there-necked flask with diethylenetriamine, and addition accounts for reaction raw materials
Gross weight is the mixed xylenes of 30wt%, and stirring is warming up to 160 DEG C, and it is little that steady temperature carries out amidation process 4.0
Time, (vacuum 0.092MPa) rising temperature of reaction system is to 240 DEG C the most under vacuum, proceeds ring
Change reaction 4.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 80 DEG C, will be with centre
Body mol ratio is the ethanol solution that the butyl acrylate compound of 1:1.5 is formulated as 80wt%, and is slowly added dropwise to centre
In body, after dropping, under the conditions of 80 DEG C, stirring carries out additive reaction 3.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 2.0wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 4.0wt% of asphalt quality (solid content account for), being regulated pH value with acid is 4.0, is heated to 55 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-70 matrix pitch being heated to 140 DEG C
Blue or green content is the emulsified asphalt of 60.0wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
2.2 μm, the bin stability of 1 day and 5 days is respectively 0.3% and 3.1%, and on sieve, surplus is 0.02%, evaporates residual
Staying thing content is 60.5wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can be 180s the mixing time, just
Solidifying time 25min.
Embodiment 7
The tetradecylic acid that mol ratio is 1:1.2 is joined in there-necked flask with triethylene tetramine, and addition accounts for reaction raw materials
Gross weight is the Mixed XYLENE of 40wt%, and stirring is warming up to 170 DEG C, and steady temperature carries out amidation process 2.0 hours,
(vacuum 0.092MPa) rising temperature of reaction system is to 250 DEG C the most under vacuum, proceeds cyclisation anti-
Answer 3.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 70 DEG C, will rub with intermediate
You are formulated as the ethanol solution of 70wt% than the tert-butyl acrylate compound for 1:1.4, and are slowly added dropwise to intermediate
In, after dropping, under the conditions of 90 DEG C, stirring carries out additive reaction 2.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 3.0wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 5.0wt% of asphalt quality (solid content account for), being regulated pH value with acid is 5.0, is heated to 65 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-90 matrix pitch being heated to 160 DEG C
Blue or green content is the emulsified asphalt of 70.0wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
2.0 μm, the bin stability of 1 day and 5 days is respectively 0.4% and 3.5%, and on sieve, surplus is 0.02%, evaporates residual
Staying thing content is 60.8wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can be 160s the mixing time, just
Solidifying time 18min.
Embodiment 8
Palmic acid that mol ratio is 1:1.8 and diethylenetriamine are joined there-necked flask, and adds that to account for reaction raw materials total
Weight is the o-Dimethylbenzene of 30wt%, and stirring is warming up to 180 DEG C, and steady temperature carries out amidation process 2.0 hours,
(vacuum 0.092MPa) rising temperature of reaction system is to 260 DEG C the most under vacuum, proceeds cyclisation anti-
Answer 2.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 70 DEG C, will rub with intermediate
You are formulated as the ethanol solution of 70wt% than the 2-(Acryloyloxy)ethanol compound for 1:1.5, and are slowly added dropwise to intermediate
In, after dropping, under the conditions of 80 DEG C, stirring carries out additive reaction 1.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 1.6wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 4.5wt% of asphalt quality (solid content account for), being regulated pH value with acid is 2.0, is heated to 65 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-70 matrix pitch being heated to 110 DEG C
Blue or green content is the emulsified asphalt of 70wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
3.0 μm, the bin stability of 1 day and 5 days is respectively 0.1% and 3.6%, and on sieve, surplus is 0.06%, evaporates residual
Staying thing content is 67.0wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can be 160s the mixing time, just
Solidifying time 26min.
Embodiment 9
Stearic acid that mol ratio is 1:1.9 and TEPA are joined there-necked flask, and adds that to account for reaction raw materials total
Weight is the o-Dimethylbenzene of 50wt%, and stirring is warming up to 160 DEG C, and steady temperature carries out amidation process 4.0 hours,
(vacuum 0.092MPa) rising temperature of reaction system is to 240 DEG C the most under vacuum, proceeds cyclisation anti-
Answer 4.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 90 DEG C, will rub with intermediate
You are formulated as the ethanol solution of 90wt% than the 2-(Acryloyloxy)ethanol compound for 1:1.3, and are slowly added dropwise to intermediate
In, after dropping, under the conditions of 100 DEG C, stirring carries out additive reaction 3.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 2.4wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 3.0wt% of asphalt quality (solid content account for), being regulated pH value with acid is 4.0, is heated to 65 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-90 matrix pitch being heated to 125 DEG C
Blue or green content is the emulsified asphalt of 55.0wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
1.7 μm, the bin stability of 1 day and 5 days is respectively 0.3% and 3.2%, and on sieve, surplus is 0.08%, evaporates residual
Staying thing content is 55.0wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can the mixing time more than 180s,
Presetting period 19min.
Embodiment 10
Your acid appropriate that mol ratio is 1:1.7 is joined in there-necked flask with TEPA, and addition accounts for reaction raw materials
Gross weight is the o-Dimethylbenzene of 40wt%, and stirring is warming up to 150 DEG C, and steady temperature carries out amidation process 3.0 hours,
(vacuum 0.092MPa) rising temperature of reaction system is to 230 DEG C the most under vacuum, proceeds cyclisation anti-
Answer 5.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 80 DEG C, will rub with intermediate
You are formulated as the ethanol solution of 80wt% than the butyl acrylate compound for 1:1.2, and are slowly added dropwise to intermediate,
After dropping, under the conditions of 110 DEG C, stirring carries out additive reaction 2.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 1.4wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 5.0wt% of asphalt quality (solid content account for), being regulated pH value with acid is 4.0, is heated to 70 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-70 matrix pitch being heated to 135 DEG C
Blue or green content is the emulsified asphalt of 70.0wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
1.4 μm, the bin stability of 1 day and 5 days is respectively 0.8% and 3.7%, and on sieve, surplus is 0.04%, evaporates residual
Staying thing content is 63.3wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can be 120s the mixing time, just
Solidifying time 23min.
Embodiment 11
Stearic acid that mol ratio is 1:2.0 and triethylene tetramine are joined there-necked flask, and adds that to account for reaction raw materials total
Weight is the xylol of 40wt%, and stirring is warming up to 170 DEG C, and steady temperature carries out amidation process 3.0 hours,
(vacuum 0.092MPa) rising temperature of reaction system is to 250 DEG C the most under vacuum, proceeds cyclisation anti-
Answer 3.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 80 DEG C, will rub with intermediate
You are formulated as the ethanol solution of 80wt% than the ethyl acrylate compound for 1:1.4, and are slowly added dropwise to intermediate,
After dropping, under the conditions of 90 DEG C, stirring carries out additive reaction 2.0 hours, i.e. obtains asphalt emulsifier product.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 2.2wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 3.7wt% of asphalt quality (solid content account for), being regulated pH value with acid is 3.0, is heated to 50 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-70 matrix pitch being heated to 120 DEG C
Blue or green content is the emulsified asphalt of 65wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
2.4 μm, the bin stability of 1 day and 5 days is respectively 0.7% and 3.7%, and on sieve, surplus is 0.02%, evaporates residual
Staying thing content is 64.9wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can the mixing time more than 180s,
Presetting period 22min.
Embodiment 12
The aphthenic acids that mol ratio is 1:1.5 is joined in there-necked flask with ethylenediamine, and addition accounts for reaction raw materials gross weight
Amount is the petroleum ether (boiling range is 90～120 DEG C) of 30wt%, and stirring is warming up to 140 DEG C, and steady temperature carries out amidatioon
Reacting 2.0 hours, (vacuum 0.092MPa) rising temperature of reaction system is to 220 DEG C the most under vacuum,
Proceed cyclization 6.0 hours, desolvation and the water of generation, obtain intermediate, after temperature is down to 70 DEG C,
The ethanol solution of 70wt% will be formulated as with the tert-butyl acrylate compound that intermediate mol ratio is 1:1.1, and slowly
Dropping in intermediate, after dropping, under the conditions of 100 DEG C, stirring carries out additive reaction 1.0 hours, i.e. obtains Colophonium
Emulsifier production.
The micro-surface area asphalt emulsifier of above-mentioned preparation is configured to aqueous solution by the 1.5wt% of emulsified asphalt gross mass, adds
Entering the SBR latex 4.7wt% of asphalt quality (solid content account for), being regulated pH value with acid is 2.0, is heated to 50 DEG C,
Drip is prepared by colloid mill and the CNOOC's Suizhong abundant shear-mixed of 36-1AH-90 matrix pitch being heated to 130 DEG C
Blue or green content is the emulsified asphalt of 60.0wt%.
Above-mentioned prepared emulsified asphalt is carried out performance test: emulsified asphalt is cationic, and volume average particle sizes is
1.5 μm, the bin stability of 1 day and 5 days is respectively 0.4% and 3.5%, and on sieve, surplus is 0.01%, evaporates residual
Staying thing content is 62.3wt%, mixes and stirs as slow breaking with MS-3 type basalt aggregate, can be 170s the mixing time, just
Solidifying time 16min.
Claims (10)
1. the method preparing asphalt emulsifier, comprises the steps:
1), after the mixing of organic acid, organic polyamine and solvent being carried out amidation process, it is cyclized under vacuum
Reaction, reacts the solvent in complete removing system and water, obtains intermediate；
2) until step 1) after the cooling of gained reaction system, by the ethanol solution of graft modification agent and step 1) in gained
Mesosome carries out additive reaction, reacts complete and obtains described asphalt emulsifier；
Described graft modification agent selected from acrylic acid methyl ester., ethyl acrylate, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate,
At least one of butyl acrylate, Isobutyl 2-propenoate, tert-butyl acrylate and hy-droxybutyl.
Method the most according to claim 1, it is characterised in that: described step 1) in, described organic acid is selected from
In capric acid, lauric acid, tetradecylic acid, Palmic acid, stearic acid, oleic acid, aphthenic acids, ready denier oil acid and rosin acid
At least one；
At least one in ethylenediamine, diethylenetriamine, triethylene tetramine and TEPA of described organic polyamine；
Described solvent is 90-120 DEG C selected from toluene, meta-xylene, o-Dimethylbenzene, xylol, mixed xylenes and boiling range
In petroleum ether at least one；Described mixed xylenes is the mixing of xylol, o-Dimethylbenzene, meta-xylene and ethylbenzene
Thing.
Method the most according to claim 1, it is characterised in that: described step 1) in, organic acid is with organic many
The molar ratio of amine is 1:1～2；
The consumption of described solvent is the 20%-50% of the gross weight of described organic acid and organic polyamine；
In described vacuum condition, vacuum is 0.080MPa-0.098MPa.
Method the most according to claim 3, it is characterised in that: in described vacuum condition, vacuum is 0.092MPa.
Method the most according to claim 1, it is characterised in that: described step 1) in, described amidation process
In step, temperature is 140 DEG C-180 DEG C, and the time is 2 hours-4 hours；
In described cyclization step, temperature is 220 DEG C-260 DEG C, and the time is 2 hours-6 hours.
Method the most according to claim 1, it is characterised in that: described step 2) in, described graft modification agent
It is 1:1-1.5 with the molar ratio of described intermediate；
In the ethanol solution of described graft modification agent, the mass percentage concentration of graft modification agent is 70%-90%.
7. according to described method arbitrary in claim 1-6, it is characterised in that: described step 2) cooling step
In, the final temperature after cooling is 70-90 DEG C；
In described additive reaction step, temperature is 80-110 DEG C, and the time is 1 hour-3 hours.
8. the asphalt emulsifier that the arbitrary described method of claim 1-7 prepares.
9. the application in asphalt emulsification of the asphalt emulsifier described in claim 8.
Application the most according to claim 9, it is characterised in that: described asphalt emulsification is to carry out at micro-surface area
Asphalt emulsification.
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| CN105664786B (en) * | 2016-01-04 | 2018-12-21 | 陕西科技大学 | Anionic tall oil Gemini surface active agent and preparation method thereof |
| CN105647209B (en) * | 2016-03-23 | 2018-09-25 | 北京盛广拓公路科技有限公司 | It is a kind of to split fast rennet regenerative agent and preparation method thereof slowly |
| CN106367041B (en) * | 2016-08-22 | 2020-02-04 | 天津天诚拓源科技发展有限公司 | Emulsifier for oil-based drilling fluid and production process and application thereof |
| CN109628089B (en) * | 2019-01-18 | 2022-01-28 | 山东建筑大学 | Asphalt-based graphene asphalt emulsifier and preparation method thereof |
| CN109852084A (en) * | 2019-01-18 | 2019-06-07 | 山东建筑大学 | A kind of pitch based graphite alkenes asphalt warm-mix agent and preparation method thereof |
| CN114507187B (en) * | 2020-11-16 | 2024-04-30 | 中国石油天然气股份有限公司 | Modified imidazoline quaternary ammonium salt type asphalt warm mix agent and preparation method thereof |
| CN113214159A (en) * | 2021-06-16 | 2021-08-06 | 湖南林特科技有限公司 | Preparation method of asphalt emulsifier |
| CN114539556B (en) * | 2022-02-24 | 2023-11-10 | 西安博望新材料科技有限公司 | Emulsifier for cold-mixed high-viscosity emulsified asphalt and preparation method thereof |
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| CN103333136B (en) * | 2013-07-05 | 2015-07-22 | 河北工业大学 | Preparation method of polyaminoamide cationic asphalt emulsifier |
| CN104530726B (en) * | 2014-12-09 | 2017-05-03 | 中国石油大学(华东) | Emulsified asphalt for micro-surfacing and preparation method of emulsified asphalt |
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Effective date of registration: 20170301 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC OIL & PETROCHEMICALS Co.,Ltd. Patentee after: CNOOC RESEARCH INSTITUTE OF REFINING AND PETROCHEMICALS (BEIJING) Co.,Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CHINA OFFSHORE OIL & GAS DEVELOPMENT & UTILIZATION Co. Patentee before: CNOOC (QINGDAO) HEAVY OIL PROCESSING ENGINEERING TECHNOLOGY RESEARCH CENTER Co.,Ltd. |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNOOC OIL & PETROCHEMICALS Co.,Ltd. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee after: CNOOC RESEARCH INSTITUTE OF REFINING AND PETROCHEMICALS (BEIJING) Co.,Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: CNOOC OIL & PETROCHEMICALS Co.,Ltd. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee before: CNOOC RESEARCH INSTITUTE OF REFINING AND PETROCHEMICALS (BEIJING) Co.,Ltd. |
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Effective date of registration: 20180503 Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNOOC OIL & PETROCHEMICALS Co.,Ltd. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee after: CNOOC RESEARCH INSTITUTE OF REFINING AND PETROCHEMICALS (BEIJING) Co.,Ltd. Co-patentee after: CNOOC (QINGDAO) HEAVY OIL PROCESSING ENGINEERING TECHNOLOGY RESEARCH CENTER Co.,Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: CNOOC OIL & PETROCHEMICALS Co.,Ltd. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee before: CNOOC RESEARCH INSTITUTE OF REFINING AND PETROCHEMICALS (BEIJING) Co.,Ltd. |