A kind of SBS modified emulsifying asphalt and preparation method thereof
Technical field
The invention belongs to modern pavement technique field, particularly the Road construction modified asphalt material is specifically related to the SBS modified emulsifying asphalt.
Background technology
Improve the modifying asphalt that asphalt performance obtains with polymkeric substance styrene-butadiene-styrene (being called for short SBS), bituminous viscosity is increased, elasticity increases, and improves bituminous high-temperature behavior and low-temperature performance.
Pitch is heated, make it have enough big flowability and enough low viscosity, prepare soap lye with emulsifying agent simultaneously, asphalt emulsification can be formed stable colloid by emulsifying device again, the preparation emulsified bitumen.But the evaporation residue softening temperature of common emulsified asphalt and SBR latex modified emulsified bitumen is lower, and high-temperature behavior is not satisfactory.
The SBS modifying asphalt has very high viscosity, causes the production of emulsified bitumen to become quite difficult, usually causes serious skinning, residual content severe overweight on the sieve, and stability of emulsion is poor, therefore, the infeasible saying of emulsified SBS modified asphalt is arranged in the industry.
Can reduce its viscosity although improve SBS modifying asphalt temperature, too high temperature might cause SBS degraded and ageing of asphalt on the one hand, make emulsifying device be difficult to bear on the other hand, be in particular in that pressure is excessive in the colloidal mill, and acid attack increases the weight of or the like.The unrestricted SBS consumption that reduces also can reduce asphalt viscosity, but asphalt performance can not get improving, and does not have the effect of modification.
Reduce asphalt high-temperature viscosity (common more than 135 ℃), domestic also have research, mentioned in interim " test and the evaluation of admixture Sasobit modifying asphalt " literary composition in 2003 05 as " China and foreign countries' highway ": the viscosity of the modifying asphalt of admixture Sasobit is higher than former state pitch in the time of 60 ℃, but after 100 ℃, the viscosity of modifying asphalt is lower than former state pitch on the contrary, and rising along with temperature, the amplitude that reduces also increases, this shows that this method can improve bituminous high-temperature behavior (raising permanent deformation resistance), simultaneously can improve asphalt workability (being easy to pave compacting).The volume of most of its properties-correcting agent of modifying asphalt all requires more than 4%, even more than 6%, just might increase substantially the bituminous softening temperature, and the Sasobit volume only is 3% just to have increased substantially the bituminous softening temperature, but this method only rests on the modifying asphalt application stage, is not applied to the emulsified modified asphalt field.
About the development of SBS modified emulsifying asphalt, the technology of using liquid SBS is arranged both at home and abroad.Liquid SBS all adopts import, and market is rare, cost an arm and a leg, so not adopt in a large number.Domestic liquid SBS also has research, but only is used to produce the SBS modifying asphalt, can not be used to produce modified emulsifying asphalt.As the Chinese patent of announcing on May 25th, 2005, the manufacture method of eu-bitumen properties-correcting agent (publication number is 1618862) discloses a kind of liquid SBS making method, solid SBS is dissolved in the organic solvent, make solid SBS become the solution shape, in this solution shape SBS, add tensio-active agent and water again, obtain the liquid SBS of emulsion form by emulsification method.But this method of manufacturing liquid SBS is more loaded down with trivial details, and liquid SBS contains more tensio-active agent, if produce emulsified bitumen with this liquid SBS, after adding this tensio-active agent of emulsifying agent, then tensio-active agent is too much, can cause emulsified bitumen defective, therefore domestic this liquid SBS is difficult to use in the production emulsified modified asphalt, and does not see that it is further studied and use in the modified emulsifying asphalt field.
At the current techniques background, SBS modified emulsifying asphalt production field faces two technical barriers: 1. how in high temperature (common more than the 135 ℃) viscosity that reduces the SBS modifying asphalt under the prerequisite that does not influence high temperature performance of asphalt (as softening temperature), thereby reduction emulsifying temperature? 2. how to reduce cost (promptly adding a small amount of SBS), significantly improve the high-temperature behavior of Asphalt Emulsion Evaporation Residue again?
Summary of the invention
The object of the invention provides a kind of SBS modified emulsifying asphalt.
Another purpose of the present invention provides SBS modified emulsifying asphalt making method.
SBS modified emulsifying asphalt of the present invention, composed of the following components by weight percentage:
Matrix pitch (road bitumen of non-modified) 54%-62%
SBS properties-correcting agent 0.6%-2.4%
Sasobit (Sha Suobide) 0.3%-1.6%
Stablizer WD-3# 0.06%-0.55%
Pitch cationic emulsifier 1.0%-3.5%
Hot water (40 ℃-75 ℃) 35%-40%
Calcium chloride 0.1-1%
Polyvinyl alcohol 0.1-1%.
The preferred heavy traffic paving asphalt AH-90 of matrix pitch of the present invention.The matrix pitch consumption better is 55%~60%.
SBS properties-correcting agent of the present invention can be linear structure, and its molecular weight is 8~150,000.SBS properties-correcting agent of the present invention can also be hub-and-spoke configuration, and its molecular weight is 20~300,000.SBS properties-correcting agent is linear structure preferably, and the consumption preferable range is 1.6%~2.2%.The preferred range of the molecular weight of linear structure SBS is 10~120,000.
Sasobit among the present invention (Sha Suobide) is that SASOL WAX company was in the novel asphalt properties-correcting agent by the exploitation of German research and development department in 1997, it is a kind of hydrocarbon polymer---synthetic straight chain aliphatic hydrocarbon, main chain is a 45-115 carbon atom, / to measure be about 1300, can play modification and visbreaking dual function, significantly improve pitch the viscosity below 80 ℃ (thereby improving pitch softening point), reduce it simultaneously the viscosity more than 135 ℃ and 135 ℃ (making modifying asphalt be easy to emulsification).Sasobit (Sha Suobide) mechanism of action is: its melt drop temperature is about 115 ℃, when asphalt temperature reduces, with part adsorbed by it and the saturated component of dissolved gradually crystallization separate out, and then locked these fat oil classes, wax class component, thereby improved bituminous softening temperature and intensity; After asphalt temperature surpassed the melt drop temperature of Sasobit (Sha Suobide), Sasobit (Sha Suobide) was a linear chain structure, and high temperature viscosity is littler than pitch, and pitch is had " dilution " effect, therefore reduced the bituminous high temperature viscosity.Sasobit density is little, modifying asphalt particulate density is changed, the density that makes pitch particle improves the stability of colloid emulsion more near the density of water, and (modified emulsifying asphalt is the colloid of " oil-in-water " usually, pitch particle density is greater than the density of water, pitch particle is condensed under deadweight, influences colloidal stability), according to colloidal theory, when the density of pitch particle near water, colloidal stability improves.
Described Sasobit (Sha Suobide) consumption preferable range is 0.8%~1.5%.
Stablizer among the present invention can improve the stability of modifying asphalt, prevents SBS properties-correcting agent segregation.The WD-3# stablizer of the preferred Guangzhou of stablizer road Xiang exploitation.Stabilizing agent dosage preferably 0.3%.
Pitch cationic emulsifier among the present invention is a kind of tensio-active agent, can reduce the surface tension of water, reduce the two-phase interface free energy, thereby the dispersed bitumens particle forms oil-in-water emulsion.The MQK-1M of the preferred U.S. of the pitch cationic emulsifier among the present invention MeadWestvaco company and the Redicote-C-450 of MQ3 or Dutch Akzo-Nobel, the preferably MQK-1M of MeadWestvaco company or MQK-MQ3.Pitch cationic emulsifier preferred amount ranges is 1.2%~1.8%.
The temperature preferred range of water is preferably 55 ℃-65 ℃ among the present invention.
Add hydrochloric acid among the present invention and regulate pH value, make emulsifying agent that enough activity be arranged.PH value preferably 1.5~3.5.
Calcium chloride consumption of the present invention preferably 0.4%.
Polyvinyl alcohol consumption of the present invention preferably 0.15%.
SBS modified emulsifying asphalt of the present invention is formed preferably:
Matrix pitch 55~60%;
SBS properties-correcting agent 0.6~2.4%;
Sasobit 0.3~1.6%;
WD-3# stablizer 0.06~0.55%;
MQK-1M 1.2~1.8%;
40~75 ℃ of hot water 35~40%;
Calcium chloride 0.4%;
Polyvinyl alcohol 0.15%.
The preparation method of SBS modified emulsifying asphalt of the present invention adopts emulsified bitumen preparation method commonly used.Concrete preparation technology can carry out according to Fig. 1.
The preparation method of SBS modified emulsifying asphalt of the present invention is: at first SBS properties-correcting agent, Sasobit (Sha Suobide) and stablizer are added acquisition SBS modifying asphalt in the matrix pitch; Add emulsifying agent, calcium chloride and polyvinyl alcohol in water, regulating pH is 1.5~3.5, obtains soap lye; Then the emulsification in soap lye of SBS modifying asphalt is disperseed to form emulsion, obtain the SBS modified emulsifying asphalt through the pressurization cooling again.
Among the preparation method of SBS modified emulsifying asphalt of the present invention, modifying asphalt prepares concrete steps and is:
At first matrix pitch is heated to 180 ℃~190 ℃, adds SBS properties-correcting agent, stir 20min; Add Sasobit (Sha Suobide) then,, add stablizer at last and grow 15min through high speed shear 1-2 hour.
The preparation method of SBS modified emulsifying asphalt of the present invention wherein adds preferably 1~1.5 hour Sasobit (Sha Suobide) high speed shear time.Among the preparation method of SBS modified emulsifying asphalt of the present invention, soap lye prepares concrete steps and is: at first add emulsifying agent in hot water, regulate pH value to 1.5~3.5; In above-mentioned solution, add calcium chloride and polyvinyl alcohol then, make soap lye.
Emulsification method of the present invention can adopt this area asphalt emulsification method commonly used.For example soap lye and modifying asphalt are respectively charged into Soap liquid pot and asphalt tank in the emulsifying device, then through colloidal mill emulsification, the pressurization cooling obtains the SBS modified emulsifying asphalt.
The softening temperature height of SBS modified emulsifying asphalt evaporation residue of the present invention under the prerequisite that adds a small amount of SBS, can significantly improve the high-temperature behavior (softening temperature can reach more than 65 ℃) of Asphalt Emulsion Evaporation Residue.Compound resistance to permanent deformation with its production is good, prevents that the high temperature season road surface from forming rut, disease such as embraces, and more adapts to the road surface construction and the maintenance needs of hot area.Reduce emulsifying temperature (being generally the temperature of pitch rotary viscosity among the present invention) more than 7 ℃ smaller or equal to 200 centipoises, make the emulsifying temperature equipment of reducing to can bear in the scope, emulsifying temperature is low, then the production difficulty of modified emulsifying asphalt descends, reduce the loss of emulsifying device, improve stability of emulsion.
Table one has provided SBS dosage and the Sasobit dosage situation that influences to modifying asphalt index and emulsifying temperature thereof, and content percentage ratio is the numerical value with respect to modifying asphalt.Contrast No. 1 and No. 2 test as can be known, add the viscosity that SBS can increase bituminous softening temperature and 135 ℃, but improve emulsifying temperature.Contrast No. 2 and No. 3 and test as can be known, add SBS and Sasobit and can further improve softening temperature, reduce by 135 ℃ viscosity simultaneously, reduce emulsifying temperature.
Table one
Modifying asphalt is formed |
Performance of modified bitumen |
Test number |
SBS consumption (%) |
Sasobit addition (%) |
135 ℃ of viscosity centipoises |
Softening temperature ℃ |
Emulsifying temperature
* ℃
|
1 |
0 |
0 |
650 |
45 |
165 |
2 |
3 |
0 |
942 |
58 |
177 |
3 |
3 |
2 |
758 |
67 |
168 |
*Annotate: pitch Heating temperature when emulsifying temperature refers to emulsification (temperature when being generally pitch rotary viscosity≤200 centipoises among the present invention) the difficult more emulsification of high more this kind of expression modifying asphalt.
Description of drawings
Fig. 1 is a SBS modified emulsifying asphalt process schematic representation.
Embodiment
Following examples make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
SBS modified emulsifying asphalt compositing formula:
Matrix pitch (%) 57
SBS properties-correcting agent (%) 1.8
Sasobit (Sha Suobide) (%) 0.9
WD-3#(%) 0.3
63 ℃ of hot water (%) 37.85
Cationic emulsifier MQK-1M 1.6
Calcium chloride 0.4
Polyvinyl alcohol 0.15
SBS emulsified bitumen preparation method:
According to compositing formula, adopt the described process flow sheet of Fig. 1 to carry out the fs:
A) matrix pitch is heated to 185 ℃, adds SBS properties-correcting agent, stir 20min.
B) add Sasobit (Sha Suobide), sheared 1.5 hours, add WD-3# reaction 15min through the high speed shear device.Subordinate phase:
C) in 63 ℃ hot water, add emulsifying agent, add hydrochloric acid again and regulate pH value to 1.8, stir, until liquid-transparent.
D) in above-mentioned solution, add calcium chloride and polyvinyl alcohol, make soap lye.
E) modifying asphalt that soap lye and fs are made is respectively charged into Soap liquid pot and the asphalt tank in the emulsifying device, then through colloidal mill emulsification, obtains finished product SBS modified emulsifying asphalt through the pressurization cooling again.
The performance of SBS modified emulsifying asphalt:
Emulsifying temperature (℃): 168
The softening temperature of evaporation residue (℃): 67
Stability in storage (5d) is (%): 3.1
Emulsifying temperature is meant when producing emulsified bitumen, and pitch is heated to suitable temperature, makes it have enough big flowability and enough low viscosity (common rotary viscosity is answered≤200 centipoises among the present invention), so that emulsification can be carried out smoothly.We are called the asphalt emulsification temperature this temperature.
The softening temperature of evaporation residue is meant modified emulsifying asphalt is evaporated, moisture is fully volatilized, make pitch phase and aqueous phase separation in the modified emulsifying asphalt, obtain evaporation residue, measure its softening point temperature then, this softening temperature just is called the softening temperature of evaporation residue.
The stability in storage of emulsified bitumen is under the container and condition of regulation, after storing specific time, the intensity of variation of sample solution concentration on the vertical direction is represented with the difference of upper and lower two portions emulsion evaporation residue quality percentage, to judge the stability of emulsion.Numerical value is more little, and stability is good more.
Embodiment 2:
SBS modified emulsifying asphalt compositing formula:
Matrix pitch (%) 56.7
SBS properties-correcting agent (%) 2.1
Sasobit (Sha Suobide) (%) 0.9
WD-3# stablizer (%) 0.3
65 ℃ of hot water (%) 37.85
Cationic emulsifier MQK-MQ3 1.6
Calcium chloride 0.4
Polyvinyl alcohol 0.15.
SBS emulsified bitumen preparation method:
According to compositing formula, adopt the described process flow sheet of Fig. 1 to carry out the fs:
A) matrix pitch is heated to 190 ℃, adds SBS properties-correcting agent, stir 20min.
B) add Sasobit (Sha Suobide), sheared 1.5 hours, add WD-3# reaction 15min through the high speed shear device.Subordinate phase:
C) in 65 ℃ of hot water, add emulsifying agent, add hydrochloric acid again and regulate pH value to 2.0, stir, until liquid-transparent.
D) in above-mentioned solution, add calcium chloride and polyvinyl alcohol, make soap lye.
E) modifying asphalt that soap lye and fs are made is respectively charged into Soap liquid pot and the asphalt tank in the emulsifying device, then through colloidal mill emulsification, obtains finished product SBS modified emulsifying asphalt through the pressurization cooling again.
The performance of SBS modified emulsifying asphalt:
Emulsifying temperature (℃): 172
The softening temperature of evaporation residue (℃): 72
Stability in storage (5d) is (%): 3.8
Embodiment 3:
SBS modified emulsifying asphalt compositing formula: weight percentage
Matrix pitch 54.9
SBS properties-correcting agent 1.6
Sasobit (Sha Suobide) 1.2
WD-3# 0.3
62 ℃ of hot water 39.85
Cationic emulsifier Redicote-C-450 1.6
Calcium chloride 0.4
Polyvinyl alcohol 0.15.
SBS emulsified bitumen preparation method:
According to compositing formula, adopt the described process flow sheet of Fig. 1 to carry out the fs:
A) matrix pitch is heated to 180 ℃, adds SBS properties-correcting agent, stir 20min.
B) add Sasobit (Sha Suobide), sheared 1.5 hours, add WD-3# reaction 15min through the high speed shear device.Subordinate phase:
C) in 62 ℃ of hot water, add emulsifying agent, add hydrochloric acid again and regulate pH value to 1.8, stir, until liquid-transparent.
D) in above-mentioned solution, add calcium chloride and polyvinyl alcohol, make soap lye.
E) modifying asphalt that soap lye and fs are made is respectively charged into Soap liquid pot and the asphalt tank in the emulsifying device, then through colloidal mill emulsification, obtains finished product SBS modified emulsifying asphalt through the pressurization cooling again.
The performance of SBS modified emulsifying asphalt:
Emulsifying temperature (℃): 162
The softening temperature of evaporation residue (℃): 65
Stability in storage (5d) is (%): 4.0
Comparative Examples 1:
Matrix pitch (%) 57.3
SBR properties-correcting agent (%) 2.4
WD-3#(%) 0.3
64 ℃ of hot water (%) 37.85
Cationic emulsifier Redicote-C-450 1.6
Calcium chloride 0.4
Polyvinyl alcohol 0.15
The emulsified bitumen preparation method:
A) in 64 ℃ of hot water, add emulsifying agent, add the agent of SBR latex modified then, add hydrochloric acid at last and regulate pH value to 1.8, stir.
B) in above-mentioned mixing liquid, add calcium chloride and polyvinyl alcohol, make soap lye.
C) modifying asphalt that soap lye and fs are made is respectively charged into Soap liquid pot and the asphalt tank in the emulsifying device, then through colloidal mill emulsification, obtains finished product SBR emulsified modified asphalt through the pressurization cooling again.
The emulsified bitumen performance:
Emulsifying temperature (℃): 160
The softening temperature of evaporation residue (℃): 54
Stability in storage (5d) is (%): 4.2
Do not add the easy emulsification of modifying asphalt of SBS and Sasobit, but the high-temperature behavior of gained emulsified bitumen is relatively poor.
Comparative Examples 2:
Compositing formula:
Matrix pitch (%) 55.9
SBS properties-correcting agent (%) 1.8
WD-3#(%) 0.3
64 ℃ of hot water (%) 39.85
Cationic emulsifier MQK-1M 1.6
Calcium chloride 0.4
Polyvinyl alcohol 0.15
Emulsified bitumen preparation method:, just do not add Sasobit with embodiment 1.
The emulsified bitumen performance:
Emulsifying temperature (℃): 177
The softening temperature of evaporation residue (℃): 61
Stability in storage (5d) is (%): 5.6
The high-temperature behavior of gained emulsified bitumen is better, but the more difficult emulsification of this modifying asphalt.
Comparative Examples 3:
Compositing formula:
Matrix pitch (%) 55.9
SBS properties-correcting agent (%) 2.1
WD-3#(%) 0.3
63 ℃ of hot water (%) 39.55
Cationic emulsifier MQK-1M 1.6
Calcium chloride 0.4
Polyvinyl alcohol 0.15
Emulsified bitumen preparation method:, just do not add Sasobit with embodiment 1.
The emulsified bitumen performance:
Emulsifying temperature (℃): 185
The softening temperature of evaporation residue (℃): 72
Stability in storage (5d) is (%): serious skinning.