CN103613941A - Preparation method of amphoteric ionic warm asphalt mixing agent and application thereof in warm mix asphalt - Google Patents
Preparation method of amphoteric ionic warm asphalt mixing agent and application thereof in warm mix asphalt Download PDFInfo
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Abstract
The invention provides an amphoteric ionic warm asphalt mixing agent and a preparation method thereof. A molecule of the amphoteric ionic warm asphalt mixing agent contains three quaternary ammonium salt ions; the preparation method of the amphoteric ionic warm asphalt mixing agent is as follows: firstly preparing a double-quaternary ammonium salt type asphalt emulsifier, then, mixing epoxy chloropropane and an inorganic acid salt with a solvent to form a reaction system to prepare an intermediate, and finally, mixing the double-quaternary ammonium salt type asphalt emulsifier with the intermediate to prepare the amphoteric ionic warm asphalt mixing agent provided by the invention, the amphoteric ionic warm asphalt mixing agent provided by the invention greatly reduces the temperature of a hot mix asphalt mixture; and meanwhile, the defect of poor water damage resistance of the asphalt mixture caused by adoption of the warm asphalt mixing agent is solved, and particularly the defect of poor blocking property on a mixture of alkaline aggregate and asphalt is solved.
Description
Technical field
The present invention relates to the preparation method of zwitter-ion asphalt warm-mix agent and the application in warm-mixed asphalt thereof, particularly a class containing the zwitterionic asphalt warm-mix agent of inorganic acid salt type and the application in warm-mixed asphalt thereof.
Background technology
Warm-Mix Bitumen Mixture starts from the nineties in last century, refer to that a class mixes and stirs temperature between hot-mix asphalt mixture (150 ℃-180 ℃) and cold mixing (10 ℃-40 ℃) asphalt, performance reaches the novel asphalt compound of hot-mix asphalt mixture.The core of warm mix technology is to adopt physics or chemical means, increases the application operability of asphalt, and these physics or chemical additive do not answer Pavement Performance in Distress to cause negative impact simultaneously.The production of asphalt is energy expenditure and environmental pollution rich and influential family in road engineering, and current China road project is in the discharge that fast-developing phase research and application Warm-Mix Bitumen Mixture are of value to the pollutents such as the energy consumption that reduces in Process of Pitch Mixture Production and greenhouse gases and dust undoubtedly.Therefore development will have cross-age significance for highway in China to greatly develop warm mix technology.
According to working mechanism, warm mix technology can be classified as three large major technique type (1) viscosity reduction type warm mix technology, use organic viscosity-depression agent, viscosity when reduction heated bitumen mixes and stirs, take wax or wax as main (2) expansion type warm mix technology, by water or organic blowing agent foamed asphalt, reduce viscosity (3) the surfactivity warm mix technology of pitch, adopt a small amount of surfactant additive water and heated bitumen acting in conjunction in the process of mixing and stirring, by the powerful dispersive ability of mixing and stirring, realize and being interlaced with one another due to Water film lubricating effect temperature influence not, when temperature declines, the effect that asphalt viscosity increases can be largely offset in Water film lubricating effect, thereby realize warm mix effect.
Three major types warm mix technology has been done to a large amount of research both at home and abroad, wherein GrahamC.Hurley and Brian D.ProweU have done comparatively comprehensively research to the Sasobit Warm-Mix Bitumen Mixture of adding, and research is found: the compactibility that adds the mixed platform material of pitch that all can make rotary compactor and the moulding of vibrating compacting instrument of Sasobit can improve. reduce the voidage of test specimen.Statistics shows, on average makes the voidage of compound reduce by 087%.Sasobit adds the modulus of resilience that can not affect asphalt.Sasobit adds the risk that generally can reduce asphalt generation rut.
In some cases, the indirect tensile strength that contains Sasobit compound is lower than common hot-mix asphalt mixture.Sasobit warm-mixing additive can cause the increase of compound Water Damage risk.And GrahamC.Hurley and Brian D.Prowell have research comparatively to find to adding the Warm-Mix Bitumen Mixture of Aspha-min zeolite: Aspha-min zeolite can improve the compaction capacity of compound, comprises SGC moulding and vibratory compaction molding.
Statistics shows, adopts vibratory compaction molding can make voidage on average decline 0.65%.In the situation that compacting temperature is identical with hot-mix asphalt mixture, can have obvious impact simple not adding of zeolite on rut.Compare with plain asphalt compound, the intensity of adding the compound of zeolite does not have difference in time and has obvious difference.Before open to traffic, do not need this Warm-Mix Bitumen Mixture health for some time.Freeze thawing Ratio of split strength (TSR) value that adds membership reduction compound of zeolite.Do not add in the situation of antistripping agent, the compound that contains zeolite is poorer than the water resistant damage capability of plain asphalt compound.In the Experiment Road of Orlando, zeolite has successfully joined in the SUPERPAVE compound that contains 20% reclaimed asphalt mixture, makes to mix and stir temperature and mold temperature and has reduced about 19 ℃, and on-the-spot density does not change simultaneously.GrahamC.Hurley and Brian D.Prowell are to surfactants based Warm-Mix Bitumen Mixture
Research conclusion has the following aspects: asphalt content is certain, Evotherrn
tMcompound test specimen, adopt its voidage of gyratory compaction molding to decrease.Adopt Evotherm
tMwarm mix technology all can improve the consolidation effect of compound.At given compacting temperature, Evotherm
tMwarm mix technology has improved the modulus of resilience of asphalt.Evotherm
tMwarm mix technology can significantly reduce the risk that rut appears in asphalt.Evotherm
tMthe indirect tensile strength of warm mix compound is compared with hot-mix asphalt mixture material, on the low side sometimes.Evotherm
tMwarm mix mixing section formula has improved pitch and the adhesive capacity of gathering materials, and avoids water to peel off the generation of situation.
China, since the Meadwestvaco company cooperation of the departments such as 2005 Tongji University of Nian You Int. of Highway Sciences, Ministry of Communications and the U.S. adopts Evotherm warm mix technology building article one warm-mixed asphalt road surface, has successively adopted warm mix technology in the multinomial important engineering project that comprises the ground such as Beijing, Chongqing, Shanghai.Yet these engineerings mainly adopt, be still external warm-mixing agent, these warm-mixing agent product prices are higher, popularization face is wide not, also do not form unified asphalt mixture warm-mixing technical specifications file, be difficult to guarantee that the construction quality on warm-mixed asphalt road surface has limited the further application of warm mix technology in road engineering.Asphalt warm-mix agent Main Function is the mix temperature that reduces hot-laid mixture.Current domestic warm-mixing agent main drawback: first, the temperature that reduces hot-laid mixture is limited.Secondly, anti-water damage scarce capacity, especially gathers materials for alkalescence.
Therefore developing efficient warm-mixing agent is a current difficult problem urgently to be resolved hurrily.
Summary of the invention
The temperature that reduces hot-laid mixture for the asphalt warm-mix agent in current pitch warm mix technology is limited; And the anti-water damage scarce capacity of the asphalt after use asphalt warm-mix agent, the defect of especially gathering materials with the adhesion property deficiency of the compound of pitch for alkalescence, the invention provides a kind of amphoteric ion type asphalt warm-mix agent of stability and high efficiency and the application in warm-mixed asphalt thereof, the molecule of described amphoteric ion type asphalt warm-mix agent is with three positively charged ions and a negatively charged ion; Can effectively improve the mix performance of asphalt and reduce construction temperature, guaranteeing the anti-water damage property of asphalt simultaneously.
The invention provides a kind of amphoteric ion type asphalt warm-mix agent, its molecule contains three quaternary ammonium salt ions, and its structure meets following formula I,
In formula I, R
1for dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl or nonadecyl, R
2=R
3=CH
3, R
2=R
3=Et, R
2=CH
3, R
3=H, R
2=H, R
3=CH
3, R
2=Et, R
3=H, R
2=Butyl, R
3=H, R
2=CH
2cH
2oH, R
3=H, R
2=CH
3or R
3=H; M is S-WAT, potassium sulfite, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, potassium primary phosphate, sodium pyrosulfate or sal enixum.
It is zwitterionic tensio-active agent that this patent is compared the maximum feature of existing warm-mixing agent, and contain three quaternary ammonium salt ions, therefore this warm-mixing agent gathers materials and has good adhesion property soda acid, so anti-water damage is more excellent, is embodied in freeze thawing cleavage strength and Marshall stability value is higher.This warm-mixing agent stability is better simultaneously, and high temperature is difficult for decomposing.And can significantly reduce the mix temperature of asphalt, that its reason is that tensio-active agent has is wetting, emulsification, dispersion, solubilising, foaming, froth breaking, infiltration, washing, the effect such as antistatic and lubricated, therefore tensio-active agent joins in pitch and can promote asphalt emulsification and dispersion, thereby reduce the viscosity of pitch, and then reduce mix temperature.
The preparation method of amphoteric ion type asphalt warm-mix agent of the present invention, comprises the steps:
Step 1) is prepared double quaternary ammonium salt type asphalt emulsifier: by long-chain fat sulfonamide derivatives and epoxy chloropropane and solvent formation reaction system, 10 ℃～50 ℃ reactions 0.5 hour～3 hours, then in reaction system, add a certain amount of amine, 60 ℃～90 ℃ reactions 3 hours～6 hours; Make double quaternary ammonium salt type asphalt emulsifier; The mol ratio of described long-chain fat amine, epoxy chloropropane and amine is 1:2～3:2～3;
Described long-chain fat sulfonamide derivatives is the compound of structure shown in structural formula II:
In formula II, R
1be selected from any one in tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, oil base, rosinyl.
Described epoxy chloropropane is the compound of structure shown in structural formula III:
Described amine is the compound of structure shown in structural formula IV:
In formula IV, R
2=R
3=CH
3, R
2=R
3=Et, R
2=CH
3, R
3=H, R
1=R
2=H, R
3=CH
3, R
1=R
2=Et, R
3=H, R
1=R
2=Butyl, R
3=H, R
1=R
2=CH
2cH
2oH, R
3=H, R
1=stearylamine, R
2=CH
3or R
3=H.
Step 2) prepare intermediate: by epoxy chloropropane and inorganic acid salt and solvent formation reaction system, 60 ℃～100 ℃ reactions, after 1～3 hour, make intermediate; The mol ratio of described epoxy chloropropane and inorganic acid salt is 1～1.5:1;
Described inorganic acid salt M is S-WAT, potassium sulfite, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, potassium primary phosphate, sodium pyrosulfate, sal enixum etc.
Step 3) makes amphoteric ion type asphalt warm-mix agent: the double quaternary ammonium salt type asphalt emulsifier of step (1) gained is joined in the system of intermediate of step (2) gained, 40 ℃～80 ℃ reactions 3～5 hours; Obtain amphoteric ion type asphalt warm-mix agent of the present invention; The ratio of bi-quaternary ammonium salt asphalt emulsifier and intermediate is 1～1.5:1
The concrete reaction formula of step (1) to (3) is as follows:
R in formula II
1with the R in formula I
1there is identical implication, the R in formula IV
2, R
3and R
4with R in formula I
2, R
3and R
4there is identical implication.
Solvent in step (1) and step (2) is any one in dimethyl sulfoxide (DMSO), DMF, dioxane, acetonitrile, octane, ethanol, toluene, methyl alcohol, tetrahydrofuran (THF), ethyl acetate, normal hexane, hexanaphthene, chloroform, methylene dichloride, water, pyridine.
A distinguishing feature of the present invention is that synthesis technique is simple, reaction conditions is gentle, productive rate is higher, is easy to realize industrialization; This asphalt warm-mix agent can effectively improve the mix performance of compound and reduce construction temperature, and the Warm-Mix Bitumen Mixture properties of preparation all meets the technical indicator that the Ministry of Communications formulates.
Embodiment
For the present invention is better illustrated,
In following examples, through post decouples computation productive rate
The condition of the separated bi-quaternary ammonium salt product of post is:
Adopt the silica gel chromatographic column of medium model, weighting agent is 20～25 centimetres, 200-400 object silica gel, and moving phase is that methanol/ethyl acetate=1/5～1/2(moving phase is determined according to the polarity of intermediate product).R
f=0.1～0.3。
The condition of the separated final product of post is:
Adopt the silica gel chromatographic column of medium model, weighting agent is 20～25 centimetres, 200-400 object silica gel, and moving phase is that methyl alcohol/sherwood oil is that 8/1～5/1(moving phase is determined according to the polarity of final product).R
f=0.1～0.2。
The method of the Performance Detection of adhesion coating modified emulsifying asphalt or standard
With reference to < < standard specification for construction and acceptance of highway asphalt pavement > > (People's Republic of China's industry standard, JTG F40-2004)
As follows for embodiment:
Embodiment 1
In there-necked flask, add 27.0g(0.1mol) stearylamine, the ethanol of 50ml and 19.4g(0.21mol) epoxy chloropropane, be heated to 40 ℃ reaction 3h obtain intermediate product.At 40 ℃, in there-necked flask, drip 22.3g(0.22mol) triethylamine.After dripping, be warmed up to 90 ℃ of reaction 10h and obtain bi-quaternary ammonium salt emulsifying agent, the ethanol that adds the sodium bisulfite of 15.5g (0.15mol), the water of 10ml and 30ml in another one there-necked flask, be heated to 80 ℃, in reaction flask, drip 9.0g(0.1mol) epoxy chloropropane, at 80 ℃, react 3h after dripping completely and obtain intermediate.Final step is blended in the bi-quaternary ammonium salt emulsifying agent of preparation at 100 ℃ and reacts 5h with intermediate, obtains zwitter-ion emulsifying agent, steams solvent, and separation obtains purer zwitter-ion emulsifying agent through post to obtain crude product.
The application examples of embodiment 1
Adopt the DAT mixture performance of AC-13 type bituminous concrete warm mix and hot asphalt and virtue Wei Shiweike to compare.
Coarse aggregate adopts basalt 10-15mm, the rubble of 5-10mm, limestone 3-5mm rubble, Machine-made Sand.Filler is breeze, cement.Pitch adopts SBS modifying asphalt.The grating of mineral aggregate is in Table one.
Table one AC-13 type mineral aggregate gradation
| Sieve aperture chi/mm | 16.0 | 13.2 | 9.5 | 4.75 | 2.36 | 1.18 | 0.6 | 0.3 | 0.15 | 0.075 |
| Percent of pass/% | 100 | 95.4 | 82.0 | 47.8 | 31.6 | 23.8 | 14.2 | 9.9 | 7.9 | 6.7 |
The contrast of table two AC-13 asphalt
| Experimental project | Hot-mix asphalt mixture | Embodiment mono-prepares warm-mixing agent | DAT |
| Mix temperature/℃ | 175 | 148 | 155 |
| Dynamic stability/mm -1 | 5451 | 6578 | 5837 |
| Low-temperature bending/μ ε | 2476 | 2748 | 2561 |
| Freeze thawing splitting/% | 86.9 | 92.1 | 87.6 |
The contrast of table three Mashell molding test specimen
| Experimental project | Hot-mix asphalt mixture | Embodiment mono-prepares warm-mixing agent | DAT | Technical requirements |
| Voidage/% | 3.26 | 3.46 | 3.52 | 3-5 |
| Pitch saturation ratio/% | 81.08 | 81.06 | 81.17 | 75-85 |
| Void in mineral aggregate/% | 17.43 | 18.6 | 18.7 | ≥17.0 |
| VCA min/% | 41.6 | 41.3 | 41.6 | ≤VCA DRC |
| VCA DRC/% | 40.01 | 40.18 | 40.16 | -- |
| Marshall stability/kN | 8.67 | 7.18 | 7.06 | ≥6.0 |
| Flow valuve/0.1mm | 31.7 | 34.8 | 33.2 | 20-50 |
Embodiment 2
In there-necked flask, add 27.0g(0.1mol) stearylamine, the chloroform of 50ml and 22.2g(0.24mol) epoxy chloropropane, be heated to 30 ℃ reaction 4h obtain intermediate product.At 30 ℃, in there-necked flask, drip 39.1g(0.23mol) Trimethylamine 99.After dripping, be warmed up to 80 ℃ of reaction 5h, obtain bi-quaternary ammonium salt emulsifying agent.The SODIUM PHOSPHATE, MONOBASIC 16.8g(0.14mol that adds 15.5g (0.15mol) in another one there-necked flask), the water of 10ml and the chloroform of 30ml, be heated to 40 ℃, in reaction flask, drip 9.2g(0.1mol) epoxy chloropropane, at 40 ℃, react 2.5h after dripping completely and obtain intermediate.Final step is blended in the bi-quaternary ammonium salt emulsifying agent of preparation at 60 ℃ and reacts 3h with intermediate, obtains zwitter-ion emulsifying agent, steams solvent, and separation obtains purer zwitter-ion emulsifying agent through post to obtain crude product.
The application examples of embodiment 2
Adopt the DAT mixture performance of AC-16 type bituminous concrete warm mix and hot asphalt and virtue Wei Shiweike to compare.
Coarse aggregate adopts basalt 10-20mm, the rubble of 5-10mm, limestone 3-8mm rubble, Machine-made Sand.Filler is breeze, cement.Pitch adopts SBS modifying asphalt.The grating of mineral aggregate is in Table four.
Table four AC-16 type mineral aggregate gradation
| Size of mesh/mm | 19.0 | 16.0 | 13.2 | 9.5 | 4.75 | 2.36 | 1.18 | 0.6 | 0.3 | 0.15 | 0.075 |
| Percent of pass/% | 100 | 95.4 | 86.4 | 74.9 | 46.3 | 33.2 | 21.6 | 13.3 | 9.1 | 7.7 | 6.4 |
The contrast of table five asphalt
| Experimental project | Hot-mix asphalt mixture | Embodiment bis-prepares warm-mixing agent | DAT |
| Mix temperature/℃ | 178 | 150 | 152 |
| Dynamic stability/mm -1 | 4240 | 4938 | 4652 |
| Low-temperature bending/μ ε | 2746 | 2748 | 2748 |
| Freeze thawing splitting/% | 86.3 | 91.2 | 87.9 |
The contrast of table six Mashell molding test specimen
| Experimental project | Hot-mix asphalt mixture | Embodiment bis-prepares warm-mixing agent | DAT | Technical requirements |
| Voidage/% | 3.62 | 3.71 | 4.06 | 3-5 |
| Pitch saturation ratio/% | 80.19 | 82.09 | 81.63 | 75-85 |
| Void in mineral aggregate/% | 17.39 | 17.18 | 17.26 | ≥17.0 |
| VCA min/% | 42.9 | 42.1 | 42.7 | ≤VCA DRC |
| VCA DRC/% | 40.01 | 40.18 | 40.16 | -- |
| Marshall stability/kN | 8.83 | 7.62 | 7.14 | ≥6.0 |
| Flow valuve/0.1mm | 28.7 | 29.3 | 28.5 | 20-50 |
Embodiment 3
In there-necked flask, add 27.0g(0.1mol) octadecyl dimethyl tertiary amine, the dioxane of 50ml and 23.1g(0.25mol) epoxy chloropropane, be heated to 35 ℃ reaction 5h obtain intermediate product.At 35 ℃, in there-necked flask, drip 35.5g(0.26mol) dimethylamine.After dripping, be warmed up to 90 ℃ of reaction 8h, obtain bi-quaternary ammonium salt emulsifying agent.The methyl alcohol that adds the Sodium phosphate dibasic of 21.3g (0.15mol), the water of 10ml and 30ml in another one there-necked flask, be heated to 80 ℃, in reaction flask, drip 13.8 g(0.15mol) epoxy chloropropane, at 60 ℃, react 2h after dripping completely and obtain intermediate.Final step is blended in the bi-quaternary ammonium salt emulsifying agent of preparation at 60 ℃ and reacts 3.5h with intermediate, obtains zwitter-ion emulsifying agent, steams solvent, and separation obtains purer zwitter-ion emulsifying agent through post to obtain crude product.
The application examples of embodiment 3:
Adopt the DAT mixture performance of SMA-13 type bituminous concrete warm mix and hot asphalt and virtue Wei Shiweike to compare.
Coarse aggregate adopts basalt 10-15mm, the rubble of 5-10mm, limestone 3-5mm rubble, Machine-made Sand.Filler is breeze, cement.Pitch adopts SBS modifying asphalt.Admixture 0.3% lignin fibre, bitumen aggregate ratio 6.0%.The grating of mineral aggregate is in Table seven
Table seven SMA-13 type mineral aggregate gradation
| Size of mesh/mm | 16.0 | 13.2 | 9.5 | 4.75 | 2.36 | 1.18 | 0.6 | 0.3 | 0.15 | 0.075 |
| ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? |
| Percent of pass/% | 100 | 97 | 63.5 | 27.7 | 21 | 17.8 | 14.9 | 13.1 | 11.7 | 10.5 |
The contrast of table eight asphalt
| Experimental project | Hot-mix asphalt mixture | Embodiment tri-prepares warm-mixing agent | DAT |
| Mix temperature/℃ | 162 | 132 | 141 |
| Freeze thawing splitting/% | 86.4 | 92.7 | 89.3 |
The contrast of table nine Mashell molding test specimen
| Experimental project | Hot-mix asphalt mixture | Embodiment tri-prepares warm-mixing agent | DAT | Technical requirements |
| Voidage/% | 4.07 | 4.07 | 4.13 | 3-5 |
| Pitch saturation ratio/% | 83.6 | 83.8 | 78.2 | 75-85 |
| Void in mineral aggregate/% | 19.45 | 21.40 | 19.28 | ≥17.0 |
| VCA min/% | 47.5 | 46.8 | 47.9 | ≤VCA DRC |
| VCA DRC/% | 43.63 | 42.66 | 43.78 | -- |
| Marshall stability/kN | 8.59 | 8.32 | 7.06 | ≥6.0 |
| Flow valuve/0.1mm | 38.65 | 40.85 | 39.47 | 20-50 |
Embodiment 4
In there-necked flask, add 27.0g(0.1mol) stearylamine, the octane of 50ml and 19.4g(0.21mol) epoxy chloropropane, be heated to 70 ℃ reaction 7.5h obtain intermediate product.At 70 ℃, in there-necked flask, drip 28.3g(0.30mol) methylamine.After dripping, be warmed up to 90 ℃ of reaction 6.5h, obtain bi-quaternary ammonium salt emulsifying agent.The octane that adds the dipotassium hydrogen phosphate of 22.6g (0.13mol), the water of 10ml and 30ml in another one there-necked flask, be heated to 40 ℃, in reaction flask, drip 11.0g(0.12mol) epoxy chloropropane, at 40 ℃, react 1h after dripping completely and obtain intermediate.Final step is blended in the bi-quaternary ammonium salt emulsifying agent of preparation at 90 ℃ and reacts 4h with intermediate, obtains zwitter-ion emulsifying agent, steams solvent, and separation obtains purer zwitter-ion emulsifying agent through post to obtain crude product.
The application examples of embodiment 4
Adopt the DAT mixture performance of AC-13 type bituminous concrete warm mix and hot asphalt and virtue Wei Shiweike to compare.
Coarse aggregate adopts basalt 10-15mm, the rubble of 5-10mm, limestone 3-5mm rubble, Machine-made Sand.Filler is breeze, cement.Pitch adopts SBS modifying asphalt.The grating of mineral aggregate is in Table ten.
Table ten AC-13 type mineral aggregate gradation
Table ten AC
-the contrast of 13 asphalts
| Experimental project | Hot-mix asphalt mixture | Embodiment tetra-prepares warm-mixing agent | DAT |
| Mix temperature/℃ | 158 | 130 | 133 |
| Dynamic stability/mm -1 | 5655 | 6943 | 6014 |
| Low-temperature bending/μ ε | 2638 | 2915 | 2732 |
| Freeze thawing splitting/% | 87.9 | 93.6 | 85.3 |
Table ten two Mashell molding test specimen contrasts
| Experimental project | Hot-mix asphalt mixture | Embodiment tetra-prepares warm-mixing agent | DAT | Technical requirements |
| Voidage/% | 3.17 | 3.18 | 3.69 | 3-5 |
| Pitch saturation ratio/% | 83.02 | 82.08 | 80.19 | 75-85 |
| Void in mineral aggregate/% | 17.79 | 17.35 | 17.21 | ≥17.0 |
| VCA min/% | 41.8 | 41.8 | 41.7 | ≤VCA DRC |
| VCA DRC/% | 40.09 | 40.11 | 40.02 | -- |
| Marshall stability/kN | 8.68 | 7.14 | 6.17 | ≥6.0 |
| Flow valuve/0.1mm | 32.3 | 33.6 | 31.4 | 20-50 |
Embodiment 5
In there-necked flask, add 24.1g(0.1mol) cetylamine, the DMF of 50ml and 21.3g(0.23mol) epoxy chloropropane, be heated to 45 ℃ reaction 3h obtain intermediate product.At 45 ℃, in there-necked flask, drip 22.3g(0.22mol) triethylamine.After dripping, be warmed up to 85 ℃ of reaction 5h.Obtain bi-quaternary ammonium salt emulsifying agent.The N that adds the potassium primary phosphate of 15.0g (0.11mol), the water of 10ml and 30ml in another one there-necked flask, dinethylformamide, be heated to 50 ℃, in reaction flask, drip 10.1g(0.11mol) epoxy chloropropane, at 50 ℃, react 1.5h after dripping completely and obtain intermediate.Final step is blended in the bi-quaternary ammonium salt emulsifying agent of preparation at 80 ℃ and reacts 4h with intermediate, obtains zwitter-ion emulsifying agent, steams solvent, and separation obtains purer zwitter-ion emulsifying agent through post to obtain crude product.
The application examples of embodiment 5
Adopt the DAT mixture performance of AC-16 type bituminous concrete warm mix and hot asphalt and virtue Wei Shiweike to compare.
Coarse aggregate adopts basalt 10-20mm, the rubble of 5-10mm, limestone 3-8mm rubble, Machine-made Sand.Filler is breeze, cement.Pitch adopts SBS modifying asphalt.The grating of mineral aggregate is in Table 13.
Table ten three AC-16 type mineral aggregate gradations
| Size of mesh/mm | 19.0 | 16.0 | 13.2 | 9.5 | 4.75 | 2.36 | 1.18 | 0.6 | 0.3 | 0.15 | 0.075 |
| Percent of pass/% | 100 | 95.4 | 86.4 | 74.9 | 46.3 | 33.2 | 21.6 | 13.3 | 9.1 | 7.7 | 6.4 |
The contrast of table ten four asphalts
| Experimental project | Hot-mix asphalt mixture | Embodiment five prepares warm-mixing agent | DAT |
| Mix temperature/℃ | 171 | 143 | 149 |
| Dynamic stability/mm -1 | 4852 | 4861 | 4537 |
| Low-temperature bending/μ ε | 2681 | 2694 | 2572 |
| Freeze thawing splitting/% | 88.1 | 90.7 | 87.5 |
Table ten five Mashell molding test specimen contrasts
| Experimental project | Hot-mix asphalt mixture | Embodiment five prepares warm-mixing agent | DAT | Technical requirements |
| Voidage/% | 4.13 | 4.37 | 4.89 | 3-5 |
| Pitch saturation ratio/% | 83.34 | 82.68 | 80.43 | 75-85 |
| Void in mineral aggregate/% | 17.35 | 17.26 | 17.30 | ≥17.0 |
| VCA min/% | 47.3 | 47.3 | 47.6 | ≤VCA DRC |
| VCA DRC/% | 45.31 | 45.32 | 46.28 | -- |
| Marshall stability/kN | 8.02 | 7.78 | 6.54 | ≥6.0 |
| Flow valuve/0.1mm | 28.2 | 28.7 | 27.6 | 20-50 |
Embodiment 6
In there-necked flask, add 21.3g(0.1mol) tetradecy lamine, the dioxane of 50ml and 23.1g(0.25mol) epoxy chloropropane, be heated to 70 ℃ reaction 9h obtain intermediate product.At 70 ℃, in there-necked flask, drip 30.4g(0.3mol) triethylamine.After dripping, be warmed up to 90 ℃ of reaction 8h, obtain bi-quaternary ammonium salt emulsifying agent.The dioxane that adds the Potassium hydrogen sulfite of 16.8g (0.14mol), the water of 10ml and 30ml in another one there-necked flask, be heated to 55 ℃, in reaction flask, drip 9.2g(0.1mol) epoxy chloropropane, at 55 ℃, react 2h after dripping completely and obtain intermediate.Final step is blended in the bi-quaternary ammonium salt emulsifying agent of preparation at 70 ℃ and reacts 4.5h with intermediate, obtains zwitter-ion emulsifying agent, steams solvent, and separation obtains purer zwitter-ion emulsifying agent through post to obtain crude product.
The application examples of embodiment 6
Adopt the DAT mixture performance of SMA-13 type bituminous concrete warm mix and hot asphalt and virtue Wei Shiweike to compare.
Coarse aggregate adopts basalt 10-15mm, the rubble of 5-10mm, limestone 3-5mm rubble, Machine-made Sand.Filler is breeze, cement.Pitch adopts SBS modifying asphalt.Admixture 0.3% lignin fibre, bitumen aggregate ratio 6.0%.The grating of mineral aggregate is in Table 16
Table ten six SMA-13 type mineral aggregate gradations
| Size of mesh/mm | 16.0 | 13.2 | 9.5 | 4.75 | 2.36 | 1.18 | 0.6 | 0.3 | 0.15 | 0.075 |
| Percent of pass/% | 100 | 97 | 63.5 | 27.7 | 21 | 17.8 | 14.9 | 13.1 | 11.7 | 10.5 |
The contrast of table ten seven asphalts
| Experimental project | Hot-mix asphalt mixture | Embodiment six prepares warm-mixing agent | DAT |
| Mix temperature/℃ | 158 | 129 | 134 |
| Freeze thawing splitting/% | 90.4 | 92.1 | 87.7 |
Table ten eight Mashell molding test specimen contrasts
| Experimental project | Hot-mix asphalt mixture | Embodiment six prepares warm-mixing agent | DAT | Technical requirements |
| Voidage/% | 4.01 | 4.02 | 4.76 | 3-5 |
| Pitch saturation ratio/% | 83.9 | 83.9 | 77.4 | 75-85 |
| Void in mineral aggregate/% | 18.71 | 20.34 | 17.06 | ≥17.0 |
| VCA min/% | 47.9 | 47.4 | 47.2 | ≤VCA DRC |
| VCA DRC/% | 47.64 | 47.18 | 46.88 | -- |
| Marshall stability/kN | 8.93 | 8.15 | 7.22 | ≥6.0 |
| Flow valuve/0.1mm | 38.24 | 39.75 | 38.37 | 20-50 |
Embodiment 7
In there-necked flask, add 18.5g(0.1mol) amino dodecane, the THF of 50ml and 27.8g(0.3mol) epoxy chloropropane, be heated to 65 ℃ reaction 5.5h obtain intermediate product.At 40 ℃, in there-necked flask, drip 28.3g(0.28mol) triethylamine.After dripping, be warmed up to 75 ℃ of reaction 8h, obtain bi-quaternary ammonium salt emulsifying agent.The THF that adds the S-WAT of 18.9g (0.15mol), the water of 10ml and 30ml in another one there-necked flask, be heated to 75 ℃, in reaction flask, drip 9.2g(0.1mol) epoxy chloropropane, at 75 ℃, react 3h after dripping completely and obtain intermediate.Final step is blended in the bi-quaternary ammonium salt emulsifying agent of preparation at 85 ℃ and reacts 5h with intermediate, obtains zwitter-ion emulsifying agent, steams solvent, and separation obtains purer zwitter-ion emulsifying agent through post to obtain crude product.
The application examples of embodiment 7
Adopt the DAT mixture performance of SMA-13 type bituminous concrete warm mix and hot asphalt and virtue Wei Shiweike to compare.
Coarse aggregate adopts basalt 10-15mm, the rubble of 5-10mm, limestone 3-5mm rubble, Machine-made Sand.Filler is breeze, cement.Pitch adopts SBS modifying asphalt.Admixture 0.3% lignin fibre, bitumen aggregate ratio 6.0%.The grating of mineral aggregate is in Table 19
Table ten nine SMA-13 type mineral aggregate gradations
| Size of mesh/mm | 16.0 | 13.2 | 9.5 | 4.75 | 2.36 | 1.18 | 0.6 | 0.3 | 0.15 | 0.075 |
| Percent of pass/% | 100 | 97 | 63.5 | 27.7 | 21 | 17.8 | 14.9 | 13.1 | 11.7 | 10.5 |
The contrast of table two ten asphalts
| Experimental project | Hot-mix asphalt mixture | Embodiment seven prepares warm-mixing agent | DAT |
| Mix temperature/℃ | 163 | 137 | 138 |
| Freeze thawing splitting/% | 89.2 | 90.8 | 72.4 |
Table two 11 Mashell molding test specimen contrasts
| Experimental project | Hot-mix asphalt mixture | Embodiment six prepares warm-mixing agent | DAT technical requirements |
| Voidage/% | 3.56 | 3.19 | 3.983-5 |
| Pitch saturation ratio/% | 82.1 | 84.3 | 76.175-85 |
| Void in mineral aggregate/% | 17.77 | 18.02 | 17.64≥17.0 |
| VCA min/% | 46.8 | 46.8 | 47.1≤VCA DRC |
| VCA DRC/% | 46.17 | 46.16 | 47.08-- |
| Marshall stability/kN | 8.88 | 8.62 | 6.54≥6.0 |
| Flow valuve/0.1mm | 33.19 | 35.62 | 34.4720-50 |
Claims (3)
1. an amphoteric ion type asphalt warm-mix agent, is characterized in that: its molecule contains three quaternary ammonium salt ions, and its structure meets following formula I,
In formula I, R
1for dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl or nonadecyl, R
2=R
3=CH
3, R
2=R
3=Et, R
2=CH
3, R
3=H, R
2=H, R
3=CH
3, R
2=Et, R
3=H, R
2=Butyl, R
3=H, R
2=CH
2cH
2oH, R
3=H, R
2=CH
3or R
3=H; M is S-WAT, potassium sulfite, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, potassium primary phosphate, sodium pyrosulfate or sal enixum.
2. the preparation method of amphoteric ion type asphalt warm-mix agent claimed in claim 1, is characterized in that: comprise the steps:
Step 1) is prepared double quaternary ammonium salt type asphalt emulsifier: by long-chain fat sulfonamide derivatives and epoxy chloropropane and solvent formation reaction system, 10 ℃～50 ℃ reactions 0.5 hour～3 hours, then in reaction system, add a certain amount of amine, 60 ℃～90 ℃ reactions 3 hours～6 hours; Make double quaternary ammonium salt type asphalt emulsifier; The mol ratio of described long-chain fat amine, epoxy chloropropane and amine is 1:2～3:2～3;
Described long-chain fat sulfonamide derivatives is the compound of structure shown in structural formula II:
In formula II, R
1be selected from any one in tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, oil base, rosinyl.
Described epoxy chloropropane is the compound of structure shown in structural formula III:
Described amine is the compound of structure shown in structural formula IV:
In formula IV, R
2=R
3=CH
3, R
2=R
3=Et, R
2=CH
3, R
3=H, R
1=R
2=H, R
3=CH
3, R
1=R
2=Et, R
3=H, R
1=R
2=Butyl, R
3=H, R
1=R
2=CH
2cH
2oH, R
3=H, R
1=stearylamine, R
2=CH
3or R
3=H;
Step 2) prepare intermediate: by epoxy chloropropane and inorganic acid salt and solvent formation reaction system, 60 ℃～100 ℃ reactions, after 1～3 hour, make intermediate; The mol ratio of described epoxy chloropropane and inorganic acid salt is 1～1.5:1;
Described inorganic acid salt M is S-WAT, potassium sulfite, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, potassium primary phosphate, sodium pyrosulfate, sal enixum etc.;
Step 3) makes amphoteric ion type asphalt warm-mix agent: the double quaternary ammonium salt type asphalt emulsifier of step (1) gained is joined in the system of intermediate of step (2) gained, 40 ℃～80 ℃ reactions 3～5 hours; Obtain amphoteric ion type asphalt warm-mix agent of the present invention; The ratio of bi-quaternary ammonium salt asphalt emulsifier and intermediate is 1～1.5:1.
3. method according to claim 2, it is characterized in that: the solvent in step (1) and step (2) is any one in dimethyl sulfoxide (DMSO), DMF, dioxane, acetonitrile, octane, ethanol, toluene, methyl alcohol, tetrahydrofuran (THF), ethyl acetate, normal hexane, hexanaphthene, chloroform, methylene dichloride, water, pyridine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968363A (en) * | 2016-05-17 | 2016-09-28 | 江苏中路新材料科技发展有限公司 | Organic silicon resin capable of improving water damage resistance of roads as well as preparation method and application of organic silicon resin |
| CN106928470A (en) * | 2017-04-13 | 2017-07-07 | 山东大学 | A kind of teritary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN106947093A (en) * | 2017-04-13 | 2017-07-14 | 山东大学 | A kind of primary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN107827772A (en) * | 2017-11-16 | 2018-03-23 | 江苏苏博特新材料股份有限公司 | A kind of cation modified asphalt emulsifying agent, its preparation method and its application |
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4313895A (en) * | 1980-06-24 | 1982-02-02 | Akzona Incorporated | Alkoxylated diquaternary ammonium compounds |
| JP2001329176A (en) * | 2000-05-25 | 2001-11-27 | Asahi Denka Kogyo Kk | Emulsifying agent for asphalt |
| CN1778459A (en) * | 2004-11-24 | 2006-05-31 | 李新宝 | Surface activator from citrate three-long chain alkyl triple quaternary ammonium salt cation and preparation thereof |
| CN1942525A (en) * | 2004-02-18 | 2007-04-04 | 米德维斯特沃克公司 | Method for producing bituminous compositions |
| CN101313031A (en) * | 2005-09-22 | 2008-11-26 | 万喜路桥公司 | Novel bitumen emulsion-based composition |
| CN101679754A (en) * | 2007-04-16 | 2010-03-24 | 米德韦斯瓦科公司 | Method for producing bitumen compositions |
| RU2407764C2 (en) * | 2008-11-27 | 2010-12-27 | ООО НПЦ "Инвента" | Bitumen emulsion |
| CN102294196A (en) * | 2011-06-23 | 2011-12-28 | 河南省道纯化工技术有限公司 | Preparation method for hydroxy sulfobetaine amphoteric surfactant |
| CN102516093A (en) * | 2011-12-08 | 2012-06-27 | 江苏博特新材料有限公司 | Gemini type asphalt emulsifier and preparation method thereof |
| CN102580607A (en) * | 2011-12-30 | 2012-07-18 | 武汉理工大学 | Technology for synthesizing bisquaternary ammonium salt slow-breaking quick-setting asphalt emulsifier |
| CN102924299A (en) * | 2012-08-24 | 2013-02-13 | 武汉理工大学 | Preparation method of novel slow-crack slow-coagulation asphalt emulsifier |
| CN102936206A (en) * | 2012-08-24 | 2013-02-20 | 武汉理工大学 | Quick-breaking and quick-curing type asphalt emulsifier preparation method |
-
2013
- 2013-12-09 CN CN201310666052.8A patent/CN103613941B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4313895A (en) * | 1980-06-24 | 1982-02-02 | Akzona Incorporated | Alkoxylated diquaternary ammonium compounds |
| JP2001329176A (en) * | 2000-05-25 | 2001-11-27 | Asahi Denka Kogyo Kk | Emulsifying agent for asphalt |
| CN1942525A (en) * | 2004-02-18 | 2007-04-04 | 米德维斯特沃克公司 | Method for producing bituminous compositions |
| CN1778459A (en) * | 2004-11-24 | 2006-05-31 | 李新宝 | Surface activator from citrate three-long chain alkyl triple quaternary ammonium salt cation and preparation thereof |
| CN101313031A (en) * | 2005-09-22 | 2008-11-26 | 万喜路桥公司 | Novel bitumen emulsion-based composition |
| CN101679754A (en) * | 2007-04-16 | 2010-03-24 | 米德韦斯瓦科公司 | Method for producing bitumen compositions |
| RU2407764C2 (en) * | 2008-11-27 | 2010-12-27 | ООО НПЦ "Инвента" | Bitumen emulsion |
| CN102294196A (en) * | 2011-06-23 | 2011-12-28 | 河南省道纯化工技术有限公司 | Preparation method for hydroxy sulfobetaine amphoteric surfactant |
| CN102516093A (en) * | 2011-12-08 | 2012-06-27 | 江苏博特新材料有限公司 | Gemini type asphalt emulsifier and preparation method thereof |
| CN102580607A (en) * | 2011-12-30 | 2012-07-18 | 武汉理工大学 | Technology for synthesizing bisquaternary ammonium salt slow-breaking quick-setting asphalt emulsifier |
| CN102924299A (en) * | 2012-08-24 | 2013-02-13 | 武汉理工大学 | Preparation method of novel slow-crack slow-coagulation asphalt emulsifier |
| CN102936206A (en) * | 2012-08-24 | 2013-02-20 | 武汉理工大学 | Quick-breaking and quick-curing type asphalt emulsifier preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 施来顺等: ""Gemini型阳离子沥青乳化剂的合成与性能测试"", 《石油沥青》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968363A (en) * | 2016-05-17 | 2016-09-28 | 江苏中路新材料科技发展有限公司 | Organic silicon resin capable of improving water damage resistance of roads as well as preparation method and application of organic silicon resin |
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| CN106947093B (en) * | 2017-04-13 | 2019-02-26 | 山东大学 | A kind of primary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN106928470B (en) * | 2017-04-13 | 2019-03-05 | 山东大学 | A kind of teritary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN108275918A (en) * | 2017-09-26 | 2018-07-13 | 深圳海川新材料科技股份有限公司 | A kind of ordor removing asphalt and preparation method thereof |
| CN107827772A (en) * | 2017-11-16 | 2018-03-23 | 江苏苏博特新材料股份有限公司 | A kind of cation modified asphalt emulsifying agent, its preparation method and its application |
| CN107827772B (en) * | 2017-11-16 | 2020-05-26 | 江苏苏博特新材料股份有限公司 | Cation modified asphalt emulsifier, preparation method and application thereof |
| CN109294254A (en) * | 2018-09-20 | 2019-02-01 | 石磊 | A kind of preparation method of emulsifying warm-mixing agent |
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