CN103804931B - A kind of modified asphalt composite and preparation method thereof - Google Patents
A kind of modified asphalt composite and preparation method thereof Download PDFInfo
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- CN103804931B CN103804931B CN201210440322.9A CN201210440322A CN103804931B CN 103804931 B CN103804931 B CN 103804931B CN 201210440322 A CN201210440322 A CN 201210440322A CN 103804931 B CN103804931 B CN 103804931B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
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Abstract
The invention discloses a kind of modified asphalt composite and preparation method thereof, modified asphalt composite is by weight percentage including following components：Matrix pitch 90%～98.7%, butadiene-styrene rubber 0.2%～6%, wherein additive 0.1%～4%, additive are one or more in ethanolamine, diethanolamine or triethanolamine.The bituminous composition ageing resistace of the present invention is strong, hence it is evident that improves ductility of the Colophonium containing butadiene-styrene rubber during high-temperature storage, has especially delayed the decrease speed of ductility after Thin Film Oven Test TFOT, and the cost of additive used is relatively low, easy to use.
Description
Technical field
The present invention relates to a kind of bituminous composition and preparation method thereof, has particularly under high-temperature storage conditions good resistance to
Modified asphalt composite of aging and preparation method thereof, is more particularly directed to a kind of high temperature age resister, specially
Delay the additive of bitumen ductility decrease speed under high-temperature storage conditions.
Background technology
By the research of relation between the pavement performance to Colophonium and its property, this area thinks that low-temperature ductility is asphalt adhesive
One of three main performances of ramming material, reflect the colloidal stability and cohesiveness for representing Colophonium.In general, Colophonium user
Very it is concerned about the ductility of Colophonium, especially the low-temperature ductility after Thin Film Oven Test TFOT（Such as 10 DEG C and 15 DEG C of ductilities）.It is generally believed that
The ductility characterizes the ductility after Colophonium and the hot mix of building stones, and used as one of the important indicator of road asphalt performance, which is big
It is little that there is good dependency with pavement cracking.
Rubber polymer, especially butadiene-styrene rubber are the elite clones for improving Colophonium low-temperature ductility, only need to be added on a small quantity
Can just increase substantially the low-temperature ductility of Colophonium, therefore butadiene-styrene rubber has become
The first-selected macromolecular material of degree.For example, 1% butylbenzene rubber in US 41305416, is added in Colophonium of 4 DEG C of ductilities for 7cm
Its ductility can be brought up to more than 150cm by glue；In US 5002987 and US6136899, with a small amount of low temperature polymerization butylbenzene rubber
Glue latex can also make 4 DEG C of ductilities of Colophonium bring up to more than 150cm.
Colophonium requires heat to uniform temperature to keep which to be chronically at flow regime, i.e. Colophonium using front generally requiring
The very long high-temperature storage phase.For example, oil plant needs to store certain hour in storage tank high temperature from asphalt production to sale, to protect
Hold integration of production and sale, reply changes in market supply and demand；The bad weather or other factors of construction period all can inevitably be delayed construction
Time, it is also desirable to which Colophonium stores a period of time under the high temperature conditions.Colophonium inevitably occurs irreversible during thermmal storage
Heat ageing, is mainly shown as that needle penetration declines, viscosity rises, softening point is improved and ductility declines.In above-mentioned qualitative change, prolong
After spending especially thin film oven, ductility declines most soon, and code requirement is very high, and manufacturer is difficult to reserve in process of production again,
Therefore longer Colophonium of many thermmal storage times is being dispatched from the factory or is being prolonged using 10 DEG C and 15 DEG C after front ductility especially thin film oven
Degree is unqualified.
It is well known that butadiene-styrene rubber is unsaturated rubber, degraded is easy under long term high temperature environment.Therefore, by fourth
Benzene rubber improves the Colophonium of ductility, especially adds butadiene-styrene rubber on a small quantity（Such as 1% or so）Colophonium, during high-temperature storage
The ductility speed that especially 10 DEG C and 15 DEG C of ductilities decline after thin film oven is quickly.
Aging point of three phases of Colophonium, i.e., during thermmal storage it is aging, and aggregate heat mix and stir during it is aging and in work
Journey during use aging.In the design asphalt of needle penetration or viscosity chassification, tested with thin film oven or rotary thin film in drying oven
Simulation Colophonium is aging with the hot mix of aggregate, and defines penetration ratio or ratio of viscosities and different temperatures ductility after the test
Etc. index, i.e. thin film oven or the property after rotary thin film in drying oven test.Ageing of asphalt be it is inevitable, but can take plus
The method for entering additive reduces aging speed.
US 5580376 can be by the rotary thin film in drying oven viscosity of Colophonium using 0.9% hydrocarbyl dithiophosphoric acid slaine
Than being reduced to 2.36 by a small margin from 2.40；US 4460723 reduces pitch and modified drip using inorganic or organic alkali metal salt
The blue or green bodying speed during high-temperature storage；US 4440886 reduces pitch or modified using alkali-metal nitrite
Bodying speed of the Colophonium during high-temperature storage, and the substantially no effect of antioxidant；US 4645538 uses alkylene two
60 DEG C of viscosity after the Thin Film Oven Test TFOT of thiocarbamate reduction Colophonium；It is sub- that 1227140 A2 of EP introduce alkyl succinyl
Amine can reduce ageing index AI after the rotary thin film in drying oven test of visbreaking Colophonium so as to reach straight asphalt level.It is above-mentioned
Patented technology especially reduces Thin Film Oven Test TFOT without reference to the ductility of Colophonium or modified pitch during high-temperature storage is delayed
The additive of 10 DEG C and 15 DEG C ductility decrease speeds afterwards.Another problem that above-mentioned patented technology is present is, in addition to slaine,
The additive price which is related to is universal higher.If if Colophonium age-inhibiting addition unit price is too high, consumption is excessive, can be to use
Unit brings cost pressure, loses the market competitiveness.
At present, drip during preventing thermmal storage using the restriction physical method such as storage temperature and time more than each asphalt production company
Blue or green property significantly declines, such as Kang Fei（ConocoPhillips）And Coriolis（Koch）Regulation, short term stored（Within 2 weeks）Temperature
Less than 135 DEG C, long term storage（More than 2 weeks）Heating should be stopped；If shell regulation must long-time storage, its temperature should be
More than softening point 20～25 DEG C, while stopping circulation.Also someone advocate in strict accordance with Colophonium viscosity-temperature curve requirement temperature heating,
Control is overheated, filling with inert gas the method such as contacts to reduce Colophonium with oxygen above the Colophonium, delays the aging of Colophonium.
Ethanolamine is simultaneously few as the document and patent of asphalt additive.CN102174264A is using diethanolamine as Colophonium
One of component of antistripping agent, asphalt have good anti-strip effect；CN101602862 is using triethanolamine as water base
One of component of warm-mixed asphalt additive, as the auxiliary agent of surfactant, rises and helps emulsification；CN101701133A is by three second
Hydramine acts primarily as rust inhibition as one of water-based emulsion Colophonium pipeline anti-corrosive paint component.
The content of the invention
To overcome weak point of the prior art, it is an object of the invention to provide a kind of modified asphalt composite and its
Preparation method.The modified asphalt composite of the present invention can improve ageing-resistant performance of the Colophonium during long term high temperature storage, especially
Which is the decrease speed of the low-temperature ductility for having delayed Colophonium Jing after long term high temperature storage.
The deterioration of the aging each index for being Colophonium during long term high temperature storage of indication of the present invention, especially stores up in high temperature
The Thin Film Oven Test TFOT of Colophonium during depositing（TFOT）10 DEG C and 15 DEG C of ductilities declines afterwards.
The modified asphalt composite of the present invention, includes following components with composition weight percentages：
（1）Matrix pitch 90%～98.7%, preferably 97.5～98.7%；
（2）Butadiene-styrene rubber（SBR）0.2%～6%, preferably 0.5%～1.5%；
（3）Additive 0.1%～4%, preferably 0.5%～1%；
Wherein additive is one or more in monoethanolamine, diethanolamine or triethanolamine.
Tapped oil is preferably added in modified asphalt composite of the present invention, tapped oil addition is modified asphalt composite weight
1% ~ 9.7%.
Matrix pitch of the present invention is residual oil and/or Colophonium, and wherein residual oil is decompression residuum He ∕ or viscous crude normal pressure slag
Oil, Colophonium refer to road asphalt, can for ordinary road Colophonium, A level road asphalts, B level road asphalts, C levels road asphalt and
Heavy-duty road asphalt etc..Residual oil is He ∕ or penetration of bitumens depend on the addition of the trade mark and tapped oil of prepared sample.
Butadiene-styrene rubber of the present invention be 1500 poly- series of low temperature breast, 1600 series, Series 1700,1800 it is serial and
One or more in its latex, preferably the 1500 of 1500 series and/or 1502 butadiene-styrene rubber.Block butadiene-styrene rubber is by cutting
Cut, crush etc. during technique directly can be added to residual oil or Colophonium by cutter or colloid mill, it is also possible to by agitator, cut
Cut machine or colloid mill is dissolved in tapped oil, form butadiene-styrene rubber mother solution, disperse in adding residual oil.
Tapped oil of the present invention is lube oil finishing tapped oil, typically requires arene content（Asphalt component is surveyed
Determine method, SH/T0509）In more than 20wt%, preferred more than 35wt%.Tapped oil includes subtracting one that each line lube oil finishing is taken out to subtracting four
One or more in the refined tapped oil of fuel-displaced and residual lubricating oil, preferably subtracts three, in the line lube oil finishing tapped oil that subtracts four
A kind of or above two extracts oil mixture out.If with the solvent classes used by lube oil finishing, lube oil finishing tapped oil can be with
Be furfural, phenol and N-Methyl pyrrolidone tapped oil in one or more.
The preparation method of modified asphalt composite of the present invention, including following content：The base that butadiene-styrene rubber, additive are added to
In matter Colophonium, it is uniformly dispersed, obtains modified asphalt composite.
In the inventive method, preferably butadiene-styrene rubber, additive and tapped oil are added in matrix pitch.
In the inventive method, dispersion temperature be 120 ~ 180 DEG C, jitter time be 10 ~ 120 minutes, preferably 30～60 minutes,
Dispersing apparatus can adopt mixing plant, cutter or colloid mill.
In the inventive method, described butadiene-styrene rubber, additive and tapped oil be added to the method in matrix pitch just like
Under it is several, but be not limited to following methods：（1）By butadiene-styrene rubber after cutting, crushing, add together with tapped oil and additive
To residual oil He in ∕ or Colophonium；（2）By butadiene-styrene rubber after cutting, crushing, dissolved by agitator, cutter or colloid mill
In tapped oil, butadiene-styrene rubber mother solution is formed, is added in matrix pitch, then adding additive；（3）First additive is added
Enter in matrix pitch, be subsequently adding crush after butadiene-styrene rubber and tapped oil or method（2）The butadiene-styrene rubber mother solution for obtaining；
（4）First tapped oil is added in matrix pitch, be subsequently adding crush after butadiene-styrene rubber and additive.Wherein, method（2）For
Method for optimizing, the method contribute to reducing dispersion butadiene-styrene rubber as the butadiene-styrene rubber after crushing is prepared into mother solution first individually
The produce load of equipment, and then it is favorably improved yield.
In the additive of the present invention, monoethanolamine and triethanolamine fusing point are respectively 10.5 DEG C and 21.6 DEG C, under room temperature are
Liquid, used in the present composition being directly added into；27.4 DEG C of diethanolamine fusing point, for convenience of using, less than this temperature
It is lower need to heat fusing after used in the way of liquid.
The modified asphalt composite of the present invention substantially increases ageing resistace, especially by adding alkamine additive
Which is the ductility for significantly improving styrene butadiene rubber modified asphalt during high-temperature storage, after especially having delayed Thin Film Oven Test TFOT
The decrease speed of ductility, and the cost of additive ethanolamine used is relatively low, it is convenient to add.
Specific embodiment
The present invention program and effect are further illustrated with reference to embodiment.
The high-temperature storage method of the present invention is that 1 liter of enamelled cup equipped with 800～900g samples is put into 140 DEG C of air blast
In drying baker, the index of the different high-temperature storage time samples of measurement, and the effect of additive is judged according to index situation of change, see
Tables 1 and 2.1500 granules of SBR used by the embodiment of the present invention, are " the Kunlun " the board butadiene-styrene rubber produced by Lan Hua companies
Grain；1502 granules of SBR are " Jilin Chemical " board butadiene-styrene rubber granules produced by Jilin Chemical company.
The preparation method of butadiene-styrene rubber mother solution：Subtracting three, line tapped oil is heated to 100 DEG C, adds SBR granules, and line is taken out to subtract three
The fuel-displaced weight ratio with SBR granules is 84：16, then the mother solution that butadiene-styrene rubber is 16wt% is made into cutter.In mother solution
During preparation, mother solution temperature is less than 180 DEG C.
Embodiment 1 ~ 3
The needle penetration that 1194g is added in 2 liters of enamelled cup is 70（1/10mm）Tahe residual oil and 52g subtract four line phenol taken out
It is fuel-displaced, it is warmed up to 140 DEG C.Then, 1500 granules of 12g SBR and 10.1g ethanolamine are added.Embodiment 1 be monoethanolamine,
Embodiment 2 is diethanolamine, embodiment 3 is triethanolamine.Meanwhile, start high shear machine and shear 30 minutes, obtain modified pitch
Compositionss.Then, 400g or so sample determination property is taken out, remaining sample loads in 1 liter of enamelled cup, and puts it into 140 DEG C
In air dry oven, high-temperature storage test is carried out.
Embodiment 4 ~ 7
The needle penetration that 1252g is added in 2 liters of enamelled cup is 107（1/10mm）Tahe residual oil, when the residual oil heats up simultaneously
It is stable to add 8gSBR1502 granules and ethanolamine at 140 DEG C, while start high shear machine shearing 30 minutes, it is modified
Bituminous composition.Then, 400g or so sample determination property is taken out, remaining sample loads in 1 liter of enamelled cup, and puts it into
In 140 DEG C of air dry ovens, high-temperature circulation test is carried out.
Wherein, 4 ethanolamine of embodiment consists of monoethanolamine 8.4g, diethanolamine and triethanolamine and is respectively 1.8g；It is real
Example 5 is applied for monoethanolamine 8.4g, diethanolamine 3.6g；Embodiment 6 is monoethanolamine 8.4g, triethanolamine 3.6g；Embodiment 7
For diethanolamine 5g, triethanolamine 6g.
Embodiment 8
In 2 liters of enamelled cup, add needle penetration to be 70（1/10mm）140 DEG C of Tahe residual oil 1200g, add
Butadiene-styrene rubber mother solution 75g of the SBR1500 concentration for 16wt%, and keep 140 DEG C of the mixture.Then, it is separately added into monoethanolamine
8g and diethanolamine 4g, starts agitator and stirs 50 minutes.Then, 400g or so sample determination property, remaining sample dress are taken out
Enter in 1 liter of enamelled cup, and put it in 140 DEG C of air dry ovens, carry out high-temperature circulation test.
Comparative example 1
According to the technique of embodiment 1, comparative example 1 does not contain additive.
The property of the bituminous composition before 1 thermmal storage of table.
| Property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 |
| Monoethanolamine, % | 0.80 | -- | -- | 0.66 | 0.66 | 0.66 | -- | 0.62 | 0 |
| Diethanolamine, % | -- | 0.80 | -- | 0.14 | 0.28 | -- | 0.39 | 0.31 | 0 |
| Triethanolamine, % | -- | -- | 0.80 | 0.14 | -- | 0.28 | 0.47 | -- | 0 |
| 25 DEG C of needle penetrations, 0.1mm | 92 | 94 | 94 | 94 | 94 | 95 | 96 | 97 | 96 |
| Softening point, DEG C | 48.9 | 48.4 | 48.5 | 48.7 | 48.6 | 48.5 | 48.5 | 48.2 | 48.0 |
| 10 DEG C of ductilities, cm | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 |
| 15 DEG C of ductilities, cm | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 |
| Property after thin film oven | |||||||||
| Penetration ratio, | 62 | 61 | 61 | 61 | 61 | 61 | 61 | 60 | 60 |
| 10 DEG C of ductilities, cm | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 |
| 15 DEG C of ductilities, cm | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 |
Ductility after the thin film oven of the different storage time bituminous compositions of 2 140 DEG C of table.
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 |
| 10 DEG C of ductilities（6 days）, cm | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | 8 |
| 15 DEG C of ductilities（6 days）, cm | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | ＞ 150 | 27 |
| 10 DEG C of ductilities（10 days）, cm | 132 | 45 | 38 | 80 | 84 | 75 | 35 | 145 | 6 |
| 15 DEG C of ductilities（10 days）, cm | ＞ 150 | 120 | 100 | ＞ 150 | ＞ 150 | ＞ 150 | 89 | ＞ 150 | 20 |
From table 2 it can be seen that ethanolamine significantly delayed thermmal storage during ductility decrease speed.In three kinds of ethanolamine
In, preferably, diethanolamine and triethanolamine effect are compared to monoethanolamine, but also can substantially delay ductility for monoethanolamine effect
Decrease speed, all shows the effect of ductility after the TFOT during good protection thermmal storage.
Claims (10)
1. a kind of modified asphalt composite, it is characterised in that：It is composed of the following components with composition weight percentages：
（1）Matrix pitch 94.16%～98.7%；
（2）Butadiene-styrene rubber 0.5%～1.5%；
（3）Additive 0.5%～1%；
Wherein additive is one or more in monoethanolamine, diethanolamine or triethanolamine；
Add tapped oil in described modified asphalt composite, tapped oil addition for modified asphalt composite weight 1% ~
9.7%, modified asphalt composite each component content sum is 100%.
2. according to the compositionss described in claim 1, it is characterised in that：Described matrix pitch is residual oil and/or Colophonium, wherein
Residual oil is decompression residuum He ∕ or viscous crude reduced crude, Colophonium is ordinary road Colophonium, A level road asphalts, B level road asphalts, C
One kind or mixture in level road asphalt and heavy-duty road asphalt.
3. according to the compositionss described in claim 1, it is characterised in that：Described butadiene-styrene rubber be low temperature breast it is poly- 1500 be
One kind or mixture in row, 1600 series, Series 1700,1800 series and its latex.
4. according to the compositionss described in claim 1, it is characterised in that：Described butadiene-styrene rubber be 1500 butadiene-styrene rubber and/or
1502 butadiene-styrene rubber.
5. according to the compositionss described in claim 1, it is characterised in that：Described tapped oil is lube oil finishing tapped oil, fragrant
Hydrocarbon content is in more than 20wt%.
6. according to the compositionss described in claim 5, it is characterised in that：Described tapped oil is to subtract one to each line lubricating oil that subtracts four
One or more in refined tapped oil and the refined tapped oil of residual lubricating oil.
7. according to the compositionss described in claim 5, it is characterised in that：Described tapped oil is to subtract three, line lubricates olein to subtract four
One kind or above two in tapped oil processed extracts oil mixture out.
8. the preparation method of the modified asphalt composite described in a kind of claim 1, it is characterised in that including following content：By fourth
Benzene rubber, additive, tapped oil are added in matrix pitch, are uniformly dispersed, and obtain modified asphalt composite.
9. in accordance with the method for claim 8, it is characterised in that：Dispersion temperature is 120 ~ 180 DEG C, and jitter time is 10 ~ 120
Minute.
10. in accordance with the method for claim 8, it is characterised in that：Described butadiene-styrene rubber, additive and tapped oil are added to
It is one of in the following manner in matrix pitch：（1）Butadiene-styrene rubber is added in matrix pitch together with tapped oil and additive；
（2）Butadiene-styrene rubber is dissolved in tapped oil, butadiene-styrene rubber mother solution is formed, is added in matrix pitch, then adds addition
Agent；（3）First additive is added in matrix pitch, butadiene-styrene rubber and tapped oil or method is subsequently adding（2）The butylbenzene for obtaining
Rubber mother solution；（4）First tapped oil is added in matrix pitch, butadiene-styrene rubber and additive is subsequently adding.
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| CN106633938B (en) * | 2015-11-02 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of asphalt additive and bituminous composition and preparation method containing the additive |
| CN106633934B (en) * | 2015-11-02 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of asphalt additive and bituminous composition and its preparation method containing the additive |
| CN112876868A (en) * | 2020-12-30 | 2021-06-01 | 贵州黔和物流有限公司 | Asphalt for upper surface layer of asphalt pavement |
| CN112876867A (en) * | 2020-12-30 | 2021-06-01 | 贵州黔和物流有限公司 | Asphalt for repairing highway pavement |
| CN113548830B (en) * | 2021-07-30 | 2022-11-25 | 青岛科凯达橡塑有限公司 | Acidic aggregate bio-based asphalt anti-stripping agent and preparation method thereof |
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| CN102757761A (en) * | 2011-04-27 | 2012-10-31 | 南京南科环境工程有限公司 | Epoxy asphalt bonding layer material for cement concrete bridge surface and preparation method thereof |
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| US4011184A (en) * | 1974-03-28 | 1977-03-08 | Shell Oil Company | Bitumen-polymer composition |
| EP0367838A1 (en) * | 1988-11-05 | 1990-05-16 | BASF Aktiengesellschaft | Setting asphalt emulsions |
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| CN103804931A (en) | 2014-05-21 |
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