CN103804929B - 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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Abstract
The invention discloses a kind of modified asphalt composite and preparation method thereof.Does modified asphalt composite comprise following component with composition quality percentages: basic asphalt 70% ~ 97%, additive A? 0.5% ~ 10%, additive B? 1.2% ~ 10%, addition of C? 0.3% ~ 5%, additive D? 0.5% ~ 5%; Wherein additive B is one or more in organic acid, and addition of C is bases inorganics, and additive D is organic polymer material.Preparation method is as follows: part basis pitch, additive A and additive B mix by (1); (2) add addition of C in the mixture obtained to step (1), carry out saponification reaction, then heat up transpiring moisture; (3) remaining basic asphalt, additive D are added in the mixture that step (2) obtains, mix, obtain product.Modified asphalt composite of the present invention has good temperature sensibility, high-temperature behavior, ageing resistance, adhesivity and low-temperature performance, and preparation method is simple, easy to operate and applied widely simultaneously.
Description
Technical field
The present invention relates to a kind of modifying asphalt and preparation method thereof, relate in particular to a kind of by chemical reaction with add the modified asphalt composite prepared of macromolecule organic and method.
Background technology
Due to the difference of region, some area winter, summer temperature difference are larger, bituminous pavement environment for use is severe, in addition the reason such as the increasing sharply of the volume of traffic, vehicle maximizes, vehicle heavy duty overload, and bituminous pavement occurs that the phenomenons such as high temperature rut, cold cracking and Moisture Damage are still more serious.At present, in heavy duty road asphalt product, majority there is high temperature viscosity and penetrative index is less than normal, the defects such as penetration ratio is little after film heating, namely high-temperature behavior, ageing resistance and temperature sensibility are poor, thus, be unfavorable for reducing pavement track and gather around the generation of the diseases such as bag and pitch rapid ageing and cause the generation of road surface premature failure phenomenon.Also often occur causing the phenomenon of peeling off in early days because of pitch and building stones poor adhesion.In addition, for some crude oil formed asphalt, there is the deficiency that wax content is higher, ductility is less, and the heavy traffic paving asphalt product meeting index request can not be produced.
In order to improve high temperature performance and the temperature sensibility of pitch, the use properties of further raising pitch, the more method of usual employing is in pitch, add a certain amount of macromolecule polymer material, as styrene-butadiene-styrene block copolymer (SBS), polyethylene (PE) and polypropylene etc., the use propertieies such as the high temperature performance of pitch can be improved to a certain extent.Also the method for useful atmospheric oxidation or catalyzed oxidation improves the technique of pitch high temperature performance.
The patents such as CN101962482A and CN1569964A utilize SBS as the modifying asphalt technology of preparing of properties-correcting agent.CN1523050A and CN101200596A utilizes SBR as the modifying asphalt technology of preparing of properties-correcting agent.Although have certain modified effect, macromolecular material is expensive, and requires strict to production unit, and production technique is more complicated, and comprehensive process cost is higher.CN101974235A is a kind of wide area modifying asphalt technology of preparing, using Powdered styrene-butadiene rubber(SBR) as the first properties-correcting agent, using polyethylene wax as the second properties-correcting agent, by the high-melting-point of polyethylene wax and the characteristic of the above fast melt of fusing point, the performance of the polyethylene wax that modifying asphalt is possessed is certain, namely the softening temperature of pitch is improved, utilize the low temperature deep drawing quality energy of styrene-butadiene rubber(SBR), the low temperature extensibility of modifying asphalt is increased, belong to physically modified category, not only cost is higher, and have problems with the consistency of pitch, namely during thermmal storage, once stop stirring, there will be demixing phenomenon.
CN1487029A carries out modification to pitch jointly with rock asphalt and organo-metallic soap and powder styrene butadiene rubber.Use wilkinite, silicate or diatomite etc. together with powder styrene butadiene rubber to asphalt modification in CN1587320A with CN1837292A, and styrene-butadiene rubber(SBR) is the main body of properties-correcting agent, belongs to and prepare styrene-butadiene rubber(SBR) composite modified asphalt technology by adding some additive.There is deficiencies such as increasing cost, easily laminated segregation equally.
CN1178822A provides a kind of preparation method of oxidized bitumen, although the method can improve the use properties such as high temperature performance and temperature sensibility of pitch, but due to oxidizing process relative complex, and can pollute air, to such an extent as to actual use is restricted.
US4874432 and CN102558887A individually discloses a kind of multistage pitch preparation process and gel modified asphalt preparation technology.The saponification process of the two is basically identical, and namely carry out saponification reaction by the Yatall MA (i.e. tall oil) added in pitch containing lipid acid and resinous acid with solid water-free alkali metal base, difference is also to add amine or acid amides in CN102558887A.Two sections of patents, while not reducing pitch low-temperature performance, improve high temperature performance of asphalt.But also there are the following problems: saponification reaction speed and reactant concn proportional, concentration is too little is unfavorable for that reaction is normally carried out, 1, directly Yatall MA and alkali are joined in whole pitch, because saponifiable matter concentration is low, greatly can reduce speed of response, generally more difficultly carry out saponification reaction well; 2, general pitch belongs to slightly acidic material, building stones for building the road are many in weakly alkaline, by adding highly basic, saponification reaction is carried out to organic acid, the colloidal structure that organic soap class changes pitch makes asphalt performance improve, and this type of soap presents alkalescence more, when can make pitch and alkaline building stones mix, there is the problem that adhesivity is bad; 3, such pitch does not improve low-temperature performance, is unsuitable for low temperature environment and builds road surface, build road, then can show stronger fragility, and affect the work-ing life on road surface for low-temperature region.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of modified asphalt composite and preparation method thereof.Modified asphalt composite of the present invention has good temperature sensibility, high-temperature behavior, ageing resistance, adhesivity and low-temperature performance, and preparation method is simple, easy to operate and applied widely simultaneously.
Modifying asphalt of the present invention, comprises following component by percentage to the quality:
(1) basic asphalt 70% ~ 97%; Be preferably 78.5% ~ 93%;
(2) additive A 0.5% ~ 10%; Be preferably 2% ~ 8%;
(3) additive B 1.2% ~ 10%; Be preferably 2.5% ~ 8%;
(4) addition of C 0.3% ~ 5%; Be preferably 1% ~ 2.5%;
(5) additive D, 0.5% ~ 5%; Be preferably 1% ~ 3%.
Wherein basic asphalt is petroleum pitch, comprise vacuum residuum, de-oiled asphalt that straight-run pitch, solvent de-asphalting process obtain, be in harmonious proportion in pitch and oxidized bitumen one or more, 25 DEG C of penetration degrees of basic asphalt are 40 ~ 3001/10mm, be preferably 50 ~ 2001/10mm, softening temperature is 25 ~ 70 DEG C, is preferably 35 ~ 65 DEG C.
Additive A, for being rich in aromatic component, derives from the mixture of one or more in the extraction oil of lubricating oil solvent, catalytically cracked oil, the vacuum distillate of naphthenic base crude and the used oil of recovery, the extraction oil of preferred lubricating oil solvent.
Additive B is one or more in organic acid, includes but not limited to the organic acids such as animal, plant fatty acid, as stearic acid (18 carbonic acid), ten dihydroxystearic acids, also comprises C
10~ C
18synthetic fatty acid, preferred C
14~ C
18synthetic fatty acid.
Addition of C mainly comprises bases inorganics, as one or more in the inorganic additivess such as sodium hydroxide, lithium hydroxide, potassium hydroxide and calcium hydroxide.
Additive D is organic polymer material, comprises one or more in polyisobutene, thiorubber, styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber etc.
In modified asphalt composite of the present invention, can also add other additive as required, as organic substances such as glycerol, rosin and naphthenic acid, its add-on generally accounts for 0.5% ~ 5% of modifying asphalt quality.
The preparation method of modified asphalt composite of the present invention, comprises following content: part basis pitch, additive A and additive B mix by (1); (2) add addition of C in the mixture obtained to step (1), carry out saponification reaction, then heat up transpiring moisture; (3) remaining basic asphalt, additive D are added in the mixture that step (2) obtains, mix, obtain modifying asphalt product.
In the inventive method, the temperature of basic asphalt is 100 ~ 170 DEG C, preferably 110 ~ 160 DEG C, the temperature of additive A is 50 ~ 120 DEG C, step (1) adds 20wt% ~ 40wt% basic asphalt, the mixing time of step (1) is 10 ~ 90 minutes, and mixing temperature is 90 ~ 150 DEG C, preferably 20 ~ 60 minutes.
In the inventive method step (2), saponification reaction temperature is 90 ~ 150 DEG C, and the saponification reaction time is 0.5 ~ 8 hour, preferably 1 ~ 5 hour; Heat up 30 ~ 90 DEG C, make moisture be evaporated to bubble-free in mixture.
In the inventive method step (3), mixing time is 20 ~ 180 minutes, and mixing temperature is 120 ~ 280 DEG C.
The inventive method can also add one or more in glycerol, rosin or naphthenic acid in step (1) and/or step (2) as required, and its add-on generally accounts for 0.5% ~ 5% of modifying asphalt quality.
The inventive method step (3) optimal way is: added by remaining basic asphalt in the mixture that step (2) obtains, with 20 ~ 150 minutes, preferably 30 ~ 120 minutes, stirring is warming up to 160 ~ 280 DEG C, preferably 180 ~ 260 DEG C, then lower the temperature 20 ~ 140 DEG C and add additive D, mix.
The inventive method adopts normal agitation equipment or high-shear to be uniformly mixed.
In the inventive method, addition of C adds in the mode of bases aqueous solution of inorganic matter or water miscible liquid, wherein the concentration of sodium hydroxide and potassium hydroxide aqueous solution is 20wt% ~ saturated solution, lithium hydroxide aqueous solution concentration is 10wt% ~ saturated solution, and calcium hydroxide is 20wt% ~ 30wt% water miscible liquid.
In the inventive method, basic asphalt and additive A be not preferably containing moisture, in case the excessive still phenomenon of generation.The object adding additive A reduces the viscosity of pitch, for subsequent reactions provides a suitable place.
Modified asphalt composite prepared by the present invention is while significantly improving the temperature sensibility of pitch, high-temperature behavior and ageing resistance, adhesivity and low-temperature performance are improved, be conducive to reducing cold cracking, the high temperature rut on road surface and the disease such as peel off, being widely used in the high-grade highway that different mix type is built in different areas.
The present inventor finds under study for action, directly in pitch medium, add the highly basic such as solid sodium hydroxide, because solid alkali disperses uneven in pitch, saponification reaction can be made to be difficult to fully carry out, and saponification reaction product is soap class and water, temperature of reaction is more than 190 DEG C, and the water that reaction produces at this temperature, very easily causes excessive still and cannot normal running during rapid evaporation.
Compared with prior art, tool of the present invention has the following advantages:
(1) adopt organic acid, synthetic fatty acid and rosin etc. to be raw material, can adjust and control raw material composition according to actual needs, and then effectively ensure the performance of modifying asphalt.
(2) alkali that reaction uses adds with the form of alkali aqueous solution or water miscible liquid, and alkali is dispersed in pitch medium, thus impels reaction to carry out fast.
(3) in reaction process, add a small amount of rich fragrant component and part basis pitch, and not all basic asphalt, while reducing dielectric viscosity, add the concentration of saponification reaction thing, be conducive to reacting at a lower temperature, improve speed of response, rapid evaporation causes the generation of excessive still phenomenon because temperature is high to be unlikely to again to make to add and react the water produced.
(4) in reaction process, add synthetic fatty acid, naphthenic acid and rosin, meet alkali and namely react, be conducive to the initial stage milk sap that System forming is fine, thus fast reaction speed.
(5) macromolecular materials such as polyisobutene, thiorubber, styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber are added, by its good adhesivity and low temperature flexibility, adhesivity and the low temperature brittleness of modifying asphalt and alkaline building stones can be improved, widen the applicable territorial scope of modifying asphalt.
(6) modified asphalt composite of the present invention has softening temperature and high temperature viscosity is moderate, the features such as penetrative index is larger, as the modifying asphalt of penetration degree 40-1001/10mm, its 60 DEG C of kinematic viscosity can reach more than 280Pa.s, penetrative index is more than 1.0, ageing index is below 2.2, and 4 DEG C of penetration degrees are more than 22.
Embodiment
Below will the present invention will be further described by embodiment, percentage ratio is wherein mass percent.
Embodiment 1
The straight-run pitch of 25 DEG C of penetration degree 701/10mm, softening temperature 47.0 DEG C is heated to 150 DEG C of meltings, taking 180g basic asphalt, to be contained in volume be in the metal vessel of 1000ml, oil is extracted in the lube oil finishing adding 50g80 DEG C out, it is made to mix with normal agitation equipment, then 40g stearic acid (secondary) is added, stirring makes it melt mixing in 20 minutes, at 105 DEG C, slowly adds the aqueous sodium hydroxide solution 21g that concentration is 30%.And continue stirring 2.0 hours, be then warming up to 160 DEG C, when bubble-free, add basic asphalt and the 12g thiorubber of 420g160 DEG C, and after being uniformly mixed 60 minutes, obtain modified asphalt composite.The character of modified asphalt composite is in table 1.
Embodiment 2
The straight-run pitch of 25 DEG C of penetration degree 901/10mm, softening temperature 46.7 DEG C is heated to 150 DEG C of meltings, taking 180g basic asphalt, to be contained in volume be in the metal vessel of 1000ml, oil is extracted in the lube oil finishing adding 45g80 DEG C out, it is made to mix with normal agitation equipment, then 35g stearic acid (secondary) and 15g rosin (one-level) is added, stirring makes it melt mixing in 40 minutes, at 105 DEG C, slowly adds the aqueous sodium hydroxide solution 25g that concentration is 30%.And continue stirring 2 hours, then 160 DEG C are warming up to, the basic asphalt of 420g160 DEG C is added again when bubble-free, be uniformly mixed with normal agitation mixing equipment, be warming up to 250 DEG C with the time of about 60 minutes simultaneously, add 10g polyisobutene when being then cooled to 160 DEG C to stir, obtain modified asphalt composite.The character of modified asphalt composite is in table 1.
Embodiment 3
The blend asphalt of 25 DEG C of penetration degree 801/10mm, softening temperature 46.1 DEG C is heated to 160 DEG C of meltings, taking 180g basic asphalt, to be contained in volume be in the metal vessel of 1000ml, oil is extracted in the lube oil finishing adding 30g80 DEG C out, make it mix with normal agitation equipment, then add 30g stearic acid (secondary) and 15g synthetic fatty acid (C
14~ C
18), stir and make it melt mixing in 20 minutes, at 105 DEG C, slowly add the aqueous sodium hydroxide solution 24g that concentration is 30%.And continue stirring 3 hours, then 160 DEG C are warming up to, the basic asphalt of 420g160 DEG C is added again when bubble-free, be uniformly mixed with normal agitation mixing equipment, be warming up to 260 DEG C with the time of about 80 minutes simultaneously, add after 14g styrene-butadiene rubber(SBR) is uniformly dispersed by shearing device when being then cooled to 160 DEG C, obtain modified asphalt composite.The character of modified asphalt composite is in table 1.
Embodiment 4
The straight-run pitch of 25 DEG C of penetration degree 1601/10mm, softening temperature 39.7 DEG C is heated to 160 DEG C of meltings, taking 200g basic asphalt, to be contained in volume be in the metal vessel of 1000ml, add 40g80 DEG C subtract four line distillates (Zhenghai refinery product), 30 minutes are stirred with normal agitation equipment, then 49g ten dihydroxystearic acid and 21g stearic acid is added, stirring makes it melt mixing in 30 minutes, at 110 DEG C, slowly adds the lithium hydroxide 86g that concentration is 10%.And continue stirring 2.5 hours, then 140 DEG C are warming up to, the basic asphalt of 410g160 DEG C is added again when bubble-free, be uniformly mixed, be warming up to 230 DEG C with the time of about 60 minutes simultaneously, add after 10g styrene-butadiene rubber(SBR) and 6g cis-1,4-polybutadiene rubber be uniformly dispersed by shearing device when being then cooled to 160 DEG C, obtain modified asphalt composite.The character of modified asphalt composite is in table 1.
Embodiment 5
The straight-run pitch of 25 DEG C of penetration degree 601/10mm, softening temperature 48.6 DEG C is heated to 160 DEG C of meltings, taking 200g basic asphalt, to be contained in volume be in the metal vessel of 1000ml, oil is extracted in the lube oil finishing adding 25g80 DEG C out, it is made to mix with normal agitation equipment, then 45g stearic acid (secondary) and 15g glycerol is added, stirring makes it melt mixing in 30 minutes, slowly adds the aqueous sodium hydroxide solution 23.5g that concentration is 30% at 110 DEG C.And continue stirring 2.5 hours, then be warming up to 160 DEG C, when bubble-free, add the basic asphalt of 400g160 DEG C again, and be under agitation warming up to 220 DEG C, add when being then cooled to 160 DEG C 6g polyisobutene and 5g thiorubber stir be mixed even after, obtain modified asphalt composite.The character of modified asphalt composite is in table 1.
Comparative example 1
By asphalt heating to 200 DEG C melting used in embodiment 1, taking this pitch of 500g, to be contained in volume be in the metal vessel of 750ml, with high-shear machine shear grinding while add 1.3g drying sodium hydrate particle and pitch in, continue shearing 2 minutes, add paper mill, the Yalu River, 10g Dandong and produce Yatall MA, and continue shear-mixed 20 minutes, analytical test cannot be carried out owing to still having a large amount of foam, therefore the baking oven relaying continuation of insurance of sample being put into 150-160 DEG C holds 20 minutes, carry out stirring with glass stick simultaneously and make foam reduce rear sampling analysis asphaltic nature.The results are shown in Table 1.
Comparative example 2
By asphalt heating to 200 DEG C melting used in embodiment 1, taking this pitch of 500g, to be contained in volume be in the metal vessel of 750ml, with high-shear machine shear grinding while add 0.78g drying lithium hydroxide particle and pitch in, continue shearing 2 minutes, add paper mill, the Yalu River, 10g Dandong and produce Yatall MA, and continue shear-mixed 20 minutes, analytical test cannot be carried out owing to still having a large amount of foam, therefore the baking oven relaying continuation of insurance of sample being put into 150-160 DEG C holds 20 minutes, carry out being stirred to foam with glass stick simultaneously and reduce rear sampling analysis asphaltic nature.The results are shown in Table 1.
Table 1 modified asphalt composite product property.
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Penetration degree (25 DEG C)/0.1mm | 59 | 75 | 50 | 89 | 65 | 50 | 49 |
| Penetration degree (4 DEG C)/0.1mm | 25 | 31 | 23 | 45 | 26 | 21 | 21 |
| Softening temperature/DEG C | 58.3 | 59.0 | 65.4 | 57.6 | 66.0 | 55.3 | 55.6 |
| Viscosity (60 DEG C)/Pa.s | 309.0 | 295.3 | 452.1 | 374.5 | 315.8 | 312.4 | 335.3 |
| Penetrative index | 1.11 | 1.94 | 2.05 | 2.18 | 2.88 | 0.04 | 0.06 |
| Thin Film Oven Test TFOT (163 DEG C, 5h) | |||||||
| Penetration ratio/% | 79.2 | 80.9 | 88.4 | 81.3 | 83.6 | 78.9 | 81.2 |
| Ageing index | 1.59 | 1.65 | 1.78 | 1.62 | 1.46 | 2.36 | 2.05 |
As can be seen from the table, compared with comparative example, 4 DEG C of penetration degrees, penetrative index and softening temperatures of the bituminous composition that the inventive method obtains are comparatively large, and ageing index is less, therefore, have that temperature sensibility is less, high temperature and low-temperature performance and the advantage such as ageing resistance is good.
Claims (10)
1. a modified asphalt composite, is characterized in that: comprise following component with composition quality percentages:
(1) basic asphalt 70% ~ 97%;
(2) additive A 0.5% ~ 10%;
(3) additive B 1.2% ~ 10%;
(4) addition of C 0.3% ~ 5%;
(5) additive D0.5% ~ 5%;
Wherein, basic asphalt is petroleum pitch, and additive A is for being rich in aromatic component, and additive B is one or more in organic acid, and addition of C is bases inorganics, and additive D is organic polymer material;
The wherein preparation method of modified asphalt composite, comprises following content: part basis pitch, additive A and additive B mix by (1); (2) add addition of C in the mixture obtained to step (1), carry out saponification reaction, then heat up transpiring moisture; (3) remaining basic asphalt, additive D are added in the mixture that step (2) obtains, mix, obtain modifying asphalt product; Step (1) adds 20wt% ~ 40wt% basic asphalt, and the mixing time of step (1) is 10 ~ 90 minutes, and mixing temperature is 90 ~ 150 DEG C; In step (2), saponification reaction temperature is 90 ~ 150 DEG C, and the saponification reaction time is 0.5 ~ 8 hour; And then be warming up to 30 ~ 90 DEG C, make moisture be evaporated to bubble-free in mixture; In step (3), mixing time is 20 ~ 180 minutes, and mixing temperature is 120 ~ 280 DEG C; Remaining basic asphalt is added in the mixture that step (2) obtains, with 20 ~ 150 minutes, stir and be warming up to 160 ~ 280 DEG C, then lower the temperature 20 ~ 140 DEG C and add additive D, mix.
2. according to composition according to claim 1, it is characterized in that: comprise following component with composition quality percentages:
(1) basic asphalt 78.5% ~ 93%;
(2) additive A 2% ~ 8%;
(3) additive B 2.5% ~ 8%;
(4) addition of C 1% ~ 2.5%;
(5) additive D1% ~ 3%.
3. according to composition according to claim 1, it is characterized in that: the de-oiled asphalt that described basic asphalt is vacuum residuum, straight-run pitch, solvent de-asphalting process obtain, be in harmonious proportion in pitch and oxidized bitumen one or more, 25 DEG C of penetration degrees of basic asphalt are 40 ~ 3001/10mm, and softening temperature is 25 ~ 70 DEG C.
4. according to composition according to claim 1, it is characterized in that: described additive A derives from the mixture of one or more in the extraction oil of lubricating oil solvent, catalytically cracked oil, the vacuum distillate of naphthenic base crude and the used oil of recovery.
5. according to composition according to claim 1, it is characterized in that: described additive B is animal, plant fatty acid and C
10~ C
18one or more in synthetic fatty acid.
6. according to composition according to claim 1, it is characterized in that: described addition of C is one or more in sodium hydroxide, lithium hydroxide, potassium hydroxide and calcium hydroxide.
7. according to composition according to claim 1, it is characterized in that: described additive D is one or more in polyisobutene, thiorubber, styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber.
8. according to composition according to claim 1, it is characterized in that: add one or more in glycerol, rosin and naphthenic acid in modified asphalt composite, its add-on accounts for 0.5% ~ 5% of modified asphalt composite quality.
9. according to composition according to claim 1, it is characterized in that: add one or more in glycerol, rosin or naphthenic acid in step (1) and/or step (2), its add-on accounts for 0.5% ~ 5% of modified asphalt composite quality.
10. according to composition according to claim 6, it is characterized in that: addition of C adds in the mode of bases aqueous solution of inorganic matter or water miscible liquid, wherein the concentration of sodium hydroxide and potassium hydroxide aqueous solution is 20wt% ~ saturated solution, lithium hydroxide aqueous solution concentration is 10wt% ~ saturated solution, and calcium hydroxide is 20wt% ~ 30wt% water miscible liquid.
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| CN105733279B (en) * | 2014-12-11 | 2019-03-12 | 中国石油天然气股份有限公司 | A kind of broad extrusion and preparation method thereof |
| CN104629389B (en) * | 2015-02-02 | 2017-06-20 | 浙江大学 | Modified flame-retardant pitch, flame-retardant pitch concrete and preparation method thereof and calcium hydroxide as fire retardant application |
| CN106675045A (en) * | 2016-05-31 | 2017-05-17 | 陈斌 | Modifier for improving corrosion resistance of asphalt and preparation method of modifier |
| CN111721799B (en) * | 2020-07-22 | 2022-03-18 | 西南石油大学 | Device and method for catalyzing pyrolysis of thickened oil into coke through clay mineral |
| CN113831615B (en) * | 2021-09-26 | 2023-01-13 | 山东高氏科工贸有限公司 | Instant SBR asphalt modifier and preparation method thereof |
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| US4874432A (en) * | 1988-06-27 | 1989-10-17 | Asphalt Materials, Inc. | Multigrade asphalt cement product and process |
| US5221703A (en) * | 1992-05-14 | 1993-06-22 | Mcconnaughay Technologies, Inc. | Engineered modified asphalt cement |
| CN1111567C (en) * | 2000-10-26 | 2003-06-18 | 中国石油化工股份有限公司 | Process for preparing modified building asphalt |
| CN1195803C (en) * | 2001-10-30 | 2005-04-06 | 中国石油化工股份有限公司 | Polymer modified compsn. of road bitumen and its prepn. method |
| US6770127B2 (en) * | 2002-05-16 | 2004-08-03 | Shandong Heritage Highway Materials Technologies | Multigrade asphalt power additive |
| CN101418128B (en) * | 2007-10-26 | 2011-01-19 | 中国石油化工股份有限公司抚顺石油化工研究院 | Road asphalt composite and preparation method thereof |
| CN102558887B (en) * | 2012-02-13 | 2014-02-12 | 山东华瑞道路材料技术有限公司 | Gel modified asphalt and preparation process thereof |
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