CN101200595B - Modified emulsified asphalt - Google Patents
Modified emulsified asphalt Download PDFInfo
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- CN101200595B CN101200595B CN2006101650110A CN200610165011A CN101200595B CN 101200595 B CN101200595 B CN 101200595B CN 2006101650110 A CN2006101650110 A CN 2006101650110A CN 200610165011 A CN200610165011 A CN 200610165011A CN 101200595 B CN101200595 B CN 101200595B
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- Prior art keywords
- asphalt
- styrene
- modified emulsifying
- emulsifying asphalt
- quaternary ammonium
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- 239000010426 asphalt Substances 0.000 title claims abstract description 61
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 33
- 229920000126 latex Polymers 0.000 claims abstract description 23
- 239000004816 latex Substances 0.000 claims abstract description 19
- 239000003208 petroleum Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 37
- 238000012545 processing Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000035515 penetration Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000011295 pitch Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000011301 petroleum pitch Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000005518 carboxamido group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A modified emulsified asphalt relates to a modified emulsified asphalt product obtained by modifying petroleum asphalt with an emulsifier, and the modified emulsified asphalt comprises the following components in percentage by weight: 55-65% of asphalt, 1.0-4.0% of petroleum acid quaternary ammonium salt cationic emulsifier, 1.5-5.0% of cationic styrene-butadiene rubber latex or a mixture of one or two of cationic styrene-butadiene-styrene triblock copolymer latex and 32-42% of water.
Description
Technical field
The present invention relates to modified oil pitch, particularly a kind of modified emulsifying asphalt product that adopts emulsifying agent that petroleum pitch is carried out modification and obtain.
Background technology
Along with the prolongation of China's expressway construction and working life, the maintenance work of motorway has become the major tasks of highway in China department.Modified emulsifying asphalt is a kind of emulsified asphalt product that adds rubber latex family macromolecule polymkeric substance; Both drawn the rubber asphalt properties of materials; The advantage that is keeping emulsified bitumen again makes the weathering resistance of emulsified bitumen improve elasticity, cohesiveness, toughness and the enhancing of anti-ageing property; Simultaneously can improve high-temperature stability, low-temperature cracking-resistance, force of cohesion, adhesivity, antistripping ability, early strength, the water resistance at little table place, thereby prolong its work-ing life.Modified emulsifying asphalt can be widely used in the making and routine servicing engineering of advanced road, and especially the treatment process at the little table of maintenance of surface place must use the modified emulsifying asphalt product, and its technical feature quality will directly influence the success or failure of little table place technology.
By introducing in " production of petroleum pitch and application " book that people such as Zhang Deqin write, Sinopec press publishes, at present, the kind of domestic modified emulsifying asphalt is a lot, and the preparation method of modified emulsifying asphalt has three kinds.First method is called the hot hybrid system of secondary, and promptly rubber latex is through twice hot blending dispersion process.Second method is called once hot hybrid system, and promptly rubber latex and bitumen emulsion are through hot blending dispersion process once.The third method is called the cold mixing method one time, and promptly rubber latex and bitumen emulsion are through a cold mixing dispersion process.This several method all exists the emulsion instability, aspect defectives such as emulsifying agent poor performance.
Fine modified emulsifying asphalt product requires to possess simultaneously dispersion stabilization and two kinds of character of breakdown of emulsion coherency in practical applications, emulsifying agent, performance and compatibility material modified and used bituminous material are the key factors of decision modified emulsifying asphalt quality.ZL02160143.7, ZL02160144.5,02160148.8 and 02160155.0 disclosed emulsified modified asphalt preparation method; After perhaps earlier properties-correcting agent latex directly being joined in the matrix pitch fully mixing; Make modified emulsifying asphalt with the emulsifier solution mixing and emulsifying again, perhaps earlier with properties-correcting agent latex and emulsifier solution thorough mixing even after, be heated to certain temperature; Pass through the mulser mixing and emulsifying with matrix pitch again; Behind the mechanical stirring froth breaking, make modified emulsifying asphalt, after perhaps earlier pitch and emulsifier solution being mixed, make emulsified bitumen through the mulser mixing and emulsifying; Then properties-correcting agent latex is added to mix in the emulsified bitumen and make modified emulsifying asphalt; Perhaps make modifying asphalt with adding properties-correcting agent in the matrix pitch earlier, in modifying asphalt, add emulsifying agent again, make emulsified modified asphalt behind the mixing and emulsifying.Mentioned emulsifier employing quaternary ammonium salts or wooden amine, carboxamido-group polyamines class, imidazolines, properties-correcting agent adopts styrene-butadiene latex or polychloroprene latex, B-S-B latex etc.But because preparation technology utilizes hydrochloric acid to improve the reactive behavior and the increase package stability of emulsifying agent, thus there is equipment corrosion, problem of environmental pollution, and there is labile factor in product.
Application number 200510077107.7 adopts papermaking wastewaters as emulsifying agent, and add stablizer, the crosslinking reaction agent makes a kind of high performanced composite emulsifying modified asphaltum material, its preparation process is comparatively complicated; ZL02122841.8 discloses a kind of polymer emulsified and re-cross-linked asphalt colloid mixture, and its preparation process need add dispersion agent and stablizer; 90107907.3, adopt yin, yang ion or nonionogenic tenside compound system to prepare emulsified bitumen, but pitch do not carried out modification with the emulsified bitumen that 200310104916.3 applications relate to.
Summary of the invention
Order of the present invention is to be to provide a kind of modified emulsifying asphalt product; Each item technical indicator of this product all satisfies the technical requirements of the modified emulsifying asphalt among the JTGF40-2004; Has excellent storage stability; With building stones good adhesion characteristic, can be widely used in the surface abrasion layer of newly-built road and the maintenance of old pavement.
For realizing above purpose; Technical scheme provided by the invention is: a kind of modified emulsifying asphalt; Modified emulsifying asphalt is made up of following component by weight percentage: 55~65% pitch; 1.0~4.0% petroleum acid quaternary ammonium salts cationic emulsifier, the mixture of one or both products of 1.5~5.0% positively charged ion styrene butadiene rubber latex or cationic styrene-butadiene-styrene ternary block polymer latex, 32~42% water.
Described pitch is one or more bituminous mixtures in oxidized bitumen, solvent deasphalting or the heavy traffic paving asphalt.25 ℃ of penetration degree scopes of said bituminous are controlled at 40~150 (0.1mm).
The molecular weight of petroleum acid quaternary ammonium salts cationic emulsifier is 300~550, and the HLB value is 10~14.For the sub product petroleum acid in the naphthenic base crude course of processing is the quaternary ammonium salts cationic emulsifier of feedstock production.
Described polymer modifiers is that the solid content of positively charged ion styrene butadiene rubber latex or cationic styrene-butadiene-styrene ternary block polymer latex is 20~60%.
The concrete preparation process of modified emulsifying asphalt product is following: (1) can sequentially join 1.0~4.0% the weight of emulsifier and 1.5~5.0% weight polymer properties-correcting agent in 32~42% weight water in no particular order, and it is for use under 40~80 ℃ of temperature, to stir 0.5~3 hour thorough mixing; (2) with 55~65% weight matrix pitches be heated to 130~160 ℃ for use; (3) first mixed aqueous solution with 40~80 ℃ joins in the colloidal mill and circulates; The matrix pitch that slowly adds 130~160 ℃ then; Treating that whole pitches add in rotating speed is 3000~5000 rev/mins colloidal mill finishes, and mixture recycling 1 minute can make the modified emulsifying asphalt product.
Technology of the present invention is simple, and is easy to operate, and etching apparatus can not produce the three wastes, environmentally safe.The modified emulsifying asphalt product of preparation, character meets the modified emulsifying asphalt technical requirement of the JTG F40-2004 of The Ministry of Communications's " highway Modified Bitumen Pavement construction technique normalizing " fully, has good adhesivity, excellent storage stability with building stones.Product is because to adopt the sub product petroleum acid in the naphthenic base crude course of processing be feedstock production quaternary ammonium salts emulsifying agent, thereby itself and matrix pitch have better compatibleness, and emulsifying effectiveness is better, and product performance are very stable.The component that the used matrix pitch of product obtains owing to the processing of employing naphthenic base crude, thus better by its modified emulsifying asphalt product low-temperature performance of preparing.
Embodiment
To use the ground matrix pitch among the embodiment be the naphthenic base crude that utilizes Kelamayi petro-chemical corporation of CNPC is the mixture of one or both or two or more asphaltic products.es in oxidized bitumen, solvent deasphalting or the heavy traffic paving asphalt of raw material production, and wherein 25 of matrix pitch ℃ of penetration degree scopes are controlled at 40~150 (0.1mm).
The emulsifying agent that uses is the petroleum acid quaternary ammonium salts cationic emulsifier of Kelamayi petro-chemical corporation of CNPC production and sales; The molecular weight of this emulsifying agent is 300~550; The HLB value is 10~14, prepares the sub product of the required petroleum acid raw material of this product for Kelamayi petro-chemical corporation processing naphthenic base crude.
The polymer modifiers that uses is the mixture of one or both products of positively charged ion styrene butadiene rubber latex or cationic styrene-butadiene-styrene ternary block polymer latex, and the solid content of product is controlled between 20~60%, and market is on sale.
Embodiment 1
In having the container of whisking appliance, add the properties-correcting agent positively charged ion styrene-butadiene latex of 5.0% weight, the NE-6 emulsifying agent of 4.0% weight and the water of 36% weight, under 40 ℃ of temperature condition, stir 3 hours even with thorough mixing, it is for use to process mixed aqueous solution.The 90# heavy traffic paving asphalt that in another container, adds the gram petro-chemical corporation processing of 55% weight; Be heated to 160 ℃ for use; Again 40 ℃ mixed aqueous solution is joined the colloidal mill circulation, slowly add 160 ℃ matrix pitch then, treat that whole pitches add to finish in rotating speed is 5000 rev/mins colloidal mill; Recycling 1 minute can make the modified emulsifying asphalt product.Product is through analyzing residual content on the sieve (1.18mm) 0.02%, normal viscosity (C
25,3) 32 seconds, 60.2%, 25 ℃ of penetration degree of evaporation residue content (0.1mm) 52,56 ℃ of softening temperatures, 5 ℃ of ductility 130cm, with the adhesivity (wrapping area)>2/3 of mineral aggregate, package stability one day be 0.13%, 5 day be 2.0%.
Embodiment 2~35 and comparative example's decalcification technological process are with embodiment 1, and each embodiment component, processing condition and product property are seen table 1~table 8 respectively.
Table 1 product processing condition and property analysis
Table 2 product processing condition and property analysis
Table 3 product processing condition and property analysis
Table 4 product processing condition and property analysis
Table 5 product processing condition and property analysis
Table 6 product processing condition and property analysis
Table 7 product processing condition and property analysis
Table 8 comparative sample property analysis
Among the above embodiment; Emulsifying agent NE-6 and emulsifying agent NE-6H are respectively to be the emulsifying agent of raw material production with sub product naphthenic acid in the Kelamayi petro-chemical corporation naphthenic base crude course of processing; And the NY-1 emulsifying agent is to be the emulsifying agent of raw material production with the Triple Pressed Stearic Acid; Can find out from the comparative example of table 8; Adopt the modified emulsifying asphalt product of NY-1 emulsifying agent preparation, 1 day modified emulsifying asphalt outward appearance of its package stability and storage is all poor than the modified emulsifying asphalt product performance that adopt emulsifying agent NE-6 and emulsifying agent NE-6H preparation.
Claims (5)
1. modified emulsifying asphalt; It is characterized in that; Modified emulsifying asphalt is made up of following component by weight percentage: 55~65% pitch; 1.0~4.0% petroleum acid quaternary ammonium salts cationic emulsifier, the mixture of one or both products of 1.5~5.0% positively charged ion styrene butadiene rubber latex or cationic styrene-butadiene-styrene ternary block polymer latex, 32~42% water; Wherein, described pitch is that the naphthenic base crude of Kelamayi petro-chemical corporation of CNPC is one or more bituminous mixtures in oxidized bitumen, solvent deasphalting or the heavy traffic paving asphalt of raw material production.
2. according to the described modified emulsifying asphalt of claim 1, it is characterized in that: 25 ℃ of penetration degree scopes of said bituminous are controlled at 40~150 0.1mm.
3. according to the described modified emulsifying asphalt of claim 1, it is characterized in that: the molecular weight of petroleum acid quaternary ammonium salts cationic emulsifier is 300~550, and the HLB value is 10~14.
4. according to the described modified emulsifying asphalt of claim 1, it is characterized in that: said petroleum acid quaternary ammonium salts cationic emulsifier is that the sub product petroleum acid in the naphthenic base crude course of processing is the quaternary ammonium salts cationic emulsifier of feedstock production.
5. according to the described modified emulsifying asphalt of claim 1, it is characterized in that the solid content of described positively charged ion styrene butadiene rubber latex or cationic styrene-butadiene-styrene ternary block polymer latex is 20~60%.
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CN101200595B true CN101200595B (en) | 2012-03-07 |
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CN102092988B (en) * | 2009-12-09 | 2012-10-17 | 中国石油天然气股份有限公司 | Warm-mixed asphalt mixture and preparation method thereof |
CN102093724B (en) * | 2009-12-09 | 2012-11-14 | 中国石油天然气股份有限公司 | Warm-mixed asphalt additive and preparation method thereof |
CN101735625B (en) * | 2009-12-25 | 2012-07-18 | 李国涛 | Special modified cold-mixing asphalt for cold-region normal-temperature mixing-type asphalt concrete |
CN101831185B (en) * | 2010-04-06 | 2012-10-03 | 惠州市贝特瑞新材料科技有限公司 | Modified emulsified bitumen and preparation method thereof |
CN102382479A (en) * | 2010-08-27 | 2012-03-21 | 安徽三缔沥青材料有限公司 | Star-shaped modified emulsified asphalt and preparation method of same |
CN102108257A (en) * | 2010-12-22 | 2011-06-29 | 北京东方雨虹防水技术股份有限公司 | Self-hardening rubber asphalt paint |
CN102504703A (en) * | 2011-09-28 | 2012-06-20 | 哈尔滨工业大学 | Condensed ice damage prevention functional protective material for asphalt pavement and preparation method thereof |
CN103554930B (en) * | 2013-10-17 | 2016-10-19 | 中国石油化工股份有限公司 | A kind of high concentration SBR modified emulsifying asphalt and preparation method thereof |
CN104804443A (en) * | 2015-04-28 | 2015-07-29 | 上海路惠环保科技有限公司 | Emulsified asphalt and preparation method and application thereof |
CN105384402A (en) * | 2015-10-31 | 2016-03-09 | 菏泽海诺知识产权服务有限公司 | Material for emulsion modified asphalt thin-layer cover face |
CN105907116A (en) * | 2016-06-30 | 2016-08-31 | 江门市强大公路材料有限公司 | High-performance hybrid modified asphalt emulsion and preparation technique thereof |
CN107033615A (en) * | 2017-06-07 | 2017-08-11 | 郑州中德新亚建筑材料有限公司 | Agent and preparation method thereof is stitched with cold welding in road |
CN109535751A (en) * | 2018-12-27 | 2019-03-29 | 山东高速建设材料有限公司 | Stress absorbing layer high solids content emulsified asphalt and its preparation and construction method |
CN110791203B (en) * | 2019-10-29 | 2021-07-16 | 山东北方创信防水科技集团股份有限公司 | Cationic liquid rubber asphalt emulsion, preparation thereof and quick-setting rubber asphalt coating |
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Effective date of registration: 20180718 Address after: 100007 Dongzhimen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNPC KARAMAY PETROCHEMICAL CO.,LTD. Patentee after: PetroChina Company Limited Address before: 100011 Beijing city Dongcheng District No. 16 Andrew intercontinental building Patentee before: PetroChina Company Limited |
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