CN1339556A - Storage stable modified asphalt and its preparing mehtod - Google Patents
Storage stable modified asphalt and its preparing mehtod Download PDFInfo
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Abstract
The storage stable modified asphalt is prepared with the material including asphalt 50-97.7 wt%, polymer 2.0-20.0 wt%, compatilizer 0.1-20.0 wt%, coupling agent 0.1-10.0 wt% and polar compound 0.1-10.0 wt%l, and through mixing and reaction at 100-250 deg.c for 5-300 min. It has excellent storage stability and softening point difference of isolation test lower than 2.5 deg.c. The preparation process of the present invention is simple and needs no special equipment.
Description
The invention belongs to a kind of bituminous material composition and method of making the same, more particularly, is polymer modified asphalt that belongs to a kind of stable storing and preparation method thereof.
Bituminous material is very fast as the pavement material development of road and building trade, but the performance of road bitumen and compound thereof is subjected to the influence of many factors, limits best performance of its performance such as visco-elasticity, plasticity-, adhesivity etc.In numerous influence factors, the influence factor maximum of climate.On motorway, the rut that summer high temperature season, driving caused is the principal element that causes the road surface infringement.Simultaneously, the winter temperature rapid drawdown and the bituminous pavement temperature draw seam that causes that heats up repeatedly are the horizontal rimose major causes in road surface.In the rainy season in south, the infringement of rainwater also will make the interface of pitch and compound have an effect, and the bituminous adhesion property is reduced, and pitch and building stones are peeled off easily.Therefore, be necessary the bituminous rheological property is improved.Adding polymkeric substance in pitch is the effective ways that improve asphalt performance.Polymkeric substance added bituminous viscosity is increased, improve bituminous high temperature resistance characteristic, reduce the bituminous temperature sensitivity, low-temperature performance also can improve simultaneously.
The Asphaltenes and Asphalts that writes at T.F.Yen etc., among the I Developments inPetroleum Science olefin polymer modifying asphalt is commented, the addition of polymkeric substance is 6 heavy %, various polymer modified asphalts stable as shown in table 1.
Table 1
| Polymer type | Do not have | ??APP | ???LDPE | ??EPDM | ??SBS | |
| Penetration degree (25 ℃, 100g, 5s), dmm | ??133 | ???145 | ????41 | ????50 | ????72 | |
| Softening temperature (ring and ball method), ℃ | ???44 | ????47 | ????98 | ????66 | ????98 | |
| Segregation experiment (163 ℃, 48 hours) | The upper strata softening temperature, ℃ | ????- | ????55 | ????＞100 | ????87 | ?＞100 |
| Lower floor's softening temperature, ℃ | ????- | ????45 | ????52 | ????52 | ????61 | |
| Softening temperature is poor, ℃ | ????- | ????10 | ????＞50 | ????35 | ??＞40 | |
As can be seen from Table 1, join polymer AP P (Atactic Polypropelene), LDPE (new LDPE (film grade)), EPDM (ethene-propene-diene terpolymer thing), SBS (styrene-butadiene-styrene triblock copolymer) in the pitch respectively, most polymers all is separated with pitch, will directly influence the use properties of bitumen/polymer composition like this.
CN1045411A discloses a kind of preparation method of modified bituminous binder and the product of making thereof, with molten asphalt and thermoplastic synthetic material or thermoplastic synthetic material mixture preferably olefin polymer mix, this mixture is carried out homogenizing to be handled, add the energy of some amount with the form of kinetic energy, preferably order about said mixture by two lay relatively and counterrotating mixing apparatus between a slit.The advantage of this method is with using with production, and is more convenient, but owing to being physically modified to pitch, the stability in storage of modifying asphalt is relatively poor.If in the area that does not possess working condition or use the applying unit of modifying asphalt in a large number, on-site preparation just can not be brought into play bigger advantage; If prepare modifying asphalt in advance, then phenomenon of phase separation takes place in pitch and polymkeric substance easily, thereby has destroyed the bituminous performance.
EP639630A1 discloses a kind of method for preparing stable asphalt-polymer composition, this method filters out the asphalt stock that the meets definite composition raw material as modifying asphalt earlier, next uses triblock polymer SBS as polymer modifiers, in inert environments, use vinyl aromatic (co) hydrocarbon compound (as vinylbenzene) to add in the asphalt-polymer composition and react, prepare the good sample of stability as auxiliary agent.This method has certain restriction to the raw material sources of modifying asphalt, and styrene compound can not help the dispersion of SBS in pitch as reaction promoter.Owing to need nitrogen as reaction environment, also will increase reaction cost.
USP5,336,705, USP5,627,225 and USP5,348,994 use oleums or other sulphonating agents with asphalt stock and polymer modifiers sulfonation earlier, make the both introduce acidic-group, neutralize with alkali again, and neutralizing agent mainly uses CaO, ZnO etc.This method will prolong technical process, increase production cost, use sulphonating agent also will cause the corrosion of equipment.
USP5,306,750 disclose a kind of polymkeric substance and bituminous reaction process and crosslinked polymer asphaltic products., and this method is that 0.05～2 heavy % contains the polymkeric substance of epoxy group(ing) and pitch in covalent reaction under the temperature more than 100 ℃ more than 1 hour.In 163 ℃～177 ℃ baking oven, store 4 days by the prepared modifying asphalt of this method, phenomenon of phase separation do not occur.
USP5,331,028 discloses a kind of polymer-modified asphalt compositions and preparation method thereof, consisting of of said composition: the reaction product that is obtained by the ethylene copolymer reaction that contains glycidyl of the pitch of 100 parts by weight and 0.5～11 parts by weight accounts for 80～99.7 heavy %, and vinylbenzene/conjugated diene block copolymer accounts for 0.3～20 heavy %; This method is that the ethylene copolymer that contains glycidyl of 70～99.2 heavy % pitches, 0.5～10 heavy % and 0.3～20 heavy % vinylbenzene/conjugated diene block copolymer are mixed, and reacts 6～36 hours down at 170 ℃～220 ℃, obtains reaction product.
Though USP5,331,028 and USP5,306,750 polymkeric substance and the bituminous compatiblenesies of using are better, the preparation cost of polymkeric substance and to react difficulty be its main controlling factor.
One of purpose of the present invention provides a kind of modifying asphalt of stable storing.
Another object of the present invention provides a kind of process for preparing modified asphalt of stable storing.
The modifying asphalt of stable storing provided by the invention, its component and content are:
Asphalt stock 50～97.7 heavy %;
Polymkeric substance 2.0～20.0 heavy %;
Compatilizer 0.1～20.0 heavy %;
Crosslinked body 0.1～10.0 heavy %;
Polar compound 0.1～10.0 heavy %.
Described asphalt stock is one or more the mixture that is selected from petroleum pitch, coal-tar pitch, oil sands bitumen and the rock asphalt, and wherein petroleum pitch is one or more the mixture that is selected from straight-run pitch, solvent deoiling pitch, oxidized bitumen and the mediation pitch.Straight-run pitch long residuum or vacuum residuum that to be crude oil obtain through normal pressure distillation or underpressure distillation, its 25 ℃ of penetration degrees are 20～300dmm (being 1/10mm); Solvent deoiling pitch is meant uses C
3～C
5The de-oiled asphalt that a kind of solvent among the hydro carbons or more than one mixed-solvent extraction residual oil obtain, its 25 ℃ of penetration degrees are 5～200dmm.
Described polymkeric substance is styrene butadiene 20～45: 80～55 polymeric triblock polymers in molar ratio, mainly refers to the SBS base polymer.The structure of SBS is star-like or line style, and molecular weight is 100,000～350, between 000.Triblock polymer can be dried glue, also can be the polymkeric substance that charges into 2～60 heavy % extending oils.
Described compatilizer be selected from styrene tar, Yatall MA, contain sour Yatall MA, catalytically cracked oil, heavy deasphalted oil, solvent treatment extract one or more the mixture in oil, desulfurization naphthenic acid, naphthenic oil, white oil and the coal tar fraction out.
Described crosslinked body is to be selected from crystallization sulphur, active sulphur, sulfur donor and " symbol " to give one or more mixture in the sulfur-crosslinked body.Wherein active sulphur is SULPHUR POWDER, colloid sulphur or its mixture, and colloid sulphur is SULPHUR POWDER or precipitation sulphur and dispersant, and the median size that makes through grinding is the colloid of 1～5 μ m.Sulfur donor is one or more the mixture in morpholine kind compound, thiuram compound and the poly sulfide that is selected from sulfur-bearing.
The thiuram compound general formula is:
X=1～4, R
1, R
2, R
3, R
4: C
1～C
4Alkyl.
Poly sulfide: R
1-(S)
n-R
2, R
1, R
2Be aliphatics, aromatic heterocyclic group, as cycloheptasulfur for imines alkylphenol sulfo-thing, alkylphenol monosulphide.
" symbol " mainly refers to the metal oxide cross-linked agent for sulfur-crosslinked body, and master metal wherein will refer to divalent metal such as Ca, Mg, Zn, Pb etc." symbol " gives sulfur-crosslinked body is one or more the mixture that is selected among CaO, MgO, ZnO and the PbO.
Described polar compound mainly is meant the compound that has polar group, is one or more the mixture that is selected from amine, acids, epoxy resin and the aldehyde compound.
Wherein said aminated compounds mainly refers to fatty amine, aromatic amine compounds.
Described acid compounds is one or more the mixture that is selected from carboxylic-acid, anhydrides, sulfonic acid class, boric acid class and the phosphate compound.
Described carboxylic acid compound is one or more the mixture that is selected from lipid acid and the aromatic acid.
Described anhydrides compound is Tetra hydro Phthalic anhydride and derivative or maleic anhydride and derivative thereof.
The general formula of described sulfonic compound is:
R
1, R
2, R
3=H or C
1～C
5Alkyl
Described phosphate compound is one or more the mixture that is selected from polyphosphoric acid, phosphorous acid, modification Tripyrophosphoric acid and the phosphate compounds.
Described aldehyde compound is one or more the mixture that is selected from glycidaldehyde, formaldehyde, dialdehyde and the furfural, and wherein dialdehyde is terephthalaldehyde and derivative or m-terephthal aldehyde and derivative thereof.
The process for preparing modified asphalt of stable storing provided by the invention is:
50～97.7 heavy % asphalt stocks, 2.0～20.0 heavy % polymkeric substance, 0.1～20.0 heavy % compatilizer, the crosslinked body of 0.1～10.0 heavy % and 0.1～10.0 heavy % polar compound mix down at 100 ℃～250 ℃, react 5～300 minutes, obtain modifying asphalt.
Described compatilizer can mix with asphalt stock earlier, can be that asphalt mother liquid mixes with the mixture of polymkeric substance and asphalt stock earlier also, also can in the end add, and can once add, and also can add at twice; Described asphalt stock can once add, and also can add at twice.
Mixing between each component can be static mixing, dynamically mixing, grinding, the powerful stirring.
Specify method provided by the invention with three kinds of embodiments below, but method provided by the invention is not limited to this three kinds of embodiments.
One of embodiment:
Method provided by the invention comprises the following steps:
(1), asphalt stock contacts 0.1～6 hour with compatilizer, the asphalt stock after obtaining handling under 100 ℃～250 ℃;
(2), the asphalt stock after will handling and mixed with polymers 0.1～10 hour, obtain asphalt mother liquid;
(3), be to add crosslinked body, polar compound and optional asphalt stock in 100 ℃～250 ℃ the asphalt mother liquid to temperature, reacted 5～300 minutes, obtain modifying asphalt.
Asphalt stock described in this mode, polymkeric substance, compatilizer, crosslinked body and polar compound account for 50～97.7 heavy %, 2.0～20.0 heavy %, 0.1～20.0 heavy %, 0.1～10.0 heavy % and 0.1～10.0 heavy % of modifying asphalt respectively.The ratio of the asphalt stock weight of step (3) and step (1) is 0～50: 100～50.
Two of embodiment:
Method provided by the invention comprises the following steps:
(1), asphalt stock contacts 0.1～6 hour with compatilizer, the asphalt stock after obtaining handling under 100 ℃～250 ℃;
(2), the asphalt stock after will handling and mixed with polymers 0.1～10 hour, obtain asphalt mother liquid;
(3), be to add crosslinked body, polar compound and optional compatilizer in 100 ℃～250 ℃ the asphalt mother liquid to temperature, reacted 5～300 minutes, obtain modifying asphalt.
Asphalt stock described in this mode, polymkeric substance, compatilizer, crosslinked body and polar compound account for 50～97.7 heavy %, 2.0～20.0 heavy %, 0.1～20.0 heavy %, 0.1～10.0 heavy % and 0.1～10.0 heavy % of modifying asphalt respectively.The ratio of the compatilizer weight of step (3) and step (1) is 0～50: 100～50.
Three of embodiment:
Method provided by the invention comprises the following steps:
(1), with 100 ℃～250 ℃ asphalt stocks and mixed with polymers 0.1～10 hour, obtain asphalt mother liquid;
(2), temperature is that 100 ℃～250 ℃ asphalt mother liquid contacts 0.1～6 hour with compatilizer, the asphalt mother liquid after obtaining handling under 100 ℃～250 ℃;
(3), after handling asphalt mother liquid in add crosslinked body, polar compound and optional asphalt stock, reacted 5～300 minutes, obtain modifying asphalt.
Asphalt stock described in this mode, polymkeric substance, compatilizer, crosslinked body and polar compound account for 50～97.7 heavy %, 2.0～20.0 heavy %, 0.1～20.0 heavy %, 0.1～10.0 heavy % and 0.1～10.0 heavy % of modifying asphalt respectively.The ratio of the asphalt stock weight of step (3) and step (1) is 0～50: 100～50.
Asphalt stock described in the aforesaid method is one or more the mixture that is selected from petroleum pitch, coal-tar pitch, oil sands bitumen and the rock asphalt, and wherein petroleum pitch is one or more the mixture that is selected from straight-run pitch, solvent deoiling pitch, oxidized bitumen and the mediation pitch.Straight-run pitch long residuum or vacuum residuum that to be crude oil obtain through normal pressure distillation or underpressure distillation, its 25 ℃ of penetration degrees are 20～300dmm (being 1/10mm); Solvent deoiling pitch is meant uses C
3～C
5The de-oiled asphalt that a kind of solvent among the hydro carbons or more than one mixed-solvent extraction residual oil obtain, its 25 ℃ of penetration degrees are 5～200dmm.
Described polymkeric substance is styrene butadiene 20～45: 80～55 polymeric triblock polymers in molar ratio, mainly refers to the SBS base polymer.The structure of SBS is star-like or line style, and molecular weight is 100,000～350, between 000.Triblock polymer can be dried glue, also can be the polymkeric substance that charges into 2～60 heavy % extending oils.
Described compatilizer be selected from styrene tar, Yatall MA, contain sour Yatall MA, catalytically cracked oil, heavy deasphalted oil, solvent treatment extract one or more the mixture in oil, desulfurization naphthenic acid, naphthenic oil, white oil and the coal tar fraction out.
Compatilizer joins can increase the consistency of polymkeric substance in pitch in the system, because compatilizer itself has good mutual solubility with polymkeric substance and bituminous solution, therefore, can play compatibilization to both.
Described crosslinked body is to be selected from crystallization sulphur, active sulphur, sulfur donor and " symbol " to give one or more mixture in the sulfur-crosslinked body.Wherein active sulphur is SULPHUR POWDER, colloid sulphur or its mixture, and colloid sulphur is SULPHUR POWDER or precipitation sulphur and dispersant, and the median size that makes through grinding is the colloid of 1～5 μ m.Sulfur donor is one or more the mixture in morpholine kind compound, thiuram compound and the poly sulfide that is selected from sulfur-bearing.
The thiuram compound general formula is:
X=1～4, R
1, R
2, R
3, R
4: C
1～C
4Alkyl.
Poly sulfide: R
1-(S)
n-R
2, R
1, R
2Be aliphatics, aromatic heterocyclic group, as cycloheptasulfur for imines alkylphenol sulfo-thing, alkylphenol monosulphide.
" symbol " mainly refers to the metal oxide cross-linked agent for sulfur-crosslinked body, and master metal wherein will refer to divalent metal such as Ca, Mg, Zn, Pb etc." symbol " gives sulfur-crosslinked body is one or more the mixture that is selected among CaO, MgO, ZnO and the PbO.
Crosslinked body adds in bitumen/polymer mother liquor blended process, can make good polymkeric substance of dispersion state and the polar compound generation crosslinking reaction in the pitch, exists with stable network structure, further prevents reunion, the segregation of polymkeric substance.
Described polar compound mainly is meant the compound that has polar group, is one or more the mixture that is selected from amine, acids, epoxy resin and the aldehyde compound.
Wherein said aminated compounds mainly refers to fatty amine, aromatic amine compounds.
Described acid compounds is one or more the mixture that is selected from carboxylic-acid, anhydrides, sulfonic acid class, boric acid class and the phosphate compound.
Described carboxylic acid compound is one or more the mixture that is selected from lipid acid and the aromatic acid.
Described anhydrides compound is Tetra hydro Phthalic anhydride and derivative or maleic anhydride and derivative thereof.
The general formula of described sulfonic compound is:
R
1, R
2, R
3=H or C
1～C
5Alkyl
Described phosphate compound is one or more the mixture that is selected from polyphosphoric acid, phosphorous acid, modification Tripyrophosphoric acid and the phosphate compounds.
Described aldehyde compound is one or more the mixture that is selected from glycidaldehyde, formaldehyde, dialdehyde and the furfural, and wherein dialdehyde is terephthalaldehyde and derivative or m-terephthal aldehyde and derivative thereof.
The effect that adds polar compound in the body series is to promote the reaction function of crosslinked body, and its dominant mechanism is environment, the polarity that can change reaction medium, makes crosslinked body can improve reaction efficiency.
Modifying asphalt provided by the invention has good preservation stability, and the difference of the softening temperature of isolation test is lower than 2.5 ℃; Preparation method's flow process provided by the invention is simple, does not need special equipment.Because the modifying asphalt viscosity and the adhesivity that make are big, and be strong with the attached ability of wrapping up in of building stones,, and needn't use the antistripping agent that is used to increase building stones and asphalt adhesion so this modifying asphalt can directly use in rainy humid area.The basic material that also be can be used as emulsified bitumen by the modifying asphalt of method provided by the invention preparation uses, and can realize by adding a certain proportion of water and emulsifying agent.
Below in conjunction with embodiment method provided by the invention is further specified, but not thereby limiting the invention.
Used asphalt stock A, the B of the present invention is respectively straight-run pitch, propane solvent de-oiled asphalt, and its character is as shown in table 2, and polymkeric substance SBS model is 1403, produced by chemical plant, the Yanshan Mountain, Beijing.The shredder model is FD3/60-20, is produced by Shanghai Fu Luke Mechanical and Electrical Equipment Company.Isolation test is to test according to the method that ASTM D 5892-96a provides, and the testing method of softening temperature is measured according to the GB/T4507 method.
Embodiment 1
The present embodiment explanation is handled the situation that asphalt stock prepares modifying asphalt with compatilizer.
Elder generation's adding 120 grams in 190 ℃ 360 gram asphalt stock A contain sour Yatall MA and (are produced by Liaoning petro-chemical fiber factory, down together), contact 1 hour down at 180 ℃, add 90 gram SBS then among the asphalt stock A after handling successively, 18 gram colloid sulphur (are produced by Maoming petro-chemical corporation, down with) and 12 restrain maleic anhydrides and (produce by Lanzhou chemical industrial company, down together), reacted 6 hours down at 120 ℃, obtain modifying asphalt, its character sees Table 3, can find out that from table 3 difference of the softening temperature of isolation test only is 2 ℃.
Embodiment 2
Present embodiment explanation compatilizer adds the situation for preparing modifying asphalt at twice.
In 190 ℃ 360 gram asphalt stock A, add 60 grams earlier and contain sour Yatall MA, contact 1 hour down at 180 ℃, add 90 gram SBS, 18 gram colloid sulphur, 12 gram maleic anhydrides and 60 grams then among the asphalt stock A after handling successively and contain sour Yatall MA, reacted 6 hours down at 220 ℃, obtain modifying asphalt, its character sees Table 3, can find out from table 3, and the difference of the softening temperature of isolation test only is 2.5 ℃.
Embodiment 3
The present embodiment explanation is handled the situation that asphalt mother liquid prepares modifying asphalt with compatilizer.
160 ℃ 470.3 gram asphalt stock A and 14.55 gram SBS were mixed 2.0 hours, obtain 484.85 gram asphalt mother liquids; In 120 ℃ asphalt mother liquid, add 4.9 gram styrene tars and contact 0.5 hour down at 180 ℃, the asphalt mother liquid after obtaining handling; After handling asphalt mother liquid in add 0.25 gram cycloheptasulfur and (produce by Lanzhou chemical industrial company for imines, down with) and 10 restrain polyphosphoric acid (by Jilin Chemical Industry Company production, down together), reacted 150 minutes, obtain modifying asphalt, its character sees Table 3, can find out from table 3, and the difference of the softening temperature of isolation test only is 1 ℃.
Comparative Examples 1
Compare with embodiment 3, this Comparative Examples does not add polar compound.
200 ℃ 479.9 gram asphalt stock A and 14.85 gram SBS were mixed 0.5 hour, obtain 494.75 gram asphalt mother liquids; In 120 ℃ asphalt mother liquid, add 5.0 gram styrene tars and contact 0.5 hour down at 200 ℃, the asphalt mother liquid after obtaining handling; After handling asphalt mother liquid in add 0.25 gram cycloheptasulfur for imines, reacted 150 minutes, obtain modifying asphalt, its character sees Table 3, can find out from table 3, the difference of the softening temperature of isolation test reaches 45 ℃.
Embodiment 4
The present embodiment explanation is handled the situation that asphalt mother liquid prepares modifying asphalt with compatilizer.
150 ℃ 436.5 gram asphalt stock A and 13.5 gram SBS were mixed 3.0 hours, obtain 450 gram asphalt mother liquids; In 150 ℃ asphalt mother liquid, add 90 gram white oils and contact 0.5 hour down at 150 ℃, the asphalt mother liquid after obtaining handling; After handling asphalt mother liquid in add 30 gram zinc oxide (producing) and 30 diamines (by the production of Lanzhou chemical industrial company) of restraining oneself by Huangyan chemical plant, Jiangsu, reacted 60 minutes, and obtained modifying asphalt, its character sees Table 4, can find out that from table 4 difference of the softening temperature of isolation test only is 0.5 ℃.
Embodiment 5
Compare with embodiment 4, A changes B into asphalt stock, and the amount of preparation method, operational condition and each component is all identical, and the modifying asphalt character that makes sees Table 4, can find out from table 4, and the difference of the softening temperature of isolation test only is 0.5 ℃.
Embodiment 6
The present embodiment explanation is with adding the situation that asphalt stock prepares modifying asphalt at twice.
180 ℃ 379.8 gram asphalt stock A and 14.7 gram SBS were mixed 2.0 hours, obtain 394.5 gram asphalt mother liquids; In 180 ℃ asphalt mother liquid, add 2.5 gram catalytically cracked oils and contact 0.5 hour down at 180 ℃, the asphalt mother liquid after obtaining handling; After handling asphalt mother liquid in add the mixtures and the 95.0 gram asphalt stock A of 5 gram dimorpholinyl disulfides (by Jilin Chemical Industry Company production), 3 gram polyphosphoric acid and glycidaldehyde (by Jilin Chemical Industry Company production), contact 0.5 hour down at 180 ℃, obtain modifying asphalt, its character sees Table 4, can find out that from table 4 difference of the softening temperature of isolation test only is 2 ℃.
Embodiment 7
The last adding of present embodiment explanation compatilizer prepares the situation of modifying asphalt.
Elder generation is mixed 185 ℃ 474.8 gram asphalt stock A and 14.7 gram SBS 2.0 hours, obtains 489.5 gram asphalt mother liquids; In 180 ℃ asphalt mother liquid, add 5 gram tetrabutylthiuram disulfides (producing), the mixture of 3 gram tosic acid (the brilliant group company of China produces by Nanjing), 2.5 gram catalytically cracked oils successively by the chemical plant, Qingdao, contact 0.5 hour down at 180 ℃, obtain modifying asphalt, its character sees Table 4, can find out that from table 4 difference of the softening temperature of isolation test only is 1 ℃.
Table 2
| Asphalt stock | ????A | ????B |
| Penetration degree (25 ℃, 100g, 5s), dmm softening temperature (ring and ball method), ℃ extensibility (15 ℃, 5cm/min), cm | ????69 ????48 ????＞150 | ????90 ????47.5 ????＞150 |
| Viscosity (135 ℃), centistoke | ????732 | ????455 |
| Sticking toughness (25 ℃), Newton meter | ????4.3 | ????3.2 |
| Stable hydrocarbon, heavy % aromatic hydrocarbon, heavy % colloid, heavy % bituminous matter, heavy % | ????18.5 ????31.3 ????35.3 ????14.9 | ????7.4 ????51.5 ????31.8 ????9.3 |
Table 3
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| Asphalt stock A, heavy % SBS, heavy % compatilizer, the crosslinked body of heavy %, heavy % polar compound, heavy % product property penetration degree (25 ℃), dmm softening temperature (ring and ball method), (5 ℃ of ℃ ductilities, 5cm/min), centimetre isolation test, ℃ viscosity (135 ℃), centistoke glues toughness (25 ℃), (163 ℃ of Newton meter thin film ovens, 5h) penetration ratio, % ductility (5 ℃), centimetre | ????60.0 ????15.0 ????20.0 ????3.0 ????2.0 ? ????50 ????86.2 ????43 ????2.0 ????2132 ????32.2 ? ????92 ????25 | ????60.0 ????15.0 ????20.0 ????3.0 ????2.0 ? ????52 ????88.8 ????38 ????2.5 ????2003 ????28.5 ? ????94 ????24.5 | ????94.06 ????2.91 ????0.98 ????0.05 ????2 ? ????67 ????58.5 ????35 ????1 ????980 ????15.3 ? ????67.5 ????22 | ????95.98 ????2.97 ????1.0 ????0.05 ????0 ? ????65 ????55.5 ????38 ????45 ????1002 ????13.2 ? ????68.4 ????28 |
Table 4
| Numbering | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Asphalt stock, heavy % SBS, heavy % compatilizer, the crosslinked body of heavy %, heavy % polar compound, heavy % product property penetration degree (25 ℃), dmm softening temperature (ring and ball method), (5 ℃ of ℃ ductilities, 5cm/min), centimetre isolation test, ℃ viscosity (135 ℃), centistoke glues toughness (25 ℃), (163 ℃ of Newton meter thin film ovens, 5h) penetration ratio, % ductility (5 ℃), centimetre | ???A/72.8 ????2.2 ????15.0 ????5.0 ????5.0 ? ????95 ????58.5 ????86 ????0.5 ????992 ????15.2 ? ????78.5 ????63 | ???B/94.06 ????2.91 ????0.98 ????0.05 ????2 ? ????83 ????61.5 ????64 ????0.5 ????1035 ????21.2 ? ????82.1 ????53 | ???A/95.0 ????2.9 ????0.5 ????1.0 ????0.6 ? ????62 ????76.3 ????54 ????2.0 ????1532 ????25.2 ? ????76.1 ????41 | ???A/95.0 ????2.9 ????0.5 ????1.0 ????0.6 ? ????61 ????78.4 ????48 ????1.0 ????1438 ????23.3 ? ????75.4 ????42 |
Claims (20)
1, a kind of modifying asphalt of stable storing, its component and content are:
Asphalt stock 50～97.7 heavy %;
Polymkeric substance 2.0～20.0 heavy %;
Compatilizer 0.1～20.0 heavy %;
Crosslinked body 0.1～10.0 heavy %;
Polar compound 0.1～10.0 heavy %.
2, according to the modifying asphalt of claim 1, it is characterized in that described asphalt stock is one or more the mixture that is selected from petroleum pitch, coal-tar pitch, oil sands bitumen and the rock asphalt, wherein petroleum pitch is one or more the mixture that is selected from straight-run pitch, solvent deoiling pitch, oxidized bitumen and the mediation pitch.
3,, it is characterized in that described polymkeric substance is vinylbenzene and divinyl 20～45: 80～55 polymeric triblock polymers in molar ratio according to the modifying asphalt of claim 1.
4, according to the modifying asphalt of claim 1, it is characterized in that described compatilizer be selected from styrene tar, Yatall MA, contain sour Yatall MA, catalytically cracked oil, heavy deasphalted oil, solvent treatment extract one or more the mixture in oil, desulfurization naphthenic acid, naphthenic oil, white oil and the coal tar fraction out.
5,, it is characterized in that described crosslinked body is to be selected from crystallization sulphur, active sulphur, sulfur donor and " symbol " to give one or more mixture in the sulfur-crosslinked body according to the modifying asphalt of claim 1.
6, according to the modifying asphalt of claim 5, it is characterized in that described active sulphur is SULPHUR POWDER, colloid sulphur or its mixture, colloid sulphur is SULPHUR POWDER or precipitation sulphur and dispersant, the median size that makes through grinding is the colloid of 1～5 μ m.
7,, it is characterized in that described sulfur donor is one or more the mixture in morpholine kind compound, thiuram compound and the poly sulfide that is selected from sulfur-bearing according to the modifying asphalt of claim 5.
8,, it is characterized in that described " symbol " gives sulfur-crosslinked body is the oxide compound linking agent of divalent metal according to the modifying asphalt of claim 5.
9,, it is characterized in that described polar compound is one or more the mixture that is selected from amine, acids, epoxy resin and the aldehyde compound according to the modifying asphalt of claim 1.
10,, it is characterized in that described acid compounds is one or more the mixture that is selected from carboxylic-acid, anhydrides, sulfonic acid class, boric acid class and the phosphate compound according to the modifying asphalt of claim 9.
11,, it is characterized in that described phosphate compound is one or more the mixture that is selected from polyphosphoric acid, phosphorous acid, modification Tripyrophosphoric acid and the phosphate compounds according to the modifying asphalt of claim 10.
12, according to the modifying asphalt of claim 9, it is characterized in that described aldehyde compound is one or more the mixture that is selected from glycidaldehyde, formaldehyde, dialdehyde and the furfural, wherein dialdehyde is terephthalaldehyde and derivative or m-terephthal aldehyde and derivative thereof.
13, the described process for preparing modified asphalt of a kind of claim 1, it is characterized in that 50～97.7 heavy % asphalt stocks, 2.0～20.0 heavy % polymkeric substance, 0.1～20.0 heavy % compatilizer, the crosslinked body of 0.1～10.0 heavy % and 0.1～10.0 heavy % polar compound mix down at 100 ℃～250 ℃, react 5～300 minutes.
14, according to the method for claim 13, it is characterized in that described compatilizer can mix with asphalt stock earlier, can be that asphalt mother liquid mixes with the mixture of polymkeric substance and asphalt stock earlier also, also can in the end add, can once add, also can add at twice.
15,, it is characterized in that described asphalt stock can once add, and also can add at twice according to the method for claim 13.
16, according to the method for claim 13 or 15, it is characterized in that described asphalt stock is one or more the mixture that is selected from petroleum pitch, coal-tar pitch, oil sands bitumen and the rock asphalt, wherein petroleum pitch is one or more the mixture that is selected from straight-run pitch, solvent deoiling pitch, oxidized bitumen and the mediation pitch.
17,, it is characterized in that described polymkeric substance is vinylbenzene and divinyl 20～45: 80～55 polymeric triblock polymers in molar ratio according to the method for claim 13.
18, according to the method for claim 13 or 14, it is characterized in that described compatilizer be selected from styrene tar, Yatall MA, contain sour Yatall MA, catalytically cracked oil, heavy deasphalted oil, solvent treatment extract one or more the mixture in oil, desulfurization naphthenic acid, naphthenic oil, white oil and the coal tar fraction out.
19,, it is characterized in that described crosslinked body is to be selected from crystallization sulphur, active sulphur, sulfur donor and " symbol " to give one or more mixture in the sulfur-crosslinked body according to the method for claim 13.
20,, it is characterized in that described polar compound is one or more the mixture that is selected from amine, acids, epoxy resin and the aldehyde compound according to the method for claim 13.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123512 CN1107099C (en) | 2000-08-18 | 2000-08-18 | Storage stable modified asphalt and its preparing mehtod |
| CA002355408A CA2355408C (en) | 2000-08-18 | 2001-08-16 | A storage-stable modified asphalt composition and its preparation process |
| US09/931,846 US6713539B2 (en) | 2000-08-18 | 2001-08-17 | Storage-stable modified asphalt composition and its preparation process |
| JP2001249485A JP4171194B2 (en) | 2000-08-18 | 2001-08-20 | Storage stability modified asphalt composition and method for producing the same |
| SA01220584A SA01220584B1 (en) | 2000-08-18 | 2001-12-23 | A modified asphalt composition that is stable in storage and a process for its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123512 CN1107099C (en) | 2000-08-18 | 2000-08-18 | Storage stable modified asphalt and its preparing mehtod |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1339556A true CN1339556A (en) | 2002-03-13 |
| CN1107099C CN1107099C (en) | 2003-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00123512 Expired - Lifetime CN1107099C (en) | 2000-08-18 | 2000-08-18 | Storage stable modified asphalt and its preparing mehtod |
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| Country | Link |
|---|---|
| CN (1) | CN1107099C (en) |
Cited By (18)
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| CN100340609C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Polymer modified asphalt with storage stability and its preparation method |
| CN100363462C (en) * | 2005-12-16 | 2008-01-23 | 中国石油天然气股份有限公司 | Preparation process of SBS modified asphalt |
| CN100451057C (en) * | 2006-12-29 | 2009-01-14 | 四川师范大学 | Adjuvant for promoting SBS modified asphalt high low temperature property and its usage method |
| CN100487056C (en) * | 2004-12-17 | 2009-05-13 | 同济大学 | Asphalt anti-stripping agent and its preparation method |
| CN102382543A (en) * | 2010-08-27 | 2012-03-21 | 安徽三缔沥青材料有限公司 | Water-based epoxy resin asphalt paint and preparation method thereof |
| CN102464989A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of high softening point asphalt |
| CN102827487A (en) * | 2012-09-13 | 2012-12-19 | 安徽路达泰克沥青新材料有限公司 | Heavy-traffic emulsified asphalt and preparation method thereof |
| CN103627192A (en) * | 2013-11-26 | 2014-03-12 | 天津东大道科技有限公司 | Modified asphalt and preparation method thereof |
| CN103834423A (en) * | 2014-03-24 | 2014-06-04 | 武汉科技大学 | Modified coal tar pitch and preparation method thereof |
| CN103834421A (en) * | 2014-03-24 | 2014-06-04 | 武汉科技大学 | Environment-friendly type modified coal asphalt and preparation method thereof |
| CN102066525B (en) * | 2008-04-07 | 2015-02-25 | 伊诺弗斯公司 | Air blown asphalt including polyphosphoric acid |
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| CN100340609C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Polymer modified asphalt with storage stability and its preparation method |
| CN100487056C (en) * | 2004-12-17 | 2009-05-13 | 同济大学 | Asphalt anti-stripping agent and its preparation method |
| CN100363462C (en) * | 2005-12-16 | 2008-01-23 | 中国石油天然气股份有限公司 | Preparation process of SBS modified asphalt |
| CN100451057C (en) * | 2006-12-29 | 2009-01-14 | 四川师范大学 | Adjuvant for promoting SBS modified asphalt high low temperature property and its usage method |
| CN102066525B (en) * | 2008-04-07 | 2015-02-25 | 伊诺弗斯公司 | Air blown asphalt including polyphosphoric acid |
| CN102382543A (en) * | 2010-08-27 | 2012-03-21 | 安徽三缔沥青材料有限公司 | Water-based epoxy resin asphalt paint and preparation method thereof |
| CN102464989B (en) * | 2010-11-04 | 2014-04-02 | 中国石油化工股份有限公司 | Preparation method of high softening point asphalt |
| CN102464989A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of high softening point asphalt |
| CN102827487A (en) * | 2012-09-13 | 2012-12-19 | 安徽路达泰克沥青新材料有限公司 | Heavy-traffic emulsified asphalt and preparation method thereof |
| CN102827487B (en) * | 2012-09-13 | 2014-08-13 | 安徽路达泰克沥青新材料有限公司 | Heavy-traffic emulsified asphalt and preparation method thereof |
| CN103627192A (en) * | 2013-11-26 | 2014-03-12 | 天津东大道科技有限公司 | Modified asphalt and preparation method thereof |
| CN108864717B (en) * | 2013-12-13 | 2020-09-22 | 辽宁永润石油制品集团有限公司 | Preparation method of asphalt |
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| CN103834421A (en) * | 2014-03-24 | 2014-06-04 | 武汉科技大学 | Environment-friendly type modified coal asphalt and preparation method thereof |
| CN103834421B (en) * | 2014-03-24 | 2015-04-29 | 武汉科技大学 | Environment-friendly type modified coal asphalt and preparation method thereof |
| CN103834423A (en) * | 2014-03-24 | 2014-06-04 | 武汉科技大学 | Modified coal tar pitch and preparation method thereof |
| CN107849304A (en) * | 2015-08-07 | 2018-03-27 | 纳幕尔杜邦公司 | Use the modified pitch of phosphorous acid |
| CN107849304B (en) * | 2015-08-07 | 2020-12-11 | 性能材料北美股份有限公司 | Modified asphalt using phosphorous acid |
| CN105176125A (en) * | 2015-09-18 | 2015-12-23 | 安徽创业机电设备有限公司 | Environment-friendly brush handle |
| CN109651830A (en) * | 2018-12-27 | 2019-04-19 | 北京紫瑞天成科技有限公司 | A kind of asphalt mixed material modifier and preparation method thereof |
| CN110218463A (en) * | 2019-07-16 | 2019-09-10 | 黄河三角洲京博化工研究院有限公司 | A kind of modified pitch and preparation method thereof |
| CN110218463B (en) * | 2019-07-16 | 2021-09-21 | 黄河三角洲京博化工研究院有限公司 | Modified asphalt and preparation method thereof |
| CN112239663A (en) * | 2020-10-19 | 2021-01-19 | 中国石油大学(华东) | Oil-in-water emulsion oil displacement agent based on styrene tar and preparation method and application thereof |
| CN112239663B (en) * | 2020-10-19 | 2022-07-08 | 中国石油大学(华东) | Oil-in-water emulsion oil displacement agent based on styrene tar and preparation method and application thereof |
| CN114921108A (en) * | 2022-07-05 | 2022-08-19 | 长沙理工大学 | Modified asphalt and preparation method thereof |
| CN114921108B (en) * | 2022-07-05 | 2023-02-17 | 长沙理工大学 | Modified asphalt and preparation method thereof |
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