CN102040848A - SBS modified asphalt prepared from low aromatics content petroleum asphalt and preparation method thereof - Google Patents
SBS modified asphalt prepared from low aromatics content petroleum asphalt and preparation method thereof Download PDFInfo
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Abstract
The invention relates to styrene-butadiene-styrene (SBS) modified asphalt prepared from low aromatics content petroleum asphalt and a preparation method thereof. The method comprises the following steps of: mixing 100 parts of low aromatics content petroleum asphalt and 2.5 to 5 parts of compatilizer, and heating to the temperature of between 140 and 190 DEG C, and stirring for 5 to 30 minutes, wherein the low aromatics content petroleum asphalt comprises four components: 5 to 15 percent of aturates, 25 to 45 percent of aromatics, 15 to 40 percent of colloids and 5 to 25 percent of asphaltenes, a ring and ball method softening point of the low aromatics content petroleum asphalt is between 42 and 52 DEG C, the 25-DEG C penetration of the low aromatics content petroleum asphalt is 60 to 120 (0.1mm), the 10-DEG C ductility of the low aromatics content petroleum asphalt is 80 to 200cm, the 100-DEG C kinematic viscosity of the compatilizer is 20 to 50cst, and the aromatics content is 75 to 100 percent; adding 4 to 6 parts of linear or star-shaped SBS, and stirring and swelling at the temperature of between 185 and 200 DEG C for 10 to 150 minutes, wherein the number average molecular weight of the SBS is 90,000 to 300,000, and a ratio of styrene to butadiene of the SBS is 28:72-40:60; and adding 0.36 to 0.5 part of stabilizer, wherein the stabilizer is a mixture of sulfur and dicumyl peroxide (DCP) and a weight ratio of the sulfur to the DCP is 40:60-70:30, shearing and grinding at the temperature of between 185 and 195 DEG C for 10 to 60 minutes, and stirring and developing at the temperature of between 180 and 195 DEG C for 240 to 360 minutes. By the method, the prejudice of the industry is overcome, and the low aromatics content petroleum asphalt is applied to the preparation of the modified asphalt with high heat storage stability.
Description
Technical field
The present invention relates to road with SBS modifying asphalt field, relate in particular to a kind of SBS modifying asphalt that content petroleum pitch makes and preparation method thereof that divides with low fragrance.
Background technology
In the SBS modifying asphalt, SBS usually with micron particles form dispersion suspension in matrix pitch, forming with the matrix pitch is that external phase, SBS are the sea-island structure of disperse phase.Physics between SBS and the matrix pitch and chemical property difference have determined that both consistencies are very poor.Thus, exist SBS phase, pitch mutually and SBS and pitch three kinds of structures such as interfacial layer between mutually in the SBS modifying asphalt.
The thickness of this interfacial layer character, particularly interfacial layer, cohesive strength and interfacial tension have decisive influence to the heat-storage stability of SBS modifying asphalt.Interfacial layer thickness is less, cohesive strength is crossed low and interfacial tension is crossed conference and caused the interfacial layer instability, and under molecular thermalmotion and action of gravity, interfacial layer is very easily destroyed in the heat-storage process, causes SBS cohesion segregation come-up.Otherwise, if interfacial layer is stable, then having preferable avidity between pitch and the SBS, SBS forms one-piece construction by this interfacial layer mutually with pitch, and has good heat-storage stability.
Industry adds compatilizer usually and improves SBS and bituminous consistency in SBS/ matrix pitch co-mixing system.In SBS, the polystyrene microcell plays physical crosslinking point.If the quantity of polystyrene microcell is many more, then the dispersion of SBS in matrix pitch is difficult more, and SBS and matrix pitch consistency are poor.After adding this compatilizer, this compatilizer enters SBS polystyrene microcell, swelling even dissolved polystyrene microcell, thus strengthen the dispersive ability of SBS in matrix pitch and the stability of raising modifying asphalt.According to the similar compatibility theory, the general petroleum fractions of selecting to be rich in the fragrance branch of this compatilizer.
Japan JSR synthetic rubber Co., Ltd. proposes parameter I c=(bituminous matter+saturated branch)/(fragrance branch+colloid) and estimates the consistency of modifying asphalt.It is generally acknowledged that Ic is little, then pitch and SBS consistency are good, and modified effect is obvious more, and Ic is more little, and pitch is soft more partially.Have the scholar to think, during as the properties-correcting agent of modifying asphalt, the component coefficient Ic of matrix pitch is preferably between 26%-32% with SBS.For paraffinic crude, its asphalt content and saturated minute content height, fragrance divide content low.That is, the Ic value of this paraffinic crude is considerably beyond this numerical range, and the diffusion of SBS molecule in matrix pitch is less, causes every performance of modifying asphalt, and especially the softening temperature index is lower and very fast with the decay of thermmal storage time lengthening.
Isolation test is commonly used to estimate SBS modifying asphalt package stability, estimates the segregation degree with the difference of softening temperature up and down of isolation test.China the Ministry of Communications modifying asphalt standard (JTJ-036-98) regulation isolation test softening temperature difference up and down is qualified product less than 2.5 ℃.The actual SBS modifying asphalt that makes can be divided into following three classes: one, segregation softening temperature difference is greater than 2.5 ℃, promptly in the heat-storage process SBS taken place serious segregation and cohesion and on float on asphalt surface and form the SBS enrichment mutually, cause the top softening temperature far above the bottom; Two, heat-storage post softening point obviously reduces, though do not emanate from softening temperature difference analysis modifying asphalt up and down, heat-storage has caused the reduction of performance of modified bitumen; Three, not only up and down the softening temperature difference meet the demands, and heat-storage post softening point does not descend.Wherein, the 3rd class SBS modifying asphalt just can be considered to have good heat-storage stability.
Homemade most of matrix pitch is a paraffin-base petroleum pitch, and its fragrance divides content generally lower, and is poor with properties-correcting agent SBS consistency commonly used.If itself and SBS are prepared road bitumen, then this road bitumen low temperature is easy to crack, hot storage stability difference and poor high temperature stability.Based on this, industry generally believes that homemade paraffin-base petroleum bituminous is unsuitable for producing the SBS modifying asphalt.Though Imported oil pitch is better with the SBS consistency, the source of goods is limited, costs an arm and a leg.For considering of cost, having on more domestic high-grade highways with homemade paraffin-base petroleum pitch is that matrix pitch prepares the SBS modifying asphalt.On the engineering, how SBS modifying asphalt processing units is docked with mixing building at present, carry out on-the-spot modification.There is following drawback in this kind preparation method: the control of (one) SBS modifying asphalt difficult quality, the frequent incident of using inferior materials and turning out substandard goods, cause the highway owner more and more to be not inclined to and use this preparation method, this causes the application of homemade paraffin-base petroleum pitch in key state project fewer and feweri undoubtedly; (2) this on-site preparation method is had relatively high expectations to mixing building Infrastructure, require configuration pitch hold-up vessel, but a lot of mixing building does not reach this requirement, has limited the ability of mass preparation SBS modifying asphalt; (3) on-the-spot modification only can be satisfied the requirement of road bitumen to hot storage stability at short notice, and along with the prolongation of time, this road bitumen often will ftracture down in low temperature environment, emanate under hot environment.
Summary of the invention
Be to widen application that homemade low fragrance divides content petroleum pitch, reduce the modifying asphalt production cost, the invention provides that a kind of to divide content petroleum pitch with low fragrance be SBS modifying asphalt of making of matrix pitch and preparation method thereof.
This SBS modifying asphalt is pressed the weight percent meter of matrix pitch, comprising: 100 parts of matrix pitches, line style or star-shaped sbs 4-6 part, compatilizer 2.5-5 part, stablizer 0.36-0.5 part.This matrix pitch divides content petroleum pitch for low fragrance, in weight ratio, its four component is distributed as: saturated minute 5-15%, fragrance divides 25-45%, colloid 15-40%, bituminous matter 5-25%, its ring is 42 ℃-52 ℃ with ball method softening temperature, 25 ℃ of penetration degrees are 60-120 (0.1mm), and 10 ℃ of ductilities are 80-200cm.The number-average molecular weight of this SBS is at 90000-300000, and the ratio of its vinylbenzene and divinyl is (28: 72)-(40: 60).This compatilizer is to be rich in the petroleum fractions that fragrance divides, and its 100 ℃ of kinematic viscosity are 20-50cst, and fragrance divides content 75-100%.This stablizer is the mixture of sulphur and dicumyl peroxide (DCP), and wherein the weight ratio of sulphur and DCP is (40: 60)-(70: 30).
This SBS modified asphalt preparation method comprises the steps: by weight percentage, takes by weighing aforementioned low fragrance and divides 100 parts in content petroleum pitch, aforementioned line style or star-shaped sbs 4-6 part, aforementioned compatilizer 2.5-5 part, aforementioned stablizer 0.36-0.5 part; Mix and to divide content petroleum pitch and this compatilizer by low fragrance, be heated to 140-190 ℃, stir 5min-30min, add this line style or star-shaped sbs, stir, be warming up to 185-200 ℃, stir swelling 10-150min, add this stablizer, adopt colloidal mill or high speed shearing machine to grind 10-60min in 185-195 ℃ of down cut, stir developmental response 240min-360min down at 180-195 ℃ then, can make aforementioned SBS modifying asphalt.
The technical program adopts means such as physical compatibilizer, stablizer and mechanical stirring, shearing, comprehensive utilization physics increase-volume and chemical reaction increase-volume principle, overcome technology prejudice, realized that the homemade low fragrance that being unsuitable for of generally believing of industry is prepared the good SBS modifying asphalt of stability in storage divides content petroleum pitch to be successfully applied to SBS modifying asphalt preparation field, widen the scope of SBS modifying asphalt selection matrix pitch, saved the raw materials cost of SBS modifying asphalt.Particularly, the technical program is by adding the churning time of physical compatibilizer, raising SBS swelling temperature and shear temperature and developmental temperature, proper extension swelling process and growth course, and force the effective dispersive time of SBS molecule in low fragrance branch petroleum pitch, increased the consistency that low fragrance divides petroleum pitch and SBS from physics increase-volume angle.In addition, the technical program is also divided in the petroleum pitch by mixture to the low fragrance that adds sulphur and peroxide vulcanizing agent, having increased SBS divides petroleum pitch molecule generation graft reaction to generate the quantity of SBS-pitch multipolymer with low fragrance, realization forcibly is permanently secured to low fragrance with the SBS molecular chain and divides in the petroleum pitch, has increased SBS and has hanged down the consistency that fragrance divides petroleum pitch from chemical increase-volume angle.
The SBS modifying asphalt that the technical program makes is under 163 ℃, and 48h segregation softening temperature difference is lower than 2.5 ℃, and the decay of thermmal storage 24h softening temperature is lower than 4 ℃.When the SBS volume accounted for matrix pitch weight ratio＞4.5%, the softening temperature of this SBS modifying asphalt was greater than 70 ℃.Therefore, the SBS modified asphalt preparation method that adopts the technical program to provide need not to adopt the mode of production unit and the on-the-spot modification of mixing building, and can be same as intermediate base or naphthenic base oil pitch production SBS modifying asphalt, adopts batch production production.This preparation method need not Infrastructure such as mixing building, has saved the production unit cost.
Embodiment
Divide SBS modifying asphalt that content petroleum pitch makes and preparation method thereof with low fragrance below with reference to what embodiment described that the technical program provides in detail.
This SBS modifying asphalt can be made by following steps: by weight percentage, take by weighing low fragrance and divide 100 parts in content petroleum pitch, line style or star-shaped sbs 4-6 part, compatilizer 2.5-5 part, stablizer 0.36-0.5 part; In weight ratio, this low fragrance divides four components of content petroleum pitch to be distributed as: saturated minute 5-15%, and fragrance divides 25-45%, colloid 15-40%, bituminous matter 5-25%, its ring is 42 ℃-52 ℃ with ball method softening temperature, 25 ℃ of penetration degrees are 60-120 (0.1mm), and 10 ℃ of ductilities are 80-200cm; The number-average molecular weight of this SBS is at 90000-300000, and the ratio of its vinylbenzene and divinyl is 28: 72-40: 60; This compatilizer is to be rich in the petroleum fractions that fragrance divides, and its 100 ℃ of kinematic viscosity are 20-50cst, and fragrance divides content 75-100%; This stablizer is the mixture of sulphur and dicumyl peroxide (DCP), and wherein the weight ratio of sulphur and dicumyl peroxide is 40: 60-70: 30; Mix and to divide content petroleum pitch and this compatilizer by low fragrance, be heated to 140-190 ℃, stir 5-30min; Add this line style or star-shaped sbs, stir, be warming up to 185-200 ℃, stir swelling 10-150min; Add this stablizer, adopt colloidal mill or high speed shearing machine to grind 10-60min in 185-195 ℃ of down cut; Stir down developmental response 240-360min at 180-195 ℃ then, promptly make stable storing, SBS modifying asphalt that softening temperature is high.
Embodiment 1
It is the method that matrix pitch prepares the SBS modifying asphalt with low fragrance branch content petroleum pitch that present embodiment provides a kind of.This method may further comprise the steps:
The first step: use compatilizer mediation matrix pitch.
This matrix pitch is that commercially available homemade low fragrance divides content for paraffin foundation stone oily bitumen.In the present embodiment, select commercially available No. 90 bi tumenf orr oad A for use, its four component is distributed as saturated branch 10.90%, and fragrance divides 38.80%, colloid 31.74%, bituminous matter 18.56%.
Described compatilizer can be commercially available common furfural extract oil.Preferably, 100 ℃ of kinematic viscosity 20-50cst of this compatilizer, by weight percentage, fragrance divides content 75-100%.Select for use commercially available Iran to produce aromatic hydrocarbon oil in the present embodiment, its 100 ℃ of kinematic viscosity 35cst, fragrance divides content 91.27%.
This compatilizer mediation matrix pitch comprises: in weight ratio, and 100 parts of these commercially available No. 90 bi tumenf orr oad A, this Iran produces 2.5 parts of aromatic hydrocarbon oil, stirs 5 to 30min down at 140 ℃-190 ℃, gets the pitch temper.
Second step: swelling SBS in this pitch temper.
Described SBS is commercially available common line style or star-shaped sbs.Select the SBS 791H of Ba Ling petrochemical iy produced in the present embodiment for use, its number-average molecular weight is about 110000, and the ratio of vinylbenzene and divinyl is 30: 70 in the molecule, and constitutional features is a line style.
The swell process of described SBS in this pitch temper comprises: in weight ratio, get 102.5 parts of described pitch tempers, SBS791H4.8 part rises to 185 ℃-200 ℃ with temperature, stirs swelling 60min.
The 3rd step: add stablizer, shear.
Described stablizer is the mixture of commercially available sulphur and dicumyl peroxide (DCP).In the present embodiment, the weight ratio of sulphur and DCP is 45: 55.Shearing technology behind the described interpolation stablizer comprises: in weight ratio, get 107.3 parts of the second step gained SBS asphalt mixtures, add 0.36 part of stablizer after, at 190 ℃ of down cut 30min.
The 4th step: stir and grow.
The speed of this stirring should not be too soon or is too slow.If it is too slow to grow stirring velocity, then the developmental capacity of modifying asphalt is bad; If it is too fast to stir development rate, then the volatilization of bituminous light constituent is very fast, and is unfavorable to the low-temperature ductility (5 ℃ of ductilities) of modifying asphalt.Preferably, this stirring development rate is 30-100rpm.The time that this stirring is grown is 240-360min.In the present embodiment, the stirring development rate is 60rpm, and the stirring development time is 240min, and this stirring developmental temperature remains between 185-190 ℃.
Embodiment 2
Present embodiment is compared with embodiment 1, and the stirring development time is 300min, and other steps and processing parameter are same as embodiment 1.
Embodiment 3
Present embodiment is compared with embodiment 1, and the stirring development time is 360min, and other steps and processing parameter are same as embodiment 1.
The comparative example 1
Present embodiment is compared with embodiment 1, and the stirring development time is 180min, and other steps and processing parameter are same as embodiment 1.
Embodiment 4
Present embodiment is compared with embodiment 1, and the compatilizer addition is 4.0 parts, and other steps and processing parameter are same as embodiment 1.
Embodiment 5
Present embodiment is compared with embodiment 1, and the compatilizer addition is 5.0 parts, and other steps and processing parameter are same as embodiment 1.
The comparative example 2
Present embodiment is compared with embodiment 1, and the compatilizer addition is 1.5 parts, and other steps and processing parameter are same as embodiment 1.
Embodiment 6
Present embodiment is compared with embodiment 1, and the stablizer addition is 0.50 part, and other steps and processing parameter are same as embodiment 1.
Embodiment 7
Present embodiment is compared with embodiment 1, and the stablizer addition is 0.42 part, and other steps and processing parameter are same as embodiment 1.
The comparative example 3
Present embodiment is compared with embodiment 1, and the stablizer addition is 0.30 part, and other steps and processing parameter are same as embodiment 1.
Embodiment 8
Present embodiment is compared with embodiment 1, and the SBS additive capacity is 4.5 parts, and other steps and processing parameter are same as embodiment 1.
Embodiment 9
Present embodiment is compared with embodiment 1, and the SBS addition is 4.0 parts, and other steps and processing parameter are same as embodiment 1.
Embodiment 10
Present embodiment is compared with embodiment 1, and the SBS addition is 6.0 parts, and other steps and processing parameter are same as embodiment 1.
The performance of each embodiment gained SBS modifying asphalt of table 2
The performance (continuing) of each embodiment gained SBS modifying asphalt of table 2
The performance (continuing) of each embodiment gained SBS modifying asphalt of table 2
The performance (continuing) of each embodiment gained SBS modifying asphalt of table 2
Claims (2)
1. SBS modifying asphalt that divides content petroleum pitch to make with low fragrance, by weight, comprise that low fragrance divides 100 parts in content petroleum pitch, line style or star-shaped sbs 4-6 part, compatilizer 2.5-5 part and stablizer 0.36-0.5 part, the ring and the ball method softening temperature that should hang down fragrance point content petroleum pitch are 42 ℃-52 ℃, 25 ℃ of penetration degrees are 60-120,10 ℃ of ductilities are 80-200cm, in weight ratio, its four component is distributed as: saturated minute 5-15%, fragrance divides 25-45%, colloid 15-40%, bituminous matter 5-25%; The number-average molecular weight of this SBS is at 90000-300000, and the ratio of its vinylbenzene and divinyl is 28: 72-40: 60; This compatilizer is to be rich in the petroleum fractions that fragrance divides, and its 100 ℃ of kinematic viscosity are 20-50cst, and fragrance divides content 75-100%; This stablizer is the mixture of sulphur and dicumyl peroxide, and wherein the weight ratio of sulphur and dicumyl peroxide is 40: 60-70: 30.
2. one kind is divided content petroleum pitch to prepare the method for SBS modifying asphalt with low fragrance, comprising:
By weight, mix 100 parts low fragrance and divide content petroleum pitch and 2.5-5 part compatilizers, stir 5min-30min after being heated to 140-190 ℃; The ring and the ball method softening temperature that should hang down fragrance point content petroleum pitch are 42 ℃-52 ℃, and 25 ℃ of penetration degrees are 60-120, and 10 ℃ of ductilities are 80-200cm, and by weight percentage, its four component is distributed as: saturated minute 5-15%, and fragrance divides 25-45%, colloid 15-40%, bituminous matter 5-25%; This compatilizer is to be rich in the petroleum fractions that fragrance divides, and its 100 ℃ of kinematic viscosity are 20-50cst, and fragrance divides content 75-100%;
Add 4-6 part line style or star-shaped sbs, in 185-200 ℃ of stirring swelling 10-150min, the number-average molecular weight of this SBS is at 90000-300000, and the ratio of its vinylbenzene and divinyl is 28: 72-40: 60; With
Add 0.36-0.5 part stablizer, this stablizer is the mixture of sulphur and dicumyl peroxide, the weight ratio of this sulphur and dicumyl peroxide is 40: 60-70: 30, grind 10-60min in 185-195 ℃ of down cut, and stir developmental response 240min.-360min. down in 180-195 ℃.
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| CN103194072A (en) * | 2013-04-25 | 2013-07-10 | 交通运输部公路科学研究所 | Complex modified asphalt composition and preparation method thereof |
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| CN103194072A (en) * | 2013-04-25 | 2013-07-10 | 交通运输部公路科学研究所 | Complex modified asphalt composition and preparation method thereof |
| CN104177845A (en) * | 2013-05-21 | 2014-12-03 | 佛山高富中石油燃料沥青有限责任公司 | Styrene-butadiene-styrene block copolymer (SBS)-modified asphalt and preparation method thereof |
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| CN103396670A (en) * | 2013-07-11 | 2013-11-20 | 河海大学 | Waterproof modified asphalt for dam asphalt well and preparation method thereof |
| CN104194361A (en) * | 2014-08-29 | 2014-12-10 | 成都工业学院 | SBS modified asphalt and preparation method thereof |
| CN104277466A (en) * | 2014-09-29 | 2015-01-14 | 青岛联康油脂制品有限公司 | Low-cancerigenic-polycyclic-aromatic-hydrocarbon-content modified petroleum asphalt and preparation method thereof |
| CN104403332A (en) * | 2014-10-29 | 2015-03-11 | 佛山市高明区生产力促进中心 | SBS (Styrene-Butadiene-Styrene)-modified asphalt and preparation method thereof |
| CN107382150A (en) * | 2017-07-28 | 2017-11-24 | 甘肃省交通科学研究院有限公司 | The rubber asphalt Matrix mixing material and preparation method that can adapt to cold area's weather conditions of a kind of rich rubber asphalt content |
| CN107892820A (en) * | 2017-12-13 | 2018-04-10 | 佛山高富中石油燃料沥青有限责任公司 | A kind of special SBS modified pitch of airfield pavement and preparation method thereof |
| CN110922769A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Direct-vat-set high-viscosity asphalt modifier and preparation method thereof |
| CN114163829A (en) * | 2020-09-11 | 2022-03-11 | 中国石油化工股份有限公司 | SBS modified asphalt and preparation method thereof |
| CN114163829B (en) * | 2020-09-11 | 2023-07-04 | 中国石油化工股份有限公司 | SBS modified asphalt and preparation method thereof |
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