CN102040848B - 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. The SBS modified asphalt can be prepared by the following method: mixing 100 parts of commercially available No. 90 road asphalt with 2.5 parts of Iran aromatic hydrocarbon oil compatilizer, and heating to the temperature of between 140 and 190 DEG C, and stirring for 5 to 30 minutes, wherein the commercially available No. 90 road asphalt comprises four components:10.90 percent of aturates, 38.80 percent of aromatics, 31.74 percent of colloids and 18.56 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 35 cst, and the aromatics content is 91.27 percent; adding 4.8 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 110000, and a ratio of styrene to butadiene of the SBS is 30:70; and adding 0.36 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 45:55, shearing and grinding at the temperature of 190 DEG C for 30 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 to hang down fragrant SBS modifying asphalt that divides content petroleum pitch to make and preparation method thereof.
Background technology
In the SBS modifying asphalt, SBS usually with micron particles form dispersion suspension in matrix pitch, form and take the sea-island structure that matrix pitch is disperse phase as external phase, SBS.Physics between SBS and matrix pitch and chemical property difference have determined that both consistencies are very poor.Thus, there are SBS phase, pitch phase and SBS phase and the 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 too low and interfacial tension is crossed conference and caused interfacial layer unstable, and in the heat-storage process, under molecular thermalmotion and action of gravity, interfacial layer is very easily destroyed, causes SBS cohesion segregation floating.Otherwise, if interfacial layer is stable, between pitch and SBS, thering is better avidity, the SBS phase forms one-piece construction by this interfacial layer mutually with pitch, and has good heat-storage stability.
Industry adds compatilizer to improve the consistency of SBS and pitch usually in SBS/ matrix pitch co-mixing system.In SBS, the polystyrene microcell plays physical crosslinking point.If the quantity of polystyrene microcell is more, the dispersion of SBS in matrix pitch is more difficult, and SBS and matrix pitch consistency are poor.After adding this compatilizer, this compatilizer enters SBS polystyrene microcell, and swelling is the dissolved polystyrene microcell even, thereby strengthens the dispersive ability of SBS in matrix pitch and the stability of raising modifying asphalt.According to the similar compatibility theory, the petroleum fractions that fragrance divides is rich in the general selection of this compatilizer.
Japan JSR synthetic rubber Co., Ltd. proposes parameter I c=(bituminous matter+saturated minute)/(divide+colloid of fragrance) and estimates the consistency of modifying asphalt.It is generally acknowledged that Ic is little, pitch and SBS consistency are good, and modified effect is more obvious, and Ic is less, and pitch is softer.Have the scholar to think, using SBS during as the properties-correcting agent of modifying asphalt, the component coefficient Ic of matrix pitch is preferably between 26%-32%.For paraffinic crude, its asphalt content and saturated minute content are high, and fragrance minute content is 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 the properties 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, with the softening point difference up and down of isolation test, estimates the segregation degree.The upper and lower softening point difference of China the Ministry of Communications modifying asphalt standard (JTJ-036-98) regulation isolation test is less than 2.5 ℃ for qualified product.The actual SBS modifying asphalt made can be divided into following three classes: one, the segregation softening point difference is greater than 2.5 ℃, in the heat-storage process SBS occurred serious segregation and cohesion and on float on asphalt surface and form the SBS enrichment phase, cause the top softening temperature far above bottom; Two, heat-storage post softening point obviously reduces, although analyze modifying asphalt from upper and lower softening point difference, does not emanate, and heat-storage has caused the reduction of performance of modified bitumen; Three, not only upper and lower softening point difference meets 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.
Domestic most of matrix pitch is paraffin-base petroleum pitch, and its fragrance minute content is generally lower, poor with properties-correcting agent SBS consistency commonly used.If itself and SBS are prepared to road bitumen, this road bitumen low temperature is easy to crack, the poor and poor high temperature stability of hot storage stability.Based on this, what industry generally believed domestic paraffin-base petroleum pitch is unsuitable for producing the SBS modifying asphalt.Though Imported oil pitch is better with the SBS consistency, the source of goods is limited, expensive.For considering of cost, the domestic paraffin-base petroleum pitch of having to take on more domestic high-grade highways prepares the SBS modifying asphalt as matrix pitch.On engineering, how the SBS equipment for processing modified asphaltum is docked with mixing building at present, carry out on-the-spot modification.There is following drawback in this kind of preparation method: (one) SBS modifying asphalt difficult quality is controlled, the frequent event 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 domestic paraffin-base petroleum pitch in key state project fewer and feweri undoubtedly; (2) this in situ preparation method is had relatively high expectations to mixing building Infrastructure, require configuration bituminous pitch storing tank, but a lot of mixing building does not reach this requirement, has limited the ability of extensive preparation SBS modifying asphalt; (3) on-the-spot modification only can meet 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 under low temperature environment, under hot environment, emanate.
Summary of the invention
For widening domestic low fragrance, divide content petroleum pitch application, reduce the modifying asphalt production cost, the invention provides a kind of take hang down SBS modifying asphalt that fragrance minute content petroleum pitch makes as matrix pitch and preparation method thereof.
This SBS modifying asphalt, press 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 is low fragrance minute content petroleum pitch, in weight ratio, its four component is distributed as: saturated minute 5-15%, fragrance minute 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), 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, fragrance minute content 75-100%.The mixture that this stablizer is sulphur and dicumyl peroxide (DCP), wherein the weight ratio of sulphur and DCP is (40:60)-(70:30).
The preparation method of this SBS modifying asphalt, comprise the steps: by weight percentage, takes aforementioned low fragrance and divide 100 parts, 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 should 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, then stir developmental response 240min-360min under 180-195 ℃, can make aforementioned SBS modifying asphalt.
The technical program adopts the means such as physical compatibilizer, stablizer and mechanical stirring, shearing, comprehensive utilization physics increase-volume and chemical reaction increase-volume principle, overcome technology prejudice, the domestic low fragrance of having realized the SBS modifying asphalt that is unsuitable for the Preparation and storage good stability that industry is generally believed 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 the time of forcing the effective dispersion of SBS molecule in low fragrance minute petroleum pitch, increased from physics increase-volume angle the consistency that low fragrance divides petroleum pitch and SBS.Separately, the technical program is also by the extremely low fragrance minute petroleum pitch of mixture that adds sulphur and peroxide vulcanizing agent, increased the quantity of SBS with low fragrance minute petroleum pitch molecule generation graft reaction generation SBS-pitch multipolymer, realization forcibly is permanently secured to the SBS molecular chain in low fragrance minute petroleum pitch, from chemical increase-volume angle, has increased the consistency of SBS with low fragrance minute petroleum pitch.
The SBS modifying asphalt that the technical program makes is under 163 ℃, and 48h segregation softening point difference is lower than 2.5 ℃, and thermmal storage 24h softening temperature is decayed lower than 4 ℃.When the SBS volume accounts for matrix pitch weight ratio>4.5%, the softening temperature of this SBS modifying asphalt is greater than 70 ℃.Therefore, the preparation method of the SBS modifying asphalt that adopts the technical program to provide is without the mode that adopts production unit with the on-the-spot modification of mixing building, and can be same as intermediate base or naphthenic base oil asphalt production SBS modifying asphalt, employing batch production production.This preparation method, without Infrastructure such as mixing buildings, has saved the production unit cost.
Embodiment
Describe below with reference to embodiment that the technical program provides in detail to hang down SBS modifying asphalt that fragrance minute content petroleum pitch makes and preparation method thereof.
This SBS modifying asphalt can be made by following steps: by weight percentage, take low fragrance minute 100 parts, 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, four components of this low fragrance minute content petroleum pitch are distributed as: saturated minute 5-15%, fragrance minute 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), 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, fragrance minute content 75-100%; The mixture that this stablizer is sulphur and dicumyl peroxide (DCP), wherein the weight ratio of sulphur and dicumyl peroxide is 40:60-70:30; Mix and should 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; Then stir developmental response 240-360min under 180-195 ℃, make stable storing, SBS modifying asphalt that softening temperature is high.
Embodiment 1
The present embodiment provide a kind of take hang down fragrance minute content petroleum pitch and prepare the method for SBS modifying asphalt as matrix pitch.The method comprises the following steps:
The first step: use compatilizer mediation matrix pitch.
This matrix pitch is that commercially available domestic low fragrance divides content for paraffin foundation stone oily bitumen.In the present embodiment, select commercially available No. 90 bi tumenf orr oad A, its four component is distributed as saturated minute 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 minute content 75-100%.In the present embodiment, select commercially available Iran to produce aromatic hydrocarbon oil, its 100 ℃ of kinematic viscosity 35cst, fragrance minute content 91.27%.
This compatilizer mediation matrix pitch comprises: in weight ratio, and these commercially available No. 90 bi tumenf orr oad A100 parts, this Iran produces 2.5 parts of aromatic hydrocarbon oil, stirs 5 to 30min under 140 ℃-190 ℃, obtains 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 SBS791H of Ba Ling petrochemical iy produced in the present embodiment, its number-average molecular weight approximately 110000, in molecule, the ratio of vinylbenzene and divinyl is 30:70, constitutional features is 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, rise to 185 ℃-200 ℃ by temperature, stirs swelling 60min.
The 3rd step: add stablizer, shear.
The mixture that described stablizer is commercially available sulphur and dicumyl peroxide (DCP).In the present embodiment, the weight ratio of sulphur and DCP is 45:55.Shearing technique after described interpolation stablizer comprises: in weight ratio, get 107.3 parts of second step gained SBS asphalt mixtures, after adding 0.36 part of stablizer, 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, the developmental capacity of modifying asphalt is bad; If it is too fast to stir development rate, the volatilization of the light constituent of pitch is very fast, 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
The 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
The 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
The 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
The 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
The 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
The 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
The 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
The 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
The 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
The 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
The 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
The 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 of table 2 SBS modifying asphalt
The performance (continuing) of each embodiment gained of table 2 SBS modifying asphalt
The performance (continuing) of each embodiment gained of table 2 SBS modifying asphalt
The performance (continuing) of each embodiment gained of table 2 SBS modifying asphalt
Claims (1)
1. the SBS modifying asphalt made to hang down fragrance minute content petroleum pitch, by weight, comprise 0.36 part of low fragrance minute 100 parts, content petroleum pitch, 4.8 parts of type SBSs, 2.5 parts of compatilizers and stablizer, should low fragrance minute content petroleum pitch be commercially available No. 90 road bitumens, its ring is 42 ℃-52 ℃ with ball method softening temperature, 25 ℃ of penetration degrees are 60-120,10 ℃ of ductilities are 80-200cm, in weight ratio, its four component is distributed as: saturated minute 10.90%, fragrance divides 38.80%, colloid 31.74%, bituminous matter 18.56%; This SBS is the SBS791H that the Ba Ling petrochemical industry is produced, and its number-average molecular weight is 110000, and the ratio of its vinylbenzene and divinyl is 30:70; This compatilizer is that Iran produces aromatic hydrocarbon oil, and its 100 ℃ of kinematic viscosity are 35cst, fragrance minute content 91.27%; The mixture that this stablizer is sulphur and dicumyl peroxide, wherein the weight ratio of sulphur and dicumyl peroxide is 45:55, described SBS modifying asphalt adopts following method to make:
By weight, the first step: mix 100 parts of described low fragrance and divide content petroleum pitch and 2.5 parts of described compatilizers, stir 5min-30min after being heated to 140-190 ℃, obtain the pitch temper;
Second step: get 102.5 parts of pitch tempers, SBS791H4.8 part, stir swelling 60min in 185-200 ℃;
The 3rd step: get 107.3 parts of second step gained SBS asphalt mixtures, add 0.36 part of described stablizer, in 190 ℃ of down cut 30min;
The 4th step: in stirring developmental response 240min between 185-190 ℃, under stirring development rate 60rpm.
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Cited By (1)
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| CN108690359A (en) * | 2018-06-04 | 2018-10-23 | 长安大学 | A kind of response type SBS compounding high-viscosity high-elasticity modified pitch and preparation method |
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| CN102337036B (en) * | 2011-08-18 | 2013-03-27 | 路翔股份有限公司 | Oxidized polyethlene wax-containing modified asphalt and preparation method thereof, and asphalt concrete |
| CN102993755B (en) * | 2011-09-14 | 2015-08-26 | 广州路翔交通材料有限公司 | The preparation method of modifying asphalt, this modifying asphalt and bituminous concrete |
| CN103044932B (en) * | 2011-10-17 | 2015-08-19 | 中国石油天然气股份有限公司 | The method of modifying asphalt is prepared with the raw material of low asphalt content |
| 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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| 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 |
| CN107382150B (en) * | 2017-07-28 | 2020-04-24 | 甘肃省交通科学研究院有限公司 | Rubber asphalt mastic mixture rich in rubber asphalt and capable of adapting to cold region climate conditions and preparation method thereof |
| 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 |
| CN110922769B (en) * | 2018-09-20 | 2022-09-09 | 中国石油化工股份有限公司 | Direct-vat-set high-viscosity asphalt modifier 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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Effective date of registration: 20140521 Address after: 510635 Guangdong city of Guangzhou province Luogang District No. 80 Guangzhou Road, science city on science and technology innovation base area D 504 Patentee after: Guangzhou Luxiang Traffic Material Co., Ltd. Address before: 510000 Guangdong city of Guangzhou province Luogang District No. 80 Guangzhou Road, science city on science and technology innovation base area D 501-503 Patentee before: Luxiang Co., Ltd. |
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