CN103773008A - High-viscosity modified asphalt and preparation method thereof - Google Patents

High-viscosity modified asphalt and preparation method thereof Download PDF

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Publication number
CN103773008A
CN103773008A CN201210411140.9A CN201210411140A CN103773008A CN 103773008 A CN103773008 A CN 103773008A CN 201210411140 A CN201210411140 A CN 201210411140A CN 103773008 A CN103773008 A CN 103773008A
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modified asphalt
viscosity modified
viscosity
agent
preparation
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CN103773008B (en
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宣根海
陈杰
徐青柏
万淼
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a high-viscosity modified asphalt and a preparation method thereof. The high-viscosity modified asphalt comprises the following components in parts by weight: 100 parts of matrix asphalt, 0.5-1.2 parts of a ductility improver, 3-6 parts of aromatic oil, 0.5-1.5 parts of a chemical modifier, and 0.1-1 part of a chemical additive, wherein the chemical modifier is one or more of orthophosphoric acid, polyphosphoric acid, polyphosphoric acid, or amine polyphosphate. The preparation method comprises the following steps: (1) mixing the ductility improver and the aromatic oil to prepare a ductility improver mother liquid; (2) mixing the ductility improver mother liquid, the chemical modifier, the chemical additive, and the matrix asphalt to react to prepare the high-viscosity modified asphalt. The high-viscosity modified asphalt is excellent in storage stability, high in viscosity at the temperature of 60 DEG C, and low in cost; the preparation method is simple and is easy to implement.

Description

A kind of high-viscosity modified asphalt and preparation method thereof
Technical field
The present invention relates to a kind of high-viscosity modified asphalt and preparation method thereof, be specifically related to a kind of high-viscosity modified asphalt and method that adopts chemical modification method to prepare.
Background technology
When high-viscosity modified asphalt refers to 60 ℃, the absolute viscosity of pitch is greater than the modifying asphalt of 20000Pas, because it has good high-temperature stability, low-temperature cracking-resistance, oxidation-resistance and good construction workability, be widely used in concrete dynamic modulus drain type asphalt road surface (OGFC) and stone matrix asphalt mixture (SMA) road surface.Mainly make by the polymer modification of adding relatively large (8% ~ 12%) in petroleum pitch at present.Add polymkeric substance petroleum pitch is carried out to modification, can obviously improve the high and low temperature performance of pitch, the anti-rut of high temperature, the low temperature cracking resistance ability of bituminous pavement is provided.But, owing to there being the difference such as molecular weight, viscosity between polymkeric substance and pitch, make polymer modified asphalt difficulties in dispersion.Meanwhile, because most polymers and pitch can not be completely compatible, and have density difference, cause modifying asphalt system at high temperature storage stability is bad so a large amount of polymkeric substance adds membership, easily layering, affects asphalt quality and normal construction.Tradition high-viscosity modified asphalt is in advance through high temperature, high shear forces Preparation and storage, is then transported to working-yard and uses, and like this stability in storage of high-viscosity modified asphalt is had higher requirement.
CN101538408A discloses a kind of asphaltum with high viscosity and preparation method thereof, wherein high-viscosity modified asphalt is made up of 100 parts of No. 70 pitches, 4~12 parts of thermoplastic elastomers, 2~80 parts of thermoplastic resins, 1~10 part of compatilizer, 8~40 parts of adjusting adhesives and 0.5~4 part of comprehensive anti-aging agent, this patent is improved the compatilizer between pitch and polymkeric substance by the compatilizer that adds high fragrance point content, by adding adjusting adhesive petroleum resin to improve the viscosity of pitch and the consumption of reduction polymkeric substance.
CN1990563A and CN102093728A disclose respectively a kind of preparation method of asphaltum with high viscosity, the two is also to adopt to add petroleum resin, obtained having the high-viscosity modified asphalt of good dispersiveness and stability, the add-on of polymkeric substance and petroleum resin is still very large.CN101613515A discloses a kind of high viscosity high elasticity asphalt modifier and preparation method thereof, and this patent is by adding sulphur also to improve the stability of polymkeric substance in pitch.
Although taked diverse ways to improve compatibility problem between polymkeric substance and pitch in above patent, the add-on of polymkeric substance is not obviously reduced, still fundamentally do not solve compatibility problem.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of high-viscosity modified asphalt and preparation method thereof.The present invention adopts the method for chemical modification to prepare high-viscosity modified asphalt, has improved the stability in storage of high-viscosity modified asphalt, 60 ℃ of viscosity are high, and with low cost, and preparation method is simple, is easy to construction.
High-viscosity modified asphalt of the present invention, comprises following component by weight: take 100 parts of matrix pitches as benchmark, increase and prolong 0.5~1.2 part of agent, 3~6 parts of aromatic hydrocarbon oil, 0.5~1.5 part of chemical modifier, 0.1~1 part of chemical additive.
Matrix pitch of the present invention is petroleum pitch, comprises one or more in straight-run pitch, oxidized bitumen or solvent deoiling pitch, and its penetration degree is 60~80 1/10mm.
In the inventive method, it is one or more in natural rubber (NR), styrene-butadiene rubber(SBR) (SBR), chloroprene rubber (CR), SBS (SBS), SIS (SIS) or polystyrene-poly ethene-polybutene-polystyrene block copolymer (SEBS) that agent is prolonged in described increasing.
Aromatic hydrocarbons oil viscosity of the present invention is 20~50(100 ℃ of kinematic viscosity, mm 2/ s), aromatic hydrocarbons mass content>=80% can be aromatic base rubber filling oil, be rich in one or more of the refining extraction oil of aromatic hydrocarbons and the reduced pressure distillate wet goods of naphthenic base crude.
Chemical modifier of the present invention is one or more in ortho-phosphoric acid, Tripyrophosphoric acid, polyphosphoric acid or polyphosphoric acid amine.
Chemical additive of the present invention be Urea,amino-, one or more in thiosemicarbazide, benzamido urea or semicarbazide derivative.
High-viscosity modified asphalt of the present invention can also need to add other additive according to application, as antistripping agent, fire retardant and antiaging agent etc.
The preparation method of high-viscosity modified asphalt of the present invention, comprises following content: (1) is prolonged agent by increasing and mixed with aromatic hydrocarbon oil, is prepared into increase to prolong agent mother liquor; (2) increasing is prolonged to agent mother liquor, chemical modifier, chemical additive and matrix pitch hybrid reaction, make high-viscosity modified asphalt.
The inventive method preferably adds part chemical modifier in step (1), in step (2), adds residue chemical modifier.Wherein step (1) adds 10%~20% of chemical modifier total mass.
In the inventive method, step (1) and step (2) can adopt stirring, shearing, Screw Extrusion or the hybrid mode such as ultrasonic.The mixing temperature of step (1) is 70 ~ 120 ℃, and mixing time is 20 ~ 80 minutes, and the mixing temperature of step (2) is 120 ~ 180 ℃, and mixing time is 20 ~ 120 minutes.
Compared with prior art, advantage of the present invention is as follows:
1, in high-viscosity modified asphalt of the present invention, do not need to add a large amount of superpolymer, to make by the method for chemical modification, significantly reduce the effective level (polymer loading is less than 1%) of polymkeric substance, greatly improve the problem of pitch and polymer phase capacitive, reduce cost, preparation method is simple, is easy to construction.
2, the present invention prepares the chemical modifier that adds part when agent mother liquor is prolonged in increasing, modification increases the performance of prolonging agent mother liquor effectively, under the katalysis of chemical modifier, increases and prolongs agent and effectively combination of aromatic hydrocarbon oil, make increasing prolong agent and be dissolved in more fully in aromatic hydrocarbon oil, do not emanate.Chemical modifier can improve and increase the viscosity of prolonging agent mother liquor simultaneously, more effectively improves the modification ability of prolonging agent that increases.
3, chemical modifier of the present invention and combination with polymers modifying asphalt can improve the performance of pitch effectively; simultaneously the group such as the acylhydrazine in chemical additive under the katalysis of chemical modifier can and pitch in the generation condensation reaction such as hydroxy-acid group; improve widely the viscosity of pitch, improved the high-temperature behavior of pitch.
4,60 ℃ of kinetic viscosities of high-viscosity modified asphalt of the present invention are greater than 60000Pas, and viscosity ratio is less than 5, have excellent high temperature resistance to flow energy and low temperature use properties and resistance to deterioration.
Embodiment
Now describe the present invention in conjunction with specific embodiments, but therefore do not limit the present invention.Wherein polyphosphoric acid, commercially available, purity by weight 84%; Polyphosphoric acid amine, commercially available, purity by weight 96%.
Embodiment 1
(1) by SBR and aromatic hydrocarbon oil, under 70 ℃ of conditions, with high emulsification shears (1500~3000r/min), shear 40 minutes, be prepared into increase and prolong agent mother liquor.
(2) increasing that step (1) makes is prolonged agent mother liquor, polyphosphoric acid amine and thiosemicarbazide and is joined in 70# pitch, and temperature is 130 ℃, and stirring reaction 60 minutes, makes high-viscosity modified asphalt.Proportioning raw materials and product characteristics are in table 1.
Embodiment 2
(1) by SBS(YH-791), part polyphosphoric acid and aromatic hydrocarbon oil, under 80 ℃ of conditions, with high emulsification shears (1500~3000r/min), shear 50 minutes, be prepared into increase and prolong agent mother liquor.Wherein step (1) adds 15% of polyphosphoric acid quality.
(2) agent mother liquor is prolonged in the increasing that step (1) makes, residue polyphosphoric acid, Urea,amino-join in 70# pitch, and temperature is 140 ℃, and stirring reaction 60 minutes, makes high-viscosity modified asphalt.Proportioning raw materials and product characteristics are in table 1.
Embodiment 3
(1) by SBR, part polyphosphoric acid and aromatic hydrocarbon oil, under 70 ℃ of conditions, with high emulsification shears (1500~3000r/min), shear 50 minutes, be prepared into increase and prolong agent mother liquor.Wherein step (1) adds 18% of polyphosphoric acid quality.
(2) agent mother liquor is prolonged in the increasing that step (1) makes, residue polyphosphoric acid, Urea,amino-join in 70# pitch, and temperature is 150 ℃, and stirring reaction 60 minutes, makes high-viscosity modified asphalt.Proportioning raw materials and product characteristics are in table 1.
Comparative example 1
(1) SBR is added in aromatic hydrocarbon oil under high emulsification shears, temperature is 70 ℃, shears 40 minutes, and preparation increases prolongs agent mother liquor.
(2) agent mother liquor is prolonged in increasing step (1) being made, polyphosphoric acid amine joins in 70# pitch, and temperature is 130 ℃, reacts 60 minutes, makes high-viscosity modified asphalt.Proportioning raw materials and product characteristics are in table 1.
Proportioning and the character of table 1 high-viscosity modified asphalt raw material.
Project Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Increase and prolong agent, part 0.7 0.9 1.1 0.8
Chemical modifier, part 0.6 1.2 0.8 0.9
Aromatic hydrocarbon oil, part 4 5 6 5
Chemical additive, part 0.2 0.4 0.6
Pitch, part 100 100 100 100
Penetration degree (25 ℃), 1/10mm 48 42 44 42
Softening temperature, ℃ 83 85 81 83
Ductility (10 ℃), cm 121 128 131 96
60 ℃ of kinetic viscosities, Pa.s 63512 84769 90243 18423
1(is continuous for table) proportioning and the character of high-viscosity modified asphalt raw material.
Segregation (163 ℃, 8h), softening point difference, ℃ 1.1 0.8 0.7 1.9
Thin Film Oven Test TFOT ? ? ? ?
Penetration ratio, % 82 83 85 81
Ductility (10 ℃), cm 15 12 15 5
Viscosity ratio, % 4.0 3.5 3.0 5.2
As can be seen from the above table, what adopt the high-viscosity modified asphalt prepared of present method has good preservation stability, and 60 ℃ of kinetic viscosities are greater than 60000Pas, and viscosity ratio is less than 5, have excellent high temperature resistance to flow can and low temperature use properties and resistance to deterioration.

Claims (10)

1. a high-viscosity modified asphalt, high-viscosity modified asphalt comprises following component by weight: take 100 parts of matrix pitches as benchmark, increase and prolong 0.5~1.2 part of agent, 3~6 parts of aromatic hydrocarbon oil, 0.5~1.5 part of chemical modifier, 0.1~1 part of chemical additive; Wherein chemical modifier is one or more in ortho-phosphoric acid, Tripyrophosphoric acid, polyphosphoric acid or polyphosphoric acid amine.
2. according to high-viscosity modified asphalt claimed in claim 1, it is characterized in that: described matrix pitch is petroleum pitch, comprise one or more in straight-run pitch, oxidized bitumen or solvent deoiling pitch, its penetration degree is 60~80 1/10mm.
3. according to high-viscosity modified asphalt claimed in claim 1, it is characterized in that: it is one or more in natural rubber, styrene-butadiene rubber(SBR), chloroprene rubber, SBS, SIS or polystyrene-poly ethene-polybutene-polystyrene block copolymer that agent is prolonged in described increasing.
4. according to high-viscosity modified asphalt claimed in claim 1, it is characterized in that: 100 ℃ of kinematic viscosity of described aromatic hydrocarbon oil are 20~50mm 2/ s, aromatic hydrocarbons mass content>=80%, derives from aromatic base rubber filling oil, is rich in one or more in the refining extraction oil of aromatic hydrocarbons and the vacuum distillate of naphthenic base crude.
5. according to high-viscosity modified asphalt claimed in claim 1, it is characterized in that: described chemical additive be Urea,amino-, one or more in thiosemicarbazide, benzamido urea or semicarbazide derivative.
6. according to high-viscosity modified asphalt claimed in claim 1, it is characterized in that: high-viscosity modified asphalt adds one or more in antistripping agent, fire retardant and antiaging agent.
7. a preparation method for high-viscosity modified asphalt claimed in claim 1, is characterized in that comprising following content: (1) is prolonged agent by increasing and mixed with aromatic hydrocarbon oil, makes to increase and prolongs agent mother liquor; (2) increasing is prolonged to agent mother liquor, chemical modifier, chemical additive and matrix pitch hybrid reaction, make high-viscosity modified asphalt.
8. according to preparation method claimed in claim 7, it is characterized in that: in step (1), add part chemical modifier, in step (2), add residue chemical modifier, wherein step (1) adds 10%~20% of chemical modifier total mass.
9. according to preparation method claimed in claim 7, it is characterized in that: the hybrid mode that step (1) and step (2) adopt be stirring, shearing, Screw Extrusion or ultrasonic in one or more.
10. according to preparation method claimed in claim 7, it is characterized in that: the mixing temperature of step (1) is 70 ~ 120 ℃, mixing time is 20 ~ 80 minutes, and the mixing temperature of step (2) is 120 ~ 180 ℃, and mixing time is 20 ~ 120 minutes.
CN201210411140.9A 2012-10-25 2012-10-25 A kind of high-viscosity modified asphalt and preparation method thereof Active CN103773008B (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105273417A (en) * 2014-06-03 2016-01-27 上海全凯新材料科技有限公司 Modified asphalt extension agent and preparation method thereof, and modified asphalt
CN105524475A (en) * 2014-09-30 2016-04-27 北京路新大成景观建筑工程有限公司 Flexible asphalt, preparation method therefor, road pavement material and road
CN105585854A (en) * 2014-10-22 2016-05-18 中国石油化工股份有限公司 High-viscosity modified asphalt being easy to construct and preparation method thereof
CN107163599A (en) * 2017-07-05 2017-09-15 河南师范大学 A kind of preparation method of road and bridge coiled material modified pitch
CN107189462A (en) * 2017-07-05 2017-09-22 河南师范大学 A kind of preparation method of composite modified asphalt
CN107715777A (en) * 2017-08-21 2018-02-23 宁波中金石化有限公司 A kind of manufacturing equipment and preparation method of multifunctional modification aromatic hydrocarbons
CN108129862A (en) * 2018-01-12 2018-06-08 黄河三角洲京博化工研究院有限公司 The preparation method of pitch age-inhibiting addition and preparation method thereof, modified pitch
CN109810522A (en) * 2019-01-17 2019-05-28 南通市港闸市政开发区道路工程有限公司 A kind of cracks with high viscous asphalt and preparation method thereof
CN110484009A (en) * 2019-09-05 2019-11-22 黄河三角洲京博化工研究院有限公司 No. 110 bi tumenf orr oads of one kind and preparation method thereof
WO2021098340A1 (en) * 2019-11-19 2021-05-27 长安大学 Storable high modulus asphalt binder and preparation method
NL2028906A (en) 2020-09-08 2022-05-09 Univ Fuzhou A high-tenacity modified asphalt with SBS/SBR and polyphosphoric acid and its preparation method

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CN101250328A (en) * 2008-04-10 2008-08-27 华东理工大学 Waste and old rubber modified asphalt
CN101492570A (en) * 2008-01-23 2009-07-29 中国石油化工股份有限公司 Hard road bitumen compositions and preparation process
CN102585525A (en) * 2012-01-12 2012-07-18 山东华瑞道路材料技术有限公司 SBS (styrene-butadiene-styrene) modified asphalt with stable thermal storage and preparation process thereof

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WO2003091339A1 (en) * 2002-04-24 2003-11-06 Asahi Kasei Chemicals Corporation Asphalt composition
CN101492570A (en) * 2008-01-23 2009-07-29 中国石油化工股份有限公司 Hard road bitumen compositions and preparation process
CN101250328A (en) * 2008-04-10 2008-08-27 华东理工大学 Waste and old rubber modified asphalt
CN102585525A (en) * 2012-01-12 2012-07-18 山东华瑞道路材料技术有限公司 SBS (styrene-butadiene-styrene) modified asphalt with stable thermal storage and preparation process thereof

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105273417B (en) * 2014-06-03 2018-06-12 上海全凯新材料科技有限公司 Agent and preparation method thereof and a kind of modified pitch are prolonged in a kind of modified pitch increasing
CN105273417A (en) * 2014-06-03 2016-01-27 上海全凯新材料科技有限公司 Modified asphalt extension agent and preparation method thereof, and modified asphalt
CN105524475A (en) * 2014-09-30 2016-04-27 北京路新大成景观建筑工程有限公司 Flexible asphalt, preparation method therefor, road pavement material and road
CN105585854A (en) * 2014-10-22 2016-05-18 中国石油化工股份有限公司 High-viscosity modified asphalt being easy to construct and preparation method thereof
CN105585854B (en) * 2014-10-22 2019-03-19 中国石油化工股份有限公司 A kind of high-viscosity modified asphalt and preparation method thereof for being easy to construct
CN107189462A (en) * 2017-07-05 2017-09-22 河南师范大学 A kind of preparation method of composite modified asphalt
CN107163599A (en) * 2017-07-05 2017-09-15 河南师范大学 A kind of preparation method of road and bridge coiled material modified pitch
CN107163599B (en) * 2017-07-05 2019-07-23 河南师范大学 A kind of preparation method of road and bridge coiled material modified pitch
CN107189462B (en) * 2017-07-05 2019-11-01 河南师范大学 A kind of preparation method of composite modified asphalt
CN107715777A (en) * 2017-08-21 2018-02-23 宁波中金石化有限公司 A kind of manufacturing equipment and preparation method of multifunctional modification aromatic hydrocarbons
CN107715777B (en) * 2017-08-21 2019-10-15 宁波中金石化有限公司 A kind of manufacturing equipment and preparation method of multifunctional modification aromatic hydrocarbons
CN108129862A (en) * 2018-01-12 2018-06-08 黄河三角洲京博化工研究院有限公司 The preparation method of pitch age-inhibiting addition and preparation method thereof, modified pitch
CN109810522A (en) * 2019-01-17 2019-05-28 南通市港闸市政开发区道路工程有限公司 A kind of cracks with high viscous asphalt and preparation method thereof
CN110484009A (en) * 2019-09-05 2019-11-22 黄河三角洲京博化工研究院有限公司 No. 110 bi tumenf orr oads of one kind and preparation method thereof
WO2021098340A1 (en) * 2019-11-19 2021-05-27 长安大学 Storable high modulus asphalt binder and preparation method
NL2028906A (en) 2020-09-08 2022-05-09 Univ Fuzhou A high-tenacity modified asphalt with SBS/SBR and polyphosphoric acid and its preparation method

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