NL2028906A - A high-tenacity modified asphalt with SBS/SBR and polyphosphoric acid and its preparation method - Google Patents
A high-tenacity modified asphalt with SBS/SBR and polyphosphoric acid and its preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The disclosure belongs to the technical field of modified asphalt and relates in particular to a high-tenacity composite-modified asphalt with SB S/SBR and polyphosphoric acid (PPA), and a preparation method thereof. Raw materials thereof comprise the following components in parts by weight: 400 parts of a base asphalt, 12-16 parts of SBS or SBR, 4-8 parts ofa plasticizer, 1.6-2.0 parts of PPA, and 0.4-0.8 parts of a stabilizer. According to the principle “like dissolves like” regarding molecular structures, a phosphate ester plasticizer is added to SB S/PPA or SBR/PPA modified asphalt in the present disclosure, which significantly improves the toughness and tenacity of the SB S/PPA or SBR/PPA composite modified asphalt, and eliminates the negative impact of PPA on toughness and tenacity of the asphalt, such that a high-tenacity SB S/PPA or SBR/PPA composite modified asphalt with comprehensive performance is consequently obtained.
Description
A high-tenacity modified asphalt with SBS/SBR and polyphosphoric acid and its preparation method
FIELD OF TECHNOLOGY The disclosure belongs to the technical field of modified asphalt and relates in particular to preparing a high-tenacity SBS/PPA or SBR/PPA composite modified asphalt, which is especially suitable for the toughening of SBS or SBR modified asphalt after PPA acidification.
BACKGROUND Polyphosphoric acid (PPA) 1s a widely used asphalt modifier in polymer modification of asphalt, especially in combination with SBS and SBR. It has been proved in practice that the addition of a small amount of PPA can significantly improve the high-temperature properties of SBS- and SBR-modified asphalt, and reduce the sensitivity of asphalt to aging, while there is no obvious effect on the low-temperature properties of asphalt. Since PPA is cheap (only 1/3 of the price of SBS), PPA is usually employed as a substitute for parts of SBS to reduce costs while further improving the high-temperature performance. Currently SBS is the most widely used polymer modifier, accounting for 80% of the total asphalt modifiers. Consequently PPA/SBS composite modification has grown into an important part of PPA application.
SBR-modified asphalt has excellent low-temperature performance, but poor high-temperature performance. The use of a small amount of PPA can significantly improve the high-temperature performance of SBR-modified asphalt, such that a SBR/PPA composite modified asphalt with high performance at both high and low temperatures is consequently obtained. Currently SBR-modified asphalt is more often employed in the cold regions of North China because of its excellent low-temperature performance. Its application would be developed further if its high-temperature performance could be improved by adding PPA. This has contributed to an important aspect of the application of PPA.
According to experimental studies, a small amount of PPA offers benefits including significantly improving the high-temperature performance of SBS- and SBR-modified asphalt, reducing the content of SBS in the asphalt, no significant effect on low-temperature performance of asphalt; however, the toughness and 1 tenacity of SBS- and SBR-modified asphalt, especially the former which has higher toughness and tenacity, are obviously affected after PPA acidification. As shown in FIG 1 (a) and (b), after the addition of PPA (0.5%) to SBS-modified (4%) asphalt, the tenacity of the asphalt dropped to only 1/3 of the original value. The physical properties before and after PPA acidification are shown in Table 1. Table 1. Effect of PPA on Physical Properties of SBS-Modified Asphalt verses | om | a1 SBS: SBS1301 4%; SBS/PPA: SBS1301 4%, PPA 0.5%; As shown in Table 1, the addition of PPA obviously lifted the softening point of SBS-modified asphalt and improved the high-temperature properties, however, the toughness and tenacity were significantly reduced, because PPA acidification induced gelation of the asphalt and lead to an increased content of hard components in the asphalt, which severely affected the swelling of SBS in the asphalt, resulting in a significantly smaller elongation of asphalt in the toughness and tenacity test, indicating reduced toughness and tenacity. Similar conclusions could be drawn for SBR-modified asphalt. The already low toughness and tenacity of SBR-modified asphalt were further reduced by the addition of PPA.
Toughness and tenacity, indication of asphalt’s capability for adhesion to aggregate and resistance to permanent deformation, are important properties of SBS- and SBR-modified asphalt. The decrease in toughness and tenacity will severely affect some essential properties of asphalt mixtures. Uniaxial tensile fatigue testing demonstrated that the fatigue life of the SBS/PPA modified asphalt mixture (4% SBS1301, 0.5% PPA) is only 1/2 of the SBS-modified asphalt mixture (4% SBS1301).
The water stability of SBS-modified asphalt mixture after acidification was also 2 significantly reduced. The freeze-thaw test showed that the addition of PPA to the asphalt (0.5%) lead to a reduction of the residual stability of the SBS-modified asphalt mixture (4% SBS1301) by 25%. In the direct tensile test, the anti-cracking performance of the SPS/PPA-modified asphalt mixture (4% SBS1301, 0.5% PPA) was significantly weaker than that of the SBS-modified asphalt mixture (4% SBS1301). Therefore, it is obvious that the decreased toughness and tenacity of SBS-modified asphalt after PPA acidification affected the major properties of the asphalt mixture adversely.
Significant amount of research on the use of PPA with SBS or SBR to modify asphalts has been carried out in China and abroad. However, many patents and literature focused on the changes of high- and low-temperature performance after modification by a combination of PPA and SBS/SBR but did not involve studies of the toughness and tenacity of the asphalt after PPA acidification, such as patents CN 110358318 A, CN 109694585 A, CN 103773008 B, CN 103773009 B, CN 015558584 B, etc.
The following major conclusions could be drawn from all types of literature on composite-modification with SBS and PPA: (1) PPA significantly improves the high-temperature performance of SBS-modified asphalt and mixtures thereof; (2) PPA of a small amount does not have significant effect on the low-temperature performance of SBS-modified asphalt and mixtures thereof, however, the low-temperature performance is reduced with the increase of PPA content; (3) PPA can reduce the water stability of SBS-modified asphalt mixtures; (4) The optimal content of PPA in SBS-modified asphalt is 0.5-1% (according to the quality of the asphalt).
However, no research on the effect of PPA on toughness and tenacity of SBS-modified asphalt is reported in China or abroad, although toughness and tenacity characterize the asphalt’s capability for adhesion to aggregate and largely limit many important properties of asphalt mixtures. Therefore, it is essential to investigate the improvement of toughness and tenacity of asphalt after PPA acidification for improving properties of the asphalt and mixtures thereof.
SUMMARY The primary objective of the disclosure is to completely eliminate the adverse 3 effect of PPA on the toughness and tenacity of SBS/PPA or SBR/PPA modified asphalt by using a specific plasticizer, such that a high-tenacity SBS/PPA or SBR/PPA modified asphalt is obtained and the corresponding asphalt formula is given.
The second objective of the disclosure is to provide a method for preparing the high-tenacity SBS/PPA or SBR/PPA modified asphalt.
In the view of above objectives, the disclosure is proposed to provide the following technical schemes.
The first technical scheme of the disclosure comprises: the high-tenacity SBS/PPA or SBR/PPA modified asphalt of the present disclosure comprises the following components in parts by weight: 400 parts of a base asphalt, 12-16 parts of SBS or SBR, 4-8 parts of a plasticizer, 1.6-2.0 parts of PPA, and 0.4-0.8 parts of a stabilizer; preferably, the base asphalt is 70# asphalt with a penetration degree of 60-80 (0.1 mm) and a softening point of 48°C; preferably, the SBS is granulated linear SBS; preferably, the SBR is solid-state powdery; preferably, the plasticizer is one or more of the group consisting of pyrophosphate, diphenyl isooctyl phosphate, orthophosphate, 2-ethylhexyl phosphate, fatty alcohol ether phosphate, and polyphosphate esters, which is of industrial grade or chemically pure, with a purity of not less than 99%; preferably, the stabilizer is solid-state powdery or flake-type sulfur, with a purity of not less than 99%; preferably, the PPA is a chemically pure or industrial grade reagent with a phosphorus pentoxide purity of not less than 85%. The second technical scheme of the disclosure comprises: the high-tenacity SBS/PPA modified asphalt is prepared according to the following steps: step S1, preparation of raw materials: weighing a base asphalt, SBS, a plasticizer, PPA and a stabilizer based on parts by weight; 4 step S2, pre-treatment of the base asphalt: heating the base asphalt to melt completely at 170-180°C; step S3, adding the plasticizer and SBS to the melted base asphalt and mixing evenly before adding PPA and the stabilizer, then stirring with a mechanical stirring device for 2 hours at a constant temperature of 180-190°C; further, the mixing evenly in step S3 is specifically implemented by a way of high-speed shearing or mechanical stirring; further, the high-speed shearing is shearing with a high-speed shearing machine for 1 hour at a speed of 5000 r/min; further, the mechanical stirring is specifically mechanically stirring for 5 hours. The high-tenacity SBR/PPA modified asphalt 1s prepared according to the following steps: step S100, preparation of raw materials: weighing a base asphalt, SBR, a plasticizer, PPA and a stabilizer based on the parts by weight; step S200, pre-treatment of the base asphalt: heating the base asphalt to melt completely at 160-170°C; step S300, adding the plasticizer and SBR to the melted base asphalt and mixing evenly before adding PPA and the stabilizer, then stirring with a mechanical stirring device for 1.5 hours at a constant temperature of 170-180°C; further, the mixing evenly in step S300 is specifically implemented by a way of high-speed shearing or mechanical stirring; further, the high-speed shearing is specifically shearing with a high-speed shearing machine for 40 minutes at a speed of 4000 r/min; further, the mechanical stirring is specifically mechanically stirring for 1 hour.
The advantage of the disclosure, as compared to prior art, is as follows: (1) the use of a specific plasticizer in the disclosure completely eliminates the adverse effect of PPA on asphalt toughness and tenacity, such that a modified asphalt with excellent toughness and tenacity is obtained; the plasticization and swelling effect are not offered by other types of plasticizers.
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(2) according to the theory on similarity of molecular structures, a phosphate ester plasticizer or polyphosphate ester plasticizer with a similar molecular structure as both PPA and asphalt is used in the present disclosure for swelling and plasticization of SBS or SBR in the asphalt, and a modified asphalt with better low-temperature performance and elastic recovery performance is obtained.
(3) the SBS/PPA or SBR/PPA modified asphalt prepared in the present disclosure has an excellent anti-aging performance, showing excellent high- and low-temperature performance before and after short-term aging and low sensitivity to aging.
BRIEF DESCRIPTION OF THE DRAWINGS FIG 1 shows the effect of PPA on toughness and tenacity of SBS (area of toughness: A+B; area of tenacity: B).
DESCRIPTION OF THE EMBODIMENTS Exemplary embodiments of the present disclosure will be described in detail hereinafter. However, the disclosure may be embodied in many different forms defined and covered by the claims.
Embodiment 1 Step S1: weigh raw materials: 400 parts of 70# base asphalt, 16 parts of SBS (linear), 2 parts of PPA (phosphorus pentoxide purity not less than 85%), 8 parts of orthophosphate (purity not less than 99%) and 0.4 parts of stabilizer sulfur (purity not less than 99%).
Step S2: heat the base asphalt o melt completely at a constant temperature of 170-180°C.
Step S3: add the plasticizer to the melted base asphalt and mix evenly, then add SBS and stir to disperse SBS in the asphalt, and next, shear with a high-speed shearing machine for 1 hour at a speed of 5000 r/min and a constant temperature of 180-190°C.
Step S4: add PPA and the stabilizer to the asphalt respectively after shearing, then stir mechanically with blades for 2 hour at a constant temperature of 180-190°C.
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Embodiment 2 Step S1: weigh raw materials: 400 parts of 70# base asphalt, 16 parts of SBS (linear), 2 parts of PPA (phosphorus pentoxide purity not less than 85%), 8 parts of orthophosphate (purity not less than 99%) and 0.4 parts of stabilizer sulfur (purity not less than 99%). Step S2: heat the base asphalt to melt completely at a constant temperature of 180-190°C.
Step S3: add the plasticizer and SBS, then stir mechanically with blades for 5 hours at a constant temperature of 180-190°C.
Step S4: add PPA and the stabilizer, then stir mechanically with blades for 2 hours at a constant temperature of 180-190°C.
See Table 2 for the physical properties in embodiments 1 and 2. Table. 2 Physical Properties in Embodiments 1 and 2 EE | ww As shown in Table 2, the obtained SBS/PPA modified asphalt featured excellent toughness and tenacity, showing good high- and low-temperature properties and elastic recovery property.
Embodiment 3 Step S1: weigh raw materials: 400 parts of 70# base asphalt, 16 parts of SBR (solid-state powdery), 2 parts of PPA (phosphorus pentoxide purity not less than 85%), 8 parts of orthophosphate (purity not less than 99%) and 0.4 parts of stabilizer sulfur 7
(purity not less than 99%). Step S2: heat the base asphalt to melt completely at a constant temperature of 160-170°C. Step S3: add the plasticizer to the melted base asphalt and mix evenly, then add SBR and stir to disperse SBR in the asphalt, and next, shear with a high-speed shearing machine for 40 minutes at a speed of 4000 r/min and a constant temperature of 170-180°C. Step S4: add PPA and the stabilizer to the asphalt after shearing, then stir mechanically with blades for 1.5 hours at a constant temperature of 170-180°C. Embodiment 4 Step S1: weigh raw materials: 400 parts of 70# base asphalt, 16 parts of SBR (solid-state powdery), 2 parts of PPA (phosphorus pentoxide purity not less than 85%), 8 parts of orthophosphate (purity not less than 99%) and 0.4 parts of sulfur. Step S2: heat the base asphalt to melt completely at a constant temperature of 170-180°C. Step S3: add the plasticizer and SBR, then stir mechanically with blades for 1 hour at a constant temperature of 170-180°C. Step S4: add PPA and the stabilizer sulfur, then stir mechanically with blades for 2 hours at a constant temperature of 170-180°C. See Table 3 for the physical properties in embodiments 3 and 4.
Table. 3 Physical Properties in Embodiments 3 and 4 ernie | ow | ws res ssciam | ws |e 8
As shown in Table 3, the obtained SBR/PPA modified asphalt featured excellent toughness and tenacity, showing good high- and low-temperature properties. In order to further compare the modification effect of the phosphate ester, additional modifications were carried out on the basis of embodiments 1 and 2 respectively, i.e. no addition of the plasticizer (embodiments 5 and 7) and use of an alternative plasticizer that is widely used, di-n-octyl phthalate (DOP) (embodiments 6 and 8); and properties were compared to those of the phosphate-ester modified samples.
Embodiment 5 Step S1: weigh raw materials: 400 parts of 70# base asphalt, 16 parts of SBS (linear), 2 parts of PPA (phosphorus pentoxide purity not less than 85%), and 0.4 part of stabilizer sulfur (purity not less than 99%). Step S2: heat the base asphalt to melt completely at a constant temperature of 170-180°C. Step S3; add SBS to the melted base asphalt and mix evenly, stir to disperse SBS in the asphalt, and next, shear with a high-speed shearing machine for 1 hour at a speed of 5000 r/min and a constant temperature of 180-190°C. Step S4: add PPA and the stabilizer to the asphalt after shearing, then stir mechanically with blades for 2 hours at a constant temperature of 180-190°C. Embodiment 6 Step S1: weigh raw materials: 400 parts of 70# base asphalt, 16 parts of SBS (linear), 8 parts of DOP (purity not less than 99%), 2 parts of PPA (phosphorus pentoxide purity not less than 85%), and 0.4 parts of stabilizer sulfur (purity not less than 99%). Step S2: heat the base asphalt to melt completely at a constant temperature of 170-180°C. Step S3: add DOP and SBS to the melted base asphalt and mix evenly, stir to 9 disperse SBS in the asphalt, and next, shear with a high-speed shearing machine for 1 hour at a speed of 5000 r/min and a constant temperature of 180-190°C.
Step S4: add PPA and the stabilizer to the asphalt after shearing, then stir mechanically with blades for 2 hours at a constant temperature of 180-190°C.
See Table 3 for the comparison of physical properties in embodiment 1 with embodiments 5 and 6. Table 3 Physical Properties in Embodiments 1, 5 and 6 Î Embodiment| Embodiment | Embodiment Testing eten non nnen SE | | wm | wn | Compliance @5°C/ ml As shown in Table 3, embodiment 1 demonstrated improved toughness and tenacity, especially the later, than embodiments 5 and 6; further, embodiment 1 showed a better ductility and compliance, indicating that with the existence of PPA, phosphate ester as a plasticizer had better swelling effect on SBS, and significantly reduced the adverse effect of PPA on tenacity of asphalt. Embodiment 7 Step S1: weigh raw materials: 400 parts of 70# base asphalt, 16 parts of SBR (solid-state powdery), 2 parts of PPA (phosphorus pentoxide purity not less than 85%), and 0.4 parts of stabilizer sulfur (purity not less than 99%. Step S2: heat the base asphalt to melt completely at a constant temperature of 160-170°C.
Step S3: add SBR to the melted base asphalt and mix evenly to disperse SBR in the asphalt, then shear with a high-speed shearing machine for 40 minutes at a speed of 4000 r/min and a constant temperature of 170-180°C.
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Step S4: add PPA and the stabilizer to the asphalt after shearing, then stir mechanically with blades for 1.5 hours at a constant temperature of 170-180°C.
Embodiment 8 Step S1: weigh raw materials: 400 parts of 70# base asphalt, 16 parts of SBR (solid-state powdery), 8 parts of DOP (purity not less than 99%), 2 parts of PPA (phosphorus pentoxide purity not less than 85%), and 0.4 parts of stabilizer sulfur (purity not less than 99%). Step S2: heat the base asphalt to melt completely at a constant temperature of 170-180°C.
Step S3: add SBR and DOP to the melted base asphalt and mix evenly to disperse SBR in the asphalt, then shear with a high-speed shearing machine for 40 minutes at a speed of 4000 r/min and a constant temperature of 170-180°C.
Step S4: add PPA, then stir mechanically with blades for 2 hours at a constant temperature of 170-180°C.
See Table 4 for the comparison of physical properties in embodiment 3 with embodiments 7 and 8. Table 4 Physical Properties in Embodiments 3, 7 and 8 3 7 8 | sotenmgPomt/cc | es | oe | 85 | ewwemonn | nr | en As shown in Table 4, embodiment 3 demonstrated better toughness and tenacity than embodiments 7 and 8, and showed an obvious improvement of tenacity; further, embodiment 3 showed better ductility and compliance, indicating that with the 11 existence of PPA, phosphate ester as a plasticizer had better swelling effect on SBR, and significantly reduced the adverse effect of PPA on the tenacity of SBR-modified asphalt. The foregoing are only preferred exemplary embodiments of the present disclosure, and the scope of the disclosure should not be construed as being limited to the embodiments set forth herein. Any equivalent structure changes or equivalent process changes made by using the contents of the specification of the present disclosure, whether directly or indirectly used in other related technical fields, are similarly included in the scope of patent protection of the present disclosure.
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| CN202010932807.4A CN111978750B (en) | 2020-09-08 | 2020-09-08 | High-toughness SBS/SBR polyphosphoric acid composite modified asphalt and preparation method thereof |
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| CN115785683B (en) * | 2022-12-08 | 2024-04-16 | 苏州卓宝科技有限公司 | PCB modified asphalt sizing material and preparation method thereof |
| CN116040987A (en) * | 2023-01-28 | 2023-05-02 | 湖北文理学院 | Preparation method of VOCs inhibition type modified asphalt mixture |
| CN116925558B (en) * | 2023-09-14 | 2023-11-21 | 鄂尔多斯市路泰新材料科技发展有限公司 | SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and preparation method thereof |
| CN117789891A (en) * | 2024-01-17 | 2024-03-29 | 哈尔滨工业大学 | Integrated learning-based modified asphalt reverse design method |
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