CN100451057C - Adjuvant for promoting SBS modified asphalt high low temperature property and its usage method - Google Patents
Adjuvant for promoting SBS modified asphalt high low temperature property and its usage method Download PDFInfo
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- CN100451057C CN100451057C CNB2006100226963A CN200610022696A CN100451057C CN 100451057 C CN100451057 C CN 100451057C CN B2006100226963 A CNB2006100226963 A CN B2006100226963A CN 200610022696 A CN200610022696 A CN 200610022696A CN 100451057 C CN100451057 C CN 100451057C
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- sbs
- auxiliary agent
- asphalt
- modifying asphalt
- high temperature
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Abstract
The invention discloses a new typed adjuvant to improve SBS modified tar high-low temperature and making method, which is characterized by the following: the adjuvant is phthalate ammonium salt with the following general formula, wherein R1 is S, Cl or olefin alcohol; R2 is primary amine or secondary amine with carbon number below 18. The invention is compatible with tar, which improves the reserving stability of modified tar.
Description
Technical field
The invention belongs to the preparing technical field of SBS modifying asphalt, particularly a kind of auxiliary agent that can improve SBS modifying asphalt high temperature performance.
Background technology
High-grade highway is the transport hub that connects main cities and important port, is bearing a large amount of passenger-cargo freight volumes.Along with high speed development of national economy, the volume of traffic increases rapidly, and bituminous concrete pavement faces a severe test, and early damages such as rut, cracking, hole groove happen occasionally.Have only multi-functional, high performance asphalt pavement material could satisfy pressing for of China's Road construction development in this case.And polymer modified asphalt is the effective way that solves these a series of problems.
What the present use of polymer modifiers in the world was more is styrene-butadiene-styrene thermoplastic elastomer (SBS), polyethylene (PE), styrene-butadiene rubber(SBR) (SBR) etc.SBS can significantly improve the bituminous pavement performance with the characteristic of rubber-like and resene properties-correcting agent, prolongs the work-ing life on road surface, has become the main products of asphalt modification, and its consumption accounts for about 65% of asphalt polymer properties-correcting agent total amount.
Along with being extensive use of of SBS modifying asphalt, requirement to the SBS modifying asphalt is also more and more higher, be mainly reflected in and require that the SBS modifying asphalt has good storage stability, (most high-grade highway engine requests are higher than more than 60 ℃ higher softening temperature, part engine request softening temperature is higher than more than 70 ℃), good low-temperature ductility (5 ℃ of ductilities of most high-grade highway engine requests are greater than 20cm, require greater than 40cm on the part engineering).
But traditional SBS modifying asphalt is physical methods such as stirring, shearing by machinery to be pulverized superpolymer SBS and be distributed in the pitch, SBS still " swims " with discontinuous individual state in pitch as disperse phase, it and pitch mainly are miscible on the physical significance, do not realize that real chemically crosslinked becomes net, show the various pavement performance requirements that just can not satisfy preferably on the high temperature performance, therefore just have certain limitation in the use.For the high temperature performance that makes the SBS modifying asphalt reaches the requirement of nature and weather inclement condition area pavement construction, just need to increase the usage quantity of SBS, but this has also just increased the cost of SBS modifying asphalt greatly.The method of seeking a kind of efficient, inexpensive raising SBS modifying asphalt high temperature performance is extremely urgent.
Correlation technique with open report generally is that SBS is carried out chemical graft at present, thereby further improves the over-all properties of SBS modifying asphalt.As patent CN1365986A, adopt double bond containing acid anhydrides series compound on SBS, to form the segment polarity group with chemical graft process, the polar group in these polar groups and the pitch forms reticulated structure, reaches the compatible stable effect of SBS and pitch.The shortcoming of this technology is a complex process, needs production equipment special, and energy consumption is big, has increased manufacturing cost.US5371121 discloses a kind of method of the SBS of preparation modifying asphalt, and it mainly improves the bituminous softening temperature by adding sulphur, but method is because the sulphur volume is too low, and used SBS volume is very high, institute so that production cost increase greatly.Can obtain higher softening temperature when reducing the SBS volume though strengthen the incorporation of sulphur, low-temperature ductility just can not be up to standard.
Summary of the invention
The purpose of this invention is to provide a kind of New-type adjuvant that can improve SBS modifying asphalt high temperature performance.Utilize the modifying asphalt of this auxiliary agent preparation, can overcome when using the SBS modifying asphalt in the past, SBS and bitumen compatibility are poor, the shortcoming of poor heat stability, improve the bituminous high temperature performance largely, and can reduce the cost of modifying asphalt.
Another object of the present invention provides a kind of using method of auxiliary agent of above-mentioned raising SBS modifying asphalt high temperature performance.
The technical solution adopted for the present invention to solve the technical problems is: a kind of auxiliary agent that improves SBS modifying asphalt high temperature performance is selected from following structural formula:
The consumption of above-mentioned auxiliary agent when preparation SBS modifying asphalt is the 3-10 ‰ of basic asphalt weight; Preferable amount is the 3-5 ‰ of basic asphalt weight.
Single-esterification can take place by Tetra hydro Phthalic anhydride and enol in above-mentioned auxiliary agent under the effect of tosic acid, generate phthalic acid monoolefine ester, generates corresponding amine with amine substance generation amidate action again, promptly.
The auxiliary agent of above-mentioned raising SBS modifying asphalt high temperature performance can adopt following using method when the preparation modifying asphalt:
Earlier basic asphalt is heated to 140-180 ℃, to mobile fully, then SBS is joined in the basic asphalt, the SBS consumption is the 3.0-5.0% of basic asphalt weight, use high-speed shearing equipment or colloidal mill mixing 10-60 minute, SBS is dispersed in the pitch uniformly with refined structure, mainly realizes physically modified; Adding consumption again is the above-mentioned auxiliary agent of basic asphalt weight 3-10 ‰, adopts common whipping device to stir then 30-60 minute, to realize chemical modification.
During the using method of above-mentioned auxiliary agent was stated, used SBS was preferably line style or star-like styrene butadiene triblock copolymer (being called for short line style or star-shaped sbs), and its molecular-weight average is between 250,000 to 500,000.
Compared with prior art, the invention has the beneficial effects as follows: auxiliary agent of the present invention is the aromatics nitrogenous compound with increase-volume, effect such as crosslinked, anti-aging, when the preparation modifying asphalt, only need add lower volume, can reach good modified effect, improve the high temperature performance of SBS modifying asphalt, make modifying asphalt have very high softening temperature (generally being higher than 79 ℃), good low-temperature ductility (5 ℃ ductility is greater than 45cm); Make simultaneously that SBS and bitumen compatibility are good, thermostability might as well, thereby improve the storage stability of modifying asphalt, can satisfy nature and weather inclement condition area pavement construction needs; And the using method of auxiliary agent of the present invention is simple, is used to prepare that the modifying asphalt cost is low, energy consumption is little.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made include within the scope of the invention.
Embodiment 1
The auxiliary agent of the raising SBS modifying asphalt high temperature performance that present embodiment is used is to generate corresponding amine by Tetra hydro Phthalic anhydride and propane thiol and reacting ethylenediamine, and its structural formula is as follows:
The using method that this auxiliary agent is used to prepare modifying asphalt is as follows:
400g Esso 70# pitch is placed in one 1 liter the reaction vessel, pitch is heated to 170 ℃, then the 12.0g star-shaped sbs is joined in the pitch, adopt the high speed shear mulser under 5000rpm/min, to mix 30 minutes, in two minutes, slowly add the above-mentioned auxiliary agent of 2.0g again, use instead in the electric blender under the 300rpm/min condition, continue to stir 30 minutes, promptly obtain modified bitumen product.
Embodiment 2
The auxiliary agent of the raising SBS modifying asphalt high temperature performance that present embodiment is used is that its structural formula is as follows by Tetra hydro Phthalic anhydride and isopropylcarbinol and the corresponding amine of n-Decylamine reaction generation:
The using method that this auxiliary agent is used to prepare modifying asphalt is as follows:
400g Esso 70# pitch is placed in one 1 liter the reaction vessel, pitch is heated to 170 ℃, then the 12.0g star-shaped sbs is joined in the pitch, adopt the high speed shear mulser under 5000rpm/min, to mix 30 minutes, in two minutes, slowly add the above-mentioned auxiliary agent of 1.2g again, use instead in the electric blender under the 300rpm/min condition, continue to stir 30 minutes, promptly obtain modified bitumen product.
Embodiment 3
The auxiliary agent of the raising SBS modifying asphalt high temperature performance that present embodiment is used is that its structural formula is as follows by Tetra hydro Phthalic anhydride and vinyl carbinol and the corresponding amine of Diisopropylamine reaction generation:
The using method that this auxiliary agent is used to prepare modifying asphalt is as follows:
400g Esso 70# pitch is placed in one 1 liter the reaction vessel, pitch is heated to 180 ℃, then the 20.0g star-shaped sbs is joined in the pitch, adopt the high speed shear mulser under 5000rpm/min, to mix 10 minutes, in two minutes, slowly add the above-mentioned auxiliary agent of 2.0g again, use instead in the electric blender under the 300rpm/min condition, continue to stir 60 minutes, promptly obtain modified bitumen product.
Embodiment 4
The auxiliary agent of the raising SBS modifying asphalt high temperature performance that present embodiment is used is to generate corresponding amine by Tetra hydro Phthalic anhydride and 3-chloro-1,2 propylene glycol and reacting ethylenediamine, and its structural formula is as follows:
The using method that this auxiliary agent is used to prepare modifying asphalt is as follows:
400g Esso 70# pitch is placed in one 1 liter the reaction vessel, pitch is heated to 140 ℃, then the star-like 411SBS of 20.0g is joined in the pitch, adopt the high speed shear mulser under 6000rpm/min, to mix 60 minutes, in two minutes, slowly add the above-mentioned auxiliary agent of 1.2g again, use instead in the electric blender under the 250rpm/min condition, continue to stir 40 minutes, promptly obtain modified bitumen product.
Embodiment 5
The auxiliary agent of the raising SBS modifying asphalt high temperature performance that present embodiment is used is to generate corresponding amine by Tetra hydro Phthalic anhydride and vinyl carbinol and 18 primary amine reactions, and its structural formula is as follows:
The using method that this auxiliary agent is used to prepare modifying asphalt is as follows:
400g Esso 70# pitch is placed in one 1 liter the reaction vessel, pitch is heated to 160 ℃, then the 18.0g type SBS is joined in the pitch, adopt the high speed shear mulser under 4000rpm/min, to mix 45 minutes, in two minutes, slowly add the above-mentioned auxiliary agent of 4.0g again, use instead in the electric blender under the 400rpm/min condition, continue to stir 50 minutes, promptly obtain modified bitumen product.
Embodiment 6
Present embodiment only adds the modifying asphalt of star-shaped sbs preparation for not adding modified additive, and its each amounts of components and preparation method are as follows:
400g Esso 70# pitch is placed in one 1 liter the reaction vessel, pitch is heated to 160 ℃, then the 20.0g star-shaped sbs is joined in the pitch, adopt the high speed shear mulser under 4000rpm/min, to mix 45 minutes, use instead in the electric blender under the 400rpm/min condition, continue to stir 50 minutes, promptly obtain modified bitumen product.
The modified bitumen product of the foregoing description 1-6 gained, its penetration degree, softening temperature, 5 ℃ of performance index such as ductility see the following form:
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Pitch weight g | 400 | 400 | 400 | 400 | 400 | 400 |
| SBS weight g | 12.0 | 12.0 | 20.0 | 20.0 | 18.0 | 20.0 |
| Auxiliary agent weight g | 2.0 | 1.2 | 2.0 | 1.2 | 4.0 | 0.0 |
| Penetration degree (25 ℃)/10 -1mm | 55.0 | 50.3 | 53.0 | 56.3 | 57.0 | 49.2 |
| Softening temperature/℃ | 82.3 | 79.5 | 84.2 | 83.1 | 85.2 | 60.4 |
| Ductility (5 ℃)/cm | 52 | 45 | 75 | 50 | 54 | 26 |
In the foregoing description 1-5, the 3-10 ‰ that the consumption of auxiliary agent of the present invention only is required to be basic asphalt weight can reach good modified effect.Press GB/T4509 respectively, GB/T4507, GB/T4508 to modification after performance index such as penetration of bitumens, softening temperature and ductility measure, the result shows: compare with the embodiment 6 prepared modified bitumen product that do not make used additives, after adding auxiliary agent of the present invention, the penetration degree of modifying asphalt slightly improves, and 5 ℃ of ductilities and softening temperature are all improved largely, reach the related request of polymer technology standard JTGF40-2004.
Claims (5)
1. New-type adjuvant that improves SBS modifying asphalt high temperature performance is selected from following structural formula:
2. the auxiliary agent of raising SBS modifying asphalt high temperature performance according to claim 1 is characterized in that:
The consumption of described auxiliary agent when preparation SBS modifying asphalt is the 3-10 ‰ of basic asphalt weight.
3. the auxiliary agent of raising SBS modifying asphalt high temperature performance according to claim 1 is characterized in that:
The consumption of described auxiliary agent when preparation SBS modifying asphalt is the 3-5 ‰ of basic asphalt weight.
4. the using method of the auxiliary agent of the described raising of a claim 1 SBS modifying asphalt high temperature performance, it is characterized in that: earlier basic asphalt is heated to 140-180 ℃, to mobile fully, then SBS is joined in the basic asphalt, the SBS consumption is the 3.0-5.0% of basic asphalt weight, use high-speed shearing equipment mixing 10-60 minute, make SBS be dispersed in the pitch uniformly with refined structure; Adding consumption again is the above-mentioned auxiliary agent of basic asphalt weight 3-10 ‰, adopts common whipping device to stir then 30-60 minute, promptly.
5. the using method of the auxiliary agent of raising SBS modifying asphalt high temperature performance according to claim 4, it is characterized in that: described SBS is line style or star-like styrene butadiene triblock copolymer, and its molecular-weight average is between 250,000 to 500,000.
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| CNB2006100226963A CN100451057C (en) | 2006-12-29 | 2006-12-29 | Adjuvant for promoting SBS modified asphalt high low temperature property and its usage method |
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| CNB2006100226963A CN100451057C (en) | 2006-12-29 | 2006-12-29 | Adjuvant for promoting SBS modified asphalt high low temperature property and its usage method |
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| CN1995110A CN1995110A (en) | 2007-07-11 |
| CN100451057C true CN100451057C (en) | 2009-01-14 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102251464B (en) * | 2011-04-21 | 2013-02-27 | 高伟 | Asphalt pavement crack pouring process and pavement crack repair agent |
| CN104356661B (en) * | 2014-11-19 | 2017-01-04 | 武汉理工大学 | A kind of Compositional type SBS modified pitch steady heat storage agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289801A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing polymer-asphalt composition |
| CN1339556A (en) * | 2000-08-18 | 2002-03-13 | 中国石油化工股份有限公司 | Storage stable modified asphalt and its preparing mehtod |
| CN1733832A (en) * | 2004-08-13 | 2006-02-15 | 中国石化镇海炼油化工股份有限公司 | Storage type SBS modified asphalt and its production method |
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- 2006-12-29 CN CNB2006100226963A patent/CN100451057C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289801A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing polymer-asphalt composition |
| CN1339556A (en) * | 2000-08-18 | 2002-03-13 | 中国石油化工股份有限公司 | Storage stable modified asphalt and its preparing mehtod |
| CN1733832A (en) * | 2004-08-13 | 2006-02-15 | 中国石化镇海炼油化工股份有限公司 | Storage type SBS modified asphalt and its production method |
Non-Patent Citations (6)
| Title |
|---|
| SBS改性沥青性能实验研究. 李水平，范维玉，杨孟龙，南国枝.石油大学学报（自然科学版），第26卷第4期. 2002 |
| SBS改性沥青性能实验研究. 李水平，范维玉，杨孟龙，南国枝.石油大学学报（自然科学版），第26卷第4期. 2002 * |
| 低掺量SBS改性沥青的相容稳定性. 孔宪明，余剑英.新型建筑材料. 2003 |
| 低掺量SBS改性沥青的相容稳定性. 孔宪明，余剑英.新型建筑材料. 2003 * |
| 基础油对SBS改性沥青低温柔性的影响. 李水平，范维玉.精细石油化工，第2期. 2003 |
| 基础油对SBS改性沥青低温柔性的影响. 李水平，范维玉.精细石油化工，第2期. 2003 * |
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