CN1854200A - Asphalt composition containing styrene-butadiene-styrene block copolymer having asymmetric polystyrene block - Google Patents
Asphalt composition containing styrene-butadiene-styrene block copolymer having asymmetric polystyrene block Download PDFInfo
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- CN1854200A CN1854200A CNA2005101054902A CN200510105490A CN1854200A CN 1854200 A CN1854200 A CN 1854200A CN A2005101054902 A CNA2005101054902 A CN A2005101054902A CN 200510105490 A CN200510105490 A CN 200510105490A CN 1854200 A CN1854200 A CN 1854200A
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C7/00—Coherent pavings made in situ
- E01C7/08—Coherent pavings made in situ made of road-metal and binders
- E01C7/18—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders
- E01C7/26—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders mixed with other materials, e.g. cement, rubber, leather, fibre
- E01C7/265—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders mixed with other materials, e.g. cement, rubber, leather, fibre with rubber or synthetic resin, e.g. with rubber aggregate, with synthetic resin binder
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
- C08L2555/80—Macromolecular constituents
- C08L2555/84—Polymers comprising styrene, e.g., polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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Abstract
The present invention provides a modified asphalt composition showing excellent ductility and thermal stability at low temperature and the resistance to permanent deformation at high temperature comprising i) 100 wt. part of natural asphalt; and ii) 0.5~40 wt. part of asymmetric styrene-butadiene-styrene triblock copolymer having number average molecular weight of 20,000~1,000,000. Modified asphalt composition of present invention can be used for pavement of road or manufacturing water proof sheet.
Description
Technical field
The present invention relates to a kind of modified asphalt composition, said composition comprises the asymmetric styrene-butadiene-styrene triblock copolymer as properties-correcting agent.Particularly, the present invention relates to a kind of modified asphalt composite, it comprises asymmetric styrene-butadiene-styrene triblock copolymer, has ductility under the low temperature and the excellent balance between the high flow resistance under the high temperature.
Background technology
When being used to pave the way or making flashing, traditional bituminous composition usually can not satisfy all requirements.Further, under the high temperature, bituminous composition is because tension set can take place in High Temperature High Pressure, equally, under the low temperature, because the rapid variation of temperature, the bituminous bottom fatigue cracking occurs under weight repeatedly, and the bituminous top crackle occurs under the multiple tensile strength.Further, as time goes by with road on the increasing of vehicle, the rock asphalt composition has the decline of anti-permanentset and temperature-sensitivity and the defectives such as appearance of fatigue cracking and/or low temperature crackle.
For addressing the above problem, now developed polymkeric substance has been joined the modified asphalt composite that obtains in the pitch.For example, new LDPE (film grade), ethylene vinyl acetate, styrene butadiene rubbers, isoprene-isobutylene rubber and/or their mixture are all resisted the bruise that tension set under the high temperature and low temperature cause owing to multiple weight and tensile strength down as asphalt modifier.Certainly, the application of modifying asphalt in industrial circle increases.
US3985694 (people such as Richard J.Petrucco) and US4130516 (people such as Duane W.Gagie) all disclose by thermoplastic elastomer being joined the modified asphalt composite that obtains in the pitch, and these thermoplastic elastomers can be linear polyethylene, ethylene vinyl acetate and/or styrene butadiene rubbers.
US3345316 discloses a kind of bituminous composition, said composition comprises the thermoplastic elastomer of poly-protochloride benzene resin and 10-30 weight part, sulfur-bearing not, described thermoplastic elastomer can be linear styrene-butadiene-styrene triblock copolymer or styrene-ethylene-butylene-styrene segmented copolymer.Further, the advantage of this bituminous composition comprises economic manufacture method and excellent consistency.
Further, have now found that radial styrene-butadiene block copolymer also can be used as asphalt modifier, this is because it can strengthen processing characteristics, softening temperature, stability and/or the viscosity of bituminous composition.This modified asphalt composite can be used as ring seal (looping), coating, hot melt, bituminous concrete and/or silane (silant) composition.
On the other hand, US4130516 discloses a kind of bituminous composition, and it comprises pitch, sulphur and/or polymkeric substance, and polymkeric substance can be natural rubber or synthetic rubber.Ductility can be strengthened by adding linear styrene-butadiene random copolymer, ductility can not be strengthened and add radial styrene butadiene random copolymer.
US5130354 discloses a kind of pitch-diene polymerization compositions, and said composition can be bonding with polar material better.A kind of silane-functionalised conjugated diene polymer is also disclosed, wherein grafted silane functional group on the polymkeric substance.Further, US4443570 discloses by the saturated styrene-ethylene-butylene-styrene segmented copolymer of hydrogen and has been used as asphalt modifier, and the softening temperature that includes the bituminous composition of pitch, organic solvent, silicon-dioxide and styrene-ethylene-butylene-styrene segmented copolymer can transfer to about 140 Fahrenheit degrees.
On the other hand, US4412019 discloses a kind of bituminous composition that comprises pitch, sulphur and styrene-ethylene-butylene-styrene segmented copolymer, points out that wherein the increase of asphalt modifier consumption will improve described bituminous composition ductility and tensile strength at low temperatures.
Further, Korean Patent Publication No. 2002-13709 discloses a kind of mixture of being made up of linear styrene-butadiene-styrene triblock copolymer and radial styrene-butadiene block copolymer as asphalt modifier, wherein the mixture that the radial styrene-butadiene block copolymer of the linear styrene-butadiene-styrene triblock copolymer of 40～100 weight parts and 60-0 weight part is formed adds to and can make pitch have excellence and equilibrated physicals in the pitch, for example, solvability, high-temperature storage stability, good ductility, good tensile strength, the softening temperature that good binding property is become reconciled.
As mentioned above, have now found that modified asphalt composite can show excellent physicals, for example, high thermotolerance, anti-old property and anti-permanentset.The enhancement of these modified asphalt composite physicalies is derived from by the increase of impact resistance under the enhancing of the resistance to flow that high viscosity caused under the high temperature, the low temperature and to the enhancing of the anti-old property of light or air, and this is because the polymkeric substance in the bituminous composition has strengthened the pitch matrix by the formation polymer areas.
Yet bituminous composition resistance to cleavage at low temperatures depends on its ductility.If the ductility of bituminous composition strengthens, modified asphalt composite flowability at low temperatures can strengthen so.Certainly, if the ductility of bituminous composition strengthens, the pitch of bituminous composition also can be reduced by the crackle that pressure fatigue or thermal distortion cause.Therefore, when the resistance to cleavage under the assessment low temperature, ductility is an important factors.
On the other hand, for flashing, low temperature is down owing to the deformation energy that be full of cracks is caused is protected by adding polymkeric substance.During performance characteristic under estimating low temperature, ductility is used as main assessment factor.
Generally speaking, asphalt polymer properties-correcting agent plays a part to strengthen the thermo-sensitivity under fluidity at low temperature and the reduction low temperature, also plays a part the deformation under the opposing high temperature.Further, this properties-correcting agent plays a part to improve physicals, for example, and tensile strength, hardness, tensity and binding property integral body.
On the other hand, the improvement of the stability under the low temperature depends on the kind of the polymkeric substance that adds as properties-correcting agent.Even the structural similitude of polymkeric substance, anti-thermo-sensitivity also are different.
For a long time, polyolefine, styrene butadiene random copolymer rubber and/or styrene-butadiene block copolymer can be used as the polymeric asphalt modifiers use.Particularly, existing known styrene butadiene random copolymer rubber or styrene-butadiene block copolymer rubber play a part to strengthen ductility, make to prevent the crackle that causes under the multiple tension force effect at low temperatures.
On the other hand, now proposed can contain the scrap tire powder of under extremely low temperature, milling in the modified asphalt composite.Yet no matter advantage economically, only the physicals of asphalt modifier is just not as styrene-butadiene block copolymer rubber.Further, the ethylene-propylene diene monomer rubber can be used as asphalt modifier.Yet the use of this properties-correcting agent is subject to its high-melting-point and high cost.
On the other hand, be separated, generally can add amine compound, sulphur compound and/or by polymkeric substance that polar group replaced in order to prevent between pitch and polymer modifiers, to form.
The present inventor has found a kind of enhanced asphalt modifier after deliberation, and it has excellent ductility at low temperatures, and at high temperature physicals can remain unchanged.We find that asymmetric styrene-butadiene-styrene block copolymer can strengthen bituminous composition ductility and thermostability at low temperatures, it is from traditional asphalt modifier, in linear or radial styrene-butadiene block copolymer rubber, can't obtain.
Summary of the invention
An object of the present invention is to provide a kind of bituminous composition, it comprises the asymmetric styrene-butadiene-styrene triblock copolymer as properties-correcting agent, said composition can show excellent at low temperatures ductility and thermostability, and anti-permanentset at high temperature.
Further, another object of the present invention provides a kind of modified asphalt composite, and it comprises: the i) rock asphalt of 100 weight parts; Ii) the number-average molecular weight shown in the formula 1 of 0.5～40 weight part is 20,000～1,000,000 asymmetric triblock copolymer.
A-B-A ' (formula 1)
Wherein, A represents vinyl aromatic polymer blocks, and number-average molecular weight is 8,000～30,000;
The B representative contains the conjugated diolefin polymer block or the conjugated diene copolymer block of small amount of ethylene base aromatic monomer; And
It is 500-5 that A ' represents number-average molecular weight, 000 vinyl aromatic polymer blocks;
Wherein, the weight of A and A ' block accounts for 5～40wt% of A-B-A ' triblock copolymer gross weight, and vi-ny l aromatic monomers accounts for 50～98% of the middle vi-ny l aromatic monomers total amount of A+B+A ' in the A+A ' block.
Further, described vinyl aromatic polymer blocks (A or A ') comprises at least a monomer that is selected from vinylbenzene, alpha-methyl styrene, o-vinyl toluene, ρ-vinyl toluene and ρ-t-butyl styrene, and described vi-ny l aromatic monomers is preferably vinylbenzene.
On the other hand, described conjugated diolefin polymer block (B) is a kind of homopolymer block, the alternation block that it contains divinyl or is made up of a large amount of divinyl and a small amount of conjugate diene monomer.
Further, the number-average molecular weight of described formula 1 compound is 50,000～400,000.
Further, bituminous composition preferably contains: i) rock asphalt of 100 weight parts and the ii) asymmetric triblock copolymer shown in the formula 1 of 1～20 weight part.
On the other hand, the present invention also provides a kind of and above-mentioned modified asphalt composite the relevant modified asphalt composite that contains linearity or radial block copolymer.
Further, the present invention also provides described polymers in modified asphalt paving the way or making purposes aspect the flashing.
Elaborating of invention
The present invention is following to be described in detail.
Asphalt modifier of the present invention is the asymmetric styrene-butadiene-styrene block copolymer shown in the formula 1.The number-average molecular weight of the asymmetric styrene-butadiene-styrene block copolymer shown in the formula 1 is 20,000～1,000,000, is preferably 50,000～400,000.
If the number-average molecular weight of described segmented copolymer is lower than 20,000, the mechanical property of this multipolymer can not all show.On the other hand, if number-average molecular weight is higher than 1,000,000, the processing characteristics of this multipolymer can reduce.
Described vinyl aromatic polymer blocks (A or A ') comprises at least a monomer that is selected from vinylbenzene, alpha-methyl styrene, o-vinyl toluene, ρ-vinyl toluene and ρ-t-butyl styrene, and described vi-ny l aromatic monomers is preferably vinylbenzene.Further, the weight of A and A ' block accounts for 5～40wt% of A-B-A ' triblock copolymer gross weight, and vi-ny l aromatic monomers accounts for 50～98% of the middle vi-ny l aromatic monomers total amount of A-B-A ' in the A+A ' block.
Difference between the number-average molecular weight of block A and block A ' is 3,000～29,500, and this expression block A and block A ' are asymmetric blocks.
Described conjugated diolefin polymer block (B) is a kind of homopolymer block, the alternation block that it contains divinyl or is made up of a large amount of divinyl and a small amount of conjugate diene monomer.
Asymmetric styrene-butadiene-styrene triblock copolymer shown in the described formula 1 can be by being prepared by traditional continuous polymerization method in the presence of anionic initiator, and this anionic initiator can be organolithium compound.
Bituminous composition of the present invention comprises: i) rock asphalt of 100 weight parts and the ii) asymmetric triblock copolymer shown in the formula 1 of 0.5～40 weight part.Be preferably the asymmetric triblock copolymer shown in the formula 1 of 1～25 weight part.If the content of the asymmetric triblock copolymer shown in the formula 1 is lower than 0.5 weight part, then this triblock copolymer just can not work as asphalt modifier, because it can not show the function of polymkeric substance fully.On the other hand, if the content of the asymmetric triblock copolymer shown in the formula 1 surpasses 40 weight parts, described triblock copolymer can cause high viscosity, makes the weakening of flowability that dispersion decline between pitch and the properties-correcting agent and dispersive sluggishness are brought.Further, in this case, mechanical crackle and thermolysis can appear in binding agent.
The content of sulphur is 0.1～20 weight part with respect to the styrene-butadiene-styrene block copolymer of 100 weight parts in the modified asphalt composite, is preferably 1～10 weight part.
As mentioned above, the styrene-butadiene-styrene triblock copolymer shown in the formula 1 contains asymmetric styrene block.Certainly, it shows excellent ductility at low temperatures, causes the ductility and the thermostability of the excellence under the low temperature, and the anti-permanentset under the high temperature.
Embodiment
Below by embodiment the present invention is done more specifically explanation.But the present invention is not limited to following embodiment.
(preparation embodiment 1)
The preparation of asymmetric styrene-butadiene-styrene triblock copolymer
Fully purge the reactor of 2L with argon gas, then, remain hexanaphthene after the purification that adds 900g under 70 ℃ the condition and the vinylbenzene of 20g in temperature.The cyclohexane solution (concentration is 1.3M) that contains 2mmol n-Butyl Lithium (BuLi) joins in the reactor initiated polymerization as initiator.After 10 minutes, add the divinyl initiated polymerization of 170g in reaction under the highest polymerization temperature.After 5 minutes, add the vinylbenzene initiated polymerization of 10g in the highest polymerization temperature reaction.Add a spot of methyl alcohol in the reaction soln and stop polymerization.After the activity of last polymkeric substance is eliminated fully, add antioxidant.
With steam with the removal of solvents in the resulting mixed with polymers solution.Then, obtain the asymmetric styrene-butadiene-styrene triblock copolymer of paste.At last, remove remaining solvent and water with roller mill.
(preparation embodiment 2)
The preparation of asymmetric styrene-butadiene-styrene triblock copolymer
Fully purge the reactor of 2L with argon gas, then, remain hexanaphthene after the purification that adds 900g under 70 ℃ the condition and the vinylbenzene of 25g in temperature.The cyclohexane solution (concentration is 1.3M) that contains 2mmol n-Butyl Lithium (BuLi) joins in the reactor initiated polymerization as initiator.After 10 minutes, add the divinyl initiated polymerization of 170g in reaction under the highest polymerization temperature.After 5 minutes, add the vinylbenzene initiated polymerization of 5g in the highest polymerization temperature reaction.Add a spot of methyl alcohol in the reaction soln and stop polymerization.After the activity of last polymkeric substance is eliminated fully, add antioxidant.
With steam with the removal of solvents in the resulting mixed with polymers solution.Then, obtain the asymmetric styrene-butadiene-styrene triblock copolymer of paste.At last, remove remaining solvent and water with roller mill.
(preparation embodiment 3)
The preparation of asymmetric styrene-butadiene-styrene triblock copolymer
Fully purge the reactor of 2L with argon gas, then, remain hexanaphthene after the purification that adds 900g under 70 ℃ the condition and the vinylbenzene of 28g in temperature.The cyclohexane solution (concentration is 1.3M) that contains 2mmol n-Butyl Lithium (BuLi) joins in the reactor initiated polymerization as initiator.After 10 minutes, add the divinyl initiated polymerization of 170g in reaction under the highest polymerization temperature.After 5 minutes, add the vinylbenzene initiated polymerization of 2g in the highest polymerization temperature reaction.Add a spot of methyl alcohol in the reaction soln and stop polymerization.After the activity of last polymkeric substance is eliminated fully, add antioxidant.
With steam with the removal of solvents in the resulting mixed with polymers solution.Then, obtain the asymmetric styrene-butadiene-styrene triblock copolymer of paste.At last, remove remaining solvent and water with roller mill.
(preparation embodiment 4)
The preparation of asymmetric styrene-butadiene-styrene triblock copolymer
Fully purge the reactor of 2L with argon gas, then, remain hexanaphthene after the purification that adds 900g under 70 ℃ the condition and the vinylbenzene of 29g in temperature.The cyclohexane solution (concentration is 1.3M) that contains 2mmol n-Butyl Lithium (BuLi) is added in the reactor initiated polymerization as initiator.After 10 minutes, add the divinyl initiated polymerization of 170g in reaction under the highest polymerization temperature.After 5 minutes, add the vinylbenzene initiated polymerization of 1g in the highest polymerization temperature reaction.Add a spot of methyl alcohol in the reaction soln and stop polymerization.After the activity of last polymkeric substance is eliminated fully, add antioxidant.
With steam with the removal of solvents in the resulting mixed with polymers solution.Then, obtain the asymmetric styrene-butadiene-styrene triblock copolymer of paste.At last, remove remaining solvent and water with roller mill.
(preparation embodiment 5)
The preparation of asymmetric styrene-butadiene-styrene triblock copolymer
Fully purge the reactor of 2L with argon gas, then, remain hexanaphthene after the purification that adds 900g under 70 ℃ the condition and the vinylbenzene of 40g in temperature.The cyclohexane solution (concentration is 1.3M) that contains 2mmol n-Butyl Lithium (BuLi) is added in the reactor initiated polymerization as initiator.After 10 minutes, add the divinyl initiated polymerization of 155g in reaction under the highest polymerization temperature.After 5 minutes, add the vinylbenzene initiated polymerization of 5g in the highest polymerization temperature reaction.Add a spot of methyl alcohol in the reaction soln and stop polymerization.After the activity of last polymkeric substance is eliminated fully, add antioxidant.
With steam with the removal of solvents in the resulting mixed with polymers solution.Then, obtain the asymmetric styrene-butadiene-styrene triblock copolymer of paste.At last, remove remaining solvent and water with roller mill.
(comparative preparation embodiment 1)
The preparation of linear styrene-butadiene block copolymer
Fully purge with argon gas in the reactor of 2L and be full of argon gas, then, remain hexanaphthene after the purification that adds 900g under 70 ℃ the condition and the vinylbenzene of 15g in temperature.The cyclohexane solution (concentration is 1.3M) that contains 2mmol n-Butyl Lithium (BuLi) is added in the reactor initiated polymerization as initiator.After 10 minutes, add the divinyl initiated polymerization of 170g in reaction under the highest polymerization temperature.After 5 minutes, add the vinylbenzene initiated polymerization of 15g in the highest polymerization temperature reaction.Add a spot of methyl alcohol in the reaction soln and stop polymerization.After the activity of last polymkeric substance is eliminated fully, add antioxidant.With steam with the removal of solvents in the resulting mixed with polymers solution.Then, obtain white linear styrene-butadiene block copolymer.At last, remove remaining solvent and water with roller mill.
The performance of the segmented copolymer for preparing among preparation embodiment and the comparative preparation embodiment is measured by following method, and the results are shown in Table 1.
(comparative preparation embodiment 2)
The preparation of linear styrene-butadiene block copolymer
Fully purge the reactor of 2L with argon gas, then, remain hexanaphthene after the purification that adds 900g under 70 ℃ the condition and the vinylbenzene of 30g in temperature.The cyclohexane solution (concentration is 1.3M) that contains 2mmol n-Butyl Lithium (BuLi) is added in the reactor initiated polymerization as initiator.After 10 minutes, add the divinyl initiated polymerization of 140g in reaction under the highest polymerization temperature.After 5 minutes, add the vinylbenzene initiated polymerization of 30g in the highest polymerization temperature reaction.Add a spot of methyl alcohol in the reaction soln and stop polymerization.After the activity of last polymkeric substance is eliminated fully, add antioxidant.With steam with the removal of solvents in the resulting mixed with polymers solution.Then, obtain white linear styrene-butadiene block copolymer.At last, remove remaining solvent and water with roller mill.
The performance of the segmented copolymer for preparing among preparation embodiment and the comparative preparation embodiment is measured by following method, and the results are shown in Table 1.
(comparative preparation embodiment 3)
The preparation of radial styrene-butadiene block copolymer
Fully purge the reactor of 2L with argon gas, then, remain hexanaphthene after the purification that adds 900g under 70 ℃ the condition and the vinylbenzene of 60g in temperature.The cyclohexane solution (concentration is 1.3M) that contains 7mmol n-Butyl Lithium (BuLi) is added in the reactor initiated polymerization as initiator.After 10 minutes, add the divinyl initiated polymerization of 140g in reaction under the highest polymerization temperature.After 5 minutes, the SiCl4 that adds 1.8mmol causes linked reaction in the highest polymerization temperature reaction.Add a spot of methyl alcohol in the reaction soln and stop polymerization.After the activity of last polymkeric substance is eliminated fully, add antioxidant.With steam with the removal of solvents in the resulting mixed with polymers solution.Then, obtain white radial styrene-butadiene block copolymer.At last, remove remaining solvent and water with roller mill.
The performance of the segmented copolymer for preparing among preparation embodiment and the comparative preparation embodiment is measured by following method, and the results are shown in Table 1.
Molecular weight analyse
The molecule quantitative analysis is measured by high performance liquid chromatography " Waters 2690 type separation modules " and detector " Waters 410 type differential refractometers ".Below be analysis condition: column temperature is 41 ℃, and solvent is THF, and flow velocity is 0.3mL/min.Vinylstyrene StyragelHR5E, HR4 are connected by linear with HR2.Polystyrene is used for measuring the difference of the refractive index that is detected by refraction detector as standard.
The microstructure of multipolymer and analysis on Content
The microstructure of vinylbenzene and butadiene content and polymkeric substance is measured with the nuclear magnetic resonance analyser NMR-200 and the NMR-400 of Bruker company.With deuterochloroform (chloroform-d) solvent setup test material.
The measurement of soltion viscosity
In the measurement of copolymer solution viscosity, polymers soln is dissolved in the concentration that forms 5.23wt% in the toluene, under 25 ℃ constant temperature, be 0.09048mm in constant K with the Ubbelohde viscosity apparatus
2/ s
2Condition under measure viscosity.
Table 1
| Styrene content | Block percentage (%) | Molecular weight (Mn) | Soltion viscosity (cps) | |
| Preparation embodiment 1 | 14.8 | 92 | 192,000 | 21 |
| Preparation embodiment 2 | 14.5 | 83 | 201,000 | 21 |
| Preparation embodiment 3 | 15.2 | 88 | 190,000 | 20 |
| Preparation embodiment 4 | 14.8 | 78 | 195,000 | 21 |
| Preparation embodiment 5 | 22.3 | 93 | 202,000 | 18 |
| Comparative preparation embodiment 1 | 14.8 | 91 | 198,000 | 21 |
| Comparative preparation embodiment 2 | 29.8 | 97 | 195,000 | 12 |
| Comparative preparation embodiment 3 | 30.1 | 96 | 209,000 | 21 |
(embodiment 1-5)
The measurement of modified asphalt composite
With resulting polymkeric substance among the preparation embodiment 1-5 get respectively 21g join 600g 180 ℃ in the rock asphalt of molten state, with efficient agitator with its stirring after, obtain the bituminous cement of polymer modification.Further, add the sulphur of 0.6g again, stir 20 minutes to prevent the difference and incompatible being separated of causing of rubber owing to density.At last, obtain the styrene-butadiene-styrene modified asphalt composition.
When measuring the ductility of bituminous composition, according to the method setup test material that may further comprise the steps: i) heat modification bituminous composition; Ii) the fused bituminous composition is poured into to mould, iii) cooling compositions (KS M 2254).The method (KS M 2254) of measuring ductility may further comprise the steps: i) test material is inserted in 5 ℃ the water-bath, ii) applies tensile strength at two ends and iii) measure test material length when being separated with the speed of 3cm/min.
Table 2 has provided the softening temperature and the ductility of test material.
(comparative example 1-3)
The measurement of modified asphalt composite
With resulting polymkeric substance among the comparative preparation embodiment 1-3 get respectively 21g join 600g 180 ℃ in the rock asphalt of molten state, after efficient agitator stirring, obtain the bituminous cement of polymer modification.Further, add the sulphur of 0.6g again, stir 20 minutes to prevent the difference and incompatible being separated of taking place of rubber owing to density.At last, obtain the styrene-butadiene-styrene modified asphalt composition.
In order to measure the ductility of bituminous composition, prepare test material: i) heating bituminous composition by following steps; Ii) the composition with fusing is fed into mould, iii) cooling compositions (KS M 2254).In order to measure ductility, measuring method (KS M 2254) may further comprise the steps: i) test material is inserted in 5 ℃ the water-bath, ii) applies tensile strength at two ends and iii) measure test material length when being separated with the speed of 3cm/min.
Table 2 has provided the softening temperature and the ductility of test material.
Table 2
| Block copolymer-modified dose content (weight part) | Softening temperature (℃) | Ductility | ||
| RTFO (rotating thin film baking oven) before (5 ℃, cm) | RTFO (rotating thin film baking oven) afterwards (5 ℃, cm) | |||
| Embodiment 1 | 3.5 | 74 | 39.5 | 24.5 |
| Embodiment 2 | 3.5 | 77 | 36.1 | 26.1 |
| Embodiment 3 | 3.5 | 79 | 36.4 | 26.1 |
| Embodiment 4 | 3.5 | 92 | 40.5 | 26.5 |
| Embodiment 5 | 3.5 | 94 | 33.8 | 24.9 |
| The comparative example 1 | 3.5 | 71 | 36.5 | 22.8 |
| The comparative example 2 | 3.5 | 93 | 36.4 | 16.1 |
| The comparative example 3 | 3.5 | 97 | 32.4 | 12.5 |
As shown in table 2, embodiment 4 compares with embodiment 1 with the bituminous composition that comprises asymmetric styrene-butadiene-styrene block copolymer of 5 preparations and has shown higher softening temperature, this means at high temperature to keep anti-permanentset.Embodiment 4 is similar with the softening temperature of the comparative example 2 with high-phenylethylene content with the softening temperature of the composition of 5 preparations.Further, compare with comparative example 2, the ductility that the compositions table of embodiment 4 and 5 preparations has revealed after using the rotating thin film baking oven significantly strengthens.Certainly, this means that also the ductility under the low temperature strengthens, and is reduced by the crackle that tired and thermal distortion cause.Therefore, can be used for paving the way as the bituminous composition that is fit to by the resulting bituminous composition of embodiment.On the other hand, compare with the comparative example 3 who has used radial polymers, the bituminous composition that obtains among the embodiment has shown better ductility, and softening temperature is higher unlike the softening temperature of radial polymers.
Claims (8)
1. one kind modified asphalt composite, it shows at low temperatures excellent ductility and thermostability and anti-permanentset at high temperature, it comprises: the i) rock asphalt of 100 weight parts, ii) the number-average molecular weight of 0.5～40 weight part is 20,000～1, asymmetric triblock copolymer shown in 000,000 the formula 1
A-B-A ' (formula 1)
Wherein, A represents vinyl aromatic polymer blocks, and number-average molecular weight is 8,000～30,000;
The B representative contains the conjugated diolefin polymer block or the conjugated diene copolymer block of small amount of ethylene base aromatic monomer; And
It is 500～5,000 vinyl aromatic polymer blocks that A ' represents number-average molecular weight;
Wherein, A and A ' block weight account for 5～40wt% of A-B-A ' triblock copolymer gross weight, and vi-ny l aromatic monomers accounts for 50～98% of the middle vi-ny l aromatic monomers total amount of A-B-A ' in the A+A ' block.
2. modified asphalt composite according to claim 1, wherein said vinyl aromatic polymer blocks (A or A ') comprises at least a monomer that is selected from vinylbenzene, alpha-methyl styrene, o-vinyl toluene, ρ-vinyl toluene and ρ-t-butyl styrene.
3. modified asphalt composite according to claim 1, wherein said vi-ny l aromatic monomers are vinylbenzene.
4. modified asphalt composite according to claim 1, wherein said conjugated diolefin polymer block (B) is a kind of homopolymer block, the alternation block that it contains divinyl or is made up of a large amount of divinyl and a small amount of conjugate diene monomer.
5. modified asphalt composite according to claim 1, the number-average molecular weight of the mixture shown in the wherein said formula 1 is 50,000～400,000.
6. modified asphalt composite according to claim 1, wherein said bituminous composition comprises i) rock asphalt of 100 weight parts, the ii) asymmetric triblock copolymer shown in the formula 1 of 1～20 weight part.
7. modified asphalt composite according to claim 1, described composition further contain linear or radial segmented copolymer.
8. the purposes of the described modified asphalt composite of claim 1, described composition is used to pave the way or make flashing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050032650A KR100639893B1 (en) | 2005-04-20 | 2005-04-20 | Asphalt composition containing styrene-butadiene-styrene block copolymers having unsymmetric polystyrene block |
| KR1020050032650 | 2005-04-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1854200A true CN1854200A (en) | 2006-11-01 |
| CN100549099C CN100549099C (en) | 2009-10-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101054902A Expired - Fee Related CN100549099C (en) | 2005-04-20 | 2005-09-28 | A kind of bituminous composition that comprises styrene-butadiene-styrene block copolymer with asymmetric polystyrene block |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20060241218A1 (en) |
| KR (1) | KR100639893B1 (en) |
| CN (1) | CN100549099C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110719924A (en) * | 2017-06-09 | 2020-01-21 | 科腾聚合物有限责任公司 | Highly asymmetric triblock polymer compositions and methods of making the same |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE489430T1 (en) * | 2007-04-26 | 2010-12-15 | Shell Int Research | METHOD FOR PRODUCING ASPHALT |
| KR101220330B1 (en) * | 2010-12-14 | 2013-01-09 | 금호석유화학 주식회사 | Tapered Asymmetric Block Copolymers and Adhesives Composition Comprising The Same |
| US8992118B2 (en) | 2013-03-15 | 2015-03-31 | William B. Coe | Pavement repair system utilizing solid phase autoregenerative cohesion |
| CA2906019C (en) | 2013-03-15 | 2021-07-13 | William B. Coe | Pavement repair system |
| US9057163B1 (en) | 2013-03-15 | 2015-06-16 | William B. Coe | Pavement repair system |
| KR101688504B1 (en) | 2014-07-15 | 2016-12-22 | 금호석유화학 주식회사 | Additive composition for polymer modified asphalt, polymer modified asphalt composition comprising the same, and method for preparing the same |
| AU2018220901B2 (en) | 2017-02-14 | 2021-09-23 | William B. Coe | Apparatus and method for preparing asphalt and aggregate mixture |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL298343A (en) * | 1962-09-27 | |||
| DE2425665C3 (en) * | 1974-05-28 | 1978-04-06 | Basf Ag, 6700 Ludwigshafen | Threads and fibers made from a mixture of bitumen and polypropylene or its copolymers and processes for their production |
| US4412019A (en) | 1980-07-12 | 1983-10-25 | Phillips Petroleum Company | Asphalt compositions |
| DE3714711A1 (en) * | 1987-05-02 | 1988-11-17 | Basf Ag | BUTADIENE-STYROL BLOCK COPOLYMERS WITH UNSYMMETRIC STRUCTURE AND THEIR PRODUCTION AND USE AS MOLDS |
| USH876H (en) * | 1987-11-16 | 1991-01-01 | Bitumen composition | |
| US5246987A (en) * | 1992-05-14 | 1993-09-21 | Shell Oil Company | Bitumen and halogenated vinyl aromatic-conjugated diolefin block copolymer compositions |
| US5721296A (en) * | 1995-02-24 | 1998-02-24 | Kao Corporation | Asphalt additive and asphalt composition |
-
2005
- 2005-04-20 KR KR1020050032650A patent/KR100639893B1/en active IP Right Grant
- 2005-08-30 US US11/213,892 patent/US20060241218A1/en not_active Abandoned
- 2005-09-28 CN CNB2005101054902A patent/CN100549099C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110719924A (en) * | 2017-06-09 | 2020-01-21 | 科腾聚合物有限责任公司 | Highly asymmetric triblock polymer compositions and methods of making the same |
| CN110719924B (en) * | 2017-06-09 | 2023-11-21 | 科腾聚合物有限责任公司 | Highly asymmetric triblock polymer compositions and methods of making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060241218A1 (en) | 2006-10-26 |
| KR100639893B1 (en) | 2006-10-30 |
| CN100549099C (en) | 2009-10-14 |
| KR20060110892A (en) | 2006-10-26 |
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