CN107619608A - A kind of block copolymer-modified asphalt emulsion and preparation method thereof - Google Patents
A kind of block copolymer-modified asphalt emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of block copolymer-modified asphalt emulsion, includes the block copolymer of formula 1：P is the block copolymer that formula is A1 B A2, and A1 and A2 are styrene block, and B is butadiene block；Wherein, styrene block (S) and the weight ratio (S/B) of butadiene block (B) are 20,/80 40/60；1 in butadiene block, 2 architecture quality percentage compositions are 25 50%；P molecular weight is 8 20 ten thousand.In addition, the invention also discloses the preparation method of the asphalt emulsion.In the present invention, the solid content raising of the asphalt emulsion of the block copolymer containing formula 1, stability enhancing, production efficiency improve.Compared with the existing asphalt emulsion that oneself knows, the asphalt emulsion bin stability increases, and emulsifying effectiveness is good.
Description
Technical field
The invention belongs to asphalt emulsion technical field, and in particular to a kind of using block copolymer-modified asphalt emulsion.
Background technology
Pitch is used to paving the way, roof waterproof and coating material.But pure pitch exists in terms of physical property
Deficiency.Therefore, it is necessary to be improved to it.In the past, people were by dienopolymer rubber (such as SBR styrene butadiene rubberses) and benzene
Ethene-rubber block copolymers (such as s-B-S and SIS)
It is added in pitch to improve the hot property of pitch and mechanical performance.But the pitch of these polymer modifications generally requires height
Temperature heating melting, its shortcoming one is not save, second, can discharge pernicious gas during high temperature, pollutes environment.Therefore, people are increasingly
It is intended to use emulsified asphalt.Emulsified asphalt is by high temperature road asphalt, by mechanical agitation and chemically stable method, is disperseed
Form under normal temperature that viscosity is very low, the good pavement construction material of mobility into water.Emulsified asphalt has energy-conservation, purposes wide
The features such as general, easy to use, it is mainly used in the upgrading and maintenance of road pavement and road.Compared with traditional heated bitumen, emulsification drip
Blue or green safer, energy-conservation and environmental protection, and avoid noxious emission and reduce environmental pollution, reduce worker and burn risk and bright
The risk of fire heating blast.
But low temperature embrittlement, the inadequate natural endowment of high temperature trickling after the construction of in general emulsified asphalt be present, constrain its application
Popularization.Therefore, prior art is mostly to add styrene-butadiene latex (SBR), polychloroprene latex, EVA emulsions etc. in emulsified asphalt to come
Improve the blue or green performance of breast, or but this method only improve the high-temperature behavior of modified pitch and its low temperature properties can not be obviously improved
Energy；Only improve the low temperature properties of modified pitch and its high-temperature behavior can not be obviously improved, Modern Traffic road pavement can not be met
Performance requirement.Also the correlation technique of useful SBS emulsions (also known as liquid SBS) modified emulsifying asphalt, such as public affairs on May 25th, 2005
The Chinese patent opened《The manufacture method of liquid asphalt modifier》(Publication No. 1618862) discloses a kind of system of liquid SBS
Preparation Method, and for example Chinese patent disclosed in 21 days January in 2009《A kind of thermoplastic butadiene styrene rubber aqueous rubber latex asphalt modifying agent and
Its preparation method》The preparation method that (Publication No. 101348598) discloses SBS emulsions, the SBS breasts disclosed in this two parts of patents
Liquor manufacture method is essentially identical, i.e., solid SBS is dissolved in organic solvent, obtained with surfactant and water by emulsification method
SBS emulsions, this SBS emulsions contain more hazardous solvent, even if Publication No. CN101348598A patent document uses
Negative pressure method reclaims organic solvent, but it is very big to reclaim organic solvent technical difficulty completely, easily causes SBS emulsion breakings, and use this
Kind SBS emulsion production emulsified asphalts, the surfactant of use is excessive, causes emulsified asphalt unqualified, therefore, is also difficult at present
For producing emulsified asphalt.
However, the research to emulsified SBS modified asphalt is very active always in the industry, set by the optimization of emulsifying agent, emulsification
Standby and technique improvement, the particularly reduction of SBS modified pitch thermoviscosity, reach the purpose of emulsified SBS modified asphalt.Such as 2006
Chinese patent disclosed on June 28, in《A kind of SBS modified emulsifying asphalts and preparation method thereof》(Publication No. CN1793234A)
Disclosing reduces the viscosity of hot SBS modified pitch using Sasobit (Sha Suo Bitsofts), is emulsified by appropriate emulsification means
The method of SBS modified pitch, and for example Chinese patent disclosed in September in 2005 7 days《Emulsified SBS modified asphalt and its processing method》
(Publication No. CN1664012A), disclose under appropriate emulsifying agent and emulsifying conditions, using ultrasonic emulsification mechanism
The method for obtaining emulsified SBS modified asphalt.
But above patent all has a shortcoming, it is exactly that its emulsifying effectiveness to pitch is poor, is less susceptible to emulsify.This
Outside, the solid content of these asphalt emulsions is not high, influences production efficiency.
The content of the invention
To solve in the prior art, the technical problem that emulsifying effectiveness is poor, solid content is not high, the invention provides a kind of easy
The high asphalt emulsion of emulsification, solid content.In addition, the present invention also includes the preparation method of the asphalt emulsion.
A kind of block copolymer-modified asphalt emulsion, include the block copolymer of formula 1：
P is the block copolymer that formula is A1-B-A2, and A1 and A2 are styrene block, and B is butadiene block；Wherein, benzene
Ethylene block (S) and the weight ratio (S/B) of butadiene block (B) are 20/80-40/60；1 in butadiene block, 2 structure matter
Amount percentage composition is 25-50%；P molecular weight is 8-20 ten thousand.
In the present invention, the solid content raising of the asphalt emulsion of the block copolymer containing formula 1, stability enhancing, production efficiency carry
It is high.Compared with existing known asphalt emulsion, the asphalt emulsion bin stability increases, and emulsifying effectiveness is good.
Preferably, 1 in butadiene block, 2 architecture quality percentage compositions are 30-45%.
Block section P molecular weight is preferably 10-18 ten thousand.
Styrene block (S) and the weight ratio (S/B) of butadiene block (B) are 25/75-35/65.
R1And R2It is independently selected from C1-C4 alkyl.
In block copolymer, R1And R2The group of selection is identical or different.Preferably, R1And R2It is independently selected from methyl, second
Base, propyl group, isopropyl, butyl or isobutyl group.
Further preferably, R1And R2It is methyl.
The inventors discovered that the block copolymer being more highly preferred to is：P molecular weight 10-18 ten thousand；Wherein, styrene block
(S) and the weight ratio (S/B) of butadiene block (B) is 25/75-35/65；1 in butadiene block, 2 architecture quality percentages contain
Measure as 30-45%；R1And R2It is methyl.
Block copolymer-modified asphalt emulsion of the present invention also includes pitch, water and emulsifying agent.It that is to say, it is described
Block copolymer-modified asphalt emulsion include pitch, water, emulsifying agent and the block copolymer.
Pitch, water, the weight ratio of emulsifying agent and the block copolymer are 50-60: 40-50: 1-3: 2.0-8.0.
The asphalt component included in the asphalt emulsion can be naturally occurring pitch or petroleum derived pitches.In addition,
The asphalt component can also be the mixture of the asphalt that cracking obtains and various asphalt materials.The reality of the asphalt component
Example includes but is not limited to distillation or straight asphalt, blown asphalt, multistage pitch etc. and their mixture.
Preferably, needle penetration is 24 to 400 pitch when asphalt component is 25 DEG C；It is preferred that needle penetration is 60-300 drip
The straight run or distillation pitch that green grass or young crops, more preferably needle penetration are 110-250.For example, it is preferable to pitch be South Korea's import SK-70.
Water is included in asphalt emulsion of the present invention, the water can be any kind of clean water, still, in order at utmost
Reduce the reaction of water mineral and emulsion system in ground, it is preferred to use softened water.
Also need to add one or more emulsifier systems in the present invention, in asphalt emulsion, the emulsifier system can be
System only containing one or more emulsifying agents, the combined system comprising one or more emulsifying agents and inorganic acid or one or more
The system of the combination of emulsifying agent and alkali.According to emulsion types (cation, anion or nonionic), emulsifying agent can be selected from：(a)
If cation emulsion, cationic emulsifier known to those skilled in the art can be selected, be selected from the salt of fatty amine, acid amides and
Imidazoline or their mixture, preferably quaternary ammonium salt cationic type emulsifying agent, such as cetyl trimethyl sal-ammoniac, octadecyl
Trimethyl ammonia chloride ammonia, DTAC, DTAB, octadecyl trimethyl Benzylmagnesium chloride
Ammonium, cetyl trimethyl benzyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride.(b), then can be with if anionic emulsion
Select conventional anion emulsifier familiar to the person skilled in the art, such as soap, rosin acid, lignosulfonates or it
Mixture, it is preferred to use oleic acid.(c) if nonionic emulsifier, amino carboxylic acid and its salt can be selected, or it is other suitable
Nonionic emulsifier.
In the present invention, the block copolymer preparation method is：It is R by formula2R1- N-Li amine lithium triggers block monomer
Polymerization, after polymerization, PLi (activity is lithium integrated) is formed, maleic anhydride is added and carries out end capping reaction, be finally acidified
Obtain.Wherein described R1And R2Identical with the structure of formula 1, both can be able to be C1 to C4 alkyl with identical or different, as methyl,
Ethyl, propyl group, isopropyl, butyl, isobutyl group etc..
The block copolymer prepares reaction equation and is exemplified below：
a)：Reactive amines lithium is prepared (equation 1)：
Prepare the alkyl lithium reagents (R used during amine lithium3Li) it is preferably n-BuLi or s-butyl lithium；(R1)R2-NH
With amount ratio=1: 1.01~1.05 of butyl lithium material, 10-40 DEG C of reaction temperature, reaction time 20-30min.Reaction is polymerizeing
Kettle is carried out in two hole ox horn bottles in advance.Synthesized reactive amines lithium reagent is the active initiator of polymerization process, and structure is led to
Formula is (R1)R2-N-Li。
b)：Polymerization：30-85 DEG C of polymeric reaction temperature, reaction time 25-85min；
b-1)：Polymerization is triggered to form styrene block A1 (equation 2)：
b-2)：Polymerization is triggered to form styrene block A1- butadiene blocks B (equation 3)：
b-3)：Polymerization is triggered to form styrene block A1- butadiene block B- styrene blocks A2 (equation 4)：
B) in, the mass ratio of styrene and butadiene is 20-40: 60-80.Wherein, b-1) and the styrene that b-3) adds
Weight it is identical；
3)：Acid blocked is reacted：End capping reaction (equation 5) is carried out for example with maleic anhydride；
In acid blocked reaction, the amount ratio of maleic anhydride and butyl lithium material is 1: 1.01~1.05, reaction temperature 40-
65 DEG C, reaction time 15-30min.
4)：It is acidified (equation 6)：
After end capping reaction, polymer glue (polymerization liquid) is acidified under the conditions of diluted acid (during pH=5-6),
20-60 DEG C of souring temperature, acidificatoin time 15-20min.
The diluted acid is preferably the aqueous solution of hydrochloric acid, sulfuric acid or phosphoric acid；Or the cyclohexane solution of hydrogen chloride；Or it is passed through dioxy
Change carbon and water.
A), aliphatic, cyclic aliphatic, alkyl-substituted cyclic aliphatic, aromatics and alkyl can be selected in the solvent that b), c) process uses
Substituted arene, ether and their mixture.Specifically, suitable solvent includes aliphatic hydrocarbon, such as butane, pentane, hexane and heptan
Alkane；Cycloaliphatic hydrocarbon, such as pentamethylene, hexamethylene and cycloheptane；Alkyl substituted fatty hydrocarbon, such as hexahydrotoluene and methylcycloheptane；
Aromatic hydrocarbons, such as benzene；Alkyl-substituted aromatic hydrocarbon, such as toluene and dimethylbenzene；Ether, such as tetrahydrofuran, diethyl ether and butyl oxide.
Preferably, the solvent for preparing the block copolymer is pentamethylene, minimum one kind in hexamethylene, hexane.
Further preferably, the solvent for preparing the block copolymer is hexamethylene or hexamethylene-hexane mixed solvent.
It is worthy of note that in addition to method proposed by the present invention, block copolymer of the present invention can also use other
Prepared by any feasible method, the method for the invention is only for reference, but can not limit the present invention.
The method for preferably preparing the block copolymer of the present invention, comprises the following steps：
Step (1)：It is prepared by reactive amines lithium：
(R1)R2- NH dissolves in a solvent, adds alkyl lithium reagents under an inert atmosphere and reacts 20- at 10-40 DEG C
30min obtains reactive amines lithium reagent；(R1)R2- NH and lithium alkylide mol ratio=1: 1.01~1.05；
Step (2)：Polymerization：
Step (2-1)：Under an inert atmosphere, reactive amines lithium made from step (1) is added after styrene (S) is dissolved to try
Agent, it polymerize at 30-85 DEG C；Polymerisation 20-30min；
Step (2-2)：After the completion of step (2-1) polymerization, butadiene (B) is added；Polymerisation 20-30min；
Step (2-3)：After the completion of step (2-2) polymerization, continue to add the styrene with step (2-1) identical weight；It is poly-
Close reaction 20-30min；
Step (3)：Acid blocked is reacted：
After the completion of step (2-3) polymerization, add maleic anhydride and carry out end capping reaction, 40-65 DEG C of end capping reaction temperature；
The amount ratio of the material of maleic anhydride and lithium alkylide is 1: 1.01~1.05,40-65 DEG C of reaction temperature, reaction time 15-
30min；
Step (4)：Acidifying
After step (3) processing terminates, the olefin(e) acid through pH=5-6 carries out acidification, then scrubbed, dry that institute is made
The block copolymer stated, wherein, 20-60 DEG C of souring temperature, acidificatoin time 15-20min.
In the preferably preparation method, the solvent that step (1) and step (2) use mixes for hexamethylene or hexamethylene-hexane
Bonding solvent.
Any method manufacture of manufacture asphalt emulsion known to skilled people, example can be used in the asphalt emulsion of the present invention
Such as, using colloidal mill or high shear mixer.
Emulsion of the present invention can be by the way that pitch component be mixed with the emulsifier solution comprising one or more emulsifier systems
To prepare.Pitch component (pitch phase) is by the way that pitch and the block copolymer composition of the present invention are blended to prepare.Prepare
Bituminous composition can use any of tank or container, as long as the tank or container can be stirred, heated.
During asphalt emulsion is prepared, pitch can be heated approximately to 130 DEG C to about 190 DEG C, be preferably heated to
About 160 DEG C to about 180 DEG C.Once asphalt component reaches preferred temperature, you can adds the block copolymer, stirs simultaneously
Mix, asphalt component and block copolymer composition is formed uniform mixture.The feed postition and shape of the block copolymer
Formula is not restricted by, and its form can be granular, fragment shape or their forms, and feed postition can be disposable adds or in batches
Add by several times.
Emulsifier solution can use simply by one or more emulsifying systems components (such as emulsifying agent and acid or emulsifying agent and
Alkali) being added to the water and heating makes it dissolve and prepare.
Then asphalt component and emulsifier solution be individually or simultaneously added in colloidal mill or high shear mixer or
In other mixing apparatus, high speed shear is scattered to form asphalt emulsion, and cooling obtains the asphalt emulsion.Shear rate is preferably
3000-3500r/min。
The temperature of asphalt component and emulsifier solution according to the type of pitch, percentage in emulsion when the type of emulsifying agent and
Change.Temperature when asphalt component adds is about 120 DEG C to about 160 DEG C, preferably about 130 DEG C to about 150 DEG C.Breast
The temperature that agent solution is added in mixture is typically about 30 DEG C to about 70 DEG C, preferably approximately 40 DEG C to about 50 DEG C.
Preferably, in asphalt emulsion of the present invention, the mass content of matrix pitch is 55-60%, block copolymer
Content is 2.5-4%, and the content of water is 40-45%, and the content of emulsifying agent is 1-3%.In addition, asphalt emulsion of the present invention can be with
Other additives such as the stabilizer comprising proper content.
A kind of preparation method of the preferable block copolymer-modified asphalt emulsion, by asphalt heating to 160 DEG C-
Described block copolymer is added after 180 DEG C, stirs to obtain pitch phase；Pitch adds emulsifying agent after being mutually cooled to 130 DEG C -150 DEG C
The aqueous solution, and form asphalt emulsion colloidal mill or high shear mixer shearing are scattered, cooling obtains the pitch breast
Liquid.
In the preparation method, the temperature of the aqueous solution of emulsifying agent is 40 DEG C -50 DEG C；Shear rate is 3000-3500r/
min.The solid content of obtained asphalt emulsion is high, stability is high.
Emulsion prepared by the present invention is generally used for all general-uses of asphalt emulsion, including roof coatings, roofing paper
Felt, the intermediate layer adhesive of rolled products, metalling sealing adhesive, pave the way slurry seal adhesive, reclaimed bituminous pavement
Additive, bituminous concrete adhesive etc..
The asphalt emulsion prepared using block copolymer of the present invention has the spy that easily emulsification, bin stability improve
Point.With existing polymer, emulsion is compared as made from YH-791H, and asphalt emulsion prepared by block copolymer of the present invention has
The characteristics of easily emulsification, bin stability improve.
Embodiment
Following examples are implemented by aforesaid operations method：
Below will be by the embodiment more detailed description present invention, it is to be noted, however, that these embodiments and not having to
In the limitation present invention.
Embodiment 1
Lead in the hole ox horn bottles of 150ml bis- of clean dried under nitrogen protection, with syringe to ox horn at 10 DEG C of room temperature
Another hole in bottle adds dimethylamine 2.5g, adds 0.5mol/L n-BuLi 112.2ml afterwards, is reacted after vibrating 20min
Completely, now dimethylamino lithium concentration is 0.48mol/L.
Embodiment 2
Lead in the hole ox horn bottles of 150ml bis- of clean dried under nitrogen protection, with syringe to ox horn at 32 DEG C of room temperature
Another hole in bottle adds diisopropylamine 5.1g, afterwards addition 0.5mol/L n-BuLi 103ml, anti-after vibration 25min
Should be complete, now the concentration of lithium diisopropyl amido is 0.47mol/L.
Embodiment 3
Under nitrogen protection, 3.5L hexane-hexamethylene mixed solvent and 54g benzene second are added in 5 liters of polymeric kettle
Alkene (S), open and stir and add 0.48mol/L prefabricated in embodiment 1 dimethylamino lithium 6ml, reacted at 30-85 DEG C
25min, butadiene (B) 252g is added afterwards and polymerize 25-30min again, then add 54g styrene reaction 25min, Ran Houjia afterwards
The tetrahydrofuran solution 10ml for entering maleic anhydride 0.29g carries out end capping reaction, 40-65 DEG C of end capping reaction temperature, during reaction
Between 20min, afterwards discharging add 1.5g BHT and 0.5mol/L watery hydrochloric acid colloidal sol 6ml and
100ml deionized waters, and 15min is stirred at room temperature.The SBS glue water vapor accumulations desolvation that is finally synthesizing, then
After drying, the number-average molecular weight 16 × 10 of product4, with reference to pendant carboxylic group content 0.032wt%, 1,2- structural content
42.3%, wherein 1,2 structural content refers to the content of butadiene block medium vinyl, using nmr for the determination (under
Together).
Embodiment 4
Except lithium diisopropyl amido prefabricated in embodiment 2 is added, (the dimethylamino lithium for substituting described 0.48mol/L is molten
Liquid) outside, other parts are same as Example 3, and it is 16.2 × 10 to prepare number-average molecular weight4, with reference to pendant carboxylic group content
0.035wt%, the SBS of 1,2- structural content 44.3%.
Embodiment 5
Matrix pitch SK-70 is heated to 180 DEG C, then adds 5% (based on polymer and pitch gross weight) embodiment 3
The polymer of preparation, stir 20 minutes, obtain pitch phase.The emulsification of 3% (weight based on water) is added in 70 DEG C of hot water
Agent cetyl benzene trimethyl ammonia chloride ammonia, stirs, and until being completely dissolved, it is 3 to reenter hydrochloric acid regulation PH, and aqueous phase (soap is made
Liquid).Under more than 3000r/min high speed shear, the good pitch phase (160 DEG C) of the melting of heat is slowly added to the aqueous phase of heat
Middle emulsification, wherein pitch phase and the weight of soap lye ratio are 55: 45, and cooling obtains emulsified asphalt.Then, according to JTJ 052-
2000《Highway engineering pitch and Asphalt Mixture Experiment code》Test method carry out emulsified asphalt evaporated residue experiment
(T0651-1993), the Asphalt Penetration (T0604-2000) of test emulsion evaporated residue, ductility (T0605-1993), softening
Point (T0606-2000) and bin stability.Wherein bin stability is according to JTJ 052-2000《Highway engineering pitch and pitch
Test mixture code》In regulation：Modified pitch emulsion storage stability is (to refer generally to room with the conditions of in defined container
Temperature), store on vertical direction, after the time as defined in arrival (1d or 5d), test residual is evaporated in upper and lower two parts emulsion respectively
The intensity of variation of amount of substance, represented with the difference of percentage, judge stability ability of the asphalt emulsion during storage.This hair
The bright middle time using placement 5d, investigate the stability of sample.
Embodiment 6
Emulsion pitch is prepared using method same as Example 5, the polymer that simply the present embodiment uses is embodiment 4
The polymer of preparation, rather than polymer prepared by embodiment 3.
Comparative example 1
In addition to adding YH-791 and replacing polymer prepared by embodiment 3, other parts are same as Example 5.
Comparative example 2
In addition to adding road and changing the polymer that 2# is prepared instead of embodiment 3, other parts are same as Example 5.
The performance of asphalt emulsion prepared by various embodiments above is as shown in table 1 below.
The performance comparison of each polymer modification emulsified asphalt of table 1
As shown in Table 1, the performance of the emulsified asphalt for the block copolymer pointed out added with the present invention improves comprehensively.
Claims (8)
1. a kind of block copolymer-modified asphalt emulsion, it is characterised in that include the block copolymer of formula 1：
P is the block copolymer that formula is A1-B-A2, and A1 and A2 are styrene block, and B is butadiene block；Wherein, styrene
Block (S) and the weight ratio (S/B) of butadiene block (B) are 20/80-40/60；1 in butadiene block, 2 architecture qualities hundred
It is 25-50% to divide content；P molecular weight is 8-20 ten thousand.
2. block copolymer-modified asphalt emulsion as claimed in claim 1, it is characterised in that 1,2 in butadiene block
Architecture quality percentage composition is 30-45%.
3. block copolymer-modified asphalt emulsion as claimed in claim 1, it is characterised in that styrene block (S) and fourth
The weight ratio (S/B) of diene block (B) is 25/75-35/65.
4. block copolymer-modified asphalt emulsion as claimed in claim 1, it is characterised in that；R1And R2It is independently selected from C1-C4
Alkyl.
5. block copolymer-modified asphalt emulsion as claimed in claim 4, it is characterised in that R1And R2Be independently selected from methyl,
Ethyl, propyl group, isopropyl, butyl or isobutyl group.
6. the block copolymer-modified asphalt emulsion as described in claim any one of 1-5, it is characterised in that：Comprising pitch,
Water, emulsifying agent and the block copolymer.
7. block copolymer-modified asphalt emulsion as claimed in claim 6, it is characterised in that：Pitch, water, emulsifying agent and institute
The weight ratio for stating block copolymer is 50-60: 40-50: 1-3: 2.0-8.0.
8. a kind of preparation method of the block copolymer-modified asphalt emulsion described in any one of claim 1-7, its feature exist
In by asphalt heating to adding described block copolymer after 160 DEG C -180 DEG C, stir to obtain pitch phase；Pitch is mutually cooled to 130
Add the aqueous solution of emulsifying agent after DEG C -150 DEG C, and in colloidal mill or high shear mixer shearing is scattered forms asphalt emulsion,
Cooling obtains the asphalt emulsion.
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| CN111484631A (en) * | 2020-05-19 | 2020-08-04 | 上海群康沥青科技股份有限公司 | Modified emulsified asphalt for micro-surfacing and preparation method and application thereof |
| CN111825855A (en) * | 2020-07-31 | 2020-10-27 | 上海缤德新材料科技有限公司 | High-viscosity emulsified asphalt for cold mixing and cold paving and preparation method thereof |
| CN112898509A (en) * | 2021-03-04 | 2021-06-04 | 苏州科技大学 | Styrene-butyl acrylate in-situ copolymerization modified asphalt |
| CN115403935A (en) * | 2021-05-28 | 2022-11-29 | 中国石油化工股份有限公司 | Micro-block nitrile butadiene rubber modified asphalt emulsion and preparation method thereof |
| CN116285400A (en) * | 2023-03-23 | 2023-06-23 | 山东交通学院 | Porous carbon polymer/block copolymer modified asphalt, and preparation method and application thereof |
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