CN106810882B - A kind of emulsified asphalt and preparation method thereof - Google Patents
A kind of emulsified asphalt and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of emulsified asphalts and preparation method thereof, on the basis of the total amount of the emulsified asphalt, the emulsified asphalt contains the polymer modified asphalt of 60-70 weight %, the emulsifier of 1-4 weight %, the antistripping agent of 0.1-0.5 weight % and the water of 28-38 weight %, the emulsifier contains the first emulsifier and the second emulsifier, first emulsifier is lignin amine, one of alkylamide polyamines and polyethylene polyamine are a variety of, second emulsifier is alkylamine, one of alkyl propylene diamine and alkyl quaternary ammonium salts are a variety of, the weight ratio of first emulsifier and the second emulsifier is 1-9:1.Emulsified asphalt provided by the invention and building stones have stronger adhesion strength, improve the service life of the mixture formed by the emulsified asphalt, improve demulsification curing rate of the mixture in the compacting process that paves, and the Emulsified Asphalt Mixture high-temperature behavior also with higher and good water resistant stability formed.
Description
Technical field
The present invention relates to a kind of emulsified asphalts and preparation method thereof.
Background technique
With the development of domestic economy, highway construction is also being skyrocketed through, and is maked rapid progress, current most of highway road
Face is realized by hot-mix asphalt mixture, is mixed in face of the highway mileage of such quantity, so huge capital input and heat
Pressure in terms of road surface bring resource and environment, for the service life for preferably keeping road surface operating status, guaranteeing road surface
With quality, protection environment, economize on resources, realize fund minimize, maximizing the benefits, preventive maintenance be asphalt pavement maintenance most
Good means.
Each breeding maintenance technology is widely applied, at present using more such as crushed stone sealing technology, slurry seal,
Micro zooming and ultra-thin wearing layer etc..However these technologies still have some shortcomings: crushed stone sealing, slurry seal, micro- table
Place's technology belongs to cold mixing and cold paving technique, but construct thickness is thin, nothing rolls, service life of road surface is short, comprehensive performance compared with
Difference, driving noise are larger；Ultra-thin wearing layer belongs to the scope that heat construction supports maintenance, there is energy consumption height although better performances
Deficiency.Therefore, research and develop one kind can room temperature construction and comprehensive performance be close to or up to heated bitumen thin overlay performance
High grade pavement support maintenance technology be of great significance.
Summary of the invention
The purpose of the present invention is overcoming the drawbacks described above of the prior art, a kind of emulsified asphalt and preparation method thereof is provided.
The present invention provides a kind of emulsified asphalt, and on the basis of the total amount of the emulsified asphalt, which contains 60-70 weight
Measure the polymer modified asphalt of %, the emulsifier of 1-4 weight %, the antistripping agent of 0.1-0.5 weight % and 28-38 weight %
Water, wherein the emulsifier contains the first emulsifier and the second emulsifier, and first emulsifier is lignin amine, alkyl acyl
One of amine polyamines and polyethylene polyamine are a variety of, and the second emulsifier is alkylamine, alkyl propylene diamine and alkyl quaternary ammonium salts
One of or it is a variety of, the weight ratio of first emulsifier and the second emulsifier is 1-9:1.
The present invention also provides the preparation methods of above-mentioned emulsified asphalt, this method comprises: by polymer modified asphalt, emulsification
Agent, antistripping agent and water are mixed and are emulsified.
Emulsified asphalt provided by the invention and building stones have stronger adhesion strength, the loose of building stones are avoided, to mention
The service life for the mixture that high emulsified asphalt provided by the present invention is formed；And mixture is improved in the compacting process that paves
In demulsification curing rate, accelerate molding, quick open to traffic；The emulsified asphalt that emulsified asphalt provided by the present invention is formed is mixed
It closes and expects high-temperature behavior also with higher and good water resistant stability, be suitable for bituminous pavement wearing course.Therefore the present invention mentions
The emulsified asphalt of confession is suitable as the dedicated emulsified asphalt of cold mixing and cold paved mixture.
In addition, the Emulsified Asphalt Mixture gradation design formed by emulsified asphalt of the invention, in conjunction with continuous grading and
The characteristics of gap gradation, increases road surface thickness and construction depth, can be improved the surface characteristic of supercrust, improves traffic safety
Property, enhance road surface comprehensive performance.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of emulsified asphalt, the emulsified asphalt contain polymer modified asphalt, emulsifier, antistripping agent and
Water.Wherein, on the basis of the total amount of the emulsified asphalt, the content of the polymer modified asphalt is 60-70 weight %, preferably
60-65 weight %；The content of the emulsifier is 1-4 weight %, preferably 1-3 weight %；The content of the antistripping agent is
0.1-0.5 weight %, preferably 0.1-0.3 weight %；The content of the water is 28-38 weight %, preferably 32-38 weight
Measure %.
According to the present invention, the emulsifier contains the first emulsifier and the second emulsifier, and first emulsifier is wooden
Plain amine, alkylamide polyamines and polyethylene polyamine；Second emulsifier is alkylamine, alkyl propylene diamine and alkyl quaternary ammonium salts
One of or it is a variety of.Mentioned emulsifier can be commercially available, for example, being commercially available from Tianjin Conservation Chemical Technology Co., Ltd.
It is real to be commercially available from virtue dimension for the alkyl propylene diamine emulsifier that the alkylamide polyamines emulsifier and the trade mark that the trade mark is 801U are 802D
Lignin amine emulsifier that alkyl amine emulsifier that the trade mark of big gram of (China) Investment Co., Ltd is AA63D, the trade mark are MQ3 and
The trade mark is the lignin amine emulsifier of W5.
The weight ratio of first emulsifier and the second emulsifier is 1-9:1, preferably 2-7:1.The present invention by using
With what specific consumption proportion was formed (type sun is split fastly including the first emulsifier (slow breaking cationic emulsifier) and the second emulsifier
Ionic emulsifying agent and/or in split type cationic emulsifier) it is compound cation emulsified, improve mixture and be compacted paving
Demulsification curing rate in journey accelerates molding；And the service life of the mixture formed by the emulsified asphalt is improved, and make
Obtain the mixture high-temperature behavior also with higher and good water resistant stability formed by the emulsified asphalt.
In order to obtain better emulsifying effectiveness, under preferable case, first emulsifier is lignin trimethylamine, lignin
One of dimethylamine, laurylamide Quito amine, octadecyl amide Quito amine and polyethylene polyamine are a variety of；Described
Two emulsifiers are hexadecylamine, octadecylamine, cetyl propylene diamine, octadecyl propylene diamine, octadecyl three
In ammonio methacrylate, hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide and Cetyltrimethylammonium bromide
It is one or more.In preferred situation, first emulsifier is polyethylene polyamine, lignin trimethylamine and octadecyl
One of amide groups polyamines is a variety of, and second emulsifier is cetyl trimethylammonium bromide, cetyl propylene two
One of amine and octadecyltrimethylammonium chloride are a variety of.
In the preferred embodiment of the present invention, when first emulsifier is polyethylene polyamine, lignin front three
One of amine and octadecyl amide Quito amine are a variety of, and second emulsifier is cetyl trimethylammonium bromide, ten
One of six alkyl propylene diamines and octadecyltrimethylammonium chloride are a variety of, and first emulsifier and the second emulsification
When the weight ratio of agent is 2-7:1, emulsified asphalt according to the present invention and building stones have stronger adhesion strength, avoid building stones
Loosely, to improve the service life of the mixture formed by emulsified asphalt of the present invention；And mixture is improved in the pressure that paves
Demulsification curing rate during reality accelerates molding, quick open to traffic；And the emulsified asphalt as made from the emulsified asphalt mixes
It closes and expects high-temperature behavior with higher and good water resistant stability, be suitable for bituminous pavement wearing course.
According to the present invention, the antistripping agent is that commonly used in the art capable of playing enhances emulsified asphalt and the centre that gathers materials
Adhesion strength various antistripping agents.Such as it can be coughed up for alkylated pyrazole, alkyl imidazole, alkyl thiazole, alkyl imidazoline, alkyl quinoline
One of quinoline, tall oil fatty amine, tall oil imidazoles, tall oil pyrroles and tall oil thiazole are a variety of.Wherein, alkylated pyrazole
It coughs up, the alkyl in alkyl imidazole, alkyl thiazole, alkyl imidazoline and alkyl quinoline refers to that carbon atom number is the full of 12-22
With alkane or unsaturated alkyl.Under preferable case, the antistripping agent is octadecylimidazoline and/or tall oil imidazoles.
Emulsified asphalt according to the present invention contains polymer modified asphalt, and the polymer modified asphalt can be this field
Common various using matrix pitch as base-material, pitch obtained from being modified using polymer to matrix pitch.
According to the present invention, the amount of the polymer modifiers can be the conventional selection of this field.Generally, relative to
The matrix pitch of 100 parts by weight, the dosage of the polymer modifiers can be 1.5-10 parts by weight, preferably 2-8 weight
Measure part.
Emulsified asphalt according to the present invention contains high molecular polymer modifying agent and antistripping agent, so that according to the present invention
Emulsified asphalt and building stones have stronger adhesion strength, the loose of building stones are avoided, to improve by emulsified asphalt of the present invention
The service life of the mixture of formation.
According to the present invention, the matrix pitch can be pitch (such as coal tar pitch, stone in various sources commonly used in the art
Oil asphalt and bitumen).Specifically, the matrix pitch can be the asphalt that needle penetration is 60-100, such as being capable of quotient
No. 70 road asphalts and/or No. 90 road asphalts bought.
Polymer modifiers in the polymer modified asphalt can be used in changing matrix pitch to be various
Property, to prepare the polymer modifiers of polymer modified asphalt.For example, the polymer modifiers can be selected from styrene-
Butadiene-styrene ternary block polymer and/or polyethylene.Preferably, the polymer modifiers is styrene-fourth two
Alkene-polystyrene ternary segmented copolymer.
According to the present invention, the styrene-butadiene-styrene ternary block copolymer can be commonly used in the art each
Kind can be as the styrene-butadiene-styrene ternary block copolymer of the polymer modifiers of matrix pitch.Preferably,
On the basis of the total amount of the styrene-butadiene-styrene ternary block copolymer, the structural unit that is formed by styrene
Content is 20-40 weight %, and the content of the structural unit formed by butadiene is 60-80 weight %, the emulsification drip being consequently formed
Blueness can have stronger adhesion strength with building stones, avoid the loose of building stones, and extend by emulsified asphalt shape of the present invention
At mixture service life；Meanwhile it is also with higher high temperatures by the Emulsified Asphalt Mixture that the emulsified asphalt is formed
It can be with good water resistant stability.
According to the present invention, not special to the molecular weight of the styrene-butadiene-styrene ternary block copolymer
It limits, under preferable case, the average molecular weight of the styrene-butadiene-styrene ternary block copolymer is 8-13 ten thousand, more
Preferably 10-12 ten thousand.
According to the present invention, it is contemplated that increase the compatibility of matrix pitch and polymer and improve polymer modified asphalt
Stability may be incorporated into stabilizer and/or compatilizer in the preparation process of the polymer modified asphalt.Preferable case
Under, in the preparation process of the polymer modified asphalt, it may be incorporated into stabilizer and compatilizer.
The present invention does not limit the dosage of the compatilizer specifically, generally, the base relative to 100 parts by weight
Matter pitch, the dosage of the compatilizer can be 0-10 parts by weight, preferably 1-9.5 parts by weight.
The present invention does not limit the dosage of the stabilizer specifically, generally, the base relative to 100 parts by weight
Matter pitch, the dosage of the stabilizer can be 0.1-1 parts by weight, preferably 0.2-0.6 parts by weight.
The compatilizer various can be improved between matrix pitch and polymer modifiers to be commonly used in the art
The substance of compatibility, such as: the compatilizer can be inverted sequence technique bright stock when by-product solvent-extracted oil and/or
The solvent-extracted oil of petroleum catalytic cracking recycle oil, wherein solvent refers to N-Methyl pyrrolidone, furfural or phenol solvent, extraction oil
In aromatic hydrocarbon content be greater than 80 weight %.Specifically, the compatilizer can be aromatic hydrocarbons extraction oil and/or furfural extract oil.
The stabilizer can be the various substances that can be improved polymer modified asphalt stability commonly used in the art, example
As the stabilizer can be in elemental sulfur, sulfur-containing compound, polyolefin, inorganic acid, inorganic, metal oxide and inorganic clay
One kind and it is a variety of.Wherein, the sulfur-containing compound can be polysulfide and/or diaryl disulfide；The polyolefin
It can be hycar and/or polyisobutene；The inorganic acid can be phosphoric acid, the inorganic metal
Object can be zinc oxide；The inorganic clay can be montmorillonite and/or kaolin.
In addition, the present invention also provides a kind of methods for preparing above-mentioned emulsified asphalt, this method comprises: by polymer modification
Pitch, emulsifier, antistripping agent and water are mixed and are emulsified.
In the case of with the method for the invention it is preferred to, polymer modified asphalt, emulsifier, antistripping agent and water are carried out
Mixing and emulsification include:
(1) with or without stabilizer and/or compatilizer in the case where, matrix pitch and polymer modifiers are mixed
It closes, to prepare 170-180 DEG C of polymer modified asphalt；
(2) emulsifier, antistripping agent and water are mixed, obtains 55-65 DEG C of soap lye；
(3) polymer modified asphalt that step (1) obtains is mixed and is emulsified with the soap lye that step (2) obtains.
According to the method for the present invention, in step (1), the polymer modified asphalt can be using commonly used in the art various
Method is made.For example, matrix pitch to be heated to 170-180 DEG C of temperature, then mixed with polymer modifiers, to prepare
170-180 DEG C of polymer modified asphalt.The mixed time can be 3-5 hours.
From the compatibility for further increasing matrix pitch and the polymer modifiers and improve polymer modified asphalt
The angle of stability set out, mix described in step (1) and preferably carried out in the presence of compatilizer and/or stabilizer, into one
Step preferably carries out in the presence of compatilizer and stabilizer.For example, can backward temperature be first in 170-180 DEG C of matrix pitch
Polymer modifiers, compatilizer and stabilizer are added, it is clipped to be uniformly mixed, to obtain polymer modified asphalt.
In order to make matrix pitch and polymer modifiers that there is better compatibility, step (1) polymer modifiers pair
The method that matrix pitch is modified further includes that the mixing of matrix pitch, polymer modifiers, compatilizer and stabilizer is resulting
Mixture, which is placed in 170-180 DEG C of baking oven, to carry out sufficiently swelling development 2-5 hours.
According to the method for the present invention, in step (2), the emulsifier, antistripping agent is mixed with water, obtain 55-65 DEG C
Soap lye.
According to the method for the present invention, when emulsifier, antistripping agent and water being mixed to form soap lye, in order to obtain better cream
Change effect, the pH value of the preferably described soap lye is acidity.Generally, the pH value of the mixture is 1.8-2.2.Ability can be used
Commonly various methods adjust the pH value of the soap lye in domain, are not particularly limited, repeats no more herein.
According to the method for the present invention, in step (3), polymer modified asphalt obtained in step (1) and step (2) are obtained
To the soap lye condition that is mixed and emulsified be not particularly limited, as long as guaranteeing to prepare emulsified asphalt.Generally,
The condition of the emulsification includes: that emulsification times are 5-15s, revolving speed 3000-5000rpm.
According to the method for the present invention, the emulsification can commonly use the cream that can be realized mixing and emulsification function in the art
Middle progress is set in makeup.Such as: colloid mill emulsifier.
A kind of preferred embodiment according to the present invention, the preparation method of the emulsified asphalt include:
(1) in the presence of compatilizer and stabilizer, matrix pitch is mixed with polymer modifiers, to prepare 170-
180 DEG C of polymer modified asphalt；
(2) emulsifier, antistripping agent and water are mixed, obtains 55-65 DEG C of soap lye, the pH value for adjusting gained soap lye is
1.8-2.2；
(3) polymer modified asphalt that step (1) obtains is mixed and is emulsified with the soap lye that step (2) obtains.
According to the method for the present invention, the matrix pitch, polymer modifiers, emulsifier, antistripping agent, stabilizer and phase
Hold agent type with it is described previously identical, details are not described herein.The matrix pitch, polymer modifiers, emulsifier, anti-strip
Agent, stabilizer, water and compatilizer dosage so that the content of each component can satisfy above in the emulsified asphalt finally prepared
Subject to the requirement.
The present invention will be described in detail with comparative example with reference to embodiments.
In following embodiment and comparative example, the performance measurement being related to is as follows:
(1) using the de-emulsification speed of the measurement emulsified asphalt of method specified in T0658-1993；Using in T0653-1993
The particulate ion charge of defined method measurement emulsified asphalt；Using the measurement emulsified asphalt of method specified in T0652-1993
Surplus on sieve, determination condition 1.18mm；Using the evaporation residual of the measurement emulsified asphalt of method specified in T0651-1993
Object content；Using the Saybolt viscosity of the measurement emulsified asphalt of method specified in T0623-1993；Using being advised in T0655-1993
The storage stability of fixed method measurement emulsified asphalt；Emulsified asphalt and mineral aggregate are measured using method specified in T0654-2011
Adhesiveness (wrapping test)；
(2) using the measurement of method specified in T0604-2011 matrix pitch, polymer modified asphalt and emulsified asphalt
The needle penetration of evaporated residue；Using the measurement matrix drip of (ring and ball method) method of bituminous softening-point test specified in T0606-2011
The softening point of the evaporated residue of green, polymer modified asphalt and emulsified asphalt；Base is measured using the method in T0605-2011
5 DEG C of ductilities of the evaporated residue of matter pitch, polymer modified asphalt and emulsified asphalt；It is surveyed using the method in T0606-2011
Determine 15 DEG C of ductilities of the evaporated residue of emulsified asphalt；Using the measurement of method specified in T0662-2000 matrix pitch, polymerization
The elasticity of the evaporated residue of object modified pitch and emulsified asphalt restores (10 DEG C)；It is surveyed using method specified in ASTM D226
Determine the force ductility ratio (4 DEG C, 5cm/min) of emulsified asphalt；Using the measurement emulsified asphalt of method specified in T0624-2011
The viscous toughness (25 DEG C, 5cm/min) of evaporated residue；Using the evaporation of the measurement emulsified asphalt of method specified in T0624-2011
The toughness (25 DEG C, 5cm/min) of residue；
(3) using the measurement of method specified in T0625-2011 matrix pitch, the rotary viscosity of polymer modified asphalt
(135℃)；The isolation test of matrix pitch, polymer modified asphalt is carried out using method specified in T0661-2011；Using
Method specified in T0610-2011 measures matrix pitch, polymer modified asphalt residue after rotating thin film heat run
Mass loss；It is heated using the measurement of method specified in T0604-2011 matrix pitch, polymer modified asphalt through rotating thin film
The penetration ratio of residue after test；Matrix pitch, polymer modified asphalt are measured using method specified in T0610-2011
5 DEG C of ductilities of residue after rotating thin film heat run；
(4) according to the method in JTG F40-2004, Emulsified Asphalt Mixture voidage, Marshall stability, residual is measured
Stay stability, freeze-thaw split TSR and dynamic stability.Wherein, voidage within the scope of index request is smaller to be shown according to this
The emulsified asphalt and building stones of invention have stronger adhesion strength, and consolidation effect is good, avoids the loose of building stones；In index request
Marshall stability, residual stability, freeze-thaw split TSR in range show more greatly the cream formed by emulsified asphalt of the invention
Changing asphalt has good water resistant stability；Dynamic stability within the scope of index request shows more greatly by of the invention
The Emulsified Asphalt Mixture high-temperature behavior with higher that emulsified asphalt is formed.
Embodiment 1
The present embodiment is for illustrating emulsified asphalt according to the present invention and preparation method thereof.
The compositing formula (in parts by weight) of emulsified asphalt:
Wherein, matrix pitch is No. 70 road asphalts for being commercially available from Zhenghai refinery, needle penetration 68.1；Polymer modifiers
To be commercially available from the s-B-S terpolymer that the trade mark of Yueyang petrochemical industry is SBS791H, wherein with benzene second
On the basis of alkene-butadiene-styrene terpolymer total amount, the content of the structural unit formed by styrene is 30 weights
% is measured, the content of the structural unit formed by butadiene is 70 weight %；The s-B-S terpolymer
Average molecular weight be 110,000；
Compatilizer is that the aromatic hydrocarbons that arene content is 92 weight % extracts oily (being commercially available from Jinan Refinery) out；
Emulsifier is to split solidifying type cationic emulsifier W5 fastly slowly (it is public to be commercially available from real big gram of (China) limited investment of virtue dimension
Department, main component is lignin amine) and split solidifying type cationic emulsifier MQ3 fastly slowly and (be commercially available from real big gram (China) throwing of virtue dimension
Co., Ltd is provided, main component is lignin amine) and split type cationic emulsifier AA63D fastly and (be commercially available from real big gram of virtue dimension
(China) Investment Co., Ltd, main component are alkylamine) compound emulsifying agent, wherein split solidifying type cationic emulsifier fastly slowly
Total amount be 2.0 parts by weight, the dosage of W5 is 1.5 parts by weight, and the dosage of MQ3 is 0.5 parts by weight；Type cationic emulsifier is split fastly
The dosage of AA63D is 0.3 parts by weight；
Sulfide stabilizer is commercially available from Shanghai Bo Qike International Trading Company Ltd, trade mark MBS；Octadecylimidazoline
It is commercially available from Shanghai Min Hao Fine Chemical Co., Ltd.
Emulsified asphalt the preparation method comprises the following steps:
Step 1: providing polymer modified asphalt
Matrix pitch is heated to 175 DEG C, polymer modifiers is then added, compatilizer is subsequently added into and sulfide is stablized
Agent after high speed shear 3 hours, then makes gained mixture sufficiently molten in 175 DEG C of baking ovens after mixing evenly under stirring
Swollen development 4 hours, to obtain polymer modified asphalt.The properties of resulting polymers modified pitch are shown in Table 1.
Step 2: preparing emulsified asphalt
Emulsifier and octadecylimidazoline are added into 55 DEG C of water, hydrochloric acid is then added, adjusts the pH value of solution
It is 2.0, stirs evenly, obtain soap lye.
Soap lye is sent into colloid mill emulsifier simultaneously with polymer modified asphalt and is emulsified, wherein polymer modification
The temperature of pitch is 175 DEG C, and the temperature of soap lye is 55 DEG C, the revolving speed in colloid mill emulsifier is 3000rpm, cut within 10 seconds
Mixing is cut, emulsified asphalt A1 of the invention is made.
Needle penetration, softening point, 5 DEG C of ductilities, the elasticity for measuring the Asphalt Emulsion Evaporation Residue of preparation are restored (10 DEG C), are surveyed
Power Ductility ratio (4 DEG C, 5cm/min), viscous toughness (25 DEG C, 5cm/min) and toughness (25 DEG C, 5cm/min)；And emulsified asphalt
De-emulsification speed, particulate ion charge, surplus, evaporated residue content, Saybolt viscosity, storage stability and rough set on sieve
The adhesiveness (wrapping test) of material, is as a result given in Table 2.
Comparative example 1
Emulsified asphalt is prepared using method same as Example 1, unlike, using the cetyl three of identical weight part
Methyl bromide ammonium replaces splitting fast solidifying type cationic emulsifier MQ3, W5 slowly and splits the Composite Milk of type cationic emulsifier AA63D fastly
Agent obtains reference emulsified asphalt D1.The properties of resulting polymers modified pitch are shown in Table 1, gained reference emulsified asphalt
Properties are shown in Table 2.
Comparative example 2
Emulsified asphalt is prepared using method same as Example 1, unlike, it is free of in the compositing formula of emulsified asphalt
Polymer modifiers s-B-S terpolymer, compatilizer and sulfide stabilizer.
Reference emulsified asphalt the preparation method comprises the following steps:
(1) matrix pitch is heated to 175 DEG C；
(2) emulsifier and octadecylimidazoline are added into 55 DEG C of water, hydrochloric acid is then added, adjusts the pH of solution
Value is 2.0, stirs evenly, obtains soap lye；
(3) by soap lye that step (2) obtains and the matrix pitch that step (1) obtains and meanwhile be sent into colloid mill emulsifier into
Row emulsification, wherein the temperature of matrix pitch is 175 DEG C, and the temperature of soap lye is 55 DEG C, and the revolving speed in colloid mill emulsifier is
3000rpm carries out 10 seconds shear-mixeds, and reference emulsified asphalt D2 is made.The properties of matrix pitch are shown in Table 1, gained ginseng
Properties than emulsified asphalt are shown in Table 2.
Embodiment 2
The present embodiment is for illustrating emulsified asphalt according to the present invention and preparation method thereof.
The compositing formula (in parts by weight) of emulsified asphalt:
Wherein, matrix pitch is No. 70 road asphalts for being commercially available from Zhenghai refinery, needle penetration 68.1；
Polymer modifiers is to be commercially available from the s-B-S ternary that the trade mark of Yueyang petrochemical industry is SBS791H
Copolymer, wherein on the basis of the total amount of s-B-S terpolymer, the structure list that is formed by styrene
The content of member is 30 weight %, and the content of the structural unit formed by butadiene is 70 weight %；Styrene-butadiene-the benzene
The average molecular weight of ethylene-dien terpolymer is 110,000；
Compatilizer is the furfural extract oil (being commercially available from Jinan Refinery) that arene content is 92 weight %；
Emulsifier is to split solidifying type cationic emulsifier 801U fastly slowly (to be commercially available from Tianjin Conservation Chemical Technology Co., Ltd., mainly
Ingredient is alkylamide polyamines) and split solidifying type cationic emulsifier MQ3 fastly slowly (being commercially available from virtue dimension real big gram (China) and investing has
Limit company, main component are lignin amine) and split fastly type cationic emulsifier AA63D (be commercially available from real big gram of virtue dimension (in
State) Investment Co., Ltd, main component is alkylamine) compound emulsifying agent, wherein split the total of fast solidifying type cationic emulsifier slowly
Amount is 2.3 parts by weight, and the dosage of 801U is 1.2 parts by weight, and the dosage of MQ3 is 1.1 parts by weight；Type cationic emulsifier is split fastly
The dosage of AA63D is 0.5 parts by weight,
Sulfide stabilizer is commercially available from Shanghai Bo Qike International Trading Company Ltd, trade mark MBS；Octadecylimidazoline
It is commercially available from Shanghai Min Hao Fine Chemical Co., Ltd.
Emulsified asphalt the preparation method comprises the following steps:
Step 1: providing polymer modified asphalt
Matrix pitch is heated to 170 DEG C, polymer modifiers is then added, compatilizer is subsequently added into and sulfide is stablized
Agent after high speed shear 4 hours, then makes gained mixture sufficiently molten in 175 DEG C of baking ovens after mixing evenly under stirring
Swollen development 4 hours, to obtain polymer modified asphalt.The properties of resulting polymers modified pitch are shown in Table 3.
Step 2: preparing emulsified asphalt
Emulsifier and octadecylimidazoline are added into 60 DEG C of water, hydrochloric acid is then added, adjusts the pH value of solution
It is 2.0, stirs evenly, obtain soap lye.
Soap lye is sent into colloid mill emulsifier simultaneously with polymer modified asphalt and is emulsified, wherein polymer modification
The temperature of pitch is 170 DEG C, and the temperature of soap lye is 60 DEG C, the revolving speed in colloid mill emulsifier is 4000rpm, cut within 15 seconds
Mixing is cut, emulsified asphalt A2 of the invention is made.
Needle penetration, softening point, 5 DEG C of ductilities, the elasticity for measuring the Asphalt Emulsion Evaporation Residue of preparation are restored (10 DEG C), are surveyed
Power Ductility ratio (4 DEG C, 5cm/min), viscous toughness (25 DEG C, 5cm/min) and toughness (25 DEG C, 5cm/min)；And emulsified asphalt
De-emulsification speed, particulate ion charge, surplus, evaporated residue content, Saybolt viscosity, storage stability and rough set on sieve
The adhesiveness (wrapping test) of material, is as a result given in Table 4.
Comparative example 3
Emulsified asphalt is prepared using formula same as Example 2, unlike, using the SBS latex of identical weight part
Instead of polymer modifiers s-B-S terpolymer.
SBS latex is the s-B-S three for being commercially available from Shanxi Xiyuefa Road and Bridge Building Materials Co., Ltd.
Membered copolymer latex, wherein on the basis of the total amount of s-B-S terpolymer, formed by styrene
The content of structural unit is 30 weight %, and the content of the structural unit formed by butadiene is 70 weight %；Solid content is 52 weights
Measure %；The average molecular weight of SBS latex is 110,000；
Reference emulsified asphalt the preparation method comprises the following steps:
Step 1:
Emulsifier and octadecylimidazoline are added into 60 DEG C of water, hydrochloric acid is then added, adjusts the pH value of solution
It is 2.0, stirs evenly, obtain soap lye；Then gained soap lye is sent into colloid mill cream with the matrix pitch for being heated to 170 DEG C simultaneously
Change and emulsified in device, the revolving speed in colloid mill emulsifier is 4000rpm, carries out 15 seconds shear-mixeds, and emulsified asphalt is made.
The properties of gained emulsified asphalt are shown in Table 3.
Step 2: polymer modification
Through high speed shear 3 hours, ginseng is made after mixing evenly in emulsified asphalt and SBS the latex mixing that the first step is obtained
Than emulsified asphalt D3.The properties of gained reference emulsified asphalt are shown in Table 4.
Embodiment 3
The present embodiment is for illustrating emulsified asphalt according to the present invention and preparation method thereof.
The compositing formula (in parts by weight) of emulsified asphalt:
Wherein, matrix pitch is No. 90 road asphalts for being commercially available from population in Zhenhai Refine-Chemical Company, and the needle penetration of the matrix pitch is
91；
Polymer modifiers is to be commercially available from the benzene second that the trade mark of Tianjin Le Jinbotian Chemical Co., Ltd. is LG501
Alkene-butadiene-styrene terpolymer, wherein on the basis of the total amount of s-B-S terpolymer,
The content of the structural unit formed by styrene is 31 weight %, and the content of the structural unit formed by butadiene is 69 weights
Measure %；The average molecular weight of the s-B-S terpolymer is 100,000；
Compatilizer is the furfural extract oil (being commercially available from Jinan Refinery) that arene content is 92 weight %；
To split solidifying type cationic emulsifier polyethylene polyamine fastly slowly, (be commercially available from Henan Luohe sky dragon Chemical Group has emulsifier
Limit company) and in split type cationic emulsifier 802D and (be commercially available from Tianjin Conservation Chemical Technology Co., Ltd., main component is alkyl
Propylene diamine) and cetyl trimethylammonium bromide (being commercially available from Tianjin Conservation Chemical Technology Co., Ltd.) compound emulsifying agent,
In, the dosage for splitting fast solidifying type cationic emulsifier polyethylene polyamine slowly is 1.4 parts by weight, and the dosage of 802D is 0.3 parts by weight, ten
Six alkyl trimethyl ammonium bromides are 0.3 parts by weight；
Sulfide stabilizer is commercially available from Shanghai Bo Qike International Trading Company Ltd, trade mark MBS；Octadecylimidazoline
It is commercially available from Shanghai Min Hao Fine Chemical Co., Ltd.
Emulsified asphalt the preparation method comprises the following steps:
Step 1: providing polymer modified asphalt
Matrix pitch is heated to 180 DEG C, polymer modifiers is then added, compatilizer is subsequently added into and sulfide is stablized
Agent after high speed shear 5 hours, then makes gained mixture sufficiently molten in 180 DEG C of baking ovens after mixing evenly under stirring
Swollen development 4 hours, to obtain polymer modified asphalt.The properties of resulting polymers modified pitch are shown in Table 5.
Step 2: preparing emulsified asphalt
Emulsifier and octadecylimidazoline are added into 65 DEG C of water, hydrochloric acid is then added, adjusts the pH value of solution
It is 2.0, stirs evenly, obtain soap lye.
Soap lye is sent into colloid mill emulsifier simultaneously with polymer modified asphalt and is emulsified, wherein polymer modification
The temperature of pitch is 180 DEG C, and the temperature of soap lye is 65 DEG C, the revolving speed in colloid mill emulsifier is 3000rpm, cut within 12 seconds
Mixing is cut, emulsified asphalt A3 of the invention is made.
Needle penetration, softening point, 5 DEG C of ductilities, the elasticity for measuring the Asphalt Emulsion Evaporation Residue of preparation are restored (10 DEG C), are surveyed
Power Ductility ratio (4 DEG C, 5cm/min), viscous toughness (25 DEG C, 5cm/min) and toughness (25 DEG C, 5cm/min)；And emulsified asphalt
De-emulsification speed, particulate ion charge, surplus, evaporated residue content, Saybolt viscosity, storage stability and rough set on sieve
The adhesiveness (wrapping test) of material, force ductility ratio (4 DEG C, 5cm/min), viscous toughness (25 DEG C, 5cm/min) and toughness (25 DEG C,
5cm/min), it is as a result given in Table 6.
Comparative example 4
Emulsified asphalt is prepared using method same as Example 3, unlike, it is not added in the compositing formula of emulsified asphalt
Enter antistripping agent octadecylimidazoline, obtains reference emulsified asphalt D4.The properties of resulting polymers modified pitch are shown in Table
5, the properties of gained reference emulsified asphalt are shown in Table 6.
Comparative example 5
Emulsified asphalt is prepared using formula and method same as Example 1, unlike, solidifying type cationic galactomannan fastly is split slowly
The weight ratio of agent (W5 and MQ3) and the dosage of fast solidifying type emulsifier (AA63D) is 13:1, wherein the dosage of W5 and the use of MQ3
Amount obtains reference emulsified asphalt D5 than being 3:1.The result shows that working as ginseng since obtained reference emulsified asphalt de-emulsification speed is excessively slow
When forming mixture than emulsified asphalt, it is unable to rapid shaping.
Table 1
Table 2
When the emulsifier used emulsifies for the first emulsifier provided by the invention and second it can be seen from the data of table 2
Dosage form at mixed emulsifier when, the emulsified asphalt that method provided by the present invention obtains have good storage stability,
Good toughness and viscous toughness.
Table 3
Table 4
When the polymer modifiers used is total to for s-B-S ternary it can be seen from the data of table 4
When polymers, the emulsified asphalt that method provided by the present invention obtains has good storage stability, good toughness and glues tough
Property.
Table 5
Table 6
Test case
Using the emulsified asphalt of embodiment 1-3 and comparative example 1-5, Emulsified Asphalt Mixture performance test is carried out.
The preparation method of mixture include: by emulsified asphalt A1-A3 and D1-D5 respectively with gather materials, filler and water are at 25 DEG C
Lower progress mix 2min, wherein gather materials including coarse aggregate and fine aggregate, coarse aggregate is that (3-5mm basalt and 5-10mm are profound for rubble
Wu Yan), fine aggregate is aggregate chips (0-3mm limestone), and the weight ratio of coarse aggregate and fine aggregate is 4.3:1, and filler is by limestone deposit
Powder and No. 42.5 portland cement compositions.Using marshall compaction instrument (Wuxi petroleum experimental instruments and equipment limited, model WSY-
103) it forms, in 60 DEG C of convection oven after health for 24 hours, demoulding forms test specimen.
The formula of mixture: on the basis of the total amount of Emulsified Asphalt Mixture, the dosage gathered materials is 88.4 weight %,
The dosage of the filler is 4.1 weight %, and the dosage of the water is 1.1 weight %, and the dosage of the emulsified asphalt is 6.4 weights
Measure %.
It is public that limestone, basalt, limestone mineral powder, portland cement are purchased from Hypon gold road construction engineering finite
Department.Gather materials, the performance test of No. 42.5 portland cements is shown in Table 7 and table 9 respectively, the grading limit gathered materials is shown in Table 8, emulsified asphalt
The gradation of mixture is shown in Table 10.
For simulated field conditions, after track molding, room temperature conserves laggard driving rut experiment in 3 days, according to JTG F40-
Method in 2004, measure the voidage of Emulsified Asphalt Mixture, Marshall stability, residual stability, freeze-thaw split TSR with
And dynamic stability, it the results are shown in Table 11.
Table 7
Table 8
| Screen size/mm | 13.2 | 9.5 | 4.75 | 2.36 | 1.18 | 0.6 | 0.3 | 0.15 | 0.075 |
| Percent of pass/weight % | 100 | 80.7 | 30.8 | 22.4 | 16.5 | 13.5 | 8.6 | 6.5 | 4.4 |
Table 9
Table 10
Table 11
Note: for simulated field conditions, after track molding, wheel tracking test is carried out after room temperature maintenance 3d.
By the data of table 11, by embodiment 1 as can be seen that when using single emulsifier hexadecane compared with comparative example 1
When base trimethylammonium bromide, by the adhesion strength variation with building stones for the Emulsified Asphalt Mixture that reference emulsified asphalt is formed, and
And the water resistant stability and high-temperature behavior of the Emulsified Asphalt Mixture are deteriorated；It can be with compared with the data of comparative example 2 by embodiment 1
Find out, when being added without polymer modifiers s-B-S ternary during preparing polymer modified asphalt
When copolymer, the Emulsified Asphalt Mixture that is formed by reference emulsified asphalt is deteriorated with the adhesion strengths of building stones, and the emulsification
The water resistant stability and high-temperature behavior of asphalt are deteriorated；By embodiment 1 as can be seen that will compared with the data of comparative example 5
When the weight ratio of first emulsifier and the second emulsifier is 1-9:1, emulsified asphalt according to the present invention has stronger with building stones
Adhesion strength, consolidation effect is good, avoids the loose of building stones；The Emulsified Asphalt Mixture tool formed by emulsified asphalt of the invention
There are good water resistant stability and higher high-temperature behavior；By embodiment 2 as can be seen that making compared with the data of comparative example 3
Polymer modifiers s-B-S terpolymer is replaced using SBS latex during standby emulsified asphalt,
The Emulsified Asphalt Mixture formed by reference emulsified asphalt is deteriorated with the adhesion strengths of building stones, and the Emulsified Asphalt Mixture
Water resistant stability and high-temperature behavior be deteriorated；By embodiment 3 as can be seen that when preparation emulsification drip compared with the data of comparative example 4
It is added without antistripping agent in green process, by the adhesion strength with building stones for the Emulsified Asphalt Mixture that reference emulsified asphalt is formed
It is deteriorated, and the water resistant stability and high-temperature behavior of the Emulsified Asphalt Mixture are deteriorated.Therefore, emulsification drip provided by the present invention
The mixture that blueness is formed is suitable for preparing bituminous pavement wearing course.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (11)
1. a kind of emulsified asphalt, on the basis of the total amount of the emulsified asphalt, which contains the polymer of 60-70 weight %
Modified pitch, the emulsifier of 1-4 weight %, the antistripping agent of 0.1-0.5 weight % and 28-38 weight % water, wherein it is described
Emulsifier contains the first emulsifier and the second emulsifier, and first emulsifier is lignin amine, alkylamide polyamines and more second
One of alkene polyamines is a variety of, and second emulsifier is one of alkylamine, alkyl propylene diamine and alkyl quaternary ammonium salts
Or it is a variety of, the weight ratio of first emulsifier and the second emulsifier is 1-9:1, and the polymer modified asphalt passes through with polymerization
Object modifying agent is modified matrix pitch and is made, and the polymer modifiers is that s-B-S ternary is embedding
Section copolymer.
2. emulsified asphalt according to claim 1, wherein first emulsifier is lignin trimethylamine, lignin two
One of methylamine, laurylamide Quito amine, octadecyl amide Quito amine and polyethylene polyamine are a variety of；Described second
Emulsifier is hexadecylamine, octadecylamine, cetyl propylene diamine, octadecyl propylene diamine, octadecyl front three
In ammonium chloride, hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide and Cetyltrimethylammonium bromide
It is one or more.
3. emulsified asphalt according to claim 1 or 2, wherein the weight ratio of first emulsifier and the second emulsifier
For 2-7:1.
4. emulsified asphalt according to claim 1, wherein the antistripping agent is alkyl pyrroles, alkyl imidazole, alkyl thiophene
One of azoles, alkyl imidazoline, alkyl quinoline, tall oil fatty amine, tall oil imidazoles, tall oil pyrroles and tall oil thiazole
Or it is a variety of.
5. emulsified asphalt according to claim 1, wherein relative to the matrix pitch of 100 parts by weight, the polymerization
The dosage of object modifying agent is 1.5-10 parts by weight.
6. emulsified asphalt according to claim 1, wherein with s-B-S tri-block copolymerization
On the basis of the total amount of object, the content of the structural unit formed by styrene is 20-40 weight %, the structure list formed by butadiene
The content of member is 60-80 weight %.
7. emulsified asphalt according to claim 1, wherein introduced in the preparation process of the polymer modified asphalt steady
Determine agent and/or compatilizer.
8. emulsified asphalt according to claim 7, wherein described compatible relative to the matrix pitch of 100 parts by weight
The dosage of agent is 0-10 parts by weight, and the dosage of the stabilizer is 0.1-1 parts by weight.
9. a kind of method for preparing emulsified asphalt described in any one of claim 1-8, this method comprises: polymer is changed
Property pitch, emulsifier, antistripping agent and water are mixed and are emulsified.
10. according to the method described in claim 9, wherein, polymer modified asphalt, emulsifier, antistripping agent and water are carried out
Mixing and emulsification include:
(1) with or without stabilizer and/or compatilizer in the case where, matrix pitch is mixed with polymer modifiers, with
Prepare 170-180 DEG C of polymer modified asphalt；
(2) emulsifier, antistripping agent and water are mixed, obtains 55-65 DEG C of soap lye；
(3) polymer modified asphalt that step (1) obtains is mixed and is emulsified with the soap lye that step (2) obtains.
11. according to the method described in claim 10, wherein, in step (3), the condition of the emulsification includes: that emulsification times are
5-15s。
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| CN102863804A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | SBS polymer modified emulsified asphalt and preparation method |
| CN103525108A (en) * | 2013-10-24 | 2014-01-22 | 北京同华道路养护有限责任公司 | High modulus cold-mixed asphalt as well as preparation method and mixture thereof |
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| CN102863804A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | SBS polymer modified emulsified asphalt and preparation method |
| CN103525108A (en) * | 2013-10-24 | 2014-01-22 | 北京同华道路养护有限责任公司 | High modulus cold-mixed asphalt as well as preparation method and mixture thereof |
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