CN1847318A - Compositions and manufacturing methods of bitumen modifiers having complex functionality - Google Patents

Compositions and manufacturing methods of bitumen modifiers having complex functionality Download PDF

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CN1847318A
CN1847318A CNA2006100743160A CN200610074316A CN1847318A CN 1847318 A CN1847318 A CN 1847318A CN A2006100743160 A CNA2006100743160 A CN A2006100743160A CN 200610074316 A CN200610074316 A CN 200610074316A CN 1847318 A CN1847318 A CN 1847318A
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asphalt
modifying agent
acid
oil
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CN1847318B (en
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许政道
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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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/68—Plasticizers; Solvents

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to compositions of bitumen modifiers for simultaneously solving problems of high temperature plastic deformation and various cracks at low temperature that are generated on bitumen pavements at a region having hot weather in summer and cold weather in winter, and to methods for manufacturing thereof. The composition of the modifier according to the present invention comprises 1 to 300 parts by weight of at least one component from a (waste or recycled) foamed polymer resin group and a (waste, recycled or virgin) thermoplastic polymer group, 1 to 300 parts by weight of at least one from a (waste, recycled or virgin) elastomer group having double bonds, and 1 to 300 parts by weight of at least on from a (waste, recycled or virgin) plasticizer group; further, if necessary, 1 to 1500 parts by weight of filler or 1 to 100 parts by weight of a chemical reaction agent can be included. The method for manufacturing the modifier is characterized in that the composition is fed into a compounding machine (a banbury mixer, a compression kneader, a single or twin screw extruder) for carrying out the vigorous shear mixing under high temperature and pressure to form a homogenous material, then passing through a extruder die to form particles, and packaging the particles in various bags including PE bags.

Description

Asphalt modifier synthetics and manufacture method with complex functionality
[detailed description of the invention]
[goal of the invention]
[prior art in technical field that the present invention belongs to and field thereof]
The present invention relates to have the asphalt modifier synthetics and manufacture method { the Compositions and manufacturing methods of bitumen modifiershaving complex functionality} of complex functionality
The invention belongs to mixed modifier in pitch, be used for road pavement, improve the shared property and the prolongation of mating formation and mat formation the life-span.Properties-correcting agent synthetics and properties-correcting agent manufacture method among the present invention have following technical characterstic: promptly, can solve pyroplastic deformability's problem and cryogenic various be full of cracks problem that the asphalt pavement of sweltering heat in summer, winter cold district can cause simultaneously.
The synthetics that has the asphalt modifier of complex functionality among the present invention is mixed by following structure: promptly, and an above key element in (discarded or regeneration) the foaming macromolecular resin group that can improve asphalt pavement high-temperature behavior (viscous deformation resistivity) and (discarded, regeneration or novel material) thermoplastic resin group's integrant; And can improve above key element among (discarded, regeneration or novel material) elastomerics group of low-temperature performance (various be full of cracks resistivity) with dual combination structure; Can reduce additive fusing point and viscosity and can improve and pitch between an above key element among (discard, regeneration or novel material) plasticizer group of avidity.The constituent material of above-mentioned synthetics is principle to use waste materials, but recommends to use twice-laid stuff when being difficult to get above-mentioned materials, if still difficult, just actively recommends to use novel material, and this can effectively save cost, and helps waste to utilize again.
Asphalt modifier manufacturing technology among the present invention also has following characteristics: promptly, above-mentioned synthetics is put into mixing tank (Banbury mixer, pressurization kneader, single pressurization double-screw type extrusion machine), shear-mixed under high-temperature pressurizing, make impartial material, and make granular by the squeeze station of extrusion machine, cool off then and drying treatment and being stored, its quantitative package is in the various sacks that comprise the PE bag, to make the properties-correcting agent product the most at last.
The most existing modifying asphalt is sneaked into high price green wood macromolecule resin or thermoplastic elastomer in the pitch, is mainly used in the modifying asphalt manufacturing, the limited phenomenon of material usage quantity that causes high cost to cause.Therefore, can only add a small amount of (the 3-8 weight % that is about the pitch amount) modifying asphalt, improve effect so can only obtain the rerum natura of the degree that limits.For example, adopt respectively in the prior art according to SBS master's macromolecule resin of the costliness of Korean Patent communique 1999-0079717 number and 2003-0046053 number with according to 1997-0070122 number LDPE and according to 2003-0039343 number damaged tire powder or according to 2002-0034496 number SBR latex.
Up to now, existing much from the angle of resource reutilization and cost savings, adopt the patented technology of useless macromolecule resin.For example, according to Korean Patent communique 2001-0044036 number, in the process of making bituminous concrete, pulverize plastic waste, as the part of aggregate; According to No. 0122302, recovery and washing have dirt and the lower a plurality of useless macromolecule resin of fusing point, and are made into micropartical, then it are heated, fuse processing and carries out combination treatment with pitch; According to 1990-0003887 number,, utilize that pitch and heavy oil and catalyzer fuse, combination treatment is made modifying asphalt to the non-renewable useless macromolecule resin of screening and separating.The spent resin of foregoing invention belongs to most of thermoplastically spent resin (LDPE, HDPE, PP etc.), can not improve low-temperature performance by elasticity fully, and the effect of mating formation that can not get expecting.That is, above-mentioned patent major part is for utilizing the depleted resin again, but for considering the cheap shared property problem (viscous deformation, various be full of cracks etc.) of mating formation.
The most existing modifying asphalt only with in the middle of a kind of main polymer or the rubber interpolation pitch, need add other auxiliary in addition.This modifying asphalt is according to the macromolecule resin characteristic of adding, though have that high temperature properties improves (1997-0070122 number) or cryogenic properties improves the deflection rerum natura of (1999-0079717 number, 2003-0046053 number, 2003-0039343 number, 2002-0034496 number).But when having sweltering heat in summer, the geographic asphalt pavement of cold climate condition in winter, above-mentioned modifying asphalt is extremely inapplicable, thereby can cause the problem of mating formation at short notice.
The method of making modifying asphalt has prior fit system (pre-mix type) (1999-0079717 number) and on-the-spot fit system (plant-mix type) (1999-0007510 number), fit system is that pitch and macromolecule resin (or rubber) are mixed and reaction treatment in the blending bin of pitch factory in advance in advance, make modifying asphalt, and be stored in the pitch hutch after transporting to bituminous concrete factory with tank wagon.The modifying asphalt of above-mentioned storage will be placed into in the pump scale tank, by the jet equipment of metering, be ejected in the aggregate and weighting agent in the stirring mixer, through the 45-50 powerful mixing processing of second, make modified asphalt concrete.
There are the following problems for above-mentioned prior fit system: promptly, the viscosity of modifying asphalt perhaps can not cause other problem when low, but when viscosity is higher, the oil tank in use car is carried, and transfer to the hutch of bituminous concrete factory from tank wagon, be sent to the scale tank with pump or in scale tank is ejected into stirring mixer the time from hutch then, cause the phenomenon that almost can not move because of the high viscosity composition.But polyploidy asphalt pavement in the reality or anti-mobile modifying asphalt are mated formation, and need to use high-viscosity modified asphalt, therefore can't adopt prior fit system.
In addition, the oil tank in use car is carried or when being stored in the hutch of bituminous concrete factory for a long time, will be caused the phenomenon that is separated from each other between modified high-molecular and the pitch.If the phenomenon of being separated from each other just can not play the function of modifying asphalt.Utilize above-mentioned prior fit system to produce Korean Patent communique 1999-0079717 number of modifying asphalt, difficulty because of processing and conveying aspect, avoid producing high-viscosity products as much as possible, and main production low viscosity product, and the oil tank in use car transports or in hutch during long-time storage, can cause the phenomenon that is separated from each other, so need give special heed to.
By comparison, on-the-spot fit system is being produced the properties-correcting agent that need be mixed in the pitch separately, and it is transported to bituminous concrete factory, when in the mixing machine of stirrer, mixing aggregate, weighting agent and pitch then, throw in an amount of properties-correcting agent, convenient carrying and processing, but the properties-correcting agent of throwing in is in of short duration mixing time (45～50 seconds), need fusion and with the pitch equalization, and impartial modifying asphalt need evenly cover on all aggregates and the weighting material surface.
In order to address the above problem, existing on-the-spot fitting method (1999-0007510 number) is made fines (1mm is following) with each integrant, so that macromolecular composition fuses in the short period of time at the utmost point, and need the merely constituent of mixed powder state, thereby cause the material separation problem between each integrant that size of particles and density difference cause.The 1999-0007510 patent merely is mixed into adequate rate with damaged tire powder and petroleum resin powder, and with in its PE bag of packing into, therefore can cause the material separation phenomenon of locality.If under pulverulence, produce the material separation phenomenon, these powder are difficult in the of short duration mixing time and mix with pitch, and become impartial modifying asphalt, thereby cause the phenomenon of aggregate and the unequal covering of weighting agent, the subject matter when becoming asphalt pavement.
Compromise form as prior fit system and on-the-spot fit system, preferential produce the properties-correcting agent that is used for on-the-spot fit system, and the same, this properties-correcting agent of appropriate amount is added in the middle of the pitch with prior fit system, and carry out combination treatment, be added with bituminous properties-correcting agent to make.This modifying asphalt can be produced in pitch production plant or bituminous concrete factory.Above-mentioned modifying asphalt will give combination treatment with aggregate in stirring mixer, to make modified asphalt concrete.This method need prevent that generation is separated from each other phenomenon between pitch and the additive after making modifying asphalt.In order to prevent the problem that is separated from each other, a large amount of weighting agents (filler) can be included in the synthetics.
[technical task that invention will realize]
The present invention is intended to solve existing the problems referred to above in the existing modifying asphalt, realizes the purpose that the cost savings performance improves.Except must using the situation of novel material, adopt cheap useless foaming macromolecular resin or useless macromolecule resin as far as possible.Its usage quantity is as the criterion with plastic dosage, when adopting novel material, considers that the problem of high cost can only adopt 3～8 weight %, but when adopting waste materials, because inexpensive and can increase to 3～30 weight %.In view of the above, can reach the effect that rerum natura improves and industrial waste utilizes again of modifying asphalt.The present invention only adopts the specific resin that is fit to corresponding to synthetics integrant among the present invention in the collection waste of fragment or film, grumeleuse, particle, lamellar form.In view of the above, by the way, utilize waste again, can effectively save the additive manufacturing expense.In the present invention, mixing machine or pressurization kneader mixing machine in the class that makes additive at first and adopted claps can hold and the waste materials of all forms such as mixed powder, film, particle, thin slice, grumeleuse, fragment, so conveniently utilize waste materials again.
In order to develop the modifying asphalt that is applicable to high temperature or cold district and even torridity summer and cold winter temperature, a kind of mixing of needs can improve the material of high-temperature behavior and low-temperature performance simultaneously, makes the technology of impartial material.At this, the material of so-called raising high-temperature behavior is meant the high relatively thermoplastically macromolecule resin of glass transformation point ((15)～(+10) ℃), even this material is under mating formation the situation of temperature more than 60 ℃ summer, also be difficult for the phenomenon that deforms, usually under the situation more than 100 ℃, just can become high viscosity fusion liquid.The material of phenomenon of also being difficult for like this deforming in high temperature (60 ℃) carries out equalization with pitch to be mixed, and will improve the bituminous high-temperature behavior, with the viscous deformation resistivity of strengthening mating formation.Though this material is suitable for the high temperature area, because glass transformation point height under the temperature about 0 ℃, can cause hard and most material contracts phenomenon.Therefore, crack performance takes place in low temperature easily.
In addition, the polymer that improves low-temperature performance is meant, as thermoplastic elastomer with dual combination structure or rubber, belong to the scope of glass transition temperature usually for (20)～(45) ℃, can keep its flexibility so in sub-zero temperature, also be difficult for hardening.Under cold condition, also can keep the material of gentle right property, very outstanding to the resistance of various be full of cracks, when mixing with pitch, will improve the bituminous low-temperature performance, so be applicable to cold district, but at high temperature, viscosity is low and easily cause the viscous deformation phenomenon.
As mentioned above, most of polymer can only improve a kind of performance in low-temperature performance or the high-temperature behavior, and the macromolecular material that all has outstanding rerum natura under low temperature and high temperature exists hardly.Therefore, the macromolecule resin of low temperature and high temperature different performance is mixed, making the single macromolecule resin that has two kinds of performances simultaneously is core content of the present invention, thereby the integrant of this synthetics is provided first.If under high-temperature pressurizing, carry out powerful shear-mixed for a long time, between the integrant of synthetics just the chemical reaction that shearing friction causes can take place, realize the impartial effect of material with this, the characteristics of properties-correcting agent manufacture method among the present invention that Here it is.
To constitute example to the synthetics that forms impartial material by the generation chemical reaction below and carry out simple declaration.For causing chemical reaction; (CH=CH-) thermoplastic elastomer of structure or rubber should be included in the synthetics, and (C=O) compound also should be included in synthetics to be used for the phenol carboxylic acid ((C=O) OH) that reacts with the dual combination structure or phosphinylidyne basic group and need have dual combination.That is, above-mentioned materials and synthetics and when depositing, the powerful shear-mixed under the high-temperature pressurizing will make the dual combination STRUCTURE DECOMPOSITION, and can cause the reaction that the compound that has phenol carboxylic acid or phosphinylidyne basic group combines.At this, the vinylacetate among organic aliphatic acid or the EVA can participate in the dual combination reaction.The vinylacetate part of multipolymer EVA will be reacted with the thermoplastic elastomer with dual combination structure, and the ethylene part of EVA then has avidity mutually with thermoplastically polymer PE, and the wax composition in PE and the pitch has avidity.At this, interpolation has avidity with pitch and can reduce the starch of fusing point, to constitute the synthetics that can form impartial material.Therefore, in above-mentioned example, thermoplastically polymer PE and EVA (high-temperature behavior raising), the thermoplastic elastomer SBS with dual combination structure and SBR (low-temperature performance raising), plasticizer pitch, starch, organic aliphatic acid (reducing fusing point and avidity) all can become the integrant of synthetics.In the middle of above-mentioned reaction,,, just the chemical reaction preparation that comprises organo-peroxide can be added in the synthetics, to cause chemical reaction rapidly with the further shortening reaction times if wish to decompose rapidly the dual combination structure.For further strengthening frictional force, obtain impartial more mixed effect, also can add a large amount of weighting agent (filler).
In the present invention, for making impartial material by chemical reaction, and should under high-temperature pressurizing, provide the process of powerful shear-mixed, and the equipment that possesses this condition is provided, the time make the essential equipment of properties-correcting agent in the present invention.Be used for the mixing equipment that macromolecular material or rubber cooperate, promptly, equipments such as mixing machine, pressurization kneader mixing machine, simple helix formula or double-screw type extrusion machine all can satisfy above-mentioned required condition in class clapped, so in the present invention, first this equipment were applicable in the asphalt modifier manufacturing process.The properties-correcting agent that utilizes above-mentioned equipment to produce, all integrants of its synthetics mutually combine, form an impartial material, but each integrant that existing properties-correcting agent constitutes thing is made into powder, be the simple separately state that stirs, so there is bigger gap between the properties-correcting agent among existing properties-correcting agent and the present invention.That is, the isotropism forfeiture between the integrant that is taken place in existing properties-correcting agent finally can cause the major defect of road pavement, so be necessary to draw attention.
In addition, another problem that exists in the on-the-spot fit system is that additive suitably mixes with pitch, and forms the problem of impartial material after could being fused in moment.Existing method is by each integrant with synthetics, makes fines respectively, and stirs merely under pulverulence, addresses the above problem with this, and this is because the more little easy more fusion of particle.But when fine-particle powder is put into mixing space,, and be suspended in the air or have gap, therefore be difficult to obtain mixed uniformly effect with the proportion of aggregate because it can not land.But in the present invention, by reducing the fusing point and the viscosity of properties-correcting agent, make properties-correcting agent easily fusion and with the pitch uniform mixing, also an amount of plasticizer is added in the synthetics simultaneously, drop into a large amount of weighting agents then.At this moment, properties-correcting agent will evenly cover weighting agent, increasing its proportion, thereby can solve landing and mix problems such as inhomogeneous.In addition, weighting agent has been in the state that is capped when mixing, so the effect that can be uniformly mixed at short notice.Through through properties-correcting agent manufacturing process, above-mentioned synthetics is made one matter, and be made into micropartical, address the above problem with this.When this method is also not fully up to expectations, also micropartical can be processed into littler particle, to satisfactorily resolve existing problem.The plasticizer that is used for above-mentioned purpose among the present invention is compared with polymer usually, and molecular weight is less relatively, and viscosity is lower, and has good avidity with pitch, can realize above-mentioned purpose only so.In the present invention, pitch also classifies as plasticizer, and in fact also with pitch as the part of plasticizer, with by being included in the pitch plasticizer in the properties-correcting agent, the avidity when improving properties-correcting agent and mixing mutually with pitch.
[invention constitutes]
The plasticizer that the present invention aims to provide the thermoplastic elastomer of the macromolecule resin of 1～300 weight portion and 1～300 weight portion and 1～300 weight portion blended mutually has the asphalt modifier synthetics of complex functionality.
Above-mentioned macromolecule resin adopts above key element in (discarded or regeneration) foaming macromolecular resin group and (discarded, regeneration or novel material) thermoplastically macromolecule resin group's the whole integrant, its usage rate should be, when integral body is 100, one is 100, two is 1～99: 1～99, and three is 1～98: 1～98: 1～98.
Above-mentioned foaming macromolecular resin group is the foaming thing of broken particle, fragment, thin slice, grumeleuse form, and it comprises an above material in LDPE (Low Density Polyethylene), HDPE (HighDensity Polyethylene), EVA (Ethylenevinylacetate), SBR (Styrenebutadiene Rubber), SBS (Styrenebutadienestyrene), PE+EVA resin compound, EVA+SBR resin compound, EVA+SBS resin compound, PE+EVA+SBR resin compound and the PE+EVA+SBS resin compound at least.
In addition, thermoplastically high score subgroup is at fines, granular, coccoid, film, thin slice, the LDPE of grumeleuse form, HDPE, LLDPE (Linear Low DensityPolyethylene), APP (Atactic Polypropylene), PS (Polystyrene), HIPS (High Impact Polystyrene), EVA, ABS (Acrylonitril ButadieneStyrene), CMC (Carboxymethylcellulose), PVA (Polyvinylacetate), PVC (Polyvinylchloride), polybutene (Polybuten), EthyleneBis-Stearamide (Bisamide wax), at least should comprise an above material among the Elvaloy.
Above-mentioned elastomerics is in the integrant of (discarded, regeneration or novel material) the elastomerics group with dual combination structure, at least adopt an above key element, and its usage rate should be, when integral body is 100, one is 100, two is 1～99: 1～99, and three is 1～98: 1～98: 1～98.
Above-mentioned elastomerics group with dual combination structure is meant fines, granular (particle), coccoid (pellet), thin slice (sheet), the thermoplastic elastomer (thermoplastic elastomer) and the rubber (rubber) of all kinds of grumeleuse (lump) form are at SBR, SBS, SEBS (Styrene-ethylene-butadiene-styrene), SIS (Styrene-isoprene-styrene), ABR rubber (Acrylonitrile-butadiene Rubber), BR rubber (PolybutadieneRubber), SBR latex (Latex), Polychloroprene rubber, NBR (NitrileButadiene Rubber) rubber, Butyl rubber, EPDM (Ethylene-Propylene-Diene-Monomer) rubber, Isoprene rubber, natural rubber, rubber for tire, at least comprise more than one material in the Polyurethanes (Polyurethane).
But above-mentioned plastic uses an above key element in (discarded, regeneration or novel material) plasticizer group's the integrant, and its usage rate should be that when integral body was 100, one is 100, two was 1～99: 1～99, and three is 1～98: 1～98: 1～98.
Above-mentioned plasticizer group is at each vegetable oil (soya-bean oil, Semen Maydis oil, sesame oil, sesame oil, the cotton seed wet goods), various animal oil (butter, lard, dog oil, various fish oil etc.), various vegetable and animals oils (mixing oils of each vegetable oil and various animal oil), various organic acid (lipid acid, fumaric acid, oxalic acid, (countless) toxilic acid, (countless) terephthalic acid, stearic acid, oleic acid, palmitinic acid etc.), hydrocarbon ils, DBP (Dibutylphthalate), DOP (Dioctyiphthalate), PPA (Polypropyleneadipate), Stockholm tar, lower molecular weight PE (Polyethylene), lower molecular weight PP (Polypropylene), rosin (rosin), rosin salt, paraffin, fine crystalline wax (Microcrystalline wax), aromatic oil (Aromatic oil), heavy oil, aliphatics (Aliphatic) petroleum resin, aromatic series (Aromatic) petroleum resin (PetroleumResin), starch, common Straight pitch, in the sulphur, should comprise an above material at least.
In addition, the chemical reaction that also should add 1～30 weight portion in above-mentioned plasticizer 100 weight portions is adjusted.
At this moment, above-mentioned chemical reaction is adjusted and is reaction modifier, catalysts and the anti-combination of cutting off agent of branch daughter, their ratio is respectively 1: 1～10: 1～10, above-mentioned reaction modifier is at DCP (Dicumyl peroxide), DBP (Dibenzoyl peroxide), MEKP (Methyl-ethyl-ketone Peroxide), t-Butylperoxy Benzoate, Di-2-ethyl hexyl peroxy neodecanoate, t-Butylperoxy Pivalate, Di-isopropylperoxy dicarbonate, bis (2,4-dichlorobenzoyl) peroxide, 1,1-bis (t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-Butylperoxyneodecanoate, t-Butylperoxy-2-ethylhexanoate, Di-3-methoxybutylperoxy dicarbonate, Di-3,5,5-trimethylhexanonyl peroxide, among the t-Butylperoxy acetate, at least represent more than one organic substance and oxide compound, above-mentioned catalysts is meant the mixture that adds stearic acid or oleic metal-salt in metal oxide, its blending ratio is 1: 1～5, above-mentioned metal oxide is at calcium oxide, magnesium oxide, titanium oxide, zinc oxide, ferric oxide, manganese oxide, at least comprise a kind of material in the cupric oxide, and above-mentioned stearic acid or oleic metal-salt are at stearic acid or oleic calcium salt, magnesium salts, zinc salt, manganese salt, mantoquita, in the molysite, at least comprise a kind of material, the anti-cut-out agent of daughter in above-mentioned minute is at sulphur, m-phenylenebismaleimide, high-1,2 (high vinyl) polybutadiene, triallyl cyanurate, diallylphthalate, among the ethylene diacrylate, should comprise a kind of material at least.
In addition, in above-mentioned plasticizer 100 weight portions, also should add the weighting agent of 1～1000 weight portion.
At this moment, above-mentioned weighting agent is in weighting agent group's integrant, adopt 1～10 kind of key element, its usage rate is, when integral body is 100, one is 100, two is 1～99: 1～99, three is 1～98: 1～98: 1～98, four is 1～97: 1～97: 1～97: 1～97, five is 1～96: 1～96: 1～96: 1～96: 1～96, six is 1～95: 1～95: 1～95: 1～95: 1～95: 1～95, seven is 1～94: 1～94: 1～94: 1～94: 1～94: 1～94: 1～94, eight is 1～93: 1～93: 1～93: 1～93: 1～93: 1～93: 1～93: 1～93, nine is 1～92: 1～92: 1～92: 1～92: 1～92: 1～92: 1～92: 1～92: 1～92, ten is 1～91: 1～91: 1～91: 1～91: 1～91: 1～91: 1～91: 1～91: 1～91: 1～94.
Above-mentioned weighting agent group should comprise a kind of material at least in carbon black, toning agent, bentonite, silica, clay, mica, limestone powder, nylon short fibre, polyester staple fiber, glass fibre, cellulosic fibre.
The asphalt modifier manufacture method that has complex functionality among the present invention is made up of following two steps: promptly, prepare to have the above-mentioned asphalt modifier synthetics that causes with the characteristic complex functionality; With above-mentioned synthetics, under the high-temperature pressurizing condition, carry out brute force and shear and combination treatment, in order to mixture.
At this moment, with above-mentioned synthetics under the high-temperature pressurizing condition, carrying out brute force shears and combination treatment, step in order to said mixture, above-mentioned synthetics should be put into the sealing holding furnace of (banbury) in pressurization kneader (kneader) or the bat of pressurization class, and under 90～200 celsius temperatures, carry out 3～90 minutes pressure treatment, continue to be mixed and reaction treatment, make impartial material, be the nozzle of 8～12 extrusion machine then by L/D, make extrudate, or adopt L/D be 15～42 mixing with single pressurization double-screw type extrusion machine, under 90～200 celsius temperatures, compress, fusion, shear-mixed is handled, and make its reaction, make impartial material, by nozzle, make extrudate then.
At this, can select a step in the following steps for use: promptly, in extrudate, utilize the blade of high speed rotating, one of them extrudate is made the granular of 0.1～20mm by the said nozzle extruding; Utilize several different methods, to above-mentioned granulated material cool off, dry, storage handles; The particle of above-mentioned storage quantitatively packed into mat formation in the sack, or utilize the various coccoids equipments of pressurization, packed after above-mentioned particle being made the micropartical state of 0.01～2mm.
In each group of above-mentioned synthetics, the usage rate when using an above material is, the ratio of main material of giving selected function is maximum, secondly is auxiliary this materials with function, secondly is the further material of additional above-mentioned functions again.In each material group, can use more than three, but because usage rate is less, so the effect of playing is very little.In above-mentioned synthetics, should preferentially adopt waste materials, if be difficult to obtain waste materials, just can adopt twice-laid stuff, or else also can adopt novel material.
In the synthetics except plasticizer (pitch) group, the limit weight value of each integrant is meant the minimum value of prior fit system, and upper limit gravimetric value is then represented the maximum value of on-the-spot fit system.In addition, making sure to keep in mind to make the pitch that modifying asphalt uses should be included among the plasticizer group.At this, it is the minimum value of on-the-spot fit system that the plasticizer group represents the limit weight value, and upper limit gravimetric value is then represented the maximum value of prior fit system.The limit weight value that chemical reaction is adjusted is meant the minimum value that can react, also can not bring the numerical value of any influence to reaction even if upper limit gravimetric value is then represented to continue to add.At this moment, the operation that weighting agent group's limit weight value is played is very little, and the viscosity of upper limit gravimetric value is too high, so be difficult to process.Therefore, suitably select the formation content of above-mentioned synthetics, so that the synthetics that can be applicable to prior fit system or on-the-spot fit system simultaneously to be provided.
That is to say,, above-mentioned synthetics and pitch are carried out combination treatment, directly make modifying asphalt by prior fit system.At this moment, except other synthetics sum of plasticizer (pitch), should be adjusted into 3～30 weight % of plasticizer content, to keep liquid state, therefore the addition of the synthetics except plasticizer should be less relatively.So the modifying asphalt of producing is fusion liquid, and the usable oils tank car is transported in the bituminous concrete factory.Therefore, in above-mentioned synthetics, represent the minimum value of prior fit system, the minimum value here except the lower value of plasticizer and be meant, when in plasticizer, adding, will any effect can occur hardly than its less amount.
But the above-mentioned synthetics in the fit system at the scene is at bituminous concrete produce in factory bituminous concrete, and in the holding furnace of aggregate and pitch being rendered to stirrer the time, produces the synthetics that the properties-correcting agent that added is used.Above-mentioned properties-correcting agent is not to belong to fusion liquid, but solid state.The pitch that is included in the properties-correcting agent synthetics is not to be used to make modifying asphalt, but as the integrant of properties-correcting agent, is used to alleviate the fusing point and the viscosity of properties-correcting agent, it is fused, to play the effect of plasticizer in moment.Therefore, pitch will be included in the plasticizer.At this moment, properties-correcting agent should be the solid state that can not be out of shape at normal temperatures, and the solid synthetics beyond the plasticizer adds content, will be far more than plasticizer.Higher limit in the above-mentioned synthetics is represented the maximum value of on-the-spot fit system, and this maximum value is meant and adds than its amount of Duoing, just because of the maximum level of the too high and very difficult manufacturing properties-correcting agent of viscosity.With pitch be, in the aggregate and pitch in the stirring mixer of rendering to bituminous concrete factory, put into above-mentioned properties-correcting agent, and when being mixed simultaneously, be convenient to properties-correcting agent rapidly and the pitch equalization as the another kind of reason of the plasticizer of properties-correcting agent.
Usually, can not fuse even if useless foamex heated also, and the burning of under hot conditions, smoldering, so be difficult to find its purposes, so belong to cheaper resin.By the technology of the present invention, sneak into this material in the plasticizer after, under high-temperature pressurizing, apply stronger shear-stress, proceed combination treatment, obtain with regard to not burning so the fusion, play the effect that is equal to the thermoplastically macromolecule resin.In view of the above, in properties-correcting agent synthetics of the present invention, added the macromolecule resin that can improve high-temperature behavior---thermoplastically high score subgroup and useless foaming macromolecular resin group.Useless foaming macromolecular resin group's chemical ingredients has PE, EVA, SBR, SBS, PE+EVA, EVA+SBR, EVA+SBS, PE+EVA+SBR, PE+EVA+SBS etc., and they exist with forms such as fragment (scrap), granular (pellet), thin slice (sheet), grumeleuses.This '+' represent macromolecule mixture (blending).
The thermoplastically macromolecule resin group that can improve the high-temperature behavior (viscous deformation resistivity) of asphalt pavement has LDPE (low density ployethylene), HDPE (high densitypolyethylene), LLDPE (linear low density polyethylene), PB (Polybutene), PVC (polyvinylchloride), PS (polystyrene), HIPS (high impact polystyrene), PVA (polyvinyacetate), EVA (ethylene-vinylacetate copolymer) etc., all right fragment (scrap) of these thermoplastic resins, granular (pellet), powder (powder), thin slice (sheet), film (film), grumeleuse forms such as (lump) comes into operation.
Increase elasticity, and improve Physical Properties of Low Temperature, promptly improve the be full of cracks resistivity of mating formation the flexible body group of material, powder, granular, thin slice, grumeleuse, the thermoplastic elastomer of fragment form, (natural, synthetic) rubber pressurization rubber powder all belong to this type.Promptly, thermoplastic elastomer has SBS (Styrene-Butadiene-Styrene), SBR (styrene-butadienerubber), SBR latex (Latex), SEBS (styrene-ethylene-butadiene-styrene), SIS (styrene-isoprene-styrene), rubber has Butyl rubber, ABR rubber (Acrylonitrile-butadiene Rubber), BR rubber (PolybutadieneRubber), Polychloroprene rubber, Isoprene rubber, natural rubber, NBR rubber (Nitrile Butadiene Rubber), EPDM (Ethylene-Propylene-Diene-Monomer) rubber, rubber powder has the powder of above-mentioned various rubber, the damaged tire powder, spent acid ammonia ester powder.
Each integrant (being called plasticizer) of plasticizer group can reduce the fusing point and the viscosity of additive, and the moment fusion, mixes with pitch is impartial, the convenient simultaneously aggregate that covers.At this, comprise various Straight pitches in the plasticizer, DBP (di-butylphthalate), DOP (di-octylphthalate), DOS (di-octylsebacate), DMP (di-methylphthalate), DOA (di-octyladipate), PPA (polypropyleneadipate), petroleum resin, Stockholm tar, lower molecular weight PE (Polyethylene), lower molecular weight PP (Polypropylene), rosin (rosin), rosin salt, heavy oil, paraffin, fine crystalline wax (Microcrystalline wax), hydrocarbon system oil, aromatic oil (Aromatic oil), starch, vegetables oil (soya-bean oil, Semen Maydis oil, sesame oil, sesame oil, the cotton seed wet goods), animal oil (butter, lard, dog oil, various fish oil etc.), animals and plants mixing oil (mixing oil of each vegetable oil and animal oil), various organic acid (lipid acid, fumaric acid, oxalic acid, (countless) toxilic acid, (countless) terephthalic acid, stearic acid, oleic acid, palmitinic acid;
Figure A20061007431600191
Deng), material such as sulphur.
Chemical reaction is adjusted and is used for opening rapidly elastomeric dual combination structure, and shortens chemical time.At this, chemical reaction is adjusted and is represented reaction modifier, catalysts, iron chains cutting agent, and its ratio is 1: 1～10: 1～10.At this moment, the value that lower value representative can not worked to reaction, and this representative of higher limit continues to add the value that also can not improve degree of influence.Reaction modifier is meant and comprises DCP (Dicumyl peroxide), DBP (Dibenzoyl peroxide), MEKP (Methyl-ethyl-ketone Peroxide), t-Butylperoxy Benzoate, Di-2-ethyl hexyl peroxy neodecanoate, t-Butylperoxy Pivalate, Di-isopropylperoxy dicarbonate, bis (2,4-dichlorobenzoyl) peroxide, t-Butylperoxy, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, acetatel, 1-bis (t-butylperoxy)-3,3,5-trimethylcyclohexane, t-Butylperoxy neodecanoate, t-Butylperoxy-2-ethylhexanoate, Di-3,5,5-trimethylhexanonylperoxide, all organic and oxide compounds of materials such as Di-3-methoxybutylperoxy dicarbonate.Catalysts is meant the mixture that adds stearic acid (stearicacid) or oleic acid metal-salts such as (oleicacid) in metal oxide, its blending ratio should be 1: 1～and 5, comprise calcium oxide (CaO), magnesium oxide (MgO), titanium oxide (TiO in the metal oxide 2), aluminum oxide (PbO), zinc oxide (ZnO), ferric oxide (Fe 2O 3), manganese oxide (MnO), cupric oxide (CuO), comprise stearic acid or oleic calcium salt, magnesium salts, zinc salt, manganese salt, mantoquita, molysite in stearic acid or the oleic metal-salt.Iron chains cutting containment agent is sulphur, m-phenylenebismaleimide, high-1,2 (high vinyl) polybutadiene, triallyl cyanurate, diallylphthalate, materials such as ethylene diacrylate, dibinylbenzene.
Each integrant of weighting agent group can prevent to be separated from each other, improve proportion, induce impartial the mixing, and the shortening mixing time, comprising materials such as (discarded, regeneration or novel material) carbon black, toning agent, bentonite, silica, clay, mica, limestone powder, nylon short fibre, polyester staple fiber, glass fibre, cellulosic fibres.
Properties-correcting agent manufacture method of the present invention has following characteristics: promptly,
In pressurization kneader (kneader) or the bat of pressurization class, add above-mentioned synthetics in the holding furnace of (banbury) sealing, and under 90～200 celsius temperatures, carry out 3～90 minutes pressure treatment, proceed to mix, reaction treatment, to make impartial material, (length/diameter=Length/Diameter) is 8～12 extruder nozzle by L/D then, make extrudate, or employing L/D is 15～42 the single pressurization double-screw type extrusion machine with mixed use, under 90～200 celsius temperatures, compress, fusion, the shear-mixed reaction, make impartial material, make extrudate by nozzle then.The extrudate that the method for will choosing any one kind of them in aforesaid method is produced, utilize the blade of high speed rotating, make the granular of 0.1～2mm, and through steps such as overcooling, drying, storages, quantitatively pack in PE (Polyethylene) sack, or utilize the various coccoids equipments of pressurization, these particles are further made the micropartical of 0.01～0.5mm, in the PE bag of packing into then.
Properties-correcting agent manufacture method of the present invention has adopted rubber to cooperate at first or polymer mixes (compounding) equipment, and the kind of this mixing tank comprises following two procedures: the same with Banbury mixer pressurization kneader, make impartial material in of high-temperature pressurizing shear mixer, and in L/D is 8～12 extrusion machine, with the dual operation of impartial material corning shape; The same with single pressurization double-screw type extrusion machine, fulfil the single operation of all process steps of pressurization fusion, shear-mixed, granular manufacturing.Properties-correcting agent manufacture of the present invention is not advocated the single operation that employing can not be adjusted mixing and reaction times arbitrarily, can adjust the time arbitrarily and recommend employing, and give stronger shear-stress, makes the dual operation of more impartial material.
The put-on method of medium pitch properties-correcting agent of the present invention causes the asphalt modifier made from particle and puts into stirrer, and obtain combination treatment with aggregate, pitch and weighting agent in stirrer, to make impartial asphalt modification bituminous concrete.
In addition, also asphalt modifier can be caused with particle and be transported to bituminous concrete factory, and in the box pitch 100 weight portions of this factory, adding properties-correcting agent causes with particle 5～30 weight portions, carry out combination treatment then, and modifying asphalt, aggregate, additive added in the stirrer mixed, to make the asphalt modification bituminous concrete.
[embodiment]
According to following embodiment and comparative example, made mutually different modifying asphalt.In order to carry out the physical property measurement of each modifying asphalt, and carried out asphalt penetration test, and for carrying out the physical property measurement of the mixture that mixed and modified pitch and aggregate make, and carried out Marshall Test.Test result following [table 1].Show according to asphalt penetration test in [table 1] and Marshall Test result, the rerum natura of the modifying asphalt that the present invention develops and modified mixture rerum natura, outstanding more than other modifying asphalt in the comparative example.
[table 1]
Test event Embodiment Comparative example
1 2 3 4 5 1 2 3
Deeply spend (25 ℃, 100g, 5 seconds) 35 32 28 25 56 67 54 46
Marshall stability, kgf 1860 1940 2070 2120 1403 1230 1480 1760
Marshall flow, 0.1mm 42 36 42 46 67 28 32 29
[embodiment 1]
Pitch (AP-5, Jinsen essential oil): the ratio of waste vegetable oil is that 80: 20 plasticizer overall weight is 100 weight portions, can improve the thermoplastically macromolecule resin of high-temperature behavior---useless foaming (EVA+SBR) resin is 100 weight portions, can improve the elastomerics of low-temperature performance---damaged tire powder (30～40 microns) is 200 weight portions, constitutes the properties-correcting agent synthetics by them.With above-mentioned synthetics put into 100 ℃ class clap in mixing machine, utilize 10 horsepowers air compressor to carry out pressure treatment, and by mixing rotating shaft, the powerful mixing of carrying out 5 minutes is handled, and has made equalization and has answered collective.The following cover of mixing machine was placed on the above-mentioned collective of answering on the cone feed (cone feeder), by the operation of cone feed in the class of opening clapped, it is in 10 the spiral extrusion machine that material is sent to L/D, under spiral rotation, advance and by squeeze station, generate thread extrudate.This extrudate is cut into minuteness particle by the high speed rotating blade before the squeeze station, and cooling rapidly after the water that sprays lands.Divide dried up and particle, make particle, in the storage silo, just can make additive by on-the-spot fit system through drying process.
With the properties-correcting agent 20 weight % that so make, under pitch (AP-5) 80 weight % and 160 ℃ of conditions, utilize powerful shear mixer to carry out 30 minutes combination treatment, making modifying asphalt, and for understanding the rerum natura of modifying asphalt, the modifying asphalt of making is fused, and pour in the pitch penetration degree jar, and in 25 ℃ of Water Tanks with Temp.-controlled, placed 1 hour, carry out the standard asphalt penetration test then immediately (by the pin of 100 grams, pin went into for 5 seconds, measured needle penetration then).
In addition, for understanding the rerum natura of mixture, with the close granularity of 19mm top layer aggregate (referring to Korea S's portion's specification sheets of establishing diplomatic relations) 1000 grams (heating is 10 hours in 155 ℃ the baking oven), pitch (AP-5, Jinsen essential oil) 44 grams (liquid of heating fusion in 165 ℃ the baking oven) and make 11 restrain properties-correcting agent and put into the Marshall mixing machine respectively, carry out 3 minutes combination treatment, then these mixtures are put into Marshall and smash mould, its two sides carried out smashing for 75 times beat, make the Marshall test portion with this.After under room temp, the Marshall test portion being carried out one day hardening treatment, in 60 ℃ Water Tank with Temp.-controlled, placed 30 minutes, with 50.8mm/ minute speed, carry out the Marshall steady testing then, to measure stability and yield point value.
[embodiment 2]
In modifying asphalt production plant, in pitch in 170 ℃ blending bin (AP-5, Jinsen essential oil) the 1000 weight portions, adding the useless HDPE of useless foaming EVA portions of resin is the thermoplastically macromolecule resin 50 weight portions of 80: 20 improved high-temperature behavior, and the ratio that adds damaged tire powder (30-40 micron) and SBR (bright and beautiful lake petroleum chemistry) is the elastomerics 100 weight portions of 75: 25 improved low-temperature performance, put into bentonite 10 weight portions again, constitute whole synthetics.All integrants of above-mentioned synthetics become till the impartial material in jar, and the powerful shear-mixed of carrying out 3 hours is handled, to make modifying asphalt by prior fit system.To the modifying asphalt of manufacturing like this, carried out the test of standard asphalt penetration degree.In addition, for understanding the rerum natura of mixture, the close granularity of 19mm top layer aggregate (referring to Korea S's portion's specification sheets of establishing diplomatic relations) 1000 grams (155 ℃ baking oven internal heating 10 hours) and above-mentioned modifying asphalt 55 grams (liquid that fuses at 185 ℃ baking oven internal heating) are put into the Marshall mixing machine respectively, carry out 3 minutes combination treatment, then mixture being poured into Marshall smashes and beats in the mould, its two sides carried out smashing for 75 times beat, make the Marshall test portion with this.After under room temp, the Marshall test portion being carried out one day hardening treatment, in 60 ℃ Water Tank with Temp.-controlled, placed 30 minutes, with 50.8mm/ minute speed, carry out the Marshall steady testing then, to measure stability and yield point value.
[embodiment 3]
Pitch (AP-5, Jinsen essential oil): 100 ones of plasticizer overall weight that by the ratio of waste vegetable oil: DOP are 75: 20: 5, the useless HIPS of useless foaming (EVA+SBR) portions of resin is 100 ones of the thermoplastically macromolecule resin gross weights of 70: 30 improved high-temperature behavior, the ratio of damaged tire powder (30～40 microns) and SBR (bright and beautiful lake petroleum chemistry) is 200 ones of the elastomerics overall weight of 90: 10 improved low-temperature performance, benzoyl peroxide: zinc oxide: Zinic stearas: the ratio of sulphur is 1: 2: 3: 4 chemical reaction is adjusted 5 ones of overall weight, constitutes the properties-correcting agent synthetics of on-the-spot fit system.Utilize the operation of above-mentioned synthetics manufacturing properties-correcting agent identical with [embodiment 1].The properties-correcting agent 20 weight % and pitch (AP-5, Jinsen essential oil) the 80 weight % that so make are given impartial combination treatment, making modifying asphalt, and this binder has been carried out the standard asphalt penetration test.In addition, utilize the method that is same as [embodiment 1], make the Marshall test portion, and measured the Marshall stability and the yield point value of this test portion under the same conditions respectively.
[embodiment 4]
Pitch (AP-5, Jinsen essential oil): by waste vegetable oil: stearic ratio is 75: 20: 5 100 ones of plasticizer overall weight, the useless LDPE of useless foaming (EVA+SBR) portions of resin: useless HIPS is 100 ones of thermoplastically macromolecule resin gross weights, damaged tire powder (30-40 micron): the SBR (bright and beautiful lake petroleum chemistry) of 70: 20: 10 improved high-temperature behavior: the ratio of SBS (LG chemistry) is 200 ones of the elastomerics overall weight of 80: 15: 5 improved low-temperature performance, constitutes the properties-correcting agent synthetics of on-the-spot fit system.Utilize the operation of above-mentioned synthetics manufacturing properties-correcting agent identical with [embodiment 1].The properties-correcting agent 20 weight % and pitch (AP-5, Jinsen essential oil) the 80 weight % that so make are given impartial combination treatment, making modifying asphalt, and this binder has been carried out the standard asphalt penetration test.In addition, utilize the method that is same as [embodiment 1], make the Marshall test portion, and measured the Marshall stability and the yield point value of this test portion under the same conditions respectively.
[embodiment 5]
Pitch (AP-5, Jinsen essential oil): be 80: 20 100 ones of plasticizer overall weight, can be improved the thermoplastically macromolecule resin of high-temperature behavior by the ratio of waste vegetable oil---useless foaming (EVA+SBR) resin 250 weight portions, can improve the elastomerics of low-temperature performance---SBR (bright and beautiful lake oil (strain)) 50 weight portions constitute the properties-correcting agent synthetics of on-the-spot fit system.Utilize the operation of above-mentioned synthetics manufacturing properties-correcting agent identical with [embodiment 1].The properties-correcting agent 20 weight % and pitch (AP-5, Jinsen essential oil) the 80 weight % that so make are given impartial combination treatment, making modifying asphalt, and, carried out the standard asphalt penetration test in its pitch penetration degree test tank of packing into.In addition, utilize the method that is same as [embodiment 1], make the Marshall test portion, and measured the Marshall stability and the yield point value of this test portion under the same conditions respectively.
[comparative example 1]
Pitch (AP-5, Jinsen essential oil) is fused processing, in its pitch penetration degree test tank of packing into, and under 25 ℃ of conditions, carried out the standard asphalt penetration test.In addition, utilize the method that is same as [embodiment 1], make the Marshall test portion, and carried out Marshall stability test.Test result is recorded in [table 1].
[comparative example 2]
((strain) SK, PG76-22) fuses processing to commercial SBS modifying asphalt, in its pitch penetration degree test tank of packing into, and carried out the standard asphalt penetration test under 25 ℃ of conditions.In addition, utilize the method that is same as [embodiment 1], make the Marshall test portion, and carried out Marshall stability test.Test result is recorded in [table 1].
[comparative example 3]
((strain) UNIXRUBBER) fuses processing to commercial CRM modifying asphalt, in its pitch penetration degree test tank of packing into, and carried out the standard asphalt penetration test under 25 ℃ of conditions.In addition, utilize the method that is same as [embodiment 1], make the Marshall test portion, and carried out Marshall stability test.Test result is recorded in [table 1].
[invention effect]
By the present invention, can according to modifier inscape and the modifier content that adds in the pitch, produce the multiple modified asphalt concrete of mating formation for modified pitch. Namely, can produce comprise that common modified pitch is mated formation, the polyploidy modified pitch is mated formation, anti-mobile modified pitch is mated formation, coldly with modified pitch mat formation, the product such as the bridge floor modified pitch is mated formation, and can be applicable to the bituminous concrete of mating formation in all top layers of mating formation, intermediate layer, gas-bearing formation.

Claims (20)

1. the asphalt modifying agent composition with complex function comprises the macromolecule resin of 1～300 weight part and the thermoplastic elastomer of 1～300 weight part, and 1～200 weight part plasticizer.
2. the described asphalt modifying agent composition of claim 1, wherein above-mentioned macromolecule resin also should possess following constructional feature: promptly, adopt above key element in (discarded or regeneration) foaming macromolecular resin group and (discarded, regeneration or novel material) thermoplastically macromolecule resin group's the whole integrant, its usage rate should be, when integral body is 100, one is 100, two is 1～99: 1～99, and three is 1～98: 1～98: 1～98.
3. the described asphalt modifying agent composition of claim 2, wherein above-mentioned foaming macromolecular resin group should possess following constructional feature: promptly, as broken particle, fragment, thin slice, the foaming thing of grumeleuse form, it comprises LDPE (new LDPE (film grade)) at least, HDPE (high density polyethylene(HDPE)), EVA (ethene-vinyl acetate base ester), SBR (styrene-butadiene rubber(SBR)), SBS (styrene-butadiene block copolymer), the PE+EVA resin compound, the EVA+SBR resin compound, the EVA+SBS resin compound, an above material in PE+EVA+SBR resin compound and the PE+EVA+SBS resin compound.
4. the described asphalt modifying agent composition of claim 2, wherein above-mentioned thermoplastically high score subgroup should possess following constructional feature: promptly, and at fines, granular, coccoid, film, thin slice, the LDPE of grumeleuse form, HDPE, LLDPE (linear low density polyethylene), APP (Atactic Polypropelene), PS (polystyrene), HIPS (impact-resistant polystyrene), EVA, ABS (acrylonitrile-butadiene-styrene copolymer), CMC (carboxymethyl cellulose), PVA (Vinyl Acetate Copolymer base ester), PVC (polyvinyl chloride), polybutene (Polybuten), ethylenebisstearamide (Bisamidewax), at least should comprise an above material among the Elvaloy.
5. the described asphalt modifying agent composition of claim 4 wherein should be selected 1～3 key element for use in above-mentioned thermoplastically high score subgroup.
6. the described asphalt modifying agent composition of claim 1, wherein above-mentioned elastomerics should be in the integrant of (discarded, regeneration or novel material) the elastomerics group with dual combination structure, at least adopt an above key element, and its usage rate should be, when integral body is 100, one is 100, two is 1～99: 1～99, and three is 1～98: 1～98: 1～98.
7. the described asphalt modifying agent composition of claim 6, wherein above-mentioned elastomerics group with dual combination structure is meant fines, granular (particle), coccoid (pellet), thin slice (sheet), the thermoplastic elastomer (thermoplastic elastomer) and the rubber (rubber) of all kinds of grumeleuse (1ump) form are at SBR, SBS, SEBS (Styrene-ethylene-butadiene-styrene), SIS (Styrene-isoprene-styrene), ABR rubber (Acrylonitrile-butadieneRubber), BR rubber (Polybutadiene Rubber), the SBR latex, chloroprene rubber, NBR (paracril), isoprene-isobutylene rubber, EPDM (Ethylene-Propylene-Diene-Monomer) rubber, synthetic polyisoprene, natural rubber, rubber for tire, at least comprise more than one material in the urethane (Polyurethane).
8. the described asphalt modifying agent composition of claim 1, but wherein above-mentioned plastic uses 1～10 key element in (discarded, regeneration or novel material) plasticizer group's the integrant, its usage rate should be, when integral body is 100, one is 100, two is 1～99: 1～99, and three is 1～98: 1～98: 1～98.
9. the described asphalt modifying agent composition of claim 8, wherein above-mentioned plasticizer group should be at each vegetable oil (soya-bean oil, Semen Maydis oil, sesame oil, sesame oil, the cotton seed wet goods), various animal oil (butter, lard, dog oil, various fish oil etc.), various vegetable and animals oils (mixing oils of each vegetable oil and various animal oil), various organic acid (lipid acid, fumaric acid, oxalic acid, (countless) toxilic acid, (countless) terephthalic acid, stearic acid, oleic acid, palmitinic acid etc.), hydrocarbon ils, DBP (Dibutylphthalate), DOP (Dioctyiphthalate), PPA (Polypropyleneadipate), Stockholm tar, lower molecular weight PE (Polyethylene), lower molecular weight PP (Polypropylene), rosin (rosin), rosin salt, paraffin, fine crystalline wax (Microcrystalline wax), aromatic oil (Aromatic oil), heavy oil, aliphatics (Aliphatic) petroleum resin, aromatic petroleum resin, starch, common Straight pitch, in the sulphur, should comprise an above material at least.
10. the described asphalt modifying agent composition of claim 1 wherein also should add the chemical reaction of 1～30 weight part and adjust in above-mentioned plasticizer 100 weight parts.
11. the described asphalt modifying agent composition of claim 10, wherein above-mentioned chemical reaction are adjusted to reaction modifier, catalysts and divided daughter the anti-combination of cutting off agent, their ratio is respectively 1: 1～10: 1～10;
Above-mentioned reaction modifier is selected from DCP (dicumyl peroxide), DBP (dibenzoyl peroxide), MEKP (methylethyl ketone peroxide), t-butylperoxyl benzoate, cross neodecanoic acid two (2-ethylhexyl) ester (Di-2-ethyl hexyl peroxy neodecanoate), cross the PIVALIC ACID CRUDE (25) tert-butyl ester, di-isopropyl peroxydicarbonate, peroxidation two (2, the 4-dichloro-benzoyl), 1,1-bis(t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, cross the neodecanoic acid tert-butyl ester, cross the 2 ethyl hexanoic acid tert-butyl ester, peroxy dicarbonate two (3-methoxyl group butyl) ester, peroxidation two-3,5, the 5-trimethyl acetyl, in the t-butyl peroxy-acetate one of at least;
Above-mentioned catalysts is meant the mixture that adds stearic acid or oleic metal-salt in metal oxide, its blending ratio is 1: 1～5, above-mentioned metal oxide one of is selected from calcium oxide, magnesium oxide, titanium oxide, zinc oxide, ferric oxide, manganese oxide, the cupric oxide at least, and above-mentioned stearic acid or oleic metal-salt one of are selected from stearic acid or oleic calcium salt, magnesium salts, zinc salt, manganese salt, mantoquita, the molysite at least;
The anti-cut-out agent of daughter in above-mentioned minute one of is selected from sulphur, meta-phenylene bismaleimide, height-1,2 (high-vinyl) polyhutadiene, triallyl cyanurate, Phthalic acid, diallyl ester, the glycol diacrylate at least.
12. the described asphalt modifying agent composition of claim 1 wherein also should add the weighting agent of 1～1500 weight part in above-mentioned plasticizer 100 weight parts.
13. the described asphalt modifying agent composition of claim 1 wherein also should add the weighting agent of 1～1500 weight part in above-mentioned asphalt modifier 100 weight parts.
14. claim 12 or 13 described asphalt modifying agent compositions, wherein above-mentioned weighting agent is in weighting agent group's integrant, should adopt 1～10 kind of key element, its usage rate is, when integral body is 100, one is 100, two is 1～99: 1～99, three is 1～98: 1～98: 1～98, four is 1～97: 1～97: 1～97: 1～97, five is 1～96: 1～96: 1～96: 1～96: 1～96, six is 1～95: 1～95: 1～95: 1～95: 1～95: 1～95, seven is 1～94: 1～94: 1～94: 1～94: 1～94: 1～94: 1～94, eight is 1～93: 1～93: 1～93: 1～93: 1～93: 1～93: 1～93: 1～93, nine is 1～92: 1～92: 1～92: 1～92: 1～92: 1～92: 1～92: 1～92: 1～92, ten is 1～91: 1～91: 1～91: 1～91: 1～91: 1～91: 1～91: 1～91: 1～91: 1～94.
15. the described asphalt modifying agent composition of claim 14, wherein above-mentioned weighting agent one of are selected from carbon black, toning agent, bentonite, silica, clay, mica, limestone powder, nylon short fibre, polyester staple fiber, glass fibre, the cellulosic fibre at least.
16. preparation has the method for the asphalt modifier of complex function, comprises following two steps:
Prepare the asphalt modifying agent composition described in any one of the claim 1-claim 13 with complex function;
With above-mentioned composition, under the high-temperature pressurizing condition, carry out brute force and shear and combination treatment, with the preparation mixture.
17. the described method of claim 16, wherein with above-mentioned composition under the high-temperature pressurizing condition, carry out that brute force is sheared and combination treatment, with the step of preparation said mixture,
The above-mentioned composition thing should be put into the sealing holding furnace of (banbury) in pressurization kneader (kneader) or the bat of pressurization class, and under 90～200 celsius temperatures, carry out 3～90 minutes pressure treatment, continue to be mixed and reaction treatment, make impartial material, be the nozzle of 8～12 extrusion machine then by L/D, make extrudate, or employing L/D is 15～42 the single pressurization double-screw type extrusion machine of mixing, under 90～200 celsius temperatures, compress, fusion, shear-mixed is handled, and make its reaction, make impartial material, by nozzle, make extrudate then.
18. the described method of claim 17, wherein said preparation have the step of the method for the asphalt modifier of complex function in comprising the steps:
In extrudate by the said nozzle extruding, utilize the blade of high speed rotating, one of them extrudate is made the granular of 0.1～20mm;
Utilize several different methods, to above-mentioned granulated material cool off, dry, storage handles;
The particle of above-mentioned storage quantitatively packed into mat formation in the sack, or utilize the various coccoids equipments of pressurization, packed after above-mentioned particle being made the micropartical state of 0.01～2mm.
19. preparation has the method for the asphalt modifier of complex function, comprises following two steps:
Prepare the asphalt modifying agent composition described in any one of the claim 1-claim 13 with complex function:
Above-mentioned asphalt modifier is put into stirrer, and in stirrer, obtain combination treatment, to make impartial asphalt modification bituminous concrete with aggregate, pitch and weighting agent.
20. have the asphalt modifier manufacture method of complex function, comprise following two steps:
Prepare the asphalt modifying agent composition described in any one of the claim 1-claim 13 with complex function:
Above-mentioned asphalt modifier caused with particle be transported to bituminous concrete factory, and in box pitch 100 weight parts of this factory, adding properties-correcting agent causes with particle 5～30 weight parts, carry out combination treatment then, and modifying asphalt, aggregate, additive added to give combination treatment in the stirrer, to make the asphalt modification bituminous concrete.
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