CN101117443A - Modified asphalt material and preparation method thereof - Google Patents
Modified asphalt material and preparation method thereof Download PDFInfo
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- CN101117443A CN101117443A CNA2006101111350A CN200610111135A CN101117443A CN 101117443 A CN101117443 A CN 101117443A CN A2006101111350 A CNA2006101111350 A CN A2006101111350A CN 200610111135 A CN200610111135 A CN 200610111135A CN 101117443 A CN101117443 A CN 101117443A
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Abstract
The invention discloses a bitumen modified material, which comprises 100 parts by weight of vinyl aromatic hydrocarbon-conjugated diene block copolymer with the flow value being less than 15g/10 minutes relative to fused mass, 0 to 100 parts by weight of tackifying resin, 5 to 100 parts by weight of blending oil and 10 to 50 parts by weight of polyolefin. In addition, the invention also discloses the method of preparation of the bitumen modified material. Due to adding polyolefin, the invention not only maintains the physical intensity of existing bitumen modified material such as abrasion resistance, impact resistance and fluidity resistance as well as the advantages of excellent dissolubility, processability and storage stability, but also improves high temperature performance of bitumen modified material.
Description
[technical field]
The present invention relates to modified asphalt material and the asphalt mixture that contains this material.More particularly, relate to and be applicable to that opener joins the modified asphalt material that the high-performance dewatering and noise reduction of mating formation etc. is mated formation.
[background technology]
For small and medium-sized car, along with the raising of travel speed, tyre noise is increasing in the ratio that automobile produces in the noise, therefore builds the noise reduction road surface and has important and practical meanings for the control traffic noise.So-called low-noise asphalt pavement also claims many spaces bituminous pavement, claims permeable (or draining) bituminous pavement again.It is that making one deck has the very asphalt of high voidage on common bituminous pavement or cement concrete pavement structure layer, its voidage is usually between 15%～25%, that have even reach 30%, the foreign study data shows, difference according to surface layer thickness, duration of service, working conditions and maintenance situation, compare with common bituminous concrete pavement, this kind road surface can reduce traffic noise 3～8dB.
The advantage of this method is: because mixture gap rate height not only can reduce noise, ride comfort can also improve drainage performance, can improve the security of travelling in the rainy day.Limitation is: to gather materials, binding material requirement height, use for some time after, the space is easily blocked.
Because the unique effects of low-noise asphalt pavement generally believes that at present promoting the build low-noise asphalt pavement more is a kind of effective environmental protection approach to weaken noise.Widely popularize the low noise road surface, good mixing material grating scheme not only will be arranged, and agglutinate is also particularly important.
High viscosity pitch is meant the pitch of 60 ℃ of viscositys greater than 20kPa.s, is applicable to paving of heavy-duty road and drainage pavement.In recent years, functional high-performance of giving water-permeable, low noise etc. is mated formation noticeable.For example, carry out good draining during for the rainy day, utilize space in the asphalt mixture to keep the opener of water-permeable to join to mat formation prominent.In addition, in order to reduce the logical out of date noise of vehicle, the opener of utilizing space in the asphalt mixture to seek to reduce noise join mat formation noticeable.Such opener is joined and is mated formation, because the pitch amount of the agglutinate that uses as unit volume is few, so add material modified that synthetic resins for example etc. constitutes mostly.Material modified by adding, can improve the physical strength of the wear resistant, shock-resistance, anti-flowability etc. of asphalt mixture.
As the general method for making of asphalt mixture, known mode of adding modified asphalt material when in the pitch mechanical means, making asphalt mixture.Adopt this mechanical means hybrid mode, can in pitch, sneak into an amount of modified asphalt material.And, do not need to be provided with in advance the special device etc. that pitch and modified asphalt material is mixed usefulness.With regard to these aspects, also have many good qualities than the pre-mixing mode of in pitch, adding modified asphalt material in advance.
Above-mentioned mechanical means hybrid mode importantly makes pitch mix with modified asphalt material when making asphalt mixture at short notice.Therefore, past is in order to improve the solubleness (consistency) of modified asphalt material in pitch, proposed the modified asphalt material that vinyl aromatic hydrocarbon one conjugation diene block copolymer and tackifying resin and mixed oil is mixed (with reference to patent documentation 1: the spy opens flat 5-295273 communique).To such modified asphalt material, also proposed to improve the modified asphalt material (with reference to patent documentation 2: the spy opens flat 9-25416 communique) of processibility when making and storage stability.In Chinese patent (application number is 200410043134.8), mention " a kind of modified asphalt material; wherein; ", but the high-temperature behavior of this modified asphalt material is not good with respect to vinyl aromatic hydrocarbon-conjugated diene block copolymer 100 weight parts of melt flow value; contain tackifying resin 0～100 weight part; mixed oil 5～100 weight parts less than the 15g/10 branch.
[summary of the invention]
The purpose of this invention is to provide a kind of modified asphalt material, this modified asphalt material not only processibility, storage stability is good and physical strengths such as wear resistant, shock-resistance, anti-flowability might as well, the more important thing is that the high-temperature behavior of this modified asphalt material and viscosity also are improved.
A kind of modified asphalt material, wherein, less than vinyl aromatic hydrocarbon-conjugated diene block copolymer 100 weight parts that 15g/10 divides, contain tackifying resin 0～100 weight part with respect to the melt flow value, mixed oil 5～100 weight parts is characterized in that: also contain polyolefine 10～50 weight parts.
Above-mentioned modified asphalt material simultaneously with respect to total amount 100 weight parts of these various compositions, contains the following rubber of 40 weight parts.
Above-mentioned modified asphalt material, wherein, polyolefine is PE, PP, EVA, APP, APAO, POE, HDPE, LDPE and/or LLDPE.Polyolefine can improve the high-temperature behavior and the viscosity of asphalt mixture.
Above-mentioned modified asphalt material preparation method is characterized in that: after being mixed into homogeneous compositions under the heating, be processed into granular vinyl aromatic hydrocarbon-conjugated diene block copolymer, tackifying resin, mixed oil and polyolefine.
Above-mentioned modified asphalt material preparation method is characterized in that: after being mixed into homogeneous compositions under the heating, be processed into granular vinyl aromatic hydrocarbon-conjugated diene block copolymer, tackifying resin, mixed oil, rubber and polyolefine.
A kind of bituminous composition is characterized in that: above-mentioned modified asphalt material and pitch is mixed.
A kind of asphalt mixture is characterized in that: modified asphalt material, pitch and aggregate class is mixed.
Above-mentioned asphalt mixture is characterized in that: it uses the asphalt-regenerating aggregate that is made by original waste material of mating formation as the aggregate class.
The preparation method of above-mentioned asphalt mixture is characterized in that: when making asphalt mixture, adopt the mechanical means hybrid mode that above-mentioned modified asphalt material is mixed with pitch and aggregate class.
Among the present invention, owing to added polyolefine, not only keep physical strengths such as the material modified wear resistant of protobitumen, shock-resistance, anti-flowability and solvability, processibility, advantage that storage stability is good, also improved the high-temperature behavior of modified asphalt material.
[embodiment]
In this specification sheets, modified asphalt material and pitch blended modifying asphalt are called " bituminous composition ", and be modified asphalt material, pitch and aggregate class blended mixture " asphalt mixture ".Generally, this asphalt mixture adopts the method that is laid on the road to mat formation.
Under the situation of mechanical means hybrid mode, add modified asphalt material when in the pitch mechanical means, making asphalt mixture.Under the situation of pre-mixing mode, prepare pitch and modified asphalt material blended bituminous composition in advance, combined aggregate class in this bituminous composition is made asphalt mixture.
Among the present invention, can also use the asphalt-regenerating aggregate that makes by the existing waste material of mating formation asphalt mixture as the aggregate class.Therefore, the regeneration aggregate that can more effective utilization makes by the waste material that is difficult to be used in again the existing asphalt pavement that high-performance mats formation in the prior art.In addition, because of toughness, the good toughness of asphalt mixture of the present invention, so, also have this regeneration aggregate and be difficult to the feature from asphalt mixture, peeling off, come off even use under the situation of regeneration aggregate.
Therefore modified asphalt material of the present invention can make modified asphalt material promptly mix with pitch because the solvability in pitch is good.Make asphalt mixture so be particularly suitable for adopting the mechanical means hybrid mode.
Modified asphalt material in the embodiment of the present invention uses by being added in the pitch, the physical strength of the wear resistant of raising asphalt mixture, shock-resistance, anti-flowability, high-temperature behavior etc.This modified asphalt material, with respect to vinyl aromatic hydrocarbon-conjugated diene block copolymer 100 weight parts, contain tackifying resin 0～100 weight part, mixed oil 5～100 weight parts and polyolefine 10～50 weight parts, with respect to total amount 100 weight parts of these various compositions, can also contain the following rubber of 40 weight parts simultaneously.
Below, these various compositions are described:
1) vinyl aromatic hydrocarbon-conjugated diene block copolymer
Vinyl aromatic hydrocarbon-the conjugated diene block copolymer that uses as the present invention (below, sometimes be called for short " segmented copolymer "), so long as generally add the multipolymer that material uses as pitch, then there is not particular restriction, for example, can be hydrogenation partially or completely, or use the multipolymer of the modifier modification of maleic anhydride etc.Specifically, can use SBS (styrene-butadiene block copolymer), SIS (styrene-isoprene block copolymer), SEBS (styrene-ethylene-butylene block-copolymer) etc.
Usually, can use have with the vinyl aromatic hydrocarbon as at least 1 of the polymer blocks (A) of main body, preferred 2 and with conjugated diene compound as at least 1 ground of main body geopolymer block (B) segmented copolymer etc.
So-called " is main body geopolymer block (A) with the vinyl aromatic hydrocarbon ", be with surpass 50 weight %, preferred 60～100 weight %, more preferably 70～100 weight %, the ratio of preferred 80～100 weight % contains the polymer blocks of vinyl aromatic hydrocarbon again, is the polymer blocks that is formed by the homopolymer of vinyl aromatic hydrocarbon or vinyl aromatic hydrocarbon and conjugated diolefine.The distribution of the conjugated diolefine in the polymer blocks (A) can be any form of random, alternation, part block-wise or these combinations.So-called " is main body geopolymer block (B) with the conjugated diene compound ", be with surpass 50 weight %, preferred 60～100 weight %, more preferably 70～100 weight %, the ratio of preferred 80～100 weight % contains the polymer blocks of conjugated diolefine again, is the homopolymer of conjugated diolefine or conjugated diolefine and the polymer blocks of vinyl-arene formation.The distribution of the vinyl aromatic hydrocarbon in the polymer blocks (B) can be any form of random, alternation, part block-wise or these combinations.
Segmented copolymer can be any of a linear structure and a chain structure, the multipolymer that preferably has structure shown in following general formula (1)-(7):
(1)(A-B)m、(2)(A-B)n-A、(3)(B-A)m-B、(4)((A-B)n)p-X、(5)((B-A)m)p-X、(6)((A-B)n-A)p-X、(7)((B-A)n-B)p-X
In these general formulas, A is to be main body geopolymer block (A) with the vinyl aromatic hydrocarbon, and B is the polymer blocks (B) based on conjugated diolefine.X is the residue of multifunctional coupling agent or the residue of multifunctional initiator.M is the integer more than 1, and preferably the integer more than 2 is more preferably 2～6 integer.N is the integer more than 1, and preferably 1～6 integer is more preferably 1.P is 2～6 integer.
The vinyl aromatic hydrocarbon in the segmented copolymer and the ratio of components of conjugated diolefine do not have particular restriction, but in order to make the agglutinate performance and the cold property height balance of toughness, toughness etc., weight ratio is 5: 95～95: 5, preferred 10: 90～50: 50, be more preferably 15: 85～45: 55 scope.
The vinyl binding capacity of the conjugated diolefine of segmented copolymer part does not have particular restriction, and is preferred 1～60% normally below 90%, preferred again 5～30% scope.When the vinyl binding capacity was too many, the penetration degree of bituminous composition reduced sometimes.
The molecular weight of the segmented copolymer that the present invention uses does not have special restriction, in order to make the agglutinate performance height balance of solvability in pitch and penetration degree, toughness, toughness, cold property etc., the polystyrene conversion weight-average molecular weight that GPC measures is 10,000～1,000,000, preferably 20,000～800,000, is more preferably 50,000～500,000.
The segmented copolymer that the present invention uses can adopt known method.In hydrocarbon solvent, use organolithium compound as initiator, vinyl aromatic hydrocarbon and polymerization of conjugated dienes are made.During polymerization, in order to regulate the reactivity ratio of vinyl aromatic hydrocarbon and conjugated diolefine, or change polymeric conjugated diolefine part microtexture, regulate polymerization velocity etc., can use polar compound.
As conjugated diolefine, for example, can enumerate 1,3-butadiene, isoprene, 1,3-isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene etc.Wherein, preferred 1,3-butadiene and isoprene, preferred especially 1,3-butadiene.Conjugated diolefine can be used separately, can also be used in combination more than 2 kinds.
The hydrocarbon solvent that uses as polymer solvent when making segmented copolymer for example, can be enumerated the aliphatic hydrocarbon of butane, pentane, hexane, iso-pentane, heptane, octane, octane-iso etc.; The alicyclic hydro carbons of pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane etc.; Benzene, ethylbenzene, dimethylbenzene etc. aromatic hydrocarbon based etc., these can use separately, can also mix more than 2 kinds and use.The consumption of hydrocarbon solvent makes above-mentioned monomer concentration become 1 weight %～50 weight % usually.
As polar compound, for example, can enumerate the ethers of tetrahydrofuran (THF), diethyl ether, phenylmethylether, dimethoxy benzene, glycol dimethyl ether etc.; The amine of triethylamine, tetramethylene-diamine, accelerine, pyridine etc.; The pure salts of thioether class, phosphine class, phosphoramide types, benzene sulfonamide acids, potassium or sodium etc. etc. can performance as requested suitably be selected.The consumption of polar compound suitably determines according to the kind of compound, the ground characteristic that requires, and usually with respect to 1 mole of organolithium compound, is 0.001～1 molar weight, the scope of 0.01～0.5 molar weight preferably.
Organolithium compound as the initiator use, can enumerate the multifunctional initiator of organic single-lithium compound or organic two lithium compounds etc., as specific examples, for example, can enumerate n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexyllithium, isohexyl lithium, phenyl lithium, naphthyl lithium, hexa-methylene two lithiums, butadienyl two lithiums, prenyl two lithiums etc.The general organic single-lithium compound that uses, these can use separately, can also be used in combination more than 2 kinds.Consumption is suitably selected according to the molecular weight of desired polymkeric substance, the kind of organolithium compound, for example, is example with the n-Butyl Lithium, with respect to monomer total amount 100 weight fraction, and normally 0.001～1 weight fraction, the scope of 0.01～1 weight fraction preferably.
Polyreaction can be any of isothermal reaction, adiabatic reaction, usually carries out at 0～150 ℃, preferred 20～120 ℃ temperature range.
As segmented copolymer, also can use and after above-mentioned polyreaction, add the multipolymer that multifunctional coupling agent is made.As multifunctional coupling agent, for example, can enumerate the metallic compound of tin tetrachloride, tindichloride, tin tetrabromide, silicon tetrachloride, Silicon bromide, silicon tetraiodide, germanium tetrachloride, lead dichloride, METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), butyl trichlorosilane, dibutyl tin dichloride, two (Trichloromonosilane base) ethane, two (trichlorine stannyl) ethane, tetramethoxy-silicane, tetramethoxy tin, tetraethoxy-silicane, tin tetraethoxide, four butoxy silicon, four butoxy tin etc.; The unsaturated nitrile of ethyl third rare nitrile etc.; The dihalo hydro carbons of dibromobenzene, dichlorobenzene, sym-dibromoethane etc.; The carboxylic acid esters of dimethyl adipate, diethylene adipate, ethyl benzoate, dimethyl terephthalate (DMT), diethyl terephthalate, dimethyl phthalate, dimethyl isophthalate etc.; The carboxylic acid halides class of p-phthaloyl chloride, phthalyl chloride, m-phthaloyl chloride, hexanedioyl chlorine etc.; Tetracol phenixin etc.
These segmented copolymers can use the partially or completely multipolymer of hydrogenation.Hydrogenation uses (1) to make the heterogeneous catalyst of metal load on the carrier of carbon, silicon-dioxide, aluminum oxide, diatomite etc. of Ni, Rt, Pd, Ru etc., can also use (2) to adopt the homogeneous catalyst of the catalytic organism agent etc. of the Ziegler-type catalyst of reductive agent of the organic acid salt of Ni, Co, Fe, Cr etc. or acetylacetonate and organoaluminum etc. or the organometallic compound of Ru, Rh etc. etc. to carry out.In general, adopt in inert solvent, hydrogenation catalyst in the presence of carry out the method for hydrogenation.
In addition, as segmented copolymer, can also use and after aforementioned polyreaction, add the multipolymer that properties-correcting agent is made.As properties-correcting agent, as the unsaturated carboxylic acid of maleic anhydride etc., imino-compound, cyanamide compound, ethylene imido-compound, aminocompound etc.
Mixed oil
2) mixed oil
Mixed oil of the present invention can use the vegetables oil of Rice pollard oil, soybean wet goods, the animal oil of fish oil, whale oil etc., and the oil of cylinder stock oil, lubricated wet goods is the heavy hydrocarbon wet goods.If the circulation on consideration economy and the market etc., using oil is heavy hydrocarbon oil, wherein, preferably uses the aromatic series hydrocarbon ils.Certainly, also can use the mixed oil of the hydrocarbon composition of alkane hydrocarbon system or naphthene series.
With regard to mixed oil, preferably the aromatic composition content in this mixed oil is that the kinematic viscosity value of 15～60 weight % and 40 ℃ is at 40～900mm
2The scope of/s.More preferably the aromatic component amount in the mixed oil is 30～55 weight %, and the kinematic viscosity value under 40 ℃ is at 100～900mm
2The scope of/s.
Here, " aromatic composition content " is meant that addition in the aromatic hydrocarbons of benzene, the bitter edible plant, anthracene etc. and these aromatic hydrocarbonss has the various functional groups' of vinyl etc. the total content of derivative.The content of the aromatic component in the mixed oil can be measured according to conventional methods.
When the aromatic composition content in the mixed oil and the value of kinematic viscosity exceed above-mentioned scope, material modified be processed into when granular to the granulation cutter produce adhere to or during storage material modified particle adhere each other etc., cause rather than ideal, when the aromatic composition content in the mixed oil and the value of kinematic viscosity are lower than above-mentioned scope, poor the conformality that modified asphalt material is processed into when for example granular.All the other compositions beyond the aromatic component for example cycloalkanes composition and paraffinic hydrocarbons components in proportions do not have particular restriction.
The usage quantity of mixed oil, with respect to segmented copolymer 100 weight fraction, preferably 5～100 weight fraction are more preferably 10～75 weight fraction.The usage quantity of mixed oil is very little the time, and the characteristic of solvability in pitch or elongation etc. is poor, otherwise when too many, characteristics such as softening temperature or toughness are poor, and are all undesirable.
3) tackifying resin
Tackifying resin as the present invention's use, so long as use on the general industry, then there is not particular determination, for example, can enumerate coumarone-indene resin, phenol resins, p-tert-butylphenol-acetylene resin, phenol-formaldehyde resin, terpenes-phenolic resin, polyterpene resin, xylene formal dehyde resin, C
5Through-stone oleo-resinous, C
9Through-stone oleo-resinous, dicyclopentadiene are resin, polybutene, rosin etc., with these the hydrogenation thing or utilize modifier of maleic anhydride etc. etc.
These tackifying resins can use separately, can also mix more than 2 kinds and use.The usage quantity of tackifying resin, with respect to segmented copolymer 100 weight parts, preferred 0～100 weight fraction.Lower value 0 means if asphalt mixture is not had special adhesivity requirement, can not mix tackifying resin.The further preferred usage quantity of tackifying resin with respect to segmented copolymer 100 weight fraction, is 5～75 weight fraction.
The usage quantity of tackifying resin is very little the time, and the characteristic of the softening temperature of asphalt mixture, 60 ℃ of viscosity, dynamic stability etc. is poor, and is also poor to the bituminous solvability.Otherwise when the usage quantity of tackifying resin was too many, the characteristic of the toughness of asphalt mixture or toughness etc. was poor.
4) polyolefine
Polyolefine is PE, PP, EVA, APP, APAO, POE, HDPE, LDPE and/or LLDPE.The main high-temperature behavior that improves asphalt mixture.
5) rubber
Modified asphalt material of the present invention with respect to above-mentioned each composition, promptly with respect to vinyl aromatic hydrocarbon-conjugated diene block copolymer, mixed oil, tackifying resin and polyolefinic total amount 100 weight fraction, adds the following rubber of 40 weight parts.The general rubber that uses gets final product in these rubber use mechanicalss etc., for example, can use SBR (styrene butadiene rubbers), chloroprene rubber, natural rubber, polyisoprene rubber, polybutadiene rubber, nitrile is rubber, the rare rubber of ethene-third, acrylic rubber, isoprene-isobutene rubber etc.Rubber can use under emulsion state, also can use under solid state.Under the situation of emulsion state, add the following rubber of 40 weight fraction when being converted into solids component.
The addition of rubber is during greater than 40 weight fraction, the poor in processability of modified asphalt material.And, physical strength variation such as the anti-flowability of asphalt mixture.
Method as adding rubber, for example can adopt following mode:
(1) hybrid mode:
When segmented copolymer is mixed with mixed oil and tackifying resin, behind the interpolation rubber, implement certain processing and make modified asphalt material.So-called certain processing is for example to be mixed into uniform composition in heating, is processed into regulation shape, size as required.For example, with after mixed oil and rubber mix become uniform composition, be processed into granular or sheet, can make modified asphalt material at following vinyl aromatic hydrocarbon-conjugated diene block copolymer of heating and tackifying resin.Do not add under the situation of rubber, after following vinyl aromatic hydrocarbon-conjugated diene block copolymer of heating and tackifying resin and mixed oil are mixed into uniform composition, be processed into granularly, can make modified asphalt material.
If adopt this mode, modified asphalt material and rubber are not needed to transport respectively, preserve, without difficulty.In addition, when in pitch, sneaking into, because can once drop into these compositions, so production efficiency improves.
(2) separate mode:
Segmented copolymer is mixed the back implement certain processing with mixed oil, tackifying resin and polyolefine, make uniform composition.When in pitch, adding modified asphalt material then, can as this separate mode, add rubber constituent and other composition respectively.Adopt this mode, can be according to an amount of rubber of interpolation such as bituminous shapes.
6) pitch
Pitch as the present invention uses does not have particular restriction, can use habitual pitch, for example can use straight-run pitch, half oxidized bitumen, oxidized bitumen, fluxed asphalt, regeneration asphalt etc.These can use separately, can also be used in combination.Also can use the high viscosity agglutinate of decolouring agglutinate or premix.
Modified asphalt material of the present invention with respect to pitch 100 weight parts, preferentially uses 1～100 weight part.More preferably select with respect to pitch 100 weight parts, use 3～50 weight parts.Most preferably, use 3～50 weight parts.When usage quantity is less than this scope, there is not the bituminous modified effect basically.Otherwise, usage quantity than this for a long time, viscosity is too high, the application property of asphalt mixture is poor, economically also significant adverse.
7) aggregate class
Under the situation that modified asphalt material of the present invention is used to mat formation, combined aggregate is made the asphalt mixture use with filler (to call the aggregate class in the following text) usually.As the aggregate class, use the employed close granularity of generally mating formation, fine granularity or coarsness mixture with or permeable pavement with, drainage aggregate and the filler that usefulness, sound absorbing mats formation and the opener compounding compound that uses in the purposes such as use to use etc. of mating formation.For example, can use rubble, cobble, sandstone, sand or these mixture etc. as aggregate.Can use stone flour, talcum, lime carbonate or these mixture etc. as filler.
As the aggregate that uses in the asphalt mixture, can be brand-new aggregate, also can use the asphalt-regenerating aggregate of system that original waste material of mating formation is pulverized.Perhaps, also can use the mixture of new aggregate and asphalt-regenerating aggregate.The usage quantity of regeneration aggregate, 0～70 weight % preferably in the usage quantity of full aggregate, be more preferably 0～50 weight %, by using the asphalt-regenerating aggregate, the regeneration aggregate that can more effective utilization obtains from the waste material that is difficult to be used in again the existing asphalt pavement that high-performance mats formation in the past.In addition, be added with the asphalt mixture of modified asphalt material of the present invention, because toughness, good toughness even use under the situation of regeneration aggregate, also has general regeneration aggregate and be difficult to the feature peeling off, come off from asphalt mixture.In addition, be added with the asphalt mixture of asphalt modifier material of the present invention, even use under the situation of regeneration aggregate, also have anti-flowability, the physical strength of shock-resistance etc. and past are quite or than better feature in the past.
The blending means of aggregate class does not have special restriction.For example, can utilize the premix mode that the bituminous composition of synthetic bituminous and asphalt modifier agent in advance and aggregate class are made up, modified asphalt material, pitch and aggregate class are carried out the method for blended mechanical means hybrid mode etc., as the method for more efficient use feature of the present invention, be the mechanical means blending means.As the mechanical means hybrid mode, (a) for example arranged filler, hot aggregates and the pre-mixing of heating mix asphalt, add modified asphalt material then and carry out the blended method, (b) filler, hot aggregates, add heated bitumen and modified asphalt material carries out the blended method simultaneously, (c), add the method that heated bitumen mixes etc. then filler, hot aggregates and modified asphalt material pre-mixing.
8) other composition
The general additive that uses in can mix asphalt composition in the asphalt mixture.Additive does not have particular determination, as the concrete example of additive, can enumerate the anti-stripper of sulfide lime, amine, amides etc.; Methylcellulose gum, the fiber reinforced material of polyester, polyacrylonitrile, polyvinyl alcohol etc.; Elasticity rising agent, viscosity reducers, viscosity enahncers, weighting agent, pigment, tenderizer, antioxidant, UV light absorber, photostabilizer, thermoplastic resin etc.
In addition, in the modified asphalt material of the present invention and can need to add anti-adhesion agent.As anti-adhesion agent, so long as industrial general use, particular restriction then do not had.
As organic anti-adhesion agent, for example, can enumerate the higher fatty acid monoamide of stearylamide, oleylamide, laurylamide palmitic amide, erucicamide, Shan Yu acid acid amides etc.; The higher fatty acid bisamide of methylene-bis stearylamide, ethylenebisstearamide, ethylenebisoleoamide, ethylenebis laurylamide etc.; The compound higher fatty acid amides of N-hard base oil acid amides, N-hard base acyl amine, N-stearyl stearylamide, N-oil base stearylamide, distearyl adipamide etc.; The higher fatty acid salt of lithium salts, sodium salt, sylvite, magnesium salts, calcium salt, barium salt, zinc salt, aluminium salt, molysite etc. such as lauric acid, nutmeg acid, hexadecanoic acid, palmitinic acid, stearic acid, Shan Yu acid, oleic acid, linolic acid, alpha-eleostearic acid, β-eleostearic acid, α-linolic acid; The resin compound of the polyolefine of polyacrylamide, polyvinyl chloride, polystyrene, high density polyethylene(HDPE) etc., polymethyl acrylic acid potassium fat, polycarbonate, styrene-acrylonitrile copolymer etc. etc.
As inorganic anti-adhesion agent, can enumerate silicon-dioxide, lime carbonate, magnesiumcarbonate, calcium sulfate, aluminium hydroxide, zinc oxide, talcum, clay etc.
These anti-adhesion agents can use separately, or be used in combination.Wherein preferred inorganic anti-adhesion agent.The usage quantity of anti-adhesion agent, per 100 weight parts are material modified, 0～50 weight part normally, preferred 0.1～10 weight part, more preferably 0.5～5 weight part.
The antioxidant that can also add hindered phenol system, sulphur system, phosphoric acid system etc. in the modified asphalt material among the present invention as required; The UV light absorber of benzophenone series etc.; The thermoplastic elastomer of the multipolymer of the block beyond the photostabilizer of hindered amine system etc., vinyl aromatic hydrocarbon-conjugated diene block copolymer of the present invention etc.; The thermoplastic resin of the polyolefin-based resins of ethylene-acrylic acid second resin copolymer, ethylene-vinyl acetate resin copolymer etc., polystyrene resin, polyvinyl chloride resin etc.; The inorganic filler of granulated glass sphere, silicon oxide, carbon black etc. etc.
The method of making modified asphalt material adopts method commonly used to get final product; for example can use the mixing machine of heating and melting still, mill, single spiral shell material forcing machine, twin screw extruder, Henschel mixer etc. to mix above-mentioned each composition, use press, tablets press, extrusion shaping machine, working and forming machine etc. to carry out forming process then.
The shape of modified asphalt material of the present invention does not have special qualification, can use shape arbitrarily.For example, can be any shape of granular, strip, tabular, bulk etc., consider from the solvability viewpoint pitch, especially preferably granular.The granulation of modified asphalt material can mix above-mentioned each composition the back, be extruded into strip with forcing machine etc., after coolings such as cold water, machines with pelletizings such as tablets presss.Be coated with anti-adhesion agent if spread on the bar before granulation, then better improve the pelletizing processibility.In addition the particulate size be 0.5～50mm, preferred 1～20mm, more preferably during 2～10mm, the solvability in pitch is significantly improved.
Below, enumerate specific embodiment explanation the present invention, but the present invention is not subjected to the restriction of following specific embodiment.
Table 1: embodiment and Comparative Examples are used following material
| The component title | Mark | Component is described in detail | |||
| Chinese | English abbreviation | Aromatic composition content (wt%) | Kinematic viscosity (40 ℃, mm 2/s) | ||
| Segmented copolymer | A | Styrene-isoprene block copolymer | SIS | Melt flow value (200 ℃ 49.03N) are 2g/10min | |
| B | Styrene-butadiene block copolymer | SBS | |||
| C | Styrene-ethylene-butylene block-copolymer | SEBS | |||
| Tackifying resin | E | Terpenes-phenolic resin | |||
| F | Terpine resin | ||||
| Mixed oil | G | 40.8 | 323 | ||
| H | 46.7 | 586 | |||
| I | 27.1 | 53 | |||
| J | 57.3 | 993 | |||
| Polyolefine | K | New LDPE (film grade) | LDPE | ||
| L | High density polyethylene(HDPE) | HEPD | |||
| M | Ethylene-vinyl acetate copolymer | EVA | |||
| Rubber | N | Styrene butadiene ribber | SBR | ||
| O | Chloroprene rubber | CR | |||
The manufacturing of modified asphalt material:
Use the material of the mark A～M in the table 1 to make modified asphalt material.Use this modified asphalt material, carry out the test of processibility, storage stability and high-temperature behavior.Table 2 is the composition and the test-results of the modified asphalt material of Comparative Examples of the present invention and embodiment manufacturing.The component ratio of modified asphalt material is represented with weight %.For rubber (NO), use 100 weight parts (weight %) expression with respect to the total amount of segmented copolymer, tackifying resin, mixed oil.
In order to make modified asphalt material, concretely, in 200 liters of Henschel mixers, add tackifying resin, low speed (25HZ) stirred 5 minutes.Add segmented copolymer then; stir after 1 minute; slowly add mixed oil; and slowly add rubber as required; (35HZ) stirred after 9 minutes at a high speed, used the single screw extrusion machine of φ 65mm to be extruded into strip, after cooling off in the cooling tank of 15 ℃ of water temperatures; spread the lime carbonate that is coated with 1 weight %, be cut into the particle of φ 3mm * 4mm with the water-cooled tablets press that has circular knife.
Workability test: observe the material modified adhesion to rotating knife of above-mentioned tablets press rotation in the time of 10 minutes, estimate by following 3 kinds of standards.The results are shown in table 2.◎ represents " not adhering to ".
Storage stability is estimated: above-mentioned material modified particle 120g is packed in the vinyl plastics bag of 7 * 10cm2, apply the loading of 50g/em2, the state that leaves standstill in 90 ℃ baking oven after 3 hours is estimated by following 3 kinds of situations.The results are shown in table 2.◎ represents " not sticking mutually ".
Table 2
| Modified asphalt material | |||||||||
| Component | Comparative Examples | Embodiment | |||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | ||
| Segmented copolymer | A | 100 | 0 | 100 | 0 | 100 | 0 | 100 | 0 |
| B | 0 | 55 | 0 | 100 | 0 | 55 | 0 | 100 | |
| C | 0 | 45 | 0 | 0 | 0 | 45 | 0 | 0 | |
| Tackifying resin | E | 0 | 25 | 50 | 0 | 0 | 25 | 50 | 0 |
| F | 0 | 0 | 0 | 10 | 0 | 0 | 0 | 10 | |
| Mixed oil | G | 15 | 0 | 0 | 0 | 15 | 0 | 0 | 0 |
| H | 0 | 0 | 15 | 0 | 0 | 0 | 15 | 0 | |
| I | 0 | 10 | 0 | 0 | 0 | 10 | 0 | 0 | |
| J | 0 | 0 | 0 | 50 | 0 | 0 | 0 | 50 | |
| Polyolefine | K | 0 | 0 | 0 | 0 | 50 | 0 | 0 | 20 |
| L | 0 | 0 | 0 | 0 | 0 | 10 | 30 | 20 | |
| M | 0 | 0 | 0 | 0 | 0 | 0 | 20 | 10 | |
| Rubber | N | 0 | 0 | 0 | 60 | 0 | 0 | 0 | 84 |
| O | 20 | 0 | 0 | 0 | 20 | 0 | 0 | 0 | |
| Test-results | Processibility | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Storage stability | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | |
By table 2 as can be known, though added polyolefine, the processibility of modified asphalt material, storage stability etc. are still good.
The manufacturing of bituminous composition:
In pitch, add the modified asphalt material shown in the table 2, make bituminous composition.Concretely, in 1 liter Glass Containers, modified asphalt material is added in the straight-run pitch that is heated to 180 ℃, continue to stir, measure the various rerum naturas of the bituminous composition of manufacturing, measurement result is shown in table 3 up to dissolving fully.In the table 3, quality standard is the quality standard of the high-viscosity modified asphalt of regulation in the Japanese modifying asphalt association criterion (JMAAS01-01).
The physical property measurement method of bituminous composition is as follows:
(1) solvability
Modified asphalt material is to the bituminous solvability, " the modifying asphalt style manufacture method " put down in writing in the test method(s) brief guide of mating formation of formulating according to Japanese road association, in being heated to 180 ℃ pitch, add modified asphalt material, stir, obtain up to the time (branch) of not understanding molten thing.
(2) penetration degree
The penetration degree of asphalt mixture (1/10mm) is measured by GB
(3) softening temperature
The softening temperature of asphalt mixture (℃) measure by GB
(4) toughness-toughness
Toughness of asphalt mixture (N-m) and toughness (N-m) are measured by the method for putting down in writing in the GB.
(5) 60 ℃ of viscosity (Pa.s) are measured by method of record in Japanese road association's volume " the test method(s) brief guide of mating formation ".
Table 3
| Bituminous composition | Quality standard | ||||||||
| Test item | Comparative Examples | Embodiment | |||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | ||
| Mixture ratio (modified asphalt material/pitch) | 12/18 | 12/18 | 12/18 | 12/18 | 12/18 | 12/18 | 12/18 | 12/18 | - |
| Dissolution time in pitch (min) | 15 | 15 | 15 | 10 | 15 | 15 | 15 | 10 | Below 20 |
| Penetration degree (1/10min) | 44 | 42 | 43 | 45 | 44 | 42 | 40 | 45 | More than 40 |
| Softening temperature (℃) | 87.1 | 88.2 | 87.6 | 90.3 | 93.2 | 93.2 | 93.6 | 95.9 | More than 80 |
| Toughness (Nm) | 28.3 | 28.1 | 27.3 | 29.6 | 34.3 | 27.8 | 28.9 | 35.2 | More than 20 |
| Toughness (Nm) | 21.7 | 21.5 | 20.6 | 22.5 | 28.3 | 27.0 | 22.3 | 34.1 | More than 15 |
| 60 ℃ of viscosity (* 10 4Pa·s) | 25.7 | 24.3 | 23.8 | 35.2 | 26.6 | 23.1 | 25.2 | 35.5 | More than 2 |
As shown in Table 3, by adding polyolefine, the softening temperature of bituminous composition obviously improves, and simultaneously, other indexs such as softening temperature, toughness, toughness, 60 degree viscosity etc. are conformance with standard also.
The manufacturing of asphalt mixture:
Modified asphalt material shown in the table 2 is mixed with pitch, aggregate class, make asphalt mixture.Measure the various rerum naturas of the asphalt mixture of making like this.Measurement result is shown in table 4.In the table 4, the embodiment of asphalt mixture and the sequence number of comparative example, corresponding with the sequence number of the embodiment of modified asphalt material and comparative example.For example, the asphalt mixture of the embodiment 1 in the table 4, the modified asphalt material of the embodiment 1 in the interpolation table 2.In addition, in the table 4, the aggregate kind is being write " twice-laid stuff ", and sign has used the regeneration aggregate of original asphalt pavement.
The physical property measurement method of asphalt mixture is as follows:
Voidage: the voidage of asphalt mixture (%), measure by the method for the use vernier of GB record.
Dynamic stability: the dynamic stability of asphalt mixture, by the method for putting down in writing in the GB, carry out the wheelmark test, the calculating dynamic stability (inferior/mm).
The canned loss rate of oxidation (%) of asphalt mixture is measured by GB.
Table 4
| Asphalt mixture | ||||||||
| Test item | Comparative Examples | Embodiment | ||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | |
| Mixture ratio (modified asphalt material/pitch) | 12/88 | 12/88 | 12/88 | 12/88 | 12/88 | 12/88 | 12/88 | 12/88 |
| The aggregate kind | Green wood | Green wood | Twice-laid stuff | Twice-laid stuff | Green wood | Green wood | Twice-laid stuff | Twice-laid stuff |
| Voidage | 21.7 | 20.5 | 20.9 | 21.2 | 20.0 | 20.2 | 20.6 | 20.5 |
| Canned loss rate of oxidation (20 ℃) | 12.9 | 9.6 | 8.1 | 10.5 | 14.5 | 13.1 | 10.9 | 17.4 |
| Canned loss rate of oxidation (20 ℃) | 22.4 | 20.2 | 19.3 | 20.2 | 24.6 | 23.4 | 21.3 | 25.5 |
| Dynamic stability (inferior/mm) | 5192 | 4256 | 4238 | 5310 | 5699 | 4612 | 4801 | 5823 |
As shown in Table 4, by adding polyolefine, the high-temperature behavior performance of asphalt mixture obviously improves (high-temperature behavior can embody by dynamic stability).
Adopt the present invention, can be provided in favorable solubility and excellent asphalt modifier material such as processibility and storage stability in the pitch.The modified asphalt material of the physical strength of further raising wear resistant, shock-resistance, anti-flowability etc. can be provided in addition.In addition, can provide and to be applicable to that with being difficult in the prior art asphalt-regenerating aggregate that makes from the existing waste material of mating formation that high-performance is mated formation is used in the modified asphalt material that high-performance is mated formation again.The more important thing is, can obviously improve the high-temperature behavior of bituminous composition and asphalt mixture.
Claims (9)
1. modified asphalt material, wherein, less than vinyl aromatic hydrocarbon-conjugated diene block copolymer 100 weight parts that 15g/10 divides, contain tackifying resin 0～100 weight part with respect to the melt flow value, mixed oil 5～100 weight parts is characterized in that: also contain polyolefine 10～50 weight parts.
2. modified asphalt material according to claim 1 is characterized in that: simultaneously with respect to total amount 100 weight parts of various compositions, contain the following rubber of 40 weight parts.
3. modified asphalt material according to claim 1 and 2, wherein, polyolefine is PE, PP, EVA, APP, APAO, POE, HDPE, LDPE and/or LLDPE.
4. prepare the method for the described modified asphalt material of claim 1, it is characterized in that: after being mixed into homogeneous compositions under the heating, be processed into granular vinyl aromatic hydrocarbon-conjugated diene block copolymer, tackifying resin, mixed oil and polyolefine.
5. prepare the method for the described modified asphalt material of claim 2, it is characterized in that: after being mixed into homogeneous compositions under the heating, be processed into granular vinyl aromatic hydrocarbon-conjugated diene block copolymer, tackifying resin, mixed oil, rubber and polyolefine.
6. bituminous composition is characterized in that: claim 1,2 or 3 one of any modified asphalt materials and pitch is mixed.
7. asphalt mixture is characterized in that: claim 1,2 or 3 one of any modified asphalt materials and pitch and aggregate class is mixed.
8. asphalt mixture according to claim 7 is characterized in that: it uses the asphalt-regenerating aggregate that is made by original waste material of mating formation as the aggregate class.
9. prepare the method for the described asphalt mixture of claim 7, it is characterized in that: when making asphalt mixture, adopt the mechanical means hybrid mode that above-mentioned modified asphalt material is mixed with pitch and aggregate class.
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