CN100408638C - Asphalt modifier and modified asphalt composition - Google Patents
Asphalt modifier and modified asphalt composition Download PDFInfo
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- CN100408638C CN100408638C CNB011354143A CN01135414A CN100408638C CN 100408638 C CN100408638 C CN 100408638C CN B011354143 A CNB011354143 A CN B011354143A CN 01135414 A CN01135414 A CN 01135414A CN 100408638 C CN100408638 C CN 100408638C
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Abstract
The invention provides an asphalt modifier which is possible to improve fluidity resistance of asphalt at a high temperature and bending characteristics thereof at a low temperature, and which has excellent mechanical stability, and excellent dispersion and solubility in the asphalt, and to provide a composition comprising compounding the modifier. The asphalt modifier comprises, as a principal component, a conjugated diene type copolymer comprising (A) a conjugated diene unit (1,3-butadiene unit, etc.) of 55-99.9 wt.%, (B) an unsaturated carboxylic acid alkali metal salt unit (sodium acrylate unit, etc.) of 0.1-5 wt.%, (C) an unsaturated carboxylic acid unit (crylic acid, etc.) of 0-4.9 wt.% (but, the total amount of (B) and (C) is of 0.1-5 wt.%), (D) an aromatic vinyl compound unit (cinnamene unit, etc.) of 0-44.9 wt.%, and (E) other monomer units ( (methyl-) acrylic ester unit, etc.) of 0.2-20 wt.%.
Description
Background technology
The present invention relates to a kind of asphalt modifier and be combined with the composition of this asphalt modifier, this asphalt modifier with a kind of unitary conjugated diene copolymer of unsaturated carboxylic acid basic metal that contains as principal constituent, when it being added to those and contains in the more pitch that at room temperature is saturated composition of buttery or aromatic component, can improve this pitch at high temperature anti-flowability and flexible at low temperatures, and the mechanical stability of this asphalt modifier and the dispersion-solvability in pitch are all good.
The bituminous material of pitch, tar etc. has water-repellancy and non-corrosibility, in uses such as material that just has been used as the pavement material of road, the top of putting up a house a long time ago and covering materials.Pitch particularly, though it can mix with an amount of aggregate, packing material etc. usually, form as asphalt is used, but when directly applying to such asphalt in the various purposes, there is the temperature sensitivity height, the shortcoming of the low and poor performance at low temperatures of binding property, wear resistance and shock-resistance.In contrast, add as the SBR (copolymer emulsion of styrene butadiene) of properties-correcting agent or the thermoplastic elastomer of CR rubber constituents such as (neoprene latex) or SBS segmented copolymer etc. if in pitch, cooperate, just can obtain to reduce the adhesivity and the wear resistance thereof of temperature sensitivity, increase and aggregate, and improve its flexible effect, the result just can obtain the modifying asphalt mixture that hot properties and cold property are significantly increased.Learn, when the pitch that uses by the middle-eastern crude manufacturing, be easy to obtain these modified effects, this class pitch is being separated with tlc, show when carrying out quantitative analysis with hydrogen flame ionization detector then, at room temperature generally account for 4～6% for the saturated composition of buttery, aromatic component generally accounts for 60～64%.
Yet, for the pitch that the crude oil of producing with countries such as China, India, Russia is made, generally all contain more at room temperature be saturated composition of buttery or aromatic component, therefore, even add properties-correcting agent such as SBR or SBS, also be difficult to obtain anti-flowability of high temperature and low temperature flexible.
Brief summary of the invention
The present invention is the invention of finishing after furtheing investigate in order to solve above-mentioned prior art problems, the objective of the invention is to contain more at room temperature the be anti-flowability of bituminous high temperature and the low temperature bendability characteristics of the saturated composition of buttery or aromatic component, the bituminous composition that the asphalt modifier that a kind of mechanical stability is good and dispersion-the solvability in pitch is all good is provided and is combined with this properties-correcting agent in order to improve those.
Of the present invention theing contents are as follows.
1. asphalt modifier, it is to be used for the bituminous properties-correcting agent that those contain the oily composition, it is characterized in that the conjugated diene copolymer that it constitutes with following (A)-(E) composition is principal constituent (A) conjugated diene unit 55～99.9 weight %, (B) unsaturated carboxylic acid an alkali metal salt unit and/or (C) unsaturated carboxylic acid unit 0.1～5 weight %, (D) aromatic ethenyl compound unit 0～44.9 weight % and (E) other monomeric units 0～20 weight %.
2. as above-mentioned 1 described asphalt modifier, wherein, above-mentioned (B) unsaturated carboxylic acid an alkali metal salt unit is 0.1～5 weight %, and above-mentioned (C) unsaturated carboxylic acid unit is 0～4.9 weight %.
3. as above-mentioned 1 described asphalt modifier, wherein, the monomer that is used to form above-mentioned (A) conjugated diene unit is to be selected from least a in 1,3-butadiene, isoprene and the 1,3-pentadiene; Be used to form the unitary monomer of above-mentioned (C) unsaturated carboxylic acid and be and be selected from least a in vinylformic acid, methacrylic acid and the toxilic acid; Be used to form the unitary monomer of above-mentioned (B) unsaturated carboxylic acid an alkali metal salt and be and be selected from least a in vinylformic acid, methacrylic acid and the toxilic acid, and this basic metal is lithium, sodium or potassium; Being used to form the unitary monomer of above-mentioned (D) aromatic ethenyl compound is vinylbenzene and/or alpha-methyl styrene; The monomer that is used to form above-mentioned (E) other monomeric units is for being selected from least a in (methyl) esters of acrylic acid, unsaturated amides, unsaturated acid imide and the cyanic acid vinyl acetate compound.
4. as above-mentioned 1 described asphalt modifier, wherein, the pitch that contains the oily composition is a kind ofly to separate with tlc, when carrying out quantitative analysis with hydrogen flame ionization detector then, wherein contains the pitch of saturated composition 7～25% and/or aromatic component 65～80%.
5. a modified asphalt composite is characterized in that, contains at asphalt modifier described in above-mentioned 1 and the pitch that contains the oily composition, contains the pitch of oily composition with respect to this, and the content of above-mentioned asphalt modifier is counted 0.2～20 weight % by solid state component.
6. as above-mentioned 5 described modified asphalt composites, wherein, the monomer that is used to form above-mentioned (A) conjugated diene unit is to be selected from least a in 1,3-butadiene, isoprene and the 1,3-pentadiene; Be used to form the unitary monomer of above-mentioned (C) unsaturated carboxylic acid and be and be selected from least a in vinylformic acid, methacrylic acid and the toxilic acid; Be used to form the unitary monomer of above-mentioned (B) unsaturated carboxylic acid an alkali metal salt and be and be selected from least a in vinylformic acid, methacrylic acid and the toxilic acid, and this basic metal is lithium, sodium or potassium; Being used to form the unitary monomer of above-mentioned (D) aromatic ethenyl compound is vinylbenzene and/or alpha-methyl styrene; The monomer that is used to form above-mentioned (E) other monomeric units is for being selected from least a in (methyl) esters of acrylic acid, unsaturated amides, unsaturated acid imide and the cyanic acid vinyl acetate compound.
7. as above-mentioned 5 described modified asphalt composites, wherein, the above-mentioned pitch that contains the oily composition is a kind ofly to separate with tlc, when carrying out quantitative analysis with hydrogen flame ionization detector then, wherein contains the pitch of saturated composition 7～25% and/or aromatic component 65～80%.
Asphalt modifier of the present invention has low viscosity and good operability under the latex state, and its mechanical stability and the dispersion-solvability in pitch are all good, contain in the more pitch at room temperature when it being added to those for saturated composition of buttery or aromatic component, when making modified asphalt composite, the composition that obtains has big sticking toughness (toughness) and toughness (tenacity), viscosity in the time of 60 ℃ is high and low to the susceptibility of temperature, and when making modified asphalt mixture with it, the dynamic stability height of the compound that obtains, anti-flowability is good, and flexible performance at low temperatures is also good.
Therefore, containing more for those at room temperature is the pitch of saturated composition of buttery or aromatic component, be difficult to obtain excellent high-temperature characteristic or cold property in the past, and asphalt modifier of the present invention can carry out modification to this class pitch effectively, make it when using, can prevent the generation of " rut " and " crack " effectively as pitch class road pavement material, this specific character has satisfied in recent years the requirement to asphalt roads, simultaneously, asphalt modifier of the present invention helps to expand the new purposes of bituminous composition, boosts productivity and reduces cost.
To detailed description of the invention
Detailed hereafter the present invention.
Hereinafter, so-called " modified asphalt composite " is meant the composition that is formed by asphalt modifier and pitch mix, and in addition, so-called " modified asphalt mixture " is meant the compound that is formed with mixs such as aggregates by asphalt modifier and pitch.
In " conjugated diene copolymer " that constitute asphalt modifier principal constituent of the present invention,, can enumerate: 1 as the example of (A) conjugated diolefine, 3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene etc.
In these conjugated diolefines, from can be easily considering in the industrial viewpoint of obtaining and can obtaining good asphalt modifier, preferably 1,3-butadiene, isoprene and 1,3-pentadiene, especially preferably 1,3-butadiene.Above-mentioned conjugated diolefine can be individually or two or more mixing use.
In conjugated diene copolymer of the present invention, the containing ratio of conjugated diolefine is 55～99.9 weight %, is preferably 60～80 weight %.
In the case, if the containing ratio deficiency of conjugated diolefine 55 weight %, then the pliability of modified asphalt composite reduces, and its toughness and low temperature extensibility etc. are impaired, on the other hand, if surpass 99.9 weight %, the then mechanical stability of conjugated diene copolymer latex and the dispersion-solvability in pitch thereof, and the sticking toughness of modified asphalt composite, the dynamic stability of modified asphalt mixture etc. all reduce.
In addition, as the example of (C) unsaturated carboxylic acid, can enumerate: vinylformic acid, methacrylic acid, Ba Dousuan, α-Lv Bingxisuan, toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, methylfumaric acid etc.In these unsaturated carboxylic acids, particularly preferably be vinylformic acid, methacrylic acid, toxilic acid.Above-mentioned unsaturated carboxylic acid can be individually or two or more mixing use.
In addition, in (B) unsaturated carboxylic acid an alkali metal salt,, can enumerate lithium, sodium, potassium etc. as alkali-metal example.These unsaturated carboxylic acid an alkali metal salts can be individually or two or more mixing use.
In conjugated diene copolymer of the present invention, the containing ratio of unsaturated carboxylic acid an alkali metal salt is generally 0.1～5 weight %, is preferably 0.3～3 weight %, and in addition, the containing ratio of unsaturated carboxylic acid is generally 0～4.9 weight %, is preferably 0～3 weight %.But the total containing ratio of unsaturated carboxylic acid an alkali metal salt and unsaturated carboxylic acid is 0.1～5 weight %.
In the case, if the containing ratio deficiency of unsaturated carboxylic acid an alkali metal salt 0.1 weight %, then the dynamic stability of the sticking toughness of the mechanical stability of conjugated diene copolymer latex and the dispersion-solvability in pitch thereof, modified asphalt composite and toughness, modified asphalt mixture etc. all reduces, on the other hand, if surpass 5 weight %, the viscosity increased of conjugated diene copolymer latex then, and the dynamic stability of the sticking toughness of its dispersion-solvability in pitch, modified asphalt composite and toughness, modifying asphalt mixture etc. all reduces.
But, if the containing ratio of unsaturated carboxylic acid surpasses 4.9 weight %, the viscosity increased of conjugated diene copolymer latex, the dynamic stability of the sticking toughness of the dispersion-solvability in pitch, modified asphalt composite and toughness and modifying asphalt mixture all reduces.
In addition, example as (D) aromatic ethenyl compound, can enumerate: vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl-dimethyl benzene, ethyl styrene, t-butyl styrene, monochlorostyrene, dichlorostyrene, phenyl-monobromide ethene, Dowspray 9,1,1-diphenyl benzene ethene, N, N-dimethyl p-aminophenyl ethene, N, N-diethyl p-aminophenyl ethene, N, the N-dimethyl is to amino-ethyl vinylbenzene, N, and N-two bases are to amino-ethyl vinylbenzene, Vinylstyrene, vinyl naphthalene, vinyl pyridine etc.In these aromatic ethenyl compounds, particularly preferably be vinylbenzene, alpha-methyl styrene.In addition, above-mentioned aromatic ethenyl compound can be used alone or mixed use of two or more.
In conjugated diene copolymer of the present invention, the containing ratio of aromatic ethenyl compound is generally 0～44.9 weight %, is preferably 15～40 weight %.In the case, if the containing ratio of aromatic ethenyl compound surpasses 44.9 weight %, then the pliability of modified asphalt composite reduces, and its toughness, low temperature extensibility etc. are all impaired, and the dynamic stability of modified asphalt mixture etc. also reduces.
And, in conjugated diene copolymer of the present invention, except above-mentioned conjugated diolefine, the unsaturated carboxylic acid an alkali metal salt, outside unsaturated carboxylic acid and the aromatic ethenyl compound, can also be as required, make its with (E) included monomer in more than one monomer carry out copolymerization, said (E) is meant other unsaturated monomers that can carry out copolymerization with above-mentioned monomer, for example: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid N, the N-dimethylaminoethyl, (methyl) vinylformic acid N, the N-lignocaine ethyl ester, (methyl) esters of acrylic acid of (methyl) glycidyl acrylate etc.; The unsaturated amides or the unsaturated acid imide of (methyl) acrylamide, N-methylol (methyl) acrylamide, maleimide etc.; The cyanic acid vinyl compound of (methyl) vinyl cyanide, cyanic acid vinylene etc. etc.The usage ratio of other above-mentioned unsaturated monomers, with respect to whole monomer components, usually below 20 weight %, preferably below 15 weight %, 0.5～10 weight % more preferably.In the present invention, contain under the situation of above-mentioned other unsaturated monomers the containing ratio when above-mentioned (A), (B), (C), (D) and each unitary containing ratio (E) all are meant and are 100 weight % with (A)～(E) each unitary total containing ratio when conjugated diene copolymer.
Conjugated diene copolymer among the present invention is the best with the use that is scattered in the latex state in the water.
Manufacture method as above-mentioned conjugated diene copolymer latex, preferred use following method 1.: respectively with the conjugated diolefine and the unsaturated carboxylic acid of predetermined amount, according to circumstances with unsaturated carboxylic acid an alkali metal salt and/or aromatic ethenyl compound or other unsaturated monomer, carry out copolymerization by known emulsion polymerization, in polymerization process and/or after polymerization finishes, the carboxyl in the copolymer emulsion is neutralized so that the pH value is adjusted to more than 6, thereby make required conjugated diene copolymer latex with caustic alkali.In the case, if pH value less than 6, then contained unsaturated carboxylic acid an alkali metal salt can not reach the amount of regulation in the conjugated diene copolymer that is obtained, therefore cause the mechanical stability of conjugated diene copolymer latex and the dispersion-solvability in pitch thereof abundant inadequately, and the dynamic stability of the sticking toughness of modified asphalt composite and toughness and modified asphalt mixture etc. all reduce.
In addition, 2. conjugated diene copolymer latex of the present invention also can make according to following method as required, that is: respectively with the conjugated diolefine and the unsaturated carboxylic acid an alkali metal salt of predetermined amount, according to circumstances, carry out copolymerization by known emulsion polymerization with unsaturated carboxylic acid and/or aromatic ethenyl compound or other unsaturated monomer.
There is not particular determination for the emulsifying agent that in the above-mentioned emulsion polymerization, uses, polymerization starter, chain-transfer agent etc., but, example as emulsifying agent, can enumerate: the anionic emulsifier of oleic sodium sulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, diphenyl ether sodium disulfonate, dialkyl succinate sodium sulfonate etc., or fluorine class tensio-active agent etc.According to the present invention, use oleic sodium sulfonate can reach excellent especially effect as emulsifying agent.
With respect to whole monomer components, the usage quantity of emulsifying agent is generally 0.5～10 weight %, is preferably 1～8 weight %.In the case, if the usage quantity deficiency of emulsifying agent 0.5 weight %, then can cause the generation of condensation product etc., thereby the polymerization stability of latex is reduced, and bring disadvantageous effect therefore for the manufacturing of conjugated diene copolymer latex, on the other hand, if surpass 10 weight %, the sticking toughness of modified asphalt composite and toughness tendency that reduction is arranged then.
As the example of polymerization starter, can enumerate: the mineral-type polymerization starter of Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc.; Hydroperoxidation benzene, hydroperoxidation are to the hydroperoxide type of Meng alkane, cumene hydroperoxide, tertbutyl peroxide etc.; And, the organic system polymerization starter of the azo-compound of azo isobutyronitrile, azo isovaleronitrile etc. etc. etc.These polymerization starters can be used alone or mixed use of two or more.
With respect to whole monomer components, the usage quantity of polymerization starter is generally 0.03～2 weight %, is preferably 0.05～1 weight %.
In addition, in order to promote letex polymerization, except using above-mentioned polymerization starter, can also merge the sequestrant of the reductive agent that uses pyrosulphite hydrogen sodium, S-WAT, sodium bisulfite, ferrous sulfate, glucose, sodium formaldehyde sulfoxylate, L-xitix and salt thereof etc. and glycine, L-Ala, sodium ethylene diamine tetracetate etc.
Example as chain-transfer agent, can enumerate: α-styrene dimer thing, it is above 2 preferably to contain 60 weight %, the α of 4-phenylbenzene-4-methyl-1-pentene composition-styrene dimer thing, terpinolene, α-terpinene, γ-terpinene, kautschin, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, n-hexadecyl mercaptan, curing dimethyl xanthogen, ethyl persulfide xanthogen, curing di-isopropyl xanthogen, tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylene thiuram disulfide etc.These chain-transfer agents can be individually or two or more mixing use.
With respect to whole monomer components, the usage quantity of chain-transfer agent is generally 0.01～5 weight %, is preferably 0.03～1 weight %.
When carrying out letex polymerization, except using above-mentioned emulsifying agent, polymerization starter, chain-transfer agent, can also merge and use various ionogen, pH regulator agent etc. as required; Measure 100 weight parts with respect to the total of above-mentioned monomer component, the usage quantity of water for example is generally 100～300 weight parts; Polymerization temperature is generally 10～80 ℃, is preferably 30～60 ℃; Polymerization time is generally 15～40 hours.
Each monomeric addition means during about letex polymerization, it can be any mode in addition manner, portion-wise addition mode and the continuous addition manner, in addition, also in these monomer components part or all can be carried out emulsification in advance, and then add, perhaps, also these addition manners can be combined.
The conjugated diene copolymer latex that makes as stated above, its viscosity is generally 10～1,000Pa second is preferably 20～500Pa second, and in addition, its solid state component is generally 40～70 weight %, is preferably 45～60 weight %.
The median size of above-mentioned conjugated diene copolymer latex is generally 60～300nm, is preferably 80～200nm.In the case, if the not enough 60nm of median size, then the viscosity of conjugated diene copolymer latex rises, it is difficult that operation becomes, in addition, its dispersion-solvability in pitch also has the tendency of reduction, on the other hand, if surpass 300nm, then dispersion-the solvability in pitch has the tendency of reduction.Should illustrate that said median size is meant the value of calculating by following assay method herein.
Conditions such as the usage quantity of water, emulsifying agent or polymerization starter when the median size of conjugated diene copolymer latex can be passed through suitably to adjust emulsion polymerization and polymerization temperature make it reach target value at an easy rate.
Gel content in the above-mentioned conjugated diene copolymer latex is generally 0.1～80 weight %, is preferably 0.1～50 weight %, more preferably 0.1～30 weight %.In the case, if gel content less than 0.1 weight %, the sticking toughness of modified asphalt composite and toughness tendency that reduction is arranged then, on the other hand, if surpass 80 weight %, then its dispersion-solvability in pitch has the tendency of reduction.Should illustrate that said gel content is meant the undissolved composition of obtaining by following assay method in toluene herein.
Gel content in the conjugated diene copolymer latex can play the kind and the consumption of the chain-transfer agent of molecular weight regulator effect when suitably being selected in letex polymerization, at an easy rate it is adjusted to target value, in addition, the consumption of the polymerization starter in the time of also can be by selected letex polymerization and polymerization temperature wait adjusts to target value with it, but, preferably these conditions are suitably combined.
Mooney viscosity (the ML of conjugated diene copolymer of the present invention the time as solid rubber
1+4, 100 ℃, down together) be generally 50～200, be preferably 80～180.In the case, if mooney viscosity less than 50, the sticking toughness of modified asphalt composite and toughness tendency that reduction is arranged then, on the other hand, if surpass 200, then its dispersion-solvability in pitch has the tendency of reduction.
The mooney viscosity of conjugated diene copolymer can be by the time with letex polymerization the kind of chain-transfer agent and the conditions such as consumption of consumption, polymerization starter suitably combine, adjust to target value at an easy rate.
" asphalt modifier " of the present invention can mix use with the conjugated diene copolymer of many kinds.
For asphalt modifier of the present invention, in not damaging its scope as the performance of the modified asphalt composite of target or modified asphalt mixture or asphalt modifier itself, can with other for example properties-correcting agent such as SBR latex, CR latex, SBS emulsion mix use.
Conjugated diene copolymer as asphalt modifier principal constituent of the present invention preferably is used in the latex that makes by above-mentioned emulsion polymerization, but, according to circumstances, also can make conjugated diene copolymer from this latex, separate out and be reclaimed, then its form as frangible shape or Powdered solid rubber be used by the solidification of for example saltouing.
Also can be as required; in asphalt modifier of the present invention, add and advance dispersion agent, stablizer, antiaging agent, UV light absorber, antistripping agent, sanitas, defoamer etc., perhaps add the protective colloid that advances sodium polyacrylate, polyvinyl alcohol, casein, gelatin, carboxymethyl cellulose, Natvosol etc.
Asphalt modifier of the present invention can be used as the modified asphalt composite that forms with following specific pitch mix and uses, and perhaps, and then mixes with aggregate, and according to circumstances mixes with packing material, supporting material etc. again, uses as modified asphalt mixture.
" pitch " as being suitable for asphalt modifier of the present invention does not have particular determination, for example can enumerate: petroleum pitch, rock asphalt, regeneration asphalt or be mixed into rock asphalt or regeneration asphalt and the mix asphalt that forms etc. in petroleum pitch.
As the example of above-mentioned petroleum pitch, can enumerate: the pitch that obtains by crude distillation with various penetration degree specifications, by in these pitches, be blown into oxidized bitumen that air makes or half oxidized bitumen in the existence of catalyzer or not, by from contain bitum petroleum fractions, isolating the desolventizing pitch that obtains behind the solvent of propane, butane etc. etc.These petroleum pitch can be used alone or mixed use of two or more.
As the example of above-mentioned rock asphalt, can enumerate: gilsonite, manjak, grahamite, Te Linida lake pitch etc.These rock asphalts can be used alone or mixed use of two or more.
In addition, above-mentioned regeneration asphalt can be to be the pitch that road pavement material etc. reclaims from used pitch for example.When using such regeneration asphalt, can with asphalt modifier of the present invention together with regeneration with additive for example one or more merging in aromatic hydrocarbons system oil, cycloalkanes hydrocarbon system oil, the alkane hydrocarbon system wet goods be used for this regeneration asphalt.
In these pitches, best is straight-run pitch, and the special preferably penetration degree in the time of 25 ℃ is 40～150 (1/10mm), preferably the straight-run pitch in 60～120 (1/10mm) scope.
As above-mentioned pitch, can enumerate those and contain the more petroleum pitch of oily composition that at room temperature is, when with tlc with above-mentioned separated from bitumen, when carrying out quantitative analysis with hydrogen flame ionization detector then, show and in petroleum pitch, contain 7～25% saturated composition and/or 65～80% aromatic component; Or those mix asphalts that in the mentioned component scope, mix by rock asphalt and regeneration asphalt.As utilizing tlc with separated from bitumen and utilize hydrogen flame ionization detector that it is carried out the device of quantitative analysis, can use IATROSCAN MK-5 that Yatron company makes etc.
The usage quantity of asphalt modifier of the present invention when mixing with pitch changes according to the application target of resulting modified asphalt composite or modified asphalt mixture, for example, under the situation of road pavement material, with respect to pitch 100 weight parts, be generally 0.2～20 weight part by solid state component, be preferably 1～10 weight part.
When using asphalt modifier preparation modified asphalt composite of the present invention or modified asphalt mixture, can use suitable equipment, for example road pavement is with pitch mix equipment, according to circumstances, in the pitch that is mixed with aggregate, packing material etc., add an amount of asphalt modifier, then it is fully stirred.
In the case, for example:
(a) asphalt modifier, pitch and aggregate etc. are mixed and stirred,, can obtain the normal temperature modified asphalt that road pavement is used then to wherein adding the kerosene equal solvent.
(b) pitch and aggregate etc. is heated to lower temperature, for example making aggregate temperature is 80～120 ℃, in the asphalt that is obtained, add asphalt modifier and add whipping agent as required, then this pitch and aggregate etc. are mixed and stirred, so can obtain the false add heat modification asphalt that road pavement is used.
(c) in temperature is the asphalt that is mixed with aggregate more than 120 ℃, add asphalt modifier equally with the general hot asphalt mixture that adds, it is mixed and stirred, so can obtain the heat modification asphalt that road pavement is used.
No matter use above-mentioned any method, all abundant oblatio effect of the present invention, but wherein particularly preferably be the heated and stirred method of (c), use this method can reach effect of the present invention best.
The mechanical stability of asphalt modifier of the present invention (Malon ' s stability hereinafter referred to as) is preferably below 0.003%, more preferably below 0.002%.
In addition, the sticking toughness of modified asphalt composite of the present invention is preferably more than 8Nm, more preferably more than 9Nm, more than 10Nm.Its toughness is preferably more than 5Nm, more preferably more than 6Nm, more than 7Nm.Its extensibility (7 ℃) is preferably more than 50cm, more preferably more than 60cm, more than 70cm.Its viscosity of 60 ℃ is preferably more than 500Pas, more preferably more than 600Pas, more than 700Pas.In addition, its dynamic stability of 60 ℃ preferably 3000 times/more than the mm, more preferably 4000 times/more than the mm, particularly preferably in 5000 times/more than the mm.Its flexural failure stiffness of-10 ℃ (bending stiffness) is preferably below 2900Mpa, more preferably below 2800Mpa, below 2700Mpa.
The modified asphalt composite or the modified asphalt mixture that use asphalt modifier of the present invention to make, except can be used as the use of road pavement material, can also be as putting up a house uses such as pre-material, covering material, waterproof and sealing material, sealing material, anti-seismic material.
(embodiment)
Enumerate embodiment below and describe embodiment of the present invention particularly.But the present invention is not subjected to any restriction of these embodiment.
Should illustrate, part and % in embodiment and comparative example, dated especially as not having, all be to be benchmark with weight.
Embodiment 1～9 and comparative example 1～7
(
Matrix pitch)
After the IATROS CAN MK-5 of use Yatron corporate system is determined at the composition of the straight-run pitch (AS-1 to AS-5 and standard A S) that uses in embodiment 1～9 and the comparative example 1～7, the results are shown in the table 1.Should son explanation, as standard asphalt, use be that the penetration degree of Nippon Mitsubishi Oil's (strain) system is 60～80 pitch.
Table 1
(
Copolymer emulsion)
Various monomeric compositions are shown in table 2 (embodiment 1～9) and the table 3 (comparative example 1～5), and using a volume is 100 liters pressure kettle, according to the various copolymer emulsions of emulsion polymerization manufactured.Should illustrate, all be to use aqueous sodium hydroxide solution that it is adjusted to the pH value shown in table 2 and the table 3 for the pH value of each latex.
The characteristic of the various copolymer emulsions that obtain is measured and is estimated according to following method.
(a) median size:
The laser particle size analysis LPA-3100 of system of Shi Yong Da mound electronics (strain) system measures the median size of various copolymer emulsions.
(b) gel content:
(a mg) places 50 ℃ toluene 100ml the dry film that is formed by various copolymer emulsions, under agitation floods 2 hours, filters with 120 purpose metallic sieves then.Draw a part (c ml) then exactly and be evaporated to driedly from this filtrate, the residual solid state component that weighing obtained (b mg) is measured gel content by following formula then.
Gel content %={[(a-b) * (100/c)]/a} * 100
(c) mooney viscosity:
From each copolymer emulsion, reclaim multipolymer, measure its mooney viscosity according to the method for JIS K6387 then.
(d) mechanical stability:
Use Malon ' s formula trier to estimate according to the method for JIS K6387.
(e) SBS segmented copolymer:
The SBS of table 3 (comparative example 6,7) has been to use the TR2601C of JSR (strain) system, and the addition of SBS is 4% of a pitch amount.
Table 2
Table 3
(
Modified asphalt composite)
Use the prescription shown in table 2 (embodiment 1～9) and the table 3 (comparative example 1～5, reference example), is that 4% ratio is added in each asphalt sample with properties-correcting agent in solid state component, the stirrer that use has 4 stirring blades is mix under the condition of 170 ℃ and speed of rotation 400～500rpm, is mixed with various modified asphalt composites.
Use the prescription shown in the table 3 (comparative example 6,7), with homogenizer (Tokushu Kika Kogyo K.K's system) SBS that adds frangible shape under the condition of 170 ℃ and speed of rotation 3000rpm when each asphalt sample 300g stirs is mixed and stirred, make various modified asphalt composites.
Outward appearance after it mixes and stirs with visual observations to the various modified asphalt composites that obtained, and estimate the dispersion-solvability of various copolymer emulsions in pitch by 3 following stages.
Excellent (zero): in 30 minutes, disperse or dissolve equably.
Common (△): dispersed or dissolved equably with interior to 1 hour at 30 minutes.
Difference (*):, still can be observed " particle " shape thing even mixing time surpasses 1 hour.
In addition, the rerum natura beyond above-mentioned dispersion-solvability can be estimated according to the method for " the test method(s) brief guide of mating formation " (clear and on November 10th, 63, the distribution of (society) Japanese road association) record.
The characteristic of the matrix pitch that uses during evaluation is shown in Table 4.
Above result gathered be shown in table 2 (embodiment 1～9) and the table 3 (comparative example 1～7, reference example).
(
Modified asphalt mixture)
(put down on June 20th, 6 according to " asphalt pavement outline ", the 6th edition, the distribution of (society) Japanese road association) the close granularity asphalt (20) of regulation in, the aggregate title complex that use is made of No. 5 rubbles 21%, No. 6 rubbles 25%, No. 7 rubbles 13%, screening (Screening) 6%, coarse sand 19%, fine sand 12%, stone flours 4%, and the modified asphalt composite that adds this aggregate title complex 5.6% is made various modified asphalt mixtures then 170～180 ℃ of mixing down.Wherein modified asphalt composite is that 4% properties-correcting agent (copolymer emulsion that embodiment 1 uses) is made by add solids component in various bitumen A S-1～AS-5.
With the various modified asphalt mixtures rolling machine compacting that is obtained, make sample, estimate its pyritous dynamic stability (anti-flowability) and low-temperature bending characteristic according to the wheel tracking test method and the bend test method of record in " the test method(s) brief guide of mating formation " (clear and on November 10th, 63, the distribution of (society) Japanese road association) then.
The performance of used matrix pitch mixture is shown in Table 4.
Table 4
(
Evaluation result)
The asphalt modifier of making by conjugated diene copolymer of the present invention (embodiment 1～9), mechanical stability (0.001～0.002%) and the dispersion in pitch-solvability height as latex, even and at room temperature contain the pitch of saturated composition of more oily or aromatic component for those, make the sticking toughness and the toughness of modified asphalt composite, the viscosity of low-temperature ductility and 60 ℃ is all good, and high temperature dynamic stability (60 ℃ the dynamic stability: 3 of this modifying asphalt mixture, 500～8,000 time/mm) and low-temperature bending characteristic (10 ℃ flexural failure stiffness: 2,300～2,900Mpa) also all good.This shows that the represented performance of these data (reference example) when using the standard A S that improves characteristic easily is good equally.
Particularly saturated composition (is in particular 4.1～5.0%) below 7% and the pitch of aromatic component 65～80% (being in particular 67.7～72.6%) (AS-4, AS-5, embodiment 4,5) for containing, its dynamic stability of 60 ℃ is very big, reach 7,000～8,000 time/mm, its flexural failure stiffness of-10 ℃ is very little, has only 2300～2400Mpa, finds out that thus these performances are all very excellent.
In contrast, as comparative example 1～5, its mechanical stability is very poor, is 0.056%, and the sticking toughness and the toughness of its modified asphalt composite are very poor, 60 ℃ viscosity is very low, and 60 ℃ of dynamic stabilities of its modified asphalt mixture (1,500～2,500 times/mm) and low-temperature bending characteristic (10 ℃ flexural failure stiffness: 3,000～3,200Mpa) all inferior.
For comparative example 6,7, the sticking toughness and the toughness of its modified asphalt composite are all inferior, 60 ℃ viscosity is very low, and 60 ℃ of dynamic stabilities (2 of its modified asphalt mixture, 000～2,500 times/mm) and the low-temperature bending characteristic (10 ℃ flexural failure stiffness: 3,000～3,100Mpa) all inferior.
Claims (2)
1. modified asphalt composite, in modified asphalt composite,
Asphalt modifier disperses-is dissolved in to contain in the pitch of oily composition, described asphalt modifier is with by (A) conjugated diene unit 55～99.9 weight %, (B) unsaturated carboxylic acid an alkali metal salt unit and/or (C) unsaturated carboxylic acid unit 0.1～5 weight %, (D) aromatic ethenyl compound unit 0～44.9 weight % and (E) conjugated diene copolymer that forms of other monomeric units 0～20 weight % as main component, described (E) other monomeric units are by (methyl) esters of acrylic acid, unsaturated amides, at least a kind of monomer in unsaturated acid imide and the acrylonitrile compound forms, gel content in this conjugated diene copolymer is 0.1～80 weight %, and the mooney viscosity of this conjugated diene copolymer is 50～200
It is characterized in that, contain the pitch of oily composition with respect to this, the content of above-mentioned asphalt modifier is counted 0.2～20 weight %. by solid state component
2. modified asphalt composite as claimed in claim 1, wherein, the above-mentioned pitch that contains the oily composition is to separate with tlc, when carrying out quantitative analysis with hydrogen flame ionization detector then, wherein contain the pitch of saturated composition 7～25% and/or aromatic component 65～80%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2000314038A JP2002121387A (en) | 2000-10-13 | 2000-10-13 | Asphalt modifier and modified asphalt composition |
| JP314038/2000 | 2000-10-13 |
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| CN1347936A CN1347936A (en) | 2002-05-08 |
| CN100408638C true CN100408638C (en) | 2008-08-06 |
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| CN (1) | CN100408638C (en) |
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| CN108299839B (en) * | 2018-02-09 | 2020-10-23 | 山东星火科学技术研究院 | High-stability modified asphalt and preparation method thereof |
| CN108299838B (en) * | 2018-02-09 | 2020-10-23 | 山东星火科学技术研究院 | High-temperature-resistant composite modified asphalt and preparation method thereof |
| CN108395719B (en) * | 2018-02-09 | 2020-10-23 | 山东星火科学技术研究院 | Composite modified asphalt beneficial to construction |
| CN108384257B (en) * | 2018-02-09 | 2020-10-23 | 山东星火科学技术研究院 | Pavement crack pouring asphalt and preparation method thereof |
| KR102463771B1 (en) * | 2018-05-09 | 2022-11-04 | (주)켐플러스 | Additive for recycled cold asphalt concrete mixture |
| CN110093043B (en) * | 2019-04-17 | 2021-07-16 | 广州鸿绵合成材料有限公司 | Asphalt viscosity reducer and preparation method and application thereof |
| CN110256681A (en) * | 2019-05-07 | 2019-09-20 | 武汉畅易达道路材料科技有限公司 | A kind of organosilicon asphalt modifier and preparation method thereof |
| CN111021194A (en) * | 2019-12-13 | 2020-04-17 | 上海浦兴路桥建设工程有限公司 | Drainage asphalt pavement pre-curing material and construction process thereof |
| CN111471128B (en) * | 2020-06-04 | 2021-02-02 | 甘肃省公路交通建设集团有限公司酒泉路衍产业开发分公司 | Water-based acrylic elastic emulsion, preparation method thereof and application thereof in asphalt pavement |
| CN113308125B (en) * | 2021-06-17 | 2022-05-20 | 北京建筑大学 | Diluted asphalt modifier and preparation method thereof |
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| US4578429A (en) * | 1984-08-31 | 1986-03-25 | Shell Oil Company | Selectively hydrogenated block copolymers modified with acid compounds or derivatives |
| CN1092788A (en) * | 1992-03-18 | 1994-09-28 | 国际壳牌研究有限公司 | Pitch water-base emulsion and dispersion liquid with the functionalized block Copolymers modification |
| CN1228454A (en) * | 1998-03-05 | 1999-09-15 | 日本合成橡胶株式会社 | Block copolymer composition for modifying asphalt and asphalt composition comprising the same |
| CN1238795A (en) * | 1996-11-21 | 1999-12-15 | 陶氏化学公司 | Asphalt modified with olefin/vinylidene aromatic monomer interpolymers |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518748B2 (en) * | 1972-11-13 | 1980-05-21 | ||
| JPS6230153A (en) * | 1985-08-01 | 1987-02-09 | Japan Synthetic Rubber Co Ltd | Asphalt paving composition |
| US5173172A (en) * | 1991-08-19 | 1992-12-22 | Exxon Research And Engineering Company | Production of hard asphalts by ultrafiltration of vacuum residua |
| JP3336833B2 (en) * | 1995-10-12 | 2002-10-21 | ジェイエスアール株式会社 | Asphalt modifier |
| JP3537598B2 (en) * | 1996-06-18 | 2004-06-14 | 株式会社コスモ総合研究所 | Straight asphalt composition for paving |
| JP3858469B2 (en) * | 1998-08-12 | 2006-12-13 | 株式会社日立製作所 | Treatment method for nitrate asphalt mixed waste |
-
2000
- 2000-10-13 JP JP2000314038A patent/JP2002121387A/en active Pending
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578429A (en) * | 1984-08-31 | 1986-03-25 | Shell Oil Company | Selectively hydrogenated block copolymers modified with acid compounds or derivatives |
| CN1092788A (en) * | 1992-03-18 | 1994-09-28 | 国际壳牌研究有限公司 | Pitch water-base emulsion and dispersion liquid with the functionalized block Copolymers modification |
| CN1238795A (en) * | 1996-11-21 | 1999-12-15 | 陶氏化学公司 | Asphalt modified with olefin/vinylidene aromatic monomer interpolymers |
| CN1228454A (en) * | 1998-03-05 | 1999-09-15 | 日本合成橡胶株式会社 | Block copolymer composition for modifying asphalt and asphalt composition comprising the same |
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| JP2002121387A (en) | 2002-04-23 |
| CN1347936A (en) | 2002-05-08 |
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