CN1876723A - Drainage pavement asphalt modifier with improved viscosity and method for preparing same - Google Patents
Drainage pavement asphalt modifier with improved viscosity and method for preparing same Download PDFInfo
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- CN1876723A CN1876723A CNA200610083568XA CN200610083568A CN1876723A CN 1876723 A CN1876723 A CN 1876723A CN A200610083568X A CNA200610083568X A CN A200610083568XA CN 200610083568 A CN200610083568 A CN 200610083568A CN 1876723 A CN1876723 A CN 1876723A
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
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- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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Abstract
Disclosed is a tar modifier which comprises: 1) 100 shares weight star styrene butadiene styrene compound block copolymer base material, wherein the styrene monomer is 15 to 50 weight percentage, and the molecular weight of copolymer is 50000 to 300000; 2) 10 to 60 shares weight sticking resin; 3) 5 to 70 shares weight at least one from aromatic radical metal working fluid, paraffinic base metal working fluid, mining metal working fluid, liquid polymer metal working fluid or fat metal working fluid; wherein the compound block copolymer comprises 1) 40 to 100 weight percentage star styrene butadiene styrene block copolymer with 2 to 6 branches, 2) 0 to 40 weight percentage linear styrene butadiene styrene block copolymer, 3) 0 to 30 weight percentage multi block styrene butadiene styrene copolymer and 4) 0 to 10 weight percentage styrene butadiene double block copolymer.
Description
Technical field
The present invention relates to drainage pavement (drainage pavement) asphalt modifier of a kind of viscosity raising and preparation method thereof.More particularly, the present invention relates to a kind of star vinyl-arene-conjugated dienes segmented copolymer of using and replace the effective constituent of linear ethylene base aromatic hydrocarbons-conjugated dienes segmented copolymer as asphalt modifier, it has increased the viscosity of bituminous composition.
Furtherly, drainage asphalt properties-correcting agent of the present invention is in 60 ℃ of viscosity that improve bituminous composition, and asphalt melting and dispersion and other mechanical propertys as perviousness, rigidity, toughness etc., still can keep.Therefore, the road oil mixture that contains described asphalt modifier and pellet both provided pellet cohesiveness, anti-rut and shock resistance good under the low temperature, had improved the viscosity of bituminous composition again.
Background technology
Two kinds of methods that prepare bituminous composition are disclosed, for example, a kind of is by pellet and the modifying asphalt that is pre-mixed that contains pitch and properties-correcting agent being mixed with the method that is pre-mixed of pitch making mixture, and another kind is to mix factory's hybrid system that pellet, pitch and properties-correcting agent prepare pitch making mixture simultaneously.Factory's hybrid system has superiority, because do not cause any being separated and the reduction of mechanical property under its high temperature.
The asphalt modifier that is used for described factory hybrid system need be dissolved in pitch rapidly.For the drainage pavement asphalt modifier that contains line style styrene-butadiene-styrene block copolymer, tackifying resin and process auxiliaries that satisfies this requirement is disclosed.
Drainage asphalt mixture needs high viscosity to form the thick supercrust of anti-Changes in weather and anti-rut.Therefore, if only adopt line style styrene-butadiene-styrene multipolymer as asphalt modifier, the demand of drainage asphalt composition medium pitch properties-correcting agent is the required 2-3 of common close-graded bituminous composition times.In order to save the cost of building the road, reduce the consumption of properties-correcting agent, must develop the properties-correcting agent of new suitable drainage asphalt composition.
According to the report of 422, No. 896 Korean Patent " manufacturing process of drainage asphalt properties-correcting agent " (" Process formanufacturing drainage asphalt modifier "), asphalt modifier will account for 11～13 weight % of bituminous composition.In addition, the amount of No. 417294 Korean Patent " multi-functional asphalt " (" Multi-functional asphalt composition ") proposition asphalt modifier accounts for 1～100 weight % of bituminous composition, and so wide scope is difficult to practical application.In actual use, if the amount of asphalt modifier less than 5 weight %, the performance of bituminous composition can not reach the requirement of drainage pavement, if instead the amount of asphalt modifier greater than 20 weight % because viscosity is too high, the processing performance of bituminous composition can variation.
Therefore, the present invention has designed drainage pavement asphalt modifier, can keep all properties of properties-correcting agent in actual amount with low cost.In addition, asphalt modifier of the present invention is designed to and can reduce other any performances of bituminous composition, as rigidity, toughness and perviousness etc. when increasing by 60 ℃ of viscosity of bituminous composition.
Along with the viscosity increase of bituminous composition, because the increase of storage modulus, the adhesion strength that pitch and pellet may occur reduces.In order to prevent that adhesion strength from descending, the high viscosity level that keeps bituminous composition, should select the properties-correcting agent that is ductile, as the styrene-butadiene-styrene multipolymer of line style or many blocks and in ethene-alpha-olefin copolymer, styrene-acrylonitrile copolymer and ethylene-vinyl acetate copolymer, be proposed one of at least use.
On the other hand, when producing the drainage pavement asphalt modifier of general type, can cause because of another component tackifying resin of asphalt modifier and condense.In order to solve the processing performance problem of condensing and bringing, need to use such as lime carbonate or emulsification silicon anti-agglomerating agents such as (oil), cause cost further to increase.Yet, among the present invention, by having solved the processing performance problem of condensing and causing as the main ingredient of properties-correcting agent and the method for restriction tackifying resin consumption with the star styrene-butadiene-styrene block copolymer.
Like this, the drainage road oil properties-correcting agent of the present invention's exploitation is by having improved the star styrene-butadiene-styrene block copolymer 60 ℃ of viscosity of bituminous composition as the way of properties-correcting agent main ingredient, and kept other performances of properties-correcting agent, also reduced the cost of the consumption of properties-correcting agent and the compound of paving the way.
Summary of the invention
The purpose of this invention is to provide a kind of asphalt modifier, it comprises: 1) the star styrene-butadiene-styrene mixed block copolymers of 100 parts of weight is as base-material, wherein styrene monomer content accounts for 15～50 weight %, the weight-average molecular weight of described mixed block copolymers is 50,000～300,000; 2) tackifying resin of 10～60 parts of weight; With 3) at least a process oil (processoil) of 5～70 parts of weight, it is selected from the aromatic base process oil, the paraffinic base process oil, mineral processes is with oily, liquid polymer process oil and fatty process oil, wherein said star styrene-butadiene-styrene mixed block copolymers comprises 1) 40～100 weight % have 2～6 ramose star styrene-butadiene-styrene block copolymers, 2) the line style styrene-butadiene-styrene block copolymer of 0～40 weight %, 3) many block styrene-butadiene-styrene copolymer and 4 of 0～30 weight %) 0～10 weight % styrene butadiene diblock copolymer.
On the other hand, described asphalt modifier can also contain the ethene-alpha-olefin (graft copolymer of C2～C20) of 5～20 parts of weight.In addition, described asphalt modifier can also contain the styrene-acrylonitrile resin of 5～30 parts of weight, and wherein the content of vinyl cyanide is 15～45 weight %, and the melt index of described resin is 1～15g/10min.In addition, described asphalt modifier can also contain the ethylene-vinyl acetate resin of 5～20 parts of weight, and wherein the content of vinyl acetate is 5～70 weight %, and the melt index of described resin is 1～40g/10min.
Furtherly, described asphalt modifier can also contain at least a wax of 0.1～3 part of weight, and it is selected from polyethylene wax, modified polyethylene wax, polyamide wax, hydroxy waxes (hydroxy wax) and sulfacetimide wax (steramide wax).
Another object of the present invention provides a kind of asphalt modifier, it contains: 1) the star styrene-butadiene-styrene mixed block copolymers of 100 parts of weight is a base-material, the content of styrene monomer is 15～50 weight % in the described mixed block copolymers, and the weight-average molecular weight of described mixed block copolymers is 50,000～300,000; 2) tackifying resin of 10～60 parts of weight; 3) at least a resin of 5～50 parts of weight, it is selected from the ethene-alpha-olefin (graft copolymer of C2～C20); Styrene-acrylonitrile resin, wherein the content of vinyl cyanide is that the melt index of 15～45 weight % and this resin is 1～15g/10min; And ethylene-vinyl acetate resin, wherein the content of vinyl acetate is that the melt index of 5～70 weight % and this resin is 1～40g/10min; And 5) at least a process oil (process oil) of 5～70 parts of weight, it is selected from the aromatic base process oil, the paraffinic base process oil, mineral processes is with oily, liquid polymer process oil and lipid acid process oil, wherein said star styrene-butadiene-styrene mixed block copolymers contains 1) 40～100 weight % have 2～6 ramose star styrene-butadiene-styrene block copolymers, 2) the line style styrene-butadiene-styrene block copolymer of 0～40 weight %, 3) many block styrene-butadiene-styrene copolymer and 4 of 0～30 weight %) the styrene butadiene diblock copolymer of 0～10 weight %.
In addition, the invention provides a kind of method for preparing asphalt modifier, comprise the following step: 1) melt down and mix with simple helix or double-screw type extrusion machine at 100～220 ℃; 2) extrude the asphalt modifier of strip; 3) cool off and form granular asphalt modifier.
Detailed Description Of The Invention
The present invention is described in detail as follows.
Star styrene-butadiene-styrene mixed block copolymers is the base-material of asphalt modifier of the present invention, and the composition that it can be used as properties-correcting agent contains the styrene monomer of 15～50 weight %.Described star styrene-butadiene-styrene mixed block copolymers can be used separately, also can be selected from other copolymer in combination uses of the styrene-butadiene-styrene multipolymer and the styrene butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of line style styrene-butadiene-styrene triblock copolymer, many blocks with one or more, to improve mechanical property and processing performance.
Described star block copolymer can be with { (S-B) general formula of n}m-X is represented, wherein n represents the integer greater than 1, and m represents 2～6 integer, and styrene monomer content is 28～33 weight %.In addition, S represents the vinyl-arene block in the following formula, and B represents conjugated diene block, and X represents the polyfunctional group coupler.
Described segmented copolymer can represent that wherein n is 2～4 integer with (S-B) n, (S-B) n-S, (B-S) n, (B-S) n-B, and styrene content is 35～50 weight %.In addition, described styrene butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock can represent that wherein styrene monomer content is 20～30 weight % with the general formula of S-B, and the viscosity of 5.43 weight % Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks is 5～15cPs in the toluene.
If the amount of star block copolymer is less than 40 weight % as the styrene-butadiene-styrene mixed block copolymers total amount of base-material, the viscosity of bituminous composition may not reach requirement.On the other hand, surpass 20 weight % if the amount of many block styrene-butadiene-styrene copolymer surpasses the amount of 30 weight % or styrene butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, the viscosity of bituminous composition may not reach requirement yet.
The kind of tackifying resin can be in the following resin one of at least: synthesizing petroleum resin, for example, aromatic hydrocarbons petroleum resin, paraffinic hydrocarbons petroleum resin, dcpd resin, polybutene and coumarone-indene resin; The natural oil resin, for example, polyterpene resin, terpene phenolic resin, rosin and rosin ester; And their hydroderivating thing.In order to improve the viscosity of bituminous composition, the softening temperature that is preferably the aromatic hydrocarbons petroleum resin is 70～170 ℃.In addition, in order to increase the adhesion strength between pellet and pitch, preferably adopt the mixture of described tackifying resin.The preferable volume of described tackifying resin is 10～60 parts of weight of base-material.If the amount of adhered resin has surpassed 60 parts of weight of base-material, may occur condensing, it can cause processing performance variation and production cost to improve.
Process oil (process oil) as process auxiliaries can be the paraffinic base process oil, also can be the aromatic base process oil.In order to improve the viscosity of bituminous composition, be preferably the aromatic component that the paraffinic base process oil contains 0～30 weight %, the naphthalene component of 20～50 weight % and the paraffinic components of 40～80 weight %.In addition, also can be with the oil that contains polar functional group, aliphatics process oil and be selected from the liquid polymer process oil of liquid butadiene rubber, polybutene and polyisobutene etc.The recommendation volume of process oil can be 5～70 parts of weight of base-material.If the amount of tackifying resin surpasses 70 parts of weight of base-material, 60 ℃ of viscosity of bituminous composition can descend, and softening temperature also can descend.
(C2～C20) preparation of graft copolymer can be adopted metalloscene catalyst to ethene-alpha-olefin, regular ground grafting C2～C20 alkene on polyolefin backbone.The weight-average molecular weight of suitable ethene-alpha-olefin graft copolymer is 20,000～200,000.In order to increase the elasticity of bituminous composition, the recommendation volume of described graft copolymer is 5～20 parts of weight of base-material.If the volume of ethene-alpha-olefin graft copolymer has surpassed 20 parts of weight of base-material, can cause pitch and the adhesion strength between pellet in the bituminous composition to reduce.In addition, also can cause other mechanical propertys, reduce, also can cause production cost to increase as Ken Tabao rate of loss (cantabro loss) and dynamic stability.
The amount of vinyl cyanide is 15～45 weight % in the described styrene-acrylonitrile resin of the present invention, the melt index of described resin be 1～15g/10min (200 ℃, 5kg).For the tensile strength that increases asphalt modifier and bending (anti-crawl agentdefiection) intensity and increase adhesion strength between bituminous composition medium pitch and pellet, the recommendation volume of described resin can be 5～30 parts of weight of base-material.If the volume of styrene-acrylonitrile resin surpasses 30 parts of weight of base-material, may cause descending with the consistency of styrene-butadiene-styrene block copolymer.
The amount of vinyl acetate is 5～70 weight % in the described ethylene-vinyl acetate resin of the present invention, the melt index of described resin be 1～40g/10min (200 ℃, 5kg).In order to increase the adhesion strength between bituminous composition medium pitch and pellet, the recommendation volume of described resin can be 5～20 parts of weight of base-material.If the volume of described resin surpasses 20 parts of weight of base-material, may cause descending with the consistency of styrene-butadiene-styrene block copolymer.
Can use release agent (releasing agent) to prevent from when stacking and store asphalt modifier, to lump between the asphalt modifier particle.For this reason, can use the release agent that is selected from polyethylene wax, modified polyethylene wax, polyamide wax, hydroxy waxes and sulfacetimide wax of 0.1～3 part of weight.If 0.1 weight part of the usefulness quantity not sufficient base-material of release agent can not reach and prevents the purpose of luming between the asphalt modifier particle.If the consumption of release agent surpasses 3 weight parts of base-material, may cause the adhesion strength between pitch and pellet to reduce.
Asphalt modifier of the present invention can contain additive, for example, and oxidation inhibitor, thermo-stabilizer, static inhibitor, lubricant, wollastonite, lime carbonate and/or mica.
Fusing and blending temperature scope are 100～220 ℃ preferably, if melt and blending temperature is lower than 100 ℃, the styrene block in the styrene-butadiene-styrene block copolymer may melt insufficient, can not with other component thorough mixing.If fusing and blending temperature are higher than 220 ℃, because the temperature of fusion height denaturant gel may occur in the described segmented copolymer, this also can cause adhesion strength and shock resistance between melting properties and pitch and pellet to reduce.
The present invention can be described more specifically by the following example, but scope of the present invention is not limited to the following example.
Embodiment
The general preparation method of asphalt modifier
Use the Henschel mixing tank, styrene-butadiene-styrene block copolymer and at least a other multipolymers and other additives that is selected from ethene-alpha-olefin copolymer, styrene-acrylonitrile resin and ethylene-vinyl acetate resin are mixed together 10 minutes.Then tackifying resin is added in the described mixed block copolymers gained resin remix more than 5 minutes in the Tumbler mixing tank.Melt blend with double-screw extrusion machine at 100～220 ℃ following mixed segmented copolymer.From the forcing machine die head, extrude the asphalt modifier of bar shaped.Obtained the granulous asphalt modifier at last.For fear of condensing, the calcium stearate powder of 0.1 part of weight is sprinkling upon granular asphalt modifier surface.
The general preparation method of bituminous composition
Bituminous composition is by earlier pitch being heated to 180 ℃, adding asphalt modifier again and prepare.Reaching asphalt modifier/pitch ratio in the 52.17g asphalt modifier adding 600g pitch is 8/92.
Measure and estimate the general method of bituminous composition performance
(1) " modifying asphalt testing method " (the Test Method for Modified Asphalt) among " test guide of paving the way " (PavementTest Guideline) of editing and publishing by Japanese road association of melting measures.
(2) 60 ℃ of viscosity are pressed the described method of ASTM D2171 and are measured with the special-purpose vacuum capillary viscometer of pitch (Asphalt Institute Vacuum Capillar Viscometer).
(4) softening temperature is pressed ASTM D 36 described methods measurements.
(5) penetration degree is pressed ASTM D 5 described methods measurements.
(6) method in rigidity and the toughness " test guide of paving the way " edited and publish by Japanese road association is measured.
Embodiment 1
Star shaped SBS with 50 parts of weight, the type SBS of 50 parts of weight, the tackifying resin of 15 parts of weight, the paraffinic base process oil of 10 parts of weight, the hindered phenol of the polyethylene wax of 0.2 part of weight and 0.3 part of weight (hindered phenol) source oxidation inhibitor adds in the Hensehl mixing tank.Mix after 10 minutes, add the aromatic hydrocarbons source tackifying resin (softening temperature is 110 ℃) of 15 parts of weight, use rolling type mixing tank (tumbler mixer) to mix again 5 minutes.Then mixture is melted down and mixes with double-screw extrusion machine at 180～200 ℃.Extrude the strip asphalt modifier from double-screw extrusion machine.At last, by cooling and cutting strip asphalt modifier, obtain the granulous asphalt modifier.The granular asphalt modifier of 8 weight % and the pitch of 92 weight % are mixed, make bituminous composition.Measure melting properties, 60 ℃ of viscosity, softening temperature, penetration degree (penetration), toughness and toughness then.Test result sees Table 1.
Embodiment 2
The star shaped SBS of 60 parts of weight, the type SBS of 40 parts of weight, the aromatic hydrocarbons source tackifying resin of 20 parts of weight (softening temperature is 110 ℃), the paraffinic base process oil of 20 parts of weight, the hindered phenol source oxidation inhibitor of the polyethylene wax of 0.2 part of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 1.
Embodiment 3
The star shaped SBS of 60 parts of weight, the type SBS of 40 parts of weight, the aromatic hydrocarbons source tackifying resin of 10 parts of weight (softening temperature is 110 ℃), the aliphatic hydrocarbon source tackifying resin of 10 parts of weight, the paraffinic base process oil of 20 parts of weight, the aromatic base process oil of 3 parts of weight, the hindered phenol deutero-oxidation inhibitor of the polyethylene wax of 0.2 part of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 1.
Embodiment 4
The star shaped SBS of 50 parts of weight, the type SBS of 35 parts of weight, many block SBSs of 15 parts of weight, the aromatic hydrocarbons source tackifying resin of 30 parts of weight (softening temperature is 110 ℃), the paraffinic base process oil of 10 parts of weight, the hindered phenol source oxidation inhibitor of the polyethylene wax of 0.2 part of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is by measuring with embodiment 1 same procedure.Test result sees Table 1.
Embodiment 5
The star shaped SBS of 50 parts of weight, the type SBS of 40 parts of weight, the styrene butadiene diblock copolymer of 10 parts of weight, 30 parts of weight aromatic hydrocarbons source tackifying resin (softening temperature is 110 ℃), the paraffinic base process oil of 10 parts of weight, the hindered phenol source oxidation inhibitor of the polyethylene wax of 0.2 part of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 1.
Embodiment 6
The star shaped SBS of 50 parts of weight, the type SBS of 50 parts of weight, the aromatic hydrocarbons source tackifying resin of 30 parts of weight (softening temperature is 110 ℃), the paraffinic base process oil of 10 parts of weight, the ethene-alpha-olefin resin of 10 parts of weight, the hindered phenol source oxidation inhibitor of the polyethylene wax of 0.2 part of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 1.
Embodiment 7
The star shaped SBS of 50 parts of weight, the type SBS of 50 parts of weight, the aromatic hydrocarbons source tackifying resin of 30 parts of weight (softening temperature is 110 ℃), the paraffinic base process oil of 10 parts of weight, the styrene-acrylonitrile resin of 15 parts of weight, the hindered phenol source oxidation inhibitor of the polyethylene wax of 0.2 part of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 1.
Embodiment 8
The star shaped SBS of 50 parts of weight, the type SBS of 50 parts of weight, 30 parts of weight aromatic hydrocarbons source tackifying resin (softening temperature is 110 ℃), the paraffinic base process oil of 10 parts of weight, the ethylene-vinyl acetate resin of 10 parts of weight, the hindered phenol source oxidation inhibitor of the polyethylene wax of 0.2 part of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 1.
The comparative example 1
Hansu road Lu Co., Ltd. (Hansu Pavement Co., Ltd.) the commercially available drainage pavement asphalt modifier commodity " Hansu " of Chaning asphalt modifier as a comparison.With 8 these asphalt modifiers of weight % with 92 weight % pitch is mixed must contrast bituminous composition.The character of contrast bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 2.
The comparative example 2
The star shaped SBS of 5 parts of weight, the type SBS of 95 parts of weight, the aromatic hydrocarbons source tackifying resin of 30 parts of weight (softening temperature is 160 ℃), the hindered phenol source oxidation inhibitor of the paraffinic base process oil of 10 parts of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is also pressed embodiment 1 described method mensuration.Test result sees Table 2.
The comparative example 3
The star shaped SBS of 100 parts of weight, the hindered phenol source oxidation inhibitor of the paraffinic base process oil of 110 parts of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 2.
The comparative example 4
The star shaped SBS of 30 parts of weight, the type SBS of 35 parts of weight, many block types SBS of 35 parts of weight, 30 parts of weight aromatic hydrocarbons source tackifying resin (softening temperature is 110 ℃), the hindered phenol source oxidation inhibitor of the paraffinic base process oil of 10 parts of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 2.
The comparative example 5
The star shaped SBS of 20 parts of weight, the type SBS of 50 parts of weight, the styrene butadiene diblock copolymer of 30 parts of weight, the aromatic hydrocarbons source tackifying resin of 30 parts of weight (softening temperature is 110 ℃), the hindered phenol source oxidation inhibitor of the paraffinic base process oil of 10 parts of weight and 0.3 part of weight is as the raw material of asphalt modifier.All the other preparation processes are described identical with embodiment 1.In addition, the character of bituminous composition is measured by the method identical with embodiment 1.Test result sees Table 2.
According to the universal measurement and the evaluation method of bituminous composition, measured the character of the bituminous composition of embodiment 1～8 preparation, test result sees Table 1.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | Requirement |
| Melting properties (minute) | 13 | 11 | 9 | 11 | 5 | 14 | 15 | 12 | Be less than 20 |
| 60 ℃ of viscosity (kPas) | 115 | 97 | 87 | 116 | 105 | 110 | 120 | 106 | Greater than 20 |
| Softening temperature (℃) | 111 | 97 | 92 | 106 | 101 | 115 | 112 | 113 | Greater than 80 |
| Penetration degree (dmm) | 59 | 60 | 61 | 60 | 63 | 61 | 56 | 57 | Greater than 40 |
| Rigidity (Nm) | 22.7 | 25.3 | 21.9 | 28.8 | 32.7 | 30.6 | 29.3 | 30.1 | Greater than 20 |
| Toughness (Nm) | 19.3 | 22.6 | 17.2 | 26.7 | 29.3 | 29.1 | 27.9 | 29.6 | Greater than 15 |
Requirement in the table 1 in a few days this modifying asphalt association criterion (JMAAS01-01) for the specification of the requirement of asphalt modifier with high viscosity.
According to the universal measurement and the evaluation method of bituminous composition, measured the character of the bituminous composition of comparative example's 1～5 preparation.Test result sees Table 2.
Table 2
| The comparative example | 1 | 2 | 3 | 4 | 5 | Requirement |
| Melting properties (minute) | 10 | 15 | 12 | 15 | 12 | Be less than 20 |
| 60 ℃ of viscosity (kPas) | 5 | 17 | 12 | 16 | 14 | Greater than 20 |
| Softening temperature (℃) | 77 | 91 | 71 | 73 | 69 | Greater than 80 |
| Penetration degree (dmm) | 63 | 50 | 52 | 62 | 63 | Greater than 40 |
| Rigidity (Nm) | 5.8 | 11.3 | 8.1 | 10.8 | 16 | Greater than 20 |
| Toughness (Nm) | 5.4 | 9.1 | 6.7 | 9.3 | 10.9 | Greater than 15 |
Requirement in the table 2 in a few days this modifying asphalt association criterion (JMAAS01-01) for the specification of the requirement of asphalt modifier with high viscosity.
As shown in table 1, the melting properties of the bituminous composition of embodiment 1～3 preparation is very good, because the fusing time of asphalt modifier is all less than 20 minutes.In addition, 60 ℃ of viscosity are also fine.Other character of bituminous composition are also very outstanding.
According to the test result of the bituminous compositions of embodiment 4 and 5 preparations as can be known, even add many block types SBS multipolymer and styrene butadiene diblock copolymer in asphalt modifier, 60 ℃ of viscosity also descend.But also realized the improvement of mechanical propertys such as rigidity and toughness.
According to the test result of the bituminous composition of embodiment 6～8 preparation as can be known, by adding ethene-alpha-olefin copolymer, styrene-acrylonitrile resin and/or having the ethylene-vinyl acetate resin of polar functional group, realized the raising of the performances such as elasticity of bituminous composition.
According to the test result of the bituminous composition of comparative example 1 preparation as can be known, 60 ℃ of viscosity of bituminous composition obviously descend.Except melting properties and penetration degree, other performances have also descended.According to the test result of the bituminous composition of comparative example 2 preparation as can be known, 60 ℃ of viscosity of bituminous composition have a little to increase, because added the star shaped SBS multipolymer that is less than 5 parts of weight in the asphalt modifier.
According to the test result of the bituminous composition of comparative example 3 preparation as can be known, cause 60 ℃ of viscosity and softening temperature to reduce after the process oil that surpasses 100 parts of weight adds asphalt modifier.But the fusing time of this bituminous composition and penetration degree still can meet the demands.According to the test result of the bituminous composition of comparative example 4 preparation as can be known, many block types SBS of 35 parts of weight adds asphalt modifier and can cause 60 ℃ of viscosity and softening temperature to reduce.According to the test result of the bituminous composition of comparative example 5 preparation as can be known, the styrene butadiene diblock copolymer of 30 parts of weight adds asphalt modifier and also can cause 60 ℃ of viscosity and softening temperature to reduce.
Beneficial effect of the present invention shows provides a kind of drainage pavement asphalt modifier, adopt the star styrene-butadiene-styrene, improve 60 ℃ of viscosity of bituminous composition, and can keep other performances of asphalt modifier and bituminous composition, also reduced the volume of asphalt modifier and the cost of paving asphalt mixture.
Claims (7)
1. asphalt modifier, it contains:
I) the star styrene-butadiene-styrene mixed block copolymers of 100 parts of weight is as base-material, styrene monomer content is 15～50 weight % in the wherein said mixed block copolymers, and the weight-average molecular weight of described mixed block copolymers is 50,000～300,000;
The ii) tackifying resin of 10～60 parts of weight; And
The iii) at least a process oil of 5～70 parts of weight, it is selected from aromatic base process oil, paraffinic base process oil, mineral processes with oil, liquid polymer process oil and aliphatics process oil,
Wherein said star styrene-butadiene-styrene mixed block copolymers contains: 1) 40～100 weight %'s has 2～6 ramose star styrene-butadiene-styrene block copolymers, 2) the line style styrene-butadiene-styrene block copolymer of 0～40 weight %, 3) many block styrene-butadiene-styrene copolymer and 4 of 0～30 weight %) the styrene butadiene diblock copolymer of 0～10 weight %.
2. asphalt modifier according to claim 1, wherein said asphalt modifier further contain the ethene-alpha-olefin (graft copolymer of C2～C20) of 5～20 parts of weight.
3. asphalt modifier according to claim 1, wherein said asphalt modifier further contains the styrene-acrylonitrile resin of 5～30 parts of weight, and wherein the content of vinyl cyanide is 15～45 weight %, and the melt index of described resin is 1～15g/10min.
4. asphalt modifier according to claim 1, wherein said asphalt modifier further contains the ethylene-vinyl acetate resin of 5～20 parts of weight, wherein vinyl acetate content is 5～70 weight %, and the melt index of described resin is 1～40g/10min.
5. according to any one described asphalt modifier in the claim 1 to 4, wherein said asphalt modifier further contains at least a wax of 0.1～3 part of weight, and it is selected from polyethylene wax, modified polyethylene wax, polyamide wax, hydroxy waxes and sulfacetimide wax.
6. asphalt modifier, it contains:
1) the star styrene-butadiene-styrene mixed block copolymers of 100 parts of weight is a base-material, styrene monomer content is 15～50 weight % in the wherein said mixed block copolymers, and the weight-average molecular weight of described mixed block copolymers is 50,000～300,000;
2) tackifying resin of 10～60 parts of weight;
3) at least a resin of 5～50 parts of weight, it is selected from the ethene-alpha-olefin (graft copolymer of C2～C20); Styrene-acrylonitrile resin, wherein acrylonitrile content is 15～45 weight %, and the melt index of this resin is 1～15g/10min; And ethylene-vinyl acetate resin, wherein vinyl acetate content is 5～70 weight %, and the melt index of this resin is 1～40g/10min; And
4) at least a process oil of 5～70 parts of weight, it is selected from the aromatic base process oil, paraffinic base process oil, mineral processes oil, liquid polymer process oil and aliphatics process oil,
Wherein said star styrene-butadiene-styrene mixed block copolymers contains: 1) 40～100 weight %'s has 2～6 ramose star styrene-butadiene-styrene block copolymers, 2) the line style styrene-butadiene-styrene block copolymer of 0～40 weight %, 3) many block styrene-butadiene-styrene copolymer and 4 of 0～30 weight %) the styrene butadiene diblock copolymer of 0～10 weight %.
7. method for preparing asphalt modifier, it comprises the following step: 1) 100～220 ℃ of fusings and with simple helix formula or the mixing of double-screw type extrusion machine down; 2) extrude the asphalt modifier of strip; 3) cool off and form granular asphalt modifier.
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| KR1020050048173 | 2005-06-07 | ||
| KR10-2005-0048173 | 2005-06-07 | ||
| KR1020050048173A KR100655635B1 (en) | 2005-06-07 | 2005-06-07 | Asphalt modifier enhancing viscosity for drainage pavement and its preparation method |
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| CN1876723A true CN1876723A (en) | 2006-12-13 |
| CN1876723B CN1876723B (en) | 2010-06-09 |
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| KR100655635B1 (en) | 2006-12-08 |
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