CN106800787B - A kind of high-temperature storage property high-viscosity high-elasticity modified pitch and preparation method thereof - Google Patents
A kind of high-temperature storage property high-viscosity high-elasticity modified pitch and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of methods for preparing modified pitch as modifying agent using SBS and waste rubber powder; this method takes the technology that physical chemistry combines; by being chemically treated with coupling agent to Modifiers Surface; so that generating coupled action between SBS and shoddy; under the synergistic effect of EVA, shoddy/SBS/EVA blended particles are obtained by extrusion granulating.Blended particles are added in pitch, dispersed by shearing, under the synergistic effect of crosslinking agent and age resister, obtain the modified pitch stored with excellent high temperature performance, anti-aging property, high resiliency recovery, high 60 DEG C of dynamic viscosities and high temperature resistant, the modified bitumen product is suitable for drainage pavement, Steel Bridge Deck making and old pavement transformation stress absorbing layer, the raw material sources that this method uses are extensive, it can be produced on existing SBS modified pitch device, without new equipment investment, it is suitable for the factorial production and long-distance transportation.
Description
Technical field
The present invention relates to a kind of road modified asphalts and preparation method thereof, are a kind of modified drips of high-temperature storage property high-viscosity high-elasticity
Blueness and preparation method thereof.
Background technique
End 12 ends, highway in China net has basically formed, and built highway and urban road will subsequently enter dimension
It repairs curing period, during which will there is a large amount of old pavement to face transformation, be a kind of main rebuilding old road in old pavement repaving asphalt coat
The highway of means, China 90% is Pavement on Semi-rigid Type Base, and cracking is one of current Pavement on Semi-rigid Type Base Major Diseases,
It has been generally acknowledged that cracking is caused by reflection crack.It was verified that being laid with stress absorbing layer among road deck and old pavement layer
Energy absorption and dispersive stress prevent crack reflection to surface layer, and the generation of reflection crack can not only be effectively relieved, can also prevent rain
Water penetrates into base, extends the service life of bituminous pavement.Stress absorbing layer has water-proof binding, the generation in delayed reflex crack etc. concurrently
Specific function, this requires the asphalt binders for stress absorbing layer with excellent high/low temperature non-deformability, preferably
Elastic recovery capability and the preferable adhesive property of building stones, since it wants the repeated action of bearing load stress and temperature stress, because
This requires also have good anti-fatigue performance when its room temperature.Common modified pitch is needed it is impossible to meet its index request
For the special asphalt binder of its performance development.
This special asphalt binder is referred to as high-viscosity high-elasticity modified pitch, production method substantially there are four types of, first is
It is modified using the high adhered modification agent TPS of Japan, gained modified pitch has the characteristics that 60 DEG C of viscosity are big, is widely used in
On Steel Bridge Deck making, however this modifying agent is expensive, and price is at 40,000 yuan/ton, and additional amount is 12% or more, modified pitch
About 10,000 yuan/ton of overall cost, the domestic conventional SBS modified asphalt market price is 5000-6000 yuan/ton, and therefore, it is difficult to promote to answer
With.Second is to be able to the high TPS modifying agent of fictitious hosts, domestic application it is more be to be modified using high-content SBS
Mode, although this method can reduce cost, but since SBS additive amount will reach 6% or more, also want to adjust viscosity
The expensive resin not less than 3% is added, the cost of this modified pitch is still higher than conventional SBS modified asphalt by 50% or so, institute
A possibility that promote and apply, is smaller.Third is waste Crumb rubber modified asphalt, compares the above several method, although production cost is big
Width reduces, but the quality control difficulty of waste Crumb rubber modified asphalt is relatively large and mostly situ modified, due to scrap rubber pitch
Viscosity it is larger, the difficulty of construction is also relatively high.Fourth is that waste Crumb rubber/SBS composite modified asphalt, this composite modified drip
Blueness under the synergistic effect of SBS and shoddy, high-temperature behavior be better than conventional SBS modified asphalt, cryogenic property with it is conventional SBS modified
Pitch is suitable, and elastic recovery capability is strong, in stress absorbing layer adhesive layer, using waste rubber powder as changing
Property agent also can solve " black pollution " problem, be the hot spot studied at present, technological difficulties are composite modifiers to be dripped in matrix
Compatible stability in blueness.
In above four kinds of methods, high-viscosity high-elasticity modified pitch is prepared with SBS/ scrap rubber is powder compound modified, not only can solve
The problem of waste and used rubber tyre pollutes, and it and SBS are used in compounding the cost that can reduce modified pitch, while having and can have
Effect improves the performance of modified pitch, is all more reasonably to select from service performance and cost factor comprehensive analysis.SBS/ scrap rubber
The powder compound modified high-viscosity high-elasticity modified pitch for preparing can be summarized as four kinds of techniques:
(1) SBS, shoddy and other additive substep shearing methods.As CN102766338A sequentially adds SBS, activation is given up
Rubber powder shearing, adds resin and stabilizer to stir to get a kind of wide temperature range modified pitch of road, and use temperature range can reach 100
DEG C or more, this method need to be activated shoddy, and the reaction time needs to reach 5-10h.CN102061100A first adds sulphur
Change rubber powder and stir to obtain mixture A, adds SBS to stir to obtain mixture B, shear, react to obtain finished product, this method need to carry out rubber powder
Vulcanizing treatment, and mixture A need to be risen to 250 DEG C by while adding SBS, so high reaction temperature easily cause polymer to be degraded and matrix
Ageing of asphalt.CN103849153A first adds waste Crumb rubber to shear to without obvious particle, then plus SBS shear to without obvious particle, most
Viscosity modifier is added afterwards, high-viscosity high-elasticity modified pitch is made, gained high-viscosity high-elasticity modified pitch has good high-temperature stable
Property, while elastic recovery capability is strong, has good low-temperature cracking-resistance, three kinds of additives must distinguish agitation cycle in production process
Shearing is stirred to react to obtain finished product to stabilizer without obvious particle, is then added, and production process is complicated.Similar techniques are also
CN103408956A、CN3232712A、CN104098918A、CN103013145A、CN101560332A、CN101629405。
(2) first plus SBS shearing grinding, then plus tackifier and expanding material, repeatedly grinding first high-viscosity modified asphalt, most
Afterwards again plus high-viscosity high-elasticity modified pitch is made in waste Crumb rubber, such as CN101629405, this method need to be into used waste Crumb rubber
Row is activated, its application is made not have popularity.
(3) SBS and waste Crumb rubber are first subjected to extrusion granulating, obtain composite modifier, then composite modifier is added and is dripped
Dispersion is sheared in blueness, obtains high-viscosity high-elasticity modified pitch, such as CN103819918A, waste Crumb rubber used in this method is usual
It needs first to carry out desulfurization process, on the one hand increases cost, on the other hand since rubber powder is after desulfurization is degraded, cross-linked structure quilt
It destroys, the low-temperature ductility of gained modified pitch is smaller, and has to matrix pitch specifically limited, is not suitable for promoting and applying.
(4) by SBS and shoddy grind into powder first, SBS powder and rubber powder is obtained, extruder then is added in the two
In, granulation obtains solid-state like SBS/ rubber powder blend, is then again added to blend and has sheared the modified drip of scattered SBS
In blueness, mixing obtains the composite modified asphalt of stable storing, such as CN103146206A, this by by SBS and shoddy
Though the method for extrusion granulating can be improved the stability of modified pitch, this extrusion molding is only a kind of physical action, the two it
Between Van der Waals force it is weaker, modified pitch unsuitable long term storage under the high temperature conditions.
Therefore, a kind of low cost, high-performance, shelf-stable and the high-viscosity high-elasticity modified pitch preparation side preferably promoted and applied are developed
Method is very urgent.
Summary of the invention
In order to overcome the various defects of the above-mentioned prior art, the purpose of the present invention is to provide a kind of low cost, high-performance,
Shelf-stable and the high-temperature storage property high-viscosity high-elasticity modified pitch preferably promoted and applied and preparation method thereof.
Above-mentioned purpose of the invention is achieved in that a kind of high-temperature storage property high-viscosity high-elasticity modified pitch, the viscous height of the height
It is composed of the following components by weight to play modified pitch:
Matrix pitch: 100 parts,
Waste Crumb rubber: 6-15 parts,
SBS:3.5-6 parts,
EVA:1-3 parts,
Coupling agent: 0.5-3 parts,
Compatilizer: 0.5-2 parts,
Crosslinking agent: 0.2-0.6 parts,
Age resister: 0.5-1.5 parts.
High-temperature storage property high-viscosity high-elasticity modified pitch of the present invention, wherein the matrix pitch is preferably No. 70 A grades
Pitch or No. 90 A grades of pitches, 25 DEG C of needle penetrations are 70-100dmm.
High-temperature storage property high-viscosity high-elasticity modified pitch of the present invention, wherein the waste Crumb rubber is preferably to recycle
Waste tire is in ambient ground and removes manufactured powdered substance after steel wire and fiber, and mesh number is preferably -80 mesh of 40 mesh.
High-temperature storage property high-viscosity high-elasticity modified pitch of the present invention, wherein the SBS is preferably linear structure,
The block ratio of middle styrene and butadiene is preferably that the weight average molecular weight of 3/7, SBS is preferably 8-12 ten thousand.
High-temperature storage property high-viscosity high-elasticity modified pitch of the present invention, wherein the content of vinyl acetate is excellent in the EVA
It is selected as 15wt%~30wt%, melt index is preferably 120-180g/10min.
High-temperature storage property high-viscosity high-elasticity modified pitch of the present invention, wherein the compatilizer is preferably split by catalysis
Carburetion slurry extraction oil, wax tailings extraction oil, the line extraction oil that subtracts four and solvent obtained in oil plant by solvent extraction process take off
At least one of formed group of frivolous oil extraction oil obtained by pitch, for arene content more preferably greater than 45%, flash-point is preferably big
In 235 DEG C.
High-temperature storage property high-viscosity high-elasticity modified pitch of the present invention, wherein the coupling agent is preferably aluminum-zirconium coupling
Agent and/or aluminium titanium composite coupler.
High-temperature storage property high-viscosity high-elasticity modified pitch of the present invention, wherein the crosslinking agent is preferably by sulphur, phosphorus
At least one of acid, polyphosphoric acids, pyrophosphoric acid, benzoyl peroxide and the formed group of zinc oxide.
High-temperature storage property high-viscosity high-elasticity modified pitch of the present invention, wherein the age resister is preferably N- phenyl-
Beta-naphthylamine, 2,2,4- trimethyl -1,2- dihyaroquinoline, 6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline or acetone
At least one of the low temperature condensation product formed respectively with diphenylamines.
The present invention also provides a kind of preparation methods of high-temperature storage property high-viscosity high-elasticity modified pitch, are above-mentioned high-viscosity high-elasticities
The preparation method of modified pitch, comprising the following steps:
S1: by 40%-60%, 3.5-6 parts by weight SBS, 1-3 parts of EVA of the waste Crumb rubber of 6-15 parts by weight, 0.5-
2 parts by weight of compatible agent and 0.5-3 parts by weight coupling agent are mixed evenly, prepared in open mill or mixer waste Crumb rubber/
SBS/EVA blend pre-processes to obtain waste Crumb rubber/SBS/EVA blended particles by mechanical pelleting and coupling agent；
S2: being heated to flow regime for 100 parts by weight matrix pitches, is warming up to 175-190 DEG C, opens high speed shear dispersion
Machine, keeping its revolving speed is 4000-6000r/min, and waste Crumb rubber/SBS/EVA blended particles high speed shear in step S1 is added
20-60min obtains waste Crumb rubber/SBS/EVA modified pitch blend A；
S3: blend A obtained by step S2 is heated to 180-200 DEG C, 0.2-0.6 parts by weight of crosslinking agent and 0.5- is added
1.5 parts by weight age resisters, are stirred to react 90-150min, obtain waste Crumb rubber/SBS/EVA modified pitch blend B；
S4: the temperature for keeping blend B obtained by step S3 is 180-200 DEG C, and the remaining 40%-60% of waste Crumb rubber is added
Continue stirring 60-90min and obtains high-temperature storage property high-viscosity high-elasticity modified pitch.
Then the present invention is obtained with the mode of extrusion molding again by being surface-treated with coupling agent to shoddy, SBS, EVA
With shoddy/SBS/EVA blended particles of coupling agent treatment, on the one hand by carrying out table to shoddy, SBS, EVA with coupling agent
Surface treatment, coupling agent can form coupled action between the carbon black and SBS in shoddy, enhance between shoddy and SBS
Active force, the addition of EVA can be improved SBS dispersibility, SBS/ shoddy/dispersibility of the EVA in pitch can be improved, point
SBS/ shoddy/EVA in pitch is dispersed under the action of stabilizer, can further improve SBS/ shoddy in pitch
Dispersion, after remaining shoddy adds in SBS/ shoddy/EVA blend modified asphalt, has been dispersed in pitch
SBS/ shoddy/EVA can play the role of compatilizer again, work as so that the shoddy being added after making is better dispersed in pitch
In, without separating from pitch, the final high-viscosity high-elasticity modified pitch for obtaining high-temperature storage property is anti-ageing due to being added to
Agent can make high-viscosity high-elasticity modified pitch have preferable anti-aging property, during transporting and mixing and stirring, modified pitch
Performance degradation is slow.
Compared with the prior art, the beneficial effects of the present invention are:
The raw material sources for preparing high-viscosity high-elasticity modified pitch are extensive, are not particularly limited to matrix pitch, common domestic
Pitch and Imported Asphalt can be used as matrix pitch of the invention, and being fit to do modified Kelamayi pitch for discomfort similarly has
Effect, waste rubber powder need not move through activation or desulfurization process and can directly use, therefore easy to promote and utilize.
The high temperature performance of high-viscosity high-elasticity modified pitch of the invention, adhesive property and elastic recovery properties are excellent, master
The performance indicator wanted is higher than the prior art, and comparing result is as shown in table 1.
The comparison of 1 main performance index of table
As shown in Table 1, high-viscosity high-elasticity modified pitch of the invention prolongs after having high softening point, 5 DEG C of ductilities and RTFOT simultaneously
The feature that degree is high, 60 DEG C of viscosity are big and elasticity has been restored, integrated performance index are better than the prior art.Again by embodiment in table 2
The property analysis of middle modified pitch is it is found that the high-temperature storage stability of high-viscosity high-elasticity modified pitch of the invention is good, in 165 DEG C of height
Temperature can store 10 days, isolate index still less than 2.5 DEG C, and 5 DEG C of ductilities are still greater than 30cm, have significant heat aging property, special
It is not suitable for the factorial production and long-distance transportation, there are no the data reports of long term high temperature thermmal storage in the prior art.
Specific embodiment
The present invention is further illustrated by the following examples, and however, the present invention is not limited to these examples.
Embodiment 1
High-viscosity high-elasticity modified pitch consists of the following compositions by weight: 100 parts of SK pitches, needle penetration 100dmm, and 8
40 mesh shoddies of part, 6 parts of SBS, weight average molecular weight are 80,000,3 parts of EVA, vinyl acetate content 15%, melt index
180g/10min, 0.5 part of aluminum-zirconium coupling agent, the 0.5 part of line that subtracts four extraction oil, 0.5 part of elemental sulfur, 1.5 parts of N- phenyl-β-naphthylamines,
High-viscosity high-elasticity modified pitch is prepared by following procedure:
S1: 4 parts of shoddies, 6 parts of SBS, 3 parts of EVA, 0.5 part of coupling agent, 0.5 part of compatilizer are uniformly mixed, in mixer
In prepare waste Crumb rubber/SBS/EVA blend, waste Crumb rubber/SBS/EVA blended particles are obtained by mechanical pelleting.
S2: being heated to flow regime for 100 parts of matrix pitches, is warming up to 190 DEG C, opens high speed shear dispersion machine, shearing
Rate is 6000r/min, and the waste Crumb rubber/SBS/EVA blended particles being added in step S1 shear 60min, obtains scrap rubber
Powder/SBS/EVA modified pitch blend A.
S3: being heated to 200 DEG C for blend A obtained by step S2, sequentially add 0.5 part of crosslinking agent, 1.5 parts of age resisters,
It is stirred to react 150min, obtains shoddy/SBS/EVA modified pitch blend B.
S4: keeping blend B temperature obtained by step S3 is 200 DEG C, and remaining 4 parts of shoddies are added and continue to stir 60min i.e.
High-temperature storage property high-viscosity high-elasticity modified pitch is obtained, property analysis is shown in Table 2.
Embodiment 2
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of Esso pitches, needle penetration 97dmm, 9 part of 50 mesh
Shoddy, 5.5 parts of SBS, weight average molecular weight are 8.8 ten thousand, 2.5 parts of EVA, vinyl acetate content 30%, melt index
120g/10min, 1 part of aluminium titanium composite coupler, 0.5 part of catalytic cracked oil pulp extraction oil, 0.5 part of phosphoric acid, 1.0 part 2,2,4- tri-
Methyl-1,2- dihyaroquinoline.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 4 parts, and step S2 medium shear rate is 5000r/min, 180 DEG C of shear temperature, is blended in shear time 50min, step S3
Object A is heated to 190 DEG C, is stirred to react 120min, and blend B temperature is 190 DEG C in step S4, and remaining 5 parts of shoddies are added and stir
It mixes 70min and obtains high-temperature storage property high-viscosity high-elasticity modified pitch, property analysis is shown in Table 2.
Embodiment 3
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of Liaohe River pitches, needle penetration 93dmm, 10 part of 60 mesh
Shoddy, 5 parts of SBS, weight average molecular weight are 9.1 ten thousand, 2.5 parts of EVA, vinyl acetate content 28%, melt index 130g/
10min, 0.5 part of aluminum-zirconium coupling agent, 1 part of aluminium titanium composite coupler, 1 part of wax tailings extraction oil, 0.5 part of polyphosphoric acids, 0.5
Part 6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 5 parts, and step S2 medium shear rate is 5500r/min, 185 DEG C of shear temperature, is blended in shear time 50min, step S3
Object A is heated to 190 DEG C, is stirred to react 120min, and blend B temperature is 190 DEG C in step S4, and remaining 5 parts of shoddies are added and stir
It mixes 70min and obtains high-temperature storage property high-viscosity high-elasticity modified pitch, property analysis is shown in Table 2.
Embodiment 4
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of Zhenghai pitches, needle penetration 88dmm, 11 part of 70 mesh
Shoddy, 4.5 parts of SBS, weight average molecular weight are 10.3 ten thousand, 2 parts of EVA, vinyl acetate content 25%, melt index
138g/10min, 1 part of aluminum-zirconium coupling agent, 1 part of aluminium titanium composite coupler, the frivolous oil extraction oil of 1 part of solvent deasphalting gained, 0.2
Part elemental sulfur, 0.2 part of polyphosphoric acids, 1.2 parts of acetone and diphenylamines low temperature condensation product.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 6 parts, and step S2 medium shear rate is 4000r/min, 180 DEG C of shear temperature, is blended in shear time 60min, step S3
Object A is heated to 200 DEG C, is stirred to react 90min, and blend B temperature is 180 DEG C in step S4, and remaining 5 parts of shoddies stirring is added
90min obtains high-temperature storage property high-viscosity high-elasticity modified pitch, and property analysis is shown in Table 2.
Embodiment 5
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of Kelamayi pitches, needle penetration 81dmm, and 12 parts
80 mesh shoddies, 4 parts of SBS, weight average molecular weight are 10.8 ten thousand, 2 parts of EVA, vinyl acetate content 20%, melt index
150g/10min, 2.5 parts of aluminum-zirconium coupling agents, the 1.5 parts of line that subtracts four extraction oil, 0.2 part of elemental sulfur, 0.4 part of zinc oxide, 1.2 part third
Ketone and diphenylamines low temperature condensation product.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 6 parts, and step S2 medium shear rate is 5000r/min, 185 DEG C of shear temperature, is blended in shear time 40min, step S3
Object A is heated to 180 DEG C, is stirred to react 120min, and blend B temperature is 180 DEG C in step S4, and remaining 6 parts of shoddies are added and stir
It mixes 90min and obtains high-temperature storage property high-viscosity high-elasticity modified pitch, property analysis is shown in Table 2.
Embodiment 6
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of Kelamayi pitches, needle penetration 75dmm, and 13 parts
40 mesh shoddies, 4 parts of SBS, weight average molecular weight are 110,000,1.2 parts of EVA, vinyl acetate content 18%, melt index
160g/10min, 3 parts of aluminium titanium composite couplers, the 1.5 parts of line that subtracts four extraction oil, 0.1 part of elemental sulfur, 0.1 part of phosphoric acid, 0.1 part of mistake
Benzoyl Oxide, 0.9 part of N- phenyl-β-naphthylamine.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 5.5 parts, and step S2 medium shear rate is 4500r/min, 190 DEG C of shear temperature, in shear time 30min, step S3 altogether
Mixed object A is heated to 190 DEG C, is stirred to react 100min, and blend B temperature is 190 DEG C in step S4, and remaining 7.5 parts of scrap rubbers are added
Powder stirring 75min obtains high-temperature storage property high-viscosity high-elasticity modified pitch, and property analysis is shown in Table 2.
Embodiment 7
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of Kelamayi pitches, needle penetration 73dmm, and 14 parts
50 mesh shoddies, 3.8 parts of SBS, weight average molecular weight are 11.3 ten thousand, 1.5 parts of EVA, and vinyl acetate content 15%, melting refers to
Number 180g/10min, 1 part of aluminum-zirconium coupling agent, 2 parts of aluminium titanium composite couplers, 2 parts of catalytic cracked oil pulp extraction oil, 0.1 part of simple substance
Sulphur, 0.1 part of polyphosphoric acids, 0.6 part 2,2,4- trimethyl -1,2- dihyaroquinolines.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 5.7 parts, and step S2 medium shear rate is 5500r/min, 185 DEG C of shear temperature, in shear time 40min, step S3 altogether
Mixed object A is heated to 195 DEG C, is stirred to react 90min, and blend B temperature is 195 DEG C in step S4, and remaining 8.3 parts of shoddies are added
Stirring 60min obtains high-temperature storage property high-viscosity high-elasticity modified pitch, and property analysis is shown in Table 2.
Embodiment 8
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of shell pitches, needle penetration 70dmm, 15 part of 60 mesh
Shoddy, 3.5 parts of SBS, weight average molecular weight are 120,000,1 part of EVA, vinyl acetate content 20%, melt index 150g/
10min, 2 parts of aluminum-zirconium coupling agents, 1 part of aluminium titanium composite coupler, the frivolous oil extraction oil of 2 parts of solvent deasphaltings gained, 0.2 part of list
Matter sulphur, 0.3 part of phosphoric acid, 0.1 part of zinc oxide, 1.2 parts of 6- ethyoxyls -2,2,4- trimethyl -1,2- dihyaroquinoline.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 6 parts, and step S2 medium shear rate is 5000r/min, 185 DEG C of shear temperature, is blended in shear time 60min, step S3
Object A is heated to 190 DEG C, is stirred to react 120min, and blend B temperature is 190 DEG C in step S4, and remaining 9 parts of shoddies are added and stir
It mixes 80min and obtains high-temperature storage property high-viscosity high-elasticity modified pitch, property analysis is shown in Table 2.
Embodiment 9
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of Sino-Kazakhstan oil pipelines, needle penetration 91dmm, and 12 parts
80 mesh shoddies, 4.5 parts of SBS, weight average molecular weight are 100,000,2 parts of EVA, vinyl acetate content 25%, melt index
138g/10min, 2 parts of aluminum-zirconium coupling agents, the 2 parts of line that subtracts four extraction oil, 0.2 part of elemental sulfur, 0.1 part of benzoyl peroxide, 0.1 part
Zinc oxide, 1.0 parts of 6- ethyoxyls -2,2,4- trimethyl -1,2- dihyaroquinoline.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 6 parts, and step S2 medium shear rate is 5000r/min, 185 DEG C of shear temperature, is blended in shear time 60min, step S3
Object A is heated to 190 DEG C, is stirred to react 120min, and blend B temperature is 190 DEG C in step S4, and remaining 6 parts of shoddies are added and stir
It mixes 80min and obtains high-temperature storage property high-viscosity high-elasticity modified pitch, property analysis is shown in Table 2.
Embodiment 10
High-viscosity high-elasticity modified pitch consists of the following compositions: 100 parts of Maoming asphalts, needle penetration 86dmm, 10 part of 80 mesh
Shoddy, 4 parts of SBS, weight average molecular weight are 10.8 ten thousand, 1.5 parts of EVA, vinyl acetate content 20%, melt index
150g/10min, 1.5 parts of aluminum-zirconium coupling agents, the frivolous oil extraction oil of 1 part of solvent deasphalting gained, 0.2 part of elemental sulfur, 0.2 part of phosphorus
Acid, 0.2 part of zinc oxide, 0.9 part of N- phenyl-β-naphthylamine.
The difference of high-viscosity high-elasticity modified pitch preparation process and step and embodiment 1 is that shoddy uses in step S1
Amount is 6 parts, and step S2 medium shear rate is 5000r/min, 190 DEG C of shear temperature, is blended in shear time 40min, step S3
Object A is heated to 190 DEG C, is stirred to react 120min, and blend B temperature is 190 DEG C in step S4, and remaining 4 parts of shoddies are added and stir
It mixes 60min and obtains high-temperature storage property high-viscosity high-elasticity modified pitch, property analysis is shown in Table 2.
Comparative example 1
The ingredient of high-viscosity high-elasticity modified pitch is compared with embodiment 3, wherein being free of coupling agent, other ingredients and preparation process
Process is same as Example 3, and the property analysis of gained modified pitch is shown in Table 2, high temperature performance, 60 DEG C of dynamic viscosities, elasticity
Restore and storage stability is all obviously not so good as embodiment 3.
Comparative example 2
For the ingredient of high-viscosity high-elasticity modified pitch compared with embodiment 4, preparation process is free of granulation process, will when shearing
Shoddy, SBS, EVA, coupling agent and compatilizer are directly added into pitch, other processes with embodiment 4, gained modified pitch
Property analysis is shown in Table 2, and high temperature performance, 60 DEG C of dynamic viscosities, elasticity are restored and storage stability is all obviously not so good as embodiment
4。
Comparative example 3
The ingredient of high-viscosity high-elasticity modified pitch is compared with embodiment 5, wherein without age resister acetone and diphenylamines low temperature
Condensation product, other ingredients and preparation process are same as Example 5, and the property analysis of gained modified pitch is shown in Table 2, long-term
Hot storage stability decline, 5 DEG C of ductilities (163 DEG C, 10d) have dropped to 21cm.
Comparative example 4
The ingredient of high-viscosity high-elasticity modified pitch is compared with embodiment 6, wherein being free of EVA, other ingredients and preparation process mistake
Journey is same as Example 6, and the property analysis of gained modified pitch is shown in Table 2, and isolation (163 DEG C, 48h) value is 8.5, isolation (163
DEG C, 10d) it is 15.7, storage stability is decreased obviously with 6 ratio of embodiment, other indexs such as softening point, ductility and 60 DEG C of power
Viscosity is also declined slightly.
The property analysis of modified pitch in 2 embodiment of table
As shown in Table 2, the high-temperature storage stability of high-viscosity high-elasticity modified pitch of the invention is good, can store up in 165 DEG C of high temperature
It deposits 10 days, isolates index still less than 2.5 DEG C, 5 DEG C of ductilities are still greater than 30cm, have significant heat aging property, are particularly suitable for
In the factorial production and long-distance transportation.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (9)
1. a kind of high-temperature storage property high-viscosity high-elasticity modified pitch, which is characterized in that the high-viscosity high-elasticity modified pitch by weight by
Following components composition:
Matrix pitch: 100 parts,
Waste Crumb rubber: 6-15 parts,
SBS:3.5-6 parts,
EVA:1-3 parts,
Coupling agent: 0.5-3 parts,
Compatilizer: 0.5-2 parts,
Crosslinking agent: 0.2-0.6 parts,
Age resister: 0.5-1.5 parts；
The preparation of the modified pitch includes the following steps:
S1: by 40%-60%, 3.5-6 parts by weight SBS, 1-3 parts of EVA of the waste Crumb rubber of 6-15 parts by weight, 0.5-2 weight
Amount part compatilizer and 0.5-3 parts by weight coupling agent are mixed evenly, and waste Crumb rubber/SBS/ is prepared in open mill or mixer
EVA blend pre-processes to obtain waste Crumb rubber/SBS/EVA blended particles by mechanical pelleting and coupling agent；
S2: being heated to flow regime for 100 parts by weight matrix pitches, is warming up to 175-190 DEG C, opens high speed shear dispersion machine,
Keeping its revolving speed is 4000-6000r/min, and waste Crumb rubber/SBS/EVA blended particles high speed shear 20- in step S1 is added
60min obtains waste Crumb rubber/SBS/EVA modified pitch blend A；
S3: being heated to 180-200 DEG C for blend A obtained by step S2, and 0.2-0.6 parts by weight of crosslinking agent and 0.5-1.5 weight is added
Part age resister is measured, 90-150min is stirred to react, obtains waste Crumb rubber/SBS/EVA modified pitch blend B；
S4: the temperature for keeping blend B obtained by step S3 is 180-200 DEG C, and the remaining 40%-60% of waste Crumb rubber is added and continues
Stirring 60-90min obtains high-temperature storage property high-viscosity high-elasticity modified pitch.
2. high-temperature storage property high-viscosity high-elasticity modified pitch according to claim 1, which is characterized in that the matrix pitch is
No. 70 A grades of pitches or No. 90 A grades of pitches, 25 DEG C of needle penetrations are 70-100dmm.
3. high-temperature storage property high-viscosity high-elasticity modified pitch according to claim 1, which is characterized in that the waste Crumb rubber is
The waste tire of recycling is in ambient ground and removes manufactured powdered substance after steel wire and fiber, and mesh number is -80 mesh of 40 mesh.
4. high-temperature storage property high-viscosity high-elasticity modified pitch according to claim 1, which is characterized in that the SBS is linear
Structure, it is 8-12 ten thousand that wherein the block ratio of styrene and butadiene, which is the weight average molecular weight of 3/7, SBS,.
5. high-temperature storage property high-viscosity high-elasticity modified pitch according to claim 1, which is characterized in that acetic acid in the EVA
The content of ethylene is 15wt%~30wt%, melt index 120-180g/10min.
6. high-temperature storage property high-viscosity high-elasticity modified pitch according to claim 1, which is characterized in that the compatilizer is served as reasons
Catalytic cracked oil pulp extraction oil, wax tailings extraction oil, the line extraction oil that subtracts four obtained by solvent extraction process in oil plant and
At least one of formed group of frivolous oil extraction oil obtained by solvent deasphalting, arene content is greater than 45%, and flash-point is greater than
235℃。
7. high-temperature storage property high-viscosity high-elasticity modified pitch according to claim 1, which is characterized in that the coupling agent is
Aluminum-zirconium coupling agent and/or aluminium titanium composite coupler.
8. high-temperature storage property high-viscosity high-elasticity modified pitch according to claim 1, which is characterized in that the crosslinking agent is served as reasons
At least one of sulphur, phosphoric acid, polyphosphoric acids, pyrophosphoric acid, benzoyl peroxide and the formed group of zinc oxide.
9. high-temperature storage property high-viscosity high-elasticity modified pitch according to claim 1, which is characterized in that the age resister is
N- phenyl-β-naphthylamine, 2,2,4- trimethyl -1,2- dihyaroquinoline, 6- ethyoxyl -2,2,4- trimethyl -1,2- dihydro quinoline
At least one of the low temperature condensation product that quinoline or acetone are formed with diphenylamines respectively.
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| CN107722650A (en) * | 2017-09-25 | 2018-02-23 | 长安大学 | A kind of environmentally friendly high viscosity modified pitch and preparation method thereof |
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| CN111253764A (en) * | 2020-03-30 | 2020-06-09 | 云南省公路科学技术研究院 | Powder SBS modified asphalt and preparation method thereof |
| CN115678291B (en) * | 2021-07-27 | 2023-10-10 | 中国石油化工股份有限公司 | Anti-falling agent and preparation method and application thereof |
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| CN115322583A (en) * | 2022-09-26 | 2022-11-11 | 厦门新立基股份有限公司 | High-viscosity high-elasticity modified asphalt mixture and preparation method thereof |
| CN116162360A (en) * | 2023-03-31 | 2023-05-26 | 新疆交建路友道路材料科技有限公司 | Preparation method of high-viscosity elastic modified asphalt |
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