CN109401349A - A kind of graphene oxide modified pitch and preparation method thereof - Google Patents
A kind of graphene oxide modified pitch and preparation method thereof Download PDFInfo
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- CN109401349A CN109401349A CN201811417705.8A CN201811417705A CN109401349A CN 109401349 A CN109401349 A CN 109401349A CN 201811417705 A CN201811417705 A CN 201811417705A CN 109401349 A CN109401349 A CN 109401349A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/26—Bituminous materials, e.g. tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention provides a kind of preparation methods of graphene oxide modified pitch, comprising the following steps: graphite is slowly added in nitration mixture, is stirred evenly, mixed material is obtained；Under agitation, potassium permanganate is slowly added into mixed material, lasting stirring is reacted, and oxidation mixture material is obtained；Under agitation, it is slowly added to hydrogen peroxide into oxidation mixture material, lasting stirring is reacted, and oxidation mixed solution is obtained；Oxidation mixed solution is cooled to room temperature, is then ultrasonically treated, is centrifuged, washs later, obtain graphene oxide mother liquor；Graphene oxide mother liquor is added in pitch, is heated to melting, then be sheared, obtains graphene oxide modified pitch.The present invention also provides a kind of graphene oxide modified pitch obtained by this method, which is exfoliated graphene oxide/pitch composite material, has excellent high-temperature stability, low-temperature cracking-resistance and thermo oxidative aging performance.
Description
Technical field
The invention belongs to modified asphalt technology field more particularly to a kind of graphene oxide modified pitch and its preparation sides
Method.
Background technique
For graphene since its excellent physically and electrically property plays very important effect in nano material, it can be with
Significantly improve the property of polymer.A key factor for restricting graphene extensive use and industrialized production is how to advise greatly
Prepare to mould single layer or few layer and the grapheme material with processability.Graphene production method common at present has
Mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, graphene oxide reduction method.Although mechanical stripping method can be prepared
Big lamella, the graphene of high quality, but it is time-consuming and laborious, the single layer rate of graphene is also extremely low in yield and product, Wu Fa great
Produce graphene to scale.The graphene film number of plies of epitaxial growth method preparation is different, and substrate is adulterated so that graphene-structured is inadequate
Completely.Chemical vapour deposition technique, which refers to, to be cracked carbon source (such as hydrocarbon) at high temperature and is deposited on solid substrate surface, is served as a contrast
Bottom is usually the transition metal such as Ni, Ru；Although the graphene quality that this method obtains is higher, what this method was prepared
Graphene film, which is only transferred in other substrates from metallic substrates, just application value.Therefore, because existing production technology
Limited, graphene is not suitable for large-scale production.
Graphene oxide is the presoma of graphene, and graphene oxide does not need to retain structure as graphene because of it
Graphite need to only be aoxidized, further be removed graphite oxide, and graphite is through peroxidating, interlayer by integrality
Away from being widened, removing is more conducively realized；Therefore the yield of production graphene oxide significantly larger than produces graphene, now on a large scale
The method for preparing graphene is that graphene oxide is carried out reduction treatment.Have since graphene oxide inherits many of graphene
Beneficial characteristic, it is polymer-modified with graphene oxide, the performance in terms of polymer calorifics, machinery and rheology can not only changed
It is kind, moreover it is possible to obstruct gas and polymer contact to a certain extent, inhibit the oxidation and aging of polymer, therefore graphene oxide
Polymer-modified is practicable.
Pitch is a kind of with viscoelastic complicated organic polymer, since it can increase substantially road-ability peace
Stability is widely used in pavement structure.However, bituminous pavement also faces many problems, for example, summer its elasticity modulus it is low
Lead to pavement track with viscosity modulus height, its elasticity modulus of winter is low and viscosity modulus height leads to pavement cracking；In addition, asphalt road
The oxidizable aging of face is also a very important problem.
Therefore, graphene oxide is the physical property for improving pitch and the potential material of ageing resistance, it is necessary to be developed
A kind of method for improving asphalt performance using graphene oxide is explored, further to promote pitch answering in ground surface material
With.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind graphene oxide modified pitch and preparation method thereof.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method of graphene oxide modified pitch, comprising the following steps:
(1) 0.17~0.58 part of graphite is slowly added in 38.19~128.16 parts of nitration mixture, stirs evenly, is mixed
Material；
(2) under agitation, 0.93~3.15 part of potassium permanganate is slowly added into the mixed material after step (1),
Lasting stirring is reacted, and oxidation mixture material is obtained；
(3) under agitation, 11.89~39.89 parts of peroxides are slowly added into the oxidation mixture material after step (2)
Change hydrogen, mixed material color becomes purplish finally to glassy yellow by black in adition process, reaction system after being all added
Bubble is no longer generated, lasting stirring is reacted, and oxidation mixed solution is obtained；
During hydrogen peroxide is added, mixed material color becomes purplish by black, is since strong oxidizer is dense
Sulfuric acid and potassium permanganate are gradually adsorbed on the edge of graphite, and carry out oxidation and intercalation to marginal portion, destroy piece interlayer
Active force between moieties generates the oxygen-containing groups such as hydroxyl, epoxy group, at this point, the extent of exfoliation of graphite flake layer is lower；With anti-
Extension and temperature between seasonable increase, and the oxidisability of the concentrated sulfuric acid and potassium permanganate gradually increases, and oxidation to graphite flake layer and insert
Layer effect is improved, and more oxygen-containing groups is generated in graphite flake layer, graphite flake layer spacing is also gradually increased, and solution starts
There is yellow, this is the performance that graphite oxidation degree is deepened and limellar stripping degree enhances, until being stripped, mixed material is in bright
Yellow.
(4) the oxidation mixed solution after step (3) is cooled to room temperature, is then ultrasonically treated, is centrifuged later
Separation, washing, obtain graphene oxide mother liquor；
(5) the graphene oxide mother liquor after step (4) is added in 100 parts of pitches, is heated to melting, is then cut
It cuts, obtains graphene oxide modified pitch.
We have discovered that when graphene oxide mother liquor is dried to obtain graphene oxide solid, in the mistake of centrifugal drying
Cheng Zhong has the tendency that recrystallizing between graphene oxide layer, can greatly shorten piece interlamellar spacing；Due to surface of graphene oxide
There are hydrophilic oxygen-containing functional group, graphene oxide solid powder can be dissolved in water, equally also may be implemented in liquid form
It is mixed with pitch, but even graphene oxide water solution, interlamellar spacing and extent of exfoliation are also not as good as the oxidation just prepared
Graphene mother liquor is big.By in graphene oxide solid powder or its aqueous solution incorporation pitch, it is intercal type nano that majority, which is formed,
Composite material, and in graphene oxide mother liquor incorporation pitch, graphene oxide can form exfoliated nano combined with pitch
Material, and segregation phenomenon is not generated, exfoliated nanocomposite can promote pitch mechanical property to a greater degree, in height
The volatilization that light components in pitch can more be inhibited under temperature state improves the high temperature stability performance and thermal oxidative aging of pitch
Energy.
Above-mentioned preparation method, it is preferred that in the step (1), graphite is natural graphite, and granularity is -80 mesh.It is more excellent
Choosing, the graphite is crystalline flake graphite.Compared with artificial graphite, natural graphite crystal is perfect, wherein the graphitization of crystalline flake graphite
Degree highest, crystal structure is complete, so that it has superior mechanical property after removing, is more suitable for the enhancing of pitch
Body.Within the scope of the invention by the granularity control of graphite, be conducive to the progress of graphite oxidation reaction, if beyond of the invention
Range will lead to reaction time extension.
Above-mentioned preparation method, it is preferred that in the step (1), nitration mixture is to be according to mass ratio by concentrated acid A and concentrated acid B
10:(1~1.5) it mixes, the concentrated acid A is the concentrated sulfuric acid, and the concentrated acid B is concentrated phosphoric acid and/or concentrated nitric acid.
Above-mentioned preparation method, it is preferred that in the step (2), the granularity of potassium permanganate is 100 mesh~140 mesh.To make
Potassium permanganate uniformly slowly participates in reaction, promotes reaction is gentle to carry out, and need to control the granularity of potassium permanganate of the invention
In range, if beyond the scope of this invention, when being aoxidized under strongly acidic conditions to graphite, it is easy at potassium permanganate particles
Vigorous oxidation reaction is formed, big energy is discharged, is generated " explosion "；If being lower than the scope of the present invention, specific grain surface was accumulated
Greatly, it is easy to absorb the moisture in air, so that particle makes moist and agglomerates.
Above-mentioned preparation method, it is preferred that in the step (4), the time of ultrasonic treatment is 1~2 hour, frequency 22
~24KHz.
Above-mentioned preparation method, it is preferred that in the step (2), stirring rate is 20rpm~40rpm, and whipping temp is
50~60 DEG C, the reaction time is 6~8 hours.
Above-mentioned preparation method, it is preferred that in the step (3), stirring rate is 20rpm~40rpm, and whipping temp is
50~60 DEG C, the reaction time is 2~3 hours.
Preparation method of the invention need to control stirring rate, whipping temp, reaction time in step (2) and step (3)
Within the scope of the invention, the reaction to be related to provides most suitable external condition, if beyond the scope of this invention, will lead to
Reaction acutely carries out, or even causes " explosion "；If being lower than the scope of the present invention, the not thorough enough of reaction progress will lead to.
Above-mentioned preparation method, it is preferred that in the step (4), the revolving speed of centrifuge separation is 2000rpm~3000rpm.
Above-mentioned preparation method, it is preferred that in the step (5), shear rate is 1500~1800rpm, shear time
It is 30~40 minutes.
Preparation method of the invention is added graphene oxide into first in the nitration mixture being made of strong acid, since nitration mixture has
Certain oxidation susceptibility can carry out preliminary oxidation to graphite flake layer edge, tentatively widen graphite flake layer spacing；But it relies solely on
The oxidisability of nitration mixture be it is far from being enough, permanganic acid is added into the mixed material of graphite and nitration mixture under stirring condition appropriate
Potassium is gradually carried out graphite using the potassium permanganate of strong oxidizing property as oxidant since lamella edge to graphite flake layer center
Oxidation, at graphite flake layer edge and is centrally generated oxygen-containing functional group, with going deep into for oxidation, graphite flake layer spacing is gradually drawn
Greatly；After oxidant reaction is complete in order to prevent, oxidant is lacked in reaction system, continuation was added under stirring condition appropriate
Hydrogen oxide provides enough oxidants for reaction system, while hydrogen peroxide can be diluted nitration mixture, in diluted process
In, system heat release provides enough energy for entire reaction system further to remove to graphite flake layer；It is fitted later
When ultrasonic treatment, lamellar structure is spread out, realize to the greatest extent removing.In reaction process, according to graphite amount and
Its chemical reaction ratio is come the graphite determined and the additive amount of all kinds of oxidants, when the amount of nitration mixture and other oxidants exceeds this hair
When bright range, booster action will not be risen to reaction, be easy to cause residual instead；When the amount of nitration mixture and other oxidants is lower than this
It, cannot be completely by graphite oxidation, so that the layer structure for farthest removing graphite can not be realized when the range of invention.Only
Have and lamellar structure has been subjected to the removing of sufficient degree, it is exfoliated nano combined to be that subsequent pitch is formed with graphene oxide
Material provides condition.
Preparation method of the invention has abandoned traditional modification mode, first passes through the preparation of Collaborative Control various process parameters
The graphene oxide mother liquor that interlamellar spacing is sufficiently large out, peeling effect is good, then using this graphene oxide mother liquor now made as changing
Property agent incorporation pitch in, dramatically improve the high-temperature stability, low-temperature cracking-resistance and thermo oxidative aging performance of pitch,
Realize the raising of pitch comprehensive performance.
The inventive concept total as one, the present invention also provides a kind of graphite oxides according to made from above-mentioned preparation method
Alkene modified pitch, the graphene oxide modified pitch are exfoliated graphene oxide/pitch composite material, and structure is referring to figure
1。
Compared with the prior art, the advantages of the present invention are as follows:
(1) preparation method of graphene oxide modified pitch of the invention, using graphene oxide mother liquor as modifying agent, benefit
It is combined together with surface of graphene oxide oxygen-containing functional group abundant with Bituminous stabilized, keeps the height temperature stability of pitch significant
It is promoted；At the same time, graphene oxide reticular structure can effectively wrap up asphaltene molecule, form space crosslinking knot
Structure, can blocking oxygen molecule to a certain degree, so as to improve the anti-aging property of pitch, gained modified pitch high temperature is not easy soft
Change, low temperature is not easy to crack, and road is long with the service life.
(2) modifying agent, is added to drip by the preparation method of graphene oxide modified pitch of the invention in the form of mother liquor
In blueness, modifying agent is added in pitch in the form of solid powder compared to other, modifying agent does not generate segregation phenomenon in pitch,
It is not easy two-phase laminated flow, dispersion effect is good, can utmostly play the modifying function of modifying agent.
(3) preparation method of graphene oxide modified pitch of the invention, before modifying agent graphene oxide is graphene
Body is driven, remains the part good physical of graphene oxide, while cheap compared to graphene, is guaranteeing modified effect
While, good economic benefit can be brought.
(4) preparation method of graphene oxide modified pitch of the invention carries out pitch using graphene oxide mother liquor
It is modified, under high temperature fused state, without carrying out long agitation to pitch, without being swollen to graphene oxide, reduce
The aging of pitch, simplifies conventional process flow, reduces process costs in preparation process, is suitable for large-scale production.
(5) graphene oxide modified pitch of the invention has excellent high-temperature stability, low-temperature cracking-resistance and heat resistanceheat resistant
Oxidative aging energy meets concerned countries standard, can effectively improve the performance of bituminous pavement.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is that modification forms exfoliated graphene oxide/pitch composite material schematic diagram in the embodiment of the present invention 1~4；
Fig. 2 is that modification forms intercal type graphene oxide/pitch composite material schematic diagram in comparative example 1~2 of the present invention.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of graphene oxide modified pitch of the invention, the graphene oxide modified pitch include the original of following parts by weight
Material: 100 parts of pitch, 0.17 part of graphite, 38.19 parts of nitration mixture, 0.93 part of potassium permanganate, 11.89 parts of hydrogen peroxide.Wherein, graphite
For natural graphite, granularity is -160 mesh；The granularity of potassium permanganate is -100 mesh；Nitration mixture is dense by 34.72 parts of concentrated sulfuric acids and 3.47 parts
Phosphoric acid mixes.
The preparation method of the graphene oxide modified pitch of the present embodiment, comprising the following steps:
(1) graphite is slowly added in nitration mixture, is stirred evenly, obtain mixed material；
(2) mixed material after step (1) is placed in heat-collecting magnetic stirring device, opens stirring, stirring rate is
20rpm, whipping temp are 50 DEG C, and potassium permanganate is slowly added into mixed material, is persistently stirred to react 6 hours, is aoxidized
Mixed material；
(3) under the stirring condition that stirring rate is 20rpm, whipping temp is 50 DEG C, to the oxidation mixing after step (2)
It is slowly added to hydrogen peroxide in material, until mixed material color becomes purplish finally to glassy yellow by black, no longer produces
It until anger bubble, is persistently stirred to react 2 hours, obtains oxidation mixed solution；
(4) the oxidation mixed solution after step (3) is cooled to room temperature, then under the conditions of frequency is 22KHz at ultrasound
Reason 1 hour, is centrifuged under the conditions of 2000rpm, then carry out carrying out washing treatment later, until solution is in neutrality, obtains oxygen
Graphite alkene mother liquor；
(5) the graphene oxide mother liquor after step (4) is added in pitch, is heated to melting, then cut in 1500rpm
It is sheared 30 minutes under cutting speed rate, is cooled to room temperature, obtains graphene oxide modified pitch.Graphite oxide obtained in the present embodiment
Alkene modified pitch is a kind of exfoliated graphene oxide/pitch composite material, and modifying process is as shown in Figure 1.
Embodiment 2:
A kind of graphene oxide modified pitch of the invention, the graphene oxide modified pitch include the original of following parts by weight
Material: 100 parts of pitch, 0.34 part of graphite, 76.38 parts of nitration mixture, 1.86 parts of potassium permanganate, 23.78 parts of hydrogen peroxide.Wherein, used
Pitch is No. 70 pitches；Graphite is natural graphite, and granularity is -160 mesh；The granularity of potassium permanganate is -100 mesh；Nitration mixture is by 69.44
Part concentrated sulfuric acid and 6.94 parts of concentrated phosphoric acids mix.
The preparation method of the graphene oxide modified pitch of the present embodiment, comprising the following steps:
(1) graphite is slowly added in nitration mixture, is stirred evenly, obtain mixed material；
(2) mixed material after step (1) is placed in heat-collecting magnetic stirring device, opens stirring, stirring rate is
20rpm, whipping temp are 50 DEG C, and potassium permanganate is slowly added into mixed material, is persistently stirred to react 6 hours, is aoxidized
Mixed material；
(3) under the stirring condition that stirring rate is 20rpm, whipping temp is 50 DEG C, to the oxidation mixing after step (2)
It is slowly added to hydrogen peroxide in material, until mixed material color becomes purplish finally to glassy yellow by black, no longer produces
It until anger bubble, is persistently stirred to react 2 hours, obtains oxidation mixed solution；
(4) the oxidation mixed solution after step (3) is cooled to room temperature, then under the conditions of frequency is 22KHz at ultrasound
Reason 1 hour, is centrifuged under the conditions of 2000rpm, then carry out carrying out washing treatment later, until solution is in neutrality, obtains oxygen
Graphite alkene mother liquor；
(5) the graphene oxide mother liquor after step (4) is added in pitch, is heated to melting, then cut in 1500rpm
It is sheared 30 minutes under cutting speed rate, is cooled to room temperature, obtains graphene oxide modified pitch.Graphite oxide obtained in the present embodiment
Alkene modified pitch is a kind of exfoliated graphene oxide/pitch composite material, and modifying process is as shown in Figure 1.
Embodiment 3:
A kind of graphene oxide modified pitch of the invention, the graphene oxide modified pitch include the original of following parts by weight
Material: 100 parts of pitch, 0.34 part of graphite, 76.38 parts of nitration mixture, 1.86 parts of potassium permanganate, 23.78 parts of hydrogen peroxide.Wherein, used
Pitch is No. 70 pitches；Graphite is natural graphite, and granularity is -200 mesh；The granularity of potassium permanganate is -140 mesh；Nitration mixture is by 69.44
Part concentrated sulfuric acid and 6.94 parts of concentrated phosphoric acids mix.
The preparation method of the graphene oxide modified pitch of the present embodiment, comprising the following steps:
(1) graphite is slowly added in nitration mixture, is stirred evenly, obtain mixed material；
(2) mixed material after step (1) is placed in heat-collecting magnetic stirring device, opens stirring, stirring rate is
30rpm, whipping temp are 50 DEG C, and potassium permanganate is slowly added into mixed material, is persistently stirred to react 7 hours, is aoxidized
Mixed material；
(3) under the stirring condition that stirring rate is 30rpm, whipping temp is 50 DEG C, to the oxidation mixing after step (2)
It is slowly added to hydrogen peroxide in material, until mixed material color becomes purplish finally to glassy yellow by black, no longer produces
It until anger bubble, is persistently stirred to react 2.5 hours, obtains oxidation mixed solution；
(4) the oxidation mixed solution after step (3) is cooled to room temperature, then under the conditions of frequency is 23KHz at ultrasound
Reason 1.5 hours, is centrifuged under the conditions of 2500rpm, then carry out carrying out washing treatment later, until solution is in neutrality, obtains
Graphene oxide mother liquor；
(5) the graphene oxide mother liquor after step (4) is added in pitch, is heated to melting, then cut in 1700rpm
It is sheared 35 minutes under cutting speed rate, is cooled to room temperature, obtains graphene oxide modified pitch.Graphite oxide obtained in the present embodiment
Alkene modified pitch is a kind of exfoliated graphene oxide/pitch composite material, and modifying process is as shown in Figure 1.
For the pavement performance and anti-aging property for verifying modified pitch of the invention, foundation " highway engineering pitch and drip
Green test mixture regulation " relevant regulations of (JTJE20-2011) carry out needle penetration, softening point, ductility, anti-to the modified pitch
Ageing properties test, specific test result are as shown in table 1.
Embodiment 4:
A kind of graphene oxide modified pitch of the invention, the graphene oxide modified pitch include the original of following parts by weight
Material: 100 parts of pitch, 0.58 part of graphite, 128.16 parts of nitration mixture, 3.15 parts of potassium permanganate, 39.89 parts of hydrogen peroxide.Wherein, used
Pitch is No. 70 pitches；Graphite is natural graphite, and granularity is -200 mesh；The granularity of potassium permanganate is -140 mesh；Nitration mixture by
116.51 parts of concentrated sulfuric acids and 11.65 parts of concentrated phosphoric acids mix.
The preparation method of the graphene oxide modified pitch of the present embodiment, comprising the following steps:
(1) graphite is slowly added in nitration mixture, is stirred evenly, obtain mixed material；
(2) mixed material after step (1) is placed in heat-collecting magnetic stirring device, opens stirring, stirring rate is
40rpm, whipping temp are 50 DEG C, and potassium permanganate is slowly added into mixed material, is persistently stirred to react 8 hours, is aoxidized
Mixed material；
(3) under the stirring condition that stirring rate is 40rpm, whipping temp is 50 DEG C, to the oxidation mixing after step (2)
It is slowly added to hydrogen peroxide in material, until mixed material color becomes purplish finally to glassy yellow by black, no longer produces
It until anger bubble, is persistently stirred to react 3 hours, obtains oxidation mixed solution；
(4) the oxidation mixed solution after step (3) is cooled to room temperature, then under the conditions of frequency is 24KHz at ultrasound
Reason 2 hours, is centrifuged under the conditions of 3000rpm, then carry out carrying out washing treatment later, until solution is in neutrality, obtains oxygen
Graphite alkene mother liquor；
(5) the graphene oxide mother liquor after step (4) is added in pitch, is heated to melting, then cut in 1800rpm
It is sheared 40 minutes under cutting speed rate, is cooled to room temperature, obtains graphene oxide modified pitch.Graphite oxide obtained in the present embodiment
Alkene modified pitch is a kind of exfoliated graphene oxide/pitch composite material, and modifying process is as shown in Figure 1.
For the pavement performance and anti-aging property for verifying modified pitch of the invention, foundation " highway engineering pitch and drip
Green test mixture regulation " (JTJE20-2011) relevant regulations to graphene oxide obtained in the embodiment of the present invention 1~4
Modified pitch carries out needle penetration, softening point, ductility, anti-aging property test, and specific test result is as shown in table 1.
Comparative example 1:
It takes and is dried with the same amount of graphene oxide mother liquor of example 1, prepare graphene oxide powder；Change identical
Property under the conditions of by graphene oxide powder mix pitch in, prepare graphene oxide modified pitch.Oxygen obtained in this comparative example
Graphite alkene modified pitch is a kind of intercal type graphene oxide/pitch composite material, and modifying process is as shown in Figure 2.
Relevant regulations according to " highway engineering pitch and Asphalt Mixture Experiment regulation " (JTJE20-2011) are to this comparison
Graphene oxide modified pitch obtained carries out needle penetration, softening point, ductility, anti-aging property test, specific test knot in example
Fruit is as shown in table 1.
Comparative example 2:
It takes and is dried with the same amount of graphene oxide mother liquor of example 3, prepare graphene oxide powder；By graphite oxide
Alkene powder, which is dissolved in deionized water, forms aqueous solution, and graphene oxide water solution is mixed pitch under identical modified condition
In, prepare graphene oxide modified pitch.Graphene oxide modified pitch obtained is a kind of intercal type oxidation in this comparative example
Graphene/pitch composite material, modifying process are as shown in Figure 2.
Relevant regulations according to " highway engineering pitch and Asphalt Mixture Experiment regulation " (JTJE20-2011) are to this comparison
Graphene oxide modified pitch obtained carries out needle penetration, softening point, ductility, anti-aging property test, specific test knot in example
Fruit is as shown in table 1.
The performance test results of graphene oxide modified pitch obtained in 1 embodiment of the present invention 1~4 of table
As shown in Table 1, the softening point of graphene oxide modified pitch of the invention, needle penetration, ductility are all satisfied " highway drip
Green pavement construction technical specification " (JTG F40-2004) associated specifications, modified pitch of the invention addition modifying agent
In the case of graphene oxide, with the increase of graphene oxide volume, softening point is improved, this illustrates that high-temperature stability obtains
It is promoted, 25 DEG C of ductilities, needle penetrations are declined slightly, but amplitude of variation is little, while thermo oxidative aging performance is also improved.This is sent out
Bright middle the above embodiments 1 and comparative example 1 compare, embodiment 3 and comparative example 2 compare it is found that in the form of graphene oxide mother liquor
Graphene oxide modified pitch obtained in graphene oxide incorporation pitch is had into higher softening point, there is better high temperature
Stability and thermo oxidative aging performance；Graphene oxide modified pitch needle penetration and 25 DEG C are made in the embodiment of the present invention 1,3
Ductility is not much different with comparative example 1 and comparative example 2, but embodiment 1,3 is bigger than 5 DEG C of ductilities of comparative example 1,2, this explanation is with oxygen
Graphene oxide modified pitch obtained in graphene oxide incorporation pitch is had better low temperature by graphite alkene mother liquor form
Cracking resistance.
As it can be seen that graphene oxide modified pitch of the invention, modifying agent are uniformly dispersed in pitch, there is ideal road to use
Performance can effectively improve the performance of bituminous pavement.
Claims (10)
1. a kind of preparation method of graphene oxide modified pitch, which comprises the following steps:
(1) 0.17~0.58 part of graphite is slowly added in 38.19~128.16 parts of nitration mixture, stirs evenly, obtains mixed material；
(2) under agitation, it is slowly added to 0.93~3.15 part of potassium permanganate into the mixed material after step (1), continues
Stirring is reacted, and oxidation mixture material is obtained；
(3) under agitation, 11.89~39.89 parts of peroxidating are slowly added into the oxidation mixture material after step (2)
Hydrogen, lasting stirring are reacted, and oxidation mixed solution is obtained；
(4) the oxidation mixed solution after step (3) is cooled to room temperature, is then ultrasonically treated, be centrifuged later,
Washing, obtains graphene oxide mother liquor；
(5) the graphene oxide mother liquor after step (4) is added in 100 parts of pitches, is heated to melting, is then sheared,
Obtain graphene oxide modified pitch.
2. preparation method according to claim 1, which is characterized in that in the step (1), graphite is natural graphite,
Granularity is -80 mesh.
3. preparation method according to claim 1, which is characterized in that in the step (1), nitration mixture is by concentrated acid A and dense
Sour B is 10:(1~1.5 according to mass ratio) it mixes, the concentrated acid A is the concentrated sulfuric acid, and the concentrated acid B is concentrated phosphoric acid and/or dense
Nitric acid.
4. preparation method according to claim 1, which is characterized in that in the step (2), the granularity of potassium permanganate is
100 mesh~140 mesh.
5. preparation method according to claim 1, which is characterized in that in the step (4), the time of ultrasonic treatment is 1
~2 hours, frequency was 22~24KHz.
6. preparation method according to claim 1, which is characterized in that in the step (2), stirring rate be 20rpm~
40rpm, whipping temp are 50~60 DEG C, and the reaction time is 6~8 hours.
7. preparation method according to claim 1, which is characterized in that in the step (3), stirring rate be 20rpm~
40rpm, whipping temp are 50~60 DEG C, and the reaction time is 2~3 hours.
8. preparation method according to claim 1, which is characterized in that in the step (4), the revolving speed of centrifuge separation is
2000rpm~3000rpm.
9. preparation method according to claim 1, which is characterized in that in the step (5), shear rate be 1500~
1800rpm, shear time are 30~40 minutes.
10. it is a kind of according to claim 1~any one of 9 described in graphene oxide modified pitch made from preparation method,
It is characterized in that, the graphene oxide modified pitch is exfoliated graphene oxide/pitch composite material.
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| CN111977643A (en) * | 2020-08-24 | 2020-11-24 | 南京林业大学 | Preparation method of nano graphene oxide for asphalt modification |
| CN112430095A (en) * | 2020-12-03 | 2021-03-02 | 中国科学院山西煤炭化学研究所 | Method for preparing high-performance graphite from graphene oxide modified coal pitch |
| CN113337136A (en) * | 2021-06-15 | 2021-09-03 | 长沙理工大学 | Modified asphalt and preparation method thereof |
| CN113773663A (en) * | 2021-10-18 | 2021-12-10 | 陕西理工大学 | Asphalt containing modified nano graphene oxide and asphalt mixture |
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| CN114316611A (en) * | 2021-10-20 | 2022-04-12 | 鄂尔多斯市路泰公路工程有限责任公司 | Composite modified asphalt based on epoxy resin rubber powder and mixture |
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| CN115368747A (en) * | 2022-09-27 | 2022-11-22 | 西南交通大学 | Dispersing agent for improving low-temperature performance of waxy asphalt, asphalt and preparation method thereof |
| CN115368747B (en) * | 2022-09-27 | 2023-04-07 | 西南交通大学 | Dispersing agent for improving low-temperature performance of waxy asphalt, asphalt and preparation method thereof |
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