CN110105778A - Nanocomposite modified pitch, preparation method and bituminous concrete - Google Patents
Nanocomposite modified pitch, preparation method and bituminous concrete Download PDFInfo
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- CN110105778A CN110105778A CN201910293559.0A CN201910293559A CN110105778A CN 110105778 A CN110105778 A CN 110105778A CN 201910293559 A CN201910293559 A CN 201910293559A CN 110105778 A CN110105778 A CN 110105778A
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/29—Frost-thaw resistance
Abstract
The present invention provides a kind of nanocomposite modified pitch, the raw material including following mass fraction: 100 parts of matrix pitches and 2~6 parts of modifying agent；The modifying agent is graphene oxide/styrene-butadiene rubber composite material, including 100 parts of graphene oxides/butadiene-styrene rubber compound, 15~30 parts of carbon blacks, 2~6 parts of magnesia, 3~6 parts of stearic acid, 2~3 parts of magnesium carbonate, 3~5 parts of anti-aging agents, 3~7 parts of promotors and 1~3 part of sulphur；The graphene oxide/butadiene-styrene rubber compound includes 0.1~1 part of graphene oxide and 15~20 parts of styrene-butadiene latexes.Thermal stability is good under nanocomposite modified pitch high temperature provided by the invention, freezing-thawing resistance is strong under low temperature, rutting resistance and anti-aging property are strong, has good durability.
Description
Technical field
The invention belongs to technical field of road engineering, and in particular to a kind of nanocomposite modified pitch, its preparation side
Method and bituminous concrete.
Background technique
Traditional bituminous mixtures for pavement surface is mostly matrix pitch compound, extraneous in road construction process and use process
The durability of condition road pavement structure causes tremendous influence.For example, construction Asphalt Mixture is being mixed under the influence of high temperature
With transport, easily short ageing in paving process；Under the action of ultraviolet light, traffic loading and day and night temperature, asphalt surface course goes out
The diseases such as existing long-term ageing, track, crack Moisture Damage, significantly reduce the durability of bituminous pavement.It leads due to the above reasons,
Cause the roads in many areas in several years after being open to traffic, occur disease emerge one after another and must not be without repairing the phenomenon that, at present
Polymer-asphalt often one or several performances but can not meet road surface comprehensively and mix and stir, pave and using each than more prominent
Demand during a.
Graphene is a kind of carbon material of two-dimensional slice structure, is one kind most thin in currently known nanofiller, has
Very excellent performance, such as: there is higher specific surface area, intensity, elasticity, thermal conductivity, conductivity, translucency and gas barrier
Property.Graphene oxide (GO) keeps its property more active compared with graphene because oxygen-containing functional group increases, can via it is various with it is oxygen-containing
The reaction of functional group and improve nature.However, one side graphene oxide is relatively numerous due to the preparation of industrialization graphene
It is trivial, and need to be aoxidized and be obtained through strong acid by graphene, it causes higher relative to other materials price, has at present direct to carbon tar
The desk study of synthesizing graphite alkene substitute, but its product is lower, product only accounts for the 12-18% of raw material；On the other hand simultaneously
It is influenced by the powerful Van der Waals force in surface, easily generates reunion as graphene is added directly into pitch.Chinese invention patent
It discloses and is added to graphene in the mixed solution of dehydrated alcohol and polyvinylpyrrolidone in CN20180502137.5, surpass
Acoustic shock, which swings to be added in pitch after above-mentioned solution, is sheared, and solution blended process is belonged to, but solvent removal mistake in this kind of method
Journey is only evaporated by baking, not can guarantee solvent removal, and also not can guarantee graphene dispersion uniform for primary shearing.Therefore, it needs
A kind of NEW TYPE OF COMPOSITE modified pitch is provided, to meet road surface mix comprehensively, pave and the needs of using during each.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, an object of the present invention is to provide a kind of nanocomposite and changes
Property pitch and preparation method thereof, thermal stability is good under the nanocomposite modified pitch high temperature, under low temperature freezing-thawing resistance it is strong,
Rutting resistance and anti-aging property are strong, have good durability；The second object of the present invention is to providing a kind of bituminous concrete.
To achieve the above object, the invention provides the following technical scheme: a kind of nanocomposite modified pitch, including such as
The raw material of lower mass fraction: 100 parts of matrix pitches and 2~6 parts of modifying agent；The modifying agent is reduction-state graphene oxide/fourth
Benzene rubber composite material, including 100 parts of graphene oxides/butadiene-styrene rubber compound, 15~30 parts of carbon blacks, 2~6 parts of magnesia, 3
~6 parts of stearic acid, 2~3 parts of magnesium carbonate, 3~5 parts of anti-aging agents, 3~7 parts of promotors and 1~3 part of sulphur；The graphite oxide
Alkene/butadiene-styrene rubber compound includes 0.1~1 part of graphene oxide and 15~20 parts of styrene-butadiene latexes.
The present invention is using graphene oxide/styrene-butadiene rubber composite material as modifying agent, and graphene oxide/butadiene-styrene rubber is multiple
Graphene oxide in condensation material can increase the internal friction of matrix pitch, viscosity and elastic component, and then can be effective
The high-temperature behavior of concrete is improved, the ability for resisting high temperature short ageing in road surface is greatly enhanced；And butadiene-styrene rubber can improve base
Binding material ability, the cryogenic property of matter pitch, so that the road surface Low-temperature antifreeze for improving concrete melts ability；The addition of carbon black can inhale
Ultraviolet light is received, is played the role of to the ageing resistance for improving concrete positive.
Further, the modifying agent is prepared using following method:
(1) above-mentioned promotor is divided into two parts of a, b, the mass ratio of a:b is 1:2；
(2) according to said ratio by graphene oxide/butadiene-styrene rubber compound, carbon black, magnesia, stearic acid, magnesium carbonate,
Anti-aging agent and b parts of promotor are mixed to get intermediate product A；
(3) above-mentioned intermediate product A is placed on vulcanizer with a parts of promotor, sulphur and is vulcanized by sulfurizing time, sulphur
Changing temperature is 140~150 DEG C, and vulcanization time is 16~20min, obtains modifying agent graphene oxide/styrene-butadiene rubber composite material.
Further, the anti-aging agent is DNP or NPC, and the promotor is TMTD or CZ.
Further, the graphene oxide/butadiene-styrene rubber compound is prepared using following method:
(a) 0.5~3 part of Cetrimide is added in 90~97 parts of distilled water, obtains suspension after stirring 10-15min；
(b) 0.1~1 part of graphene oxide and 15~20 parts of styrene-butadiene latexes are added in Xiang Shangshu suspension, continue to stir 30-
After 45min, 6~8 parts of flocculants are added, 10-20min are reacted under ice bath and ultrasound, then under 6000-7000r/min revolving speed
5-10min is reacted, then keeping temperature is 50~60 DEG C, and adjusting solution ph is 7.5~8.5, keeps 1~2h；
(c) 80~85 DEG C are continuously heating to, 4-5h is reacted, sodium hydroxide solution to solution ph is added into solution is
10, washing is dried to get graphene oxide/butadiene-styrene rubber compound is arrived.
Further, total solids ingredient is 64~69% in butadiene-styrene latex described in step (b), styrene-content 83.5
~87%, the flocculant is polymer alumina.
Further, the graphene oxide uses following preparation method:
1) 0.5~1 part of 70# matrix pitch and 1.5~2.5 parts of calcium carbonate are sufficiently mixed, by mixture in air atmosphere
Lower heating, heating rate are 5~15 DEG C/min, and heating temperature is 300~500 DEG C, heating time 4h, natural cooling；
2) 100 parts of hydrochloric acid are added into said mixture, add 100 parts of hydrochloric acid after crystal precipitation, then with distillation
Water adjust mixture pH value be 6.5-7.5, stand overnight, last evaporation drying to get arrive graphene oxide.
The present invention prepares graphene oxide, simple process in matrix pitch, and calcium carbonate is added during preparation,
So that forming the barrier for hindering the substances such as fragrant phenol evaporation escape in matrix pitch in graphene oxide generating process, promote
The generation of graphene oxide；Carbonate can form the non-volatile phenates of reactivity as graphene oxide with matrix pitch simultaneously
One of component part increases the yield of graphene oxide.
Further, the mass concentration of hydrochloric acid is 37-38% in step 2).
The preparation method of above-mentioned nanocomposite modified pitch, preparation process are as follows:
According to said ratio, modifying agent reduction-state graphene oxide/styrene-butadiene rubber composite material is added to matrix pitch
In, it is placed on controllable temperature electrothermal furnace, is stirred using high speed shear instrument, whipping temp is 150~165 DEG C, stirring rate
For 2500r/min~3000r/min, mixing time is 25~40min to get nanocomposite modified pitch is arrived.
A kind of bituminous concrete, the raw material including following mass fraction, nanocomposite described in claim 1-7 change
4~5 parts of pitch of property, gather materials 95~97 parts, 3~5 parts of miberal powder and 0.3~0.5 part of fiber.
Further, described to gather materials for limestone or basalt.
Fiber is added in bituminous concrete of the invention can play the role of reinforcement, improve the anti-fatigue performance of concrete.
It is compared with the prior art, the invention has the following beneficial effects:
1, the present invention obtains graphene oxide by the secondary treatment in matrix pitch through hydrochloric acid, and graphene oxide is again
Incorgruous latex occurs with butadiene-styrene latex to solidify, wherein positively charged graphene oxide and negatively charged butadiene-styrene latex particle phase
Mutually close, butadiene-styrene latex particle is inserted into graphene oxide multilayered structure and develops together, on the one hand shape on a microscopic level
At stable network structure；On the other hand different degrees of take is occurred along Impact direction in intrinsic silicon by external force
To, more outside energies are consumed, performance is drawn in the strength agents bending resistance for improving butadiene-styrene rubber itself, thus after being mixed with pitch,
It is not susceptible to agglomeration, and pitch is uniform disperse system after mixing, there is the concrete of preparation strong under high temperature
Thermal stability, strong freezing-thawing resistance under low temperature, rutting resistance and the strong feature of ageing resistance.
2, nanocomposite modified pitch of the invention and bituminous concrete preparation are simple, while later maintenance cost
It is low, have good wearability, is suitable for large range promotion use.
Detailed description of the invention
Fig. 1 is the pavement structure schematic diagram of 5-7 of the embodiment of the present invention；
Fig. 2 is the pavement structure schematic diagram of comparative example 1；
Fig. 3 is the pavement structure schematic diagram of comparative example 2；
Fig. 4 is graphene oxide/butadiene-styrene rubber compound generating process.
Specific embodiment
Combined with specific embodiments below, the method for the present invention is described in detail.The implementation case is with the technology of the present invention
Premised under implemented, now provide detailed embodiment and specific operating process, but protection scope of the present invention is unlimited
In embodiment below.
One, nanocomposite modified pitch is prepared
Embodiment 1
A: a kind of preparation method of graphene oxide includes the following steps:
1) 0.5 part of 70# matrix pitch and 1.5 parts of calcium carbonate are sufficiently mixed, mixture is put into crucible, it is big in standard
It under air pressure, is heated under air atmosphere, heating rate is 5 DEG C/min, and heating temperature is 300 DEG C, heating time 4h, naturally cold
But；
2) the hydrochloric acid removal residual calcium carbonate that 100 parts of mass concentrations are 37%, crystal to be had are added into said mixture
The hydrochloric acid that 100 parts of mass concentrations are 37% is added after precipitation and carries out secondary reprocessing, then adjusts mixture with distilled water
PH value be 6.5, stand overnight, last evaporation drying to get arrive graphene oxide.
B: a kind of preparation method of graphene oxide/butadiene-styrene rubber compound is calculated, the graphite oxide in parts by mass
Alkene/butadiene-styrene rubber compound includes 0.1 part of graphene oxide and 15 parts of styrene-butadiene latexes, it is specific the preparation method is as follows:
(a) 0.5 part of Cetrimide is added in 90 parts of distilled water, obtains suspension after stirring 10min；
(b) be added in Xiang Shangshu suspension 0.1 part of graphene oxide and 15 parts of styrene-butadiene latexes (in butadiene-styrene latex total solids at
Be divided into 64%, styrene-content 83.5%), continue after stirring 30min, 6 parts of polymerization oxidation aluminium flocculating agents be added, in ice bath and
Ultrasound is lower to react 10min, then carries out reaction 5min in homogenizer under 6000r/min revolving speed, and then keeping temperature is 50 DEG C,
Adjusting solution ph is 7.5, keeps 1h；Cationic oxidation graphene particles and anion butadiene-styrene latex particle phase in the process
It is mutually close, realize incorgruous latex solidification；
(c) 80 DEG C are continuously heating to, 4h is reacted, it is 10 that sodium hydroxide solution to solution ph is added into solution, washing,
It dries to get graphene oxide/butadiene-styrene rubber compound is arrived.
C: a kind of preparation method of graphene oxide/styrene-butadiene rubber composite material modifying agent is calculated, the oxygen in parts by mass
Graphite alkene/styrene-butadiene rubber composite material modifying agent includes 100 parts of graphene oxides/butadiene-styrene rubber compound, 15 parts of carbon blacks, 2
Part magnesia, 3 parts of stearic acid, 2 parts of magnesium carbonate, 3 parts of antioxidant D NP, 3 parts of Vulcanization accelerator TMTDs and 1 part of sulphur, specific preparation method
It is as follows:
(1) above-mentioned Vulcanization accelerator TMTD is divided into two parts of a, b, a parts: b part of mass ratio is 1:2；
(2) according to said ratio by graphene oxide/butadiene-styrene rubber compound, carbon black, magnesia, stearic acid, magnesium carbonate,
Antioxidant D NP and b parts of Vulcanization accelerator TMTD are mixed to get intermediate product A；
(3) above-mentioned intermediate product A is placed on vulcanizer with Vulcanization accelerator TMTD a parts, sulphur and carries out sulphur by sulfurizing time
Change, curing temperature is 140 DEG C, vulcanization time 16min, obtains modifying agent graphene oxide/styrene-butadiene rubber composite material.
D: a kind of preparation method of nanocomposite modified pitch is calculated, the nanocomposite changes in parts by mass
Property pitch include 100 parts of matrix pitches and 2 parts of modifying agent, the modifying agent be graphene oxide/styrene-butadiene rubber composite material, tool
Preparation is as follows:
According to said ratio, modifying agent graphene oxide/styrene-butadiene rubber composite material is added in matrix pitch, juxtaposition
In on controllable temperature electrothermal furnace, it is stirred using high speed shear instrument, whipping temp is 150 DEG C, stirring rate 2500r/min,
Mixing time be 25min to get arrive nanocomposite modified pitch.
Embodiment 2
A: a kind of preparation method of graphene oxide includes the following steps:
1) 1 part of 70# matrix pitch and 2.5 parts of calcium carbonate are sufficiently mixed, mixture is put into crucible, in normal atmosphere
It depresses, is heated under air atmosphere, heating rate is 15 DEG C/min, and heating temperature is 500 DEG C, heating time 4h, natural cooling；
2) the hydrochloric acid removal residual calcium carbonate that 100 parts of mass concentrations are 38%, crystal to be had are added into said mixture
The hydrochloric acid that 100 parts of mass concentrations are 38% is added after precipitation and carries out secondary reprocessing, then adjusts mixture with distilled water
PH value be 7.5, stand overnight, last evaporation drying to get arrive graphene oxide.
B: a kind of preparation method of graphene oxide/butadiene-styrene rubber compound is calculated, the graphite oxide in parts by mass
Alkene/butadiene-styrene rubber compound includes 1 part of graphene oxide and 20 parts of styrene-butadiene latexes, it is specific the preparation method is as follows:
(a) 3 parts of Cetrimides are added in 97 parts of distilled water, obtain suspension after stirring 15min；
(b) 1 part of graphene oxide and 20 parts of styrene-butadiene latexes (total solids ingredient in butadiene-styrene latex are added in Xiang Shangshu suspension
It is 69%, styrene-content 87%), continue after stirring 45min, 8 parts of polymerization oxidation aluminium flocculating agents be added, in ice bath and ultrasound
Lower reaction 20min, then reaction 10min is carried out in homogenizer under 7000r/min revolving speed, then keeping temperature is 60 DEG C, is adjusted
Saving solution ph is 8.5, keeps 2h；Cationic oxidation graphene particles and anion butadiene-styrene latex particle are mutual in the process
It is close, realize incorgruous latex solidification；
(c) 85 DEG C are continuously heating to, 5h is reacted, it is 10 that sodium hydroxide solution to solution ph is added into solution, washing,
It dries to get graphene oxide/butadiene-styrene rubber compound is arrived.
C: a kind of preparation method of graphene oxide/styrene-butadiene rubber composite material modifying agent is calculated in parts by mass, described to go back
Ortho states graphene oxide/styrene-butadiene rubber composite material modifying agent includes 100 parts of graphene oxides/butadiene-styrene rubber compound, 30 parts
Carbon black, 6 parts of magnesia, 6 parts of stearic acid, 3 parts of magnesium carbonate, 5 parts of antioxidant D NP, 7 parts of accelerant CZs and 3 parts of sulphur, it is specific to prepare
Method is as follows:
(1) above-mentioned accelerant CZ is divided into two parts of a, b, a parts: b part of mass ratio is 1:2；
(2) according to said ratio by graphene oxide/butadiene-styrene rubber compound, carbon black, magnesia, stearic acid, magnesium carbonate,
Antioxidant D NP and b parts of accelerant CZ are mixed to get intermediate product A；
(3) above-mentioned intermediate product A is placed on vulcanizer with accelerant CZ a parts, sulphur and carries out sulphur by sulfurizing time
Change, curing temperature is 150 DEG C, vulcanization time 20min, obtains modifying agent graphene oxide/styrene-butadiene rubber composite material.
D: a kind of preparation method of nanocomposite modified pitch is calculated, the nanocomposite changes in parts by mass
Property pitch include 100 parts of matrix pitches and 6 parts of modifying agent, the modifying agent be reduction-state graphene oxide/butadiene-styrene rubber it is compound
Material, it is specific the preparation method is as follows:
According to said ratio, modifying agent reduction-state graphene oxide/styrene-butadiene rubber composite material is added to matrix pitch
In, it is placed on controllable temperature electrothermal furnace, is stirred using high speed shear instrument, whipping temp is 165 DEG C, and stirring rate is
3000r/min, mixing time be 40min to get arrive nanocomposite modified pitch.
Embodiment 3
A: a kind of preparation method of graphene oxide includes the following steps:
1) 0.75 part of 70# matrix pitch and 2 parts of calcium carbonate are sufficiently mixed, mixture is put into crucible, it is big in standard
It under air pressure, is heated under air atmosphere, heating rate is 10 DEG C/min, and heating temperature is 400 DEG C, heating time 4h, naturally cold
But；
2) the hydrochloric acid removal residual calcium carbonate that 100 parts of mass concentrations are 37.5%, crystalline substance to be had are added into said mixture
Body adds the hydrochloric acid that 100 parts of mass concentrations are 37.5% and carries out secondary reprocessing after being precipitated, then adjusted with distilled water mixed
Close object pH value be 7, stand overnight, last evaporation drying to get arrive graphene oxide.
B: a kind of preparation method of graphene oxide/butadiene-styrene rubber compound is calculated, the graphite oxide in parts by mass
Alkene/butadiene-styrene rubber compound includes 0.5 part of graphene oxide and 17 parts of styrene-butadiene latexes, it is specific the preparation method is as follows:
(a) 2.5 parts of Cetrimides are added in 94 parts of distilled water, obtain suspension after stirring 15min；
(b) be added in Xiang Shangshu suspension 0.5 part of graphene oxide and 17 parts of styrene-butadiene latexes (in butadiene-styrene latex total solids at
Be divided into 66.5%, styrene-content 85%), continue after stirring 40min, 7 parts of polymerization oxidation aluminium flocculating agents be added, in ice bath and
Ultrasound is lower to react 15min, then carries out reaction 7min in homogenizer under 6500r/min revolving speed, and then keeping temperature is 55 DEG C,
Adjusting solution ph is 7, keeps 1.5h；Cationic oxidation graphene particles and anion butadiene-styrene latex particle phase in the process
It is mutually close, realize incorgruous latex solidification；
(c) 83 DEG C are continuously heating to, 4.5h is reacted, it is 10 that sodium hydroxide solution to solution ph is added into solution, water
It washes, dry to get graphene oxide/butadiene-styrene rubber compound is arrived.
C: a kind of preparation method of graphene oxide/styrene-butadiene rubber composite material modifying agent is calculated, the oxygen in parts by mass
Graphite alkene/styrene-butadiene rubber composite material modifying agent includes 100 parts of graphene oxides/butadiene-styrene rubber compound, 20 parts of carbon blacks, 4
Part magnesia, 4.5 parts of stearic acid, 2.5 parts of magnesium carbonate, 4 parts of anti-aging agent NPC, 5 parts of accelerant CZs and 2 parts of sulphur, specific preparation side
Method is as follows:
(1) above-mentioned accelerant CZ is divided into two parts of a, b, a parts: b part of mass ratio is 1:2；
(2) according to said ratio by graphene oxide/butadiene-styrene rubber compound, carbon black, magnesia, stearic acid, magnesium carbonate,
Anti-aging agent NPC and b parts of accelerant CZ are mixed to get intermediate product A；
(3) above-mentioned intermediate product A is placed on vulcanizer with accelerant CZ a parts, sulphur and carries out sulphur by sulfurizing time
Change, curing temperature is 145 DEG C, vulcanization time 18min, obtains modifying agent reduction-state graphene oxide/butadiene-styrene rubber composite wood
Material.
D: a kind of preparation method of nanocomposite modified pitch is calculated, the nanocomposite changes in parts by mass
Property pitch include 100 parts of matrix pitches and 6 parts of modifying agent, the modifying agent be graphene oxide/styrene-butadiene rubber composite material, tool
Preparation is as follows:
According to said ratio, modifying agent graphene oxide/styrene-butadiene rubber composite material is added in matrix pitch, juxtaposition
In on controllable temperature electrothermal furnace, it is stirred using high speed shear instrument, whipping temp is 155 DEG C, stirring rate 2750r/min,
Mixing time be 30min to get arrive nanocomposite modified pitch.
Embodiment 4
A: a kind of preparation method of graphene oxide includes the following steps:
1) 0.8 part of 70# matrix pitch and 2.2 parts of calcium carbonate are sufficiently mixed, mixture is put into crucible, it is big in standard
It under air pressure, is heated under air atmosphere, heating rate is 10 DEG C/min, and heating temperature is 450 DEG C, heating time 4h, naturally cold
But；
2) the hydrochloric acid removal residual calcium carbonate that 100 parts of mass concentrations are 38%, crystal to be had are added into said mixture
The hydrochloric acid that 100 parts of mass concentrations are 38% is added after precipitation and carries out secondary reprocessing, then adjusts mixture with distilled water
PH value be 7, stand overnight, last evaporation drying to get arrive graphene oxide.
B: a kind of preparation method of graphene oxide/butadiene-styrene rubber compound is calculated, the graphite oxide in parts by mass
Alkene/butadiene-styrene rubber compound includes 0.7 part of graphene oxide and 18 parts of styrene-butadiene latexes, it is specific the preparation method is as follows:
(a) 1.5 parts of Cetrimides are added in 95 parts of distilled water, obtain suspension after stirring 15min；
(b) be added in Xiang Shangshu suspension 0.7 part of graphene oxide and 18 parts of styrene-butadiene latexes (in butadiene-styrene latex total solids at
It is divided into 66.5%, styrene-content 85%), continue after stirring 40min, 7.5 parts of polymerization oxidation aluminium flocculating agents is added, in ice bath
And the lower reaction 15min of ultrasound, then reaction 7min is carried out in homogenizer under 6500r/min revolving speed, then keeping temperature is 50
DEG C, adjusting solution ph is 7, keeps 1.5h；Cationic oxidation graphene particles and anion butadiene-styrene latex in the process
Grain is close to each other, realizes incorgruous latex solidification；
(c) 85 DEG C are continuously heating to, 4h is reacted, it is 10 that sodium hydroxide solution to solution ph is added into solution, washing,
It dries to get graphene oxide/butadiene-styrene rubber compound is arrived.
C: a kind of preparation method of graphene oxide/styrene-butadiene rubber composite material modifying agent is calculated, the oxygen in parts by mass
Graphite alkene/styrene-butadiene rubber composite material modifying agent include 100 parts of graphene oxides/butadiene-styrene rubber compound, 25 parts of carbon blacks,
4.5 parts of magnesia, 5 parts of stearic acid, 2.8 parts of magnesium carbonate, 4.5 parts of anti-aging agent NPC, 7 parts of Vulcanization accelerator TMTDs and 2.5 parts of sulphur, tool
Preparation is as follows:
(1) above-mentioned Vulcanization accelerator TMTD is divided into two parts of a, b, a parts: b part of mass ratio is 1:2；
(2) according to said ratio by graphene oxide/butadiene-styrene rubber compound, carbon black, magnesia, stearic acid, magnesium carbonate,
Anti-aging agent NPC and b parts of Vulcanization accelerator TMTD are mixed to get intermediate product A；
(3) above-mentioned intermediate product A is placed on vulcanizer with Vulcanization accelerator TMTD a parts, sulphur and carries out sulphur by sulfurizing time
Change, curing temperature is 150 DEG C, vulcanization time 17min, obtains modifying agent graphene oxide/styrene-butadiene rubber composite material.
D: a kind of preparation method of nanocomposite modified pitch is calculated, the nanocomposite changes in parts by mass
Property pitch include 100 parts of matrix pitches and 5 parts of modifying agent, the modifying agent be reduction-state graphene oxide/butadiene-styrene rubber it is compound
Material, it is specific the preparation method is as follows:
According to said ratio, modifying agent reduction-state graphene oxide/styrene-butadiene rubber composite material is added to matrix pitch
In, it is placed on controllable temperature electrothermal furnace, is stirred using high speed shear instrument, whipping temp is 160 DEG C, and stirring rate is
2800r/min, mixing time be 35min to get arrive nanocomposite modified pitch.
In 1-4 of the embodiment of the present invention, involved matrix pitch is 70# matrix pitch, the pitch of other certain models
It can also be with such as the double dragon 70# matrix pitches of South Korea, SK70# matrix pitch, East Sea 70# matrix pitch, the drip of Kelamayi 90# matrix
Blueness, furthermore in embodiment 1-4 before preparing nanocomposite modified pitch, used matrix pitch is required to be placed in
2~3h is kept the temperature in 130~150 DEG C of baking ovens, to guarantee that matrix pitch has sufficient mobility.
Table 1 gives the performance of the nanocomposite modified pitch and comparative example pitch that prepare using method of the invention
Comparison, the results are shown in Table 1.
The performance comparison table of table 1 nanocomposite modified pitch of the invention and comparative example pitch
By nanocomposite modified pitch it can be seen from 1 compared with generic media pitch and SBS modified pitch, needle
In-degree is reduced, and softening point, ductility have increase, and after ultraviolet long-term ageing process, needle penetration, ductility and softening point index
Change amplitude is minimum, and reduced performance is minimum, illustrates the high temperature resistant property, low temperature ductility and anti-aging energy of high performance modified bitumen
Power is better than matrix pitch and SBS modified pitch.
Two, bituminous concrete is prepared
Embodiment 5
A kind of bituminous concrete, the raw material including following mass fraction: 4 parts of nanocomposite modified pitch, collection work stone
95 parts of limestone, 3 parts and 0.3 part of fiber of miberal powder.
Embodiment 6
A kind of bituminous concrete, the raw material including following mass fraction: 5 parts of nanocomposite modified pitch, gather materials it is profound
97 parts of military rock, 5 parts and 0.5 part of fiber of miberal powder.
Embodiment 7
A kind of bituminous concrete, the raw material including following mass fraction: 4.5 parts of nanocomposite modified pitch gathers materials
96 parts of limestone, 4 parts and 0.4 part of fiber of miberal powder.
The bituminous concrete of above-described embodiment 5-7 is all made of following preparation method: by the high-performance modified drip of said components
Blueness is gathered materials, miberal powder and fiber the uniform stirring formation asphalt at 160~170 DEG C.
That gives employed in 5-7 of the embodiment of the present invention gathers materials including partial size >=4.75mm coarse aggregate and partial size≤4.75mm
Fine aggregate.
Comparison is mixed using bituminous concrete prepared by the present invention and matrix pitch concrete (comparative example 1), SBS modified pitch
Solidifying soil (comparative example 2) is paved the way, wherein the upper, middle and lower layer of Fig. 1 is bituminous concrete prepared by the present invention；Fig. 2 it is upper,
In, lower layer be matrix pitch concrete；The upper, middle and lower layer of Fig. 3 is SBS modified asphalt concrete, Pavement Performance comparison
It the results are shown in Table 2.
The comparison of the pavement performance of 2 embodiment of table and comparative example
Nanocomposite modified asphalt concrete and matrix pitch concrete and SBS are modified it can be seen from 1 data of table
Bituminous concrete is compared, and high-temperature stability, Low-temperature antifreeze, which are melted ability, rutting resistance and anti-fatigue performance and had, substantially to be mentioned
Height, durability enhancing, and can be applied to each bitumen layer position.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (10)
1. a kind of nanocomposite modified pitch, which is characterized in that the raw material including following mass fraction: 100 parts of matrix drips
Green and 2~6 parts of modifying agent；The modifying agent is graphene oxide/styrene-butadiene rubber composite material, including 100 parts of graphene oxides/
Butadiene-styrene rubber compound, 15~30 parts of carbon blacks, 2~6 parts of magnesia, 3~6 parts of stearic acid, 2~3 parts of magnesium carbonate, 3~5 parts it is anti-old
Agent, 3~7 parts of promotors and 1~3 part of sulphur；The graphene oxide/butadiene-styrene rubber compound includes 0.1~1 part of graphite oxide
Alkene and 15~20 parts of styrene-butadiene latexes.
2. nanocomposite modified pitch according to claim 1, which is characterized in that the modifying agent uses following
Method preparation:
(1) above-mentioned promotor is divided into two parts of a, b, the mass ratio of a:b is 1:2；
(2) according to said ratio by graphene oxide/butadiene-styrene rubber compound, carbon black, magnesia, stearic acid, magnesium carbonate, anti-old
Agent and b parts of promotor are mixed to get intermediate product A；
(3) above-mentioned intermediate product A is placed on vulcanizer with a parts of promotor, sulphur and is vulcanized by sulfurizing time, vulcanization temperature
Degree is 140~150 DEG C, and vulcanization time is 16~20min, obtains modifying agent graphene oxide/styrene-butadiene rubber composite material.
3. nanocomposite modified pitch according to claim 2, which is characterized in that the anti-aging agent be DNP or
NPC, the promotor are TMTD or CZ.
4. nanocomposite modified pitch according to claim 2, which is characterized in that the graphene oxide/butylbenzene
Rubber composite is prepared using following method:
(a) 0.5~3 part of Cetrimide is added in 90~97 parts of distilled water, obtains suspension after stirring 10-15min；
(b) 0.1~1 part of graphene oxide and 15~20 parts of styrene-butadiene latexes are added in Xiang Shangshu suspension, continue to stir 30-
After 45min, 6~8 parts of flocculants are added, 10-20min are reacted under ice bath and ultrasound, then under 6000-7000r/min revolving speed
5-10min is reacted, then keeping temperature is 50~60 DEG C, and adjusting solution ph is 7.5~8.5, keeps 1~2h；
(c) 80~85 DEG C are continuously heating to, 4-5h is reacted, it is 10 that sodium hydroxide solution to solution ph is added into solution, water
It washes, dry to get graphene oxide/butadiene-styrene rubber compound is arrived.
5. nanocomposite modified pitch according to claim 4, which is characterized in that the cream of butylbenzene described in step (b)
Total solids ingredient is 64~69% in glue, and styrene-content is 83.5~87%, and the flocculant is polymer alumina.
6. nanocomposite modified pitch according to claim 4, which is characterized in that the graphene oxide is using such as
Under preparation method:
1) 0.5~1 part of 70# matrix pitch and 1.5~2.5 parts of calcium carbonate are sufficiently mixed, mixture is added in air atmosphere
Heat, heating rate are 5~15 DEG C/min, and heating temperature is 300~500 DEG C, heating time 4h, natural cooling；
2) 100 parts of hydrochloric acid are added into said mixture, 100 parts of hydrochloric acid are added after crystal precipitation, then with distilled water tune
Save mixture pH value be 6.5-7.5, stand overnight, last evaporation drying to get arrive graphene oxide.
7. nanocomposite modified pitch according to claim 7, which is characterized in that the quality of hydrochloric acid is dense in step 2)
Degree is 37-38%.
8. a kind of preparation method of nanocomposite modified pitch as claimed in claim 1, which is characterized in that system
Standby process is as follows:
According to said ratio, modifying agent graphene oxide/styrene-butadiene rubber composite material is added in matrix pitch, being placed in can
It on control-temperature electric heating furnace, is stirred using high speed shear instrument, whipping temp is 150~165 DEG C, stirring rate 2500r/min
~3000r/min, mixing time be 25~40min to get arrive nanocomposite modified pitch.
9. a kind of bituminous concrete, which is characterized in that the raw material including following mass fraction, nanometer described in claim 1-7
4~5 parts of composite modification pitch, gather materials 95~97 parts, 3~5 parts of miberal powder and 0.3~0.5 part of fiber.
10. bituminous concrete according to claim 9, which is characterized in that described to gather materials for limestone or basalt.
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