CN107868278B - A kind of preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch - Google Patents
A kind of preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch Download PDFInfo
- Publication number
- CN107868278B CN107868278B CN201711176257.2A CN201711176257A CN107868278B CN 107868278 B CN107868278 B CN 107868278B CN 201711176257 A CN201711176257 A CN 201711176257A CN 107868278 B CN107868278 B CN 107868278B
- Authority
- CN
- China
- Prior art keywords
- carbon nanomaterial
- pitch
- modifying agent
- preparation
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the preparation methods of a kind of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch, the following steps are included: 1b) matrix pitch is placed in container, container is toasted again, keeps matrix pitch in a molten state, the moisture being then stirred in evaporation matrix pitch；Carbon nanomaterial modifying agent 2b) is taken, then carbon nanomaterial modifying agent is added in container, then is stirred, until submerging carbon nanomaterial modifying agent all by matrix pitch, obtains mixture；3b) mixture that step 5) obtains is stirred by mechanical agitator, constant temperature shearing is carried out again, obtain carbon nanomaterial modified pitch, the modified pitch that this method is prepared has the characteristics that temperature sensitivity, high-temperature stability, storage stability and anti-aging property are excellent, while the requirement to matrix pitch and mixing plant reduces.
Description
Technical field
The invention belongs to field of asphalt modification, it is related to a kind of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch
Preparation method.
Background technique
Currently, SBS excellent comprehensive performance becomes the modified bitumen product of mainstream.But SBS modified pitch there is also
Certain deficiencies such as require height, aging at temperature high to mixing plant requirement, in process, storage stability to matrix pitch
Difference and accelerated material aging etc. of degrading under action of ultraviolet radiation.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, a kind of carbon nanomaterial modifying agent and carbon are provided
The preparation method of nano-material modified pitch, the modified pitch that this method is prepared have temperature sensitivity, high-temperature stability,
Storage stability and the excellent feature of anti-aging property, while the requirement to matrix pitch and mixing plant reduces.
In order to achieve the above objectives, carbon nanomaterial modifying agent of the present invention preparation method the following steps are included:
DC5700 graft grapheme 1a) is obtained, then DC5700 graft grapheme is added to and fills methanol and deionization
In the three-necked flask of water mixed solution, RGO-DC5700 dispersion liquid is obtained after ultrasonic disperse；
NPES-10 aqueous solution 2a) is taken, then NPES-10 aqueous solution is added to step 1a) obtained RGO-DC5700 dispersion
It in liquid, is then stirred to react under the conditions of water bath with thermostatic control, after the reaction was completed to it, obtains reaction product；
3a) reaction product for obtaining step 2a) carries out dialysis treatment by dialysis membrane, is then dried in vacuo again,
Obtain carbon nanomaterial modifying agent.
The ratio of NPES-10 aqueous solution, DC5700 graft grapheme and methanol and the mixed solution of deionized water is
The concentration of 0.2g:40mL:5ml, NPES-10 aqueous solution is 10.5%wt./voi.
The volume ratio of methanol and deionized water is 1:1 in methanol and the mixed solution of deionized water.
Step 2a) in water bath with thermostatic control temperature be 70 DEG C；
Step 3a) in vacuum drying carried out under 60 DEG C of environment.
Step 3a) in dialysis membrane molecular cut off be 8000-14000.
Further include: graphene is prepared, then DC5700 grafted graphene oxide is synthesized based on graphene, is then based on
DC5700 grafted graphene oxide synthesizes DC5700 graft grapheme.
The preparation method of carbon nanomaterial modified pitch of the present invention the following steps are included:
1b) matrix pitch is placed in container, then container is toasted, keeps matrix pitch in a molten state, so
The moisture being stirred in evaporation matrix pitch afterwards；
Carbon nanomaterial modifying agent 2b) is taken, then carbon nanomaterial modifying agent is added in container, then is stirred, is made
Until carbon nanomaterial modifying agent is all submerged by matrix pitch, mixture is obtained；
The mixture that step 5) obtains is stirred by mechanical agitator 3b), then carries out constant temperature shearing, obtains carbon nanometer
Material modification pitch.
Step 1b) in stirring evaporation matrix pitch in moisture concrete operations are as follows: container is placed in and is equipped with asbestos
On the electric furnace of net, and the moisture in evaporation matrix pitch is stirred, mixing time 10min stirs evaporation process mesostroma pitch
Temperature be 170 DEG C.
Step 3b) in the obtained mixture of step 2b) is stirred by mechanical agitator during mixing speed
For 2000 turns/min, mixing time 20min.
Step 3b) in constant temperature shearing during, shear velocity be 5000~6000 turns/min, shear time 40min.
The invention has the following advantages:
The preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch of the present invention is in concrete operations
When, skin effect, bulk effect and quantum size effect are had the characteristics that based on nano material, with DC5700 graft grapheme
For raw material, carbon nanomaterial modifying agent is prepared by DC5700 graft grapheme, then using carbon nanomaterial modifying agent from point
Matrix pitch is modified in sub- size, to obtain carbon nanomaterial modified pitch, to effectively improve carbon nanomaterial
Temperature sensitivity, high-temperature stability, storage stability and the anti-aging property of modifying agent.It should be noted simultaneously that the present invention
During the preparation process, lower to the requirement of matrix pitch, while general mechanical agitator only being needed to be stirred, and
It is simple, convenient, while having broken the less situation of current modified pitch type, enrich the type of modified pitch.
Detailed description of the invention
Fig. 1 is the schematic diagram that graphene is prepared in the present invention；
Fig. 2 is carbon nanotube surface sweeping electron microscope；
Fig. 3 is different addition quantity carbon nanomaterial modified pitch PI test result figure；
Fig. 4 a is 15 DEG C of penetration test result figures；
Fig. 4 b is 25 DEG C of penetration test result figures；
Fig. 4 c is 30 DEG C of penetration test result figures；
Fig. 5 a is carbon nanomaterial modified pitch softening point test result figure；
Fig. 5 b is carbon nanomaterial modified pitch equivalent softening point test result figure；
Fig. 6 a is carbon nanomaterial modified pitch ductility test result figure under different addition quantity；
Fig. 6 b is carbon nanomaterial modified pitch equivalent brittle point test result figure under different addition quantity；
Fig. 7 is carbon nanomaterial modified pitch aging front and back softening point increment test result figure under different addition quantity；
Fig. 8 is to remain penetration ratio test result figure under different addition quantity before and after the aging of carbon nanomaterial modified pitch；
Fig. 9 is carbon nanomaterial modified pitch aging front and back viscosity ageing index test result figure under different addition quantity；
Figure 10 a is 90 DEG C of viscosity test result figures；
Figure 10 b is 105 DEG C of viscosity test result figures；
Figure 10 c is 90 DEG C of viscosity test result figures；
Figure 10 d is 120 DEG C of viscosity test result figures.
Specific embodiment
The invention will be described in further detail with reference to the accompanying drawing:
With reference to Fig. 1, the preparation method of carbon nanomaterial modifying agent of the present invention the following steps are included:
DC5700 graft grapheme 1a) is obtained, then DC5700 graft grapheme is added to and fills methanol and deionization
In the three-necked flask of water mixed solution, RGO-DC5700 dispersion liquid is obtained after ultrasonic disperse；
NPES-10 aqueous solution 2a) is taken, then NPES-10 aqueous solution is added to step 1a) obtained RGO-DC5700 dispersion
It in liquid, is then stirred to react under the conditions of water bath with thermostatic control, after the reaction was completed to it, obtains reaction product；
3a) reaction product for obtaining step 2a) carries out dialysis treatment by dialysis membrane, is then dried in vacuo again,
Obtain carbon nanomaterial modifying agent.
The ratio of NPES-10 aqueous solution, DC5700 graft grapheme and methanol and the mixed solution of deionized water is
The concentration of 0.2g:40mL:5ml, NPES-10 aqueous solution is 10.5%wt./voi.
The volume ratio of methanol and deionized water is 1:1 in methanol and the mixed solution of deionized water.
Step 2a) in water bath with thermostatic control temperature be 70 DEG C；
Step 3a) in vacuum drying carried out under 60 DEG C of environment.
Step 3a) in dialysis membrane molecular cut off be 8000-14000.
The invention also includes: graphene is prepared, then DC5700 grafted graphene oxide is synthesized based on graphene, then base
DC5700 graft grapheme is synthesized in DC5700 grafted graphene oxide, wherein the preparation process of graphene are as follows:
The natural flake graphite powder of 2.25~2.75g and 0.45~0.55g sodium nitrate 1c) are placed in three in ice-water bath
In mouth flask, it is then that 98% concentrated sulfuric acid is poured slowly into three-necked flask by 50ml, concentration, is stirring evenly, in whipping process
Guarantee that the temperature of liquid in three-necked flask is less than or equal to 1 DEG C, mixing time 1h；
The potassium permanganate of 5~6g is put into three-necked flask in 0.5h while stirring in three times 2c), and keeps three mouthfuls of burnings
The temperature of liquid is less than or equal to 10 DEG C in bottle；
3c) the obtained product of step 2c) is placed in 35 DEG C of water bath with thermostatic control, reaction 2h is stirred for, then places into
100 DEG C of water bath with thermostatic control carries out deep oxidation reaction, and the deionization of 120~130ml is added while stirring after the reaction was completed to it
Water obtains mixed solution；
4c) into the mixed solution that step 3c) is obtained be added 127.5~132.5ml deionized water and 29.5~
The hydrogen peroxide of 30.5ml, then be stirred to react, after the reaction was completed to it, obtain glassy yellow graphite oxide dispersion；
5c) the glassy yellow graphite oxide dispersion for obtaining step 4c) passes through 0.22 μm of PTFE polytetrafluoroethylene (PTFE) micropore filter
Film is filtered by vacuum, then using concentration be 10% hydrochloric acid washed and filtered as solvent, then again use deionized water into
Row washing, then be dried in vacuo under 60 DEG C of environment, obtain graphite oxide；
The graphite oxide of 0.09~0.11g 6c) is weighed, and is pulverized, 39~41ml deionized water is then added to
In, graphene oxide dispersion is obtained after ultrasonic disperse, and the hydrazine hydrate of 85 μ L is then sequentially added into graphene oxide dispersion
And the ammonium hydroxide of 1.42ml, and 95 DEG C at a temperature of reacted, after the reaction was completed to it, obtain graphene dispersing solution；
7c) graphene dispersing solution for obtaining step 6c) is carried out true by 0.22 μm of PTFE polytetrafluoroethylene (PTFE) miillpore filter
Empty pump filter, then washed with deionized water, it is then dried in vacuo in the environment of 60 DEG C, obtains graphene.
DC5700 grafted graphene oxide process is synthesized based on graphene are as follows:
1d) 0.09~0.11g graphene oxide is placed in the three-necked flask for filling 99~101mL deionized water, ultrasound
Graphene oxide dispersion is obtained after dispersion, and then three-necked flask is placed in 95 DEG C of waters bath with thermostatic control；
Two parts of 4mlDC5700 methanol solutions 2d) are taken, while stirring drip first part of 4mlDC5700 methanol solution in three times
Enter in three-necked flask, the DC5700 methanol solution for instilling second part of 4ml again after the reaction was completed to it after the reaction was completed to it obtains
Reaction product, wherein the concentration of DC5700 methanol solution is 40wt.%,
3d) the obtained reaction product of step 2d) is dissolved in the tetra oxygen furyl of 100mL, after centrifugal treating, takes out supernatant
Then liquid carries out dialysis treatment with the dialysis membrane that molecular cut off is 8000-14000, until dialysis film quality quality is no longer reduced
Until；
5d) product in bag filter is dried in vacuo, obtains the graphene oxide of DC5700 grafting.
Detailed process based on DC5700 grafted graphene oxide synthesis DC5700 graft grapheme are as follows:
1e) the DC5700 graphene oxide being grafted is placed in and is contained with the three of 40ml methanol and deionized water mixed solution
In mouth flask, wherein the volume ratio of methanol and deionized water is 1:1, then carries out ultrasonic disperse again, obtains GO-DC5700 dispersion
Liquid；
85 μ L hydrazine hydrates and 1.42ml ammonium hydroxide 2e) are added into the GO-DC5700 dispersion liquid that step 1e) is obtained, then 95
It is reacted in DEG C water bath with thermostatic control, after the reaction was completed to it, obtains dispersion liquid；
3e) dispersion liquid that step 2e) is obtained is filtered by vacuum by 0.22 μm of PTFE polytetrafluoroethylene (PTFE) miillpore filter,
It is cleaned again with deionized water, is then dried in vacuo under conditions of 60 DEG C again, obtains DC5700 graft grapheme.
The preparation method of carbon nanomaterial modified pitch of the present invention the following steps are included:
1b) matrix pitch is placed in container, then container is toasted, keeps matrix pitch in a molten state, so
The moisture being stirred in evaporation matrix pitch afterwards；
Carbon nanomaterial modifying agent 2b) is taken, then carbon nanomaterial modifying agent is added in container, then is stirred, is made
Until carbon nanomaterial modifying agent is all submerged by matrix pitch, mixture is obtained；
The mixture that step 5) obtains is stirred by mechanical agitator 3b), then carries out constant temperature shearing, obtains carbon nanometer
Material modification pitch.
Step 1b) in stirring evaporation matrix pitch in moisture concrete operations are as follows: container is placed in and is equipped with asbestos
On the electric furnace of net, and the moisture in evaporation matrix pitch is stirred, mixing time 10min stirs evaporation process mesostroma pitch
Temperature be 170 DEG C.
Step 3b) in the obtained mixture of step 2b) is stirred by mechanical agitator during mixing speed
For 2000 turns/min, mixing time 20min.
Step 3b) in constant temperature shearing during, shear velocity be 5000~6000 turns/min, shear time 40min.
Comparative test
Using Kelamayi 90# as matrix pitch, wherein Kelamayi 90# is that the performance of matrix pitch is as shown in table 1:
Table 1
Modified pitch is prepared as modifying agent using carbon nanomaterial, graphene and the present invention, then respectively to its performance
It is tested, wherein carbon nanomaterial is the multi-walled carbon nanotube of Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences's production
(MWCNT), main indicator are as follows: outer diameter 815nm, OH content is 3.70wt%, and length is 50 μm, and purity > 95wt% is swept
Electromicroscopic photograph is retouched as shown in Fig. 2, referred to as MWCNT, it is shown that test result is as follows:
1, temperature-sensitive performance
Using penetration index PI as Susceptibility Indexes, change to study carbon nanomaterial under matrix pitch and different addition quantity
Property pitch response to temperature, from the figure 3, it may be seen that after three kinds of carbon nanomaterials are mixed pitch with different mass fraction, needle penetration
Indices P I is correspondingly improved, and illustrates that the addition of carbon nanomaterial reduces matrix pitch to the sensibility of temperature.Meanwhile three
Kind carbon nanomaterial is not quite similar to the influence degree of temperature susceptibility for asphalt, wherein the influence degree of carbon nanotube is most obvious, stone
The influence degree of black alkene is most weak, and influence of the invention is placed in the middle.
2, high-temperature behavior
By Fig. 4 a, Fig. 4 b and Fig. 4 c it is found that with several carbon nanomaterial volumes increase, modified pitch at three temperature
Needle penetration all reducing, the consistency of pitch increases.Wherein, carbon nanotube influences bitumen consistency minimum, and graphene is to pitch
Consistency influences maximum, and the present invention influences to reduce on bitumen consistency, in addition, the present invention shows better compatibility in pitch,
Bitumen consistency is influenced smaller.
As shown in Figure 5, three kinds of carbon nanomaterials and pitch melt blending are prepared into modified pitch, softening point and equivalent softening
Point has corresponding raising, i.e. the addition of modifying agent increases the viscosity of matrix pitch, and high-temperature behavior is all improved.The present invention
The modified pitch effect of preparation is preferable, this is closely related with the two-dimensional layered structure that graphene has, flake graphite alkene and pitch
Polymer segment is mutually wound, and hinders the movement of asphaltene molecule chain, affects the high-temperature behavior of pitch.
3, cryogenic property
Numerous studies data shows that influence of the asphalt binder to Cracks of Bituminous Pavement at Low-temperature is than more sensitive, at present
There are many evaluation and asphalt binder crack resistance at low-temperature index, such as low temperature susceptibility ratio, brittle point, equivalent brittle point and low-temperature ductility
Equivalent brittle point T is used Deng, the present invention1.2And 10 DEG C of ductilities evaluate the cryogenic property of pitch.
By Fig. 6 a and Fig. 6 b it is found that after graphene-doped and carbon nanotube, the low-temperature ductility value of pitch declines, and low temperature is anti-
Impaired performance is split, this is because graphene and carbon nanotube are reunited in pitch, so that defect increases in pitch, outer masterpiece
Pitch is broken more early with lower stress concentration.Meanwhile after the present invention mixes pitch, fail the cryogenic property for improving pitch,
Illustrate that the flexible layer of graphene surface cladding hinders the interaction between graphene sheet layer, influences the performance of graphene performance.
4, carbon nanomaterial modified pitch aging research
In order to preferably reflect the decay degree of performance after ageing of asphalt, the ageing properties of pitch are evaluated, before aging
The amplitude of variation of each performance analyzes the ageing properties of asphalt sample afterwards, i.e., softening point increment, residual penetration ratio and
Viscosity ageing index VAI.
(1) softening point increment
The variation of asphalt softening point has also reacted asphalt sample to the sensitivity of aging, with the softening point after aging and always
The difference of softening point before change indicates that test results are shown in figure 7.
(2) penetration ratio is remained
Pitch volatilizees in ageing process mainly due to light components, and low molecule is converted to macromolecule, to show as dripping
Green viscosity increases, and needle penetration reduces, therefore the variation of penetration index can react the old of asphalt binder to a certain degree before and after aging
Change degree, test result are as shown in Figure 8.
(3) viscosity ageing index
The viscosity of modified pitch all increased after hot air aging, this is because during thermo-oxidative ageing, free oxygen
It is aoxidized into modified pitch, pitch relative molecular mass is caused to become larger, and the environment heated accelerates in pitch light group
The volatilization divided allows it to vibrate or move so that molecular motion is obstructed without enough spaces, and macro manifestations are exactly poor fluidity,
So the viscosity of pitch has a degree of increase after aging.
Viscosity is the window for reacting asphaltic nature, and the variation of viscosity can react the process of ageing of asphalt before and after ageing of asphalt,
It is used to characterize the degree of ageing of asphalt using viscosity ageing index (VAI), test result is as shown in table 1.
As seen from Figure 7, after TFOT aging, with the increase of three kinds of carbon nanomaterial dosages, the softening point of pitch increases
Magnitude is all reducing, and the softening point increment of matrix pitch is 7.2 DEG C, and carbon nanotube, graphene and this hair when volume is 0.5%
Bright corresponding softening point increment is respectively 5.4,4.9 and 5.4, i.e. the later modified pitch degree of aging of admixture carbon nanomaterial
Both less than matrix pitch.As seen from Figure 8, after aging, with the increase of three kinds of carbon nanomaterial dosages, the residual needle of pitch
In-degree is increasing than all, and the residual penetration ratio of matrix pitch is 0.658, and carbon nanotube when volume is 0.5%, graphene and
The corresponding residual penetration ratio of the present invention is respectively 0.689,0.772 and 0.759, i.e. the later modification of admixture carbon nanomaterial
Ageing of asphalt degree is both less than matrix pitch.As seen from Figure 9, after TFOT aging, with three kinds of carbon nanomaterial dosages
Increase, the viscosity ageing index of pitch all reducing, and the softening point increment of matrix pitch is 0.83, and carbon when volume is 0.5%
Corresponding softening point increment is respectively 0.63,0.58 and 0.61 when nanotube, graphene and the present invention, i.e. admixture carbon nanometer material
Expect that later modified pitch degree of aging is both less than matrix pitch.
In summary analysis is it can be found that three kinds of modified materials have different degrees of improvement to pitch ageing-resistant performance,
Modified pitch resistance to ag(e)ing prepared by graphene and the present invention is better than what carbon nano-tube modification pitch showed.
5, carbon nanomaterial modified pitch viscosity is studied
This test is using carbon nanotube, graphene and the present invention under Bu Shi viscosity apparatus measurement different addition quantity to pitch viscosity
It influences, test temperature is respectively 90 DEG C, 105 DEG C, 120 DEG C and 135 DEG C.Figure 10 a, Figure 10 b, Figure 10 c and Figure 10 d are provided respectively
Effect tendency figure of the different carbon nanomaterials to pitch viscosity at four temperature.
With reference to Figure 10 a, Figure 10 b, Figure 10 c and Figure 10 d it can be found that influence of several carbon nanomaterials to pitch viscosity not
It is identical to the greatest extent, using 0.3% volume as cut-point, the carbon nanomaterial modified pitch viscosity size at a temperature of first four of this volume
It is arranged as graphene > carbon nanotube > present invention, the macromolecular under high speed shear and churned mechanically external force, in pitch
Chain enters the piece interlayer of graphene, increases the distance of piece interlayer, intercal type and exfoliated composite construction is formd, in high temperature
Under, Sheet Graphite alkene hinders the molecular chain movement in pitch, molecule constricted flow, to can more promote the k value of pitch.?
Carbon nanomaterial modified pitch large viscosity float is classified as carbon nanotube > graphene > present invention at four temperature after this volume,
Reason is: compared under large dosage, after carbon nanotube is blended with pitch, and the carbon nanometer of macromolecular chain and tubular structure in pitch
Pipe is cross-linked with each other, so that frictional resistance becomes larger pitch between its interior molecules when flowing, shows as carbon nanotube and more can
Improve the viscosity of pitch.
Claims (9)
1. a kind of preparation method of carbon nanomaterial modifying agent, which comprises the following steps:
DC5700 graft grapheme 1a) is obtained, then DC5700 graft grapheme is added to and fills methanol and deionized water mixing
In the three-necked flask of solution, RGO-DC5700 dispersion liquid is obtained after ultrasonic disperse；
NPES-10 aqueous solution 2a) is taken, then NPES-10 aqueous solution is added to step 1a) obtained RGO-DC5700 dispersion liquid
In, it is then stirred to react under the conditions of water bath with thermostatic control, after the reaction was completed to it, obtains reaction product；
3a) reaction product for obtaining step 2a) carries out dialysis treatment by dialysis membrane, is then dried in vacuo again, obtains carbon
Nano-material modified dose.
2. the preparation method of carbon nanomaterial modifying agent according to claim 1, which is characterized in that methanol and deionized water
Mixed solution in the volume ratio of methanol and deionized water be 1:1.
3. the preparation method of carbon nanomaterial modifying agent according to claim 1, which is characterized in that step 2a) in constant temperature
The temperature of water-bath is 70 DEG C；
Step 3a) in vacuum drying carried out under 60 DEG C of environment.
4. the preparation method of carbon nanomaterial modifying agent according to claim 1, which is characterized in that step 3a) in dialysis
The molecular cut off of film is 8000-14000.
5. the preparation method of carbon nanomaterial modifying agent according to claim 1, which is characterized in that further include: prepare stone
Black alkene, then DC5700 grafted graphene oxide is synthesized based on graphene, it is then based on the synthesis of DC5700 grafted graphene oxide
DC5700 graft grapheme.
6. a kind of preparation method of carbon nanomaterial modified pitch, which comprises the following steps:
1b) matrix pitch is placed in container, then container is toasted, keeps matrix pitch in a molten state, then again
Moisture in stirring evaporation matrix pitch；
The carbon nanomaterial modifying agent for 2b) taking claim 1 to be prepared, then carbon nanomaterial modifying agent is added to container
In, then be stirred, until submerging carbon nanomaterial modifying agent all by matrix pitch, obtain mixture；
The mixture that step 2b) is obtained is stirred by mechanical agitator 3b), then carries out constant temperature shearing, obtains carbon nanometer material
Expect modified pitch.
7. the preparation method of carbon nanomaterial modified pitch according to claim 6, which is characterized in that step 1b) in stir
Mix the concrete operations of the moisture in evaporation matrix pitch are as follows: container is placed on the electric furnace for being equipped with asbestos gauge, and stirs steaming
The moisture in matrix pitch, mixing time 10min are sent out, the temperature of stirring evaporation process mesostroma pitch is 170 DEG C.
8. the preparation method of carbon nanomaterial modified pitch according to claim 6, which is characterized in that step 3b) in will
Step 2b) mixing speed is 2000 turns/min during obtained mixture is stirred by mechanical agitator, when stirring
Between be 20min.
9. the preparation method of carbon nanomaterial modified pitch according to claim 6, which is characterized in that step 3b) in it is permanent
During temperature shearing, shear velocity is 5000~6000 turns/min, shear time 40min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711176257.2A CN107868278B (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711176257.2A CN107868278B (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107868278A CN107868278A (en) | 2018-04-03 |
| CN107868278B true CN107868278B (en) | 2019-08-27 |
Family
ID=61754545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711176257.2A Active CN107868278B (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107868278B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587196A (en) * | 2018-04-20 | 2018-09-28 | 石梦成 | A kind of building asphalt and preparation method thereof that graphene is modified |
| CN108752850B (en) * | 2018-05-08 | 2021-03-16 | 上海浦兴路桥建设工程有限公司 | Graphene oxide modified colored asphalt cement and preparation method thereof |
| CN109554072A (en) * | 2018-11-22 | 2019-04-02 | 武汉纺织大学 | A kind of water-based anticorrosive paint preparation method |
| CN110951266B (en) * | 2019-10-23 | 2021-12-17 | 长安大学 | High-performance modified asphalt and preparation method thereof |
| CN111983321A (en) * | 2020-08-19 | 2020-11-24 | 南京林业大学 | Preparation and electric heating performance evaluation method of nano graphene oxide modified asphalt mixture |
| CN112179936A (en) * | 2020-10-12 | 2021-01-05 | 南京林业大学 | Method for preparing nano graphene oxide modified asphalt and evaluating anti-aging performance |
| CN113817222A (en) * | 2021-09-15 | 2021-12-21 | 南京林业大学 | Method for improving dispersion degree of graphene powder and preparation of modified asphalt |
| CN115322410B (en) * | 2022-08-16 | 2023-07-14 | 哈尔滨工业大学 | Preparation method of uniformly-dispersed and oriented graphene reinforced asphalt composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391299A (en) * | 2011-08-06 | 2012-03-28 | 江苏迅扬环保新材料有限公司 | Preparation method for organosilicon quaternary ammonium salt composite and application thereof |
| CN105372274A (en) * | 2015-10-30 | 2016-03-02 | 长安大学 | Method for evaluating dispersed state of nano ZnO in pitch |
-
2017
- 2017-11-22 CN CN201711176257.2A patent/CN107868278B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391299A (en) * | 2011-08-06 | 2012-03-28 | 江苏迅扬环保新材料有限公司 | Preparation method for organosilicon quaternary ammonium salt composite and application thereof |
| CN105372274A (en) * | 2015-10-30 | 2016-03-02 | 长安大学 | Method for evaluating dispersed state of nano ZnO in pitch |
Non-Patent Citations (2)
| Title |
|---|
| 欧美石墨烯增强型复合材料项目近况眼镜;苏东艳 等;《江苏科技信息》;20161231(第34期);第55-59页 * |
| 添加氧化石墨烯对煤沥青成焦行为的影响;蔡秋红 等;《煤炭学报》;20130731;第38卷(第7期);第1260-1264页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107868278A (en) | 2018-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107868278B (en) | A kind of preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch | |
| Jin et al. | Rheological and adhesion properties of nano-organic palygorskite and linear SBS on the composite modified asphalt | |
| Gonzalez-Torre et al. | Recent advances on self-healing of bituminous materials by the action of encapsulated rejuvenators | |
| Arabani et al. | Characterization of CNTs-modified HMA’s mechanical properties | |
| Ali et al. | Performance evaluation of Al2O3 nanoparticle-modified asphalt binder | |
| Hasan et al. | Evaluation of different conditions on the mixing bitumen and carbon nano-tubes | |
| CN107805019B (en) | A kind of carbon nanotube enhancing superfine cement composite grout and preparation method thereof | |
| CN108084719B (en) | Nano-cellulose modified emulsified asphalt material and preparation method thereof | |
| Luo et al. | Comprehensive performances of carbon nanotube reinforced foam concrete with tetraethyl orthosilicate impregnation | |
| Yao et al. | Evaluation of asphalt blended with low percentage of carbon micro-fiber and nanoclay | |
| CN106832980A (en) | A kind of epoxy modified asphalt and preparation method thereof | |
| Shah et al. | Performance of OMMT/SBS on the rheological properties of asphalt binder | |
| CN106479203B (en) | A kind of carbon nanotube reinforced epoxy pitch composite material and preparation method | |
| CN106832977A (en) | A kind of composite asphalt modifier containing modified graphene microplate and its preparation method and application | |
| Zhang et al. | Effect of different inorganic nanoparticles on physical and ultraviolet aging properties of bitumen | |
| Kou et al. | Rheological behaviors of asphalt binders reinforced by various fibers | |
| Yu et al. | Effect of various organomodified montmorillonites on the properties of montmorillonite/bitumen nanocomposites | |
| CN109627689A (en) | A kind of preparation method of graphene-epoxy resin composite material | |
| Li et al. | Efficiently stabilized spherical vaterite CaCO3 crystals by carbon nanotubes in biomimetic mineralization | |
| Jing et al. | The non-uniform spatial dispersion of graphene oxide: A step forward to understand the inconsistent properties of cement composites | |
| Zhang et al. | Modification of asphalt by dispersing waste polyethylene and carbon fibers in it | |
| CN106083177A (en) | Foam warm mix SMA 13 asphalt, preparation method and method of evaluating performance | |
| Zhang et al. | Preparation and performance of graphene nanoplatelets-modified epoxy asphalt | |
| CN108752850A (en) | A kind of graphene oxide Modified coloured asphalt cementitious matter and preparation method thereof | |
| Kang et al. | Multiwalled carbon nanotube pretreatment to enhance tensile properties, process stability, and filler dispersion of polyamide 66 nanocomposites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |