CN107118575B - The application of azotized carbon nano piece raising pitch anti-aging property - Google Patents
The application of azotized carbon nano piece raising pitch anti-aging property Download PDFInfo
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- CN107118575B CN107118575B CN201710245086.8A CN201710245086A CN107118575B CN 107118575 B CN107118575 B CN 107118575B CN 201710245086 A CN201710245086 A CN 201710245086A CN 107118575 B CN107118575 B CN 107118575B
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention provides a kind of azotized carbon nano piece and is improving the application in pitch anti-aging property, the preparation method of the azotized carbon nano piece includes: by melamine, urea or dimerization cdicynanmide carry out 550 DEG C~600 DEG C, the reaction of 4h~5h high temperature thermopolymerization, obtain layered nitride toner body, it is added in stabilizer after ground 200~500 mesh, carries out 2h~4h, centrifugation after 6000r/min~8000r/min high speed shear, dry azotized carbon nano piece.It is stirred the matrix pitch of azotized carbon nano piece and melting to obtain modified pitch.Compared with prior art, azotized carbon nano piece of the present invention is two-dimension nano materials, and slabbing and pitch are melted, pitch composite material is made using azotized carbon nano sheet material as reinforced phase, pitch composite material exhibits can be made to go out good anti-aging property.
Description
Technical field
The invention belongs to pavement material fields, are related to modified asphalt material, and in particular to the modification of nitrogen carbon nanosheet
Pitch.
Background technique
Being modified using inorganic nano material to pitch becomes one of the effective measures for improving asphalt material performance.It is existing
In technology, the inorganic nano material of researcher's selection mainly has titanium oxide, zinc oxide and calcium carbonate etc..These nano material grains
Diameter is small, mostly spherical in shape, is easy to reunite, is difficult to effectively disperse in pitch, so that the advantage of nano material can not be played.Example
Such as, Wuhan University of Technology Yu Jianying, Wu Shaopeng, once rotation etc. carry out fusion intercalation to pitch using organic layered silicate salt as modifying agent
It is modified, the results showed that the addition of phyllosilicate improves high temperature complex modulus and Rutting parameter, illustrates that pitch can be improved
High-temperature behavior and rutting resistance, but phyllosilicate is 2 be made of two layers of oxygen-octahedrons one layer of magnalium oxygen octahedra of folder:
Silicate mineral of 1 type containing the crystallization water, it is poor with bitumen compatibility due to the characteristic of inorganic material, so in phyllosilicate
Need to carry out organic-treating to it could to use in modified pitch, it is troublesome in poeration.Therefore well dispersed nano material is found
Inorganic nanometer modified pitch is had a very important significance applied in asphalt material.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of modification of nitrogen carbon nanosheet
Pitch significantly improves the anti-aging property of pitch.
In order to solve the above-mentioned technical problem, the present invention is realised by adopting the following technical scheme:
Application of the azotized carbon nano piece in raising pitch anti-aging property, the azotized carbon nano piece lamellar spacing are
1.5~3.5nm.The azotized carbon nano piece is obtained by high speed shear layered nitride toner body；The nitridation toner body is stone
Black phase carbon nitride, 25~75 μm of partial size.
The preparation method of the azotized carbon nano piece include: by melamine, urea or dimerization cdicynanmide carry out 550 DEG C~
600 DEG C, the reaction of 4h~5h high temperature thermopolymerization obtains layered nitride toner body, is added to stabilizer after ground 200~500 sieve
In, carry out 2h~4h, centrifugation after 6000r/min~8000r/min high speed shear, dry azotized carbon nano piece.
The stabilizer includes isopropanol, methanol, ethyl alcohol or dimethyl sulfoxide.
The present invention also provides a kind of modified pitch, including matrix pitch and azotized carbon nano piece.
The mass percent of the azotized carbon nano piece and matrix pitch is 5~20:80~95, azotized carbon nano piece and base
The sum of mass percent of matter pitch is 100%.
The preparation method of the modified pitch includes: by azotized carbon nano piece at 120 DEG C~140 DEG C of temperature, 3000r/min
Under~5000r/min revolving speed, it is stirred 60~120min with the matrix pitch of melting, obtains modified pitch.
Compared with prior art, the present invention having the following technical effect that
(1) compared with prior art, azotized carbon nano piece of the present invention is two-dimension nano materials, slabbing and drip
Blueness melting, pitch composite material is made using azotized carbon nano sheet material as reinforced phase, pitch composite material exhibits can be made good out
Good anti-aging characteristic, significantly improves the performance of pitch composite material.
(2) present invention uses azotized carbon nano piece, has C-N key composition, has compatibility well with the organic matter in pitch,
Compared with other inorganic laminated silicate materials, azotized carbon nano piece can be uniformly dispersed in pitch, to be more advantageous to nitrogen
Change the raising of carbon nanosheet performance of modified bitumen.
(3) azotized carbon nano piece of the present invention can be made by melamine heat polymerization, low in cost, with higher
Cost performance, while preparation process is simple, is not required to by other dispersing apparatus, therefore azotized carbon nano piece modified pitch can be used as one
The novel asphalt pavement material of kind.
Detailed description of the invention
Fig. 1 is azotized carbon nano piece scanning electron micrographs.
Fig. 2 is the transmission electron micrograph of azotized carbon nano piece.
Fig. 3 is complex modulus and temperature relation figure before and after asphalt sample aging.
Fig. 4 is phase angle and temperature relation figure before and after asphalt sample aging.
Explanation is further explained in detail to particular content of the invention with reference to embodiments.
Specific embodiment
The study found that nano particle diameter is small, large specific surface area is dripping inventor so that their own is easy to reunite
Be difficult to be uniformly dispersed in blueness, this is the biggest obstacle that current inorganic nano-material modified asphalt encounters, graphite phase carbon nitride be by
Two kinds of elements of carbon and nitrogen composition organic polymer, it have and graphite-phase as interlayer structure, interlayer spacing be 0.326nm.
With excellent physical and chemical performance, high thermal stability simultaneously can absorb ultraviolet-visible.In fields such as electricity, optics, catalysis
With widely applying.Lamellar graphite phase carbon nitride can by removing form nanometer chip architecture, the C-N key in lamellar structure with
Other polymer have compatibility well.
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited to following embodiment, it is all
The equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
The trade mark of matrix pitch of the present invention is No. 70 bi tumenf orr oads.
Embodiment 1: the present embodiment provides a kind of modified pitch, preparation method include: by melamine, 550 DEG C of urea into
Row high temperature thermopolymerization reacts 4h, obtains layered nitride toner body, is added in stabilizer alcohol after ground 200 sieve, progress 2h,
It is centrifuged after 6000r/min high speed shear, is dry that azotized carbon nano piece is as depicted in figs. 1 and 2, it will be seen from figure 1 that carbonitride
Typical laminated structure is presented；Azotized carbon nano piece is transparent in Fig. 2, and lamellar spacing is in 2nm or so.By 25 grams of azotized carbon nano pieces
It is added in No. 70 heavy-duty road asphalts of 475 grams of meltings, keeping temperature is 140 DEG C, the high speed under the shear rate of 3000r/min
60min is stirred, it is uniformly mixed, modified pitch can be obtained.
According to " highway engineering pitch and Asphalt Mixture Experiment regulation " T0610-2011 asphalt rotating thin-film heat run
Standard prepares test specimen, using dynamic shear rheometer (DSR), measure pitch complex modulus and phase angle with temperature change
Change situation, test result is as shown in Figure 3 and Figure 4, short ageing test, penetration test, ductility test and the softening point of pitch
Experimental test result is as shown in table 1.
Embodiment 2:
The present embodiment provides a kind of modified pitch, and the preparation method is the same as that of Example 1, the difference lies in that 50 grams of carbonitrides are received
Rice piece is added in No. 70 heavy-duty road asphalts of 450 grams of meltings, and keeping temperature is 120 DEG C, under the shear rate of 5000r/min
High-speed stirred 70min is uniformly mixed it, modified pitch can be obtained.
The present embodiment test method is same as Example 1, and test result is as shown in Fig. 3, Fig. 4 and table 1.
Embodiment 3:
The present embodiment provides a kind of modified pitch, and the preparation method is the same as that of Example 1, the difference lies in that 75 grams of carbonitrides are received
Rice piece is added in No. 70 heavy-duty road asphalts of 425 grams of meltings, and keeping temperature is 140 DEG C, under the shear rate of 3000r/min
High-speed stirred 80min is uniformly mixed it, modified pitch can be obtained.
The present embodiment test method is same as Example 1, and test result is as shown in Fig. 3, Fig. 4 and table 1.
Embodiment 4:
The present embodiment provides a kind of modified pitch, and the preparation method is the same as that of Example 1, the difference lies in that 100 grams of carbonitrides are received
Rice piece is added in No. 70 heavy-duty road asphalts of 400 grams of meltings, and keeping temperature is 130 DEG C, under the shear rate of 4000r/min
High-speed stirred 120min is uniformly mixed it, modified bitumen product can be obtained.
The present embodiment test method is same as Example 1, and test result is as shown in Fig. 3, Fig. 4 and table 1.
Comparative example 1:
This comparative example provides a kind of pitch, for No. 70 matrix pitches of no addition azotized carbon nano piece.This comparative example is surveyed
Method for testing is same as Example 1, and test result is as shown in Fig. 3, Fig. 4 and table 1.
Comparative example 2:
This comparative example provides a kind of pitch, and No. 70 matrix pitches for no addition azotized carbon nano piece are rotated by pitch
No. 70 aging matrix pitches that film is tested.
This comparative example test method is same as Example 1, and test result is as shown in Figure 3 and Figure 4.
Effect analysis:
The variation that the complex modulus of pitch and phase angle at different temperatures can be characterized using dynamic shear rheometer, when
When aging occurs for pitch, the complex modulus of pitch can become larger, and phase angle can reduce.Fig. 3 and Fig. 4 show: No. 70 matrix pitches
After aging occurs, complex modulus numerical value increases, and phase angle becomes smaller, and apparent aging character occurs；And add the nitrogen of different proportion
The complex modulus increasing degree for changing carbon modified pitch becomes smaller, and the amplitude that phase angle reduces also obviously becomes smaller, and degree of aging subtracts significantly
It is slow.The result shows that the pitch for being added to azotized carbon nano piece in ageing process, prevents infiltration of the oxygen in pitch, so that pitch
Component keeps relatively stable, to also greatly slow down the speed of ageing of asphalt.
The obtained azotized carbon nano piece modified pitch of embodiment 1-4 and 1 matrix pitch of comparative example are used into Rotational Thin
Film baking oven (RTFO) carries out short ageing test, and experiment is according in " highway engineering pitch and Asphalt Mixture Experiment regulation " the
T0610-2011 item regulation carries out, and asphalt penetration test is according to " highway engineering pitch and Asphalt Mixture Experiment regulation " the
T0604-2011 item regulation carries out, and bitumen ductility test is according to " highway engineering pitch and Asphalt Mixture Experiment regulation " the
T0605-2011 item regulation carries out, and bituminous softening-point test is according to " highway engineering pitch and Asphalt Mixture Experiment regulation " the
T0606-2011 item regulation carries out.Test result is as shown in table 1.
Performance comparison before and after the azotized carbon nano piece modified pitch prepared by the present invention of table 1 and matrix pitch aging
By table 1 it can be found that matrix pitch and azotized carbon nano piece modified pitch are after short ageing is tested, needle
In-degree becomes smaller, and softening point becomes larger, and ductility reduces.Compared with matrix pitch aging, the residual needle of azotized carbon nano piece modified pitch
In-degree is enhanced；Softening point change rate is being gradually reduced；Residual ductility becomes larger.It is bigger to remain needle penetration, softening point
Change rate is smaller, and residual ductility is bigger, and the anti-aging property of pitch is better.The experimental results showed that azotized carbon nano piece is added to drip
In blueness, the anti-aging property of matrix pitch is substantially improved.
Claims (10)
1. the application of azotized carbon nano piece raising pitch anti-aging property.
2. application as described in claim 1, which is characterized in that the preparation method of the azotized carbon nano piece includes: by melamine
Amine and urea carry out high temperature thermopolymerization reaction, obtain layered nitride toner body, are added in stabilizer after being ground up, sieved, and carry out high
Centrifugation, dry azotized carbon nano piece after speed shearing.
3. application as claimed in claim 2, which is characterized in that the high speed shear time is 2h~4h, rate 6000r/min
~8000r/min.
4. application as claimed in claim 2, which is characterized in that the reaction temperature of the high temperature thermopolymerization reaction is 550 DEG C~600
DEG C, the reaction time is 4h~5h.
5. application as claimed in claim 2, which is characterized in that 200~500 mesh sieve of the sieving.
6. application as claimed in claim 2, which is characterized in that the stabilizer includes that isopropanol, methanol, ethyl alcohol or dimethyl are sub-
Sulfone.
7. application as claimed in claim 2, which is characterized in that the nitridation toner body is graphite phase carbon nitride, and partial size is 25 μm
~75 μm.
8. a kind of modified pitch, which is characterized in that it includes matrix pitch and azotized carbon nano piece that the modified pitch, which prepares raw material,.
9. modified pitch as claimed in claim 8, which is characterized in that the quality percentage of the azotized carbon nano piece and matrix pitch
Than for 5~20:80~95, the sum of mass percent of azotized carbon nano piece and matrix pitch is 100%.
10. modified pitch as claimed in claim 8, which is characterized in that the preparation method of the modified pitch includes: by carbonitride
Nanometer sheet is stirred under 120 DEG C~140 DEG C of temperature, 3000r/min~5000r/min revolving speed with the matrix pitch of melting
60min~120min obtains modified pitch.
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| CN201710245086.8A CN107118575B (en) | 2017-04-14 | 2017-04-14 | The application of azotized carbon nano piece raising pitch anti-aging property |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752944B (en) * | 2018-05-22 | 2021-01-22 | 山东交通学院 | Graphite-phase carbon nitride modified emulsified asphalt and photocatalytic application thereof |
| CN111218082A (en) * | 2020-02-28 | 2020-06-02 | 江苏凯信环保材料有限公司 | Carbon-based composite anti-aging modifier suitable for asphalt and preparation method thereof |
| CN112047311A (en) * | 2020-09-09 | 2020-12-08 | 天津工业大学 | Stripping method of graphite phase carbon nitride |
| CN115394888B (en) * | 2022-06-13 | 2024-02-09 | 武汉中科先进材料科技有限公司 | Blue-violet light carbon nitride nanosheet, preparation method thereof and blue-violet light LED device |
Citations (3)
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|---|---|---|---|---|
| CN104401948A (en) * | 2014-11-17 | 2015-03-11 | 长安大学 | Preparation method for single-layer graphite-type carbon nitride nanosheet solution |
| CN106496701A (en) * | 2016-12-20 | 2017-03-15 | 佛山市高明区塑料行业协会 | A kind of modified abrasion resistant high impact-resistant butadiene-styrene rubber |
| CN106542509A (en) * | 2016-10-19 | 2017-03-29 | 张家港市东大工业技术研究院 | A kind of efficient method for preparing class Graphene carbonitride |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401948A (en) * | 2014-11-17 | 2015-03-11 | 长安大学 | Preparation method for single-layer graphite-type carbon nitride nanosheet solution |
| CN106542509A (en) * | 2016-10-19 | 2017-03-29 | 张家港市东大工业技术研究院 | A kind of efficient method for preparing class Graphene carbonitride |
| CN106496701A (en) * | 2016-12-20 | 2017-03-15 | 佛山市高明区塑料行业协会 | A kind of modified abrasion resistant high impact-resistant butadiene-styrene rubber |
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