CN104961891B - Degradation method of carbon nanotube/triazine composite - Google Patents
Degradation method of carbon nanotube/triazine composite Download PDFInfo
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Abstract
The invention relates to a degradation method of a carbon nanotube/triazine composite. The invention aims to solve the problems of complex technique and high cost in the existing method, and the problem of environmental pollution due to low degradability of the prepared carbon nanotube/triazine composite. The method comprises the following steps: preparation of acyl-chlorinated carbon nanotubes, and synthesis of carbon nanotube/PHT composite. The method has the advantages of low cost and simple degradation process, is simple to operate, can recover and reutilize the raw materials, and is a favorable environment-friendly method. The method is applicable to the field of chemical industry.
Description
Technical field
The present invention relates to a kind of biodegrading process of CNT/triazine complex.
Background technology
Nitrogenous thermosetting polymer, such as polyamide, polyimides, polybenzimidazoles etc., it is hot well due to it
Energy, mechanical performance, electrical property, resist chemical performance etc. may be advantageously employed in and prepare foam, adhesive, automobile, aviation, electricity
Sub- equipment etc..It is well known that, thermosetting polymer is different from thermoplastic polymer, the performance with " insoluble not melt ".Institute
It is difficult to process with the product being difficult after transformation, use once preparation molding.According to statistics, to account for solid refuse total for annual plastic garbage
The 20-30% of amount, its degraded will be for a long time.At present biodegrading process has light degradation, thermal degradation, microorganism etc., work of typically degrading
Skill requirement is higher, and the time is longer, relatively costly.So want prepare one kind both met using when there is good hot property, resist
Corrosive nature, strong mechanical performance etc., while the material that can be very good to obtain processing after application is that current people compel to be essential again
Want.
The content of the invention
The invention aims to CNT/the triazine for solving the preparation simultaneously of existing method complex process, high cost is multiple
Compound
It is not degradable, cause the problem of environmental pollution, there is provided a kind of biodegrading process of CNT/triazine complex.
A kind of preparation method of CNT/triazine complex of the present invention includes step in detail below：
First, the preparation of acyl chlorides carbon nano tube：A, surface oxidation：CNT is placed in mixed acid, at 50～80 DEG C
6～9h of lower stirring reaction, obtains the acidifying CNT that surface connects carboxyl, wherein the quality volume of CNT and mixed acid
Than being 1g：(40～80) mL, mixed acid be by concentrated nitric acid that mass concentration is 98% and concentration for 18.4mol/L concentrated sulphuric acid by
Volume ratio 1:3 ratio is mixed；B, chloride：The acidifying CNT that surface connects carboxyl is placed in into SOCl2In, then add
Enter N, then N '-dimethyl Methanamide heats 20～28h of magnetic agitation under conditions of nitrogen protection, temperature are for 75～80 DEG C,
Obtain acyl chlorides carbon nano tube, wherein the acidifying CNT and SOCl of surface connection carboxyl2Proportionate relationship be 1g:(60～
120) mL, SOCl2And N, the volume ratio (0.0025～0.0125) of N '-dimethyl Methanamide：1；
2nd, the synthesis of CNT/triazine complex：By p-phenylenediamine, paraformaldehyde, acyl chlorides carbon nano tube and formylmerphalan
Base ketopyrrolidine is put in three-necked bottle, nitrogen environment, 20～100min of ultrasound, heats 180～200 DEG C of 2～4h of magnetic agitation, instead
Temperature is down to room temperature after should terminating, and is then settled with acetone, and sucking filtration vacuum drying obtains CNT/triazines complex；Its
In, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:The molal volume ratio of (1～5), p-phenylenediamine and N-methyl ketopyrrolidine
1mmol:(2-5) mL, acyl chlorides carbon nano tube is the 0.5%～10% of p-phenylenediamine and paraformaldehyde gross mass.
A kind of biodegrading process of CNT/triazine complex of the present invention is that CNT/triazine complex is put into into pH
In=0 aqueous sulfuric acid, solid formation is filtered to remove after 0.5～1.5h, solid is added in filtrate under the conditions of ice-water bath
NaHCO3To pH=7, solid formation is filtered to take, vacuum drying obtains p-phenylenediamine, that is, complete degraded；Wherein CNT/triazine
Complex is (2～3) mg with the mass volume ratio of aqueous sulfuric acid:1mL.
Advantage of the present invention：First, low cost, biodegrading process is simple, easily operation, it is only necessary to which preparing a certain amount of acid just can be with
Implement, it is not necessary to complex instrument；2nd, CNT is acidified, is then carried out chloride, it is therefore an objective to which chloride activity is high,
Easily react, then by being doped with CNT, the complex that hardness, modulus are improved can be obtained；3rd, energy-saving ring
Protect, thermoset composite can be recycled recycling.The biodegrading process of the present invention is simple and convenient, low cost, and can return
Receive raw material to reuse again, be a kind of good environment protection method.
Description of the drawings
Fig. 1 is the synthetic route chart of embodiment one；
Fig. 2 is the electron-microscope scanning figure of the CNT/triazine complex of the synthesis of embodiment one；
The acidifying CNT of the surface connection carboxyl that Fig. 3 is prepared for embodiment one, 0.5% CNT/triazine are combined
The infrared spectrogram of thing and the PHT of embodiment five；Wherein a is the acidifying CNT that surface connects carboxyl, and b is 0.5% carbon nanometer
Pipe/triazine complex, c are PHT；
The acidifying CNT of the surface connection carboxyl that Fig. 4 is prepared for embodiment one, 0.5% CNT/triazine are combined
Thing and the polymer x-ray photoelectron energy spectrum diagram of embodiment five；Wherein a is the acidifying CNT that surface connects carboxyl, and b is
0.5% CNT/triazine complex, c are PHT；
Fig. 5 is the thermal gravimetric analysis curve of embodiment PHT and complex, and wherein a is PHT, and b is 0.5% CNT/triazine
Complex, c is 1% CNT/triazine complex, and d is 2% CNT/triazine complex, and e is 5% CNT/tri-
Piperazine complex；
Fig. 6 is the hardness curve of embodiment PHT and complex, and wherein a is PHT, and b is compound for 0.5% CNT/triazine
Thing, c is 1% CNT/triazine complex, and d is 2% CNT/triazine complex, and e is that 5% CNT/triazine is multiple
Compound；
Fig. 7 is the modulus curve of embodiment PHT and complex, and wherein a is PHT, and b is compound for 0.5% CNT/triazine
Thing, c is 1% CNT/triazine complex, and d is 2% CNT/triazine complex, and e is that 5% CNT/triazine is multiple
Compound；
Fig. 8 is the infrared spectrum of the product of solid formation A and vacuum drying in embodiment six；Wherein a is solid formation A, and b is true
The product of sky drying.
Specific embodiment
Specific embodiment one：A kind of preparation method of CNT of present embodiment/triazine complex includes following tool
Body step：
First, the preparation of acyl chlorides carbon nano tube：A, surface oxidation：CNT is placed in mixed acid, at 50～80 DEG C
6～9h of lower stirring reaction, obtains the acidifying CNT that surface connects carboxyl, wherein the quality volume of CNT and mixed acid
Than being 1g：(40～80) mL, mixed acid be by concentrated nitric acid that mass concentration is 98% and concentration for 18.4mol/L concentrated sulphuric acid by
Volume ratio 1:3 ratio is mixed；B, chloride：The acidifying CNT that surface connects carboxyl is placed in into SOCl2In, then add
Enter N, then N '-dimethyl Methanamide heats 20～28h of magnetic agitation under conditions of nitrogen protection, temperature are for 75～80 DEG C,
Obtain acyl chlorides carbon nano tube, wherein the acidifying CNT and SOCl of surface connection carboxyl2Proportionate relationship be 1g:(60～
120) mL, SOCl2And N, the volume ratio (0.0025～0.0125) of N '-dimethyl Methanamide：1；
2nd, the synthesis of CNT/triazine complex：By p-phenylenediamine, paraformaldehyde, acyl chlorides carbon nano tube and formylmerphalan
Base ketopyrrolidine is put in three-necked bottle, nitrogen environment, 20～100min of ultrasound, heats 180～200 DEG C of 2～4h of magnetic agitation, instead
Temperature is down to room temperature after should terminating, and is then settled with acetone, and sucking filtration vacuum drying obtains CNT/triazines complex；Its
In, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:The molal volume ratio of (1～5), p-phenylenediamine and N-methyl ketopyrrolidine
1mmol:(2-5) mL, acyl chlorides carbon nano tube is the 0.5%～10% of p-phenylenediamine and paraformaldehyde gross mass.
Used in present embodiment is the SOCl for analyzing pure rank2。
Present embodiment advantage：First, low cost, biodegrading process is simple, easily operation, it is only necessary to prepare a certain amount of acid just
Can implement, it is not necessary to complex instrument；2nd, CNT is acidified, is then carried out chloride, it is therefore an objective to chloride activity
It is high, it is easier to react, then by being doped with CNT, the complex that hardness, modulus are improved can be obtained；3rd, save
Can be environmentally friendly, thermoset composite can be recycled recycling.
Specific embodiment two：Present embodiment from unlike specific embodiment one：Described in step a at 70 DEG C
Stirring reaction 6h.Other steps and parameter are identical with specific embodiment one.
Specific embodiment three：Present embodiment from unlike specific embodiment one or two：It is super described in step 2
Acoustical power is 600W, and frequency is 40/60KHz.Other steps and parameter are identical with specific embodiment one or two.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Described in step 2
P-phenylenediamine, paraformaldehyde, acyl chlorides carbon nano tube and N-methyl ketopyrrolidine are put in three-necked bottle, nitrogen environment, surpass
Sound 60min, is heated to 200 DEG C of magnetic agitation 3h, and reaction terminates rear temperature and is down to room temperature, is then settled with acetone, sucking filtration vacuum
It is dried to obtain CNT/triazine complex；Wherein, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:5, p-phenylenediamine and nitrogen
The molal volume of methyl pyrrolidone compares 1mmol：3mL, CNT is the 0.5% of p-phenylenediamine and paraformaldehyde gross mass.
Other steps and parameter are identical with one of specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Described in step 2
P-phenylenediamine, paraformaldehyde, acyl chlorides carbon nano tube and N-methyl ketopyrrolidine are put in three-necked bottle, nitrogen environment, surpass
Sound 60min, is heated to 200 DEG C of magnetic agitation 3h, and reaction terminates rear temperature and is down to room temperature, is then settled with acetone, sucking filtration vacuum
It is dried to obtain CNT/triazine complex；Wherein, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:5, p-phenylenediamine and nitrogen
The molal volume of methyl pyrrolidone compares 1mmol：3mL, CNT is the 1% of p-phenylenediamine and paraformaldehyde gross mass.Its
Its step and parameter are identical with one of specific embodiment one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Described in step 2
P-phenylenediamine, paraformaldehyde, acyl chlorides carbon nano tube and N-methyl ketopyrrolidine are put in three-necked bottle, nitrogen environment, surpass
Sound 60min, is heated to 200 DEG C of magnetic agitation 3h, and reaction terminates rear temperature and is down to room temperature, is then settled with acetone, sucking filtration vacuum
It is dried to obtain CNT/triazine complex；Wherein, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:5, p-phenylenediamine and nitrogen
The molal volume of methyl pyrrolidone compares 1mmol：3mL, CNT is the 2% of p-phenylenediamine and paraformaldehyde gross mass.Its
Its step and parameter are identical with one of specific embodiment one to five.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Described in step 2
P-phenylenediamine, paraformaldehyde, acyl chlorides carbon nano tube and N-methyl ketopyrrolidine are put in three-necked bottle, nitrogen environment, surpass
Sound 60min, is heated to 200 DEG C of magnetic agitation 3h, and reaction terminates rear temperature and is down to room temperature, is then settled with acetone, sucking filtration vacuum
It is dried to obtain CNT/triazine complex；Wherein, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:5, p-phenylenediamine and nitrogen
The molal volume of methyl pyrrolidone compares 1mmol：3mL, CNT is the 5% of p-phenylenediamine and paraformaldehyde gross mass.Its
Its step and parameter are identical with one of specific embodiment one to six.
Specific embodiment eight：A kind of biodegrading process of CNT of present embodiment/triazine complex is：By carbon nanometer
Pipe/triazine complex is put in the aqueous sulfuric acid of pH=0, solid formation A is filtered to remove after 24～72h, under the conditions of ice-water bath
Solid NaHCO is added in filtrate3To pH=7, solid formation B is filtered to take, vacuum drying obtains p-phenylenediamine, that is, complete degraded；
Wherein CNT/triazine complex and the mass volume ratio of aqueous sulfuric acid are (2～3) mg:1mL.
Present embodiment method is simple and convenient, low cost, and can reclaim raw material and reuse again, be it is a kind of very well
Environment protection method.
Specific embodiment nine：Present embodiment from unlike specific embodiment eight：It is filtered to remove after described 60h
Solid formation.Other steps and parameter are identical with specific embodiment one.
Specific embodiment ten：Present embodiment from unlike specific embodiment eight or nine：Described CNT/
Triazine complex is 2.5mg with the mass volume ratio of aqueous sulfuric acid:1mL.Other steps and parameter and specific embodiment eight
Or nine is identical.
Beneficial effects of the present invention are verified by following examples：
Embodiment one：A kind of preparation method of CNT of the present embodiment/triazine complex is:First, chloride carbon nanometer
The preparation of pipe：A, surface oxidation：2g CNTs are placed in mixed acid, mixed acid is by the nitre that 40mL mass concentrations are 98%
Sulphuric acid of the acid with 120mL concentration for 18.4mol/L mixes stirring reaction 6h at 70 DEG C, is down to room temperature, sucking filtration, and difference
With, to property, vacuum drying obtains the acidifying CNT that surface connects carboxyl in ethanol, water washing filtrate；B, chloride：Take 0.2g
The acidifying CNT of surface connection carboxyl is placed in 20mLSOCl2In, add 0.15mLN, N '-dimethyl Methanamide, then
Under nitrogen protection, temperature is heating magnetic agitation 24h under conditions of 80 DEG C, and vacuum distillation obtains acyl chlorides carbon nano tube；
2nd, the synthesis of CNT/triazine complex：By p-phenylenediamine, paraformaldehyde, acyl chlorides carbon nano tube and formylmerphalan
Base ketopyrrolidine is put in three-necked bottle, nitrogen environment, ultrasonic 60min, is heated to 200 DEG C of magnetic agitation 3h, and reaction is warm after terminating
Degree is down to room temperature, is then settled with acetone, and sucking filtration vacuum drying obtains CNT/triazine complex；Wherein, p-phenylenediamine and
The mol ratio of paraformaldehyde is 1:5, p-phenylenediamine compares 1mmol with the molal volume of N-methyl ketopyrrolidine：3mL, chloride carbon
Nanotube is the 0.5% of p-phenylenediamine and paraformaldehyde gross mass.
The synthetic route of embodiment one as shown in figure, is carried out to the CNT/triazine complex of the present embodiment synthesis
Electron-microscope scanning, as a result as shown in Fig. 2 can become apparent from carbon nano tube surface by Fig. 2 has one layer of coating, it may be said that bright
Polymer and CNT are successfully made grafting.
A kind of preparation method of CNT of embodiment two, the present embodiment/triazine complex is：By p-phenylenediamine, poly
Formaldehyde, acyl chlorides carbon nano tube and N-methyl ketopyrrolidine are put in three-necked bottle, nitrogen environment, and ultrasonic 60min is heated to 200
DEG C magnetic agitation 3h, reaction terminates rear temperature and is down to room temperature, is then settled with acetone, sucking filtration vacuum drying obtain CNT/
Triazine complex；Wherein, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:5, p-phenylenediamine rubs with N-methyl ketopyrrolidine
That volume ratio 1mmol：3mL, acyl chlorides carbon nano tube is the 1% of p-phenylenediamine and paraformaldehyde gross mass.
A kind of preparation method of CNT of embodiment three, the present embodiment/triazine complex is：By p-phenylenediamine, poly
Formaldehyde, acyl chlorides carbon nano tube and N-methyl ketopyrrolidine are put in three-necked bottle, nitrogen environment, and ultrasonic 60min is heated to 200
DEG C magnetic agitation 3h, reaction terminates rear temperature and is down to room temperature, is then settled with acetone, sucking filtration vacuum drying obtain CNT/
Triazine complex；Wherein, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:5, p-phenylenediamine rubs with N-methyl ketopyrrolidine
That volume ratio 1mmol：3mL, acyl chlorides carbon nano tube is the 2% of p-phenylenediamine and paraformaldehyde gross mass.
A kind of preparation method of example IV, the present embodiment CNT/triazine complex is：By p-phenylenediamine, poly
Formaldehyde, acyl chlorides carbon nano tube and N-methyl ketopyrrolidine are put in three-necked bottle, nitrogen environment, and ultrasonic 60min is heated to 200
DEG C magnetic agitation 3h, reaction terminates rear temperature and is down to room temperature, is then settled with acetone, sucking filtration vacuum drying obtain CNT/
Triazine complex；Wherein, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:5, p-phenylenediamine rubs with N-methyl ketopyrrolidine
That volume ratio 1mmol：3mL, acyl chlorides carbon nano tube is the 5% of p-phenylenediamine and paraformaldehyde gross mass.
The acyl chlorides carbon nano tube of embodiment two～tetra- is prepared using the method for embodiment one.
The synthesis of embodiment five, the present embodiment aerotex：
10mmol p-phenylenediamine, 50mmol paraformaldehydes and 30mLNMP are put in three-necked bottle, nitrogen environment, 50 DEG C are stirred
1h is mixed, continues to be heated to 200 DEG C, and react 3h, reaction terminates rear temperature and is down to room temperature, then settled with acetone, sucking filtration vacuum
1.1530g aerotexs (PHT) are dried to obtain, the yield of the present embodiment is 87.30%.
0.5% CNT/triazine complex and the infrared spectrogram of the polymer P HT of embodiment five prepared by embodiment one
As shown in figure 3, Fig. 3 understands, 3446cm-1The weak peak at place be acidified CNT hydroxyl peak, 1295cm in polymer-1It is C-N
Stretching vibration, complex is 3420,1295cm-1The peak at place contains the characteristic peak of two kinds of materials.It can be seen that polymer and carbon nanometer
Pipe is successfully compounded with.
0.5% CNT/triazine complex and the X-ray photoelectricity of the polymer P HT of embodiment five prepared by embodiment one
Sub- energy spectrum diagram as shown in figure 4, Fig. 4 understand, be respectively the characteristic peak of C1s, N1s, O1s 285eV, 399eV, 531eV at, acidifying carbon
Nanotube has the characteristic peak of carbon and oxygen element, and knowable to the molecular formula of polymer, polymer contains carbon, nitrogen, three kinds of units of oxygen
Element, XRD spectrum figure is demonstrated well, and has the characteristic peak of three kinds of elements in complex, and peak intensity and ratio all occur
Change, it is seen that each material successfully synthesizes.
Carry out thermogravimetric analysiss using embodiment five as controlled trial and embodiment one～tetra-, as a result as shown in figure 5, a, b, c,
D, e are respectively the thermogravimetric curves that aerotex (PHT) is combined with CNT, compare and understand, straight polymer weight-loss ratio is
Temperature when 10% and 50% is respectively 248 and 584 DEG C, and residual volume when temperature reaches 1200 DEG C is 40%, when itself and acidifying
After CNT carries out being combined, the residual volume of (from 0.5%-5%) when temperature reaches 1200 DEG C complex is respectively 49%,
54%, 54%, 55%.It can be seen that hot property is greatly improved, can be used widely in terms of heat resistance.
The hardness curve of embodiment one～five is as shown in fig. 6, it will be appreciated from fig. 6 that with the increase of content of carbon nanotubes, each thing
The hardness of matter gradually strengthens, and the hardness of polymer is 0.423GPa at 500nm, and hardness of the complex herein is respectively
0.477,0.663,0.712,0.637GPa, complex hardness is greatly improved, and content of carbon nanotubes is 5% complex
Hardness decreases, and occurs to reunite because of content of carbon nanotubes is too high.In general, the introducing of CNT can be with
The hardness of complex is improved very well.
The modulus curve of embodiment one～five is as shown in fig. 7, as shown in Figure 7, each multiple with the increase of content of carbon nanotubes
The Young's moduluss of compound (0.5%-2%) gradually strengthen, and the Young's moduluss of polymer are 12.28GPa at 500nm, and complex
Young's moduluss herein are respectively 13.33,13.73,16.02,14.08GPa, and composite strength is greatly improved, carbon
Nanotube content is that 5% complex Young's moduluss decrease, and occurs to reunite because of content of carbon nanotubes is too high.
In general, the introducing of CNT can very well improve the modulus of complex.
The biodegrading process of embodiment six, the present embodiment CNT/triazine complex prepares carbon to take 50mg embodiments one
Nanotube/triazine complex is put into 20mL, in the aqueous sulfuric acid of pH=0, solid formation A is filtered to remove after 60h, in ice-water bath bar
Under part in filtrate add solid NaHCO3To pH=7, solid formation B is filtered to take, vacuum drying obtains 16.88mg p-phenylenediamine,
Complete degraded.
The infrared spectrum of the product of the present embodiment solid formation A vacuum dryings as shown in figure 8, the material got of decomposition unit with
The infrared spectrum of p-phenylenediamine is completely superposed, and undecomposed fraction solids Jing compares similar with the infrared spectrum of p-phenylenediamine monomer
Seemingly, it may be possible to which complex Jing acid treatments are broken down into containing two amine-terminated oligomer.The present embodiment degradation rate is 38.7%.
Claims (2)
1. the biodegrading process of a kind of CNT/triazine complex, it is characterised in that the method is to be combined CNT/triazine
Thing is put in the aqueous sulfuric acid of pH=0, and solid formation A is filtered to remove after 24～72h, is added in filtrate under the conditions of ice-water bath
Solid NaHCO3To pH=7, solid formation B is filtered to take, vacuum drying obtains p-phenylenediamine, that is, complete degraded；Wherein carbon nanometer
Pipe/triazine complex is (2～3) mg with the mass volume ratio of aqueous sulfuric acid:1mL；
The preparation method of the CNT/triazine complex is：
First, the preparation of acyl chlorides carbon nano tube：A, surface oxidation：CNT is placed in mixed acid, is stirred at 50～80 DEG C
6～9h of reaction is mixed, the acidifying CNT that surface connects carboxyl is obtained, wherein CNT is with the mass volume ratio of mixed acid
1g：(40～80) mL, mixed acid is by volume by the concentrated nitric acid that mass concentration is 98% with the concentrated sulphuric acid that concentration is 18.4mol/L
Than 1:3 ratio is mixed；B, chloride：The acidifying CNT that surface connects carboxyl is placed in into SOCl2In, N is added,
N '-dimethyl Methanamide, then heats 20～28h of magnetic agitation under conditions of nitrogen protection, temperature are for 75～80 DEG C, obtains acyl
The acidifying CNT and SOCl of chlorination CNT, wherein surface connection carboxyl2Proportionate relationship be 1g:(60～120) mL,
SOCl2And N, the volume ratio (0.0025～0.0125) of N '-dimethyl Methanamide：1；
2nd, the synthesis of CNT/triazine complex：By p-phenylenediamine, paraformaldehyde, acyl chlorides carbon nano tube and N-methyl pyrrole
Pyrrolidone is put in three-necked bottle, nitrogen environment, after 20～100min of ultrasound, reheats 180～200 DEG C of 2～4h of magnetic agitation, instead
Temperature is down to room temperature after should terminating, and is then settled with acetone, sucking filtration vacuum drying, obtains CNT/triazines complex；Its
In, the mol ratio of p-phenylenediamine and paraformaldehyde is 1:The molal volume ratio of (1～5), p-phenylenediamine and N-methyl ketopyrrolidine
1mmol:(2-5) mL, acyl chlorides carbon nano tube is the 0.5%～10% of p-phenylenediamine and paraformaldehyde gross mass.
2. a kind of biodegrading process of CNT/triazine complex according to claim 1, it is characterised in that described carbon
Nanotube/triazine complex is 2.5mg with the mass volume ratio of aqueous sulfuric acid:1mL.
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| CN102295775A (en) * | 2011-06-09 | 2011-12-28 | 黑龙江大学 | Carbon nanotube/poly Schiff base polymer, preparation method thereof, and application thereof |
| CN103524784A (en) * | 2012-05-04 | 2014-01-22 | 艾达索高新材料无锡有限公司 | Degrading and recovering method of epoxy resin composite material |
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| KR101469185B1 (en) * | 2013-04-22 | 2014-12-09 | 인제대학교 산학협력단 | Manufacturing method of carbon nanotube grafted with pei and electroconducting polymer, carbon nanotube grafted with pei and electroconducting polymer made by the same, and voc detecting sensor comprising the same |
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| CN101671478A (en) * | 2009-09-27 | 2010-03-17 | 西南交通大学 | Preparation method of carbon nano tube/polyaniline netty compound material |
| CN102295775A (en) * | 2011-06-09 | 2011-12-28 | 黑龙江大学 | Carbon nanotube/poly Schiff base polymer, preparation method thereof, and application thereof |
| CN103524784A (en) * | 2012-05-04 | 2014-01-22 | 艾达索高新材料无锡有限公司 | Degrading and recovering method of epoxy resin composite material |
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