CN109935873A - The preparation method of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube - Google Patents
The preparation method of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube Download PDFInfo
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- CN109935873A CN109935873A CN201910204166.8A CN201910204166A CN109935873A CN 109935873 A CN109935873 A CN 109935873A CN 201910204166 A CN201910204166 A CN 201910204166A CN 109935873 A CN109935873 A CN 109935873A
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Abstract
The present invention relates to the preparation methods of a kind of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube, carbon nanotube is processed into acidification carbon nanotube with nitration mixture first, then asparagine grafting carbon nanotube is made, static spinning membrane is prepared into sulfonated polyether-ether-ketone again, preparation process is simple, it is at low cost, there is good mechanical performance, thermal stability, proton conductivity, can be used as fuel battery proton exchange film.
Description
Technical field
The invention belongs to sulfonated polyether-ether-ketone field of compound material, and in particular to a kind of sulfonated polyether-ether-ketone and carbon nanotube
Static spinning membrane preparation method.
Background technique
The method for preparing nanofiber at present has pulling method, template synthesis method, phase separation method, self-assembly method, electrostatic spinning
Method etc..Electrostatic spinning technique is that is developed in recent years prepare a kind of important method of nanofiber, it is to utilize electrification macromolecule
The flowing and deformation of melt or solution in electrostatic field prepare the one of nanofiber by melt cooling and solidifying or solvent evaporation
Kind method.Compared with other several methods, electrostatic spinning technique effectively can directly prepare continuous polymer nanofiber,
It is with a wide range of applications in terms of electronic device, bio-medical material, sensing material, protective materials and filtering material.
The higher proton conductivity of SPEEK excellent chemical, lower keeps the alcohol-rejecting ability of film bright alcohol electro-osmosis coefficient
Aobvious to be better than Nafion membrane, the special scale of carbon nanotube and structure impart the mechanical property of its superelevation, unique electric property
And a variety of excellent performances such as calorifics, optics, Flied emission, absorption, it is resolved that it has great application prospect multi-field.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of a kind of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube.
The technical solution adopted by the present invention to solve the technical problems is: the Static Spinning of sulfonated polyether-ether-ketone and carbon nanotube
The preparation method of cortina, comprising the following steps:
1) at 100 DEG C, carbon nanotube is added by reacting back in the nitric acid that volume ratio is 3:1 and the nitration mixture that sulfuric acid forms
4-5h is flowed, is cooled to room temperature, deionized water vacuum filtration is added, is washed to pH repeatedly with deionized water into neutrality, 60 DEG C of vacuum
It is so dry that be acidified carbon nanotube；
2) acidification carbon nanotube is added in DMF, then mass concentration 5-15wt% sequentially adds asparagine and two
Carbodicyclo hexylimide is ultrasonically treated 30-60min, and 50-60 DEG C of heating water bath be stirred to react 24-36h, filters, then with DMF,
Acetone, deionization washing, until pH=7,70 DEG C of vacuum drying for 24 hours, obtain asparagine grafting carbon nanotube；
3) it takes sulfonated polyether-ether-ketone to be added in solvent, is configured to the sulfonated polyether-ether-ketone dispersion liquid that concentration is 10-20wt%；
4) asparagine grafting carbon nanotube is added in dimethylformamide, surfactant is then added, stirred
30min, is then added sulfonated polyether-ether-ketone dispersion liquid, and 40-50 DEG C of stirring 6-8h obtains spinning solution；
5) spinning solution electrostatic spinning is obtained into composite cellulosic membrane, composite cellulosic membrane is soaked in 12h in deionized water, taken out true
Sky is drying to obtain the static spinning membrane of sulfonated polyether-ether-ketone and carbon nanotube.
Specifically, acidification carbon nanotube in the step 2), asparagine, dicyclohexylcarbodiimide mass ratio be
20-30:8-13:5-7。
Specifically, solvent is one of dimethylformamide, dimethyl acetamide, dimethyl sulfoxide in the step 3)
Or several mixture.
Specifically, in the step 4) asparagine grafting carbon nanotube, surfactant, sulfonated polyether-ether-ketone quality
Than for
Specifically, surfactant is neopelex or beta-cyclodextrin in the step 4).
Specifically, in the step 5) electrostatic spinning condition are as follows: spinning voltage 12-15kV, spinning flow velocity 0.2-
0.5mL/h receives distance 12-15cm.
The invention has the following advantages: the present invention first uses asparagine grafting carbon nanotube, it is then poly- with sulfonation again
Static spinning membrane is made in ether ether ketone, and preparation process is simple, at low cost, has good mechanical performance, thermal stability, proton conductive
Rate can be used as fuel battery proton exchange film.
Specific embodiment
The following is specific embodiments of the present invention, is described further to technical solution of the present invention, but of the invention
Protection scope is not limited to these examples.It is all to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute
Protection scope within.
Embodiment 1
The preparation method of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube, comprising the following steps:
1) at 100 DEG C, carbon nanotube is added by reacting back in the nitric acid that volume ratio is 3:1 and the nitration mixture that sulfuric acid forms
4-5h is flowed, is cooled to room temperature, deionized water vacuum filtration is added, is washed to pH repeatedly with deionized water into neutrality, 60 DEG C of vacuum
It is so dry that be acidified carbon nanotube；
2) acidification carbon nanotube is added in DMF, then mass concentration 12wt% sequentially adds asparagine and two rings
Hexyl carbodiimide, acidification carbon nanotube, asparagine, dicyclohexylcarbodiimide mass ratio be 25:13:5, ultrasonic treatment
40min, 55 DEG C of heating water baths are stirred to react 30h, filter, and are then washed with DMF, acetone, deionization, until pH=7,70 DEG C of vacuum
Drying for 24 hours, obtains asparagine grafting carbon nanotube；
3) it takes sulfonated polyether-ether-ketone to be added in dimethyl acetamide, is configured to the sulfonated polyether-ether-ketone point that concentration is 18wt%
Dispersion liquid；
4) asparagine grafting carbon nanotube is added in dimethylformamide, neopelex is then added,
30min is stirred, sulfonated polyether-ether-ketone dispersion liquid, asparagine grafting carbon nanotube, surfactant, sulfonated polyether is then added
The mass ratio of ether ketone is 17:2:20, and 45 DEG C of stirring 8h obtain spinning solution；
5) spinning solution electrostatic spinning is obtained into composite cellulosic membrane, the condition of electrostatic spinning are as follows: spinning voltage 12-15kV, spinning
Flow velocity 0.2-0.5mL/h receives distance 12-15cm, and composite cellulosic membrane is soaked in 12h in deionized water, it is dry to take out vacuum
The dry static spinning membrane up to sulfonated polyether-ether-ketone and carbon nanotube.
Embodiment 2
The preparation method of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube, comprising the following steps:
1) at 100 DEG C, carbon nanotube is added by reacting back in the nitric acid that volume ratio is 3:1 and the nitration mixture that sulfuric acid forms
4-5h is flowed, is cooled to room temperature, deionized water vacuum filtration is added, is washed to pH repeatedly with deionized water into neutrality, 60 DEG C of vacuum
It is so dry that be acidified carbon nanotube；
2) acidification carbon nanotube is added in DMF, then mass concentration 5wt% sequentially adds asparagine and two rings
Hexyl carbodiimide, acidification carbon nanotube, asparagine, dicyclohexylcarbodiimide mass ratio be 28:9:5, ultrasonic treatment
30min, 60 DEG C of heating water baths are stirred to react 36h, filter, and are then washed with DMF, acetone, deionization, until pH=7,70 DEG C of vacuum
Drying for 24 hours, obtains asparagine grafting carbon nanotube；
3) it takes sulfonated polyether-ether-ketone to be added in dimethylformamide, is configured to the sulfonated polyether-ether-ketone point that concentration is 20wt%
Dispersion liquid；
4) asparagine grafting carbon nanotube is added in dimethylformamide, neopelex is then added,
30min is stirred, sulfonated polyether-ether-ketone dispersion liquid, asparagine grafting carbon nanotube, surfactant, sulfonated polyether is then added
The mass ratio of ether ketone is 15:1:23, and 50 DEG C of stirring 6h obtain spinning solution；
5) spinning solution electrostatic spinning is obtained into composite cellulosic membrane, the condition of electrostatic spinning are as follows: spinning voltage 12-15kV, spinning
Flow velocity 0.2-0.5mL/h receives distance 12-15cm, and composite cellulosic membrane is soaked in 12h in deionized water, it is dry to take out vacuum
The dry static spinning membrane up to sulfonated polyether-ether-ketone and carbon nanotube.
Embodiment 3
The preparation method of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube, comprising the following steps:
1) at 100 DEG C, carbon nanotube is added by reacting back in the nitric acid that volume ratio is 3:1 and the nitration mixture that sulfuric acid forms
4-5h is flowed, is cooled to room temperature, deionized water vacuum filtration is added, is washed to pH repeatedly with deionized water into neutrality, 60 DEG C of vacuum
It is so dry that be acidified carbon nanotube；
2) acidification carbon nanotube is added in DMF, then mass concentration 10wt% sequentially adds asparagine and two rings
Hexyl carbodiimide, acidification carbon nanotube, asparagine, dicyclohexylcarbodiimide mass ratio be 30:11:6, ultrasonic treatment
50min, 55 DEG C of heating water baths are stirred to react for 24 hours, filter, and are then washed with DMF, acetone, deionization, until pH=7,70 DEG C of vacuum
Drying for 24 hours, obtains asparagine grafting carbon nanotube；
3) it takes sulfonated polyether-ether-ketone to be added in dimethyl sulfoxide, is configured to the sulfonated polyether-ether-ketone that concentration is 10wt% and disperses
Liquid；
4) asparagine grafting carbon nanotube is added in dimethylformamide, beta-cyclodextrin is then added, stirred
Then sulfonated polyether-ether-ketone dispersion liquid, asparagine grafting carbon nanotube, surfactant, sulfonated polyether-ether-ketone is added in 30min
Mass ratio be 18:2:25,40 DEG C of stirring 7h obtain spinning solution；
5) spinning solution electrostatic spinning is obtained into composite cellulosic membrane, the condition of electrostatic spinning are as follows: spinning voltage 12-15kV, spinning
Flow velocity 0.2-0.5mL/h receives distance 12-15cm, and composite cellulosic membrane is soaked in 12h in deionized water, it is dry to take out vacuum
The dry static spinning membrane up to sulfonated polyether-ether-ketone and carbon nanotube.
Embodiment 4
The preparation method of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube, comprising the following steps:
1) at 100 DEG C, carbon nanotube is added by reacting back in the nitric acid that volume ratio is 3:1 and the nitration mixture that sulfuric acid forms
4-5h is flowed, is cooled to room temperature, deionized water vacuum filtration is added, is washed to pH repeatedly with deionized water into neutrality, 60 DEG C of vacuum
It is so dry that be acidified carbon nanotube；
2) acidification carbon nanotube is added in DMF, then mass concentration 15wt% sequentially adds asparagine and two rings
Hexyl carbodiimide, acidification carbon nanotube, asparagine, dicyclohexylcarbodiimide mass ratio be 20:8:7, ultrasonic treatment
60min, 50 DEG C of heating water baths are stirred to react 30h, filter, and are then washed with DMF, acetone, deionization, until pH=7,70 DEG C of vacuum
Drying for 24 hours, obtains asparagine grafting carbon nanotube；
3) take sulfonated polyether-ether-ketone that the in the mixed solvent of dimethylformamide and dimethyl sulfoxide is added, being configured to concentration is
The sulfonated polyether-ether-ketone dispersion liquid of 15wt%；
4) asparagine grafting carbon nanotube is added in dimethylformamide, beta-cyclodextrin is then added, stirred
Then sulfonated polyether-ether-ketone dispersion liquid, asparagine grafting carbon nanotube, surfactant, sulfonated polyether-ether-ketone is added in 30min
Mass ratio be 20:1.5:22,45 DEG C of stirring 7h obtain spinning solution；
5) spinning solution electrostatic spinning is obtained into composite cellulosic membrane, the condition of electrostatic spinning are as follows: spinning voltage 12-15kV, spinning
Flow velocity 0.2-0.5mL/h receives distance 12-15cm, and composite cellulosic membrane is soaked in 12h in deionized water, it is dry to take out vacuum
The dry static spinning membrane up to sulfonated polyether-ether-ketone and carbon nanotube.
Claims (6)
1. the preparation method of sulfonated polyether-ether-ketone and the static spinning membrane of carbon nanotube, which comprises the following steps:
1) at 100 DEG C, carbon nanotube is added by reacting reflux 4- in the nitric acid that volume ratio is 3:1 and the nitration mixture that sulfuric acid forms
5h is cooled to room temperature, and deionized water vacuum filtration is added, and is washed to pH repeatedly with deionized water into neutrality, 60 DEG C of vacuum drying
Carbon nanotube must be acidified；
2) acidification carbon nanotube is added in DMF, then mass concentration 5-15wt% sequentially adds asparagine and two hexamethylenes
Base carbodiimide is ultrasonically treated 30-60min, and 50-60 DEG C of heating water bath is stirred to react 24-36h, filters, and then uses DMF, third
Ketone, deionization washing, until pH=7,70 DEG C of vacuum drying for 24 hours, obtain asparagine grafting carbon nanotube；
3) it takes sulfonated polyether-ether-ketone to be added in solvent, is configured to the sulfonated polyether-ether-ketone dispersion liquid that concentration is 10-20wt%；
4) asparagine grafting carbon nanotube is added in dimethylformamide, surfactant is then added, stir 30min,
Then sulfonated polyether-ether-ketone dispersion liquid is added, 40-50 DEG C of stirring 6-8h obtains spinning solution；
5) spinning solution electrostatic spinning is obtained into composite cellulosic membrane, composite cellulosic membrane is soaked in 12h in deionized water, it is dry to take out vacuum
The dry static spinning membrane up to sulfonated polyether-ether-ketone and carbon nanotube.
2. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and the static spinning membrane of carbon nanotube, feature exist
In, the step 2) acidification carbon nanotube, asparagine, dicyclohexylcarbodiimide mass ratio be 20-30:8-13:5-
7。
3. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and the static spinning membrane of carbon nanotube, feature exist
In solvent is the mixing of one or more of dimethylformamide, dimethyl acetamide, dimethyl sulfoxide in the step 3)
Object.
4. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and the static spinning membrane of carbon nanotube, feature exist
In the mass ratio of, asparagine grafting carbon nanotube in the step 4), surfactant, sulfonated polyether-ether-ketone be 15-20:1-
2:20-25。
5. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 or 4 and the static spinning membrane of carbon nanotube, feature
It is, surfactant is neopelex or beta-cyclodextrin in the step 4).
6. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and the static spinning membrane of carbon nanotube, feature exist
In the condition of electrostatic spinning in the step 5) are as follows: spinning voltage 12-15kV, spinning flow velocity 0.2-0.5mL/h, receive away from
From 12-15cm.
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| CN110534384A (en) * | 2019-07-26 | 2019-12-03 | 宁波工程学院 | A kind of nano-particle modified dendritic TiO of Au2Application of the nanometer stick array as filed emission cathode material |
| CN115125634A (en) * | 2022-08-11 | 2022-09-30 | 吉林大学 | Method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fiber based on electrostatic spinning technology, polyarylether composite material and application |
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| CN101230211A (en) * | 2007-12-27 | 2008-07-30 | 同济大学 | Method for preparing small-molecule imide modified carbon nano-tube |
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| CN110534384A (en) * | 2019-07-26 | 2019-12-03 | 宁波工程学院 | A kind of nano-particle modified dendritic TiO of Au2Application of the nanometer stick array as filed emission cathode material |
| CN115125634A (en) * | 2022-08-11 | 2022-09-30 | 吉林大学 | Method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fiber based on electrostatic spinning technology, polyarylether composite material and application |
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Application publication date: 20190625 |