CN109867781A - A kind of porous conjugated polymer material and preparation method thereof - Google Patents
A kind of porous conjugated polymer material and preparation method thereof Download PDFInfo
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- CN109867781A CN109867781A CN201910084488.3A CN201910084488A CN109867781A CN 109867781 A CN109867781 A CN 109867781A CN 201910084488 A CN201910084488 A CN 201910084488A CN 109867781 A CN109867781 A CN 109867781A
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Abstract
The invention discloses a kind of porous conjugated polymer material and preparation method thereof, include the following steps: a) using domino annulation, with to R benzaldehyde, to X base aniline and 2,3- diacetyl is that raw material obtains monomer cyanopyrrole and pyrroles；Wherein, when R is cyano, X is cyano and methyl；When R is methyl, X is cyano；B) by the monomer cyanopyrrole and after pyrroles mixes with zinc chloride, high-temperature fusion polymerize to obtain a puff under argon atmosphere；C) the remaining zinc chloride of removal reaction is washed in washing, pickling again after smashing the puff to pieces, obtains black powder；D) nitrogen-doped porous carbon material is obtained after being dried the black powder.Products of the present invention has apparent porous structure and big specific surface area and N doping, can be widely applied to gas load, heterogeneous catalysis, gas separation, lithium ion battery and supercapacitor etc..In addition, this method has the characteristics that simple, cheap and can amplify generation simultaneously.
Description
Technical field
The present invention relates to porous material technical fields；In particular it relates to a kind of porous conjugated polymer material and its preparation
Method.
Background technique
In recent years nano-porous polymer material due to its high-specific surface area, lightweight skeleton construction, it is abundant building with
Method of modifying and excellent gas absorption property rapidly become the research hotspot of Material Field.Existing some nanoporous are organic
Polymer has very big promotion in terms of specific surface area and microstructure.But their preparation method is usually associated with height
The specific reaction condition such as pressure, high temperature, expensive synthesis device and technique it is cumbersome the problems such as.Therefore, it explores cheap, simple
It is of great significance with generation technique can be expanded to prepare nano-porous polymer material.
Summary of the invention
The purpose of the invention is to overcome above-mentioned preparation process defect of the existing technology, a kind of porous conjugation is provided
The porous conjugated polymer material product of polymer material and preparation method thereof, preparation has apparent porous structure and big ratio
Surface area and N doping, and preparation method has the advantages that simple, cheap and can amplify production.
To achieve the goals above, in the embodiment on basis, one aspect of the present invention provides a kind of porous conjugated polymers
The preparation method of object material, includes the following steps:
A) utilize domino annulation, with to R benzaldehyde, to X base aniline and 2, it is single that 3- diacetyl is that raw material obtains
Body cyanopyrrole and pyrroles (CNPP)；Wherein, when R is cyano, X is cyano and methyl；When R is methyl, X is cyano；
B) by the monomer cyanopyrrole and after pyrroles mixes with zinc chloride, high-temperature fusion polymerize under argon atmosphere
To a puff；
C) the remaining zinc chloride of removal reaction is washed in washing, pickling again after smashing the puff to pieces, obtains black powder；
D) nitrogen-doped porous carbon material is obtained after being dried the black powder.
In a preferred embodiment, it is described to R benzaldehyde, to X base aniline and 2, the molar ratio of 3- diacetyl
For 2:2:1-1.5.
In a preferred embodiment, the domino annulation in the step a) are as follows: will to R benzaldehyde,
X base aniline is placed in acetic acid, mixture is obtained, the mixture is heated with stirring to 80-100 DEG C, 20 minutes-after forty minutes
2,3- diacetyl is added dropwise, after 2-4 hours, is filtered after standing room temperature, acetic acid washs to obtain monomer CNPP.
In a preferred embodiment, the domino annulation in the step a) are as follows: will to R benzaldehyde,
X base aniline is placed in acetic acid, mixture is obtained, the mixture is heated with stirring to 90 DEG C, 2,3- fourth is added dropwise after 30 minutes
Diketone after 3 hours, filters, acetic acid washs to obtain monomer CNPP after standing room temperature.
In a preferred embodiment, mole of monomer cyanopyrrole and pyrroles and zinc chloride in the step b)
Than being 1:10.
In a preferred embodiment, step b) the high temperature melt polymerization are as follows: with the heating of 3-6 DEG C/min
Rate is warming up to 350-500 DEG C, constant temperature 30-50 hours, is then down to room temperature with the rate of temperature fall of 4-8 DEG C/min, obtains bulk
Black puff.
In a preferred embodiment, step b) the high temperature melt polymerization are as follows: with the heating speed of 5 DEG C/min
Rate is warming up to 400 DEG C, constant temperature 40 hours, is then down to room temperature with the rate of temperature fall of 5-6 DEG C/min, it is fluffy to obtain bulk black
Object.
In a preferred embodiment, pickling uses hydrochloric acid in the step c), and the concentration of hydrochloric acid is 1mol/
L。
In a preferred embodiment, being dried in the step d) includes: to set the black powder
In a vacuum drying oven, it dries 8-12 hours at 120-150 DEG C and obtains the porous conjugated polymer material of N doping.
In a preferred embodiment, being dried in the step d) includes: to set the black powder
In a vacuum drying oven, it dries 10 hours at 130 DEG C and obtains the porous conjugated polymer material of N doping.
Another aspect of the present invention provides the porous conjugated polymer material of N doping made from above-mentioned preparation method.
Through the above technical solutions, the present invention with it is common to R benzaldehyde, to X base aniline and 2,3- diacetyl is original
Material is come after synthesizing four cyano pyrrolopyrrole (CNPP), using the hot high-temperature fusion polymerization reaction of chlorination zinc ion after optimization,
Synthesizing new organic nano porous polymer material under argon atmosphere.Products of the present invention have apparent porous structure and
Big specific surface area and N doping can be widely applied to gas load, heterogeneous catalysis, gas separation, lithium ion battery, light are urged
Catalyst and the supercapacitor etc. for changing degradation are the hot spots of current porous material research.In addition, this method has simultaneously
Simply, it is cheap and the features such as generation can be amplified.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the monomer CNPP of the embodiment of the present invention 1；
Fig. 2 is 1 monomer CNPP of the embodiment of the present invention and prepares the infrared spectrogram of porous polymer material CTF-CN；
Fig. 3 is the ultrahigh resolution awkward silence at a meeting scanning electron microscope of porous polymer material CTF-CN prepared by the embodiment of the present invention 1
Figure；
Fig. 4 is the isothermal nitrogen adsorption desorption curve graph of porous polymer material CTF-CN prepared by the embodiment of the present invention 1；
Fig. 5 is the thermogravimetric analysis test curve of porous polymer material CTF-CN prepared by the embodiment of the present invention 1；
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of the monomer CNPP-3 of the embodiment of the present invention 4；
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of the monomer CNPP-4 of the embodiment of the present invention 5.
Specific embodiment
In order to better understand the above technical scheme, being done below by specific embodiment to technical scheme detailed
Explanation, it should be understood that the specific features in the embodiment of the present application and embodiment be to technical scheme specifically
It is bright, rather than the restriction to technical scheme, in the absence of conflict, the skill in the embodiment of the present application and embodiment
Art feature can be combined with each other.It should be understood that term "and/or" used herein above includes listed by one of them or more
Any and all combinations of associated item out.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Below with reference to specific embodiment, the present invention will be described in detail.Material used in embodiment can be by commercially available
Channel obtains.
Embodiment 1
A) 5.9g is weighed respectively to cyano-aniline, and 6.55g is placed in the flask of the acetic acid containing 70ml cyanobenzaldehyde, stirring
Be heated to 90 DEG C, be added dropwise 2.2ml 2 after half an hour, 3- diacetyl, after 3 hours, it is quiet to filter after room temperature, acetic acid washs to obtain list
Body CNPP；
B) 435mg monomer CNPP is uniformly mixed with 1.36g zinc chloride, vessel used are porcelain boat；Mixing is placed on Muffle
In tube furnace, high-temperature fusion polymerize to obtain a puff under argon atmosphere；
Wherein, high-temperature fusion polymerization procedure are as follows: 400 DEG C are warming up to the heating rate of 5 DEG C/min, constant temperature 40 hours, so
Room temperature is down to the rate of temperature fall of 5-6 DEG C/min afterwards, obtains a black puff；
C) washing, pickling wash the remaining zinc chloride of removal reaction again and obtain black powder after smashing the puff to pieces；
Wherein, washing and pickling are using tap water and hydrochloric acid, concentration of hydrochloric acid 1mol/L respectively.
D) black powder is placed in a vacuum drying oven, is dried 10 hours at 130 DEG C and obtains the porous conjugation of N doping
Polymer material.
Reaction equation is as follows:
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the monomer CNPP of the embodiment of the present invention 1.Fig. 2 is 1 monomer of the embodiment of the present invention
CNPP and the infrared spectrogram for preparing porous polymer material CTF-CN；Fig. 3 is porous polymer prepared by the embodiment of the present invention 1
The ultrahigh resolution awkward silence at a meeting scanning electron microscope (SEM) photograph of material C TF-CN；Fig. 4 is porous polymer material prepared by the embodiment of the present invention 1
The isothermal nitrogen adsorption desorption curve graph of CTF-CN；Fig. 5 is the heat of porous polymer material CTF-CN prepared by the embodiment of the present invention 1
Weight analysis test curve.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of 1 monomer CNPP of embodiment；From the comparison of the infared spectrum of Fig. 2 as can be seen that monomer
The infrared spectrum of CNPP is in 2222cm-1There are the characteristic peaks of cyano, and this peak is not present on the infrared spectrum of polymer CTF-CN
But there is 1592cm-1Characteristic peak, it was demonstrated that during the reaction cyano fundamental reaction completely and generate three cyanogen structural units.Fig. 3
Illustrate that polymer CTF-CN is random pattern.The isothermal nitrogen adsorption desorption that Fig. 4 is polymer CTF-CN is tested, it can be seen that its
Specific surface area is more than 1000m2/g.Fig. 5 illustrates that it still has 85% quality remaining after temperature is raised to 700 DEG C, thermal stability
It is good.
The isothermal nitrogen adsorption desorption curve graph of ultrahigh resolution awkward silence at a meeting scanning electron microscope (SEM) photograph N doping porous material；Instrument model
For ASAP2020, the thermogravimetric analysis test curve of the N doping porous material of preparation.Instrument model is the resistance to TG209F3 that speeds of Germany.
Embodiment 2
A) 5.9g is weighed respectively to cyano-aniline, and 6.55g is placed in the flask of the acetic acid containing 70ml cyanobenzaldehyde, stirring
Be heated to 80 DEG C, be added dropwise 2.2ml 2 after 40min, 3- diacetyl, after 4 hours, it is quiet to filter after room temperature, acetic acid washs to obtain list
Body CNPP；
B) 435mg monomer CNPP is uniformly mixed with 1.36g zinc chloride, vessel used are porcelain boat；Mixing is placed on Muffle
In tube furnace, high-temperature fusion polymerize to obtain a puff under argon atmosphere；
Wherein, high-temperature fusion polymerization procedure are as follows: 350 DEG C are warming up to the heating rate of 3 DEG C/min, constant temperature 30 hours, so
Room temperature is down to the rate of temperature fall of 5 DEG C/min afterwards, obtains a black puff；
C) washing, pickling wash the remaining zinc chloride of removal reaction again and obtain black powder after smashing the puff to pieces；
Wherein, washing and pickling are using tap water and hydrochloric acid, concentration of hydrochloric acid 1mol/L respectively.
D) black powder is placed in a vacuum drying oven, is dried 12 hours at 120 DEG C and obtains the porous conjugation of N doping
Polymer material.
Reaction equation is the same as embodiment 1.
Embodiment 3
A) 5.9g is weighed respectively to cyano-aniline, and 6.55g is placed in the flask of the acetic acid containing 70ml cyanobenzaldehyde, stirring
Be heated to 100 DEG C, be added dropwise 2.2ml 2 after 20min, 3- diacetyl, after 2 hours, it is quiet to filter after room temperature, acetic acid washs to obtain list
Body CNPP；
B) 435mg monomer CNPP is uniformly mixed with 1.36g zinc chloride, vessel used are porcelain boat；Mixing is placed on Muffle
In tube furnace, high-temperature fusion polymerize to obtain a puff under argon atmosphere；
Wherein, high-temperature fusion polymerization procedure are as follows: 500 DEG C are warming up to the heating rate of 6 DEG C/min, constant temperature 50 hours, so
Room temperature is down to the rate of temperature fall of 6 DEG C/min afterwards, obtains a black puff；
C) washing, pickling wash the remaining zinc chloride of removal reaction again and obtain black powder after smashing the puff to pieces；
Wherein, washing and pickling are using tap water and hydrochloric acid, concentration of hydrochloric acid 1mol/L respectively.
D) black powder is placed in a vacuum drying oven, dries that obtain within 8 hours the porous conjugation of N doping poly- at 150 DEG C
Close object material.
Embodiment 4
A) 5.9g is weighed respectively to cyano-aniline, and 6.55g p-tolyl aldehyde is placed in the flask of the acetic acid containing 70ml, stirring
Be heated to 90 DEG C, be added dropwise 2.2ml 2 after half an hour, 3- diacetyl, after 3 hours, it is quiet to filter after room temperature, acetic acid washs to obtain list
Body CNPP-3；
B) 435mg monomer CNPP is uniformly mixed with 1.36g zinc chloride, vessel used are porcelain boat；Mixing is placed on Muffle
In tube furnace, high-temperature fusion polymerize to obtain a puff under argon atmosphere；
Wherein, high-temperature fusion polymerization procedure are as follows: 400 DEG C are warming up to the heating rate of 5 DEG C/min, constant temperature 40 hours, so
Room temperature is down to the rate of temperature fall of 6 DEG C/min afterwards, obtains a black puff；
C) washing, pickling wash the remaining zinc chloride of removal reaction again and obtain black powder after smashing the puff to pieces；
Wherein, washing and pickling are using tap water and hydrochloric acid, concentration of hydrochloric acid 1mol/L respectively.
D) black powder is placed in a vacuum drying oven, is dried 10 hours at 130 DEG C and obtains the porous conjugation of N doping
Polymer material.
Reaction equation is as follows:
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of the monomer CNPP-3 of the embodiment of the present invention 4.
Embodiment 5
A) 5.9g open-chain crown ether is weighed respectively, and 6.55g is placed in the flask of the acetic acid containing 70ml cyanobenzaldehyde, stirring
Be heated to 90 DEG C, be added dropwise 2.2ml 2 after half an hour, 3- diacetyl, after 3 hours, it is quiet to filter after room temperature, acetic acid washs to obtain list
Body CNPP-4；
B) 435mg monomer CNPP-4 is uniformly mixed with 1.36g zinc chloride, vessel used are porcelain boat；Mixing is placed on horse
Not in tube furnace, high-temperature fusion polymerize to obtain a puff under argon atmosphere；
Wherein, high-temperature fusion polymerization procedure are as follows: 400 DEG C are warming up to the heating rate of 5 DEG C/min, constant temperature 40 hours, so
Room temperature is down to the rate of temperature fall of 5 DEG C/min afterwards, obtains a black puff；
C) washing, pickling wash the remaining zinc chloride of removal reaction again and obtain black powder after smashing the puff to pieces；
Wherein, washing and pickling are using tap water and hydrochloric acid, concentration of hydrochloric acid 1mol/L respectively.
D) black powder is placed in a vacuum drying oven, is dried 10 hours at 130 DEG C and obtains the porous conjugation of N doping
Polymer material.
Reaction equation is as follows:
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of the monomer CNPP-4 of the embodiment of the present invention 5.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of porous conjugated polymer material, characterized by the following steps:
A) utilize domino annulation, with to R benzaldehyde, to X base aniline and 2,3- diacetyl is that raw material obtains monomer cyanogen
Base pyrrolopyrrole；Wherein, when R is cyano, X is cyano and methyl；When R is methyl, X is cyano；
B) by the monomer cyanopyrrole and after pyrroles mixes with zinc chloride, high-temperature fusion, which polymerize, under argon atmosphere is rolled into a ball
Shape puff；
C) the remaining zinc chloride of removal reaction is washed in washing, pickling again after smashing the puff to pieces, obtains black powder；
D) nitrogen-doped porous carbon material is obtained after being dried the black powder.
2. the preparation method of porous conjugated polymer material according to claim 1, it is characterised in that: in the step a)
To R benzaldehyde, be 2:2:1-1.5 to the molar ratio of X base aniline and 2,3- diacetyl.
3. the preparation method of porous conjugated polymer material according to claim 1, it is characterised in that: in the step a)
Domino annulation are as follows: will be placed in acetic acid to R benzaldehyde, to X base aniline, and mixture be obtained, by the mixture
It is heated with stirring to 80-100 DEG C, 20 minutes -2,3- diacetyl is added dropwise after forty minutes, after 2-4 hours, stands suction filtration, vinegar after room temperature
Acid elution obtains monomer cyanopyrrole and pyrroles.
4. the preparation method of porous conjugated polymer material according to claim 3, it is characterised in that: in the step a)
Domino annulation are as follows: will be placed in acetic acid to R benzaldehyde, to X base aniline, and mixture be obtained, by the mixture
90 DEG C are heated with stirring to, 2,3- diacetyl is added dropwise after 30 minutes, after 3 hours, is filtered after standing room temperature, acetic acid washs to obtain monomer
Cyanopyrrole and pyrroles.
5. the preparation method of porous conjugated polymer material according to claim 3, it is characterised in that: the step b)
The molar ratio of middle monomer cyanopyrrole and pyrroles and zinc chloride is 1:10.
6. the preparation method of porous conjugated polymer material according to claim 1, it is characterised in that: the step b)
High temperature melt polymerization are as follows: 350-500 DEG C is warming up to the heating rate of 3-6 DEG C/min, constant temperature 30-50 hours, then with 4-8
DEG C/rate of temperature fall of min is down to room temperature, obtain bulk black puff.
7. the preparation method of porous conjugated polymer material according to claim 6, it is characterised in that: the step b)
High temperature melt polymerization are as follows: 400 DEG C are warming up to the heating rate of 5 DEG C/min, constant temperature 40 hours, then with 5-6 DEG C/min's
Rate of temperature fall is down to room temperature, obtains bulk black puff.
8. the preparation method of porous conjugated polymer material according to claim 1, it is characterised in that: the step c)
Middle pickling uses hydrochloric acid, and the concentration of hydrochloric acid is 1mol/L.
9. the preparation method of porous conjugated polymer material according to claim 1, it is characterised in that: the step d)
Middle drying process includes: to be placed in a vacuum drying oven the black powder, dries at 120-150 DEG C and obtains nitrogen within 8-12 hours and mix
Miscellaneous porous conjugated polymer material.
10. the porous conjugated polymer material of N doping made from the preparation method as described in claim any one of 1-9.
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| CN111634909A (en) * | 2020-05-22 | 2020-09-08 | 上海应用技术大学 | Preparation method and application of nitrogen-doped porous carbon material based on trichloro-aza-acene fused-ring aromatic hydrocarbon |
| CN113880974A (en) * | 2021-10-21 | 2022-01-04 | 天津理工大学 | Photocurable liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, and preparation method and application thereof |
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Application publication date: 20190611 |