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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- polymer material
- preparation
- conjugated polymer
- porous
- monomer
- 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.)
- Pending
Links
- 239000002861 polymer material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 18
- 239000011592 zinc chloride Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000005554 pickling Methods 0.000 claims description 14
- 230000004927 fusion Effects 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- BQMPGKPTOHKYHS-UHFFFAOYSA-N 1h-pyrrole-2-carbonitrile Chemical compound N#CC1=CC=CN1 BQMPGKPTOHKYHS-UHFFFAOYSA-N 0.000 claims description 7
- 150000003233 pyrroles Chemical class 0.000 claims description 7
- 238000010719 annulation reaction Methods 0.000 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000010828 elution Methods 0.000 claims 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000007789 gas Substances 0.000 abstract description 5
- QZVFCZDUSCDFMF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5-carbonitrile Chemical compound C(#N)C=1C=C2C(=CC=N2)N1 QZVFCZDUSCDFMF-UHFFFAOYSA-N 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 2
- 239000003990 capacitor Substances 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000021615 conjugation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 description 4
- JLXXLCJERIYMQG-UHFFFAOYSA-N phenylcyanamide Chemical compound N#CNC1=CC=CC=C1 JLXXLCJERIYMQG-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
本发明公开了一种多孔共轭聚合物材料及其制备方法，包括如下步骤：a)利用多米诺成环反应，以对R基苯甲醛、对X基苯胺和2,3‑丁二酮为原料获得单体氰基吡咯并吡咯；其中，R为氰基时，X为氰基和甲基；R为甲基时，X为氰基；b)将所述的单体氰基吡咯并吡咯与氯化锌混合后，在氩气氛围下高温熔融聚合得到一团蓬松物；c)将所述的蓬松物捣碎后水洗、酸洗再水洗去除反应残余氯化锌，得到黑色粉末；d)将所述的黑色粉末干燥处理后得到氮掺杂多孔碳材料。本发明制备的产品具有明显的多孔结构和大的比表面积以及氮掺杂，可广泛应用于气体负载、多相催化、气体分离、锂离子电池和超级电容器等方面。另外，该方法同时具有简单、低廉和可放大生成等特点。
The invention discloses a porous conjugated polymer material and a preparation method thereof, comprising the following steps: a) utilizing a domino ring-forming reaction, using p-R-based benzaldehyde, p-X-based aniline and 2,3-butanedione as raw materials Obtaining monomer cyanopyrrolopyrrole; wherein, when R is cyano, X is cyano and methyl; when R is methyl, X is cyano; b) combining the monomer cyanopyrrolopyrrole with After the zinc chloride is mixed, high temperature melting polymerization under argon atmosphere obtains a mass of fluff; c) the fluff is smashed, washed with water, pickled and washed with water to remove the reaction residual zinc chloride to obtain black powder; d) The nitrogen-doped porous carbon material is obtained after the black powder is dried. The product prepared by the invention has obvious porous structure, large specific surface area and nitrogen doping, and can be widely used in gas loading, heterogeneous catalysis, gas separation, lithium ion battery, super capacitor and the like. In addition, the method is simple, inexpensive and scalable.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910084488.3A CN109867781A (en) | 2019-01-29 | 2019-01-29 | A kind of porous conjugated polymer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910084488.3A CN109867781A (en) | 2019-01-29 | 2019-01-29 | A kind of porous conjugated polymer material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109867781A true CN109867781A (en) | 2019-06-11 |
Family
ID=66918265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910084488.3A Pending CN109867781A (en) | 2019-01-29 | 2019-01-29 | A kind of porous conjugated polymer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109867781A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 materials based on trichloroazaacene fused-ring aromatic hydrocarbons |
| CN113880974A (en) * | 2021-10-21 | 2022-01-04 | 天津理工大学 | A kind of photocuring liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150246921A1 (en) * | 2012-11-05 | 2015-09-03 | Instytut Chemi Organicznej Polskiej Akademii Nauk | Strongly fluorescent heterocycles and a method for their synthesis |
| CN108976417A (en) * | 2018-06-05 | 2018-12-11 | 广东工业大学 | A kind of covalent organic polymer of triazine ring, electrode material and its preparation method and application |
-
2019
- 2019-01-29 CN CN201910084488.3A patent/CN109867781A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150246921A1 (en) * | 2012-11-05 | 2015-09-03 | Instytut Chemi Organicznej Polskiej Akademii Nauk | Strongly fluorescent heterocycles and a method for their synthesis |
| CN104870447B (en) * | 2012-11-05 | 2017-10-13 | 波兰科学院有机化学研究所 | Fluorescent both heterocyclic and their synthetic method |
| CN108976417A (en) * | 2018-06-05 | 2018-12-11 | 广东工业大学 | A kind of covalent organic polymer of triazine ring, electrode material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| ZHE PENG ET AL: "A strategy for the molecular design of aggregation-induced emission units further modified by substituents", 《MATER.CHEM.FRONT.》 * |
| 王维: "含三嗪环的新型多孔芳香骨架化合物的设计、合成与性质研究", 《中国博士学位论文全文数据库工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 materials based on trichloroazaacene fused-ring aromatic hydrocarbons |
| CN111634909B (en) * | 2020-05-22 | 2021-09-24 | 上海应用技术大学 | Preparation method and application of nitrogen-doped porous carbon materials based on trichloroazaacene fused-ring aromatic hydrocarbons |
| CN113880974A (en) * | 2021-10-21 | 2022-01-04 | 天津理工大学 | A kind of photocuring liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ding et al. | Flexible, mechanically stable, porous self‐standing microfiber network membranes of covalent organic frameworks: preparation method and characterization | |
| CN111001439B (en) | A kind of perylene imide and its composite photocatalytic material, preparation method and application in removing organic pollutants in water | |
| CN110038614B (en) | A kind of cobalt nitride supported nitrogen-doped carbon material and preparation method thereof | |
| CN109749092B (en) | Construction method of [4+3] type two-dimensional organic conjugated framework material based on Schiff base reaction | |
| CN105566589B (en) | Amino functional ordered mesoporous phenolic resin material and preparation method thereof | |
| CN109867781A (en) | A kind of porous conjugated polymer material and preparation method thereof | |
| CN104528688B (en) | Method for preparing porous conductive carbon with rice husks as raw materials | |
| CN109054039B (en) | Synthesis and application of porous covalent organic frameworks with imine structures | |
| CN108855219A (en) | A kind of hollow covalent organic frame cage composite material of yolk-eggshell structural metal@and its preparation and application | |
| CN114874591B (en) | Conductive super-crosslinked conjugated polymer electromagnetic wave absorbing material and preparation method thereof | |
| CN106517178A (en) | Preparing method of expanded graphite composite wrapped by crosslinking carbon fibers | |
| CN113292690A (en) | Phenoxazine two-dimensional covalent organic framework material and preparation method and application thereof | |
| CN110204738B (en) | A kind of covalent organic framework material based on 1,3,5-tris (4-aldehyde pyridyl) triazine and preparation method thereof | |
| CN101781457A (en) | Molecular sieve assembled chiral polyaniline wave absorbing material and preparation method thereof | |
| CN109095450B (en) | High-specific-surface magnetic porous carbon particles and preparation method thereof | |
| CN103922421A (en) | A kind of preparation method of α-Fe2O3 | |
| CN107324311A (en) | A kind of synthetic method of CNT | |
| CN110835413B (en) | Hypercrosslinked Metallopolymers and Their Applications in Suzuki Coupling Reaction | |
| CN109741959A (en) | A kind of graphene/iron-based MOF supercapacitor material and preparation method thereof | |
| CN114524946A (en) | Zirconium-based metal organic framework material and preparation method and application thereof | |
| CN100415363C (en) | Preparation method of resin-based spherical activated carbon with excellent middle molecular adsorption performance | |
| CN104744617B (en) | Five yuan of melon ring bridging acrylate copolymer microballoons and preparation method and application | |
| CN111495320A (en) | Magnetic porous carbon microsphere adsorption material with adjustable aperture and preparation method thereof | |
| CN106467297B (en) | A kind of preparation method of carbon molecular sieve | |
| CN111644161B (en) | A kind of modified fiber ball loaded polyaniline composite material and its preparation method and use |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190611 |
|
| RJ01 | Rejection of invention patent application after publication |