CN108503828A - A kind of controllable method for preparing of covalent organic porous polymer material different-shape - Google Patents
A kind of controllable method for preparing of covalent organic porous polymer material different-shape Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002861 polymer material Substances 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000006392 deoxygenation reaction Methods 0.000 claims description 9
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- -1 o-dichlorohenzene Chemical compound 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000002360 preparation method Methods 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000010586 diagram Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 101710120757 Pheromone-binding protein 1 Proteins 0.000 description 7
- 101710181935 Phosphate-binding protein PstS 1 Proteins 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 101710205263 Peptidoglycan D,D-transpeptidase MrdA Proteins 0.000 description 6
- 101710120756 Pheromone-binding protein 2 Proteins 0.000 description 6
- 101710181937 Phosphate-binding protein PstS 2 Proteins 0.000 description 6
- 101710116427 Probable peptidoglycan D,D-transpeptidase PenA Proteins 0.000 description 6
- 101710105699 D-alanyl-D-alanine carboxypeptidase DacB Proteins 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- NXUBVBMQRSLBHQ-UHFFFAOYSA-N O1OOCC=C1.C1=CC=CC=C1 Chemical compound O1OOCC=C1.C1=CC=CC=C1 NXUBVBMQRSLBHQ-UHFFFAOYSA-N 0.000 description 4
- 101710146026 Peptidoglycan D,D-transpeptidase FtsI Proteins 0.000 description 4
- 101710181936 Phosphate-binding protein PstS 3 Proteins 0.000 description 4
- 101710202103 Putative beta-lactamase HcpD Proteins 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 101100277015 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) dbp-3 gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical class C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of controllable method for preparing of covalent organic porous polymer material different-shape.Preparation method provided by the present invention is suitable for solvent-thermal process method and synthesizes covalent organic porous polymer material：By changing speed of agitator or reaction density in building-up process, pattern and the controllable material of size can be obtained.The preparation method mild condition, it is easy to operate effectively, universality is good, has a wide range of application, this to expand material application range, to greatest extent realize material utility value have particularly important meaning.
Description
Technical field
The invention belongs to covalent organic porous polymer material fields, and in particular to a kind of covalent organic porous polymer material
Expect the controllable method for preparing of different-shape.
Background technology
Porous material is due to its excellent physico-chemical property and is widely applied and becomes the hot spot that modern science man studies.Altogether
Valence organic porous polymer material (Covalent organic porous polymers, COPs) is as a kind of novel porous
Material causes people due to its larger specific surface area, lower skeletal density, higher thermal stability and chemical stability
Extensive concern, present huge potential answer in photoelectricity, sensing, gas absorption and separation, catalysis and medicine etc.
With value.The study found that covalently chemical composition, pattern and the size of organic porous polymer material have very greatly its performance
Influence.For example, Zhao seminars report hollow spheres material SIOC-COF-7 to the capture of unwanted volatile matter, inclusion or
Efficiency of storage is higher；Granular material Tp-DANT-COF and the Tb-DANT-COF of Bu seminars report are used as lithium-ion cathode
Battery；The platy structure PAF-6 of Zhu seminars report is used for the sustained release etc. of drug.Therefore, the pattern of material is effectively controlled, it is right
The application of material has practical significance.
Solvent-thermal method is a kind of most common method for synthesizing covalent organic porous polymer material.
In the synthesis process, Effective Regulation is carried out to the pattern and size of material by distinct methods, to obtain pattern more
Diversification while the more uniform material of size are beneficial to expand the application range of same material, realize more efficient rational profit
With value.However, the example for the related covalent organic porous polymer material being had been reported that at present, same frame molecular structure is logical
Often only one to two kinds of arbitrary patterns, can not accomplish the controllability of pattern and size, this just significantly limits the application of material.
Invention content
It is an object of the present invention to can in order to solve above-mentioned covalent organic porous polymer material different-shape and size
Standby bottleneck is controlled, a kind of controllable method for preparing of covalent organic porous polymer material different-shape is provided.In the present invention
Preparation method in, propose to control product morphology using mixing speed or reaction density, this method is suitable for solvent-thermal process method
Synthesize COPs, have a wide range of application, it is easy to operate effectively, universality it is good, this application range to expanding material is real to greatest extent
The utility value of existing material has particularly important meaning.
Preparation method provided by the present invention is suitable for solvent-thermal process method and synthesizes COPs, herein only with several schiff bases
For reaction, technical scheme of the present invention is described in further detail.
A kind of controllable method for preparing of covalent organic porous polymer material different-shape, includes the following steps：
In the reaction vessel, two kinds of reaction monomers are added, organic solvent is added and is uniformly mixed, continue to add in above-mentioned system
Enter proper amount of acetic acid aqueous solution to be placed under different temperatures and mixing speed and react after sealing reaction vessel deoxygenation as catalyst
Several days, are filtered by vacuum after reaction, are dried in vacuo after fully being washed with organic solvent and polymerize to get to covalent Porous-Organic
Object material.
The basic operation that can refer to this field and condition, following methods specifically preferred according to the invention and condition：
The reaction vessel is heavy wall pressure bottle.
The organic solvent is mesitylene, toluene, 1,4- dioxane, methyl phenyl ethers anisole, o-dichlorohenzene, n-butanol, ethyl alcohol
In one or any two kinds of mixed solvent.
The single solvent, the volume of single solvent are 1 with the volume ratio of reaction solution total volume:1~1:30.
The mixed solvent, mixed solvent volume ratio are 1:1~100:1, the volume ratio of mixed solvent volume and reaction solution
It is 1:1.1~1:30.
A concentration of 1~the 15mol/L of aqueous acetic acid.
The monomer and aqueous acetic acid molar ratio are 1:10~1:150.
The temperature is 20~150 DEG C.
The speed of agitator is 0~1200rpm.
The time is 0.5~10 day.
Compared with prior art, the positive effect of the present invention is that：
1, the controllable method for preparing of covalent organic porous polymer material different-shape of the present invention, is put forward for the first time and passes through
Change speed of agitator or reaction density, obtains the covalent organic porous polymer material of pattern and size controllably；
2, the method for the invention is suitable for solvent-thermal process method and synthesizes COPs, and universality is good, has a wide range of application；
3, the method for the invention, it is easy to operate pollution-free, it is efficient, this to expand material application range, maximum limit
The utility value of the realization material of degree has particularly important meaning.
Description of the drawings
Attached drawing 1 is PBP and DBP method schematic diagrams prepared by the present invention；
Attached drawing 2 is the scanning electron microscope diagram of the embodiment of the present invention 1；
Attached drawing 3 is the transmission electron microscope figure of the embodiment of the present invention 1；
Attached drawing 4 is the scanning electron microscope diagram of the embodiment of the present invention 2；
Attached drawing 5 is the transmission electron microscope figure of the embodiment of the present invention 2；
Attached drawing 6 is the scanning electron microscope diagram of the embodiment of the present invention 3；
Attached drawing 7 is the transmission electron microscope figure of the embodiment of the present invention 3；
Attached drawing 8 is the scanning electron microscope diagram of the embodiment of the present invention 4；
Attached drawing 9 is the transmission electron microscope figure of the embodiment of the present invention 4；
Attached drawing 10 is the scanning electron microscope diagram of the embodiment of the present invention 5；
Attached drawing 11 is the scanning electron microscope diagram of the embodiment of the present invention 6；
Attached drawing 12 is Fourier transform-infrared spectrogram that the present invention is embodiment 5 and example 6；
Attached drawing 13 is Fourier transform-infrared spectrogram that the present invention is the test of 5 chemical stability of embodiment；
Attached drawing 14 is thermogravimetric curve of the embodiment of the present invention 1 in nitrogen atmosphere；
Attached drawing 15 is thermogravimetric curve of the embodiment of the present invention 5 in nitrogen atmosphere；
Attached drawing 16 is the X-ray powder diffraction spectrogram of the embodiment of the present invention 5；
Attached drawing 17 is the scanning electron microscope diagram of the embodiment of the present invention 8.
Specific implementation mode
The embodiment of the present invention is illustrated below in conjunction with attached drawing, it should be understood that embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.In the following examples, the experimental methods for specific conditions are not specified, presses
More solito and condition, or selected according to product manual.
In solvent thermal reaction, most of schiff base reaction temperature are generally 120 DEG C.Therefore, we are first with the temperature
Under the conditions of reaction for, illustrate the feasibility of preparation method of the present invention.
Attached drawing 1 is PBP and DBP method schematic diagrams prepared by the present invention
Embodiment 1
Be added in heavy wall pressure bottle 2,7- diamino luxuriant and rich with fragrance (125.3mg, 0.6mmol), equal benzene trioxin (64.8mg,
0.4mmol) with a clean magneton, mesitylene (20mL) and 6mol/L acetic acid aqueous solutions (2mL) is then added and mixes equal
It is even.Above-mentioned system is placed in liquid nitrogen, freeze-vacuumizing-and thaws-change operating under nitrogen, deoxygenation in triplicate.Sealing, sets
In 120 DEG C, is reacted 3 days under 0rpm, after reaction, be cooled to room temperature, product vacuum is filtered, filled with acetone, tetrahydrofuran
Divide washing, 120 DEG C are dried in vacuo 10 hours, obtain brown solid powder (181mg, yield 95%), name PBP-1.
Attached drawing 2 is the scanning electron microscope diagram of PBP-1, illustrates that PBP-1 is the smooth regular spherical structure in surface.
Attached drawing 3 is the transmission electron microscope figure of PBP-1, illustrates that PBP-1 is solid spherical structure, average diameter is 1.1 μ
m。
Embodiment 2
Be added in heavy wall pressure bottle 2,7- diamino luxuriant and rich with fragrance (125.3mg, 0.6mmol), equal benzene trioxin (64.8mg,
0.4mmol) with a clean magneton, mesitylene (20mL) and 6mol/L acetic acid aqueous solutions (2mL) is then added and mixes equal
It is even.Above-mentioned system is placed in liquid nitrogen, freeze-vacuumizing-and thaws-change operating under nitrogen, deoxygenation in triplicate.Sealing, sets
In 120 DEG C, is reacted 3 days under 900rpm, after reaction, be cooled to room temperature, product vacuum is filtered, with acetone, tetrahydrofuran
Fully washing, 120 DEG C are dried in vacuo 10 hours, obtain brown solid powder (178mg, yield 93%), name PBP-2.
Attached drawing 4 is the scanning electron microscope diagram of PBP-2, shows that PBP-2 is flattened spherical structure.
Attached drawing 5 is the transmission electron microscope figure of PBP-2, shows that the PBP-2 generated at 900rpm is core shell construction,
Average diameter is 627nm.
It is found by Examples 1 and 2 data comparison, under same frame molecule, is only turned by regulating and controlling stirring in building-up process
The size of speed, you can realize the transformation by medicine ball to nuclear shell ball, that is, realize the regulation and control of pattern and size.
Further, preparation method of the present invention can also regulate and control pattern in the case where controlling mixing speed by temperature.
Embodiment 3
Be added in heavy wall pressure bottle 2,7- diamino luxuriant and rich with fragrance (125.3mg, 0.6mmol), equal benzene trioxin (64.8mg,
0.4mmol) with a clean magneton, mesitylene (20mL) and 6mol/L acetic acid aqueous solutions (2mL) is then added and mixes equal
It is even.Above-mentioned system is placed in liquid nitrogen, freeze-vacuumizing-and thaws-change operating under nitrogen, deoxygenation in triplicate.Sealing, sets
In 80 DEG C, is reacted 3 days under 900rpm, after reaction, be cooled to room temperature, product vacuum is filtered, filled with acetone, tetrahydrofuran
Divide washing, 120 DEG C are dried in vacuo 10 hours, obtain brown solid powder (152mg, yield 80%), name PBP-3.
Attached drawing 6 is the scanning electron microscope diagram of PBP-3.
Attached drawing 7 is the transmission electron microscope figure of PBP-3, shows 80 DEG C, and the PBP-3 under 900rpm is the piece of accumulation, this
Sharp contrast is formed with the spherical structure of PBP-1 and PBP-2.
Embodiment 4
Be added in heavy wall pressure bottle 2,7- diamino luxuriant and rich with fragrance (125.3mg, 0.6mmol), equal benzene trioxin (64.8mg,
0.4mmol) with a clean magneton, mesitylene (20mL) and 6mol/L acetic acid aqueous solutions (2mL) is then added and mixes equal
It is even.Above-mentioned system is placed in liquid nitrogen, freeze-vacuumizing-and thaws-change operating under nitrogen, deoxygenation in triplicate.Sealing, sets
In 28 DEG C, is reacted 3 days under 900rpm, after reaction, be cooled to room temperature, product vacuum is filtered, filled with acetone, tetrahydrofuran
Divide washing, 120 DEG C are dried in vacuo 10 hours, obtain brown solid powder (160mg, yield 84%), name PBP-4.
Attached drawing 8 is the scanning electron microscope diagram of PBP-4.
Attached drawing 9 is the transmission electron microscope figure of PBP-4, shows that PBP-4 is the structure that uniform ball and continuous film coexist,
Average diameter is 437nm.
Compare the result of above-described embodiment 1-4, it is obvious that the covalent Porous-Organic that preparation method of the present invention obtains
Polymer further controls temperature, the different-shape under same chemical reaction and difference may be implemented by controlling mixing speed
The regulation and control of size.For above-described embodiment, transformation of the medicine ball to nuclear shell ball may be implemented in the increase of mixing speed, and
The reduction of temperature can reduce the size of spherical structure.
In order to prove the universality of this preparation method, for we choose another reaction, to realize the regulation and control of structure.
Embodiment 5
In heavy wall pressure bottle be added 1,5- diaminonaphthalenes (23.7mg, 0.15mmol), m-terephthal aldehyde (13.4mg,
0.1mmol) with a clean magneton, mesitylene (5mL) and 6mol/L acetic acid aqueous solutions (0.5mL) is then added and mixes equal
It is even.Above-mentioned system is placed in liquid nitrogen, freeze-vacuumizing-and thaws-change operating under nitrogen, deoxygenation in triplicate.Sealing, sets
In 28 DEG C, is reacted 3 days under 0rpm, after reaction, be cooled to room temperature, product vacuum is filtered, it is abundant with acetone, tetrahydrofuran
Washing, 120 DEG C are dried in vacuo 10 hours, obtain yellow solid powder (26mg, yield 70%), name DBP-1.
Attached drawing 10 is the scanning electron microscope diagram of DBP-1, it can be found that DBP-1 is the accumulation of a variety of disordered structures,
One property and dispersibility are poor.
Embodiment 6
In heavy wall pressure bottle be added 1,5- diaminonaphthalenes (23.7mg, 0.15mmol), m-terephthal aldehyde (13.4mg,
0.1mmol) with a clean magneton, mesitylene (5mL) and 6mol/L acetic acid aqueous solutions (0.5mL) is then added and mixes equal
It is even.Above-mentioned system is placed in liquid nitrogen, freeze-vacuumizing-and thaws-change operating under nitrogen, deoxygenation in triplicate.Sealing, sets
In 28 DEG C, is reacted 3 days under 900rpm, after reaction, be cooled to room temperature, product vacuum is filtered, filled with acetone, tetrahydrofuran
Divide washing, 120 DEG C are dried in vacuo 10 hours, obtain yellow solid powder (28mg, yield 75%), name DBP-2.
Attached drawing 11 is the scanning electron microscope diagram of DBP-2, it can be found that the spherical structure of the uniform dispersions of DBP-2, average
A diameter of 575nm, and generate large stretch of continuous membrane structure.The disordered structure of this and DBP-1 constitute striking contrast,
Also the feasibility of the preparation method is further demonstrated.
Attached drawing 12 is Fourier transform-infrared spectrogram of DBP-1 and DBP-2, wherein 1 represents DBP-1,2 represent DBP-
2.By spectrogram it can be seen that, DBP-1 is obtained under the conditions of two kinds and the position at the peak of DBP-2 and intensity are almost consistent, explanation
Its chemical composition does not have significant change after Morphological control.
Embodiment 7
Chemical stability is tested.DBP-1 is respectively placed in the conventional organic solvents such as water, tetrahydrofuran, methanol, ethyl acetate and salt
Lower 24 hours of the harsh conditions such as acid and sodium hydroxide carry out Fourier transform-examination of infrared spectrum after filtering drying.
Attached drawing 13 is Fourier transform-infrared spectrogram of DBP-1 chemical stabilities test.By being obtained after above-mentioned processing
Material peak position and intensity it is almost consistent, do not decompose, illustrate material have excellent chemical stability.
Attached drawing 14 is thermogravimetric curves of the PBP-1 in nitrogen atmosphere.
Attached drawing 15 is thermogravimetric curves of the DBP-1 in nitrogen atmosphere.
For thermogravimetric curve there are two apparent weightless step, 200 DEG C or so of first step may be due to material itself
Caused by the partial solvent that intrinsic porosity and adsorptivity has been adsorbed is desorbed during heating；With the raising of temperature, go out
Second weightless step is showed, has about started to 400 DEG C, this may be due to caused by the decomposition of carbon skeleton.It is noticeable
It is when temperature is increased to 800 DEG C, still to have 60% or more quality to retain, illustrate that two materials all have excellent thermostabilization
Property.
Attached drawing 16 is the X-ray powder diffraction spectrogram of DBP-1.Without there is apparent diffraction maximum in spectrogram, illustrate DBP-
1 is amorphous material.
Further, preparation method of the present invention also proposes that pattern can be regulated and controled by reaction density.
Embodiment 8
In heavy wall pressure bottle be added 1,5- diaminonaphthalenes (23.7mg, 0.15mmol), m-terephthal aldehyde (13.4mg,
0.1mmol) with a clean magneton, mesitylene (50mL) and 6mol/L acetic acid aqueous solutions (5mL) is then added and mixes equal
It is even.Above-mentioned system is placed in liquid nitrogen, freeze-vacuumizing-and thaws-change operating under nitrogen, deoxygenation in triplicate.Sealing, sets
In 28 DEG C, is reacted 3 days under 0rpm, after reaction, be cooled to room temperature, product vacuum is filtered, it is abundant with acetone, tetrahydrofuran
Washing, 120 DEG C are dried in vacuo 10 hours, obtain yellow solid powder (28mg, yield 75%), name DBP-3.
Attached drawing 17 is the scanning electron microscope diagram of DBP-3, shows that DBP-3 is the flocculent structure of accumulation, compares DBP-1 shapes
Looks, it can be deduced that conclusion：Under other reaction condition same cases, the change of reaction density can also cause the change of pattern.
Finally it should be noted that above-described embodiment is only intended to clearly illustrate made by technical scheme of the present invention lifts
Example, and do not limit the embodiments.Apply protection a kind of covalent organic porous polymer material different-shape can
Preparation Method is controlled, above-mentioned material is not only applicable to, is also applied for the other covalent organic porous polymers of solvent structure
Material.Preparation method of the present invention is easy to operate, pollution-free, efficient, universality is good, this to expand material application range, most
The utility value of the realization material of limits has particularly important meaning.
Claims (10)
1. a kind of controllable method for preparing of covalent organic porous polymer material different-shape is suitable for solvent-thermal process method and synthesizes
Covalent organic porous polymer material, is characterized in that, includes the following steps：
In the reaction vessel, reaction monomers are added, organic solvent is added and is uniformly mixed, appropriate vinegar is continuously added in above-mentioned system
Aqueous acid is placed under different temperatures and mixing speed after sealing reaction vessel deoxygenation as catalyst and reacts several days, instead
It is filtered by vacuum after answering, is dried in vacuo to get to covalent organic porous polymer material after fully being washed with organic solvent.
2. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, the reaction vessel is heavy wall pressure bottle.
3. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, the organic solvent is mesitylene, toluene, Isosorbide-5-Nitrae-dioxane, methyl phenyl ethers anisole, o-dichlorohenzene, n-butanol, ethyl alcohol
In one or any two kinds of mixed solvent.
4. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, the volume of the single solvent is 1 with the volume ratio of reaction solution total volume:1~1:30.
5. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, the mixed solvent volume ratio is 1:1~100:1, the volume ratio of mixed solvent volume and reaction solution is 1:1.1~
1:30。
6. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, a concentration of 1~15mol/L of aqueous acetic acid.
7. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, the monomer and aqueous acetic acid molar ratio are 1:10~1:150.
8. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, the temperature is 20~150 DEG C.
9. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, the speed of agitator is 0~1200rpm.
10. a kind of controllable method for preparing of covalent organic porous polymer material different-shape according to claim 1,
It is characterized in that, the time is 0.5~10 day.
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| CN111019149A (en) * | 2019-12-12 | 2020-04-17 | 武汉理工大学 | COF-5 one-dimensional rod-like crystal material and preparation method thereof |
| CN116284629A (en) * | 2022-12-31 | 2023-06-23 | 安徽工业大学 | Low-cost porous organic polymer material and preparation method thereof |
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| CN105295044A (en) * | 2015-09-17 | 2016-02-03 | 上海交通大学 | Preparation method and application of macroporous covalent organic framework |
| CN106554484A (en) * | 2015-09-25 | 2017-04-05 | 中国科学院大连化学物理研究所 | The preparation of covalent organic frame material and covalent organic frame material and its application |
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