CN104927050A - Imine-bonded covalent organic framework - Google Patents
Imine-bonded covalent organic framework Download PDFInfo
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- CN104927050A CN104927050A CN201510290059.3A CN201510290059A CN104927050A CN 104927050 A CN104927050 A CN 104927050A CN 201510290059 A CN201510290059 A CN 201510290059A CN 104927050 A CN104927050 A CN 104927050A
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- organic frame
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- imine linkage
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- imine
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- 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
- C08G73/02—Polyamines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an imine-bonded covalent organic framework. A preparation method for the covalent organic framework comprises the following steps: adding 2,5-dipropargyl terephthalaldehyde and sym(4-aminophenyl) benzene into a solvent to obtain a mixture, and ultrasonically dispersing the mixture to form a suspension liquid, wherein the solvent is a mixed solvent of sym-trimethylbenzene, n-butyl alcohol and an acetic acid solution; carrying out liquid nitrogen freezing, vacuum-pumping and degassing on the suspension liquid, sealing the suspension liquid, and carrying out a microwave-assisted solvothermal reaction to obtain a crude product; and collecting insoluble substances after centrifuging the crude product, washing and drying the insoluble substances to obtain the imine-bonded covalent organic framework. The preparation method is free of pollution, gentle and simple in reaction conditions, simple in requirements on equipment, and suitable for large-scale industrial production.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of polymer materials, specifically covalency organic frame of connecting of a kind of imine linkage and preparation method thereof.
Background technology
Covalency organic frame (Covalent Organic Frameworks; COFs) being connected by covalent linkage by organic structure ele and formed, is the plane macromolecule that a class has regular vesicular structure, has larger specific surface area, the diversity of structure and regulatable physicochemical property.Literature search through prior art finds, Donglin JIANG in 2012 etc. " Chemical Society Reviews " 41 volume 6010-6022 page deliver Covalent Organic Framework (covalency organic frame).As compared to traditional linear and three-dimensional polymer, covalency organic frame has distinct constitutional features, its atomic shell clear in structure, and mode of connection is clear and definite, and structural unit arrangement is regular, has accurate periodicity; Material crystalline degree is high, can form perfect stratiform and pile up framework.It has huge potential application foreground in novel energy-storing devices field such as lithium cell/super capacitors.
At present, in novel energy-storing devices field such as lithium cell/super capacitors, existing covalent organic frame material can not be satisfied the demand far away, and production method is higher to equipment requirements, and cost is high, also cannot realize suitability for industrialized production.Because need design and synthesis to contain the novel covalent organic frame material of specific skeleton, carry out modification to the electrode of the novel energy-storing devices such as lithium cell/super capacitor, improve specific storage and cycle performance, and then improve chemical property.
Summary of the invention
For defect of the prior art, the object of this invention is to provide covalency organic frame of a kind of imine linkage connection and preparation method thereof.
The present invention is achieved by the following technical solutions:
First aspect, the invention provides the covalency organic frame that a kind of imine linkage connects, shown in the following formula I of structure of described covalency organic frame:
Second aspect, the present invention relates to the preparation method of the covalency organic frame that a kind of imine linkage connects, described preparation method comprises the steps:
Add in solvent by 2,5-diine propoxy-terephthalaldehyde, equal three (4-aminophenyl) benzene, ultrasonic disperse forms suspension; Described solvent is the mixed solvent of sym-trimethylbenzene, propyl carbinol and acetum;
By described suspension through liquid nitrogen freezing-vacuumize-degassed process, sealing, carries out microwave-assisted solvent thermal response, obtains crude product;
After centrifugal for described crude product, collect insolubles, washing, drying, obtain the described covalency organic frame connected containing imine linkage.
Preferably, described 2,5-diine propoxy-terephthalaldehyde (C
14h
10o
4) and equal three (4-aminophenyl) benzene (C
24h
21n
3) mol ratio be 1:1.
Preferably, the volume ratio of described sym-trimethylbenzene, propyl carbinol and acetum is 2:2:1.
Preferably, the concentration of described acetum is 6mol/L.
Preferably, the number of times of described liquid nitrogen freezing-vacuumize-degassed process is at least 3 times.
Preferably, the temperature of described microwave-assisted solvent thermal response is 130 DEG C, and the time is 2h; The present invention is only under the temperature of reaction of 130 DEG C, and the covalency organic frame containing imine linkage connection that high-specific surface area, good crystallinity, stability are high could fully be formed.
Preferably, described microwave-assisted solvent thermal response is specially: react putting into microwave reactor after the suspension sealing after liquid nitrogen freezing-vacuumize-degassed process, the oscillation frequency of described microwave reactor is 2450MHz per second, and output rating is 700W.
Preferably, described washing is specially and uses propyl carbinol and washing with acetone successively.
Compared with prior art, the present invention has following beneficial effect:
1, the imine linkage that method of the present invention synthesizes first containing alkynyl connects covalency organic frame, has high specific surface area, good crystallinity, stability are high, hold out broad prospects in novel energy-storing devices field such as lithium cell/super capacitors;
2, method green non-pollution of the present invention, simple to the requirement of equipment, be applicable to industrialization scale operation.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is that the imine linkage containing alkynyl connects covalency organic framework formula and reaction formula;
Fig. 2 is the electromicroscopic photograph of the connection of the imine linkage containing alkynyl covalency organic frame prepared by embodiment 1;
Fig. 3 is the X ray diffracting spectrum of the connection of the imine linkage containing alkynyl covalency organic frame prepared by embodiment 1;
Fig. 4 is the infared spectrum of the connection of the imine linkage containing alkynyl covalency organic frame prepared by embodiment 1;
Fig. 5 is the covalency organic frame that imine linkage of the present invention connects.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
The imine linkage containing alkynyl that in the present invention prepared by embodiment connects the structural formula of covalency organic frame and reaction formula as shown in Figure 1.
embodiment 1
Present embodiments provide the preparation method of the imine linkage connection covalency organic frame containing alkynyl, step is as follows:
Step one, gets 2, the 5-diine propoxy-terephthalaldehyde (C of 54mg
14h
10o
4), equal three (4-aminophenyl) benzene (C of 78mg
24h
21n
3), add sym-trimethylbenzene/propyl carbinol/6mol/L acetic acid (volume ratio: the 2:2:1) solvent of 5ml, put into the thermal glass reaction tubes of 10ml, ultrasonic disperse forms suspending liquid A in 5 minutes;
Step 2, suspending liquid A, through 3 liquid nitrogen freezings-vacuumize-de-airing step, puts into microwave reactor after sealing, 130 DEG C of thermotonuses 2 hours, obtains crude product B;
Step 3, after centrifugal for crude product B, collect insolubles, respectively cleans 2 times with the propyl carbinol of 2ml and the acetone solvent of 2ml, and drying obtains connecting covalency organic frame containing the imine linkage of alkynyl, as shown in Figure 5.
Implementation result, the imine linkage containing alkynyl prepared by the present embodiment connects the electromicroscopic photograph of covalency organic frame as shown in Figure 2; X-ray diffractogram as shown in Figure 3, shows that it has higher crystalline, wherein in figure, 2.68,4.72,5.46,7.42 degree be covalency organic frame characteristic peak, completely the same with analog calculation result; Infared spectrum as shown in Figure 4, has occurred significantly connecting covalency organic frame alkynyl key characteristic peak containing the imine linkage of alkynyl; Experimentally data are calculated material from adsorption isothermal line had higher specific surface area (1865m by BET theories
2g
-1); Remeasure X-ray diffraction, infrared and specific surface area after at room temperature placing January, do not have considerable change, show to connect covalency organic frame stability containing the imine linkage of alkynyl higher.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. a covalency organic frame for imine linkage connection, is characterized in that, shown in the following structure formula I of structure of described covalency organic frame:
2. a preparation method for the covalency organic frame of imine linkage connection described in claim 1, it is characterized in that, described preparation method comprises the steps:
Add in solvent by 2,5-diine propoxy-terephthalaldehyde, equal three (4-aminophenyl) benzene, ultrasonic disperse forms suspension; Described solvent is the mixed solvent of sym-trimethylbenzene, propyl carbinol and acetum;
By described suspension through liquid nitrogen freezing-vacuumize-degassed process, sealing, carries out microwave-assisted solvent thermal response, obtains crude product;
After centrifugal for described crude product, collect insolubles, washing, drying, obtain the described covalency organic frame connected containing imine linkage.
3. the preparation method of the covalency organic frame of imine linkage connection according to claim 2, it is characterized in that, the mol ratio of described 2,5-diine propoxy-terephthalaldehydes and equal three (4-aminophenyl) benzene is 1:1.
4. the preparation method of the covalency organic frame of imine linkage connection according to claim 2, it is characterized in that, the volume ratio of described sym-trimethylbenzene, propyl carbinol and acetum is 2:2:1.
5. the preparation method of the covalency organic frame that the imine linkage according to claim 2 or 4 connects, it is characterized in that, the concentration of described acetum is 6mol/L.
6. the preparation method of the covalency organic frame of imine linkage connection according to claim 2, it is characterized in that, the number of times of described liquid nitrogen freezing-vacuumize-degassed process is at least 3 times.
7. the preparation method of the covalency organic frame of imine linkage connection according to claim 2, it is characterized in that, the temperature of described microwave-assisted solvent thermal response is 130 DEG C, and the time is 2h.
8. the preparation method of the covalency organic frame of imine linkage connection according to claim 2, it is characterized in that, described microwave-assisted solvent thermal response is specially: react putting into microwave reactor after the suspension sealing after liquid nitrogen freezing-vacuumize-degassed process, the oscillation frequency of described microwave reactor is 2450MHz per second, and output rating is 700W.
9. the preparation method of the covalency organic frame of imine linkage connection according to claim 2, it is characterized in that, described washing is specially uses propyl carbinol and washing with acetone successively.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510290059.3A CN104927050A (en) | 2015-05-29 | 2015-05-29 | Imine-bonded covalent organic framework |
| CN201610270205.0A CN105860061A (en) | 2015-05-29 | 2016-04-27 | Imine bond linked covalent organic framework (COF) |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108117526A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of alkynyl functionalization covalent organic frame material and its synthetic method and application |
| CN108864435A (en) * | 2018-05-07 | 2018-11-23 | 上海交通大学 | A kind of two-dimentional covalently organic frame and its preparation method and application |
| CN109575308A (en) * | 2019-01-02 | 2019-04-05 | 南京大学 | A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method |
| CN109942827A (en) * | 2019-05-22 | 2019-06-28 | 武汉理工大学 | A kind of method that covalent organic frame material is modified |
| CN110669190A (en) * | 2019-09-09 | 2020-01-10 | 东华大学 | Covalent organic framework fluorescent probe for iron ion detection and preparation method thereof |
| CN111607081A (en) * | 2020-06-15 | 2020-09-01 | 四川大学 | Multi-alkylated sub-nanopore COF material and preparation method and application thereof |
| CN115010883A (en) * | 2022-06-17 | 2022-09-06 | 华中农业大学 | Preparation method and product of non-substituted quinoline bridged covalent organic framework |
| CN115010883B (en) * | 2022-06-17 | 2024-05-14 | 华中农业大学 | Preparation method and product of unsubstituted quinoline bridged covalent organic framework |
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| CN111607102B (en) * | 2020-06-30 | 2021-07-23 | 中山大学 | Covalent organic framework material and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005023856A1 (en) * | 2005-05-24 | 2006-11-30 | Basf Ag | Process for the preparation of porous metal-organic frameworks |
| EP2832767A1 (en) * | 2013-07-31 | 2015-02-04 | Fundación Imdea Nanociencia | Method for the Synthesis of Covalent Organic Frameworks |
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2015
- 2015-05-29 CN CN201510290059.3A patent/CN104927050A/en active Pending
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- 2016-04-27 CN CN201610270205.0A patent/CN105860061A/en active Pending
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| CN108117526B (en) * | 2016-11-29 | 2020-11-03 | 中国科学院大连化学物理研究所 | Alkynyl functionalized covalent organic framework material and synthesis method and application thereof |
| CN108117526A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of alkynyl functionalization covalent organic frame material and its synthetic method and application |
| CN108864435A (en) * | 2018-05-07 | 2018-11-23 | 上海交通大学 | A kind of two-dimentional covalently organic frame and its preparation method and application |
| CN109575308A (en) * | 2019-01-02 | 2019-04-05 | 南京大学 | A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method |
| CN109575308B (en) * | 2019-01-02 | 2021-04-27 | 南京大学 | Non-catalytic preparation method of two-dimensional fluorine-containing covalent organic framework compound |
| CN109942827A (en) * | 2019-05-22 | 2019-06-28 | 武汉理工大学 | A kind of method that covalent organic frame material is modified |
| CN109942827B (en) * | 2019-05-22 | 2022-03-01 | 武汉理工大学 | Method for modifying covalent organic framework material |
| CN110669190A (en) * | 2019-09-09 | 2020-01-10 | 东华大学 | Covalent organic framework fluorescent probe for iron ion detection and preparation method thereof |
| CN110669190B (en) * | 2019-09-09 | 2021-11-09 | 东华大学 | Covalent organic framework fluorescent probe for iron ion detection and preparation method thereof |
| CN111607081A (en) * | 2020-06-15 | 2020-09-01 | 四川大学 | Multi-alkylated sub-nanopore COF material and preparation method and application thereof |
| CN111607081B (en) * | 2020-06-15 | 2022-01-07 | 四川大学 | Multi-alkylated sub-nanopore COF material and preparation method and application thereof |
| CN115010883A (en) * | 2022-06-17 | 2022-09-06 | 华中农业大学 | Preparation method and product of non-substituted quinoline bridged covalent organic framework |
| CN115010883B (en) * | 2022-06-17 | 2024-05-14 | 华中农业大学 | Preparation method and product of unsubstituted quinoline bridged covalent organic framework |
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Application publication date: 20150923 |