CN105295044A - Preparation method and application of macroporous covalent organic framework - Google Patents

Preparation method and application of macroporous covalent organic framework Download PDF

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Publication number
CN105295044A
CN105295044A CN201510594825.5A CN201510594825A CN105295044A CN 105295044 A CN105295044 A CN 105295044A CN 201510594825 A CN201510594825 A CN 201510594825A CN 105295044 A CN105295044 A CN 105295044A
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CN
China
Prior art keywords
preparation
macropore
solvent
organic frame
macroporous
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CN201510594825.5A
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Chinese (zh)
Inventor
魏浩
柴双志
张雪
韩洋
顾军辉
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Shanghai Shikun Electric Co ltd
Shanghai Jiaotong University
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Shanghai Shikun Electric Co ltd
Shanghai Jiaotong University
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Priority to CN201510594825.5A priority Critical patent/CN105295044A/en
Publication of CN105295044A publication Critical patent/CN105295044A/en
Priority to CN201610270284.5A priority patent/CN105949463A/en
Pending legal-status Critical Current

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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
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • 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
    • 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
    • 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 provides a preparation method and application of a macroporous covalent organic framework. The structure of the macroporous covalent organic framework is as shown in a formula I; the preparation method of the macroporous covalent organic framework comprises the following steps of adding pyromellitic dianhydride and tris(4-(p-hydroxyphenyl)-phenyl)benzene into solvent, and dispersing to form a suspension, wherein the solvent is a mixed solvent of methylbenzene, dioxane and isoquinoline; performing liquid nitrogen freezing-vacuumizing-degassing treatment on the suspension for at least three times, sealing and carrying out microwave-assisted thermal reaction on the solvent at the temperature of 120DEG C to obtain a crude product; centrifuging the crude product, then collecting insoluble matters, and sequentially washing and drying with tetrahydrofuran and methylbenzene to obtain the macroporous covalent organic framework. The preparation method and the application provided by the invention have the beneficial effects that the method is pollution-free, mild and simple in reaction conditions and simple in requirement on the equipment, and is suitable for industrial large-scale production.

Description

The preparation method of macropore covalency organic frame and purposes
Technical field
The present invention relates to a kind of preparation method and purposes of macropore covalency organic frame, belong to technical field of polymer materials.
Background technology
Covalency organic frame (CovalentOrganicFrameworks; COFs) be the high-molecular porous material that a class has regular vesicular structure, connected by covalent linkage by organo units and formed, its atomic shell clear in structure, mode of connection is clear and definite, structural unit arrangement is regular, has accurate periodicity, larger specific surface area, multifarious structure and regulatable physicochemical property.Literature search through prior art finds, DonglinJIANG in 2012 etc. " ChemicalSocietyReviews " 41 volume 6010-6022 page deliver CovalentOrganicFramework (covalency organic frame).As compared to traditional linear and three-dimensional polymer, covalent organic frame material has stable skeleton structure and permanent nanochannel, and the electrode materials as lithium cell/super capacitor has huge potential and wide application prospect.
At present, covalency organic frame is generally by solvent structure, and need reaction times (3-7 days) of growing very much and higher temperature of reaction (being greater than 120 DEG C), production method is higher to equipment requirements, and cost is high, cannot realize suitability for industrialized production.In addition, in current lithium cell/super capacitor field, covalency organic frame pore size also cannot be satisfied the demand, also need the synthetic method exploring the larger covalent organic frame material in aperture, study the adsorpting characteristic of its specific large pore material and transform the application with storage art at lithium cell/super capacitor homenergic.
Summary of the invention
For defect of the prior art, the object of this invention is to provide a kind of preparation method and purposes of macropore covalency organic frame.The present invention has high-specific surface area, covalency organic frame that stability is high with the preparation of rapid microwave secondary solvent thermal means.
The present invention is achieved by the following technical solutions:
First aspect, the invention provides a kind of macropore covalency organic frame, and its structure is such as formula shown in (I):
I。
Second aspect, present invention also offers a kind of preparation method of macropore covalency organic frame as the aforementioned, it comprises the steps:
Add in solvent by pyromellitic acid anhydride and equal three (4-(p-aminophenyl)-phenyl) benzene, dispersion forms suspension; Described solvent is the mixed solvent of toluene, dioxane and isoquinoline 99.9;
By the liquid nitrogen freezing-vacuumize-degassed process of described suspension through at least 3 times, sealing, at 120 DEG C, microwave-assisted solvent thermal response 2 hours, obtains crude product;
After centrifugal for described crude product, collect insolubles, use tetrahydrofuran (THF) and toluene wash, drying successively, obtain described for macropore covalency organic frame.
Preferably, described solvent is the mixed solvent of toluene, dioxane and isoquinoline 99.9.
Preferably, the volume ratio of described toluene, dioxane and isoquinoline 99.9 is 5:5:1.
Preferably, the mol ratio of described pyromellitic acid anhydride and equal three (4-(p-aminophenyl)-phenyl) benzene is 1.3:1.
Preferably, the concrete operations of described microwave-assisted solvent thermal response are: react putting into microwave reactor (output rating 700W) after the suspension sealing after the liquid nitrogen freezing-vacuumize-degassed process of at least 3 times.
The third aspect, present invention also offers the purposes of a kind of macropore organic frame as the aforementioned in lithium cell or super capacitor.
Compared with prior art, the present invention has following beneficial effect:
1, method of the present invention adopts the synthesis of rapid microwave secondary solvent thermal response for the macropore covalency organic frame of lithium cell/super capacitor first, has high-specific surface area, stability is high, hold out broad prospects in Conversion of energy and storage art;
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 pyromellitic acid anhydride (C 10h 2o 6) structural formula;
Fig. 2 is equal three (4-(p-aminophenyl)-phenyl) benzene (C 42h 33n 3) structural formula;
Fig. 3 is the stereoscan photograph of macropore covalency organic frame prepared by embodiment 1;
Fig. 4 is the XRD figure spectrum of macropore covalency organic frame prepared by embodiment 1.
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.
embodiment 1
Present embodiments provide the microwave-assisted preparation method of the macropore covalency organic frame for lithium cell/super capacitor, step is as follows:
Step one, gets the pyromellitic acid anhydride (C of 28.3mg 10h 2o 6, as shown in Figure 1), equal three (4-(p-aminophenyl)-phenyl) benzene (C of 35.1mg 42h 33n 3, as shown in Figure 2), add toluene/dioxane/isoquinoline 99.9 (volume ratio of toluene, dioxane and isoquinoline 99.9: the 5:5:1) solvent of 2.2ml, put into the thermal glass reaction tubes of 10ml, disperse to form suspending liquid A in 10 minutes;
Step 2, suspending liquid A, through 3 liquid nitrogen freezings-vacuumize-de-airing step, puts into microwave reactor after sealing, 120 degree of thermotonuses 2 hours, obtains crude product B;
Step 3, after centrifugal for crude product B, collect insolubles, respectively clean 3 times with the tetrahydrofuran (THF) of 10ml and the toluene solvant of 10ml, drying obtains the macropore covalency organic frame that can be used for lithium cell/super capacitor.
Implementation result, as shown in Figure 3, the macropore covalency organic frame that the present invention obtains is sheet structure to the stereoscan photograph of the macropore covalency organic frame for lithium cell/super capacitor prepared by the present embodiment; X-ray diffraction result as shown in Figure 4, show respectively corresponding 110/220/310/400 crystal face, and analog calculation result is completely the same, and wherein 110 crystal faces is macropore covalency organic frame characteristic peak for lithium cell/super capacitor; Experimentally data are calculated material from adsorption isothermal line had higher specific surface area (2578m by BET theories 2g -1); Infrared test result is: 1778,1716,1604,1551,1490,1380,1367,1283,1195,1111,990,910,852,800,622,523cm -1all there is characteristic peak, be consistent with bibliographical information experimental value.
Remeasure X-ray diffraction, infrared and specific surface area after at room temperature placing January, do not have considerable change, show that the macropore covalency organic frame stability for lithium cell/super capacitor is 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 (6)

1. a preparation method for macropore covalency organic frame, is characterized in that, comprises the steps:
Add in solvent by pyromellitic acid anhydride and equal three (4-(p-aminophenyl)-phenyl) benzene, dispersion forms suspension; Described solvent is the mixed solvent of toluene, dioxane and isoquinoline 99.9;
By the liquid nitrogen freezing-vacuumize-degassed process of described suspension through at least 3 times, sealing, at 120 DEG C, microwave-assisted solvent thermal response 2 hours, obtains crude product;
After centrifugal for described crude product, collect insolubles, use tetrahydrofuran (THF) and toluene wash, drying successively, obtain described macropore covalency organic frame.
2. the preparation method of macropore covalency organic frame as claimed in claim 1, it is characterized in that, described solvent is the mixed solvent of toluene, dioxane and isoquinoline 99.9.
3. the preparation method of macropore covalency organic frame as claimed in claim 2, it is characterized in that, the volume ratio of described toluene, dioxane and isoquinoline 99.9 is 5:5:1.
4. the preparation method of macropore covalency organic frame as claimed in claim 1, it is characterized in that, the mol ratio of described pyromellitic acid anhydride and equal three (4-(p-aminophenyl)-phenyl) benzene is 1.3:1.
5. the preparation method of macropore covalency organic frame as claimed in claim 1, it is characterized in that, the concrete operations of described microwave-assisted solvent thermal response are: react putting into microwave reactor after the suspension sealing after the liquid nitrogen freezing-vacuumize-degassed process of at least 3 times.
6. one kind as the purposes of macropore organic frame in lithium cell or super capacitor in Claims 1 to 5 as described in any one.
CN201510594825.5A 2015-09-17 2015-09-17 Preparation method and application of macroporous covalent organic framework Pending CN105295044A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328391A (en) * 2016-08-30 2017-01-11 上海交通大学 Preparation method and application of covalent organic framework composite material and combination electrode
CN108503828A (en) * 2018-05-23 2018-09-07 青岛科技大学 A kind of controllable method for preparing of covalent organic porous polymer material different-shape
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
CN109265464A (en) * 2018-09-27 2019-01-25 兰州大学 A kind of chirality covalent organic frame material and its preparation method and application
CN109627441A (en) * 2018-12-14 2019-04-16 中南民族大学 Tubulose covalent organic framework polyimides and preparation method thereof and battery applications
CN113912803A (en) * 2021-08-31 2022-01-11 山西大学 Humidity-sensitive covalent organic framework and preparation method thereof
CN114016068A (en) * 2021-12-14 2022-02-08 齐齐哈尔大学 Covalent organic framework material as hydrogen evolution catalyst and preparation method and application thereof

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CN108976138A (en) * 2018-07-31 2018-12-11 湖南工业大学 A kind of function Triamine monomer and its preparation method and application

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CN103755588B (en) * 2014-01-09 2015-09-23 兰州大学 A kind of synthetic method of covalent organic frame material and application

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328391A (en) * 2016-08-30 2017-01-11 上海交通大学 Preparation method and application of covalent organic framework composite material and combination electrode
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
CN108503828A (en) * 2018-05-23 2018-09-07 青岛科技大学 A kind of controllable method for preparing of covalent organic porous polymer material different-shape
CN109265464A (en) * 2018-09-27 2019-01-25 兰州大学 A kind of chirality covalent organic frame material and its preparation method and application
CN109627441A (en) * 2018-12-14 2019-04-16 中南民族大学 Tubulose covalent organic framework polyimides and preparation method thereof and battery applications
CN109627441B (en) * 2018-12-14 2020-12-01 中南民族大学 Tubular covalent organic framework polyimide, preparation method thereof and battery application
CN113912803A (en) * 2021-08-31 2022-01-11 山西大学 Humidity-sensitive covalent organic framework and preparation method thereof
CN114016068A (en) * 2021-12-14 2022-02-08 齐齐哈尔大学 Covalent organic framework material as hydrogen evolution catalyst and preparation method and application thereof

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Application publication date: 20160203