CN105061757A - Conjugated microporous polymer adopting ketone-enamine bond connection and preparation method thereof - Google Patents
Conjugated microporous polymer adopting ketone-enamine bond connection and preparation method thereof Download PDFInfo
- Publication number
- CN105061757A CN105061757A CN201510504527.2A CN201510504527A CN105061757A CN 105061757 A CN105061757 A CN 105061757A CN 201510504527 A CN201510504527 A CN 201510504527A CN 105061757 A CN105061757 A CN 105061757A
- Authority
- CN
- China
- Prior art keywords
- microporous polymer
- preparation
- ketone
- conjugated microporous
- bond connection
- 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
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a conjugated microporous polymer adopting ketone-enamine bond connection and a preparation method thereof. The structure of a repetitive unit of the conjugated microporous polymer is shown in the formula (I) (shown in the description). The preparation method of the conjugated microporous polymer adopting the ketone-enamine bond connection comprises the following steps: fully mixing 2, 4, 6-trialdehyde phloroglucinol and an acetic acid aqueous solution under the oxygen-free condition, and adding m-phenylenediamine for reaction, so as to obtain the conjugated microporous polymer adopting ketone-enamine bond connection, of which the repetitive unit has a structure shown in the formula (I) (shown in the description). Compared with the prior art, the conjugated microporous polymer and the preparation method have the benefits as follows: 1, the conjugated microporous polymer adopting the ketone-enamine bond connection, synthesized by the preparation method for the first time has higher specific surface area and high stability, and has wide prospect in the fields of carbon dioxide adsorptive separation and the like; 2, the preparation method is environment-friendly, pollution-free and simple in equipment requirements, thereby being suitable for industrialized large-scale production.
Description
Technical field
The present invention relates to the conjugation microporous polymer that a kind of ketone enamine bonds connects, belong to technical field of polymer materials.
Background technology
Conjugation capillary copolymer material (ConjugatedMicroporousPolymer; CMPs) be that a class has special microvoid structure, the compound of larger specific surface area, the diversity of structure and regulatable physicochemical property.Literature search through prior art finds, JIANG in 2007 etc. " Angew.Chem.Int.Ed. " 46 volume 8574-8578 page report the synthesis of microcellular polyamide epoxy polyamine chloropropane resin (ConjugatedMicroporousPoly (aryleneethynylene) Networks), its specific surface area is up to 834m
2/ g.Due to performance and the potential application foreground of its uniqueness, this kind of poromerics attracts wide attention and studies.With common are compared with machine porous material, CMP has large, the excellent chemical stability of specific surface area, good thermostability, adjustability of structure etc., in gas adsorption, separation, storage etc., there is application prospect widely.
At present, in the fractionation by adsorption field of gas particularly carbonic acid gas, existing porous 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 have the novel conjugation capillary copolymer material of considerable micropore and polar functional group, effectively catch and storing carbon dioxide, and then mitigation of global climate is warmed the thinking providing some brand-new.
Summary of the invention
For defect of the prior art, the object of this invention is to provide conjugation microporous polymer of a kind of ketone enamine bonds connection and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
First aspect, the invention provides the conjugation microporous polymer that a kind of ketone enamine bonds connects, the structure of the repeating unit of described conjugation microporous polymer is such as formula shown in (I):
Second aspect, present invention also offers the preparation method of the conjugated polymers that a kind of ketone ethylene linkage as the aforementioned connects, it comprises the steps:
After 2,4,6-tri-aldehyde radical Phloroglucinol and aqueous acetic acid are fully mixed under anaerobic, add mphenylenediamine and react, the conjugated polymers that the structure obtaining repeating unit connects such as formula the ketone ethylene linkage shown in I.
Preferably, the mol ratio of described 2,4,6-tri-aldehyde radical Phloroglucinols and mphenylenediamine is 1:1.5.
Preferably, the temperature that described 2,4,6-tri-aldehyde radical Phloroglucinols and mphenylenediamine react is 150 DEG C.
Preferably, the concentration of described aqueous acetic acid is 3mol/L.
Compared with prior art, the present invention has following beneficial effect:
1, method of the present invention synthesizes the conjugation microporous polymer that a kind of ketone enamine bonds connects first, has high specific surface area, stability is high, holds out broad prospects in the field such as fractionation by adsorption of carbonic acid gas;
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 the stereoscan photograph of the conjugation microporous polymer of ketone enamine bonds connection prepared by embodiment 1;
Fig. 2 is the infared spectrum of the conjugation microporous polymer of ketone enamine bonds connection 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 preparation method of the conjugation microporous polymer that ketone enamine bonds connects, step is as follows:
Step one, gets 2,4, the 6-tri-aldehyde radical Phloroglucinol (C of 189mg
9h
6o
6), the 3mol/L acetic acid of 3mL, adds the DMF of 20ml, puts into the reaction flask of 50ml, stirring reaction 5 minutes under oxygen free condition;
Step 2, gets the mphenylenediamine (C of 144mg
6h
8n
2) add in reaction flask, 150 DEG C of thermotonuses 72 hours under anaerobic, filter, obtain crude product A;
Step 3, respectively cleans 3 times with the anhydrous propanone of the DMF of 30ml, the tetrahydrofuran (THF) of 30ml and 30ml successively by crude product A, and drying obtains the conjugation microporous polymer that ketone enamine bonds connects.
Implementation result, the electromicroscopic photograph of the conjugation microporous polymer that ketone enamine bonds prepared by the present embodiment connects is as shown in Figure 1; As shown in Figure 2, there is the conjugation microporous polymer carbon-oxygen bond (1623cm that obvious ketone enamine bonds connects in infared spectrum
-1), carbon-carbon bond (1580cm
-1) characteristic peak; Experimentally data are calculated material from adsorption isothermal line had higher specific surface area (691m by BET theories
2g
-1); At room temperature place and remeasure infrared and specific surface area in 7 days later, do not have considerable change, show that the conjugation microporous polymer stability that ketone enamine bonds connects is higher.Experiment through carbon dioxide adsorption shows, under 273K and 1 normal atmosphere, is 10wt% to carbon dioxide adsorption.
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 (5)
1. a conjugation microporous polymer for ketone enamine bonds connection, it is characterized in that, the structure of the repeating unit of described conjugation microporous polymer is such as formula shown in (I):
2. a preparation method for the conjugation microporous polymer of ketone ethylene linkage connection as claimed in claim 1, is characterized in that, comprise the steps:
After 2,4,6-tri-aldehyde radical Phloroglucinol and aqueous acetic acid are fully mixed under anaerobic, add mphenylenediamine and react, the conjugation microporous polymer that the structure obtaining repeating unit connects such as formula the ketone ethylene linkage shown in I.
3. the preparation method of the conjugated polymers of ketone ethylene linkage connection as claimed in claim 2, it is characterized in that, the mol ratio of described 2,4,6-tri-aldehyde radical Phloroglucinols and mphenylenediamine is 1:1.5.
4. the preparation method of the conjugated polymers of ketone ethylene linkage connection as claimed in claim 2, it is characterized in that, the temperature that described 2,4,6-tri-aldehyde radical Phloroglucinols and mphenylenediamine react is 150 DEG C.
5. the preparation method of the conjugated polymers of ketone ethylene linkage connection as claimed in claim 2, it is characterized in that, the concentration of described aqueous acetic acid is 3mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510504527.2A CN105061757A (en) | 2015-08-17 | 2015-08-17 | Conjugated microporous polymer adopting ketone-enamine bond connection and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510504527.2A CN105061757A (en) | 2015-08-17 | 2015-08-17 | Conjugated microporous polymer adopting ketone-enamine bond connection and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105061757A true CN105061757A (en) | 2015-11-18 |
Family
ID=54491300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510504527.2A Pending CN105061757A (en) | 2015-08-17 | 2015-08-17 | Conjugated microporous polymer adopting ketone-enamine bond connection and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105061757A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107684928A (en) * | 2017-09-19 | 2018-02-13 | 华中科技大学 | Contain graphite-phase C3N4The organic porous material of structure, it is prepared and application |
| CN108892759A (en) * | 2018-06-07 | 2018-11-27 | 台州学院 | A kind of conjugation microporous polymer and preparation method thereof |
| CN110358101A (en) * | 2019-07-11 | 2019-10-22 | 首都师范大学 | Covalent organic framework material, the preparation method of capillary electric chromatographic column, method for separating and detecting |
| US10490825B2 (en) | 2016-12-06 | 2019-11-26 | Savannah River Nuclear Solutions, Llc | Non-platinum group oxygen reduction reaction catalysts |
| CN116284629A (en) * | 2022-12-31 | 2023-06-23 | 安徽工业大学 | Low-cost porous organic polymer material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190797A (en) * | 2010-03-08 | 2011-09-21 | 安徽大学 | Quick synthesizing method of triazinyl covalent bond organic framework material with nano pores and application thereof |
| WO2014057504A1 (en) * | 2012-10-12 | 2014-04-17 | Council Of Scientific & Industrial Research | Porous crystalline frameworks, process for the preparation therof and their mechanical delamination to covalent organic nanosheets (cons) |
| WO2014203283A4 (en) * | 2013-06-21 | 2015-02-26 | Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxi Of 1860) | Porphyrin containing covalent organic frameworks and process for the preparation thereof |
-
2015
- 2015-08-17 CN CN201510504527.2A patent/CN105061757A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190797A (en) * | 2010-03-08 | 2011-09-21 | 安徽大学 | Quick synthesizing method of triazinyl covalent bond organic framework material with nano pores and application thereof |
| WO2014057504A1 (en) * | 2012-10-12 | 2014-04-17 | Council Of Scientific & Industrial Research | Porous crystalline frameworks, process for the preparation therof and their mechanical delamination to covalent organic nanosheets (cons) |
| WO2014203283A4 (en) * | 2013-06-21 | 2015-02-26 | Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxi Of 1860) | Porphyrin containing covalent organic frameworks and process for the preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAO WEI ET AL: "The microwave-assisted solvothermal synthesis of a crystalline two-dimensional covalent organic framework with high CO2 capacity", 《CHEMISTRY COMMUNICATION》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10490825B2 (en) | 2016-12-06 | 2019-11-26 | Savannah River Nuclear Solutions, Llc | Non-platinum group oxygen reduction reaction catalysts |
| CN107684928A (en) * | 2017-09-19 | 2018-02-13 | 华中科技大学 | Contain graphite-phase C3N4The organic porous material of structure, it is prepared and application |
| CN108892759A (en) * | 2018-06-07 | 2018-11-27 | 台州学院 | A kind of conjugation microporous polymer and preparation method thereof |
| CN108892759B (en) * | 2018-06-07 | 2020-09-15 | 台州学院 | Conjugated microporous polymer and preparation method thereof |
| CN110358101A (en) * | 2019-07-11 | 2019-10-22 | 首都师范大学 | Covalent organic framework material, the preparation method of capillary electric chromatographic column, method for separating and detecting |
| CN116284629A (en) * | 2022-12-31 | 2023-06-23 | 安徽工业大学 | Low-cost porous organic polymer material and preparation method thereof |
| CN116284629B (en) * | 2022-12-31 | 2024-04-26 | 安徽工业大学 | Low-cost porous organic polymer material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105061757A (en) | Conjugated microporous polymer adopting ketone-enamine bond connection and preparation method thereof | |
| Ning et al. | A novel strategy to enhance the performance of CO2 adsorption separation: grafting hyper-cross-linked polyimide onto composites of UiO-66-NH2 and GO | |
| Li et al. | Metal–organic framework/PVDF composite membranes with high H2 permselectivity synthesized by ammoniation | |
| CN102492117B (en) | Organic conjugated polymer film, its synthetic method and its application | |
| CN110746608B (en) | Nitrogen-containing cyclodextrin polymer porous material and preparation method and application thereof | |
| CN110270232B (en) | Metal organic framework nanosheet composite membrane and preparation method and application thereof | |
| CN113351037B (en) | ZIF-8/PDMS mixed matrix pervaporation membrane and preparation method and application thereof | |
| CN105879704A (en) | Preparation method and application of mixed matrix membrane containing zeolite imidazolate framework material | |
| CN114632430B (en) | Covalent organic polymer material nanosheet composite matrix membrane for gas separation and preparation method thereof | |
| Zhang et al. | Biomimetic material functionalized mixed matrix membranes for enhanced carbon dioxide capture | |
| CN111001394A (en) | Graphene oxide/sodium alginate composite aerogel efficient adsorbent and preparation method and application thereof | |
| CN104258828A (en) | Carbon dioxide adsorbent and preparation method thereof | |
| CN113209841A (en) | Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol and preparation method and application thereof | |
| CN106866741A (en) | A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr) | |
| CN108744991B (en) | Preparation method and application of organic-inorganic mixed matrix membrane doped with zeolite imidazole ester framework porous carbon nano material | |
| Khan et al. | Mixed Dimensional Nanostructure (UiO‐66‐Decorated MWCNT) as a Nanofiller in Mixed‐Matrix Membranes for Enhanced CO2/CH4 Separation | |
| Li et al. | A defects-free ZIF-90/6FDA-Durene membrane based on the hydrogen bonding/covalent bonding interaction for gas separation | |
| CN113385055B (en) | Preparation method of composite material UiO-66@ HNT-based mixed matrix film | |
| Hu et al. | Mixed-linker MOF-303 membranes for pervaporation | |
| Dong et al. | Efficient CO 2 capture by metallo-supramolecular polymers as fillers to fabricate a polymeric blend membrane | |
| CN104399436A (en) | Preparation method of zinc phthalocyanine-pyrene-covalent organic frame/single wall carbon nanotube composite | |
| CN111232957A (en) | Carbon material dispersant, and preparation method and application thereof | |
| CN103570938B (en) | A kind of polymeric amide and its preparation method and application | |
| CN112898584B (en) | Solid-solid supermolecule phase change material and preparation method and application thereof | |
| CN106058034B (en) | Preparation method of (1, 3-disulfide-2-carbonyl) fused naphthalimide/carbon nano tube composite thermoelectric material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151118 |
|
| RJ01 | Rejection of invention patent application after publication |