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WO2019033611A1 - Matériau d'ossature organique conjugué de type porphyrine et procédé de préparation associé - Google Patents

Matériau d'ossature organique conjugué de type porphyrine et procédé de préparation associé Download PDF

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Publication number
WO2019033611A1
WO2019033611A1 PCT/CN2017/113584 CN2017113584W WO2019033611A1 WO 2019033611 A1 WO2019033611 A1 WO 2019033611A1 CN 2017113584 W CN2017113584 W CN 2017113584W WO 2019033611 A1 WO2019033611 A1 WO 2019033611A1
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WIPO (PCT)
Prior art keywords
porphyrin
conjugated organic
acid
organic framework
preparation
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Ceased
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PCT/CN2017/113584
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English (en)
Chinese (zh)
Inventor
张强
李博权
张书源
唐城
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Tsinghua University
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Tsinghua University
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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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds

Definitions

  • the invention belongs to the technical field of new material design and preparation, and particularly relates to a preparation method of a porphyrin conjugated organic skeleton material.
  • the synthesis strategy of organic framework materials is based on organic synthesis methodology.
  • the organic small molecules are connected by covalent bonds and extend infinitely in three-dimensional space to obtain regularly arranged framework materials.
  • the organic framework material can easily realize the modulation of its chemical structure, and obtain a material system with regular pore structure, ultra-high specific surface area and rich coordination sites.
  • the object of the present invention is to overcome the difficulty that the general materials are difficult to precisely control, and design a class of porphyrin conjugated organic skeleton materials based on covalent bond connection, thereby realizing precise controllable preparation and chemical structure control of the skeleton materials at the molecular level;
  • the synthesis method of organic framework materials is complex, and it is difficult to realize the bottleneck of large-scale preparation and application.
  • a one-step direct synthesis of porphyrin conjugated organic framework materials is proposed, which can effectively promote the mass production of organic framework materials, and is a practical application of organic framework materials. Offer possible.
  • porphyrin conjugated organic framework material characterized in that the porphyrin conjugated organic framework material is a two-dimensional sheet structure material obtained by linking structural units, and the structural unit is derived from porphyrin and porphyrin. The structural units are all connected by covalent bonds.
  • the inner ring hetero atom of the porphyrin and the porphyrin derivative is one or more of N, O and S.
  • the structural unit is connected in a two-dimensional sheet structure, and the force between the sheets is an intermolecular force.
  • the method for preparing a porphyrin conjugated organic skeleton material according to the present invention comprises the following steps:
  • the five-membered heterocyclic ring is one or more of pyrrole, furan and thiophene; the polyaldehyde is three carbons or more and has two or more aldehyde functional groups.
  • the acid is one or more of formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, trifluorocarboxylic acid, and trifluoroacetic acid;
  • the oxidizing agent is air, One or more of oxygen, nitrobenzene, dinitrobenzene, trinitrobenzene, potassium nitrate, sodium nitrate and ammonium nitrate;
  • the organic solvent is methanol, ethanol, propanol, isopropanol, B Glycol, propylene glycol, glycerol, toluene, ethylbenzene, xylene, trimethylbenzene, dichloromethane, chloroform, tetrachloromethane, dioxane, tetrahydrofuran, N-methylpyrrolidone, N, N-di One or more of methyl formamide and N,N-
  • the porphyrin conjugated organic framework material of the invention realizes the precise design and regulation of the framework material at the molecular level, has the diversity and stability of the chemical structure; the synthesis method is simple and efficient, and the preparation condition is mild.
  • the preparation method greatly simplifies the synthesis route, can effectively realize the mass preparation of the porphyrin conjugated organic skeleton material, obtains the high quality porphyrin conjugated organic skeleton material, has simple process and low cost, and is suitable for engineering enlargement and batch preparation. It can help promote the application of public organic skeleton materials in practical systems, and provide new possibilities for the renewal of material systems.
  • Figure 1 is a scanning electron micrograph of a porphyrin conjugated organic framework material synthesized using pyrrole and terephthalaldehyde as substrates.
  • FIG. 2 is a transmission electron micrograph of a porphyrin conjugated organic skeleton material synthesized using pyrrole and terephthalaldehyde as substrates.
  • Figure 3 is a high resolution transmission electron micrograph of a porphyrin conjugated organic framework material synthesized using pyrrole and terephthalaldehyde as substrates.
  • FIG. 4 is an atomic force microscope photograph of a porphyrin conjugated organic skeleton material synthesized using pyrrole and terephthalaldehyde as substrates.
  • Figure 5 is an infrared spectrum of a porphyrin conjugated organic skeleton material synthesized using pyrrole and terephthalaldehyde as substrates.
  • Fig. 6 is an X-ray diffraction spectrum of a porphyrin conjugated organic skeleton material synthesized using pyrrole and terephthalaldehyde as a substrate.
  • the porphyrin conjugated organic framework material proposed by the invention is a two-dimensional sheet structural material formed by connecting structural units, wherein the structural unit is a porphyrin and a porphyrin derivative, and all structural units are covalently bonded. connection.
  • the inner ring hetero atom of the porphyrin and the porphyrin derivative is one or more of N, O and S.
  • the structural unit is connected in a two-dimensional sheet structure, and the force between the sheets is an intermolecular force.
  • the method for preparing a porphyrin conjugated organic skeleton material comprises the following steps:
  • the oxidizing agent is air, oxygen, nitrobenzene, dinitrogen One or more of benzene, trinitrobenzene, potassium n
  • Example 1 A nitrogen porphyrin conjugated organic skeleton material was obtained by a one-pot method using pyrrole and terephthalaldehyde as substrates.
  • Example 2 A cobalt-coordinated nitrogen porphyrin conjugated organic framework material was obtained by one-pot method using pyrrole and malondialdehyde as substrates.
  • Example 3 A thioporphyrin conjugated organic framework material was obtained by a one-pot method using pyrrole, thiophene and terephthalaldehyde as substrates.
  • Example 4 An oxoporphyrin conjugated organic skeleton material was obtained by a one-pot method using pyrrole, furan and terephthalaldehyde as substrates.
  • Example 5 Iron-complexed nitrogen porphyrin conjugated organic framework material was obtained by one-pot method using pyrrole and adipaldehyde as substrates.
  • adipaldehyde 15.0 g was weighed and added to 200 mL of toluene, stirred, sufficiently dissolved, and transferred to a 500 mL flask. 7.4 mL of pyrrole, 15 mL of trifluoroformic acid, 2.5 mL of trinitrobenzene, and 7.6 g of ferric chloride were added to the flask, and the mixture was uniformly mixed with stirring. The flask was placed in an oil bath, kept stirring, and reacted at 95 ° C for 48 h. The obtained product was subjected to filtration, ethanol washing, and dried to obtain an iron-coordinated nitrogen porphyrin conjugated organic skeleton material. The reaction yield was 95%.
  • Example 6 An oxoporphyrin conjugated organic framework material was obtained by a one-pot method using pyrrole, furan and succinaldehyde as substrates.
  • Example 7 A nitrogen porphyrin conjugated organic framework material was obtained by a one-pot method using pyrrole and biphenyldialdehyde as substrates.
  • Example 8 A thioporphyrin conjugated organic framework material was obtained by one-pot method using pyrrole, thiophene and glutaraldehyde as substrates.
  • Example 9 A nitrogen porphyrin conjugated organic skeleton material was obtained by a one-pot method using pyrrole and 2,4-dimethylterephthalaldehyde as a substrate.

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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)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Catalysts (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un matériau d'ossature organique conjugué de type porphyrine et un procédé de préparation associé, relevant des domaines techniques des nouveaux matériaux et la préparation associée. Ledit matériau est un matériau de structure laminaire bidimensionnel formé par liaison de motifs structuraux. Les motifs structuraux sont la porphyrine et des dérivés de porphyrine, tous les motifs structuraux sont liés par des liaisons covalentes et une force intermoléculaire est présente entre les couches. Dans le procédé de préparation de la présente invention, un hétérocycle à cinq chaînons et un polyaldéhyde dans un rapport donné sont utilisés en tant que réactifs et soumis à une réaction de polymérisation sous l'action d'un acide et d'un agent oxydant, ce qui permet d'obtenir directement le matériau d'ossature organique conjugué de type porphyrine au moyen d'un procédé monotope. La présente invention conçoit un matériau d'ossature dont la structure et les propriétés peuvent être efficacement régulées sur une échelle moléculaire, réalisant une synthèse en une étape d'un matériau d'ossature organique conjugué de type porphyrine. Le procédé est de fonctionnement simple, présente de faibles coûts, peut être facilement agrandi et favorise efficacement la recherche et la préparation de base de matériaux de squelette organique, fournissant ainsi de nouvelles possibilités pour une application pratique de matériaux d'ossature organique.
PCT/CN2017/113584 2017-08-17 2017-11-29 Matériau d'ossature organique conjugué de type porphyrine et procédé de préparation associé Ceased WO2019033611A1 (fr)

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CN201710707614.7A CN107641185B (zh) 2017-08-17 2017-08-17 一种卟啉共轭有机骨架材料及其制备方法
CN201710707614.7 2017-08-17

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CN108164667B (zh) * 2018-02-12 2021-02-26 清华大学 一种卟啉有机骨架膜材料及其制备方法
CN108219160B (zh) * 2018-02-12 2021-02-26 清华大学 一种卟啉有机骨架杂化物及其制备方法
CN109134830B (zh) * 2018-09-26 2021-01-29 台州学院 一种卟啉-苯并噻二唑双功能的共价有机骨架材料及其制备方法和应用
CN109967127B (zh) * 2019-03-06 2021-04-13 清华大学 一种氧析出和氧还原反应双功能催化剂及其制备方法
US11428440B2 (en) * 2019-05-09 2022-08-30 Uchicago Argonne, Llc Method for making porphyrin covalent organic framework-based interface
CN114907535A (zh) * 2022-05-27 2022-08-16 上海屹锂新能源科技有限公司 一种COFs框架材料及其制备方法和应用
CN116693787A (zh) * 2023-06-07 2023-09-05 宁波大学附属人民医院 基于卟啉基并固定Zr离子的多孔有机聚合物的制备方法及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006038823A1 (fr) * 2004-10-08 2006-04-13 Massey University Porphyrines a substitution beta
CN102985465A (zh) * 2010-04-16 2013-03-20 株式会社大赛璐 交联性组合物
CN103228663A (zh) * 2010-09-27 2013-07-31 加利福尼亚大学董事会 传导性开放骨架
CN106432656A (zh) * 2016-04-25 2017-02-22 台州学院 基于半刚性单体新型三维聚卟啉的制备方法

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CN105061776A (zh) * 2015-08-10 2015-11-18 北京工业大学 一种Fe卟啉配体的金属有机骨架材料和制备方法及其应用
CN105348303B (zh) * 2015-11-13 2017-07-21 中国科学院化学研究所 一种卟啉二维共价有机框架共轭聚合物、其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006038823A1 (fr) * 2004-10-08 2006-04-13 Massey University Porphyrines a substitution beta
CN102985465A (zh) * 2010-04-16 2013-03-20 株式会社大赛璐 交联性组合物
CN103228663A (zh) * 2010-09-27 2013-07-31 加利福尼亚大学董事会 传导性开放骨架
CN106432656A (zh) * 2016-04-25 2017-02-22 台州学院 基于半刚性单体新型三维聚卟啉的制备方法

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