WO2023065714A1 - Pyrimidine- and cyano group-based bifunctional conjugated microporous polymer, and preparation method therefor and application thereof - Google Patents

Pyrimidine- and cyano group-based bifunctional conjugated microporous polymer, and preparation method therefor and application thereof Download PDF

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WO2023065714A1
WO2023065714A1 PCT/CN2022/102340 CN2022102340W WO2023065714A1 WO 2023065714 A1 WO2023065714 A1 WO 2023065714A1 CN 2022102340 W CN2022102340 W CN 2022102340W WO 2023065714 A1 WO2023065714 A1 WO 2023065714A1
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pyrimidine
preparation
reaction
conjugated microporous
cyano group
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陈飞鸿
林菊琴
任世斌
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浙江时间新材料有限公司
台州学院
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
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    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/124—Copolymers alternating
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    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/143—Side-chains containing nitrogen
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3422—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms conjugated, e.g. PPV-type
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/411—Suzuki reactions
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • the invention relates to the technical field of organic synthesis, in particular to a bifunctional conjugated microporous polymer based on pyrimidine and cyano groups, a preparation method and application thereof.
  • POPs are a new type of polymer materials with high specific surface area and adjustable pore structure. Compared with metal-organic framework materials and inorganic porous materials, POPs have the characteristics of molecular designability, tunable pore structure and function. Based on the structural characteristics of POPs materials, they can be divided into four types, namely, covalent organic framework polymers (COFs), hypercrosslinked polymers (HCPs), self-polymerizing microporous polymers (PIMs) and conjugated microporous polymers ( CMPs).
  • COFs covalent organic framework polymers
  • HCPs hypercrosslinked polymers
  • PIMs self-polymerizing microporous polymers
  • CMPs conjugated microporous polymers
  • CMPs materials as emerging organic porous materials, have attracted the attention of many researchers.
  • the biggest feature of this material is the diversity of its building unit ⁇ -conjugated structures.
  • the building blocks include phenyl, arene, heterocyclic aromatic and macrocycle, and since there are less restrictions on the size, geometry, and functional groups of the building blocks, the porosity of CMPs can be systematically tuned and their structures optimized as needed .
  • the synthetic methods of linear conjugated polymers can be effectively used in the preparation of CMPs, such as Suzuki coupling reaction, Yamamoto reaction, Sonogashira coupling reaction, oxidative coupling reaction, Schiff base reaction, and ring condensation reaction, etc.
  • CMPs materials Based on the diversity of building units and reaction types, CMPs materials provide a valuable platform for the development of novel organic porous materials. It is precisely these characteristics of CMPs materials that make them widely used in gas adsorption, heterogeneous catalysis, electrochemistry, photocatalysis, light-emitting devices, chemical sensors and other fields.
  • the object of the present invention is to provide bifunctional conjugated microporous polymers based on pyrimidine and cyano groups, as well as their preparation methods and applications.
  • the bifunctional conjugated microporous polymer based on pyrimidine and cyano group provided by the invention broadens the types of conjugated microporous polymers; meanwhile, it has excellent catalytic activity for hydrogen production by photolysis of water.
  • the present invention provides a bifunctional conjugated microporous polymer based on pyrimidine and cyano, which has a structural unit shown in formula I:
  • the present invention also provides the preparation method of the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme, comprising the following steps:
  • 2,4,6-trichloropyrimidine and 4-formylphenylboronic acid were subjected to a Suzuki coupling reaction under alkaline conditions to obtain 2,4,6-tris(4-formylphenyl)pyrimidine;
  • the 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile are subjected to a nucleophilic addition and elimination reaction under basic conditions to obtain the pyrimidine and cyano-based Bifunctional Conjugated Microporous Polymers.
  • the molar ratio of 2,4,6-trichloropyrimidine to 4-formylphenylboronic acid is (0.8-1.2):(4-6).
  • the pH value of the alkaline condition is independently 6-8; the alkaline condition is provided by inorganic carbonate.
  • the reaction system of the Suzuki coupling reaction also includes a catalyst; the catalyst includes tetrakis (triphenylphosphine) palladium; the molar ratio of the 2,4,6-trichloropyrimidine and the catalyst is (1.8 ⁇ 2.3 ): (0.25 ⁇ 0.35).
  • the catalyst includes tetrakis (triphenylphosphine) palladium; the molar ratio of the 2,4,6-trichloropyrimidine and the catalyst is (1.8 ⁇ 2.3 ): (0.25 ⁇ 0.35).
  • the reaction system of the Suzuki coupling reaction also includes a reaction solvent;
  • the reaction solvent is a mixed solvent comprising toluene, dehydrated alcohol and water; the volume ratio of toluene, dehydrated alcohol and water in the mixed solvent is 5:1:1.
  • the temperature of the Suzuki coupling reaction is 80-120°C; the holding time is 60-84h.
  • the molar ratio of 2,4,6-tris(4-formylphenyl)pyrimidine to 1,4-benzenediacetonitrile is (1.9-2.2):(2.5-3.5).
  • the temperature of the nucleophilic addition and elimination reaction is 100-150° C.
  • the holding time is 60-84 hours.
  • the present invention also provides the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme or the bifunctional conjugated microporous polymer based on pyrimidine and cyano group prepared by the preparation method described in the above technical scheme.
  • the invention provides a bifunctional conjugated microporous polymer based on pyrimidine and cyano, which has a structural unit represented by formula I.
  • the bifunctional conjugated microporous polymer based on pyrimidine and cyano group of the present invention has carried out the bifunctionalization of pyrimidine and cyano group simultaneously, has widened the material type of conjugated microporous polymer; Simultaneously, because pyrimidine and cyano group
  • the bifunctional conjugated microporous polymer contains pyrimidine group and pyridine group, which makes it have excellent catalytic activity for photolysis of water to produce hydrogen.
  • the present invention also provides the preparation method of the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme, comprising the following steps: combining 2,4,6-trichloropyrimidine and 4-formylbenzene Base boronic acid is carried out Suzuki coupling reaction under basic condition, obtains 2,4,6-three (4-formyl phenyl) pyrimidines; The described 2,4,6-three (4-formyl phenyl) Pyrimidine and 1,4-benzenediacetonitrile undergo nucleophilic addition and elimination reaction under alkaline conditions to obtain the bifunctional conjugated microporous polymer based on pyrimidine and cyano groups.
  • the preparation method provided by the invention has short process flow, simple operation, easy industrialization, and can efficiently prepare bifunctional conjugated microporous polymers based on pyrimidine and cyano groups.
  • the present invention also provides the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme or the bifunctional conjugated microporous polymer based on pyrimidine and cyano group prepared by the preparation method described in the above technical scheme.
  • Fig. 1 is the infrared spectrogram of 2,4,6-three (4-formylphenyl) pyrimidine;
  • Fig. 2 is the NMR spectrum of 2,4,6-three (4-formylphenyl) pyrimidine
  • Fig. 3 is ZLD-CMP, 1,4-phenylenediacetonitrile and 2,4,6-three (4-formylphenyl) pyrimidine infrared spectrum contrast chart;
  • Fig. 4 is the ultraviolet absorption spectrum comparison chart of ZLD-CMP, 1,4-benzenediacetonitrile and 2,4,6-three (4-formylphenyl) pyrimidine;
  • Fig. 5 is the XRD diffraction pattern of ZLD-CMP
  • Figures 6 to 7 are scanning electron microscope images of ZLD-CMP at different magnifications.
  • the present invention provides a bifunctional conjugated microporous polymer based on pyrimidine and cyano, which has a structural unit shown in formula I:
  • the present invention also provides the preparation method of the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme, comprising the following steps:
  • 2,4,6-trichloropyrimidine and 4-formylphenylboronic acid were subjected to a Suzuki coupling reaction under alkaline conditions to obtain 2,4,6-tris(4-formylphenyl)pyrimidine;
  • the 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile are subjected to a nucleophilic addition and elimination reaction under basic conditions to obtain the pyrimidine and cyano-based Bifunctional Conjugated Microporous Polymers.
  • the raw materials used in the present invention are preferably commercially available products.
  • 2,4,6-trichloropyrimidine and 4-formylphenylboronic acid are subjected to Suzuki coupling reaction under alkaline conditions to obtain 2,4,6-tris(4-formylphenyl)pyrimidine.
  • the molar ratio of the 2,4,6-trichloropyrimidine to 4-formylphenylboronic acid is preferably (0.8-1.2):(4-6), more preferably 1:4.5.
  • the pH value of the alkaline condition is preferably 6-8; the alkaline condition is preferably provided by inorganic carbonate; the inorganic carbonate preferably includes potassium carbonate and cesium carbonate; the potassium carbonate The molar ratio of cesium carbonate and cesium carbonate is preferably 1:1.
  • the amount of the inorganic carbonate used is not specifically limited, as long as the pH value of the alkaline condition can be made to be 6-8.
  • the reaction system of the Suzuki coupling reaction preferably also includes a catalyst; the catalyst preferably includes tetrakis (triphenylphosphine) palladium; the molar ratio of the 2,4,6-trichloropyrimidine and the catalyst is preferably (1.8-2.3): (0.25-0.35), more preferably 2:0.3.
  • the reaction system of the Suzuki coupling reaction preferably also includes a reaction medium; the reaction medium is preferably a mixed solvent comprising toluene, absolute ethanol and water; in the mixed solvent, toluene, absolute ethanol and The volume ratio of water is preferably 5:1:1.
  • the ratio of the 2,4,6-trichloropyrimidine to the reaction medium is preferably 2mmol:30mL.
  • the reaction system of the Suzuki coupling reaction includes reaction raw materials, a reagent for adjusting alkaline conditions, a catalyst and a reaction medium.
  • the method of adding the reaction system of the Suzuki coupling reaction preferably includes: mixing the reaction raw materials with the adjusting reagent, catalyst and reaction medium in the alkaline condition in sequence.
  • the present invention before carrying out the Suzuki coupling reaction, preferably also include: degassing the reaction system of the Suzuki coupling reaction, the present invention does not specifically limit the operation of the degassing, adopting methods well known to those skilled in the art The degassing operation is sufficient.
  • the temperature of the Suzuki coupling reaction is preferably 80-120°C, more preferably 100°C; the holding time is preferably 60-84h, more preferably 72h.
  • the Suzuki coupling reaction is preferably carried out under reflux conditions.
  • the present invention preferably further includes: after cooling the coupling reaction feed liquid obtained by the Suzuki coupling reaction to room temperature, extracting the obtained cooled coupling reaction feed liquid; drying the obtained organic phase and rotary evaporation to obtain viscous matter; after redissolving the viscous matter, recrystallization and drying were carried out to obtain 2,4,6-tris(4-formylphenyl)pyrimidine.
  • the extracted reagent preferably includes water and methylene chloride; the volume ratio of the water and methylene chloride is preferably 1:1; the volume ratio of the water and the cooling coupling reaction feed solution is preferably 2 :1.
  • the drying is preferably performed using a desiccant; the desiccant preferably includes anhydrous magnesium sulfate.
  • the reagent for reconstitution preferably includes absolute ethanol; the volume ratio of the viscous substance to the reagent for reconstitution is preferably 1:1.
  • the reagent for recrystallization preferably includes acetone.
  • the drying temperature is preferably 45° C., and the drying time is preferably 12 hours.
  • the present invention After obtaining 2,4,6-tris(4-formylphenyl)pyrimidine, the present invention combines said 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile in alkali Under neutral conditions, a nucleophilic addition and elimination reaction is carried out to obtain the bifunctional conjugated microporous polymer based on pyrimidine and cyano groups.
  • the molar ratio of 2,4,6-tris(4-formylphenyl)pyrimidine to 1,4-benzenediacetonitrile is preferably (1.9 ⁇ 2.2):(2.5 ⁇ 3.5), more preferably 2.0:3.0.
  • the pH value of the alkaline condition is preferably 6 to 8; the alkaline condition is preferably provided by inorganic carbonate; the inorganic carbonate preferably includes cesium carbonate;
  • the amount of acid salt used is not specifically limited, as long as the pH value of the alkaline condition can be made to be 6-8.
  • the reaction system of the nucleophilic addition and elimination reaction preferably further includes a reaction medium, the reaction medium preferably includes a polar solvent, and the polar solvent preferably includes 1,4-dioxane;
  • the ratio of the amount of 2,4,6-tris(4-formylphenyl)pyrimidine to the reaction medium of the nucleophilic addition and elimination reaction is preferably 0.064mmol:2mL.
  • the reaction system of the nucleophilic addition and elimination reaction includes reaction raw materials, catalyst and reaction medium.
  • nucleophilic addition elimination reaction before carrying out nucleophilic addition elimination reaction, preferably also include: the reaction system of described nucleophilic addition elimination reaction is subjected to ultrasonic treatment and degassing successively;
  • the time of described ultrasonic treatment is preferably 2min;
  • the present invention The degassing operation is not specifically limited, and the degassing operation well known to those skilled in the art can be used.
  • the temperature of the nucleophilic addition and elimination reaction is preferably 100-150°C, more preferably 120°C; the holding time is preferably 60-84h, more preferably 72h.
  • the present invention preferably also includes cooling the elimination reaction feed liquid obtained by the nucleophilic addition elimination reaction, solid-liquid separation, and washing and drying the obtained solid to obtain the Bifunctionalized conjugated microporous polymers of pyrimidine and cyano groups.
  • the method of solid-liquid separation preferably includes filtration.
  • the washing preferably includes washing with water and washing with tetrahydrofuran in sequence; the number of washing with water is preferably 3-5 times; the number of washing with tetrahydrofuran is preferably 4-6 times.
  • the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 120° C., and the time is preferably 10 h.
  • the present invention also provides the application of the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical solution in the field of hydrogen production by photolysis of water.
  • the reaction feed liquid is cooled to room temperature, the mixture after the reaction is extracted with distilled water (100mL) and dichloromethane (100mL), the organic phase liquid of the lower floor is obtained after separation, and anhydrous magnesium sulfate is added to dry, and the filtrate is obtained by filtration, and the filtrate is spun After steaming, add a small amount of absolute ethanol to wash out with ultrasonic vibration. Afterwards, recrystallization was carried out with acetone, and the temperature was kept at 45° C. in an oven for 12 hours to obtain an off-white solid. Yield was 0.3735 g, 47.8% yield.
  • Figure 2 is the NMR spectrum of 2,4,6-tris(4-formylphenyl)pyrimidine, as can be seen from Figure 2: ⁇ (ppm) 10.17 (s, 3H) is the peak of H in an aldehyde group ; ⁇ (ppm) 8.15-8.05 (s, 6H) is the peak of H in 2 benzene rings; ⁇ (ppm) 8.52-8.45 (s, 6H) is the peak of H in 3 benzene rings; ⁇ (ppm) 8.20 (s,1H) is the peak of H in 4 pyrimidine rings; other peaks: ⁇ (ppm) 7.26 is the peak of H in CDCl 3 ; ⁇ (ppm) 1.56 is the peak of H in H 2 O.
  • Figure 3 is a comparison chart of infrared spectra of ZLD-CMP, 1,4-benzenediacetonitrile and 2,4,6-tris(4-formylphenyl)pyrimidine, as can be seen from Figure 3: 1,4-benzenediacetonitrile
  • the sharp peak at wavelength 2248.9cm -1 in the infrared spectrum of the cyano group is the characteristic absorption peak of the C ⁇ N bond in the cyano group (between 2260cm -1 and 2210cm -1 ), but this characteristic peak cannot be observed in ZLD-CMP. This is due to the enhanced conjugation degree of the polymer, resulting in a red shift of the characteristic absorption peak of the C ⁇ N bond to a wavelength of 2362.8 cm -1 .
  • Fig. 4 is the ultraviolet absorption spectrum comparison chart of ZLD-CMP, 1,4-benzenediacetonitrile and 2,4,6-three (4-formylphenyl) pyrimidine, as can be seen from Fig. 4: 2,4,6 - Tris(4-formylphenyl)pyrimidine has the strongest absorption peak at a wavelength of 337.5nm. 1,4-Benzenediacetonitrile has the strongest absorption peak at the wavelength of 342.5nm. ZLD-CMP has the strongest absorption peak at the wavelength of 347.5nm to 464.5nm, and has a certain ability to absorb ultraviolet light and visible light. This is because after the reaction of 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile, the degree of conjugation of the system increases, which makes the absorption band shift to the long-wave direction.
  • Figure 5 is the XRD diffraction pattern of ZLD-CMP; it can be seen from Figure 5 that: ZLD-CMP has several sharp peaks in the figure, indicating that ZLD-CMP belongs to crystal materials.
  • Figures 6 to 7 are scanning electron microscope images of ZLD-CMP at different magnifications, and it can be seen from Figures 6 to 7 that ZLD-CMP has a fibrous structure.

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Abstract

The present invention relates to the technical field of organic synthesis, and provides a pyrimidine- and cyano group-based bifunctional conjugated microporous polymer, and a preparation method therefor and an application thereof. The pyrimidine- and cyano group-based bifunctional conjugated microporous polymer in the present invention has a structural unit as shown in the following formula. According to the pyrimidine- and cyano group-based bifunctional conjugated microporous polymer in the present invention, bifunctionalization based on both a pyrimidine and a cyano group is carried out, and substance types of conjugated microporous polymers are increased. Moreover, the pyrimidine- and cyano group-based bifunctional conjugated microporous polymer contains a pyrimidine group and a cyano group, and thus has excellent catalytic activity on photolysis of water to produce hydrogen.

Description

一种基于嘧啶和氰基的双功能化共轭微孔聚合物及其制备方法和应用A bifunctional conjugated microporous polymer based on pyrimidine and cyano group and its preparation method and application 技术领域technical field
本发明涉及有机合成技术领域，尤其涉及一种基于嘧啶和氰基的双功能化共轭微孔聚合物及其制备方法和应用。The invention relates to the technical field of organic synthesis, in particular to a bifunctional conjugated microporous polymer based on pyrimidine and cyano groups, a preparation method and application thereof.
背景技术Background technique
有机多孔聚合物(POPs)是一种比表面积较高且可对孔结构进行调控的新型聚合物材料。与金属有机框架材料和无机多孔材料相比，POPs具有分子的可设计性、孔结构和功能可调控等特点。而基于POPs材料结构特点可分为4种类型，即共价有机骨架聚合物(COFs)、超交联聚合物(HCPs)、自聚微孔聚合物(PIMs)和共轭微孔聚合物(CMPs)。Organic porous polymers (POPs) are a new type of polymer materials with high specific surface area and adjustable pore structure. Compared with metal-organic framework materials and inorganic porous materials, POPs have the characteristics of molecular designability, tunable pore structure and function. Based on the structural characteristics of POPs materials, they can be divided into four types, namely, covalent organic framework polymers (COFs), hypercrosslinked polymers (HCPs), self-polymerizing microporous polymers (PIMs) and conjugated microporous polymers ( CMPs).
而近年来，CMPs材料作为新兴的有机多孔材料受到广大研究者的关注。该材料的最大特点就是其构建单元π-共轭结构的多样性。构建单元包括苯基、芳烃、杂环芳香族和大环，并且由于对构建单元的尺寸、几何构型和官能团的限制性较少，所以可以根据需要系统地调节CMPs的多孔性，优化其结构。线性共轭聚合物的合成方法可以有效地用于CMPs的制备，如Suzuki耦合反应、Yamamoto反应、Sonogashira耦合反应、氧化耦合反应、希夫碱反应和环缩合反应等。In recent years, CMPs materials, as emerging organic porous materials, have attracted the attention of many researchers. The biggest feature of this material is the diversity of its building unit π-conjugated structures. The building blocks include phenyl, arene, heterocyclic aromatic and macrocycle, and since there are less restrictions on the size, geometry, and functional groups of the building blocks, the porosity of CMPs can be systematically tuned and their structures optimized as needed . The synthetic methods of linear conjugated polymers can be effectively used in the preparation of CMPs, such as Suzuki coupling reaction, Yamamoto reaction, Sonogashira coupling reaction, oxidative coupling reaction, Schiff base reaction, and ring condensation reaction, etc.
基于构建单元和反应类型的多样性，CMPs材料为新型有机多孔材料的发展提供了一个宝贵平台。也正是CMPs材料的这些特点，使其在气体吸附、异相催化、电化学、光催化、发光器件、化学传感器等领域具有广泛的应用。Based on the diversity of building units and reaction types, CMPs materials provide a valuable platform for the development of novel organic porous materials. It is precisely these characteristics of CMPs materials that make them widely used in gas adsorption, heterogeneous catalysis, electrochemistry, photocatalysis, light-emitting devices, chemical sensors and other fields.
尽管近年来，CMPs材料在多个领域取得了较大的发展，不同应用的CMPs材料被广泛的研究和制备。但是，CMPs材料的类型有限，限制了其应用。Although in recent years, CMPs materials have achieved great development in many fields, and CMPs materials for different applications have been extensively studied and prepared. However, the types of materials for CMPs are limited, limiting their applications.
发明内容Contents of the invention
有鉴于此，本发明的目的在于提供基于嘧啶和氰基的双功能化共轭微孔聚合物及其制备方法和应用。本发明提供的基于嘧啶和氰基的双功能化共轭微孔聚合物拓宽了共轭微孔聚合物的类型；同时，对光解水产氢具有优异的催化活性。In view of this, the object of the present invention is to provide bifunctional conjugated microporous polymers based on pyrimidine and cyano groups, as well as their preparation methods and applications. The bifunctional conjugated microporous polymer based on pyrimidine and cyano group provided by the invention broadens the types of conjugated microporous polymers; meanwhile, it has excellent catalytic activity for hydrogen production by photolysis of water.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种基于嘧啶和氰基的双功能化共轭微孔聚合物，具有式I所示的结构单元：The present invention provides a bifunctional conjugated microporous polymer based on pyrimidine and cyano, which has a structural unit shown in formula I:
Figure PCTCN2022102340-appb-000001
Figure PCTCN2022102340-appb-000001
本发明还提供了上述技术方案所述的基于嘧啶和氰基的双功能化共轭微孔聚合物的制备方法，包括以下步骤：The present invention also provides the preparation method of the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme, comprising the following steps:
将2,4,6-三氯嘧啶和4-甲酰基苯基硼酸在碱性条件下，进行Suzuki偶联反应，得到2,4,6-三(4-甲酰基苯基)嘧啶；2,4,6-trichloropyrimidine and 4-formylphenylboronic acid were subjected to a Suzuki coupling reaction under alkaline conditions to obtain 2,4,6-tris(4-formylphenyl)pyrimidine;
将所述2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈在碱性条件下，进行亲核加成消去反应，得到所述基于嘧啶和氰基的双功能化共轭微孔聚合物。The 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile are subjected to a nucleophilic addition and elimination reaction under basic conditions to obtain the pyrimidine and cyano-based Bifunctional Conjugated Microporous Polymers.
优选地，所述2,4,6-三氯嘧啶和4-甲酰基苯基硼酸的摩尔比为(0.8～1.2)：(4～6)。Preferably, the molar ratio of 2,4,6-trichloropyrimidine to 4-formylphenylboronic acid is (0.8-1.2):(4-6).
优选地，所述碱性条件的pH值独立地为6～8；所述碱性条件由无机碳酸盐提供。Preferably, the pH value of the alkaline condition is independently 6-8; the alkaline condition is provided by inorganic carbonate.
优选地，所述Suzuki偶联反应的反应体系还包括催化剂；所述催化剂包括四(三苯基膦)钯；所述2,4,6-三氯嘧啶和催化剂的摩尔比为(1.8～2.3)：(0.25～0.35)。Preferably, the reaction system of the Suzuki coupling reaction also includes a catalyst; the catalyst includes tetrakis (triphenylphosphine) palladium; the molar ratio of the 2,4,6-trichloropyrimidine and the catalyst is (1.8～2.3 ): (0.25～0.35).
优选地，所述Suzuki偶联反应的反应体系还包括反应溶剂；所述反应溶剂为包括甲苯、无水乙醇和水的混合溶剂；所述混合溶剂中甲苯、无水乙醇和水的体积比为5：1：1。Preferably, the reaction system of the Suzuki coupling reaction also includes a reaction solvent; the reaction solvent is a mixed solvent comprising toluene, dehydrated alcohol and water; the volume ratio of toluene, dehydrated alcohol and water in the mixed solvent is 5:1:1.
优选地，所述Suzuki偶联反应的温度为80～120℃；保温时间为60～84h。Preferably, the temperature of the Suzuki coupling reaction is 80-120°C; the holding time is 60-84h.
优选地，所述2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈的摩尔比为(1.9～2.2)：(2.5～3.5)。Preferably, the molar ratio of 2,4,6-tris(4-formylphenyl)pyrimidine to 1,4-benzenediacetonitrile is (1.9-2.2):(2.5-3.5).
优选地，所述亲核加成消去反应的温度为100～150℃，保温时间为60～84h。Preferably, the temperature of the nucleophilic addition and elimination reaction is 100-150° C., and the holding time is 60-84 hours.
本发明还提供了上述技术方案所述的基于嘧啶和氰基的双功能化共轭微孔聚合物或上述技术方案所述的制备方法制得的基于嘧啶和氰基的双功能化共轭微孔聚合物在光解水产氢领域中的应用。The present invention also provides the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme or the bifunctional conjugated microporous polymer based on pyrimidine and cyano group prepared by the preparation method described in the above technical scheme. Application of porous polymer in the field of hydrogen production by photolysis of water.
本发明提供一种基于嘧啶和氰基的双功能化共轭微孔聚合物，具有式I所示的结构单元。本发明的基于嘧啶和氰基的双功能化共轭微孔聚合物同时进行了嘧啶和氰基的双功能化，拓宽了共轭微孔聚合物的物质类型；同时，由于嘧啶和氰基的双功能化共轭微孔聚合物含有嘧啶基团和吡啶基团，使其对光解水产氢具有优异的催化活性。The invention provides a bifunctional conjugated microporous polymer based on pyrimidine and cyano, which has a structural unit represented by formula I. The bifunctional conjugated microporous polymer based on pyrimidine and cyano group of the present invention has carried out the bifunctionalization of pyrimidine and cyano group simultaneously, has widened the material type of conjugated microporous polymer; Simultaneously, because pyrimidine and cyano group The bifunctional conjugated microporous polymer contains pyrimidine group and pyridine group, which makes it have excellent catalytic activity for photolysis of water to produce hydrogen.
本发明还提供了上述技术方案所述的基于嘧啶和氰基的双功能化共轭微孔聚合物的制备方法，包括以下步骤：将2,4,6-三氯嘧啶和4-甲酰基苯基硼酸在碱性条件下，进行 Suzuki偶联反应，得到2,4,6-三(4-甲酰基苯基)嘧啶；将所述2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈在碱性条件下，进行亲核加成消去反应，得到所述基于嘧啶和氰基的双功能化共轭微孔聚合物。本发明提供的制备方法工艺流程短、操作简单，易于工业化，且能够高效率制备得到基于嘧啶和氰基的双功能化共轭微孔聚合物。The present invention also provides the preparation method of the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme, comprising the following steps: combining 2,4,6-trichloropyrimidine and 4-formylbenzene Base boronic acid is carried out Suzuki coupling reaction under basic condition, obtains 2,4,6-three (4-formyl phenyl) pyrimidines; The described 2,4,6-three (4-formyl phenyl) Pyrimidine and 1,4-benzenediacetonitrile undergo nucleophilic addition and elimination reaction under alkaline conditions to obtain the bifunctional conjugated microporous polymer based on pyrimidine and cyano groups. The preparation method provided by the invention has short process flow, simple operation, easy industrialization, and can efficiently prepare bifunctional conjugated microporous polymers based on pyrimidine and cyano groups.
本发明还提供了上述技术方案所述的基于嘧啶和氰基的双功能化共轭微孔聚合物或上述技术方案所述的制备方法制得的基于嘧啶和氰基的双功能化共轭微孔聚合物在光解水产氢领域中的应用。由于嘧啶和氰基的双功能化共轭微孔聚合物含有嘧啶基团和吡啶基团，使其对光解水产氢具有优异的催化活性。The present invention also provides the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme or the bifunctional conjugated microporous polymer based on pyrimidine and cyano group prepared by the preparation method described in the above technical scheme. Application of porous polymer in the field of hydrogen production by photolysis of water. Since the bifunctional conjugated microporous polymer of pyrimidine and cyano contains pyrimidine and pyridine groups, it has excellent catalytic activity for photolysis of water to produce hydrogen.
附图说明Description of drawings
图1为2,4,6-三(4-甲酰基苯基)嘧啶的红外光谱图；Fig. 1 is the infrared spectrogram of 2,4,6-three (4-formylphenyl) pyrimidine;
图2为2,4,6-三(4-甲酰基苯基)嘧啶的核磁谱图；Fig. 2 is the NMR spectrum of 2,4,6-three (4-formylphenyl) pyrimidine;
图3为ZLD-CMP、1,4-苯二乙腈和2,4,6-三(4-甲酰基苯基)嘧啶红外光谱对比图；Fig. 3 is ZLD-CMP, 1,4-phenylenediacetonitrile and 2,4,6-three (4-formylphenyl) pyrimidine infrared spectrum contrast chart;
图4为ZLD-CMP、1,4-苯二乙腈和2,4,6-三(4-甲酰基苯基)嘧啶的紫外吸收光谱对比图；Fig. 4 is the ultraviolet absorption spectrum comparison chart of ZLD-CMP, 1,4-benzenediacetonitrile and 2,4,6-three (4-formylphenyl) pyrimidine;
图5为ZLD-CMP的XRD衍射图谱；Fig. 5 is the XRD diffraction pattern of ZLD-CMP;
图6～图7为ZLD-CMP不同倍率下的扫描电镜图。Figures 6 to 7 are scanning electron microscope images of ZLD-CMP at different magnifications.
具体实施方式Detailed ways
本发明提供了一种基于嘧啶和氰基的双功能化共轭微孔聚合物，具有式I所示的结构单元：The present invention provides a bifunctional conjugated microporous polymer based on pyrimidine and cyano, which has a structural unit shown in formula I:
Figure PCTCN2022102340-appb-000002
Figure PCTCN2022102340-appb-000002
本发明还提供了上述技术方案所述的基于嘧啶和氰基的双功能化共轭微孔聚合物的制备方法，包括以下步骤：The present invention also provides the preparation method of the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical scheme, comprising the following steps:
将2,4,6-三氯嘧啶和4-甲酰基苯基硼酸在碱性条件下，进行Suzuki偶联反应，得到2,4,6-三(4-甲酰基苯基)嘧啶；2,4,6-trichloropyrimidine and 4-formylphenylboronic acid were subjected to a Suzuki coupling reaction under alkaline conditions to obtain 2,4,6-tris(4-formylphenyl)pyrimidine;
将所述2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈在碱性条件下，进行亲核加成消去反应，得到所述基于嘧啶和氰基的双功能化共轭微孔聚合物。The 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile are subjected to a nucleophilic addition and elimination reaction under basic conditions to obtain the pyrimidine and cyano-based Bifunctional Conjugated Microporous Polymers.
在本发明中，如无特殊说明，本发明所用原料均优选为市售产品。In the present invention, unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.
本发明将2,4,6-三氯嘧啶和4-甲酰基苯基硼酸在碱性条件下，进行Suzuki偶联反应，得到2,4,6-三(4-甲酰基苯基)嘧啶。In the invention, 2,4,6-trichloropyrimidine and 4-formylphenylboronic acid are subjected to Suzuki coupling reaction under alkaline conditions to obtain 2,4,6-tris(4-formylphenyl)pyrimidine.
在本发明中，所述2,4,6-三氯嘧啶和4-甲酰基苯基硼酸的摩尔比优选为(0.8～1.2)：(4～6)，进一步优选为1：4.5。In the present invention, the molar ratio of the 2,4,6-trichloropyrimidine to 4-formylphenylboronic acid is preferably (0.8-1.2):(4-6), more preferably 1:4.5.
在本发明中，所述碱性条件的pH值优选为6～8；所述碱性条件优选由无机碳酸盐提供；所述无机碳酸盐优选包括碳酸钾和碳酸铯；所述碳酸钾和碳酸铯的摩尔比优选为1：1。本发明对所述无机碳酸盐的用量不做具体限定，只要能够使碱性条件的pH值为6～8即可。In the present invention, the pH value of the alkaline condition is preferably 6-8; the alkaline condition is preferably provided by inorganic carbonate; the inorganic carbonate preferably includes potassium carbonate and cesium carbonate; the potassium carbonate The molar ratio of cesium carbonate and cesium carbonate is preferably 1:1. In the present invention, the amount of the inorganic carbonate used is not specifically limited, as long as the pH value of the alkaline condition can be made to be 6-8.
在本发明中，所述Suzuki偶联反应的反应体系优选还包括催化剂；所述催化剂优选包括四(三苯基膦)钯；所述2,4,6-三氯嘧啶和催化剂的摩尔比优选为(1.8～2.3)：(0.25～0.35)，进一步优选为2：0.3。In the present invention, the reaction system of the Suzuki coupling reaction preferably also includes a catalyst; the catalyst preferably includes tetrakis (triphenylphosphine) palladium; the molar ratio of the 2,4,6-trichloropyrimidine and the catalyst is preferably (1.8-2.3): (0.25-0.35), more preferably 2:0.3.
在本发明中，所述Suzuki偶联反应的反应体系优选还包括反应介质；所述反应介质优选为包括甲苯、无水乙醇和水的混合溶剂；所述混合溶剂中，甲苯、无水乙醇和水的体积比优选为5：1：1。在本发明中，所述2,4,6-三氯嘧啶和反应介质的用量比优选为2mmol：30mL。In the present invention, the reaction system of the Suzuki coupling reaction preferably also includes a reaction medium; the reaction medium is preferably a mixed solvent comprising toluene, absolute ethanol and water; in the mixed solvent, toluene, absolute ethanol and The volume ratio of water is preferably 5:1:1. In the present invention, the ratio of the 2,4,6-trichloropyrimidine to the reaction medium is preferably 2mmol:30mL.
在本发明中，所述Suzuki偶联反应的反应体系包括反应原料、碱性条件的调节试剂、催化剂和反应介质。在本发明中，所述Suzuki偶联反应的反应体系的加入方式优选包括：将反应原料依次和碱性条件的调节试剂、催化剂和反应介质混合。In the present invention, the reaction system of the Suzuki coupling reaction includes reaction raw materials, a reagent for adjusting alkaline conditions, a catalyst and a reaction medium. In the present invention, the method of adding the reaction system of the Suzuki coupling reaction preferably includes: mixing the reaction raw materials with the adjusting reagent, catalyst and reaction medium in the alkaline condition in sequence.
在本发明中，进行Suzuki偶联反应前，优选还包括：将所述Suzuki偶联反应的反应体系进行脱气，本发明对所述脱气的操作不做具体限定，采用本领域技术人员熟知的脱气操作即可。In the present invention, before carrying out the Suzuki coupling reaction, preferably also include: degassing the reaction system of the Suzuki coupling reaction, the present invention does not specifically limit the operation of the degassing, adopting methods well known to those skilled in the art The degassing operation is sufficient.
在本发明中，所述Suzuki偶联反应的温度优选为80～120℃，进一步优选为100℃；保温时间优选为60～84h，进一步优选为72h。在本发明中，所述Suzuki偶联反应优选在回流的条件下进行。In the present invention, the temperature of the Suzuki coupling reaction is preferably 80-120°C, more preferably 100°C; the holding time is preferably 60-84h, more preferably 72h. In the present invention, the Suzuki coupling reaction is preferably carried out under reflux conditions.
在本发明中，所述Suzuki偶联反应的反应式如式1所示：In the present invention, the reaction formula of the Suzuki coupling reaction is shown in formula 1:
Figure PCTCN2022102340-appb-000003
Figure PCTCN2022102340-appb-000003
所述Suzuki偶联反应后，本发明优选还包括：将所述Suzuki偶联反应得到的偶联反应料液冷却至室温后，对所得冷却偶联反应料液进行萃取；将所得有机相进行干燥和旋蒸后，得到粘稠物；将所述粘稠物进行复溶后，进行重结晶和干燥，得到2,4,6-三(4-甲酰基苯基)嘧啶。After the Suzuki coupling reaction, the present invention preferably further includes: after cooling the coupling reaction feed liquid obtained by the Suzuki coupling reaction to room temperature, extracting the obtained cooled coupling reaction feed liquid; drying the obtained organic phase and rotary evaporation to obtain viscous matter; after redissolving the viscous matter, recrystallization and drying were carried out to obtain 2,4,6-tris(4-formylphenyl)pyrimidine.
在本发明中，所述萃取的试剂优选包括水和二氯甲烷；所述水和二氯甲烷的体积比优选为1：1；所述水和冷却偶联反应料液的体积比优选为2：1。在本发明中，所述干燥优选使用干燥剂干燥；所述干燥剂优选包括无水硫酸镁。在本发明中，所述复溶的试剂优选包括无水乙醇；所述粘稠物和复溶的试剂的体积比优选为1：1。在本发明中，所述重结晶的试剂优选包括丙酮。在本发明中，所述干燥的温度优选为45℃，时间优选为12h。In the present invention, the extracted reagent preferably includes water and methylene chloride; the volume ratio of the water and methylene chloride is preferably 1:1; the volume ratio of the water and the cooling coupling reaction feed solution is preferably 2 :1. In the present invention, the drying is preferably performed using a desiccant; the desiccant preferably includes anhydrous magnesium sulfate. In the present invention, the reagent for reconstitution preferably includes absolute ethanol; the volume ratio of the viscous substance to the reagent for reconstitution is preferably 1:1. In the present invention, the reagent for recrystallization preferably includes acetone. In the present invention, the drying temperature is preferably 45° C., and the drying time is preferably 12 hours.
得到2,4,6-三(4-甲酰基苯基)嘧啶后，本发明将所述2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈在碱性条件下，进行亲核加成消去反应，得到所述基于嘧啶和氰基的双功能化共轭微孔聚合物。After obtaining 2,4,6-tris(4-formylphenyl)pyrimidine, the present invention combines said 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile in alkali Under neutral conditions, a nucleophilic addition and elimination reaction is carried out to obtain the bifunctional conjugated microporous polymer based on pyrimidine and cyano groups.
在本发明中，所述2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈的摩尔比优选为(1.9～2.2)：(2.5～3.5)，进一步优选为2.0：3.0。In the present invention, the molar ratio of 2,4,6-tris(4-formylphenyl)pyrimidine to 1,4-benzenediacetonitrile is preferably (1.9~2.2):(2.5~3.5), more preferably 2.0:3.0.
在本发明中，所述碱性条件的pH值优选为6～8；所述碱性条件优选由无机碳酸盐提供；所述无机碳酸盐优选包括碳酸铯；本发明对所述无机碳酸盐的用量不做具体限定，只要能够使碱性条件的pH值为6～8即可。In the present invention, the pH value of the alkaline condition is preferably 6 to 8; the alkaline condition is preferably provided by inorganic carbonate; the inorganic carbonate preferably includes cesium carbonate; The amount of acid salt used is not specifically limited, as long as the pH value of the alkaline condition can be made to be 6-8.
在本发明中，所述亲核加成消去反应的反应体系优选还包括反应介质，所述反应介质优选包括极性溶剂，所述极性溶剂优选包括1,4-二氧六环；所述2,4,6-三(4-甲酰基苯基)嘧啶和亲核加成消去反应的反应介质的用量比优选为0.064mmol：2mL。In the present invention, the reaction system of the nucleophilic addition and elimination reaction preferably further includes a reaction medium, the reaction medium preferably includes a polar solvent, and the polar solvent preferably includes 1,4-dioxane; The ratio of the amount of 2,4,6-tris(4-formylphenyl)pyrimidine to the reaction medium of the nucleophilic addition and elimination reaction is preferably 0.064mmol:2mL.
在本发明中，所述亲核加成消去反应的反应体系包括反应原料、催化剂和反应介质。In the present invention, the reaction system of the nucleophilic addition and elimination reaction includes reaction raw materials, catalyst and reaction medium.
在本发明中，进行亲核加成消去反应前，优选还包括：将所述亲核加成消去反应的反应体系依次进行超声处理和脱气；所述超声处理的时间优选为2min；本发明对所述脱气的操作不做具体限定，采用本领域技术人员熟知的脱气操作即可。In the present invention, before carrying out nucleophilic addition elimination reaction, preferably also include: the reaction system of described nucleophilic addition elimination reaction is subjected to ultrasonic treatment and degassing successively; The time of described ultrasonic treatment is preferably 2min; The present invention The degassing operation is not specifically limited, and the degassing operation well known to those skilled in the art can be used.
在本发明中，所述亲核加成消去反应的温度优选为100～150℃，进一步优选为120℃；保温时间优选为60～84h，进一步优选为72h。In the present invention, the temperature of the nucleophilic addition and elimination reaction is preferably 100-150°C, more preferably 120°C; the holding time is preferably 60-84h, more preferably 72h.
在本发明中，所述亲核加成消去反应的反应式如式2所示：In the present invention, the reaction formula of the nucleophilic addition elimination reaction is shown in formula 2:
Figure PCTCN2022102340-appb-000004
Figure PCTCN2022102340-appb-000004
所述亲核加成消去反应后，本发明优选还包括将所述亲核加成消去反应得到的消去反应料液冷却后，固液分离，将得到的固体进行洗涤和干燥，得到所述基于嘧啶和氰基的双功能化共轭微孔聚合物。After the nucleophilic addition elimination reaction, the present invention preferably also includes cooling the elimination reaction feed liquid obtained by the nucleophilic addition elimination reaction, solid-liquid separation, and washing and drying the obtained solid to obtain the Bifunctionalized conjugated microporous polymers of pyrimidine and cyano groups.
在本发明中，所述固液分离的方式优选包括过滤。在本发明中，所述洗涤优选包括依次进行水洗和四氢呋喃洗；所述水洗的次数优选为3～5次；所述四氢呋喃洗的次数优选为4～6次。在本发明中，所述干燥优选为真空干燥；所述真空干燥的温度优选为120℃，时间优选为10h。In the present invention, the method of solid-liquid separation preferably includes filtration. In the present invention, the washing preferably includes washing with water and washing with tetrahydrofuran in sequence; the number of washing with water is preferably 3-5 times; the number of washing with tetrahydrofuran is preferably 4-6 times. In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 120° C., and the time is preferably 10 h.
本发明还提供了上述技术方案所述的基于嘧啶和氰基的双功能化共轭微孔聚合物在光解水产氢领域中的应用。The present invention also provides the application of the bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in the above technical solution in the field of hydrogen production by photolysis of water.
下面结合实施例对本发明提供的基于嘧啶和氰基的双功能化共轭微孔聚合物及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The bifunctional conjugated microporous polymer based on pyrimidine and cyano group provided by the present invention and its preparation method and application will be described in detail below in conjunction with the examples, but they should not be understood as limiting the protection scope of the present invention.
实施例1Example 1
2,4,6-三(4-甲酰基苯基)嘧啶的制备Preparation of 2,4,6-tris(4-formylphenyl)pyrimidine
用电子天平准确称取2,4,6-三氯嘧啶(0.3750g，2mmol)、4-甲酰基苯基硼酸(1.4020g，9mmol)、碳酸钾(0.7501g，6mmol)、铯碳酸盐(1.9504g，6mmol)、四(三苯基膦)钯(3.5008g，0.3mmol)依次加入到三颈烧瓶中。再向其中依次加入甲苯(25mL)、无水乙醇(5mL)和蒸馏水(5mL)作为反应溶剂。放入磁石后用氮气鼓泡5min，之后在100℃下回流并搅拌反应72h。结束反应，反应料液冷却至室温，用蒸馏水(100mL)和二氯甲烷(100mL)萃取反应后的混合物，分离后得到下层有机相液体，加入无水硫酸镁干燥，过滤得到滤液，将滤液 旋蒸后加入少量的无水乙醇进行超声震荡洗出。之后用丙酮进行重结晶，在烘箱内保持温度45℃放置烘干12h，最终得到灰白色固体。产量为0.3735g，产率为47.8％。Accurately weigh 2,4,6-trichloropyrimidine (0.3750g, 2mmol), 4-formylphenylboronic acid (1.4020g, 9mmol), potassium carbonate (0.7501g, 6mmol), cesium carbonate ( 1.9504g, 6mmol), tetrakis(triphenylphosphine)palladium (3.5008g, 0.3mmol) were successively added into the three-necked flask. Toluene (25 mL), absolute ethanol (5 mL) and distilled water (5 mL) were sequentially added thereto as a reaction solvent. After putting in the magnet, bubble with nitrogen for 5 minutes, then reflux and stir the reaction at 100°C for 72 hours. End the reaction, the reaction feed liquid is cooled to room temperature, the mixture after the reaction is extracted with distilled water (100mL) and dichloromethane (100mL), the organic phase liquid of the lower floor is obtained after separation, and anhydrous magnesium sulfate is added to dry, and the filtrate is obtained by filtration, and the filtrate is spun After steaming, add a small amount of absolute ethanol to wash out with ultrasonic vibration. Afterwards, recrystallization was carried out with acetone, and the temperature was kept at 45° C. in an oven for 12 hours to obtain an off-white solid. Yield was 0.3735 g, 47.8% yield.
图1为2,4,6-三(4-甲酰基苯基)嘧啶的红外光谱图，从图1可以看出：波长在1697.3cm -1处的尖峰为醛基中C＝O键的伸缩振动峰(1710cm -1～1695cm -1)；波长在1566.1cm -1处的尖峰为嘧啶中C＝N键的伸缩振动峰(1580cm -1～1520cm -1)；波长在1207.4cm -1处的尖峰为苯环骨架中的C-C键的弯曲振动峰(1000cm -1～1300cm -1之间)；波长为779.2cm -1处的尖峰是的不饱和C-H键的面外弯曲振动峰(1000cm -1～650cm -1之间)。初步确定说明：2,4,6-三(4-甲酰基苯基)嘧啶成功合成。 Fig. 1 is the infrared spectrogram of 2,4,6-three (4-formylphenyl) pyrimidine, as can be seen from Fig. 1: the sharp peak at the wavelength of 1697.3cm -1 is the expansion and contraction of the C=O bond in the aldehyde group Vibration peak (1710cm -1 ～1695cm -1 ); the peak at 1566.1cm -1 is the stretching vibration peak of C=N bond in pyrimidine (1580cm -1 ～1520cm -1 ); the peak at 1207.4cm -1 The sharp peak is the bending vibration peak of the CC bond in the benzene ring skeleton (between 1000cm -1 and 1300cm -1 ); the peak at the wavelength of 779.2cm -1 is the out-of-plane bending vibration peak of the unsaturated CH bond (1000cm -1 ~650cm -1 ). Preliminary confirmation: 2,4,6-tris(4-formylphenyl)pyrimidine was successfully synthesized.
图2为2,4,6-三(4-甲酰基苯基)嘧啶的核磁谱图，从图2可以看出：δ(ppm)10.17(s,3H)为1处醛基中H的峰；δ(ppm)8.15-8.05(s,6H)为2处苯环中H的峰；δ(ppm)8.52-8.45(s,6H)为3处苯环中H的峰；δ(ppm)8.20(s,1H)为4处嘧啶环中H的峰；其余峰：δ(ppm)7.26为CDCl 3中H的峰；δ(ppm)1.56为H 2O中H的峰。 Figure 2 is the NMR spectrum of 2,4,6-tris(4-formylphenyl)pyrimidine, as can be seen from Figure 2: δ (ppm) 10.17 (s, 3H) is the peak of H in an aldehyde group ; δ (ppm) 8.15-8.05 (s, 6H) is the peak of H in 2 benzene rings; δ (ppm) 8.52-8.45 (s, 6H) is the peak of H in 3 benzene rings; δ (ppm) 8.20 (s,1H) is the peak of H in 4 pyrimidine rings; other peaks: δ (ppm) 7.26 is the peak of H in CDCl 3 ; δ (ppm) 1.56 is the peak of H in H 2 O.
基于嘧啶和氰基的双功能化共轭微孔聚合物(ZLD-CMP)的制备：Preparation of bifunctional conjugated microporous polymer (ZLD-CMP) based on pyrimidine and cyano groups:
在反应釜中加入2,4,6-三(4-甲酰基苯基)嘧啶(25.18mg，0.064mmol)，1,4-苯二乙腈(14.99mg，0.096mmol)，1,4-二氧六环(2mL)和碳酸铯(124mg，0.575mmol)。将混合物用超声处理2min，之后用氮气鼓泡5min，在真空下密封，并在120℃下加热反应72h。待反应后反应釜冷却至室温后离心取出沉淀物，并用H 2O和四氢呋喃(THF)洗涤数次，并在120℃下真空干燥10h，得到黄色粉末，分离产率为82％。 Add 2,4,6-tris(4-formylphenyl)pyrimidine (25.18mg, 0.064mmol), 1,4-benzenediacetonitrile (14.99mg, 0.096mmol), 1,4-dioxo Hexacyclic (2 mL) and cesium carbonate (124 mg, 0.575 mmol). The mixture was sonicated for 2 min, then bubbled with nitrogen for 5 min, sealed under vacuum, and the reaction was heated at 120 °C for 72 h. After the reaction, the reactor was cooled to room temperature, and the precipitate was taken out by centrifugation, washed several times with H 2 O and tetrahydrofuran (THF), and vacuum-dried at 120° C. for 10 h to obtain a yellow powder with an isolated yield of 82%.
图3为ZLD-CMP、1,4-苯二乙腈和2,4,6-三(4-甲酰基苯基)嘧啶红外光谱对比图，从图3可以看出：1,4-苯二乙腈的红外光谱图中波长为2248.9cm -1的尖峰为氰基中C≡N键的特征吸收峰(2260cm -1～2210cm -1之间)，而在ZLD-CMP中观察不到此特征峰，这是由于聚合物共轭程度增强，导致C≡N键的特征吸收峰红移至波长为2362.8cm -1的位置。而对比2,4,6-三(4-甲酰基苯基)嘧啶和ZLD-CMP的红外光谱图，可以看出原来位于1697.3cm -1的醛基中C＝O键的伸缩振动峰消失，这是由于2,4,6-三(4-甲酰基苯基)嘧啶上的醛基被其他基团所取代，因此可以证明该化合物为ZLD-CMP。 Figure 3 is a comparison chart of infrared spectra of ZLD-CMP, 1,4-benzenediacetonitrile and 2,4,6-tris(4-formylphenyl)pyrimidine, as can be seen from Figure 3: 1,4-benzenediacetonitrile The sharp peak at wavelength 2248.9cm -1 in the infrared spectrum of the cyano group is the characteristic absorption peak of the C≡N bond in the cyano group (between 2260cm -1 and 2210cm -1 ), but this characteristic peak cannot be observed in ZLD-CMP. This is due to the enhanced conjugation degree of the polymer, resulting in a red shift of the characteristic absorption peak of the C≡N bond to a wavelength of 2362.8 cm -1 . And comparing the infrared spectra of 2,4,6-tris(4-formylphenyl)pyrimidine and ZLD-CMP, it can be seen that the stretching vibration peak of the C=O bond in the aldehyde group originally located at 1697.3cm -1 disappeared, This is because the aldehyde group on 2,4,6-tris(4-formylphenyl)pyrimidine is replaced by other groups, so it can be proved that this compound is ZLD-CMP.
图4为ZLD-CMP、1,4-苯二乙腈和2,4,6-三(4-甲酰基苯基)嘧啶的紫外吸收光谱对比图，从图4可以看出：2,4,6-三(4-甲酰基苯基)嘧啶在波长为337.5nm时出现最强吸收峰。1,4-苯二乙腈在波长为342.5nm时出现最强吸收峰。ZLD-CMP在波长为347.5nm～464.5nm时出现最强吸收峰，有一定的紫外光和可见光吸收能力。这是由于2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈反应之后，体系的共轭程度增大，使得吸收带向长波方向移动。Fig. 4 is the ultraviolet absorption spectrum comparison chart of ZLD-CMP, 1,4-benzenediacetonitrile and 2,4,6-three (4-formylphenyl) pyrimidine, as can be seen from Fig. 4: 2,4,6 - Tris(4-formylphenyl)pyrimidine has the strongest absorption peak at a wavelength of 337.5nm. 1,4-Benzenediacetonitrile has the strongest absorption peak at the wavelength of 342.5nm. ZLD-CMP has the strongest absorption peak at the wavelength of 347.5nm to 464.5nm, and has a certain ability to absorb ultraviolet light and visible light. This is because after the reaction of 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile, the degree of conjugation of the system increases, which makes the absorption band shift to the long-wave direction.
图5为ZLD-CMP的XRD衍射图谱；从图5可以看出：ZLD-CMP在图中存在若干个尖峰，说明ZLD-CMP属于晶体类材料。Figure 5 is the XRD diffraction pattern of ZLD-CMP; it can be seen from Figure 5 that: ZLD-CMP has several sharp peaks in the figure, indicating that ZLD-CMP belongs to crystal materials.
图6～图7为ZLD-CMP不同倍率下的扫描电镜图，从图6～7可以看出：ZLD-CMP为纤维状结构。Figures 6 to 7 are scanning electron microscope images of ZLD-CMP at different magnifications, and it can be seen from Figures 6 to 7 that ZLD-CMP has a fibrous structure.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种基于嘧啶和氰基的双功能化共轭微孔聚合物，其特征在于，具有式I所示的结构单元：A bifunctional conjugated microporous polymer based on pyrimidine and cyano, characterized in that it has a structural unit shown in formula I:
    Figure PCTCN2022102340-appb-100001
    Figure PCTCN2022102340-appb-100001
  2. 权利要求1所述的基于嘧啶和氰基的双功能化共轭微孔聚合物的制备方法，包括以下步骤：The preparation method of the bifunctional conjugated microporous polymer based on pyrimidine and cyano according to claim 1, comprising the following steps:
    将2,4,6-三氯嘧啶和4-甲酰基苯基硼酸在碱性条件下，进行Suzuki偶联反应，得到2,4,6-三(4-甲酰基苯基)嘧啶；2,4,6-trichloropyrimidine and 4-formylphenylboronic acid were subjected to a Suzuki coupling reaction under alkaline conditions to obtain 2,4,6-tris(4-formylphenyl)pyrimidine;
    将所述2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈在碱性条件下，进行亲核加成消去反应，得到所述基于嘧啶和氰基的双功能化共轭微孔聚合物。The 2,4,6-tris(4-formylphenyl)pyrimidine and 1,4-benzenediacetonitrile are subjected to a nucleophilic addition and elimination reaction under basic conditions to obtain the pyrimidine and cyano-based Bifunctional Conjugated Microporous Polymers.
  3. 根据权利要求2所述的制备方法，其特征在于，所述2,4,6-三氯嘧啶和4-甲酰基苯基硼酸的摩尔比为(0.8～1.2)：(4～6)。The preparation method according to claim 2, characterized in that the molar ratio of the 2,4,6-trichloropyrimidine to 4-formylphenylboronic acid is (0.8-1.2): (4-6).
  4. 根据权利要求2所述的制备方法，其特征在于，所述碱性条件的pH值独立地为6～8；所述碱性条件由无机碳酸盐提供。The preparation method according to claim 2, characterized in that, the pH value of the alkaline condition is independently 6-8; the alkaline condition is provided by an inorganic carbonate.
  5. 根据权利要求2所述的制备方法，其特征在于，所述Suzuki偶联反应的反应体系还包括催化剂；所述催化剂包括四(三苯基膦)钯；所述2,4,6-三氯嘧啶和催化剂的摩尔比为(1.8～2.3)：(0.25～0.35)。The preparation method according to claim 2, wherein the reaction system of the Suzuki coupling reaction also includes a catalyst; the catalyst includes tetrakis (triphenylphosphine) palladium; the 2,4,6-trichloro The molar ratio of pyrimidine and catalyst is (1.8-2.3): (0.25-0.35).
  6. 根据权利要求2所述的制备方法，其特征在于，所述Suzuki偶联反应的反应体系还包括反应溶剂；所述反应溶剂为包括甲苯、无水乙醇和水的混合溶剂；所述混合溶剂中甲苯、无水乙醇和水的体积比为5：1：1。preparation method according to claim 2, is characterized in that, the reaction system of described Suzuki coupling reaction also comprises reaction solvent; Described reaction solvent is the mixed solvent that comprises toluene, dehydrated alcohol and water; In described mixed solvent The volume ratio of toluene, absolute ethanol and water is 5:1:1.
  7. 根据权利要求2～6任一项所述的制备方法，其特征在于，所述Suzuki偶联反应的温度为80～120℃；保温时间为60～84h。The preparation method according to any one of claims 2-6, characterized in that, the temperature of the Suzuki coupling reaction is 80-120°C; the holding time is 60-84h.
  8. 根据权利要求2所述的制备方法，其特征在于，所述2,4,6-三(4-甲酰基苯基)嘧啶和1,4-苯二乙腈的摩尔比为(1.9～2.2)：(2.5～3.5)。The preparation method according to claim 2, characterized in that the molar ratio of the 2,4,6-tris(4-formylphenyl)pyrimidine to 1,4-benzenediacetonitrile is (1.9-2.2): (2.5～3.5).
  9. 根据权利要求2或8所述的制备方法，其特征在于，所述亲核加成消去反应的温度为100～150℃，保温时间为60～84h。The preparation method according to claim 2 or 8, characterized in that the temperature of the nucleophilic addition and elimination reaction is 100-150° C., and the holding time is 60-84 hours.
  10. 权利要求1所述的基于嘧啶和氰基的双功能化共轭微孔聚合物或权利要求2～9任一项所述的制备方法制得的基于嘧啶和氰基的双功能化共轭微孔聚合物在光解水产氢领域中的应用。The bifunctional conjugated microporous polymer based on pyrimidine and cyano group described in claim 1 or the bifunctional conjugated microporous polymer based on pyrimidine and cyano group prepared by the preparation method described in any one of claims 2 to 9 Application of porous polymer in the field of hydrogen production by photolysis of water.
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