Phthalocyanine-based metal organic framework catalyst as well as synthesis method and application thereof
Through the design and application of phthalocyanine-based metal organic framework catalyst, the problems of difficulty in separation and recovery of existing catalysts and unstable catalytic activity in the reaction of CO2 and alkylene oxides have been solved, efficient catalytic conversion and multiple recycling of catalysts have been achieved, and industrial production of cyclic carbonates and the development of carbonized polymers have been promoted.
Patent Information
- Application Number
- CN202510099628.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-22
- Publication Date
- 2025-05-02
AI Technical Summary
When the existing catalysts catalyze the reaction of CO2 with alkylene oxide to prepare cyclic carbonate, they have problems such as difficulty in separation and recovery, unstable catalytic activity and harsh reaction conditions, which limit their industrial application.
The phthalocyanine-based metal organic framework catalyst is used to combine the hexafluorophthalocyanine metal coordination compound with tetrahydroamine or tetrahydrophenol to form a catalyst with a porous structure, and the catalyst is efficiently separated, recovered and reused by methods such as freezing-thawing cycle and solvent exchange washing.
The efficient conversion of catalytic CO2 and polycyclic alkylene oxides was achieved to prepare polycyclic carbonate, and solid-state fluorescence-free carbonated polymer points were prepared by reaction with polyamines, which improved the recycling performance and catalytic activity of the catalyst.
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Abstract
Description
Technical Field
[0001] The invention relates to a method for synthesizing (di)polycyclic carbonate, and in particular to a phthalocyanine-based metal organic framework catalyst and a synthesis method and application thereof. Background Art
[0002] CO2 is stable, non-toxic, non-flammable, renewable, cheap and readily available. It is the main greenhouse gas and the most abundant C1 resource on Earth. A large amount of basic research is devoted to designing and developing methods that can efficiently capture, store and utilize CO2. Therefore, whether from the perspective of environmental protection or resource utilization, exploring effective ways to rationally utilize CO2 is of great significance.
[0003] Although many CO2 chemical fixation methods for preparing high-value-added chemicals have been reported in the literature, there are still few that have truly achieved industrial production (T. Sakakura, et al. Chemical Review, 2007, 107, 2365). Among them, the catalytic synthesis of cyclic carbonates using CO2 and epoxides as raw materials is particularly important, and related products are widely used, covering polar aprotic solvents, lithium battery electrolytes, fine chemicals and pharmaceutical intermediates (Michael North, et al. Green Chem., 2021, 23, 77-118). The researchers used CO2 to react with multifunctional epoxy monomers to prepare multifunctional cyclic carbonates, and prepared solid-state fluorescent carbonized polymer dots with polyamines by a one-step solvothermal method, and realized the construction of light-emitting diodes or LEDs (Zhang Xinghong et al., Adv. Opti cal Mater. 2019, 7, 1900659).
[0004] At present, the use of catalysts to catalyze carbon dioxide and epoxides to synthesize cyclic carbonates has been widely studied (Chemical Review, 1996, 96, 951, Current Opinion in Green and Sustainable Chemistry 2020, 26: 100365). At present, the catalytic system mainly includes quaternary ammonium salts, alkali metal salts, transition metal complexes and ionic liquids, as well as molecular sieves and organometallic coordination polymers (Green Chem., 2015, 17, 108-122, Catal. Sci. Technol., 2014, 4, 1513-1528, Coordination Chemistry Reviews 492 (2023) 215277). The above catalytic systems are either metal coordination compounds or organic compounds, and are all small molecule catalytic systems. The related synthesis and purification processes are complex and cumbersome, and the synthesis conditions are harsh. Due to their small molecular weight, related catalysts often have good solubility, and the catalytic synthesis process is mostly a homogeneous system. After the reaction is completed, the catalyst is easily mixed with the cyclic carbonate, and it is relatively difficult to separate, recover or remove the catalyst, and the reusability performance is poor.
[0005] Phthalocyanine metal coordination compounds, with the metal center acting as a Lewis acid and the phthalocyanine base part acting as a Lewis base, have catalytic activity. In recent years, it has played an important role in catalyzing the reaction of CO2 and alkylene oxide to prepare cyclic carbonates (Journal of Organometallic Chemistry 950 (2021) 121979, Materials Today Communications 41 (2024) 110875). This type of catalyst can catalyze various types of alkylene oxides to participate in the reaction, and the catalytic effect is better. However, it also has the problem of relatively difficult separation, recovery or removal, which easily causes catalyst residues, which is not conducive to recycling and reducing costs.
[0006] As a porous coordination polymer, metal organic framework materials have adjustable pore size, large specific surface area, good thermal stability and excellent catalytic activity. They have been used in the field of catalytic synthesis of cyclic carbonates, such as UIO-66, Mg-MOF-74, ZIF-8 and MIL-101 (Catal. Sci. Technol., 2014, 4, 1513-1528; M. Zhu, et al. Catalysis Communications, 2013, 32, 36). However, the above metal organic framework materials still have the disadvantages of difficult preparation and purification, harsh catalytic reaction conditions (usually requiring high temperature and high pressure), and low catalytic activity; therefore, it is urgent to prepare related metal organic framework catalytic systems with high catalytic activity, easy separation and purification, and efficient catalytic conversion under mild conditions. In addition, we hope to be able to prepare related metal organic framework catalytic systems to achieve efficient catalytic conversion of CO2 and multifunctional epoxy monomers to prepare multifunctional cyclic carbonates, and later use them to prepare carbonized polymer dots with high fluorescence quantum yield. Summary of the invention
[0007] In view of the above-mentioned problems existing in the prior art and in view of the high efficiency of phthalocyanine metal coordination compounds and metal organic framework nanomaterials in catalytic synthesis, the present invention provides a method for synthesizing a type of phthalocyanine-based metal organic framework catalyst and its application in catalyzing the reaction of CO2 and polycyclic alkylene oxides to prepare polycyclic carbonates, and preparing solid-state fluorescent carbonized polymer dots with polyamine compounds through a solvothermal method, which can not only achieve efficient catalytic conversion, but also achieve efficient separation, recovery and reuse of the catalyst.
[0008] To achieve the above purpose, the technical scheme adopted by the present invention is: dissolving hexafluorophthalocyanine metal coordination compound and tetraamine or tetraphenol into a solvent, adding an acid binding agent such as potassium carbonate or triethylamine, removing dissolved oxygen through three freeze-thaw cycles, and heating the reaction for a certain period of time, and then filtering and solvent exchange washing and other purification methods to obtain a phthalocyanine-based metal organic framework nanomaterial catalyst. Using hexadecyltrimethylammonium bromide as a co-catalyst or not, catalyzing carbon dioxide and di- or poly-epoxyalkylene to synthesize (di) polycyclic carbonates, recovering the catalyst by dissolving, precipitating, filtering or centrifuging and then washing, and recycling the catalyst for multiple times for catalytic conversion.
[0009] The phthalocyanine-based metal organic framework catalyst of the present invention is formed by a nitrogen-containing Lewis base phthalocyanine-based composite Lewis acid metal center as an organic complex and a tetraamine or tetraphenol containing an electric-rich amino group or hydroxyl group through a defluorination coupling reaction. The structure presents a porous structure and can achieve catalytic conversion efficiently. The structure of the phthalocyanine-based metal organic framework catalyst is as follows:
[0010]
[0011] Where: M is the central metal ion, selected from Fe 2+ , Cu 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ ; X is selected from NH, O, and the bridging unit (polyamine or polyphenol) bonded to the metal coordination compound is selected from: phenylene tetramine, 2,3,6,7-tetraaminonaphthalene, 3,3',4,4'-tetraaminobiphenyl, anthracene-2,3,6,7-tetramine, 1,1'-biphenyl-3,3',4,4'-tetrol, 2,3,6,7-tetrahydroxynaphthalene, 2,3,6,7-tetraol-anthracene.
[0012] The present invention also provides a method for synthesizing the above-mentioned phthalocyanine-based metal organic framework catalyst, which comprises: dissolving a hexadecafluorophthalocyanine metal coordination compound and a tetrahydric amine or a tetrahydric phenol in a solvent, adding an acid binding agent, removing dissolved oxygen through a freeze-thaw cycle, and heating to 70-120° C. to react for 48-144 hours, and then obtaining a phthalocyanine-based metal organic framework nanomaterial catalyst through purification methods such as filtration and solvent exchange washing.
[0013] Furthermore, in the above technical scheme, the hexadecafluorophthalocyanine metal coordination compound is selected from hexadecafluorophthalocyanine zinc (II), hexadecafluorophthalocyanine cobalt (II), hexadecafluorophthalocyanine iron (II), hexadecafluorophthalocyanine copper (II), hexadecafluorophthalocyanine nickel (II), and the heating reaction temperature is selected from 70-120°C.
[0014] The above synthesis method is expressed as follows using a chemical reaction formula:
[0015]
[0016] The invention also describes the use of the phthalocyanine-based metal organic framework catalyst in catalyzing the synthesis of (di)polycyclic carbonates from carbon dioxide and di- or poly-epoxyalkylenes.
[0017] The reaction equation is expressed as:
[0018]
[0019] Furthermore, in the above technical solution, the catalytic system further comprises a co-catalyst, and the co-catalyst is selected from hexadecyltrimethylammonium bromide;
[0020] Furthermore, in the above technical solution, the alkylene oxide is ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether or pentaerythritol glycidyl ether.
[0021] Furthermore, in the above technical solution, the mass ratio of the phthalocyanine-based metal organic framework catalyst to the epoxide is 1:50-300; the pressure of the carbon dioxide is 0.5-5MPa; the reaction temperature is 60-150°C; and the reaction time is 5-48 hours.
[0022] Furthermore, in the above technical scheme, after the catalytic reaction is completed, the mixed system is recovered by solvent dissolution and centrifuged or filtered, the precipitate is fully washed with the dissolving solvent, and the precipitated solid is recovered after drying; the solid after drying continues to act as a metal organic framework catalyst and the catalytic synthesis is repeated multiple times.
[0023] In addition, the present invention also describes that the (two) polycyclic carbonates synthesized by the phthalocyanine-based metal organic framework catalyst can be further reacted with polyamine compounds to prepare carbonized polymer dots capable of solid-state fluorescence by a one-step water / solvothermal method. The reaction equation is expressed as:
[0024]
[0025] Furthermore, in the above technical solution, the polyamine is selected from polyetherimide, tetraethylenepentamine, melamine, diethylenetriamine, ethylenediamine, o-phenylenediamine, m-phenylenediamine, butanediamine, hexamethylenediamine, octanediamine, 1,12-dodecanediamine and the like.
[0026] Furthermore, in the above technical solution, the reaction temperature is selected from 80-160° C., the reaction solvent is selected from water, ethanol, acetonitrile, chloroform and acetone, and the reaction time is selected from 12-72 h.
[0027] The present invention aims to provide a method for synthesizing a phthalocyanine-based metal organic framework catalyst, and apply the method to catalyze the reaction of carbon dioxide (CO2) and (two) polycyclic alkylene oxides to prepare (two) polycyclic carbonates, and further prepare solid-state fluorescent carbonized polymer dots with polyamine compounds through a one-step water / solvothermal method. The phthalocyanine-based metal organic framework catalyst can be recovered by dissolving, precipitating, filtering or centrifuging the reaction mixture for catalyzing the synthesis of cyclic carbonates, and then washing, and the catalyst can be recycled multiple times.
[0028] The present invention provides a method for synthesizing a phthalocyanine-based metal organic framework catalyst. By adjusting the type of the coordinated metal center of the reaction precursor hexafluorophthalocyanine metal coordination compound and the type of the bridging polyamine or polyphenol, a phthalocyanine-based metal organic framework catalyst with rich structure can be obtained. The structure is different and the catalytic activity is adjustable. The catalyst can be applied to the reaction of carbon dioxide (CO2) and (two) polycyclic alkylene oxides to prepare (two) polycyclic carbonates. By regulating the pressure ratio of the alkylene oxide to the catalyst and CO2, the conversion rate of the polycyclic carbonate can be effectively regulated. The system can also realize the efficient separation, recovery and reuse of the catalyst. After recovery, the catalyst can still effectively catalyze the conversion, which has many advantages. The (two) polycyclic carbonates obtained by catalytic synthesis can be further prepared with polyamine compounds through a one-step water / solvothermal method to prepare carbonized polymer dots that can emit solid fluorescence, which has important guiding significance for the development of light-emitting diodes or LEDs.
[0029] Advantageous Effects of the Invention
[0030] 1. The synthesis method of the phthalocyanine-based metal organic framework catalyst of the present invention is relatively simple. By adjusting the type of the coordinated metal center of the reaction precursor hexadecafluorophthalocyanine metal coordination compound and the type of the bridging polyamine or polyphenol, a catalyst system with rich structures can be obtained, with different structures and adjustable catalytic activity;
[0031] 2. Phthalocyanine-based metal organic framework catalysts can be used to react carbon dioxide (CO2) and (di)polycyclic alkylene oxides to prepare (di)polycyclic carbonates, and further react with polyamine compounds to prepare solid-state fluorescent carbonized polymer dots through a one-step water / solvothermal method; the existing catalytic conversion technology mainly uses metal coordination compounds or organic compounds as catalysts, all of which are small molecule catalytic systems, and the related synthesis and purification processes are complicated and cumbersome, and the synthesis conditions are harsh; and the related catalysts often have good solubility. After the catalysis is completed, it is relatively difficult to separate, recover or remove the catalyst; some catalytic systems are metal organic framework materials, but most of them still have the disadvantages of difficult preparation and purification, harsh catalytic reaction conditions (usually requiring high temperature and high pressure), and low catalytic activity;
[0032] 3. Epoxides are abundant in variety and inexpensive. At the same time, epoxides are easy to chemically modify, which is conducive to the functionalization of materials. Using phthalocyanine-based metal organic framework catalysts to catalyze the reaction of polycyclic alkylene oxides with CO2 can obtain structurally rich polycyclic carbonates.
[0033] 4. The phthalocyanine-based metal organic framework catalyst can be used to catalyze the reaction of some oxirane and CO2 to obtain polycyclic carbonates, which can be further reacted with polyamine compounds through a one-step water / solvothermal method to prepare carbonized polymer dots that can emit solid fluorescence, which has important guiding significance for the development of light-emitting diodes or LEDs. The catalytic system is not only highly efficient and recyclable, but also can effectively fix CO2, effectively promoting green chemistry. BRIEF DESCRIPTION OF THE DRAWINGS
[0034] Figure 1 FT-IR image of the zinc phthalocyanine organic framework catalyst obtained in Example 1;
[0035] Figure 2 The XRD pattern of the zinc phthalocyanine organic framework catalyst obtained in Example 1;
[0036] Figure 3 This is a SEM image of the zinc phthalocyanine organic framework catalyst obtained in Example 1;
[0037] Figure 4 The tetracyclic carbonate obtained in Example 5 1 H NMR spectrum;
[0038] Figure 5 is the XRD pattern of carbonized polymer dots obtained in Example 32;
[0039] Figure 6 This is the fluorescence image of the carbonized polymer dots obtained in Example 32. DETAILED DESCRIPTION
[0040] The present invention will be further described below in conjunction with specific implementations. The structures of the phthalocyanine-based metal organic framework catalysts obtained in the following examples of the present invention are characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy analysis, and the structures of the four-membered cyclic carbonates are characterized by 1 H NMR was used for determination, and the structure and fluorescence properties of carbonized Pdots were characterized by X-ray diffraction (XRD) and fluorescence spectrometer.
[0041] The technical solution of the present invention is described below through specific examples, which only provide some catalysts and catalytic conversion examples.
[0042] The structures and numbers of some of the prepared catalysts are as follows:
[0043]
[0044]
[0045] Example 1: Preparation of Cat.1
[0046] 0.01mmol hexafluorophthalocyanine zinc (II) and 0.02mmol pyridine were dissolved and dispersed in 2mL dioxane, ultrasonically dispersed for 10 minutes, and then 100 microliters of triethylamine were added. The solution was frozen-thawed and vacuumed and filled with nitrogen for 3-5 times to fully remove the dissolved oxygen, and finally nitrogen was introduced to react in a nitrogen atmosphere, and the reaction was carried out at 90°C for 96 hours. After the reaction was completed, solid precipitates appeared in the reaction system, which were collected by high-speed centrifugation, and repeatedly washed with acetone, chloroform and tetrahydrofuran for multiple times, and vacuum dried to obtain Cat.1.
[0047] Example 2: Preparation of Cat.2
[0048] 0.01mmol hexafluorophthalocyanine zinc (II) and 0.02mmol 2,3,6,7-tetraaminonaphthalene were dissolved and dispersed in 2mL dioxane, ultrasonically dispersed for 10 minutes, and then 100 microliters of triethylamine were added. The solution was frozen-thawed and vacuumed and filled with nitrogen for 3-5 times to fully remove the dissolved oxygen, and finally nitrogen was introduced to react in a nitrogen atmosphere, and the reaction was carried out at 90°C for 96 hours. After the reaction was completed, solid precipitates appeared in the reaction system, which were collected by high-speed centrifugation, and repeatedly washed with acetone, chloroform and tetrahydrofuran for many times, and vacuum dried to obtain Cat.2.
[0049] Example 3: Preparation of Cat.3
[0050] 0.01mmol hexafluorophthalocyanine zinc (II) and 0.02mmol anthracene-2,3,6,7-tetramine were dissolved and dispersed in 2mL dioxane, ultrasonically dispersed for 10 minutes, and then 100 microliters of triethylamine were added. The solution was frozen-thawed and vacuumed and filled with nitrogen for 3-5 times to fully remove the dissolved oxygen, and finally nitrogen was introduced to allow the reaction to proceed in a nitrogen atmosphere. The reaction was carried out at 90°C for 96 hours. After the reaction was completed, solid precipitates appeared in the reaction system, which were collected by high-speed centrifugation, and repeatedly washed with acetone, chloroform and tetrahydrofuran for multiple times, and vacuum dried to obtain Cat.3.
[0051] Example 4: Preparation of Cat.4
[0052] 0.01mmol hexafluorophthalocyanine zinc (II) and 0.02mmol 1,1'-biphenyl-3,3',4,4'-tetrol were dissolved and dispersed in 2mL dioxane, ultrasonically dispersed for 10 minutes, and then 100 microliters of triethylamine were added. The solution was frozen-thawed and vacuumed and filled with nitrogen for 3-5 times to fully remove the dissolved oxygen, and finally nitrogen was introduced to allow the reaction to proceed in a nitrogen atmosphere. The reaction was carried out at 90°C for 96 hours. After the reaction was completed, a solid precipitate appeared in the reaction system, which was collected by high-speed centrifugation, and repeatedly washed with acetone, chloroform and tetrahydrofuran for several times, and then vacuum dried to obtain Cat.4.
[0053] Example 5: Preparation of Cat.5
[0054] 0.01mmol hexafluorophthalocyanine zinc (II) and 0.02mmol 2,3,6,7-tetrahydroxynaphthalene were dissolved and dispersed in 2mL dioxane, ultrasonically dispersed for 10 minutes, and then 100 microliters of triethylamine were added. The solution was frozen-thawed and vacuumed and filled with nitrogen for 3-5 times to fully remove the dissolved oxygen, and finally nitrogen was introduced to allow the reaction to proceed in a nitrogen atmosphere. The reaction was carried out at 90°C for 96 hours. After the reaction was completed, solid precipitates appeared in the reaction system, which were collected by high-speed centrifugation, and repeatedly washed with acetone, chloroform and tetrahydrofuran for multiple times, and vacuum dried to obtain Cat.5.
[0055] Example 6: Preparation of Cat.6
[0056] 0.01mmol hexafluorophthalocyanine zinc (II) and 0.02mmol 2,3,6,7-tetraol-anthracene were dissolved and dispersed in 2mL dioxane, ultrasonically dispersed for 10 minutes, and then 100 microliters of triethylamine were added. The solution was frozen-thawed and vacuumed and filled with nitrogen for 3-5 times to fully remove the dissolved oxygen, and finally nitrogen was introduced to allow the reaction to proceed in a nitrogen atmosphere. The reaction was carried out at 90°C for 96 hours. After the reaction was completed, solid precipitates appeared in the reaction system, which were collected by high-speed centrifugation, and repeatedly washed with acetone, chloroform and tetrahydrofuran for multiple times, and vacuum dried to obtain Cat.6.
[0057] Examples 7-10: Preparation of Cat.7-Cat.10
[0058] Similar to the synthesis of Cat.1-6, the hexadecafluorophthalocyanine metal coordination compound was replaced by hexadecafluorophthalocyanine zinc (II) to hexadecafluorophthalocyanine cobalt (II).
[0059] Examples 11-14: Preparation of Cat.11-Cat.14
[0060] Similar to the synthesis of Cat.1-6, the hexadecafluorophthalocyanine metal coordination compound was replaced by hexadecafluorophthalocyanine zinc (II) to hexadecafluorophthalocyanine iron (II).
[0061] Examples 15-18: Preparation of Cat.15-Cat.18
[0062] Similar to the synthesis of Cat.1-6, the hexadecafluorophthalocyanine metal coordination compound was replaced by hexadecafluorophthalocyanine zinc (II) to hexadecafluorophthalocyanine nickel (II).
[0063] Condition optimization test
[0064] Application Example 1-24: Synthesis of (di)polycyclic carbonates by catalyzing carbon dioxide and di- or poly-epoxyalkylenes using a phthalocyanine-based metal organic framework catalyst in combination with or without cetyltrimethylammonium bromide (CTAB).
[0065]
[0066] Application Example 1: In a nitrogen-filled glove box or a dry double-row pipe system, a certain amount of Cat.1, trimethylolpropane triglycidyl ether (TMPEG) and an appropriate amount of hexadecyl trimethylammonium bromide are added to a dry high-pressure reactor. After the feeding is completed, the mixture is shaken evenly to allow the monomer and catalyst to be completely dissolved and dispersed under stirring. Then 3MPa CO2 is charged, and the mixture is placed in a 120°C oil bath pot under magnetic stirring for 48 hours. After the reaction is completed, a small amount of crude product is taken for nuclear magnetic resonance testing to calculate the conversion rate. Subsequently, the crude product is dissolved in dichloromethane, filtered to recover the catalyst, and the solution is passed through an alkaline alumina column and spin-dried to obtain a ternary cyclic carbonate. The results are shown in Table 2.
[0067] Application Example 2: In a nitrogen-filled glove box or a dry double-row pipe system, a certain amount of Cat.1 and trimethylolpropane triglycidyl ether are added to a dry high-pressure reactor. After the feeding is completed, the mixture is shaken evenly to allow the monomer and catalyst to be completely dissolved and dispersed under stirring. Then 3MPa CO2 is charged, and the mixture is placed in a 120°C oil bath pot under magnetic stirring for 48 hours. After the reaction is completed, a small amount of crude product is taken for nuclear magnetic resonance testing to calculate the conversion rate. The crude product is then dissolved in dichloromethane and filtered to recover the catalyst, and the solution is passed through an alkaline alumina column and spin-dried to obtain no ternary cyclic carbonate. The results are shown in Table 2.
[0068] Application Example 3-4: The synthesis and post-treatment are similar to those of Application Example 1, except that the ratio of the phthalocyanine-based metal organic framework catalyst, the co-catalyst and the polycyclic epoxide is changed. The relevant results are shown in Table 2.
[0069] Application Examples 5-6: The synthesis and post-treatment are similar to those of Application Example 1, except that the type of polycyclic epoxide is changed from trimethylolpropane triglycidyl ether (TMPEG) to pentaerythritol glycidyl ether (PETGE) or ethylene glycol diglycidyl ether (EGDEG).
[0070] Application Examples 7, 9-24: The synthesis and post-treatment are similar to those of Application Example 1, except that the type of phthalocyanine-based metal organic framework catalyst is changed.
[0071] Application Example 8: The synthesis and post-treatment are similar to those of Application Example 7, except that no co-catalyst is added.
[0072] The relevant results of the above application examples are as follows.
[0073] Catalytic conversion results using different catalytic systemsa
[0074]
[0075]
[0076] a No additional solvent was added in the reaction 1-24; b [polycyclic epoxide]:[phthalocyanine metal organic framework catalyst]:[cocatalyst] molar ratio; c Phthalocyanine metal organic framework catalysts; d Promoter catalyst; e CO2 pressure is 3MPa; f The conversion of polycyclic epoxides was determined by H-NMR spectroscopy.
[0077] Application Example 25: Catalyst Recovery and Reuse
[0078] After the synthesis is completed, the reaction mixture is redissolved with a large amount of dichloromethane and filtered to retain the insoluble matter. During the filtration process, the precipitate (insoluble matter) is repeatedly washed with dichloromethane and then placed in a vacuum drying oven to be fully dried.
[0079] In a nitrogen-filled glove box or a dry double-row tube system, add a certain amount of recovered phthalocyanine-based metal organic framework catalyst, trimethylolpropane triglycidyl ether (TMPEG) and an appropriate amount of hexadecyl trimethylammonium bromide into a dry high-pressure reactor. After the feeding is completed, shake evenly to allow the monomer and catalyst to be completely dissolved and dispersed under stirring. Then fill with 3MPa CO2, place it in a 120℃ oil bath pot under magnetic stirring for 48 hours, and after the reaction, take a small amount of crude product for nuclear magnetic resonance testing to calculate the conversion rate. Subsequently, the crude product is dissolved in dichloromethane and filtered to recover the catalyst, and the solution is passed through an alkaline alumina column and spin-dried to obtain a ternary cyclic carbonate.
[0080] Application Examples 26-29: Catalyst recovery and reuse. The catalyst recovery and resynthesis process in the system is consistent with that in Application Example 25. The only difference is that different phthalocyanine-based metal organic framework catalysts are used.
[0081] Application Example 30: The phthalocyanine-based metal organic framework catalyst Cat.1 is recovered for the second time and reused to participate in catalytic conversion. The catalyst recovery and catalytic synthesis methods are consistent with those in Application Example 25.
[0082] Application Example 31: The phthalocyanine-based metal organic framework catalyst Cat.1 is recovered for the third time and reused to participate in catalytic conversion. The catalyst recovery and catalytic synthesis methods are consistent with those in Application Example 25.
[0083] The experimental results of the above application examples are as follows:
[0084] The results of catalytic synthesis of recycled phthalocyanine-based metal organic framework catalysts
[0085]
[0086]
[0087] a [polycyclic epoxide]:[phthalocyanine metal organic framework catalyst]:[cocatalyst] molar ratio; b Phthalocyanine metal organic framework catalysts; c Promoter catalyst; d The CO2 pressure was 3 MPa; e polycyclic epoxide conversion was determined by H-NMR spectroscopy; f 30 is the catalytic synthesis effect of the catalyst after the second recovery, and 31 is the catalytic polymerization effect of the third recovery.
[0088] Application Example 32
[0089] The (di)polycyclic carbonates synthesized by phthalocyanine-based metal organic framework catalysts are further reacted with polyamine compounds through a solvothermal method to prepare carbonized polymer dots capable of solid-state fluorescence.
[0090] Application Example 32: Add 494 mg (0.92 mmol) of tetracyclic carbonate, 149 mg (1.38 mmol) of m-phenylenediamine and 5.0 mL of acetonitrile to a 10 mL polytetrafluoroethylene hydrothermal reactor, and react in a 130 ° C oven for 24 hours. After the reaction is completed, cool naturally to room temperature, wash the prepared yellow solid precipitate repeatedly with acetonitrile, and then place it in a 40 ° C vacuum oven to dry until constant weight. The fluorescence properties of carbonized polymer dots are analyzed and characterized by a fluorescence spectrometer. The specific synthesis reaction formula is shown as follows:
[0091]
[0092] The above embodiments describe the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the scope of the principles of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of protection of the present invention.
Claims
1. A phthalocyanine-based metal organic framework catalyst, characterized in that: The nitrogen-containing Lewis base phthalocyanine moiety and the Lewis acid metal center are used as organic complexes, and are formed by defluorination coupling reaction with tetraamine / tetraphenol containing electron-rich amino / hydroxyl groups. The structure presents a porous structure, and the general structural formula is as follows: Where: M is the central metal ion, selected from Fe 2+ , Cu 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ ; X is selected from NH, O; in the bridging unit of the bonded metal coordination compound, the polyamine is selected from phenylenetetramine, 2,3,6,7-tetraaminonaphthalene, 3,3',4,4'-tetraaminobiphenyl, anthracene-2,3,6,7-tetraamine; the polyphenol is selected from 1,1'-biphenyl-3,3',4,4'-tetrol, 2,3,6,7-tetrahydroxynaphthalene, 2,3,6,7-tetrol-anthracene.
2. The method for synthesizing the phthalocyanine-based metal organic framework catalyst according to claim 1, characterized in that: The method comprises the following steps: carrying out defluorination coupling reaction on hexafluorophthalocyanine metal coordination compound and tetrahydric amine or tetrahydric phenol and purifying the mixture to obtain phthalocyanine-based metal organic framework catalyst.
3. The method for synthesizing the phthalocyanine-based metal organic framework catalyst according to claim 2, characterized in that: The specific synthesis steps are: dissolving the hexadecafluorophthalocyanine metal coordination compound and tetraamine or tetraphenol in a solvent, adding an acid binding agent, removing dissolved oxygen through a freeze-thaw cycle, heating to 70-120°C for reaction for 48-144 hours, filtering and solvent exchange washing and purification to obtain a phthalocyanine-based metal organic framework nanomaterial catalyst.
4. The method for synthesizing the phthalocyanine-based metal organic framework catalyst according to claim 2, characterized in that: The hexadecafluorophthalocyanine metal coordination compound is selected from hexadecafluorophthalocyanine zinc (II), hexadecafluorophthalocyanine cobalt (II), hexadecafluorophthalocyanine iron (II), hexadecafluorophthalocyanine copper (II), and hexadecafluorophthalocyanine nickel (II).
5. Use of the phthalocyanine-based metal organic framework catalyst as claimed in claim 1 in catalyzing the synthesis of di- / polycyclic carbonates from carbon dioxide and di- / polycyclic alkylene oxides.
6. The use of the phthalocyanine-based metal organic framework catalyst according to claim 5 in catalyzing the synthesis of carbon dioxide and di- or poly-epoxyalkylene / di- or poly-cyclic carbonates, characterized in that: The reaction equation is expressed as: The catalytic system comprises a co-catalyst, which is hexadecyltrimethylammonium bromide; the alkylene oxide is ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether or pentaerythritol glycidyl ether.
7. The use of the phthalocyanine-based metal organic framework catalyst in catalyzing the synthesis of carbon dioxide and di- or poly-epoxyalkylene / di- or poly-cyclic carbonates according to claim 6, characterized in that: The mass ratio of the phthalocyanine-based metal organic framework catalyst to the epoxide is 1:50-300; the pressure of the carbon dioxide is 0.5-5MPa; the reaction temperature is 60-150°C; and the reaction time is 5-48 hours.
8. The use of the phthalocyanine-based metal organic framework catalyst according to claim 6 in catalyzing the synthesis of di- / polycyclic carbonates from carbon dioxide and di- / polycyclic alkylene oxides, characterized in that: After the catalytic reaction is completed, the mixed system is recovered by solvent dissolution and centrifuged or filtered, the precipitate is fully washed with the dissolving solvent, and the precipitated solid is recovered after drying; the solid after drying continues to act as a metal organic framework catalyst for repeated catalytic synthesis.
9. The use of the phthalocyanine-based metal organic framework catalyst in catalyzing the synthesis of carbon dioxide and di- or poly-epoxyalkylene / di- or poly-cyclic carbonates according to claim 6, characterized in that: The obtained di- / polycyclic carbonates and polyamine compounds are used to prepare solid-state fluorescent carbonized polymer dots through a one-step water / solvothermal method.
10. The use of the phthalocyanine-based metal organic framework catalyst according to claim 9 in catalyzing the synthesis of carbon dioxide and di- or poly-epoxyalkylene / di- and poly-cyclic carbonates, characterized in that: The polyamine is selected from polyetherimide, tetraethylenepentamine, melamine, diethylenetriamine, ethylenediamine, o-phenylenediamine, m-phenylenediamine, butanediamine, hexamethylenediamine, octanediamine, and 1,12-dodecanediamine; the reaction temperature is selected from 80-160°C, the reaction solvent is selected from water, ethanol, acetonitrile, chloroform or acetone, and the reaction time is selected from 12-72h.