Use of a polynuclear metalloporphyrin complex based on a cyclophosphazene backbone

Abstract

The application discloses application of a multi-center metal porphyrin complex based on a cyclic phosphazene skeleton and belongs to the technical field of catalysts. The multi-center metal porphyrin complex based on the cyclic phosphazene skeleton has excellent catalytic activity (TOF / h ‑1 ) of 10 6 orders of magnitude when applied to the reaction of copolymerization of carbon dioxide and an epoxide to synthesize polycarbonates. The number of active centers of the multi-center metal porphyrin complex based on the cyclic phosphazene skeleton is definite and can be adjusted through the cyclic phosphazene species to obtain structures with different numbers of active centers. In addition, the content of carbonates in the polymer can be adjusted by adjusting the linking group between the porphyrin and the cyclic phosphazene. The complex can be used to catalytically prepare polycarbonate materials at high temperature with high selectivity and ultrahigh activity.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to the application of a multi-center metalloporphyrin complex based on a cyclophosphonitrile framework. Background Technology

[0002] Carbon dioxide, a major component of greenhouse gases, can be transformed into high-value-added polymers through ring-opening copolymerization with epoxides. This copolymerization not only reduces the environmental burden caused by carbon dioxide but also decreases the dependence of polymer materials on petroleum supplies. Furthermore, polycarbonate (PPC), a copolymer of carbon dioxide and epoxides, possesses full degradability, excellent transparency, and superior barrier properties, making it suitable for use as engineering plastics, disposable pharmaceutical and food packaging materials, and adhesives. For example, propylene oxide's alternating polymerization product, PPC, can be used in agricultural mulch films, while its telomeres can be used to prepare polyurethane for applications such as high-speed rail interiors.

[0003] Since Inoue first achieved the copolymerization of carbon dioxide and propylene oxide in 1969, various catalytic systems have been developed, such as alkyl zinc / active hydrogen catalytic systems, metal carboxylate systems, bimetallic cyanide catalysts, rare earth ternary catalysts, metal porphyrin catalysts, zinc phenolate catalytic systems, and zinc diimide catalysts. These catalytic systems have greatly improved the activity and selectivity of the polymerization reaction. However, current catalysts not only have low preparation efficiency, but their activity is also far from satisfactory.

[0004] To improve the activity and selectivity of the copolymerization reaction of propylene oxide and carbon dioxide, synergistic catalysis mechanisms have been incorporated into the design of catalytic systems. This has led to the development of bicomponent catalytic systems composed of SalenCo catalysts and quaternary ammonium or quaternary phosphate co-catalysts, bifunctional catalysts based on cation-anion synergistic effects, and bimetallic center catalysts. These catalytic systems have significantly enhanced the activity and selectivity of the polymerization reaction. Among them, the bifunctional SalenCo catalyst for carbon dioxide / propylene oxide achieved a TOF of 26,000 h⁻¹. -1 The activity record is available, but for large-scale industrial production, the reactivity is far from sufficient. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an application of a multi-center metalloporphyrin complex based on a cyclophosphonitrile framework. The multi-center metalloporphyrin complex based on a cyclophosphonitrile framework has multiple metal centers and exhibits excellent catalytic activity, reaching up to 10, when applied to the copolymerization of carbon dioxide and epoxides into polycarbonate. 6 Order of magnitude.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] This invention is the first to propose the application of multi-center metalloporphyrin complexes based on cyclophosphonitrile frameworks as catalysts for the copolymerization reaction of carbon dioxide and epoxides.

[0008] When the multi-center metalloporphyrin complex based on the cyclophosphonitrile framework catalyzes the copolymerization reaction of carbon dioxide and epoxides, it can achieve 10 6 Orders of magnitude catalytic activity.

[0009] The spatial confinement of the cyclophosphine skeleton creates a powerful synergistic effect among multiple active sites, promoting rapid ring-opening of the epoxide and thus significantly enhancing its activity. Simultaneously, this powerful synergistic effect also leads to the continuous insertion of epoxides, resulting in an increase in the ether content.

[0010] The present invention also provides a method for preparing polycarbonate, which uses a multi-center metalloporphyrin complex based on a cyclophosphonitrile framework as a catalyst to catalyze the copolymerization reaction of carbon dioxide and epoxide to prepare polycarbonate.

[0011] The multicenter metalloporphyrin complex based on the cyclophosphonitrile framework was prepared by a nucleophilic substitution reaction of hydroxyl-containing porphyrin with cyclophosphonitrile. The preparation method is simple and efficient.

[0012] This invention employs a multi-center metalloporphyrin complex based on a cyclophosphonitrile framework as a catalyst for the copolymerization reaction of carbon dioxide and epoxides, which can maintain high selectivity at high temperatures while achieving a yield of 10... 6 Super-high activity catalysis for polycarbonate preparation.

[0013] Preferably, the multicenter metalloporphyrin complex based on the cyclophosphonitrile framework of the present invention has the structure shown in Formula I:

[0014]

[0015] The active centers of the aforementioned multi-center metalloporphyrin complexes based on cyclophosphonitrile skeletons are modulated by the type of cyclophosphonitrile. When the skeleton is hexachlorocyclotriphosphonitrile or octachlorocyclotetraphosphonitrile, it can link 6 and 8 porphyrin molecules, respectively, thus obtaining complex structures with different numbers of active centers.

[0016] Preferably, n is an integer between 3 and 7; more preferably, it is 3, 4 or 5, that is, the cyclophosphonitrile skeleton of the multicenter metalloporphyrin complex based on the cyclophosphonitrile skeleton is hexachlorocyclotriphosphonitrile, octachlorocyclotetraphosphonitrile or decachlorocyclopentaphosphonitrile.

[0017] When n=4, the multicenter metalloporphyrin complex based on the cyclophosphonitrile framework has the structure shown in Formula I-a:

[0018]

[0019]

[0020] The preferred method for attaching the linking group to the complex is as follows: after attaching the linking group to a single hydroxyl-substituted hydroxyl group of the porphyrin, the hydroxyl group at the other end of the linking group undergoes a nucleophilic substitution reaction with the halogen of the cyclophosphonitrile under alkaline conditions.

[0021] In this invention, the asterisk (*) indicates a connection position.

[0022] Preferably, the metalloporphyrin complex of the present invention has the structure shown in Formula II:

[0023]

[0024] Among them, the preferred values ​​are R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 Independently selected from hydrogen, halogens, substituted or unsubstituted C1-C 10 Aliphatic groups, substituted or unsubstituted C1-C 10 Heteroaliphatic groups, substituted or unsubstituted C6-C 12 Aryl, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups;

[0025] The C1~C 10 The aliphatic group is preferably C1 to C2. 10 Straight-chain or branched alkyl groups, C1-C2 10 Straight-chain or branched alkoxy groups or C3-C6 groups 10 Cycloalkyl.

[0026] The C1~C 10 Aliphatic groups, C1-C 10 The substituents of the heteroaliphatic groups are preferably halogen, methyl, ethyl, or methoxy.

[0027] The C6~C 12 Aryl, C1-C 12 The substituents of the heteroaryl group are preferably methyl or ethyl.

[0028] The C1~C 10 The heteroaliphatic group is preferably a substituted or unsubstituted C1-C1 group. 10 Heterocyclic groups.

[0029] The C1~C 10 The straight-chain or branched alkyl group is preferably a C1-C4 straight-chain or branched alkyl group, specifically including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. The C1-C4... 10 The straight-chain or branched alkoxy group is preferably a C1 to C4 straight-chain or branched alkoxy group, specifically including but not limited to methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.

[0030] The C3~C 10 The cycloalkyl group is preferably a C3-C6 cycloalkyl group, specifically including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0031] The C6~C 12 The aryl group is preferably a C6-C8 aryl group, and more preferably a phenyl or benzyl group.

[0032] Preferably, X is selected from halogens, -NO3, CH3COO - CCl3COO - CF3COO - ClO4 - BF4 - BPh4 - -CN, -N3, p-toluenebenzoate, p-toluenesulfonate, o-nitrophenoloxy, p-nitrophenoloxy, m-nitrophenoloxy, 2,4-dinitrophenoloxy, 3-5-dinitrophenoloxy, 2,4,6-trinitrophenoloxy, 3,5-dichlorophenoloxy, 3,5-difluorophenoloxy, 3,5-di-trifluoromethylphenoloxy or pentafluorophenoloxy anion; more preferably halogen or p-toluenesulfonate.

[0033] Preferably, M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel, or ruthenium; more preferably, it is magnesium, aluminum, zinc, or chromium; and even more preferably, it is aluminum.

[0034] Preferably, in this invention, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 Independently selected from hydrogen, halogens, C1 to C 10 Straight-chain or branched alkyl groups, C1-C2 10 Straight-chain or branched alkoxy groups, C3-C610 cycloalkyl, C1-C 10 heterocyclic group, C6~C 12 aryl, C1-C 12 One or more of the heteroaryl groups.

[0035] The C1~C 10 Straight-chain or branched alkyl groups, C1-C2 10 Straight-chain or branched alkoxy groups, C3-C6 10 cycloalkyl, C1-C 10 heterocyclic group, C6~C 12 aryl, C1-C 12 The scope of heteroaryl groups is the same as above, and will not be repeated here.

[0036] X is selected from halogens or p-toluenesulfonate;

[0037] M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel, or ruthenium;

[0038] Preferably, in this invention, the It has the structure shown in Equation II-a:

[0039]

[0040] Preferably, R1, R8, R 13 Independently selected from hydrogen, halogens, C1 to C 10 Straight-chain or branched alkyl groups, C1-C2 10 Straight-chain or branched alkoxy groups, C3-C6 10 cycloalkyl, C1-C 10 heterocyclic group, C6~C 12 aryl, C1-C 12 One or more of the heteroaryl groups.

[0041] More preferably, R1, R8, R 13 Independently selected from one or more of hydrogen, halogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy.

[0042] More preferably, R1, R8, R 13 Independently selected from bromine or ethyl.

[0043] Preferably, X is selected from halogens or p-toluenesulfonate; more preferably, X is selected from Cl or p-toluenesulfonate.

[0044] Preferably, M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel, or ruthenium; more preferably, it is magnesium, aluminum, zinc, or chromium; and even more preferably, it is aluminum.

[0045] In some specific embodiments of the present invention, the It has the structure shown in Equation II-b:

[0046]

[0047]

[0048] This invention can regulate the synergistic effect by adjusting the linking group between porphyrin and cyclophosphine, thereby...

[0049]

[0050] Preferably, q is selected from an integer between 1 and 16; more preferably, it is an integer between 3 and 12;

[0051] In some specific embodiments of the present invention, when the linking group is selected as formula III-a, the catalyst structure is EC1, EC3, EC5 or EC6, and the carbonate content is 28%, 30%, 31%, 35%, 37%, 38%, 39%, 42% or 47% (the ether segment content is higher than the carbonate content), which tends to generate ether units.

[0052] When the linking group is selected as formula III-b (n=6), the catalyst structure is EC2 or EC4, and the carbonate content is 56%, 89%, 91%, 95%, or 96% (the ether segment content is lower than the carbonate content), which means it tends to generate carbonate units.

[0053] Preferably, the multicenter metalloporphyrin complex based on the cyclophosphonitrile framework of the present invention has any of the following structures:

[0054]

[0055]

[0056] When the aforementioned multi-center metalloporphyrin complexes EC1, EC2, EC3, EC4, EC5, or EC6 based on the cyclophosphonitrile framework are applied to the copolymerization reaction of propylene oxide and carbon dioxide, a TOF value of up to 226,300 h⁻¹ can be obtained. -1 .

[0057] This invention also provides a multicenter metalloporphyrin complex based on a cyclophosphonitrile framework, having the structure shown in Formula IV:

[0058]

[0059] Preferably, n is an integer between 3 and 7; more preferably, it is 3, 4, or 5. In some specific embodiments of the present invention, 3 or 4 is preferred.

[0060] Preferably, q is selected from an integer between 1 and 16; more preferably, it is an integer between 3 and 12; and even more preferably, it is 6.

[0061] Preferably, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 Independently selected from hydrogen, halogens, substituted or unsubstituted C1-C 10 Aliphatic groups, substituted or unsubstituted C1-C 10 Heteroaliphatic groups, substituted or unsubstituted C6-C 12 Aryl, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups.

[0062] Preferably, X is selected from halogens, -NO3, CH3COO - CCl3COO - CF3COO - ClO4 - BF4 - BPh4 - -CN, -N3, p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoloxy, p-nitrophenoloxy, m-nitrophenoloxy, 2,4-dinitrophenoloxy, 3-5-dinitrophenoloxy, 2,4,6-trinitrophenoloxy, 3,5-dichlorophenoloxy, 3,5-difluorophenoloxy, 3,5-di-trifluoromethylphenoloxy or pentafluorophenoloxy anions.

[0063] Preferably, M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel, or ruthenium.

[0064] Preferably, the multicenter metalloporphyrin complex based on the cyclophosphonitrile framework of the present invention has any of the following structures:

[0065]

[0066] Applying the multicenter metalloporphyrin complexes EC2 and EC4 based on the cyclophosphonitrile skeleton to the preparation of polycarbonate is more conducive to increasing the carbonate content in the polymer.

[0067] Preferably, the molar ratio of the multi-center metalloporphyrin complex and the epoxide based on the cyclophosphazene skeleton of this invention is 1:(2000-2000000); more preferably, it is 1:(10000-1000000). In some specific embodiments of this invention, the molar ratio of the multi-center metalloporphyrin complex and the epoxide based on the cyclophosphazene skeleton is 1:60000, 1:300000, 1:80000, or 1:400000.

[0068] Preferably, the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1,2-epoxybutane, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, and styrene epoxyalkane; more preferably, it is selected from one or more of ethylene oxide, propylene oxide, and 1,2-epoxybutane. In some specific embodiments of the present invention, propylene oxide is preferred.

[0069] Preferably, the pressure of the carbon dioxide is 0.1–8 MPa; more preferably 1–6 MPa. In this invention, 4 MPa is particularly preferred.

[0070] Preferably, the temperature of the copolymerization reaction is 20–150°C; more preferably 25–120°C; and even more preferably 50°C, 70°C, 80°C, 120°C, or 25°C.

[0071] Preferably, the copolymerization reaction takes 0.1 to 48 hours; more preferably 0.2 to 5 hours. In some specific embodiments of the present invention, it is preferably 0.15 hours, 0.5 hours, 1 hour, or 3 hours.

[0072] Compared with existing technologies, the multi-center metalloporphyrin complex based on the cyclophosphonitrile framework provided by this invention exhibits excellent catalytic activity (TOF / h) when applied to the copolymerization of carbon dioxide and epoxides into polycarbonate. -1 ), up to 10 6 The number of active centers in the multi-center metalloporphyrin complex based on the cyclophosphonitrile framework is clearly defined and can be adjusted by the type of cyclophosphonitrile, resulting in structures with different numbers of active centers. Furthermore, the carbonate content in the polymer can be adjusted by changing the linking groups between the porphyrin and the cyclophosphonitrile. This complex can maintain high selectivity while catalyzing the preparation of polycarbonate materials with ultra-high activity at high temperatures. Detailed Implementation

[0073] To further illustrate the present invention, the application of the multicenter metalloporphyrin complex based on the cyclophosphonitrile framework provided by the present invention will be described in detail below with reference to the embodiments.

[0074] Example 1

[0075] In a 2000 mL three-necked flask, 98 g of finely ground ammonium chloride, 600 mL of chlorobenzene, 2.5 g of magnesium oxide, and 20 mL of pyridine were added sequentially. The mixture was heated and stirred until the chlorobenzene was refluxed. Then, a chlorobenzene solution containing approximately 298 g (800 mL) of phosphorus pentachloride was added dropwise over about 3 hours. The solution was then kept under reflux for 2–3 hours until the HCl concentration in the gas delivery tube significantly decreased, at which point heating was stopped. After completely purging the HCl gas from the system, the reaction system was cooled, filtered, and a pale yellow solution was obtained. The solution was washed 2–3 times with distilled water until the organic layer was clear and transparent. The chlorobenzene layer was separated, dried overnight with anhydrous sodium sulfate, filtered, and the chlorobenzene was removed by vacuum distillation to obtain a yellow crude product. Recrystallization from n-heptane yielded white rhombic crystals, which were then sublimated under reduced pressure at 60 °C to obtain product EL1. The yield was approximately 40%. 31 P-NMR (CDCl3, ppm): 20.1. High-resolution electrospray mass spectrometry analysis showed that [Cl6N3P3]: 347.64, found: 347.37.

[0076] 15 g (120 mmol) of 3-hydroxybenzaldehyde, 68.1 g (370 mmol) of 4-bromobenzaldehyde and 33 g (490 mmol) of pyrrole were added to 500 mL of propionic acid. The mixture was heated to about 130 °C and refluxed for 1.5 h. After the reaction was completed, the mixture was cooled to room temperature and concentrated to 200 mL. Methanol was added and the mixture was cooled in a refrigerator overnight. The obtained product was filtered and purified by silica gel column chromatography (CHCl3 / CH3OH) to obtain product EL2, with a yield of about 7.8%. 1 ¹H-NMR (CDCl₃, ppm): 8.9, 8.8, 8.1, 7.8, 7.2, -2.8. High-resolution electrospray mass spectrometry analysis, the results are [C 44 H 27 Br3N4O]: 863.97, found: 863.86.

[0077] Under nitrogen protection, 0.037 mmol EL2 and 0.037 mmol cesium carbonate were added to a solution of hexachlorocyclotriphosphazene (0.0057 mmol) in tetrahydrofuran. The reaction mixture was stirred at room temperature for 0.5 h, followed by stirring at 80 °C for 6 h. The reaction mixture was filtered, and the resulting filtrate precipitated as a solid under ice-cold diethyl ether. The solid was thoroughly washed with diethyl ether to give a purple solid EL3 in 95% yield. 31 P-NMR (CDCl3, ppm): 9.3; high-resolution electrospray mass spectrometry analysis, the results are [C 264 H 156 Br 18 N 27 O6P3]: 5333.53, found: 5333.62.

[0078] Under nitrogen protection, the above ligand EL3 was dissolved in dichloromethane, and AlEt2Cl (diethylaluminum chloride) was added dropwise. The mixture was stirred at room temperature for 2 hours. The resulting product was purified by column chromatography and dried to obtain the desired complex EC1.

[0079]

[0080] Example 2

[0081] Under nitrogen protection, 2.18 g (2.50 mmol) of EL2, 0.50 mL (3.25 mmol) of 6-bromo-1-hexanol, 0.17 g of potassium carbonate, and 0.01 g of potassium iodide were dissolved in 200 mL of anhydrous THF. After thorough stirring, the mixture was heated under reflux for 12 h. After the reaction was complete, the product was evaporated to dryness, dissolved in dichloromethane, and extracted and washed three times with water. The organic phase was dried over anhydrous magnesium sulfate and then evaporated to dryness. The solid product was purified by alumina column chromatography with dichloromethane as the eluent to obtain approximately 2.03 g of product EL4. High-resolution electrospray ionization mass spectrometry analysis showed the following results: [C 50 H 39 Br3N4O2]: 967.60, found: 967.12.

[0082] Under nitrogen protection, 0.037 mmol of EL4 and 0.037 mmol of cesium carbonate were added to a 0.0057 mmol solution of hexachlorocyclotriphosphazene (EL1) in tetrahydrofuran. The reaction mixture was stirred at room temperature for 0.5 h, followed by stirring at 80 °C for 6 h. The reaction mixture was filtered, and the resulting filtrate precipitated as a solid under ice-cold diethyl ether. The solid was thoroughly washed with diethyl ether to give a purple solid EL5 in 95% yield. 31 P-NMR (CDCl3, ppm): 9.0; high-resolution electrospray mass spectrometry analysis, the results are [C 300 H 228 Br 18 N 27 O 12 P3]: 5931.82, found: 5931.22.

[0083] Under nitrogen protection, the above ligand EL5 was dissolved in dichloromethane, and AlEt2Cl (diethylaluminum chloride) was added dropwise. The mixture was stirred at room temperature for 2 hours. The resulting product was purified by column chromatography and dried to obtain the desired complex EC2.

[0084]

[0085] Example 3

[0086] In a 2000 mL three-necked flask, 98 g of finely ground ammonium chloride, 600 mL of chlorobenzene, 2.5 g of magnesium oxide, and 20 mL of pyridine were added sequentially. The mixture was heated and stirred until the chlorobenzene was refluxed. Then, a chlorobenzene solution containing approximately 298 g (800 mL) of phosphorus pentachloride was added dropwise over about 3 hours. The solution was then kept under reflux for 2–3 hours until the HCl concentration in the gas delivery tube significantly decreased, at which point heating was stopped. After completely purging the HCl gas from the system, the reaction system was cooled, filtered, and a pale yellow solution was obtained. The solution was washed 2–3 times with distilled water until the organic layer was clear and transparent. The chlorobenzene layer was separated, dried overnight with anhydrous sodium sulfate, filtered, and the chlorobenzene was removed by vacuum distillation to obtain a yellow crude product. Recrystallization from n-heptane yielded white rhombic crystals, which were then sublimated under reduced pressure at 60 °C to obtain hexachlorocyclotriphosphazene (EL1). The unsublimated solid was the target product, octachlorocyclotetraphosphazene (EL6). The yield was approximately 30%. 31 P-NMR (CDCl3, ppm): 21.3; High-resolution electrospray mass spectrometry analysis results: [Cl8N4P4]: 463.53, found: 463.20.

[0087] Under nitrogen protection, 0.037 mmol of EL2 and 0.037 mmol of cesium carbonate were added to a 0.0057 mmol solution of octachlorocyclotetraphosphazene (EL6) in tetrahydrofuran. The reaction mixture was stirred at room temperature for 0.5 h, followed by stirring at 80 °C for 6 h. The reaction mixture was filtered, and the resulting filtrate precipitated as a solid under ice-cold diethyl ether. The solid was thoroughly washed with diethyl ether to give a purple solid EL7 in 95% yield. 31 P-NMR (CDCl3, ppm): 10.6, high-resolution electrospray mass spectrometry analysis, the analysis result is [C 352 H 208 Br 24 N 36 O8P4]: 7111.37, found: 7111.26.

[0088] Under nitrogen protection, the above ligand EL7 was dissolved in dichloromethane, and AlEt2Cl (diethylaluminum chloride) was added dropwise. The mixture was stirred at room temperature for 2 hours. The resulting product was purified by column chromatography and dried to obtain the desired complex EC3.

[0089]

[0090] Example 4

[0091] Under nitrogen protection, 0.037 mmol of EL4 and 0.037 mmol of cesium carbonate were added to a 0.0057 mmol solution of octachlorocyclotetraphosphazene (EL6) in tetrahydrofuran. The reaction mixture was stirred at room temperature for 0.5 h, followed by stirring at 80 °C for 6 h. The reaction mixture was filtered, and the resulting filtrate precipitated as a solid under ice-cold diethyl ether. The solid was thoroughly washed with diethyl ether to give a purple solid, EL8, in 95% yield. 31 P-NMR (CDCl3, ppm): 10.1, high-resolution electrospray mass spectrometry analysis, the analysis results are [C 400 H 304 Br 24 N 36 O 16 P4]: 7909.15, found: 7909.05.

[0092] Under nitrogen protection, the above ligand EL8 was dissolved in dichloromethane, and AlEt2Cl (diethylaluminum chloride) was added dropwise. The mixture was stirred at room temperature for 2 hours. The resulting product was purified by column chromatography and dried to obtain the desired complex EC4.

[0093]

[0094] Example 5

[0095] 15 g (120 mmol) of 3-hydroxybenzaldehyde, 49.6 g (370 mmol) of 4-ethylbenzaldehyde and 33 g (490 mmol) of pyrrole were added to 500 mL of propionic acid. The mixture was heated to about 130 °C and refluxed for 1.5 h. After the reaction was completed, the mixture was cooled to room temperature and concentrated to 200 mL. Methanol was added and the mixture was cooled in a refrigerator overnight. The product obtained by filtration was purified by silica gel column chromatography (CHCl3 / CH3OH) to obtain product EL2, with a yield of about 7.8%. 1 ¹H-NMR (CDCl₃, ppm): 8.9, 8.8, 8.1, 7.8, 7.2, 3.2, 1.5, -2.8. High-resolution electrospray mass spectrometry analysis, the results are [C 50 H 42 N4O]: 714.91, found: 715.2.

[0096] Under nitrogen protection, 0.037 mmol of EL9 and 0.037 mmol of cesium carbonate were added to a solution of hexachlorocyclotriphosphazene (0.0057 mmol) in tetrahydrofuran. The reaction mixture was stirred at room temperature for 0.5 h, followed by stirring at 80 °C for 6 h. The reaction mixture was filtered, and the resulting filtrate precipitated as a solid under ice-cold diethyl ether. The solid was thoroughly washed with diethyl ether to give a purple solid EL10 in 95% yield. 31P-NMR (CDCl3, ppm): 9.6; high-resolution electrospray mass spectrometry analysis, the result is [C 300 H 246 N 27 O6P3]: 4418.37, found: 4419.80.

[0097] Under nitrogen protection, the above ligand EL10 was dissolved in dichloromethane, and AlEt2Cl (diethylaluminum chloride) was added dropwise. The mixture was stirred at room temperature for 2 hours. The resulting product was purified by column chromatography and dried to obtain the desired complex EC5.

[0098]

[0099] Example 6

[0100] At room temperature, 0.3 mmol of EC1 was dissolved in a chloroform / acetonitrile mixture, followed by the addition of 1.9 mmol of silver p-toluenesulfonate (AgOTs). The resulting mixture was then stirred overnight in the dark. After the reaction was complete, the solvent was evaporated, chloroform was added to dissolve the mixture completely, and the precipitate was filtered off. The resulting filtrate was evaporated to dryness to obtain a purple powder, which was then dried in a vacuum oven at 70°C for 48 hours to obtain the desired complex EC6.

[0101]

[0102] Example 7

[0103] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC1 prepared in Example 1 and 90 mmol of dry propylene oxide were added to a 15 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 50°C for 0.5 h for polymerization. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and a sample was taken immediately after opening the reactor for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0104] pass 1 H-NMR analysis of the polycarbonate prepared in Example 7 showed that the polycarbonate contained 47% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 9289 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was determined to be 84,000 and the molecular weight distribution was 1.22 by GPC.

[0105] Example 8

[0106] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC1 prepared in Example 1 and 450 mmol of dry propylene oxide were added to a 25 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 70°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0107] pass 1 H-NMR analysis of the polycarbonate prepared in Example 8 showed that the polycarbonate contained 30% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 15200 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 198,000 and the molecular weight distribution was 1.27, as determined by GPC.

[0108] Example 9

[0109] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC1 prepared in Example 1 and 450 mmol of dry propylene oxide were added to a 25 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 80°C for polymerization for 0.5 h. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0110] pass 1 H-NMR analysis of the polycarbonate prepared in Example 9 showed that the polycarbonate contained 31% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 35600 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 156,000 and the molecular weight distribution was 1.21, as determined by GPC.

[0111] Example 10

[0112] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC1 prepared in Example 1 and 450 mmol of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 120 °C for polymerization reaction for 0.15 h. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0113] pass 1 H-NMR analysis of the polycarbonate prepared in Example 10 showed that the polycarbonate contained 38% carbonate units and less than 0.1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 105000 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 135,000 and the molecular weight distribution was 1.27, as determined by GPC.

[0114] Example 11

[0115] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC1 prepared in Example 1 and 90 mmol of dry propylene oxide were added to a 25 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 25°C for polymerization for 3 hours. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0116] pass 1 H-NMR analysis of the polycarbonate prepared in Example 11 showed that the polycarbonate contained 42% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 1560 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was determined to be 63,000 and the molecular weight distribution was 1.23 by GPC.

[0117] Example 12

[0118] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC2 prepared in Example 2 and 90 mmol of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 50°C for 0.5 h for polymerization. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and a sample was taken immediately after opening the reactor for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0119] pass 1 H-NMR analysis of the polycarbonate prepared in Example 12 showed that the polycarbonate contained 96% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 8500 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 10,600 and the molecular weight distribution was 1.19, as determined by GPC.

[0120] Example 13

[0121] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC2 prepared in Example 2 and 450 mmol of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 70°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0122] pass 1 H-NMR analysis of the polycarbonate prepared in Example 13 showed that the polycarbonate contained 89% carbonate units and less than 1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 12100 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 168,000 and the molecular weight distribution was 1.22, as determined by GPC.

[0123] Example 14

[0124] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC2 prepared in Example 2 and 450 mmol of dry propylene oxide were added to a 50 ml high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 120°C for polymerization for 0.5 h. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0125] pass 1 H-NMR analysis of the polycarbonate prepared in Example 14 showed that the polycarbonate contained 89% carbonate units and less than 0.1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 30200 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was determined to be 99,000 and the molecular weight distribution was 1.33 by GPC.

[0126] Example 15

[0127] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC3 prepared in Example 3 and 600 mmol of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 70°C for polymerization for 0.15 h. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and samples were taken immediately after opening the reactor for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0128] pass 1 H-NMR analysis of the polycarbonate prepared in Example 15 showed that the polycarbonate contained 28% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 129,700 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 153,000 and the molecular weight distribution was 1.25, as determined by GPC.

[0129] Example 16

[0130] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC3 prepared in Example 3 and 600 mmol of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 120 °C for polymerization for 0.15 h. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0131] pass 1 H-NMR analysis of the polycarbonate prepared in Example 16 showed that the polycarbonate contained 30% carbonate units and less than 0.1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 226,300 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 191,000 and the molecular weight distribution was 1.51, as determined by GPC.

[0132] Example 17

[0133] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC3 prepared in Example 3 and 120 mmol of dry propylene oxide were added to a 15 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 25°C for 0.5 h for polymerization. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0134] pass 1 H-NMR analysis of the polycarbonate prepared in Example 17 showed that the polycarbonate contained 35% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 6622 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was determined to be 97,000 and the molecular weight distribution was 1.21 by GPC.

[0135] Example 18

[0136] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC4 prepared in Example 4 and 600 mmol of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 50°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0137] pass 1 H-NMR analysis of the polycarbonate prepared in Example 18 showed that the polycarbonate contained 95% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 13300 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 153,000 and the molecular weight distribution was 1.25, as determined by GPC.

[0138] Example 19

[0139] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC4 prepared in Example 4 and 600 mmol of dry propylene oxide were added to a 50 ml high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 70°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0140] pass 1 H-NMR analysis of the polycarbonate prepared in Example 19 showed that the polycarbonate contained 91% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 25497 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 167,000 and the molecular weight distribution was 1.29, as determined by GPC.

[0141] Example 20

[0142] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC4 prepared in Example 4 and 600 mmol of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 120°C for polymerization for 0.5 h. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0143] pass 1 H-NMR analysis of the polycarbonate prepared in Example 20 showed that the polycarbonate contained 56% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 52893 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was determined to be 92,000 and the molecular weight distribution was 1.13 by GPC.

[0144] Example 21

[0145] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC5 prepared in Example 5 and 450 mmol of dry propylene oxide were added to a 25 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 70°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0146] pass 1 H-NMR analysis of the polycarbonate prepared in Example 21 showed that the polycarbonate contained 37% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 12200 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 118,000 and the molecular weight distribution was 1.21, as determined by GPC.

[0147] Example 22

[0148] In a glove box, 0.0015 mmol of the aluminum porphyrin complex EC6 prepared in Example 6 and 450 mmol of dry propylene oxide were added to a 25 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 70°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect a sample for analysis. 1 H-NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate.

[0149] pass 1 H-NMR analysis of the polycarbonate prepared in Example 22 showed that the polycarbonate contained 39% carbonate units and less than 0.01% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 18200 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was determined to be 218,000 and the molecular weight distribution was 1.31 by GPC.

[0150] As can be seen from the above embodiments, the multi-center metalloporphyrin complex based on the cyclophosphonitrile framework prepared by the present invention has extremely high activity, good product selectivity and high temperature stability when used as a catalyst to catalyze the preparation of polycarbonate materials.

[0151] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing polycarbonate, characterized in that, Polycarbonate was prepared by using a multi-center metalloporphyrin complex based on a cyclophosphonitrile framework of Formula I as a catalyst to catalyze the copolymerization reaction of carbon dioxide and epoxide. Formula I; Where n is an integer between 3 and 7; As a linking group, it has the structure shown in formula III-a or formula III-b: Formula III-a; Formula III-b; Where q is selected from integers between 1 and 16; It is a metalloporphyrin complex with the structure shown in Formula II: Formula II; Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 Independently selected from hydrogen, halogen, substituted or unsubstituted C1~C 10 Aliphatic groups, substituted or unsubstituted C1~C 10 Heteroaliphatic groups, substituted or unsubstituted C6~C 12 Aryl, substituted or unsubstituted C1~C 12 One or more of the heteroaryl groups; X is selected from halogen, -NO3, CH3COO - CCl3COO - CF3COO - ClO4 - BF4 - BPh4 - -CN, -N3, p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoloxy, p-nitrophenoloxy, m-nitrophenoloxy, 2,4-dinitrophenoloxy, 3,5-dinitrophenoloxy, 2,4,6-trinitrophenoloxy, 3,5-dichlorophenoloxy, 3,5-difluorophenoloxy, 3,5-di-trifluoromethylphenoloxy or pentafluorophenoloxy anions; M is selected from aluminum.

2. The method for preparing polycarbonate according to claim 1, characterized in that, The R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 Independently selected from hydrogen, halogens, C1~C 10 Straight-chain or branched alkyl groups, C1~C 10 Straight-chain or branched alkoxy groups, C3~C 10 cycloalkyl, C1~C 10 heterocyclic group, C6~C 12 aryl, C1~C 12 One or more of the heteroaryl groups; X is selected from halogens or p-toluenesulfonate; M is selected from aluminum.

3. The method for preparing polycarbonate according to claim 1, characterized in that, The multicenter metalloporphyrin complex based on the cyclophosphonitrile framework has any of the following structures: 。 4. The method for preparing polycarbonate according to claim 1, characterized in that, The molar ratio of the multicenter metalloporphyrin complex and the epoxide based on the cyclophosphonitrile framework is 1:(2000~2000000). The epoxide is selected from one or more of ethylene oxide, propylene oxide, 1,2-epoxybutane, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, and phenyl glycidyl ether.

5. A multicenter metalloporphyrin complex based on a cyclophosphonitrile framework, characterized in that, It has the structure shown in Equation IV: Formula IV; Where n is an integer between 3 and 7; q is an integer between 1 and 16; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 Independently selected from hydrogen, halogen, substituted or unsubstituted C1~C 10 Aliphatic groups, substituted or unsubstituted C1~C 10 Heteroaliphatic groups, substituted or unsubstituted C6~C 12 Aryl, substituted or unsubstituted C1~C 12 One or more of the heteroaryl groups; X is selected from halogen, -NO3, CH3COO - CCl3COO - CF3COO - ClO4 - BF4 - BPh4 - -CN, -N3, p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoloxy, p-nitrophenoloxy, m-nitrophenoloxy, 2,4-dinitrophenoloxy, 3,5-dinitrophenoloxy, 2,4,6-trinitrophenoloxy, 3,5-dichlorophenoloxy, 3,5-difluorophenoloxy, 3,5-di-trifluoromethylphenoloxy or pentafluorophenoloxy anions; M is selected from aluminum.

6. The multicenter metalloporphyrin complex based on a cyclophosphonitrile framework according to claim 5, characterized in that, The multicenter metalloporphyrin complex based on the cyclophosphonitrile framework has any of the following structures: 。

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