CN117106166A - Application of multi-center metalloporphyrin complex based on cyclophosphazene skeleton - Google Patents

Application of multi-center metalloporphyrin complex based on cyclophosphazene skeleton Download PDF

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CN117106166A
CN117106166A CN202311066554.7A CN202311066554A CN117106166A CN 117106166 A CN117106166 A CN 117106166A CN 202311066554 A CN202311066554 A CN 202311066554A CN 117106166 A CN117106166 A CN 117106166A
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cyclophosphazene
skeleton
polycarbonate
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杨列航
刘顺杰
卓春伟
王献红
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Changchun Institute of Applied Chemistry of CAS
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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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
    • 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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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses an application of a multi-center metalloporphyrin complex based on a cyclophosphazene skeleton, and belongs to the technical field of catalysts. The multi-center metalloporphyrin complex based on the cyclophosphazene skeleton has excellent catalytic activity (TOF/h) when applied to the reaction of synthesizing polycarbonate by copolymerizing carbon dioxide and epoxide ‑1 ) Can reach 10 6 On the order of magnitude. The multi-center metalloporphyrin complex based on the cyclophosphazene skeleton has definite number of active centers and can be regulated by the cyclophosphazene type to obtain structures with different numbers of active centers. In addition, the carbonate content of the polymer can be adjusted by adjusting the linking group between the porphyrin and the cyclic phosphazene. The complex can be used for preparing the polycarbonate material by ultra-high activity catalysis at high temperature while maintaining high selectivity.

Description

Application of multi-center metalloporphyrin complex based on cyclophosphazene skeleton
Technical Field
The invention relates to the technical field of catalysts, in particular to application of a multi-center metalloporphyrin complex based on a cyclophosphazene skeleton.
Background
Carbon dioxide is a major component of greenhouse gases, which can be converted to high value-added polymers by ring-opening copolymerization with epoxides. The copolymerization reaction not only reduces the environmental burden caused by carbon dioxide, but also reduces the dependence of high polymer materials on petroleum supply. In addition, the polycarbonate (PPC) which is a copolymerization product of carbon dioxide and epoxide has full degradability, excellent transparency and excellent barrier property, and can be used as engineering plastics, disposable medicines, food packaging materials, adhesives and the like. Taking propylene oxide as an example, the PPC of an alternate polymerization product can be used in agricultural mulching films, and the telomer can be used for preparing polyurethane and is used in the fields of high-speed rail internal decoration and the like.
Since Inoue in 1969 first realized copolymerization of carbon dioxide and propylene oxide, various catalytic systems such as alkyl zinc/active hydrogen catalytic systems, metal carboxylate systems, double metal cyanide catalysts, rare earth three-way catalysts, metalloporphyrin catalysts, phenolic zinc salt catalytic systems, diimine zinc catalysts and the like have been researched. These catalytic systems provide a great increase in the activity and selectivity of the polymerization reaction. However, the current catalysts are not only inefficient to prepare, but also have far from satisfactory activity.
In order to improve the activity, selectivity, etc. in the copolymerization of propylene oxide and carbon dioxide, synergistic catalytic mechanisms have been introduced into the design of catalytic systems. A two-component catalytic system consisting of SalenCo catalyst and quaternary ammonium salt or quaternary phosphonium salt catalyst promoter, a difunctional catalyst based on anion-cation synergistic effect and a double-center catalyst based on a double-metal center catalytic mechanism are sequentially presented. These catalytic systems provide a great increase in the activity and selectivity of the polymerization reaction. Wherein, the difunctional SalenCo creates TOF of 26,000 h for carbon dioxide/propylene oxide -1 But the reactivity is far from sufficient for large-scale industrial production.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an application of a multi-center metalloporphyrin complex based on a cyclophosphazene skeleton. The multi-center metalloporphyrin complex based on the cyclophosphazene skeleton has a plurality of metal centers, and has excellent catalytic activity up to 10 when being applied to the reaction of synthesizing polycarbonate by copolymerizing carbon dioxide and epoxide 6 On the order of magnitude.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides application of a multi-center metalloporphyrin complex based on a cyclophosphazene skeleton as a catalyst for copolymerization of carbon dioxide and epoxide for the first time.
When the multi-center metalloporphyrin complex based on the cyclophosphazene skeleton catalyzes the copolymerization reaction of carbon dioxide and epoxide, the number of the cyclophosphazene skeleton can reach 10 6 Catalytic activity of the order of magnitude.
The cyclic phosphazene skeleton space limiting effect enables a plurality of active centers to generate a super-strong synergistic effect, and promotes the rapid ring opening of epoxide, thereby greatly improving the activity. At the same time, the super synergistic effect also leads to the continuous insertion of epoxy, so that the content of ether segments is increased.
The invention also provides a preparation method of the polycarbonate, which adopts the multi-center metalloporphyrin complex based on the cyclophosphazene skeleton as a catalyst to catalyze the copolymerization reaction of carbon dioxide and epoxide, thus preparing the polycarbonate.
The multi-center metalloporphyrin complex based on the cyclophosphazene skeleton is prepared by nucleophilic substitution reaction of hydroxyl-containing porphyrin and cyclophosphazene, and the preparation method is simple and efficient.
The invention adopts the multi-center metalloporphyrin complex based on the cyclophosphazene skeleton as the catalyst for the copolymerization reaction of carbon dioxide and epoxide, and can keep high selectivity at high temperature and simultaneously take 10 percent 6 Ultra-high activity on the order of magnitude catalyzes the preparation of polycarbonates.
Preferably, the multi-center metalloporphyrin complex based on the cyclophosphazene skeleton has a structure shown in formula I:
the active center of the above-mentioned multi-center metalloporphyrin complex based on the cyclophosphazene skeleton is regulated by the kind of cyclophosphazene. When the skeleton is hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene, 6 and 8 porphyrin molecules can be linked respectively, so that complex structures with different numbers of active centers can be obtained.
Wherein, preferably, n is an integer between 3 and 7; more preferably 3, 4 or 5, i.e. the cyclophosphazene skeleton of the multicenter metalloporphyrin complex based on a cyclophosphazene skeleton is hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene or decachlorocyclophosphazene, respectively.
When n=4, the multi-center metalloporphyrin complex based on cyclophosphazene skeleton has the structure shown in formula i-a:
the specific method for accessing the linking group into the complex is preferably as follows: after the linking group is connected with the hydroxyl of the monohydroxy substituted porphyrin, the hydroxyl at the other end of the linking group reacts with the halogen of the cyclophosphazene in a nucleophilic substitution reaction under an alkaline condition.
In the present invention, the expression connection position.
Preferably, the metalloporphyrin complex has a structure represented by formula II:
wherein, preferably, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、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 C 1 ～C 10 Aliphatic radical, substituted or unsubstituted C 1 ～C 10 Heteroaliphatic, substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 1 ～C 12 In heteroaryl groupsOne or more of;
the C is 1 ～C 10 The aliphatic group is preferably C 1 ～C 10 Straight-chain or branched alkyl, C 1 ～C 10 Straight-chain or branched alkoxy or C 3 ～C 10 Cycloalkyl groups.
The C is 1 ～C 10 Aliphatic radicals, C 1 ～C 10 The substituents of the heteroaliphatic group are preferably halogen, methyl, ethyl, methoxy.
The C is 6 ～C 12 Aryl, C 1 ～C 12 The substituents of the heteroaryl group are preferably methyl or ethyl.
The C is 1 ～C 10 The heteroaliphatic radical is preferably a substituted or unsubstituted C 1 ～C 10 Heterocyclic groups of (a).
The C is 1 ～C 10 The linear or branched alkyl radical of (2) is preferably C 1 ～C 4 The straight or branched alkyl groups of (a) include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc. The C is 1 ～C 10 The linear or branched alkoxy radical of (2) is preferably C 1 ～C 4 The straight-chain or branched alkoxy group of (a) includes, but is not limited to, specifically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.
The C is 3 ～C 10 Cycloalkyl is preferably C 3 ～C 6 Cycloalkyl groups include, in particular, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
The C is 6 ～C 12 Aryl of (2) is preferably C 6 ～C 8 More preferably phenyl or benzyl.
Preferably, X is selected from halogen, -NO 3 、CH 3 COO - 、CCl 3 COO - 、CF 3 COO - 、ClO 4 - 、BF 4 - 、BPh 4 - 、-CN、-N 3 P-methylbenzoic acid radicalP-toluenesulfonate, o-nitrophenoxy, p-nitrophenoxy, m-nitrophenoxy, 2, 4-dinitrophenol oxy, 3-5 dinitrophenol oxy, 2,4, 6-trinitrophenol oxy, 3, 5-dichlorophenol oxy, 3, 5-difluorophenol oxy, 3, 5-di-trifluoromethyl phenol oxy or pentafluorophenol oxy anions; more preferably halogen or p-toluenesulfonate.
Preferably, M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium; more preferably magnesium, aluminium, zinc or chromium; further preferably aluminum.
Preferably, the R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、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, C 1 ～C 10 Straight-chain or branched alkyl, C 1 ～C 10 Straight-chain or branched alkoxy, C 3 ～C 10 Cycloalkyl, C 1 ～C 10 Heterocyclic groups of C 6 ～C 12 Aryl, C of (2) 1 ～C 12 One or more of the heteroaryl groups of (a).
The C is 1 ～C 10 Straight-chain or branched alkyl, C 1 ～C 10 Straight-chain or branched alkoxy, C 3 ～C 10 Cycloalkyl, C 1 ～C 10 Heterocyclic groups of C 6 ～C 12 Aryl, C of (2) 1 ～C 12 The heteroaryl groups of (2) are the same as those described above, and the description thereof will not be repeated here.
The X is selected from halogen or p-toluenesulfonate;
the M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
the invention preferably provides thatHaving a structure represented by II-a：
Preferably, said R 1 、R 8 、R 13 Independently selected from hydrogen, halogen, C 1 ～C 10 Straight-chain or branched alkyl, C 1 ～C 10 Straight-chain or branched alkoxy, C 3 ～C 10 Cycloalkyl, C 1 ～C 10 Heterocyclic groups of C 6 ～C 12 Aryl, C of (2) 1 ～C 12 One or more of the heteroaryl groups of (a).
More preferably, said R 1 、R 8 、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, tert-butoxy.
Further preferably, said R 1 、R 8 、R 13 Independently selected from bromine or ethyl.
Preferably, said X is selected from halogen or p-toluenesulfonate; more preferably, the X is selected from Cl or p-toluenesulfonate.
Preferably, the M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium; more preferably magnesium, aluminium, zinc or chromium; further preferably aluminum.
In some embodiments of the invention, theHas a structure shown in a formula II-b:
the invention can regulate and control the synergistic effect by regulating the connecting group between porphyrin and cyclophosphazene, thereby
Wherein, preferably, q is selected from integers between 1 and 16; more preferably an integer between 3 and 12; feeding in
In some embodiments of the invention, when the linking group is selected from 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) is prone to form ether units.
When the linking group is of formula iii-b (n=6), the catalyst structure is EC2 or EC4 and the carbonate content is 56%, 89%, 91%, 95%, 96% (the ether segment content is lower than the carbonate content), i.e. carbonate units tend to be formed.
Preferably, the multi-center metalloporphyrin complex based on the cyclophosphazene skeleton has any one of the following structures:
the multi-center metalloporphyrin complex EC1, EC2, EC3, EC4, EC5 or EC6 based on the cyclophosphazene skeleton is applied to copolymerization reaction of propylene oxide and carbon dioxide, and the TOF value can be obtained up toUntil 226300h -1 。
The invention also provides a multi-center metalloporphyrin complex based on a cyclophosphazene skeleton, which has a structure shown in a formula IV:
wherein, preferably, n is an integer between 3 and 7; more preferably 3, 4, 5. In some embodiments of the invention, 3 or 4 is preferred.
Preferably, q is selected from integers between 1 and 16; more preferably an integer of 3 to 12; further preferably 6.
Preferably, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、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 C 1 ～C 10 Aliphatic radical, substituted or unsubstituted C 1 ～C 10 Heteroaliphatic, substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 1 ～C 12 One or more of heteroaryl.
Preferably, X is selected from halogen, -NO 3 、CH 3 COO - 、CCl 3 COO - 、CF 3 COO - 、ClO 4 - 、BF 4 - 、BPh 4 - 、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoxy, p-nitrophenoxy, m-nitrophenoxy, 2, 4-dinitrophenol oxy, 3-5 dinitrophenol oxy, 2,4, 6-trinitrophenol oxy, 3, 5-dichlorophenol oxy, 3, 5-difluorophenol oxy, 3, 5-di-trifluoromethyl phenol oxy or pentafluorophenol oxy anions.
Preferably, M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
Preferably, the multi-center metalloporphyrin complex based on the cyclophosphazene skeleton has any one of the following structures:
the multi-center metalloporphyrin complex EC2 and EC4 based on the cyclic phosphazene skeleton are applied to the preparation of polycarbonate, which is more beneficial to improving the carbonate content in the polymer.
Preferably, the molar ratio of the multi-center metalloporphyrin complex based on the cyclic phosphazene skeleton to the epoxide is 1: (2000-2000000); more preferably 1: (10000 ～ 1000000). In some embodiments of the invention, the molar ratio of the multicenter metalloporphyrin complex based on the cyclic phosphazene skeleton to the epoxide is 1:60000 or 1:300000 or 1:80000 or 1:400000.
Preferably, the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide; more preferably one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide. In some embodiments of the invention, propylene oxide is preferred.
Preferably, the pressure of the carbon dioxide is 0.1-8 MPa; more preferably 1 to 6MPa. In the present invention, it is particularly preferably 4MPa.
Preferably, the temperature of the copolymerization reaction is 20-150 ℃; more preferably from 25 to 120 ℃; further preferably 50℃or 70℃or 80℃or 120℃or 25 ℃.
Preferably, the copolymerization reaction time is 0.1 to 48 hours; more preferably 0.2 to 5 hours. In some embodiments of the invention, it is preferably 0.15h or 0.5h or 1h or 3h.
Compared with the prior art, the multi-center metalloporphyrin complex based on the cyclophosphazene skeleton is applied to carbon dioxide and carbon dioxideHas excellent catalytic activity (TOF/h) in the reaction of synthesizing polycarbonate by epoxide copolymerization -1 ) Can reach 10 6 On the order of magnitude. The multi-center metalloporphyrin complex based on the cyclophosphazene skeleton has definite number of active centers and can be regulated by the cyclophosphazene type to obtain structures with different numbers of active centers. In addition, the carbonate content of the polymer can be adjusted by adjusting the linking group between the porphyrin and the cyclic phosphazene. The complex can be used for preparing the polycarbonate material by ultra-high activity catalysis at high temperature while maintaining high selectivity.
Detailed Description
To further illustrate the present invention, the following describes in detail the application of the multi-center metalloporphyrin complex based on cyclophosphazene skeleton provided in the present invention in connection with examples.
Example 1
In a 2000mL three-necked flask, 98g of ground ammonium chloride, 600mL of chlorobenzene, 2.5g of magnesium oxide and 20mL of pyridine were sequentially added, and the mixture was heated and stirred until the chlorobenzene was refluxed. Then, a chlorobenzene solution containing about 298g (800 mL) of phosphorus pentachloride was added dropwise, and after about 3 hours, the solution was kept under reflux for 2 to 3 hours until the HCl in the gas-guide tube was significantly reduced, and the heating was stopped. And thoroughly discharging HCl gas in the system, cooling the reaction system, and filtering to obtain a pale yellow solution. Washing the solution with distilled water for 2-3 times until the organic layer is clear and transparent, separating the chlorobenzene layer, adding anhydrous sodium sulfate, drying overnight, filtering, distilling under reduced pressure to remove chlorobenzene to obtain yellow crude product, recrystallizing with n-heptane to obtain white diamond crystal, and sublimating under reduced pressure at 60 ℃ to obtain the product EL1. The yield was about 40%. 31 P-NMR(CDCl 3 Ppm): 20.1, high resolution electrospray Mass Spectrometry analysis, the result of the analysis was [ Cl ] 6 N 3 P 3 ]：347.64，found：347.37。
15g (120 mmol) of 3-hydroxybenzaldehyde, 68.1g (370 mmol) of 4-bromobenzaldehyde and 33g (490 mmol) of pyrrole are added to 500mL of propionic acid, the mixture is heated to about 130 ℃ and refluxed for 1.5h, the reaction mixture is cooled to room temperature after the completion of the reaction, the reaction mixture is concentrated to 200mL, the mixture is cooled overnight in a refrigerator after methanol is added, and the obtained product is filtered by silica gel column chromatography (CHCl) 3 /CH 3 OH) to yield the product EL2 in about 7.8%. 1 H-NMR(CDCl 3 Ppm): 8.9,8.8,8.1,7.8,7.2, -2.8. High resolution electrospray mass spectrometry analysis, analysis result is [ C 44 H 27 Br 3 N 4 O]：863.97，found：863.86。
To a solution of hexachlorocyclotriphosphazene (0.0057 mmol) in tetrahydrofuran, 0.037mmole EL2 and 0.037mmole cesium carbonate were added under nitrogen. The reaction mixture was stirred at room temperature for 0.5h, followed by stirring at 80℃for 6h. The reaction mixture was filtered, and the resulting filtrate was subjected to precipitation of a solid under glacial diethyl ether and thorough washing with diethyl ether to give a purple solid EL3 in 95% yield. 31 P-NMR(CDCl 3 Ppm): 9.3, high resolution electrospray Mass Spectrometry analysis, analysis results were [ C ] 264 H 156 Br 18 N 27 O 6 P 3 ]：5333.53，found：5333.62。
Dissolving the ligand EL3 in dichloromethane under the protection of nitrogen, and dropwise adding AlEt 2 Cl (diethylaluminum chloride), and stirred at room temperature for 2h. The obtained product is purified by column chromatography and then dried to obtain the required complex EC1.
Example 2
2.18g (2.50 mmol) of EL2, 0.50mL (3.25 mmol) of 6-bromo-1-hexanol, 0.17g of potassium carbonate and 0.01g of potassium iodide were dissolved in 200mL of anhydrous THF under nitrogen, and the mixture was stirred and heated under reflux for 12 hours. After the reaction was completed, the product was dried by spin-drying and dissolved with methylene chloride, and extracted and washed 3 times with water, and the organic phase was dried over anhydrous magnesium sulfate and dried by spin-drying. The solid product obtained was purified by column chromatography on an alumina column with methylene chloride as eluting phase to give about 2.03g of product EL 4. High resolution electrospray mass spectrometry analysis, analysis result is [ C 50 H 39 Br 3 N 4 O 2 ]：967.60，found：967.12。
Under nitrogen, 0.037mmol EL4 and 0.037mmol cesium carbonate were added to 0.0057mmol hexachlorocyclotrixPhosphazene (EL 1) tetrahydrofuran solution. The reaction mixture was stirred at room temperature for 0.5h, followed by stirring at 80℃for 6h. The reaction mixture was filtered, and the resulting filtrate was subjected to precipitation of a solid under glacial diethyl ether and thorough washing with diethyl ether to give a purple solid EL5 in 95% yield. 31 P-NMR(CDCl 3 Ppm): 9.0, high resolution electrospray mass spectrometry analysis, analysis results were [ C 300 H 228 Br 18 N 27 O 12 P 3 ]：5931.82，found：5931.22。
Dissolving the ligand EL5 in dichloromethane under the protection of nitrogen, and dropwise adding AlEt 2 Cl (diethylaluminum chloride), and stirred at room temperature for 2h. The obtained product is purified by column chromatography and then dried to obtain the required complex EC2.
Example 3
In a 2000mL three-necked flask, 98g of ground ammonium chloride, 600mL of chlorobenzene, 2.5g of magnesium oxide and 20mL of pyridine were sequentially added, and the mixture was heated and stirred until the chlorobenzene was refluxed. Then, a chlorobenzene solution containing about 298g (800 mL) of phosphorus pentachloride was added dropwise, and after about 3 hours, the solution was kept under reflux for 2 to 3 hours until the HCl in the gas-guide tube was significantly reduced, and the heating was stopped. And thoroughly discharging HCl gas in the system, cooling the reaction system, and filtering to obtain a pale yellow solution. Washing the solution with distilled water for 2-3 times until the organic layer is clear and transparent, separating the chlorobenzene layer, adding anhydrous sodium sulfate, drying overnight, filtering, distilling under reduced pressure to remove chlorobenzene to obtain yellow crude product, recrystallizing with n-heptane to obtain white diamond crystal, and sublimating under reduced pressure at 60 ℃ to obtain hexachlorocyclotriphosphazene (EL 1), wherein the non-sublimated solid is the target product octachlorocyclotetraphosphazene (EL 6). The yield was about 30%. 31 P-NMR(CDCl 3 Ppm): 21.3 high resolution electrospray Mass Spectrometry analysis, the analysis result was [ Cl ] 8 N 4 P 4 ]：463.53，found：463.20。
Under nitrogen, 0.037mmole EL2 and 0.037mmole cesium carbonate were added to a solution of 0.0057 mmole octachlorocyclotetraphosphazene (EL 6) in tetrahydrofuran. The reaction mixture was stirred at room temperature for 0.5h, followed by stirring at 80℃for 6h. The reaction mixture was filtered, and the resulting filtrate was subjected to precipitation of a solid under glacial diethyl ether and thorough washing with diethyl ether to give a purple solid EL7 in 95% yield. 31 P-NMR(CDCl 3 Ppm): 10.6, high resolution electrospray Mass Spectrometry analysis, analysis results [ C 352 H 208 Br 24 N 36 O 8 P 4 ]：7111.37，found：7111.26。
Dissolving the ligand EL7 in dichloromethane under the protection of nitrogen, and dropwise adding AlEt 2 Cl (diethylaluminum chloride), and stirred at room temperature for 2h. The obtained product is purified by column chromatography and then dried to obtain the required complex EC3.
Example 4
To a solution of 0.0057mmol of octachlorocyclotetraphosphazene (EL 6) in tetrahydrofuran, 0.037mmole of EL4 and 0.037mmole of cesium carbonate are added under nitrogen. The reaction mixture was stirred at room temperature for 0.5h, followed by stirring at 80℃for 6h. The reaction mixture was filtered, and the resulting filtrate was subjected to precipitation of a solid under glacial diethyl ether and thorough washing with diethyl ether to give a purple solid EL8 in 95% yield. 31 P-NMR(CDCl 3 Ppm): 10.1, high resolution electrospray Mass Spectrometry analysis, analysis results were [ C ] 400 H 304 Br 24 N 36 O 16 P 4 ]：7909.15，found：7909.05。
The ligand EL8 was dissolved in methylene chloride under the protection of nitrogen, alEt2Cl (diethylaluminum chloride) was added dropwise thereto, and the reaction was stirred at room temperature for 2 hours. The obtained product is purified by column chromatography and then dried to obtain the required complex EC4.
Example 5
15g (120 mmol) of 3-hydroxybenzaldehyde, 49.6g (370 mmol) are reacted4-ethylbenzaldehyde and 33g (490 mmol) of pyrrole were added to 500mL of propionic acid, heated to 130℃and refluxed for 1.5 hours, cooled to room temperature after the reaction was completed, concentrated to 200mL, cooled overnight in a refrigerator after methanol was added, and the obtained product was filtered through silica gel column chromatography (CHCl 3 /CH 3 OH) to yield the product EL2 in about 7.8%. 1 H-NMR(CDCl 3 Ppm): 8.9,8.8,8.1,7.8,7.2,3.2,1.5, -2.8. High resolution electrospray mass spectrometry analysis, analysis result is [ C 50 H 42 N 4 O]：714.91，found：715.2。
To a solution of hexachlorocyclotriphosphazene (0.0057 mmol) in tetrahydrofuran, 0.037mmol EL9 and 0.037mmol cesium carbonate were added under nitrogen. The reaction mixture was stirred at room temperature for 0.5h, followed by stirring at 80℃for 6h. The reaction mixture was filtered, and the resulting filtrate was subjected to precipitation of a solid under glacial diethyl ether and thorough washing with diethyl ether to give a purple solid EL10 in 95% yield. 31 P-NMR(CDCl 3 Ppm): 9.6, high resolution electrospray Mass Spectrometry analysis, analysis results [ C ] 300 H 246 N 27 O 6 P 3 ]：4418.37，found：4419.80。
Dissolving the ligand EL10 in dichloromethane under the protection of nitrogen, and dropwise adding AlEt 2 Cl (diethylaluminum chloride), and stirred at room temperature for 2h. The obtained product is purified by column chromatography and then dried to obtain the required complex EC5.
Example 6
0.3mmol of EC1 was dissolved in a chloroform/acetonitrile mixed solution at room temperature, followed by addition of 1.9mmol of silver p-methylbenzenesulfonate (AgOTs), and the resulting mixture was stirred overnight under dark conditions. After the reaction is finished, spin-drying the solvent, adding chloroform for fully dissolving, filtering out precipitate, spin-drying the obtained filtrate to obtain purple powder, and carrying out heat preservation for 48 hours in a vacuum oven at 70 ℃ to obtain the required complex EC6.
Example 7
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC1 prepared in example 1 and 90mmol of dried propylene oxide were added into 15mL of a high-pressure reaction kettle which had been dehydrated and deoxygenated, the high-pressure reaction kettle was taken out of the glove box, carbon dioxide was then introduced into the high-pressure reaction kettle through a carbon dioxide supply line having a pressure regulating function, the pressure in the high-pressure reaction kettle was brought to 4MPa, and the polymerization reaction was carried out at a temperature of 50℃for 0.5 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The H-NMR nuclear magnetism of the polycarbonate prepared in example 7 shows that the content of carbonate units in the polycarbonate is 47%, and the content of cyclic carbonate byproducts is less than 0.01%; the TOF value of the catalytic system is 9289h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate thus obtained was 84000 and the molecular weight distribution was 1.22 as determined by GPC.
Example 8
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC1 prepared in example 1 and 450mmol of dry propylene oxide were added into a 25mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the temperature of the autoclave was controlled at 70℃to conduct polymerization for 1 hour. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 H-NMR Nuclear magnetic pair example8, the result shows that the content of carbonate units in the polycarbonate is 30 percent, and the content of cyclic carbonate byproducts is less than 0.01 percent; the TOF value of the catalytic system is 15200h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 198000 and the molecular weight distribution was 1.27 as measured by GPC.
Example 9
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC1 prepared in example 1 and 450mmol of dry propylene oxide were added into a 25mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at a temperature of 80℃for 0.5 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The H-NMR nuclear magnetism of the polycarbonate prepared in example 9 shows that the content of carbonate units in the polycarbonate is 31%, and the content of cyclic carbonate byproducts is less than 0.01%; the TOF value of the catalytic system is 35600h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 156000 and the molecular weight distribution was 1.21 as measured by GPC.
Example 10
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC1 prepared in example 1 and 450mmol of dry propylene oxide were added into a 50mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at 120℃for 0.15 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, opening the reaction kettle for taking a sample for the first time, and feedingRow of lines 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The H-NMR nuclear magnetism of the polycarbonate prepared in example 10 showed that the polycarbonate contains 38% of carbonate units and less than 0.1% of cyclic carbonate by-product; the TOF value of the catalytic system is 105000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 135000 and the molecular weight distribution was 1.27 as determined by GPC.
Example 11
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC1 prepared in example 1 and 90mmol of dried propylene oxide were added into a 25mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at a temperature of 25℃for 3 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The H-NMR nuclear magnetism of the polycarbonate prepared in example 11 showed that the polycarbonate contains 42% of carbonate units and less than 0.01% of cyclic carbonate by-product; the TOF value of the catalytic system is 1560h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate thus obtained was 63000 and the molecular weight distribution was 1.23 as determined by GPC.
Example 12
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC2 prepared in example 2 and 90mmol of dried propylene oxide are added into a 50mL high-pressure reaction kettle which is dehydrated and deoxidized, then the high-pressure reaction kettle is taken out of the glove box, and carbon dioxide is filled into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure regulating function, so that the pressure in the high-pressure reaction kettle reachesTo 4MPa, the temperature of the autoclave was controlled at 50℃to carry out polymerization for 0.5h. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The H-NMR nuclear magnetism of the polycarbonate prepared in example 12 shows that the content of carbonate units in the polycarbonate is 96%, and the content of cyclic carbonate byproducts is less than 0.01%; the TOF value of the catalytic system is 8500h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 10600 as measured by GPC, and the molecular weight distribution was 1.19.
Example 13
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC2 prepared in example 2 and 450mmol of dry propylene oxide were added into a 50mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at a temperature of 70℃for 1 hour. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 13 was examined by H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 89% and a cyclic carbonate by-product content of less than 1%; the TOF value of the catalytic system is 12100h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 168000 and the molecular weight distribution was 1.22 as measured by GPC.
Example 14
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC2 prepared in example 2 and 450mmol of dry propylene oxide were added to a high volume of 50ml after water removal and oxygen removalAnd taking the high-pressure reaction kettle out of the glove box, filling carbon dioxide into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure regulating function to enable the pressure in the high-pressure reaction kettle to reach 4MPa, and controlling the temperature of the high-pressure reaction kettle at 120 ℃ for polymerization reaction for 0.5h. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 14 was examined by H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 89% and a cyclic carbonate by-product content of less than 0.1%; the TOF value of the catalytic system is 30200h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 99000 and the molecular weight distribution was 1.33 as determined by GPC.
Example 15
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC3 prepared in example 3 and 600mmol of dried propylene oxide were added into a 50mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at a temperature of 70℃for 0.15 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 15 was examined by H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 28% and a cyclic carbonate by-product content of less than 0.01%; the TOF value of the catalytic system is 129700h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 153000 and the molecular weight distribution was 1.25 as measured by GPC.
Example 16
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC3 prepared in example 3 and 600mmol of dried propylene oxide were added into a 50mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at 120℃for 0.15 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The H-NMR nuclear magnetism of the polycarbonate prepared in example 16 showed that the polycarbonate contains 30% of carbonate units and less than 0.1% of cyclic carbonate by-product; the TOF value of the catalytic system is 226300h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 191000 and the molecular weight distribution was 1.51 as measured by GPC.
Example 17
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC3 prepared in example 3 and 120mmol of dried propylene oxide were added into a 15mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at a temperature of 25℃for 0.5 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The polycarbonate obtained in example 17 was examined for H-NMR nuclear magnetism, and it was found that the polycarbonate had a carbonate unit content of 35% and a cyclic carbonateThe content of byproducts is less than 0.01%; the TOF value of the catalytic system is 6622h through calculation -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate thus obtained was 97000 and the molecular weight distribution was 1.21 as determined by GPC.
Example 18
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC4 prepared in example 4 and 600mmol of dry propylene oxide were added to a 50mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at a temperature of 50℃for 1 hour. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 18 was examined by H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 95% and a cyclic carbonate by-product content of less than 0.01%; the TOF value of the catalytic system is 13300h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 153000 and the molecular weight distribution was 1.25 as measured by GPC.
Example 19
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC4 prepared in example 4 and 600mmol of dried propylene oxide were added to a 50ml autoclave which had been dehydrated and deoxygenated, and then the autoclave was taken out of the glove box, and carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, so that the pressure in the autoclave became 4MPa, and the polymerization was carried out at a temperature of 70℃for 1 hour. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. Pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonAcid esters.
By passing through 1 The polycarbonate prepared in example 19 was examined by H-NMR nuclear magnetism, which revealed that the polycarbonate had a carbonate unit content of 91% and a cyclic carbonate by-product content of less than 0.01%; the TOF value of the catalytic system is 25497h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 167000 and the molecular weight distribution was 1.29 as measured by GPC.
Example 20
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC4 prepared in example 4 and 600mmol of dried propylene oxide were added into a 50mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at 120℃for 0.5 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The H-NMR nuclear magnetism of the polycarbonate prepared in example 20 shows that the content of carbonate units in the polycarbonate is 56%, and the content of cyclic carbonate byproducts is less than 0.01%; the TOF value of the catalytic system is 52893h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 92000 and the molecular weight distribution was 1.13 as measured by GPC.
Example 21
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC5 prepared in example 5 and 450mmol of dry propylene oxide were added into a 25mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the temperature of the autoclave was controlled at 70℃to conduct polymerization for 1 hour. Slowly releasing after the polymerization reaction is finishedDropping carbon dioxide in the high-pressure reaction kettle, opening the reaction kettle to take a sample for the first time, and performing 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 21 was examined by H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 37% and a cyclic carbonate by-product content of less than 0.01%; the TOF value of the catalytic system is 12200h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 118000 and the molecular weight distribution was 1.21 as measured by GPC.
Example 22
In a glove box, 0.0015mmol of the aluminum porphyrin complex EC6 prepared in example 6 and 450mmol of dry propylene oxide were added into a 25mL autoclave which had been dehydrated and deoxygenated, the autoclave was then taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 4MPa, and the polymerization was carried out at a temperature of 70℃for 1 hour. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle to take a sample for the first time to perform 1 H-NMR nuclear magnetic measurement. The unreacted propylene oxide was removed in a vacuum oven at 45℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 22 was examined by H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 39% and a cyclic carbonate by-product content of less than 0.01%; calculated TOF value of the catalytic system is 18200h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 218000 and the molecular weight distribution was 1.31 as measured by GPC.
As can be seen from the above examples, the multi-center metalloporphyrin complex based on cyclophosphazene skeleton prepared by the present invention has ultra-high activity, good product selectivity and high temperature stability when being used as a catalyst for preparing polycarbonate materials.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims (10)

1. The use of a multi-centered metalloporphyrin complex based on a cyclophosphazene skeleton as a catalyst for the copolymerization of carbon dioxide and epoxides.
2. A preparation method of polycarbonate is characterized in that a multi-center metalloporphyrin complex based on a cyclophosphazene skeleton is used as a catalyst to catalyze copolymerization reaction of carbon dioxide and epoxide, so that polycarbonate is prepared.
3. The method for preparing polycarbonate according to claim 2, wherein the multi-center metalloporphyrin complex based on cyclophosphazene skeleton has a structure represented by formula i:
wherein n is an integer between 3 and 7;
4. the method of claim 3, wherein the metalloporphyrin complex has a structure represented by formula ii:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、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 C 1 ～C 10 Aliphatic radical, substituted or unsubstituted C 1 ～C 10 Heteroaliphatic, substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 1 ～C 12 One or more of heteroaryl;
x is selected from halogen, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 - 、BF 4 - 、BPh 4 - 、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoxy, p-nitrophenoxy, m-nitrophenoxy, 2, 4-dinitrophenol oxy, 3-5 dinitrophenol oxy, 2,4, 6-trinitrophenol oxy, 3, 5-dichlorophenol oxy, 3, 5-difluorophenol oxy, 3, 5-di-trifluoromethyl phenol oxy or pentafluorophenol oxy anions;
m is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
5. The method for producing a polycarbonate according to claim 4, wherein R is as defined in claim 4 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、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, C 1 ～C 10 Straight-chain or branched alkyl, C 1 ～C 10 Straight-chain or branched alkoxy, C 3 ～C 10 Cycloalkyl, C 1 ～C 10 Heterocyclic groups of C 6 ～C 12 Aryl, C of (2) 1 ～C 12 One or more of the heteroaryl groups of (a);
the X is selected from halogen or p-toluenesulfonate;
the M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
6.
Wherein q is an integer from 1 to 16.
7. The method for producing a polycarbonate according to claim 2, wherein the multi-center metalloporphyrin complex based on a cyclophosphazene skeleton has any one of the following structures:
8. the multi-center metalloporphyrin complex based on the cyclophosphazene skeleton is characterized by having a structure shown in a formula IV:
wherein n is an integer between 3 and 7;
q is an integer from 1 to 16;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、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 C 1 ～C 10 Aliphatic radical, substituted or unsubstituted C 1 ～C 10 Heteroaliphatic, substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 1 ～C 12 One or more of heteroaryl;
x is selected from halogen, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 - 、BF 4 - 、BPh 4 - 、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoxy, p-nitrophenoxy, m-nitrophenoxy, 2, 4-dinitrophenol oxy, 3-5 dinitrophenol oxy, 2,4, 6-trinitrophenol oxy, 3, 5-dichlorophenol oxy, 3, 5-difluorophenol oxy, 3, 5-di-trifluoromethyl phenol oxy or pentafluorophenol oxy anions;
m is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
9. The cyclophosphazene skeleton-based multi-center metalloporphyrin complex according to claim 8, wherein the cyclophosphazene skeleton-based multi-center metalloporphyrin complex has any one of the following structures:
10. the method for producing a polycarbonate according to claim 2, wherein the molar ratio of the multicenter metalloporphyrin complex based on the cyclic phosphazene skeleton to the epoxide is 1: (2000-2000000);
the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1, 2-epoxybutane, epoxycyclohexane, epoxycyclopentane, epoxychloropropane, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.
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