CN115838453A - High-molecular heteronuclear porphyrin complex and preparation method and application thereof - Google Patents

High-molecular heteronuclear porphyrin complex and preparation method and application thereof Download PDF

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CN115838453A
CN115838453A CN202211475029.6A CN202211475029A CN115838453A CN 115838453 A CN115838453 A CN 115838453A CN 202211475029 A CN202211475029 A CN 202211475029A CN 115838453 A CN115838453 A CN 115838453A
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oxygen
independently selected
heteronuclear
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porphyrin complex
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张若禹
刘顺杰
王献红
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a macromolecular heteronuclear porphyrin complex which has a structure shown in a formula I. The porphyrin complex is obtained by randomly copolymerizing a pre-metallized porphyrin monomer and an unmetallized porphyrin monomer and complexing with another metal, so that the porphyrin complex containing a plurality of different metal centers can be rapidly prepared, and the metals can respectively realize different functions in the polymerization process. Compared with the prior art, the performance of the high-molecular heteronuclear porphyrin complex can be adjusted by changing the substituent of the porphyrin monomer and the types and the proportion of two metals, and the high-molecular heteronuclear porphyrin complex serving as a catalyst can realize the conversion from olefin to degradable polyester by a one-pot method, which is difficult at the present stage, and has high polymer selectivity.

Description

High-molecular heteronuclear porphyrin complex and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a high-molecular heteronuclear porphyrin complex, a preparation method and application thereof, in particular to a metalloporphyrin complex, olefin epoxidation and ring-opening polymerization of epoxides.
Background
In industrial production, since carbon-carbon single bond is difficult to degrade, the preparation of degradable high molecular materials by olefin is a challenging subject, and is an important research direction when the influence of white pollution on environment is increasingly emphasized.
In 2014, nozaki prepared the six-membered cyclic monomer EVL by reacting carbon dioxide with 1,3-butadiene. In subsequent researches, preparation of polyester is realized by means of anionic polymerization or cationic copolymerization and the like on EVL, and the obtained polyester has excellent degradability and recycling performance. Under such a development, it is now common to improve the degradability of olefin polymers by introducing ester bonds into the main chain.
However, the existing means for introducing ester bonds have high requirements on the types of olefins, and are often limited to a few double bond monomers, thereby limiting the further development of the field. It is worth noting that olefins are important raw materials for epoxides, and epoxides can be copolymerized alternately with anhydrides or carbon dioxide to make degradable materials. Thus, the preparation of polyesters or polyesters by epoxidation of olefins and in situ copolymerization in a one-pot process is a new route that can be used for the conversion of various olefin monomers to degradable materials.
Disclosure of Invention
In view of the above, the present invention aims to provide a high molecular heteronuclear porphyrin complex, and a preparation method and an application thereof, and the high molecular heteronuclear porphyrin complex provided by the present invention can realize the conversion from olefin to degradable polyester, and has high polymer selectivity.
The invention provides a high-molecular heteronuclear porphyrin complex which has a structure shown in a formula I:
Figure BDA0003959553860000021
in the formula I, R 1 ～R 6 Independently selected from hydrogen, halogen, fatA group, a substituted aliphatic group, a substituted heteroaliphatic group, an aryl group, a substituted aryl group, or a substituted heteroaryl group;
M 1 、M 2 independently selected from magnesium, aluminium, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
X 1 、X 2 independently selected from halo, -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-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2,4-dinitrophenol oxygen, 3,5-dinitrophenol oxygen, 2,4,6-trinitrophenol oxygen, 3,5-dichlorophenol oxygen, 3,5-difluorophenol oxygen, 3,5-bis-trifluoromethylphenol oxygen, or pentafluorophenol oxygen anions;
m and n are polymerization degrees and are independently selected from 3 to 40.
Preferably, it has the structure of formula II:
Figure BDA0003959553860000022
in the formula II, R 7 、R 8 Independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl.
Preferably, said R is 7 ，R 8 Independently selected from hydrogen, halogen; said X 1 、X 2 Independently selected from Cl; and m and n are independently selected from 3 to 10.
The invention provides a preparation method of a high-molecular heteronuclear porphyrin complex in the technical scheme, which comprises the following steps:
a compound having the structure of formula V and a compound containing M 2 And X 2 The compound (b) is subjected to a third reaction to obtain a high-molecular heteronuclear porphyrin complex;
Figure BDA0003959553860000031
preferably, the preparation method of the compound with the structure of the formula V comprises the following steps:
reacting a compound of formula III with a compound containing M 1 And X 1 The compound (b) is subjected to a first reaction to obtain a monomer with metalloporphyrin;
carrying out a second reaction on the monomer with metalloporphyrin and the compound with the structure of formula IV to obtain a compound with a structure of formula V;
Figure BDA0003959553860000032
the invention provides a method for preparing polyester by an olefin one-pot method, which comprises the following steps:
under the catalytic action of a high-molecular heteronuclear porphyrin complex, reacting olefin, iodosobenzene and acid anhydride to obtain polyester; the macromolecular heteronuclear porphyrin complex is the macromolecular heteronuclear porphyrin complex in the technical scheme.
Preferably, the olefin is selected from one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene and styrene; the acid anhydride is selected from one or more of succinic anhydride, glutaric anhydride, 1,2-cyclosuccinic anhydride, 1,2-cyclohexane dicarboxylic anhydride, phthalic anhydride, bicyclo [2.2.2] octane-2,3-dicarboxylic anhydride.
Preferably, the temperature of the reaction is 20 to 80 ℃.
Preferably, the reaction time is 0 to 120 hours.
Preferably, the mass ratio of olefin to anhydride is 1: (0.5 to 2); the mass ratio of the olefin to the iodosobenzene is 1: (1-2); the mass ratio of the olefin to the high molecular heteronuclear porphyrin complex is (500-10000): 1.
the invention provides a macromolecular heteronuclear porphyrin complex for preparing polyester by olefin one-pot epoxidation-ring-opening copolymerization, which adopts iodosobenzene as an oxidant and two metals for catalyzing epoxidation and ring-opening copolymerization respectively. The high-molecular heteronuclear porphyrin complex provided by the invention can realize the conversion from olefin to degradable polyester by a one-pot method, and has higher polymer selectivity.
The porphyrin complex is obtained by randomly copolymerizing a pre-metallized porphyrin monomer and an unmetallized porphyrin monomer and complexing with another metal, so that the porphyrin complex containing a plurality of different metal centers can be rapidly prepared, and the metals can respectively realize different functions in the polymerization process. Compared with the prior art, the invention can adjust the performance by changing the substituent group of the porphyrin monomer and the types and the proportion of the two metals. The catalyst provided by the invention can realize the conversion from olefin to degradable polyester in a one-pot method which is difficult at the present stage, and has higher polymer selectivity.
Experimental results show that the molecular weight of the polyester obtained by the olefin epoxidation and the copolymerization of the olefin and the anhydride is 700-1500 g/mol, the molecular weight distribution is 1.1-1.3, and the cyclic by-product in the reaction product can be reduced to 2%.
Drawings
FIG. 1 is a reaction scheme showing preparation of a complex EL3 in an example of the present invention
FIG. 2 is a reaction scheme for the preparation of EC1, EC2 and EC3 in examples of the invention;
FIG. 3 is a reaction scheme for the preparation of EC4 in an example of the present invention;
FIG. 4 is a reaction scheme for the preparation of EC5 in an example of the invention;
FIG. 5 is a nuclear magnetic detection spectrum of EL3 in an example of the present invention;
FIG. 6 is a nuclear magnetic detection spectrum of EC1 in an example of the present invention;
FIG. 7 is a GPC chart of the polyester prepared in application example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a high-molecular heteronuclear porphyrin complex, which has a structure shown in a formula I:
Figure BDA0003959553860000051
in the present invention, in formula I, R 1 ～R 6 Independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl; m 1 、M 2 Independently selected from magnesium, aluminium, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium; x 1 、X 2 Independently selected from halo, -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-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2,4-dinitrophenol oxygen, 3,5-dinitrophenol oxygen, 2,4,6-trinitrophenol oxygen, 3,5-dichlorophenol oxygen, 3,5-difluorophenol oxygen, 3,5-bis-trifluoromethylphenol oxygen, or pentafluorophenol oxygen anions; m and n are polymerization degrees and are independently selected from 3 to 40, preferably independently selected from 3 to 30, more preferably independently selected from 3 to 10, and most preferably independently selected from 5 to 8.
In the present invention, the structure of formula I is preferably a structure of formula II:
Figure BDA0003959553860000052
in the present invention, in formula II, R 7 、R 8 Independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl or substituted heteroaryl, preferably independently selected from hydrogen, halogen; m 1 、M 2 Independently selected from magnesium, aluminium, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium; x 1 、X 2 Independently selected fromHalogen, preferably independently selected from Cl; m and n are polymerization degrees and are independently selected from 3 to 40; preferably independently selected from 3 to 10.
In the present invention, the formula II structure is preferably one of the following formulae:
Figure BDA0003959553860000061
the invention provides a preparation method of a high-molecular heteronuclear porphyrin complex in the technical scheme, which comprises the following steps:
a compound having the structure of formula V and a compound containing M 2 And X 2 The compound of (a) is subjected to a third reaction to obtain a high-molecular heteronuclear porphyrin complex;
Figure BDA0003959553860000062
in the present invention, the compound containing M 2 And X 2 The compound (b) is preferably selected from diethylaluminium chloride; said group containing M 2 And X 2 Preferably the compound (D) contains M 2 And X 2 A solution of the compound of (a); the solvent in the solution is preferably n-hexane; said group containing M 2 And X 2 The concentration of the solution of the compound (4) is preferably 1 to 3mol/L, more preferably 2mol/L.
In the invention, the compound with the structure V and the compound containing M 2 And X 2 The mass ratio of the compounds of (a) is preferably 1: (1.2 to 1.5), more preferably 1: (1.3-1.4).
In the present invention, the temperature of the third reaction is preferably 20 to 40 ℃, more preferably 25 to 35 ℃, and most preferably 30 ℃. The time for the third reaction is preferably 1 to 3 hours, and more preferably 2 hours.
In the present invention, the third reaction is preferably carried out in a solvent; the solvent is preferably dichloromethane; preferably, the compound with the structure V is dissolved in dichloromethane, and M is dropwise added 2 And X 2 A compound of (1); the third reaction is preferably carried out under stirring; the third reaction is preferably carried out inUnder the protection of nitrogen; after the third reaction is completed, the obtained reaction product is preferably purified by column chromatography and then dried.
In the present invention, the preparation method of the compound with the structure of formula V preferably comprises:
reacting a compound of formula III with a compound containing M 1 And X 1 The compound (b) is subjected to a first reaction to obtain a monomer with metalloporphyrin;
carrying out a second reaction on the monomer with metalloporphyrin and the compound with the structure of formula IV to obtain a compound with a structure of formula V;
Figure BDA0003959553860000071
the source of the compound of formula III and the compound of formula IV is not particularly limited in the present invention, and the compound of formula III and the compound of formula IV can be obtained from the market, or prepared according to the methods well known to those skilled in the art, such as: carrying out one-pot reaction on p-hydroxybenzaldehyde, substituted benzaldehyde and pyrrole under the condition of propionic acid reflux, and collecting a second color band by using a column chromatography separation technology to obtain monohydroxy substituted asymmetric porphyrin; the hydroxyl of the monohydroxy substituted porphyrin and the halogen of the methacrylic chloride are subjected to nucleophilic substitution reaction under the alkaline condition to obtain the compound.
In the present invention, the compound containing M 1 And X 1 The compound of (b) is preferably selected from manganese chloride.
In the present invention, the compound of formula III and the compound containing M 1 And X 1 The mass ratio of the compounds of (a) is preferably 1: (5 to 10), more preferably 1: (6 to 9), most preferably 1: (7-8).
In the present invention, the temperature of the first reaction is preferably 100 to 160 ℃, more preferably 110 to 150 ℃, more preferably 120 to 140 ℃, and most preferably 130 ℃; the time for the first reaction is preferably 20 to 30 hours, more preferably 22 to 28 hours, and most preferably 24 to 26 hours.
In the present invention, the first reaction is preferably carried out in a solvent; the solvent is preferably N, N-dimethylformamide; the first reaction is preferably temperature-rising reflux; after the first reaction is finished, the solvent is preferably removed by distillation under reduced pressure, the dichloromethane is used for dissolving, the saturated saline solution is used for extraction and washing, the obtained organic phase is dried by sodium chloride and then is dried by spinning, and then the dichloromethane is used as an elution phase to be purified by an aluminum peroxide column.
In the present invention, the ratio of the amount of the monomer having metalloporphyrin to the amount of the substance having the structure of formula IV is preferably 1: (0.5 to 8), more preferably 1: (1 to 6), more preferably 1: (2 to 5), most preferably 1: (3-4).
In the present invention, the temperature of the second reaction is preferably 65 to 80 ℃, more preferably 70 to 75 ℃; the time for the second reaction is preferably 30 to 40 hours, more preferably 32 to 38 hours, and most preferably 34 to 36 hours.
In the present invention, the second reaction is preferably carried out under the action of azobisisobutyronitrile and a RAFT agent; the RAFT agent is preferably 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid (DDMAT); the molar ratio of the monomer of the metalloporphyrin, the azobisisobutyronitrile and the RAFT reagent is preferably (10-30): 1: (1 to 3), more preferably (15 to 25): 1: (1.5 to 2.5), most preferably 20:1:2. in the present invention, the second reaction is preferably carried out in a solvent; the solvent is preferably THF; the second reaction is preferably preceded by the removal of oxygen; the method for removing oxygen is preferably freezing-air extraction-thawing; oxygen removal is preferably carried out three times; after the second reaction is completed, the reaction system is preferably quenched in liquid nitrogen and thawed without repeatedly dissolving the precipitate by a dichloromethane-diethyl ether system.
In the present invention, the central metal M 1 、M 2 With co-ligands X 1 、X 2 Coordinating to the porphyrin ring through the metalation reaction of the porphyrin ligand in dichloromethane solution.
The invention provides a method for preparing polyester by an olefin one-pot method, which comprises the following steps:
under the catalytic action of a high-molecular heteronuclear porphyrin complex, reacting olefin, iodosobenzene and acid anhydride to obtain polyester; the macromolecular heteronuclear porphyrin complex is the macromolecular heteronuclear porphyrin complex in the technical scheme.
In the invention, under the catalytic action of the macromolecular heteronuclear porphyrin complex, olefin and iodosobenzene firstly undergo oxidation reaction to generate corresponding epoxide, and the epoxide is copolymerized with anhydride to obtain the polyester.
In the present invention, the olefin is preferably selected from one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene, styrene. In the present invention, the anhydride is selected from one or more of succinic anhydride, glutaric anhydride, 1,2-cyclosuccinic anhydride, 1,2-cyclohexane dicarboxylic anhydride, phthalic anhydride, bicyclo [2.2.2] octane-2,3-dicarboxylic anhydride.
In the present invention, the mass ratio of the olefin to iodosobenzene is preferably 1: (1-2), more preferably 1: (1.3 to 1.7), most preferably 1:1.5. in the present invention, the mass ratio of the olefin to the acid anhydride is preferably 1: (0.5 to 2), more preferably 1: (1-1.5), most preferably 1: (1.2-1.3). In the present invention, the mass ratio of the olefin to the high molecular heteronuclear porphyrin complex is preferably (500 to 10000): 1, more preferably (1000 to 8000): 1, more preferably (2000 to 6000): 1, more preferably (3000 to 5000): 1, most preferably 4000:1.
in the present invention, the reaction is preferably carried out in a bulk reaction or a solution reaction; the solution adopted for the solution reaction is preferably one or more selected from dichloromethane, trichloromethane, tetrahydrofuran, acetonitrile and N, N-dimethylformamide. In the present invention, the reaction is preferably carried out under a protective atmosphere.
In the present invention, the temperature of the reaction is preferably 20 to 80 ℃, more preferably 30 to 70 ℃, more preferably 40 to 60 ℃, and most preferably 50 ℃. In the present invention, the reaction time is preferably 0 to 120 hours, more preferably 10 to 100 hours, more preferably 20 to 80 hours, more preferably 30 to 60 hours, and most preferably 40 to 50 hours.
In the invention, the macromolecular heteronuclear porphyrin complex can realize the conversion from olefin to polyester by connecting two metal complexes of porphyrin on the same polymer chain, and the catalyst has excellent polymer selectivity due to the interaction between the metal porphyrin complexes.
Example 1
Compound EL3 was prepared according to the reaction scheme shown in figure 1:
adding 15g (120 mmol) of 4-hydroxybenzaldehyde, 39g (370 mmol) of benzaldehyde and 33g (490 mmol) of pyrrole into 500mL of propionic acid, heating to 130 ℃, refluxing for 1.5h, cooling to room temperature after the reaction is finished, concentrating the reaction solution to 200mL, adding methanol, cooling in a refrigerator overnight, filtering to obtain a product, and performing silica gel column chromatography (CHCl) 3 /CH 3 OH) to obtain a product EL1 with the yield of about 8.8 percent; 1 H-NMR(CDCl 3 ppm): 8.8,8.2,8.1,7.8,7.2, -2.8; the analysis result of high-resolution electrospray mass spectrometry is [ C ] 44 H 30 N 4 O]：630.24，found：630.42。
Under the protection of nitrogen, 1.45g (2.3 mmol) of EL1 is dissolved in 20mL of anhydrous THF, 0.26g (2.5 mmol) of methacryloyl chloride and 0.25g (2.5 mmol) of triethylamine are dropped at low temperature, and after fully stirring, the mixture is reacted at room temperature for 12 hours; after the reaction is finished, spin-drying the product, dissolving the product by using dichloromethane, extracting and washing the product for 3 times by using water, and spin-drying the organic phase after drying the organic phase by using anhydrous magnesium sulfate; the solid product obtained was purified by means of an alumina column with dichloromethane as the elution phase, giving approximately 1.5g of product EL2; the analysis result of high-resolution electrospray mass spectrometry is [ C ] 48 H 34 N 4 O 2 ]：698.27，found：698.33。
Dissolving 1.5g of EL2 and 3.0g of manganese chloride in 30mLN in an air atmosphere, fully stirring, and heating the mixture to 165 ℃ for refluxing for 24 hours; after the reaction is finished, distilling under reduced pressure to remove the solvent, dissolving with dichloromethane, extracting and washing with saturated saline water for 3 times, drying the organic phase through sodium chloride, then spin-drying, and purifying by using an aluminum peroxide column with dichloromethane as an elution phase to obtain about 1.6g of a product EL 3; by passing 1 And (4) performing HNMR nuclear magnetic detection, and judging that the reaction is complete when a peak at-2.8 ppm chemical shift disappears as shown in figure 5.
The preparation of EC1 according to the reaction scheme shown in fig. 2 gives:
under a nitrogen atmosphere, 1g (1.27 mmol) of EL3 and 0.89g (1.27 mmol) of the mixture were mixed)EL2，10.43mg(6.35×10 - 2 mmol) Azobisisobutyronitrile (AIBN) and 46.26mg (0.127 mmol) RAFT reagent (DDMAT) were dissolved in 40mL anhydrous THF, and after three freeze-pump-thaw cycles to remove oxygen, the mixture was warmed to 70 ℃ for 36h; after the reaction is finished, placing the reaction container in liquid nitrogen for quenching and unfreezing, repeatedly dissolving and precipitating through a dichloromethane/ether system, and separating to obtain 1.25g of multifunctional porphyrin ligand EL4; by passing 1 HNMR NMR and GPC testing gave an m of 7,n of 9;
under the protection of nitrogen, 1g of the ligand EL4 is dissolved in dichloromethane, and 0.4ml of AlEt is added dropwise 2 A Cl solution (diethyl aluminum chloride, 2mol/L n-hexane solution) is stirred and reacts for 2 hours at room temperature; purifying the obtained product by column chromatography, drying to obtain complex EC1, and purifying by column chromatography 1 H NMR nuclear magnetic detection, the disappearance of peaks at-2.8 to-3.6 ppm chemical shift judges that the reaction is complete, and the nuclear magnetic spectrum is shown in figure 6.
Example 2
EL3 and EL2 were obtained according to the method of example 1; EC2 was prepared according to the reaction scheme shown in fig. 2:
under a nitrogen atmosphere, 1g (1.27 mmol) of EL3, 0.45g (0.64 mmol) of EL2, 10.43mg (6.35X 10 mmol) - 2 mmol) Azobisisobutyronitrile (AIBN) and 46.26mg (0.127 mmol) RAFT reagent ((DDMAT) were dissolved in 40mL anhydrous THF, and after removal of oxygen by three freeze-pump-thaw cycles, the mixture was warmed to 70 ℃ for 36h; after the reaction is finished, placing the reaction container in liquid nitrogen for quenching and unfreezing, repeatedly dissolving and precipitating through a dichloromethane/ether system, and separating to obtain 0.82g of multifunctional porphyrin ligand EL5; m by 1H NMR nuclear magnetic resonance and GPC testing gave 9,n of 4;
under the protection of nitrogen, 1g of the ligand EL5 is dissolved in dichloromethane, and 0.2ml of AlEt is added dropwise 2 A Cl solution (diethyl aluminum chloride, 2mol/L n-hexane solution) is stirred and reacts for 2 hours at room temperature; and purifying the obtained product by column chromatography, and drying to obtain the complex EC2.
Example 3
EL3 and EL2 were obtained according to the method of example 1; EC3 was prepared according to the reaction scheme shown in fig. 2:
under a nitrogen atmosphere, 0.5g (0.64 mmol) of EL3, 0.89g (1.27 mmol) of EL2, 10.43mg (6.35X 10 mmol) - 2 mmol) Azobisisobutyronitrile (AIBN) and 46.26mg (0.127 mmol) RAFT reagent (DDMAT) were dissolved in 40mL anhydrous THF, and after three freeze-pump-thaw cycles to remove oxygen, the mixture was warmed to 70 ℃ for 36h; after the reaction is finished, placing the reaction container in liquid nitrogen for quenching and unfreezing, repeatedly dissolving and precipitating through a dichloromethane/ether system, and separating to obtain 0.74g of multifunctional porphyrin ligand EL6; by passing 1 H NMR nuclear magnetic resonance and GPC measurements gave an m of 5,n of 8;
under the protection of nitrogen, 1g of the ligand EL6 is dissolved in dichloromethane, and 0.6ml of AlEt is added dropwise 2 A Cl solution (diethyl aluminum chloride, 2mol/L n-hexane solution) is stirred and reacts for 2 hours at room temperature; and purifying the obtained product by column chromatography, and drying to obtain the complex EC3.
Example 4
EC4 was prepared according to the reaction scheme shown in fig. 3:
adding 15g (120 mmol) of 4-hydroxybenzaldehyde, 52g (370 mmol) of 4-chlorobenzaldehyde and 33g (490 mmol) of pyrrole into 500mL of propionic acid, heating to 130 ℃ or so, refluxing for 1.5h, cooling to room temperature after the reaction is finished, concentrating the reaction solution to 200mL, adding methanol, cooling in a refrigerator overnight, filtering to obtain a product, and performing silica gel column chromatography (CHCl) 3 /CH 3 OH) to obtain a product EL7 with the yield of about 6.2 percent; 1 H-NMR(CDCl 3 ppm): 8.8,8.2,8.0,7.8,7.2, -2.8; the analysis result of high-resolution electrospray mass spectrometry is [ C ] 44 H 27 Cl 3 N 4 O]：732.13，found：732.22。
Under nitrogen protection, 1.69g (2.3 mmol) of EL7 was dissolved in 20mL of anhydrous THF, 0.26g (2.5 mmol) of methacryloyl chloride and 0.25g (2.5 mmol) of triethylamine were added dropwise at low temperature, and the mixture was reacted at room temperature for 12 hours after stirring sufficiently; after the reaction is finished, spin-drying the product, dissolving the product by using dichloromethane, extracting and washing the product for 3 times by using water, and spin-drying the organic phase after drying the organic phase by using anhydrous magnesium sulfate; the solid product obtained was purified by means of an alumina column with dichloromethane as the elution phase to give about 1.9g of product EL 8; the analysis result of high-resolution electrospray mass spectrometry is [ C ] 48 H 31 Cl 3 N 4 O 2 ]：800.15，found：800.33。
Dissolving 1.9g EL8 and 3.0g manganese chloride in 30mL N, N-dimethylformamide in the air atmosphere, fully stirring, and then heating the mixture to 165 ℃ for refluxing for 24 hours; after the reaction is finished, the solvent is removed by reduced pressure distillation, the dichloromethane is used for dissolving, the saturated saline solution is used for extraction and washing for 3 times, the organic phase is dried by sodium chloride and then is dried in a spinning way, and the dichloromethane is used as an elution phase to be purified by an aluminum peroxide column, so that about 2.0g of the product EL9 is obtained.
Under a nitrogen atmosphere, 1.00g (0.98 mmol) of EL9, 0.68g (0.98 mmol) of EL2,8.02mg (6.35X 10 mmol) - 2 mmol) Azobisisobutyronitrile (AIBN) and 35.70mg (0.098 mmol) RAFT reagent (DDMAT) were dissolved in 40mL anhydrous THF, and after removing oxygen by three times of freeze-suction-thawing, the mixture was heated to 70 ℃ for 36h; after the reaction is finished, placing the reaction container in liquid nitrogen for quenching and unfreezing, repeatedly dissolving and precipitating through a dichloromethane/ether system, and separating to obtain 1.32g of multifunctional porphyrin ligand EL10; by passing 1 H NMR nuclear magnetic resonance and GPC measurements gave an m of 8,n of 9;
under the protection of nitrogen, 1g of the ligand EL10 is dissolved in dichloromethane, and 0.3ml of AlEt is added dropwise 2 A Cl solution (diethyl aluminum chloride, 2mol/L n-hexane solution) is stirred and reacts for 2 hours at room temperature; purifying the obtained product by column chromatography, drying to obtain a complex EC4, and purifying by column chromatography 1 And (4) performing HNMR nuclear magnetic detection, and judging that the reaction is complete when a peak at a chemical shift of-2.8 to-3.6 ppm disappears.
Example 5
EC5 was prepared according to the reaction scheme shown in fig. 4:
adding 15g (120 mmol) of 3-hydroxybenzaldehyde, 68.1g (370 mmol) of 4-bromobenzaldehyde and 33g (490 mmol) of pyrrole into 500mL of propionic acid, heating to about 130 ℃, carrying out reflux reaction for 1.5h, cooling to room temperature after the reaction is finished, concentrating the reaction solution to 200mL, adding methanol, cooling in a refrigerator overnight, filtering, and purifying the obtained product by silica gel column chromatography (CHCl 3/CH3 OH) to obtain a product EL11, wherein the yield is about 7.8%; 1 H-NMR (CDCl 3, ppm): 8.9,8.8,8.1,7.8,7.2, -2.8; the analysis result of high-resolution electrospray mass spectrometry is [ C ] 44 H 27 Br 3 N 4 O]：863.97，found：863.86。
Under the protection of nitrogen, 2g (2.3 mmol) of EL11 is dissolved in 20mL of anhydrous THF, 0.26g (2.5 mmol) of methacryloyl chloride and 0.25g (2.5 mmol) of triethylamine are dropped at low temperature, and after fully stirring, the mixture is reacted at room temperature for 12 hours; after the reaction is finished, the product is dried in a spinning mode and dissolved by dichloromethane, extraction washing is carried out for 3 times by water, the organic phase is dried by anhydrous magnesium sulfate, the obtained solid product is dried in a spinning mode, an aluminum oxide column is used for purification by taking dichloromethane as an elution phase, and about 2.03g of the product EL12 is obtained; the analysis result of high-resolution electrospray mass spectrometry is [ C ] 48 H 31 Br 3 N 4 O 2 ]：932.00，found：932.06。
Under a nitrogen atmosphere, 1.00g (0.98 mmol) of EL9, 0.91g (0.98 mmol) of EL12, and 8.02mg (4.88X 10 mmol) of EL12 were mixed - 2 mmol) Azobisisobutyronitrile (AIBN) and 35.70mg (0.098 mmol) RAFT reagent (DDMAT) were dissolved in 40mL anhydrous THF, frozen-evacuated-thawed three times to remove oxygen and the mixture was warmed to 70 ℃ for 36h; after the reaction is finished, placing the reaction container in liquid nitrogen for quenching and unfreezing, repeatedly dissolving and precipitating through a dichloromethane/ether system, and separating to obtain 1.53g of multifunctional porphyrin ligand EL12; by passing 1 H NMR nuclear magnetic resonance and GPC measurements gave an m of 9,n of 7;
under the protection of nitrogen, 1g of the ligand EL13 is dissolved in dichloromethane, and 0.3ml of AlEt is added dropwise 2 A Cl solution (diethyl aluminum chloride, 2mol/L n-hexane solution) is stirred and reacts for 2 hours at room temperature; purifying the obtained product by column chromatography, drying to obtain a complex EC5, and purifying by column chromatography 1 H NMR nuclear magnetic detection, and determining that the reaction is complete when the peak at-2.8 to-3.6 ppm chemical shift disappears.
Application example 1
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC1 prepared in example 1, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24h; opening the reaction tube for the first time after the polymerization reaction is finishedGet 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 1 for detection, and the detection result shows that the characteristic peaks of the polyester are as follows: 6.5-6.0 ppm (br, 1H), 5.0-4.2 ppm (br, 2H), characteristic peaks of raw material styrene are 6.7ppm (dd, 1H), 5.7ppm (d, 1H), 5.2ppm (d, 1H), characteristic peaks of aldehyde by-products are 10.5-9.5 ppm (s, 1H), the conversion rate is 40.2% and the content of the aldehyde by-products is 8.3% by calculation.
The polyester obtained by the preparation was examined by GPC, and the results are shown in FIG. 7, whereby the number average molecular weight of the polyester was 1200 and the molecular weight distribution was 1.12.
Application example 2
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC1 prepared in example 1, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane were added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and polymerization was carried out for 24 hours while controlling the temperature of the pressure-resistant reaction tube at 20 ℃; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 2 for detection, and the result shows that the conversion rate is 31.3 percent, and the content of aldehyde by-products is 4.2 percent; the number average molecular weight of the polyester obtained was 1300 and the molecular weight distribution was 1.14 as determined by GPC.
Application example 3
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC1 prepared in example 1, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 60 ℃ to carry out polymerization reaction for 24h; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 3 for detection, and the result shows that the conversion rate is 63.1 percent, and the content of aldehyde by-products is 16.7 percent; the number average molecular weight of the polyester obtained was 1200 and the molecular weight distribution was 1.23 as determined by GPC.
Application example 4
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC1 prepared in example 1, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane were added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and polymerization was carried out for 24 hours while controlling the temperature of the pressure-resistant reaction tube at 80 ℃; opening the reaction tube for the first time after the polymerization reaction is finished 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 4 to be detected, and the result shows that the conversion rate is 33.1 percent, and the content of aldehyde by-products is 21.2 percent; the number average molecular weight of the polyester obtained by GPC was 900, and the molecular weight distribution was 1.26.
Application example 5
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC1 prepared in example 1, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.25g of phthalic anhydride and 1mL of dichloromethane were added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and polymerization was carried out for 24 hours while controlling the temperature of the pressure-resistant reaction tube at 40 ℃; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetic resonance corresponds to the reaction system of the example 5 to be detected, and the result shows that the conversion rate is 61.4 percent, and the content of aldehyde by-products is 7.3 percent; the number average molecular weight of the polyester obtained was 800 and the molecular weight distribution was 1.11 as determined by GPC.
Application example 6
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC1 prepared in example 1, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.38g of phthalic anhydride, and 1mL of bisAdding methyl chloride into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and controlling the temperature of the pressure-resistant reaction tube at 40 ℃ to perform polymerization reaction for 24h; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system prepared in the example 6 to be detected, and the result shows that the conversion rate is 54.4 percent, and the content of aldehyde by-products is 9.2 percent; the number average molecular weight of the polyester obtained was 900 and the molecular weight distribution was 1.14 as determined by GPC.
Application example 7
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC2 prepared in example 2, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24h; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetic resonance corresponds to the reaction system of the example 7 to be detected, and the result shows that the conversion rate is 47.5 percent, and the content of aldehyde by-products is 12.6 percent; the number average molecular weight of the polyester obtained was 1100 and the molecular weight distribution was 1.22 as determined by GPC.
Application example 8
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC3 prepared in example 3, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24h; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 8 to be detected, and the result shows that the conversion rate is 35.2 percent, and the content of aldehyde by-products is 4.3 percent; miningThe number average molecular weight of the polyester obtained was 1200 and the molecular weight distribution was 1.10 as determined by GPC.
Application example 9
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC4 prepared in example 4, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24h; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 9 to be detected, and the result shows that the conversion rate is 57.3 percent, and the content of aldehyde by-products is 6.9 percent; the number average molecular weight of the polyester obtained by GPC was 1200, and the molecular weight distribution was 1.22.
Application example 10
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC5 prepared in example 5, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24h; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 10 to be detected, and the result shows that the conversion rate is 75.2 percent, and the content of aldehyde by-products is 1.2 percent; the number average molecular weight of the polyester obtained was 1400 and the molecular weight distribution was 1.16 as determined by GPC.
Application example 11
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC5 prepared in example 5, 3.5mmol of dried styrene, 0.76g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24h;the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetic resonance detection is carried out on the reaction system in application example 11, and the result shows that the conversion rate is 52.3 percent, and the content of aldehyde by-products is 2.9 percent; the number average molecular weight of the polyester obtained was 1300 and the molecular weight distribution was 1.14 as determined by GPC.
Application example 12
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC5 prepared in example 5, 3.5mmol of dried styrene, 1.52g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of dichloromethane are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24h; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 12 to be detected, and the result shows that the conversion rate is 78.3 percent, and the content of aldehyde by-products is 3.6 percent; the number average molecular weight of the polyester obtained was 1200 and the molecular weight distribution was 1.16 as determined by GPC.
Application example 13
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC5 prepared in example 5, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mLN, N-dimethylformamide are added into a pressure-resistant reaction tube of 5mL after water and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24 hours; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 13 to be detected, and the result shows that the conversion rate is 81.4 percent, and the content of aldehyde by-products is 2.1 percent; the number average molecular weight of the polyester obtained was 1400 and the molecular weight distribution was 1.12 as determined by GPC.
Application example 14
In a glove box, 0.007mmol of the macromolecular heteronuclear porphyrin complex EC5 prepared in example 5, 3.5mmol of dried styrene, 1.14g of iodosobenzene, 0.51g of phthalic anhydride and 1mL of tetrahydrofuran are added into a 5mL pressure-resistant reaction tube after water removal and oxygen removal, and the temperature of the pressure-resistant reaction tube is controlled at 40 ℃ to carry out polymerization reaction for 24h; the first time when the reaction tube is opened after the polymerization reaction is finished is taken 1 H-NMR nuclear magnetic samples, and performing nuclear magnetic measurement; the polyester was precipitated in methanol/n-hexane.
By passing 1 H-NMR nuclear magnetism corresponds to the reaction system of the example 14 to be detected, and the result shows that the conversion rate is 26.2 percent, and the content of aldehyde by-products is 7.1 percent; the number average molecular weight of the polyester obtained was 800 and the molecular weight distribution was 1.22 as determined by GPC.
The invention provides a macromolecular heteronuclear porphyrin complex for preparing polyester by olefin one-pot epoxidation-ring-opening copolymerization, which adopts iodosobenzene as an oxidant and two metals for catalyzing epoxidation and ring-opening copolymerization respectively. The high-molecular heteronuclear porphyrin complex provided by the invention can realize the conversion from olefin to degradable polyester by a one-pot method, and has higher polymer selectivity.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. A macromolecular heteronuclear porphyrin complex has a structure of formula I:
Figure FDA0003959553850000011
in the formula I, R 1 ～R 6 Independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl;
M 1 、M 2 independently selected from magnesium, aluminium, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
X 1 、X 2 independently selected from halo, -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-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2,4-dinitrophenol oxygen, 3,5-dinitrophenol oxygen, 2,4,6-trinitrophenol oxygen, 3,5-dichlorophenol oxygen, 3,5-difluorophenol oxygen, 3,5-bis-trifluoromethylphenol oxygen, or pentafluorophenol oxygen anions;
m and n are polymerization degrees and are independently selected from 3 to 40.
2. The polymeric heteronuclear porphyrin complex of claim 1, having the structure of formula II:
Figure FDA0003959553850000012
in the formula II, R 7 、R 8 Independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl;
M 1 、M 2 independently selected from magnesium, aluminium, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
X 1 、X 2 independently selected from halogen;
m and n are polymerization degrees and are independently selected from 3 to 40.
3. The polymeric heteronuclear porphyrin complex of claim 2, wherein R is a hydrogen atom or a nitrogen atom 7 ，R 8 Independently selected from hydrogen, halogen;
said X 1 、X 2 Independently selected from Cl;
and m and n are independently selected from 3 to 10.
4. A method for preparing a polymeric heteronuclear porphyrin complex according to claim 1, comprising:
a compound having the structure of formula V and a compound containing M 2 And X 2 The compound of (a) is subjected to a third reaction to obtain a high-molecular heteronuclear porphyrin complex;
Figure FDA0003959553850000021
in the formula V, R 1 ～R 6 Independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl;
M 1 independently selected from magnesium, aluminium, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
X 1 independently selected from halo, -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-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2,4-dinitrophenol oxygen, 3,5-dinitrophenol oxygen, 2,4,6-trinitrophenol oxygen, 3,5-dichlorophenol oxygen, 3,5-difluorophenol oxygen, 3,5-bis-trifluoromethylphenol oxygen, or pentafluorophenol oxygen anions;
m and n are polymerization degrees and are independently selected from 3 to 40.
5. The method of claim 4, wherein the compound having the structure of formula V is prepared by a process comprising:
reacting a compound of formula III with a compound containing M 1 And X 1 The compound (b) is subjected to a first reaction to obtain a monomer with metalloporphyrin;
carrying out a second reaction on the monomer with metalloporphyrin and the compound with the structure of the formula IV to obtain a compound with the structure of the formula V;
Figure FDA0003959553850000031
in the formula III, R 1 ～R 3 Independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl;
Figure FDA0003959553850000032
in the formula IV, R 4 ～R 6 Independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl.
6. A process for the olefin one-pot preparation of polyester comprising:
under the catalytic action of a high-molecular heteronuclear porphyrin complex, reacting olefin, iodosobenzene and acid anhydride to obtain polyester;
the macromolecular heteronuclear porphyrin complex is the macromolecular heteronuclear porphyrin complex according to claim 1.
7. The process of claim 6, wherein the olefin is selected from one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene, styrene;
the anhydride is selected from one or more of succinic anhydride, glutaric anhydride, 1,2-cyclosuccinic anhydride, 1,2-cyclohexane dicarboxylic anhydride, phthalic anhydride, bicyclo [2.2.2] octane-2,3-dicarboxylic anhydride.
8. The process according to claim 6, wherein the temperature of the reaction is 20 to 80 ℃.
9. The process according to claim 6, wherein the reaction time is 0 to 120 hours.
10. The process according to claim 6, characterized in that the mass ratio of olefins to anhydrides is 1: (0.5-2);
the mass ratio of the olefin to the iodosobenzene is 1: (1-2);
the mass ratio of the olefin to the high molecular heteronuclear porphyrin complex is (500-10000): 1.
CN202211475029.6A 2022-11-23 2022-11-23 High-molecular heteronuclear porphyrin complex and preparation method and application thereof Pending CN115838453A (en)

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