CN114989207A - Supported metalloporphyrin complex, preparation method and application - Google Patents

Supported metalloporphyrin complex, preparation method and application Download PDF

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CN114989207A
CN114989207A CN202210508275.0A CN202210508275A CN114989207A CN 114989207 A CN114989207 A CN 114989207A CN 202210508275 A CN202210508275 A CN 202210508275A CN 114989207 A CN114989207 A CN 114989207A
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oxyanion
metalloporphyrin complex
polycarbonate
reaction
carrier
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匡青仙
刘顺杰
王献红
王佛松
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Changchun Institute of Applied Chemistry of CAS
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    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention provides a supported metalloporphyrin complex, a preparation method and application thereof, belonging to the technical field of catalyst preparation. The supported porphyrin complex consists of a carrier, a linking group, an active component and an auxiliary agent which are chemically linked on the carrier, and has a structure shown in a formula I. The complex is prepared by loading a metalloporphyrin complex and a quaternary ammonium salt monomer on a specific functional carrier, the supported metalloporphyrin complex can be further synthesized to obtain a two-component supported metalloporphyrin complex, and simultaneously can be used as a catalyst to efficiently catalyze the copolymerization reaction of carbon dioxide and epoxide to obtain a polycarbonate product, and the catalyst shows high polymer selectivity, high carbonate content, high activity and high recovery rate after separation when catalyzing the copolymerization of carbon dioxide and epoxide.
Figure DDA0003638265690000011

Description

Supported metalloporphyrin complex, preparation method and application
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a supported metalloporphyrin complex, a preparation method and application thereof.
Background
Carbon dioxide is taken as an ideal C1 resource with abundant reserves, and the realization of the cyclic utilization of the carbon dioxide is expected to improve the environmental benefit while meeting the development of the industrial process. The alternating copolymerization of the carbon dioxide and the epoxide can prepare the polycarbonate with full degradability, and provides a good substitute for the increasingly scarce non-renewable resources such as petroleum. This path through carbon recycling can respond aggressively and hopefully achieve the "carbon neutralization" strategic goal. In addition, the obtained polycarbonate also has excellent transparency and barrier property, and can be used as engineering plastics, disposable medicine and food packaging materials, adhesives and the like.
In 1969, Inoue utilized ZnEt 2 -H 2 O system first catalyzes CO 2 The ring-opening copolymerization (ROOP) with epoxides, produces degradable polycarbonate materials, on the basis of which various heterogeneous and homogeneous catalytic systems for this reaction have been developed successively. Heterogeneous catalytic systems such as an alkyl zinc/active hydrogen catalytic system, a metal carboxylate system, a double metal cyanide catalyst, a rare earth ternary catalyst and the like have the characteristics of being separable and recyclable, and the obtained polymer has a light color, can be recycled for multiple times in the reaction, and effectively reduces the cost, but further improvement of activity and selectivity is severely limited due to the intrinsic heterogeneous reaction. Similarly, homogeneous catalysts such as zinc diimine catalysts, metalloporphyrin catalysts and metal salen catalysts can break through the limitation of heterogeneous catalysts, and realize the advantages of high activity, high selectivity, high stability and the like of catalysis, but the essentially homogeneous reaction thereof causes that the catalysts are difficult to separate from polymers, and always faces the problems of metal residue, influenced polymer quality and the like. Meanwhile, the catalysts have the defects of insufficient activity, more cyclic byproducts in the polymerization process, difficult control of the composition ratio of the polymerization product and the like.
In order to combine the advantages of high activity and high selectivity of a homogeneous catalyst and easy separation and recovery of the heterogeneous catalyst, heterogeneous catalysis of the homogeneous catalyst is attempted, and a catalytic system with a complex microporous structure, such as a Metal Organic Framework (MOF), a Conjugated Microporous Polymer (CMP) and the like, is designed, and although complete heterogeneous catalysis is achieved, the catalysts are not ideal in polymer synthesis, and the advantage loss of the homogeneous catalyst occurs; meanwhile, in order to further improve the factors such as activity, selectivity and the like in the copolymerization reaction of the epoxide and the carbon dioxide, a synergistic catalysis mechanism is introduced into the design of a catalytic system. Comprises the synergistic action of multiple central metals of bimetallic and multi-metal catalysts, a two-component catalytic system consisting of a SalencO catalyst and a quaternary ammonium salt or quaternary phosphonium salt cocatalyst and the synergistic action of Lewis acid and base of a bifunctional catalyst. These catalytic systems enable polymerization at lower catalyst concentrations and provide significant improvements in the control of the amount of selectively formed polymer or carbonate segments, but exhibit homogeneous properties that are still difficult to meet market demands.
Disclosure of Invention
In view of this, the invention aims to provide a supported metalloporphyrin complex, a preparation method and an application thereof, and the supported metalloporphyrin complex is used as a catalyst for preparing polycarbonate, and has high catalytic performance and good separation and recovery performance.
The invention provides a supported metalloporphyrin complex, which has a structure shown in a formula I:
Figure BDA0003638265670000021
the Carrier is selected from an inorganic Carrier, a high molecular Carrier or a composite Carrier of the inorganic Carrier and the high molecular Carrier;
the inorganic carrier is selected from SiO 2 、Al 2 O 3 Or SiO after bromo-, chloromethyl-, carboxyl-, amino-, hydroxyl-or thiol-functionalization 2 、Al 2 O 3 One or more of the above;
the macromolecular carrier is selected from one or more of crosslinked polystyrene, polyamide, polyethylene-glycol resin or crosslinked polystyrene, polyamide or polyethylene-glycol resin after bromination, chloromethyl, carboxyl, amino, hydroxyl and mercaptan functionalization;
the Linker 1 is a linking group with a structure shown in a formula II-a or a formula II-b;
Figure BDA0003638265670000022
wherein the N atom or O atom is
Figure BDA0003638265670000031
Connecting;
the Linker2 is a linking group with a structure shown as a formula II-c:
Figure BDA0003638265670000032
wherein < u > is attached to R;
the ranges of x and y are that x is more than 0 and less than 100 percent, and y is more than or equal to 0 and less than 100 percent;
r is selected from dimethylamino, diethylamino, di-n-propylamino, diisopropylamine, diphenylamino, triethylammonium chloride, trihexylammonium chloride,
Figure BDA0003638265670000033
The described
Figure BDA0003638265670000034
Is a metalloporphyrin complex with a structure shown in a formula III;
Figure BDA0003638265670000035
x is 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-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-Dinitrophenol oxyanion, 3,5 dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bis-trifluoromethylphenol oxyanion or pentafluorophenol oxyanion;
R 1 ～R 19 each independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl;
m is magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
Preferably, the Carrier is selected from cross-linked polystyrene resin after chloromethyl functionalization.
Preferably, the Linker 1 is selected from the group consisting of formula II-a:
Figure BDA0003638265670000041
wherein the N atom is
Figure BDA0003638265670000042
Are connected.
Preferably, said R is selected from triethylammonium chloride.
Preferably, the metalloporphyrin complex is specifically selected from the structures shown in formula III-a:
Figure BDA0003638265670000043
in the formula III-a, R 20 Selected from hydrogen, halogen, aliphatic groups of C1-C10, substituted alkoxy groups of C1-C10, cycloalkyl groups substituted by C3-C10, heterocyclic groups of C1-C10, aryl groups substituted by C6-C12 or heteroaryl groups substituted by C1-C12;
X 1 selected from halogens;
m is aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
The invention provides a preparation method of a supported metalloporphyrin complex in the technical scheme, which comprises the following steps:
reacting porphyrin ligand with a structure shown in formula IV with an organic compound containing M and X groups to obtain a metalloporphyrin complex with a structure shown in formula III;
reacting the metalloporphyrin complex and the tertiary amine monomer with functional groups on the carrier to obtain a supported metalloporphyrin complex with a structure shown in a formula I;
Figure BDA0003638265670000051
m is magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
x is 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-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bis-trifluoromethylphenol oxyanion, or pentafluorophenol oxyanion;
R 1 ～R 19 independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl.
The invention also provides application of the supported metalloporphyrin complex as a catalyst in preparation of polycarbonate.
The invention also provides a preparation method of the polycarbonate, which comprises the following steps:
under the catalytic action of the supported metalloporphyrin complex, carbon dioxide and epoxide are subjected to copolymerization reaction to obtain the polycarbonate.
Preferably, the temperature of the copolymerization reaction is 20-150 ℃, the time of the copolymerization reaction is 8-72 h, the pressure of carbon dioxide is 2-8 MPa, and the mass ratio of the supported metalloporphyrin complex to the epoxide is 1: 1000-50000.
Preferably, the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexene oxide, cyclopentane oxide, glycidyl epichlorohydrin methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.
The invention has the advantages of
The invention provides a supported metalloporphyrin complex and a preparation method and application thereof. The supported metalloporphyrin catalyst is a heterogeneous catalyst, is easy to separate from a system after reaction, realizes recycling, reduces metal residues in a polymer, and is more environment-friendly.
The complex is prepared by loading a metalloporphyrin complex and a quaternary ammonium salt monomer on a specific functionalized carrier. In the synthesis stage of the supported catalyst, the supported metalloporphyrin complex with different loading amounts of the metalloporphyrin complex and the tertiary amine monomer on the carrier can be synthesized by regulating and controlling the molar ratio (1:2x: y, 0< x < 100%, and 0< y < 100%) of the functional group, the metalloporphyrin complex and the tertiary amine monomer on the carrier. In addition, by changing the metal center of the porphyrin monomer, the substituent of the porphyrin monomer and the type of the quaternary ammonium salt monomer, the supported metalloporphyrin complex with different catalytic performances can be obtained;
compared with the prior art, the supported metalloporphyrin complex can be further synthesized to obtain a two-component supported metalloporphyrin complex, and can be used as a catalyst to efficiently catalyze the copolymerization reaction of carbon dioxide and epoxide to obtain a polycarbonate product, the supported metalloporphyrin complex has heterogeneous properties as the catalyst, and can be easily separated from a reaction system after reaction, so that the supported metalloporphyrin complex can be recycled; meanwhile, the catalyst simultaneously meets the coordination effect of multi-center metal and the coordination effect of Lewis acid and base between the metalloporphyrin complex and the quaternary ammonium salt monomer, and the interaction of the catalyst can improve the catalytic performance by changing the metal center of the porphyrin monomer, the substituent of the porphyrin monomer, the load of the porphyrin monomer, the type of the quaternary ammonium salt monomer and the load of the quaternary ammonium salt monomer. The catalyst shows high polymer selectivity, high carbonate content, high activity and high recovery rate after separation when catalyzing the copolymerization of carbon dioxide and epoxide. Experimental results show that in the ring-opening copolymerization reaction of catalytic carbon dioxide and epoxide, the number average molecular weight of the product is 12000-280000 g/mol, and the molecular weight distribution is 1.01-2.61; the polymer selectivity in the reaction product can reach 99% at most, and the content of the carbonic ester unit can be regulated and controlled within a wide range of 0-95%.
Drawings
FIG. 1 is a scheme showing the preparation reaction of complex EL 1-3;
FIG. 2 is a preparation reaction scheme of EC 1;
FIG. 3 is a preparation reaction scheme of EC 2-6;
FIG. 4 is a preparation reaction scheme of EC 7-9;
FIG. 5 is a preparation reaction scheme of EC 10;
FIG. 6 is a scheme of a reaction for the preparation of polycarbonate;
FIG. 7 is a nuclear magnetic hydrogen spectrum of complex EL-1;
FIG. 8 is a nuclear magnetic hydrogen spectrum of complex EL-3;
FIG. 9 is a nuclear magnetic hydrogen spectrum of EC-1.
Detailed Description
The invention provides a supported metalloporphyrin complex, which has a structure shown in a formula I:
Figure BDA0003638265670000071
the Carrier is a Carrier selected from an inorganic Carrier, a high molecular Carrier or a composite Carrier of the inorganic Carrier and the high molecular Carrier;
the inorganic carrier is selected from SiO 2 、Al 2 O 3 Or bromo, chloromethyl, carboxyl, amino, hydroxyThiol functionalized SiO 2 、Al 2 O 3 One or more of the above;
the macromolecular carrier is selected from one or more of crosslinked polystyrene, polyamide, polyethylene-glycol resin or crosslinked polystyrene, polyamide or polyethylene-glycol resin after bromination, chloromethyl, carboxyl, amino, hydroxyl and mercaptan functionalization; preferably, the Carrier is selected from cross-linked polystyrene resin after chloromethyl functionalization.
The Linker 1 is a linking group with a structure shown in a formula II-a or a formula II-b, and is preferably selected from a linking group with a structure shown in a formula II-a;
Figure BDA0003638265670000072
wherein the N atom or O atom is
Figure BDA0003638265670000073
Connecting;
the Linker2 is a linking group with a structure shown in formula II-c:
Figure BDA0003638265670000081
wherein < u > is attached to R;
the ranges of x and y are that x is more than 0 and less than 100 percent, and y is more than or equal to 0 and less than 100 percent;
r is selected from dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, diphenylamino, triethylammonium chloride, trihexylammonium chloride,
Figure BDA0003638265670000082
Preferably triethylammonium chloride;
the described
Figure BDA0003638265670000083
Is a metalloporphyrin complex with a structure shown in a formula III:
Figure BDA0003638265670000084
x is halogen radical, -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 oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bis-trifluoromethylphenol oxyanion, or pentafluorophenol oxyanion;
R 1 ～R 19 each independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl;
m is magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
Preferably, the metalloporphyrin complex is specifically selected from the structures shown in III-a:
Figure BDA0003638265670000091
in the formula III-a, R 20 Selected from hydrogen, halogen, aliphatic groups of C1-C10, substituted alkoxy groups of C1-C10, cycloalkyl groups substituted by C3-C10, heterocyclic groups of C1-C10, aryl groups substituted by C6-C12 or heteroaryl groups substituted by C1-C12; preferably hydrogen;
X 1 selected from halogens, preferably Cl;
m is aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium, preferably aluminum.
Preferably, the supported metalloporphyrin complex has a specific structure shown in formula V:
Figure BDA0003638265670000092
in the present invention, the
Figure BDA0003638265670000093
The preparation method of (b) is not particularly limited, and may be generally commercially available or prepared according to a method well known to those skilled in the art;
in the invention
Figure BDA0003638265670000094
The specific preparation method comprises the following steps:
benzaldehyde and pyrrole are subjected to one-pot reaction under the condition of propionic acid reflux, and a first color band is collected by a column chromatography separation technology to obtain tetraphenylporphyrin;
tetraphenylporphyrin is dissolved in trifluoroacetic acid and undergoes a nitration reaction with sodium nitrite at room temperature. After the reaction is finished, quenching the mixture by using ice deionized water, neutralizing an organic phase by using a saturated sodium bicarbonate solution, and extracting and combining the organic phase to obtain mononitrotetraphenylporphyrin;
under nitrogen atmosphere, mononitrotetraphenylporphyrin is dissolved in concentrated hydrochloric acid and reacts with concentrated hydrochloric acid solution of stannous chloride at 65 ℃ for reduction reaction. After the reaction is finished, adding concentrated ammonia water to quench the reaction until the system is neutral, and collecting a second color band of the filter cake obtained by suction filtration through a column chromatographic separation technology to obtain the monoamino porphyrin.
The central metal M and the co-ligand X are coordinated into the porphyrin ring through the metallization reaction of the porphyrin ligand in a dichloromethane solution,
Figure BDA0003638265670000101
the group access mode is as follows: nucleophilic substitution reaction of the amino group of the single amino substituted porphyrin and the benzyl chloride group on the carrier under an alkaline condition, regulating and controlling the proportion of the single amino metalloporphyrin and the benzyl chloride group on the carrier according to a required load rate, taking potassium carbonate as an acid-binding agent, wherein the molar ratio of the benzyl chloride group on the carrier to the single amino porphyrin to the potassium carbonate is 1:2x: x, and the carrier and the single amino metalloporphyrin are fully mixedSwelling or dissolving in anhydrous N, N-Dimethylformamide (DMF), and fully reacting for 72h at 90 ℃. The R group access mode is as follows: after the metalloporphyrin complex is loaded on the carrier, a tertiary amine monomer with the molar quantity equal to that of benzyl chloride group in the carrier is further added, and anhydrous DMF is used as a solvent to fully react for 24 hours at the temperature of 90 ℃.
The invention provides a preparation method of a supported metalloporphyrin complex in the technical scheme, which comprises the following steps:
reacting porphyrin ligand with a structure shown in formula IV with an organic compound containing M and X groups to obtain a metalloporphyrin complex with a structure shown in formula III; the organic compound containing M and X groups is preferably diethyl aluminum chloride, the reaction temperature is preferably room temperature (25 ℃), the reaction time is preferably 2 hours, and the molar ratio of the porphyrin ligand with the structure of formula IV to the organic compound containing M and X groups is preferably 1: 1.2.
Reacting the metalloporphyrin complex and the tertiary amine monomer with functional groups on the carrier to obtain a supported metalloporphyrin complex with a structure shown in a formula I; the tertiary amine monomer is preferably triethylamine, the reaction temperature is preferably 90 ℃, the reaction time is preferably 72-100h, the molar weight of the corresponding metalloporphyrin complex and the tertiary amine monomer is calculated according to the molar weight of the functional group on the carrier with a certain mass, wherein the molar ratio of the functional group on the carrier, the metalloporphyrin complex and the tertiary amine monomer is 1:2x: y, wherein x is more than 0 and less than 100%, and y is more than or equal to 0 and less than 100%.
Figure BDA0003638265670000111
M is magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
x is 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-nitrophenol oxyanion, p-nitrophenol oxyanion,M-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bis-trifluoromethylphenol oxyanion or pentafluorophenol oxyanion;
R 1 ～R 19 independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl or substituted heteroaryl, preferably hydrogen.
The invention also provides an application of the supported metalloporphyrin complex as a catalyst in preparation of polycarbonate, which comprises the following steps:
under the catalytic action of the supported metalloporphyrin complex, carrying out copolymerization reaction on carbon dioxide and epoxide to obtain polycarbonate;
in the present invention, the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexene oxide, cyclopentane oxide, glycidyl epichlorohydrin methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.
In the invention, the pressure of the carbon dioxide is preferably 2-8 MPa.
In the invention, the temperature of the copolymerization reaction is preferably 20-150 ℃, high polymer selectivity (> 99%) can be realized at a low temperature, the reaction activity is increased along with the rise of the temperature, and the time of the copolymerization reaction is preferably 8-72 h.
In the present invention, the mass ratio of the supported metalloporphyrin complex and the epoxide is preferably 1: 1000-50000.
In the invention, the supported metalloporphyrin complex can be used for preparing a polycarbonate material by high-activity catalysis by loading porphyrin and tertiary amine on the same polymer chain. After the reaction is finished, the catalyst can be separated from the reaction system, and the catalyst can be recycled.
In order to further illustrate the present invention, the following examples are provided to describe the supported metalloporphyrin complex of the present invention and the preparation method thereof and the preparation method of polycarbonate in detail, but they should not be construed as limiting the scope of the present invention.
EXAMPLE 1 preparation of metalloporphyrin complexes
Adding 50g (470mmol) of benzaldehyde and 31g (470mmol) 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 give the product EL1 in about 20% yield. 1 H-NMR(CDCl 3 Ppm): 8.9,8.2,7.8, -2.8, as shown in FIG. 7, high resolution electrospray mass spectrometry analysis, the analysis result is [ C 44 H 31 N 4 ]：615.2，found：615.2；
1g (1.63mmol) of EL1 was dissolved in 10mL (1.63mmol) of trifluoroacetic acid, 0.2g (2.93mmol) of sodium nitrite was added, and the mixture was reacted at room temperature for 3min after stirring sufficiently. After the reaction is finished, adding 50-100mL of ice deionized water for quenching, adding 50mL of chloroform for dilution, extracting until the water phase is colorless, combining the organic phases, extracting and washing for three times by using saturated sodium bicarbonate solution, and drying to obtain the product EL 2. The dried EL2 was dissolved in 20mL of concentrated hydrochloric acid under nitrogen atmosphere, 1.44g (7.58mmol) of stannous chloride was dissolved in concentrated hydrochloric acid, and after stirring sufficiently, a concentrated hydrochloric acid solution of stannous chloride was added to EL2, followed by reaction at 65 ℃ for 1 hour. After the reaction is finished, adding concentrated ammonia water to quench the reaction system to be neutral, performing suction filtration, fully washing the filter cake for 3 times by deionized water, and then drying. The solid product was purified by silica gel column using methylene chloride as an elution phase to obtain about 0.43g of product EL 3. 1 H-NMR(CDCl 3 Ppm): 8.9,8.2,8.0,7.8,7.0,4.0, -2.8. The analysis result of high-resolution electrospray mass spectrometry is [ C ] 44 H 31 N 5 ]: 629.77, found: 629.26. the reaction scheme is schematically shown in figure 1; the nuclear magnetic hydrogen spectrum is shown in FIG. 8.
Under nitrogen protection, 0.4g of the ligand EL3(0.64mmol) was dissolved in dichloromethane and 0.4ml of LAlEt was added dropwise 2 Cl (diethylaluminum chloride) (2mol/L, 0.77mmol), ambient temperature conditionsThe reaction was stirred for 2 h. The obtained product is purified by column chromatography and then dried to obtain the required complex EC 1.
FIG. 2 is a reaction scheme of EC1, and the nuclear magnetic hydrogen spectrum is shown in FIG. 9.
Example 2 preparation of Supported metalloporphyrin complexes
0.5g of crosslinked polystyrene resin (Merrifield resin) (DVB: 1%, Cl: 0.8-1.3mmol/g) was fully swollen in 10mL of anhydrous DMF at 70 ℃ for 24h under nitrogen protection. 0.5g (0.7mmol) of EC1 was sufficiently dissolved in 10mL of anhydrous DMF, and added to the swollen crosslinked polystyrene resin, to which K was further added 2 CO 3 35 mg (0.25mmol), the temperature is raised to 90 ℃ and the reaction is continued for 72 h. And after the reaction is finished, carrying out suction filtration, and fully washing a filter cake with anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane repeatedly until the filtrate is colorless, and drying to obtain the required complex EC 2. The ICP analysis gave 53.8% x and 0 y. The scheme for the preparation reaction is shown in FIG. 3.
EXAMPLE 3 preparation of Supported metalloporphyrin complexes
1g of crosslinked polystyrene resin (Merrifield resin) (DVB: 1%, Cl: 0.8-1.3mmol/g) was fully swollen in 10mL of anhydrous DMF at 70 ℃ for 24h under nitrogen protection. 1g (1.4mmol) of EC1 was fully dissolved in 10mL of anhydrous DMF and added to the swollen crosslinked polystyrene resin, to which K was further added 2 CO 3 76 mg (0.55mmol), the temperature was raised to 90 ℃ and the reaction was continued for 72 h. And after the reaction is finished, carrying out suction filtration, and fully washing a filter cake with anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane repeatedly until the filtrate is colorless, and drying to obtain the required complex EC 3. The ICP analysis gave 20.6% x, 0. The scheme for the preparation reaction is shown in FIG. 3.
Example 4 preparation of Supported metalloporphyrin complexes
Under nitrogen, 2g of crosslinked polystyrene resin (Merrifield resin) (DVB: 1%, Cl: 0.8-1.3mmol/g) was fully swollen in 20mL of anhydrous DMF at 70 ℃ for 24 h. 1g (1.4mmol) of EC1 was fully dissolved in 10mL of anhydrous DMF and added to the swollen crosslinked polystyrene resin, to which K was further added 2 CO 3 87 mg (0.62mmol), the temperature is raisedThe reaction was continued to 90 ℃ for 72 h. And after the reaction is finished, carrying out suction filtration, and fully washing a filter cake with anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane repeatedly until the filtrate is colorless, and drying to obtain the required complex EC 4. Analysis by ICP gave x 18.0% and y 0. The scheme for the preparation reaction is shown in FIG. 3.
EXAMPLE 5 preparation of Supported metalloporphyrin complexes
Under nitrogen, 2g of crosslinked polystyrene resin (Merrifield resin) (DVB: 1%, Cl: 0.8-1.3mmol/g) was fully swollen in 10mL of anhydrous DMF at 70 ℃ for 24 h. 0.5g (0.7mmol) of EC1 was sufficiently dissolved in 10mL of anhydrous DMF, and added to the swollen crosslinked polystyrene resin, to which K was further added 2 CO 3 29 mg (0.21mmol), the temperature was raised to 90 ℃ and the reaction was continued for 72 h. After the reaction is finished, carrying out suction filtration operation, and washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane in an inverted way fully until a filtrate is colorless, and then drying to obtain the required complex EC 5. The ICP analysis gave x 4.38% and y 0. The scheme for the preparation reaction is shown in FIG. 3.
Example 6 preparation of Supported metalloporphyrin complexes
Under nitrogen, 2g of crosslinked polystyrene resin (Merrifield resin) (DVB: 1%, Cl: 0.8-1.3mmol/g) was fully swollen in 10mL of anhydrous DMF at 70 ℃ for 24 h. 3g (4.3mmol) of EC1 was fully dissolved in 10mL of anhydrous DMF and added to the swollen crosslinked polystyrene resin, to which K was further added 2 CO 3 69 mg (0.5mmol), the temperature was raised to 90 ℃ and the reaction was continued for 72 h. And after the reaction is finished, carrying out suction filtration, and fully washing a filter cake with anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane repeatedly until the filtrate is colorless, and drying to obtain the required complex EC 6. By ICP analysis, x was 44.6% and y was 0. The scheme for the preparation reaction is shown in FIG. 3.
EXAMPLE 7 preparation of two-component supported metalloporphyrin complexes
0.8g of EC4 was fully swollen in 8mL of anhydrous DMF under nitrogen protection, to which was added 0.1g (1mmol) of triethylamine (NEt) 3 ) And reacting at 90 ℃ for 24 h. After the reaction is finished, carrying out suction filtration operation, and reusing anhydrous DMF, anhydrous chloroform and anhydrous dimethyl formamide in a filter cake reactionAnd (3) fully washing the chloromethane until the filtrate is colorless, and drying to obtain the required complex EC 7. X was 18.0% and y was 82.0% as calculated by ICP analysis. The scheme for the preparation reaction is shown in FIG. 4.
EXAMPLE 8 preparation of two-component supported metalloporphyrin complexes
0.8g of EC5 was fully swollen in 8mL of anhydrous DMF under nitrogen protection, to which was added 0.1g (1mmol) of triethylamine (NEt) 3 ) And reacting at 90 ℃ for 24 h. And after the reaction is finished, carrying out suction filtration, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane till the filtrate is colorless, and drying to obtain the required complex EC 8. X was 4.38% and y was 95.6% as calculated by ICP analysis. The scheme for the preparation reaction is shown in FIG. 4.
EXAMPLE 9 preparation of two-component supported metalloporphyrin complexes
0.5g of EC6 was fully swollen in 8mL of anhydrous DMF under nitrogen protection, to which 0.5g (0.5mmol) of triethylamine (NEt) was added 3 ) And reacting at 90 ℃ for 24 h. And after the reaction is finished, carrying out suction filtration, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane till the filtrate is colorless, and drying to obtain the required complex EC 9. X was 44.6% and y was 55.4% as calculated by ICP analysis. The scheme for the preparation reaction is shown in FIG. 4.
EXAMPLE 10 preparation of two-component supported metalloporphyrin complexes
0.5g of EC6 was fully swollen in 8mL of anhydrous DMF under nitrogen protection, to which was added 0.13g (0.5mmol) of trihexylamine (N (C) 6 H 13 ) 3 ) And reacting at 90 ℃ for 24 h. And after the reaction is finished, carrying out suction filtration, and washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane in an inverted way fully until a filtrate is colorless, and drying to obtain the required complex EC 10. X was 44.6% and y was 55.4% as calculated by ICP analysis. The scheme for the preparation reaction is shown in FIG. 5.
EXAMPLE 11 preparation of polycarbonate
In a glove box, 0.015mmol (calculated as the aluminum content in the resin) of the aluminum porphyrin complex EC2 of example 2 and 75mmol of dry propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, and the autoclave was then chargedThe reaction kettle is taken out from the glove box, carbon dioxide is filled into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle reaches 3MPa, and the temperature of the high-pressure reaction kettle is controlled at 70 ℃ for carrying out polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC2 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate obtained in example 11 revealed that the polycarbonate had a carbonate unit content of 59% and a polymer selectivity of 84%; the TOF value of the catalytic system is 140h through calculation -1 (ii) a The polycarbonate obtained had a number average molecular weight of 43600g/mol and a molecular weight distribution of 1.61 as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 12 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC3 of example 3 and 75mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Drying at 45 deg.C under vacuumAnd pumping out unreacted and complete propylene oxide in the tank to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC3 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate prepared in example 12 showed that the polycarbonate had a carbonate unit content of 67% and a polymer selectivity of 82%; the TOF value of the catalytic system is 40h through calculation -1 (ii) a The number average molecular weight of the polycarbonate obtained was 21600g/mol, and the molecular weight distribution was 1.27, as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 13 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC4 of example 4 and 75mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC4 1 For catalyzing a new polymerization reaction; collecting the liquid part, and dripping methanol dropwiseOf these, a pale-colored or white polycarbonate gradually precipitated out.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate obtained in example 13 revealed that the polycarbonate had a carbonate unit content of 77% and a polymer selectivity of 87%; the TOF value of the catalytic system is calculated to be 30h -1 (ii) a The polycarbonate thus obtained had a number average molecular weight of 25100g/mol and a molecular weight distribution of 1.91 as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 14 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC5 of example 5 and 75mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. The unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to obtain a polycarbonate coated with the catalyst.
Fully dissolving the polymer by using 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts by using acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, and recycling the solid parts as a catalyst EC5 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate prepared in example 14 showed that the polycarbonate had a carbonate unit content of 95% and a polymer selectivity of 79%; the TOF value of the catalytic system is calculated to be 71h -1 (ii) a The polycarbonate obtained was found to have a number average molecular weight of 21400g/mol and a molecular weight distribution of 1.17 by GPC. Preparation reactionThe route pattern is shown in fig. 6.
EXAMPLE 15 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC6 of example 6 and 75mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer by using 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts by using acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, and recycling the solid parts as a catalyst EC6 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate prepared in example 15 showed that the polycarbonate had a carbonate unit content of 51% and a polymer selectivity of 90%; the TOF value of the catalytic system is calculated to be 72h -1 (ii) a The polycarbonate obtained had a number average molecular weight of 47700g/mol and a molecular weight distribution of 1.71 as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 16 preparation of polycarbonate
In a glove box, 0.015mmol (in terms of aluminum content in the resin) of the aluminum porphyrin complex EC7 of example 4 and 7mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, and the autoclave was taken out of the glove box and then fed to the autoclave via a carbon dioxide supply line having a pressure regulating functionCarbon dioxide is filled in the autoclave, the pressure in the autoclave is 3MPa, and the temperature of the autoclave is controlled at 70 ℃ to carry out polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC7 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate obtained in example 16 revealed that the polycarbonate had a carbonate unit content of 92% and a polymer selectivity of 46%; the TOF value of the catalytic system is calculated to be 139h -1 (ii) a The polycarbonate obtained was found to have a number average molecular weight of 13200g/mol and a molecular weight distribution of 1.97 by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 17 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC8 of example 5 and 210mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out.
The solid-liquid separation is carried out on the reaction system, and the solid part is washed for 3 times by dichloromethane or acetoneAs catalyst EC8 1 Recovered for a new polymerization reaction.
By passing 1 H-NMR nuclear magnetic resonance examination of the product obtained in example 17 showed that PO had been completely converted to cyclic carbonate; the TOF value of the catalytic system is calculated to be 583h -1 . The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 18 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC9 of example 6 and 75mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC9 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate obtained in example 18 showed that the polycarbonate had a carbonate unit content of 65% and a polymer selectivity of 94%; the TOF value of the catalytic system is calculated to be 97h -1 (ii) a The polycarbonate obtained by GPC had a number average molecular weight of 64000g/mol and a molecular weight distribution of 1.47. The preparative reaction scheme is shown in figure 6.
EXAMPLE 19 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC6 of example 6 and 75mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 50 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC6 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 19 shows that the polycarbonate has a carbonate unit content of 42% and a polymer selectivity of more than 99%; the TOF value of the catalytic system is calculated to be 15h -1 (ii) a The polycarbonate thus obtained had a number average molecular weight of 26600g/mol and a molecular weight distribution of 1.32 as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 20 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to the aluminum content in the resin) of the aluminum porphyrin complex EC6, 0.0075mmol of PPNCl and 75mmol of dried propylene oxide in example 6 are added into a 5mL high-pressure reaction kettle after water removal and oxygen removal, then the high-pressure reaction kettle is taken out of the glove box, carbon dioxide is filled into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle reaches 3MPa, and the temperature of the high-pressure reaction kettle is controlledThe polymerization was carried out at 70 ℃ for 24 h. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC6 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 20 shows that the polycarbonate has a carbonate unit content of 51% and a polymer selectivity of more than 76%; the TOF value of the catalytic system is calculated to be 72h -1 (ii) a The number average molecular weight of the polycarbonate obtained by GPC was 39500g/mol, and the molecular weight distribution was 1.65. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 21 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC5 of example 5 and 210mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
The polymer was thoroughly dissolved in 10mL of dichloromethane, and the insoluble material was used as a catalyst, which was extracted byPerforming solid-liquid separation, repeatedly washing the solid part with acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid part, and recovering the solid part serving as a catalyst EC5 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate obtained in example 21 showed that the polycarbonate had a carbonate unit content of 80% and a polymer selectivity of 44%; the TOF value of the catalytic system is calculated to be 90h -1 (ii) a The polycarbonate obtained by the preparation had a number average molecular weight of 5300g/mol and a molecular weight distribution of 3.38 as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 22 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of polycarbonate preparation, namely, 0.015mmol of aluminum porphyrin complex EC5 and 420mmol of dried propylene oxide in example 5 are added into a 5mL high-pressure reaction kettle after water removal and oxygen removal, then the high-pressure reaction kettle is taken out of the glove box, carbon dioxide is filled into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle reaches 3MPa, and the temperature of the high-pressure reaction kettle is controlled at 70 ℃ to carry out polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC5 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate obtained in example 22 revealed that,polycarbonate had a carbonate unit content of 94% and a polymer selectivity of 62%; the TOF value of the catalytic system is calculated to be 76h -1 (ii) a The number average molecular weight of the polycarbonate obtained was 3400g/mol and the molecular weight distribution was 2.13 as determined by GPC. The preparative reaction scheme is shown in figure 6.
EXAMPLE 23 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC5 of example 5 and 150mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. The unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to obtain a polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC5 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance on the polycarbonate prepared in example 23 shows that the polycarbonate contains 82% of carbonate units and the polymer selectivity is 55%; the TOF value of the catalytic system is calculated to be 87h -1 (ii) a The polycarbonate obtained had a number average molecular weight of 15900g/mol and a molecular weight distribution of 1.52 as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 24 preparation of polycarbonate
In a glove box, 0.015mmol (based on the aluminum content of the resin) was addedCalculation) of the recovered catalyst EC5 in example 4 1 And 75mmol of dry propylene oxide are added into a 5mL high-pressure reaction kettle after water removal and oxygen removal, then the high-pressure reaction kettle is taken out from a glove box, carbon dioxide is filled into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle reaches 3MPa, and the temperature of the high-pressure reaction kettle is controlled at 70 ℃ for polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. The unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to obtain a polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC5 2 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance on the polycarbonate prepared in example 24 shows that the carbonate unit content in the polycarbonate is 73%, and the polymer selectivity is 79%; the TOF value of the catalytic system is 40h through calculation -1 (ii) a The number average molecular weight of the polycarbonate obtained by the preparation was 10700g/mol and the molecular weight distribution was 1.27 as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
EXAMPLE 25 preparation of polycarbonate
In a glove box, 0.015mmol (calculated by the aluminum content in the resin) of the aluminum porphyrin complex EC10 of example 6 and 75mmol of dried propylene oxide were added to a 5mL autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to conduct a polymerization reaction for 24 hours. After the polymerization reaction is finished, slowly dischargingThe carbon dioxide in the high-pressure reaction kettle falls off, and the carbon dioxide is taken at the first time when the reaction kettle is opened 1 H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out unreacted propylene oxide in a vacuum drying oven at 45 ℃ to obtain the polycarbonate coated with the catalyst.
Fully dissolving the polymer with 10mL of dichloromethane, using insoluble substances as a catalyst, carrying out solid-liquid separation by extraction, repeatedly washing solid parts with acetone until the solids are mutually dispersed and no obvious polymer is wrapped, and recovering the solid parts as a catalyst EC10 1 For catalyzing a new polymerization reaction; the liquid portion was collected and dropped dropwise into methanol, and a light-colored or white polycarbonate was gradually precipitated.
By passing 1 H-NMR nuclear magnetic resonance analysis of the polycarbonate obtained in example 25 showed that the polycarbonate had a carbonate unit content of 64% and a polymer selectivity of 89%; the TOF value of the catalytic system is calculated to be 87h -1 (ii) a The polycarbonate thus obtained had a number average molecular weight of 57900g/mol and a molecular weight distribution of 1.38 as determined by GPC. The scheme for the preparation reaction is shown in FIG. 6.
As can be seen from the above examples, the present invention provides a supported metalloporphyrin complex having the structure of formula I. The preparation method is characterized in that the metalloporphyrin complex and the tertiary amine monomer are loaded on a specific functional carrier. Compared with the prior art, the complex has heterogeneous property as a catalyst, is easy to separate from a reaction system after reaction, and realizes recycling; meanwhile, the catalyst simultaneously meets the coordination effect of multi-center metal and the coordination effect of Lewis acid and base between the metalloporphyrin complex and the quaternary ammonium salt monomer, and the interaction of the catalyst can be adjusted by changing the metal center of the porphyrin monomer, the substituent of the porphyrin monomer, the load of the porphyrin monomer, the type of the quaternary ammonium salt monomer and the load of the quaternary ammonium salt monomer, so that the catalytic performance is improved. The catalyst shows high polymer selectivity, high carbonate content, high activity and high recovery rate after separation when catalyzing the copolymerization of carbon dioxide and alkylene oxide.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (10)

1. A supported metalloporphyrin complex is characterized by having a structure shown as formula I:
Figure FDA0003638265660000011
the Carrier is selected from an inorganic Carrier, a high-molecular Carrier or a composite Carrier of the inorganic Carrier and the high-molecular Carrier;
the inorganic carrier is selected from SiO 2 、Al 2 O 3 Or SiO after bromo-, chloromethyl-, carboxyl-, amino-, hydroxyl-or thiol-functionalization 2 、Al 2 O 3 One or more of the above;
the macromolecular carrier is selected from one or more of crosslinked polystyrene, polyamide, polyethylene-glycol resin or crosslinked polystyrene, polyamide or polyethylene-glycol resin after bromination, chloromethyl, carboxyl, amino, hydroxyl and mercaptan functionalization;
the Linker 1 is a linking group with a structure shown in a formula II-a or a formula II-b;
Figure FDA0003638265660000012
wherein the N atom or O atom is
Figure FDA0003638265660000015
Connecting;
the Linker2 is a linking group with a structure shown in formula II-c:
Figure FDA0003638265660000013
wherein < u > is attached to R;
the ranges of x and y are that x is more than 0 and less than 100 percent, and y is more than or equal to 0 and less than 100 percent;
r is selected from dimethylamino, diethylamino, di-n-propylamino, diisopropylamine, diphenylamino, triethylammonium chloride, trihexylammonium chloride,
Figure FDA0003638265660000014
The described
Figure FDA0003638265660000024
Is a metalloporphyrin complex with a structure shown in a formula III;
Figure FDA0003638265660000021
x is halogen radical, -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 oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bis-trifluoromethylphenol oxyanion, or pentafluorophenol oxyanion;
R 1 ～R 19 each independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl;
m is magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
2. A supported metalloporphyrin complex according to claim 1, wherein said Carrier is selected from the group consisting of cross-linked polystyrene resin after chloromethyl functionalization.
3. A supported metalloporphyrin complex according to claim 1, wherein Linker 1 is selected from the group consisting of formula ii-a:
Figure FDA0003638265660000022
wherein the N atom is
Figure FDA0003638265660000023
Are connected.
4. A supported metalloporphyrin complex according to claim 1, wherein R is selected from triethylammonium chloride.
5. The supported metalloporphyrin complex according to claim 1, wherein the metalloporphyrin complex is specifically selected from the structures shown in formula III-a:
Figure FDA0003638265660000031
in the formula III-a, R 20 Selected from hydrogen, halogen, aliphatic groups of C1-C10, substituted alkoxy groups of C1-C10, cycloalkyl groups substituted by C3-C10, heterocyclic groups of C1-C10, aryl groups substituted by C6-C12 or heteroaryl groups substituted by C1-C12;
X 1 selected from halogens;
m is aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
6. The method for preparing a supported metalloporphyrin complex according to claim 1, comprising the steps of:
reacting porphyrin ligand with a structure shown in formula IV with an organic compound containing M and X groups to obtain a metalloporphyrin complex with a structure shown in formula III;
reacting the metalloporphyrin complex and the tertiary amine monomer with functional groups on the carrier to obtain a supported metalloporphyrin complex with a structure shown in a formula I;
Figure FDA0003638265660000032
m is magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
x is 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-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bis-trifluoromethylphenol oxyanion, or pentafluorophenol oxyanion;
R1-R19 are independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl.
7. Use of the supported metalloporphyrin complex of claim 1 as a catalyst in the preparation of polycarbonate.
8. The method of claim 7, comprising the steps of:
under the catalytic action of the supported metalloporphyrin complex, carbon dioxide and epoxide are subjected to copolymerization reaction to obtain the polycarbonate.
9. The method for preparing polycarbonate according to claim 8, wherein the temperature of the copolymerization reaction is 20-150 ℃, the time of the copolymerization reaction is 8-72 h, the pressure of carbon dioxide is 2-8 MPa, and the mass ratio of the supported metalloporphyrin complex to the epoxide is 1: 1000-50000.
10. The method of claim 7, wherein the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, glycidyl epichlorohydrin methacrylate, methyl glycidyl ether, phenyl glycidyl ether, and styrene alkylene oxide.
CN202210508275.0A 2022-05-11 2022-05-11 Supported metalloporphyrin complex, preparation method and application Pending CN114989207A (en)

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