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CN114989207B - A supported metal porphyrin complex, preparation method and application thereof - Google Patents

A supported metal porphyrin complex, preparation method and application thereof Download PDF

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CN114989207B
CN114989207B CN202210508275.0A CN202210508275A CN114989207B CN 114989207 B CN114989207 B CN 114989207B CN 202210508275 A CN202210508275 A CN 202210508275A CN 114989207 B CN114989207 B CN 114989207B
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polycarbonate
metalloporphyrin complex
complex
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carbon dioxide
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CN114989207A (en
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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 Table
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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Abstract

本发明提供了一种负载型金属卟啉配合物、制备方法及应用，属于催化剂制备技术领域。该负载型卟啉配合物由载体、链接基团和通过化学链接在载体上的活性组分和助剂共同组成，具有式Ⅰ所示结构。该配合物是通过将金属卟啉配合物与季铵盐单体负载在特定的功能化载体上制备获得，该负载型金属卟啉配合物可进一步合成得到双组元负载型金属卟啉配合物，同时均可作为催化剂对二氧化碳与环氧化物的共聚反应进行高效催化得到聚碳酸酯产物，该催化剂在催化二氧化碳与环氧化物共聚时表现出高聚合物选择性、高碳酸酯含量、高活性以及可分离后的高回收利用率。

The present invention provides a supported metal porphyrin complex, a preparation method and an application, and belongs to the technical field of catalyst preparation. The supported porphyrin complex is composed of a carrier, a linking group, an active component and an auxiliary agent chemically linked to the carrier, and has a structure shown in Formula I. The complex is prepared by loading the metal porphyrin complex and a quaternary ammonium salt monomer on a specific functionalized carrier. The supported metal porphyrin complex can be further synthesized to obtain a two-component supported metal porphyrin complex, and both can be used as a catalyst to efficiently catalyze the copolymerization reaction of carbon dioxide and epoxide to obtain a polycarbonate product. The catalyst exhibits high polymer selectivity, high carbonate content, high activity and high recovery rate after separation when catalyzing the copolymerization of carbon dioxide and epoxide.

Description

Supported metalloporphyrin complex, preparation method and application
Technical Field
The invention relates to the technical field of catalysts, in particular to a supported metalloporphyrin complex, a preparation method and application thereof.
Background
Carbon dioxide is used as 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 carbon dioxide and epoxide are alternately copolymerized to prepare the polycarbonate with full degradability, so that the polycarbonate provides a good substitute for increasingly lacking petroleum and other non-renewable resources. This pathway through carbon recycling can be positively responded to and is expected to achieve the "carbon neutralization" strategic goal. Moreover, the obtained polycarbonate has excellent transparency and excellent barrier property, and can be used as engineering plastics, disposable medicines and food packaging materials, adhesives and the like.
In 1969, inoue used the ZnEt 2-H2 O system to catalyze the ring-opening copolymerization of CO 2 and epoxide for the first time (ROCOP) to prepare degradable polycarbonate materials, and based on this, various heterogeneous and homogeneous catalytic systems for this reaction were 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 separability and recovery, and the obtained polymer has a light color, can be recycled for multiple times in the reaction, and effectively reduces the cost, but the further improvement of the activity and the selectivity is severely limited due to the intrinsic heterogeneous reaction. Similarly, although 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 catalytic activity, high selectivity, high stability and the like, the catalyst is difficult to separate from the polymer due to the intrinsic homogeneous reaction, and the problems of metal residues, influenced polymer quality and the like are always faced. 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 products 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 a heterogeneous catalyst, attempts are made to heterogenize the homogeneous catalyst, and catalytic systems with complex micropore structures, such as Metal Organic Frameworks (MOFs), conjugated Micropore Polymers (CMP) and the like, are designed, and although complete heterogenization is realized, the catalysts are not ideal in polymer synthesis and have the advantage of losing homogeneous catalyst, and in order to further improve factors such as activity, selectivity and the like in epoxide and carbon dioxide copolymerization, synergistic catalytic mechanisms are introduced into the design of catalytic systems. The catalyst comprises a multi-center metal synergistic effect of a bi-metal and a multi-metal catalyst, a bi-component catalytic system consisting of SalenCo catalyst and a quaternary ammonium salt or a quaternary phosphonium salt cocatalyst and a Lewis acid base synergistic effect of a bi-functional catalyst. These catalytic systems are capable of polymerization at lower catalyst concentrations and offer significant improvements in the control of the selectively produced polymer or carbonate segment content, but still exhibit homogeneous properties that are difficult to meet market demands.
Disclosure of Invention
In view of the above, the present invention aims to provide a supported metalloporphyrin complex, a preparation method and an application thereof, wherein 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:
The Carrier is selected from an inorganic Carrier, a high polymer Carrier or a composite Carrier of the inorganic Carrier and the high polymer Carrier;
The inorganic carrier is selected from one or more of SiO 2、Al2O3, bromo, chloromethyl, carboxyl, amino, hydroxyl and thiol functionalized SiO 2、Al2O3;
The high molecular carrier is selected from one or more of crosslinked polystyrene, polyamide, polyethylene-glycol resin or brominated, chloromethyl, carboxyl, amino, hydroxyl and mercaptan functionalized crosslinked polystyrene, polyamide or polyethylene-glycol resin;
the Linker 1 is a linking group with a structure shown in a formula II-a or a formula II-b;
wherein the N or O atoms Are connected;
the Linker 2 is a linking group with a structure shown in a formula II-c:
Wherein' is linked to R;
The range of x and y is 0< x <100%, and y is more than or equal to 0 and less than 100%;
the R is selected from dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, diphenylamino, triethylammonium chloride, trihexylammonium chloride,
The saidIs metalloporphyrin complex with a structure shown in formula III;
the X is halogeno 、-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3、 p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoxy anion, p-nitrophenoxy anion, m-nitrophenoxy anion, 2, 4-dinitrophenol oxy anion, 3, 5-dinitrophenol oxy anion, 2,4, 6-trinitrophenol oxy anion, 3, 5-dichlorophenol oxy anion, 3, 5-difluorophenol oxy anion, 3, 5-di-trifluoromethyl phenol oxy anion or pentafluorophenol oxy anion;
R 1～R19 are 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 chloromethyl functionalized crosslinked polystyrene resins.
Preferably, the Linker 1 is selected from formula II-a:
Wherein the N atom is Are connected.
Preferably, R is selected from triethylammonium chloride.
Preferably, the metalloporphyrin complex is specifically selected from the structures shown in formula III-a:
In formula III-a, R 20 is selected from hydrogen, halogen, C1-C10 aliphatic, C1-C10 substituted alkoxy, C3-C10 substituted cycloalkyl, C1-C10 heterocyclyl, C6-C12 substituted aryl, or substituted C1-C12 heteroaryl;
X 1 is selected from halogen;
m is aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
The invention provides a preparation method of the supported metalloporphyrin complex, which comprises the following steps:
reacting a porphyrin ligand with a structure of formula IV with an organic compound containing M and X groups to obtain a metalloporphyrin complex with a structure of formula III;
reacting metalloporphyrin complex and tertiary amine monomer with functional groups on a carrier to obtain a supported metalloporphyrin complex with a structure shown in formula I;
the M is magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
the X is halogeno 、-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3、 p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoxy anion, p-nitrophenoxy anion, m-nitrophenoxy anion, 2, 4-dinitrophenol oxy anion, 3, 5-dinitrophenol oxy anion, 2,4, 6-trinitrophenol oxy anion, 3, 5-dichlorophenol oxy anion, 3, 5-difluorophenol oxy anion, 3, 5-di-trifluoromethyl phenol oxy anion or pentafluorophenol oxy anion;
R 1～R19 is 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 preparing polycarbonate.
The invention also provides a preparation method of the polycarbonate, which comprises the following steps:
under the catalysis of the supported metalloporphyrin complex, the carbon dioxide and the 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, cyclohexane oxide, cyclopentane oxide, epichlorohydrin glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.
The beneficial effects of the invention are that
The invention provides a supported metalloporphyrin complex, a preparation method and application thereof, wherein the supported metalloporphyrin 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 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 metalloporphyrin complex and quaternary ammonium salt monomer on a specific functionalized carrier. In the synthesis stage of the supported catalyst, the supported metalloporphyrin complex with different loadings of the metalloporphyrin complex and the tertiary amine monomer on the carrier can be synthesized by regulating and controlling the molar ratio of the functional group, the metalloporphyrin complex and the tertiary amine monomer on the carrier (1:2x:y, 0< x <100%, 0.ltoreq.y < 100%). In addition, the supported metalloporphyrin complex with different catalytic performances can be obtained by changing the metal center of the porphyrin monomer, the substituent of the porphyrin monomer and the type of the quaternary ammonium salt monomer;
Compared with the prior art, the supported metalloporphyrin complex can be further synthesized to obtain a bi-component supported metalloporphyrin complex, and can be used as a catalyst to carry out efficient catalysis on the copolymerization reaction of carbon dioxide and epoxide to obtain a polycarbonate product, and 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 multi-center metal synergistic effect and the Lewis acid-base synergistic effect between the metalloporphyrin complex and the quaternary ammonium salt monomer, and the interaction can be improved by changing the metal center of the porphyrin monomer, the substituent of the porphyrin monomer, the loading of the porphyrin monomer, the type of the quaternary ammonium salt monomer and the loading thereof, so that the catalytic performance is improved. The catalyst shows high polymer selectivity, high carbonate content, high activity and high recycling rate after being separated when catalyzing copolymerization of carbon dioxide and epoxide. Experimental results show that in the ring-opening copolymerization reaction of catalyzing carbon dioxide and epoxide, the number average molecular weight of the product is 12000-280000 g/mol, the molecular weight distribution is 1.01-2.61, the polymer selectivity in the reaction product can be up to 99%, and the carbonate unit content can be regulated and controlled within a wider range of 0-95%.
Drawings
FIG. 1 is a scheme showing the preparation reaction of complexes EL 1-3;
FIG. 2 is a scheme of the preparation reaction of EC 1;
FIG. 3 is a preparation reaction scheme for 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 preparation reaction of polycarbonate;
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the complex EL-1;
FIG. 8 is a nuclear magnetic resonance hydrogen spectrum of the 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:
the Carrier is a Carrier selected from an inorganic Carrier, a high polymer Carrier or a composite Carrier of the inorganic Carrier and the high polymer Carrier;
The inorganic carrier is selected from one or more of SiO 2、Al2O3, bromo, chloromethyl, carboxyl, amino, hydroxyl and thiol functionalized SiO 2、Al2O3;
The polymer Carrier is selected from one or more of crosslinked polystyrene, polyamide, polyethylene-glycol resin or brominated, chloromethyl, carboxyl, amino, hydroxyl and mercaptan functionalized crosslinked polystyrene, polyamide or polyethylene-glycol resin, and preferably the Carrier is selected from chloromethyl functionalized crosslinked polystyrene resin.
The Linker 1 is a linking group with a structure shown in a formula II-a or a formula II-b, preferably a linking group with a structure shown in the formula II-a;
wherein the N or O atoms Are connected;
the Linker2 is a linking group with a structure shown in a formula II-c:
Wherein' is linked to R;
The range of x and y is 0< x <100%, and y is more than or equal to 0 and less than 100%;
the R is selected from dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, diphenylamino, triethylammonium chloride, trihexylammonium chloride, Preferably triethylammonium chloride;
The said Is a metalloporphyrin complex having a structure represented by formula III:
the X is halogeno 、-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3、 p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoxy anion, p-nitrophenoxy anion, m-nitrophenoxy anion, 2, 4-dinitrophenol oxy anion, 3, 5-dinitrophenol oxy anion, 2,4, 6-trinitrophenol oxy anion, 3, 5-dichlorophenol oxy anion, 3, 5-difluorophenol oxy anion, 3, 5-di-trifluoromethyl phenol oxy anion or pentafluorophenol oxy anion;
R 1～R19 are 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 structures shown in III-a:
In formula III-a, R 20 is selected from hydrogen, halogen, C1-C10 aliphatic, C1-C10 substituted alkoxy, C3-C10 substituted cycloalkyl, C1-C10 heterocyclyl, C6-C12 substituted aryl or substituted C1-C12 heteroaryl;
X 1 is selected from halogen, 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:
in the present invention, the The method of preparation of (2) is not particularly limited and may be generally commercially available or prepared according to a method well known to those skilled in the art;
The invention is described in The specific preparation method of (2) comprises the following steps:
Carrying out one-pot reaction on benzaldehyde and pyrrole under the condition of propionic acid reflux, and collecting a first color band through a column chromatographic separation technology to obtain tetraphenylporphyrin;
tetraphenylporphyrin is dissolved in trifluoroacetic acid and subjected to nitration reaction with sodium nitrite at room temperature. Quenching with ice deionized water after the reaction is finished, neutralizing the organic phase with saturated sodium bicarbonate solution, and extracting and combining the organic phase to obtain mono-nitro tetraphenyl porphyrin;
Under the nitrogen environment, the mono-nitro tetraphenyl porphyrin is dissolved in concentrated hydrochloric acid and undergoes a reduction reaction with a concentrated hydrochloric acid solution of stannous chloride at 65 ℃. After the reaction is finished, adding concentrated ammonia water to quench until the system is neutral, and collecting a second color band of a filter cake obtained by suction filtration through a column chromatographic separation technology to obtain monoaminoporphyrin.
The central metal M and the co-ligand X coordinate into the porphyrin ring through the metallization reaction of the porphyrin ligand in methylene dichloride solution,The group access mode is nucleophilic substitution reaction of amino of mono-amino substituted porphyrin and benzyl chloride group on carrier under alkaline condition, according to the required load rate, regulating and controlling the proportion of mono-amino metalloporphyrin and benzyl chloride group on carrier, potassium carbonate is used as acid-binding agent, the mole ratio of benzyl chloride group on carrier, mono-amino porphyrin and potassium carbonate is 1:2x:x, carrier and mono-amino metalloporphyrin are fully swelled or dissolved in anhydrous N, N-Dimethylformamide (DMF), and fully reacted for 72h under 90 deg.C condition. The R group is connected in such a way that after the metalloporphyrin complex is loaded on the carrier, tertiary amine monomer with the same molar quantity as benzyl chloride group in the carrier is further added, anhydrous DMF is taken as a solvent, and the reaction is fully carried out for 24 hours at the temperature of 90 ℃.
The invention provides a preparation method of the supported metalloporphyrin complex, which comprises the following steps:
The porphyrin ligand with the structure of the formula IV is reacted with an organic compound containing M and X groups to obtain a metalloporphyrin complex with the structure of the formula III, wherein the organic compound containing M and X groups is preferably diethylaluminum 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 the formula IV to the organic compound containing M and X groups is preferably 1:1.2.
The metalloporphyrin complex and tertiary amine monomer react with functional groups on a carrier to obtain a supported metalloporphyrin complex with a structure of formula I, wherein the tertiary amine monomer is preferably triethylamine, the reaction temperature is preferably 90 ℃, the reaction time is preferably 72-100h, and the molar quantity of the corresponding metalloporphyrin complex and tertiary amine monomer is calculated according to the molar quantity of the functional groups on the carrier, wherein the molar ratio of the added functional groups on the carrier, metalloporphyrin complex and tertiary amine monomer is 1:2x:y, wherein 0< x <100%, and 0.ltoreq.y <100%.
The M is magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;
the X is halogeno 、-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3、 p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenoxy anion, p-nitrophenoxy anion, m-nitrophenoxy anion, 2, 4-dinitrophenol oxy anion, 3, 5-dinitrophenol oxy anion, 2,4, 6-trinitrophenol oxy anion, 3, 5-dichlorophenol oxy anion, 3, 5-difluorophenol oxy anion, 3, 5-di-trifluoromethyl phenol oxy anion or pentafluorophenol oxy anion;
R 1～R19 is 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 preparing polycarbonate, which comprises the following steps:
Under the catalysis 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, cyclohexane oxide, cyclopentane oxide, epichlorohydrin glycidyl 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 ℃, the higher polymer selectivity (> 99%) can be realized when the temperature is lower, the reactivity is increased along with the temperature, and the time of the copolymerization reaction is preferably 8-72 h.
In the invention, the mass ratio of the supported metalloporphyrin complex to the epoxide is preferably 1:1000-50000.
In the invention, the supported metalloporphyrin complex can prepare the polycarbonate material with high activity by supporting porphyrin and tertiary amine on the same polymer chain. After the reaction is finished, the catalyst can be separated from the reaction system, so that the catalyst can be recycled.
In order to further illustrate the present invention, the following examples are provided to describe in detail a supported metalloporphyrin complex and a preparation method thereof, and a preparation method of polycarbonate, which are not to be construed as limiting the scope of the present invention.
EXAMPLE 1 preparation of metalloporphyrin Complex
50G (470 mmol) of benzaldehyde and 31g (470 mmol) of pyrrole were added to 500mL of propionic acid, heated to about 130 ℃, refluxed for 1.5h, cooled to room temperature after the reaction, concentrated to 200mL, cooled overnight in a refrigerator after methanol was added, and the product obtained by filtration was purified by silica gel column chromatography (CHCl 3/CH3 OH) to give product EL1, the yield of which was about 20%. 1H-NMR(CDCl3 8.9,8.2,7.8, -2.8, high resolution electrospray mass spectrometry as shown in FIG. 7, analysis results [ C 44H31N4 ]:615.2, found:615.2;
1g (1.63 mmol) of EL1 was dissolved in 10mL (1.63 mmol) of trifluoroacetic acid, 0.2g (2.93 mmol) of sodium nitrite was added, and the mixture was reacted at room temperature for 3min after sufficient stirring. 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 organic phases, extracting and washing three times by using saturated sodium bicarbonate solution, and drying to obtain a product EL2. The dried EL2 was dissolved in 20mL of concentrated hydrochloric acid under nitrogen atmosphere, 1.44g (7.58 mmol) of stannous chloride was additionally prepared and dissolved in the concentrated hydrochloric acid, and after stirring sufficiently, a concentrated hydrochloric acid solution of stannous chloride was added to the EL2 and reacted for 1 hour at 65 ℃. After the reaction is finished, adding concentrated ammonia water to quench the reaction system to be neutral, carrying out suction filtration, fully washing a filter cake with deionized water for 3 times, and then drying. The solid product obtained was purified by column chromatography on silica gel using methylene chloride as eluting phase to give about 0.43g of product EL 3. 1H-NMR(CDCl3 Ppm): 8.9,8.2,8.0,7.8,7.0,4.0, -2.8. High-resolution electrospray mass spectrometry analysis, analysis results were [ C 44H31N5 ]:629.77, found:629.26. The reaction route is schematically shown in figure 1, and the nuclear magnetic hydrogen spectrogram is shown in figure 8.
Under the protection of nitrogen, 0.4g of EL3 (0.64 mmol) of the ligand is dissolved in methylene chloride, and 0.4mLAlEt 2 Cl (diethylaluminum chloride) (2 mol/L,0.77 mmol) is added dropwise, and the reaction is stirred at room temperature for 2 hours. The obtained product is purified by column chromatography and then dried to obtain the required complex EC1.
FIG. 2 is a scheme showing the preparation reaction of EC1, and the nuclear magnetic resonance hydrogen spectrum is shown in FIG. 9.
Example 2 preparation of Supported metalloporphyrin Complex
Under nitrogen, 0.5g of crosslinked polystyrene resin (MERRIFIELD RESIN) (DVB: 1%, cl:0.8-1.3 mmol/g) was fully swollen in 10mL of anhydrous DMF at 70℃for 24h. After 0.5g (0.7 mmol) of EC1 was sufficiently dissolved in 10mL of anhydrous DMF, it was added to the swollen crosslinked polystyrene resin, K 2CO3 35: 35 mg (0.25 mmol) was further added thereto, and the temperature was raised to 90℃and the reaction was continued for 72 hours. And after the reaction is finished, carrying out suction filtration operation, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate is colorless, and then drying to obtain the required complex EC2. X was 53.8% by ICP analysis, y=0. The preparation scheme is shown in FIG. 3.
EXAMPLE 3 preparation of Supported metalloporphyrin Complex
Under nitrogen, 1g of crosslinked polystyrene resin (MERRIFIELD RESIN) (DVB: 1%, cl:0.8-1.3 mmol/g) was fully swollen in 10mL of anhydrous DMF at 70℃for 24h. After 1g (1.4 mmol) of EC1 was sufficiently dissolved in 10mL of anhydrous DMF, it was added to the swollen crosslinked polystyrene resin, K 2CO3 76 mg (0.55 mmol) was further added thereto, and the temperature was raised to 90℃and the reaction was continued for 72 hours. And after the reaction is finished, carrying out suction filtration operation, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate is colorless, and then drying to obtain the required complex EC3. X was 20.6% by ICP analysis, y=0. The preparation scheme is shown in FIG. 3.
EXAMPLE 4 preparation of Supported metalloporphyrin Complex
2G of crosslinked polystyrene resin (MERRIFIELD RESIN) (DVB: 1%, cl:0.8-1.3 mmol/g) was fully swollen under nitrogen in 20mL of anhydrous DMF at 70℃for 24h. After 1g (1.4 mmol) of EC1 was sufficiently dissolved in 10mL of anhydrous DMF, it was added to the swollen crosslinked polystyrene resin, K 2CO3 87 mg (0.62 mmol) was further added thereto, and the temperature was raised to 90℃and the reaction was continued for 72 hours. And after the reaction is finished, carrying out suction filtration operation, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate is colorless, and then drying to obtain the required complex EC4. X was 18.0% by ICP analysis, y=0. The preparation scheme is shown in FIG. 3.
EXAMPLE 5 preparation of Supported metalloporphyrin Complex
2G of crosslinked polystyrene resin (MERRIFIELD RESIN) (DVB: 1%, cl:0.8-1.3 mmol/g) was fully swollen under nitrogen in 10mL of anhydrous DMF at 70℃for 24h. After 0.5g (0.7 mmol) of EC1 was sufficiently dissolved in 10mL of anhydrous DMF, it was added to the swollen crosslinked polystyrene resin, K 2CO3 29 (mg) (0.21 mmol) was further added thereto, and the temperature was raised to 90℃and the reaction was continued for 72 hours. And after the reaction is finished, carrying out suction filtration operation, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate is colorless, and then drying to obtain the required complex EC5. X was 4.38% by ICP analysis, y=0. The preparation scheme is shown in FIG. 3.
EXAMPLE 6 preparation of Supported metalloporphyrin Complex
2G of crosslinked polystyrene resin (MERRIFIELD RESIN) (DVB: 1%, cl:0.8-1.3 mmol/g) was fully swollen under nitrogen in 10mL of anhydrous DMF at 70℃for 24h. 3g (4.3 mmol) of EC1 were dissolved in 10mL of anhydrous DMF and added to the swollen crosslinked polystyrene resin, K 2CO3 69 mg (0.5 mmol) was added thereto, the temperature was raised to 90℃and the reaction was continued for 72h. And after the reaction is finished, carrying out suction filtration operation, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate is colorless, and then drying to obtain the required complex EC6. X was 44.6% by ICP analysis, y=0. The preparation scheme is shown in FIG. 3.
EXAMPLE 7 preparation of two-component Supported metalloporphyrin Complex
0.8G of EC4 was fully swelled in 8mL of anhydrous DMF under nitrogen, to which was added 0.1g (1 mmol) of triethylamine (NEt 3) and reacted at 90℃for 24h. And after the reaction is finished, carrying out suction filtration operation, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate is colorless, and then drying to obtain the required complex EC7. X was calculated to be 18.0% and y was calculated to be 82.0% by ICP analysis. The preparation scheme is shown in FIG. 4.
Example 8 preparation of a two-component Supported metalloporphyrin Complex
0.8G of EC5 was fully swelled in 8mL of anhydrous DMF under nitrogen, to which was added 0.1g (1 mmol) of triethylamine (NEt 3) and reacted at 90℃for 24h. And after the reaction is finished, carrying out suction filtration operation, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate is colorless, and then drying to obtain the required complex EC8. X was calculated to be 4.38% and y was calculated to be 95.6% by ICP analysis. The preparation scheme is shown in FIG. 4.
Example 9 preparation of a two-component Supported metalloporphyrin Complex
0.5G of EC6 was fully swelled in 8mL of anhydrous DMF under nitrogen, and 0.5g (0.5 mmol) of triethylamine (NEt 3) was added thereto and reacted at 90℃for 24 hours. And after the reaction is finished, carrying out suction filtration operation, and fully washing a filter cake by using anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate is colorless, and then drying to obtain the required complex EC9. X was calculated to be 44.6% and y was calculated to be 55.4% by ICP analysis. The preparation scheme is shown in FIG. 4.
EXAMPLE 10 preparation of binary Supported metalloporphyrin Complex
0.5G of EC6 was fully swelled in 8mL of anhydrous DMF under the protection of nitrogen, 0.13g (0.5 mmol) of trihexylamine (N (C 6H13)3) was added thereto, and reacted at 90 ℃ for 24 hours, after the reaction was completed, suction filtration operation was performed, and the filter cake was fully washed with anhydrous DMF, anhydrous chloroform and anhydrous dichloromethane until the filtrate was colorless, and then dried to obtain the desired complex EC10. X was 44.6% and y was 55.4% as calculated by ICP analysis, and the reaction scheme was prepared as shown in FIG. 5.
Example 11 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to the aluminum content in the resin) of the aluminum porphyrin complex EC2 in example 2 and 75mmol of dried propylene oxide were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and the polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC2 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 11 was examined by 1 H-NMR nuclear magnetism, and it was found that the polycarbonate had a carbonate unit content of 59% and a polymer selectivity of 84%, and that the TOF value of the catalyst system was calculated to be 140H -1, and that the number average molecular weight of the polycarbonate obtained by the measurement by GPC was 43600g/mol and the molecular weight distribution was 1.61. The preparation scheme is shown in FIG. 6.
Example 12 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to the aluminum content in the resin) of the aluminum porphyrin complex EC3 in example 3 and 75mmol of dried propylene oxide were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and the polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC3 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 12 was examined by 1 H-NMR nuclear magnetism, and the result showed that the polycarbonate had a carbonate unit content of 67% and a polymer selectivity of 82%, that the TOF value of the catalyst system was 40H -1 by calculation, and that the number average molecular weight of the polycarbonate obtained by GPC measurement was 21600g/mol and the molecular weight distribution was 1.27. The preparation scheme is shown in FIG. 6.
Example 13 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to the aluminum content in the resin) of the aluminum porphyrin complex EC4 in example 4 and 75mmol of dried propylene oxide were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and the polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC4 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 13 was examined by 1 H-NMR nuclear magnetism, and the result showed that the polycarbonate had a carbonate unit content of 77% and a polymer selectivity of 87%, that the TOF value of the catalyst system was calculated to be 30H -1, that the number average molecular weight of the polycarbonate obtained by GPC was 25100g/mol, and that the molecular weight distribution was 1.91. The preparation scheme is shown in FIG. 6.
Example 14 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to the aluminum content in the resin) of the aluminum porphyrin complex EC5 in example 5 and 75mmol of dried propylene oxide were added to a 5mL autoclave which had been dehydrated and deoxygenated, and then the autoclave was taken out of the glove box, and carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC5 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 14 was examined by 1 H-NMR nuclear magnetism, and the result showed that the polycarbonate had a carbonate unit content of 95% and a polymer selectivity of 79%, the TOF value of the catalyst system was calculated to be 71H -1, and the number average molecular weight of the polycarbonate obtained by GPC measurement was 21400g/mol and the molecular weight distribution was 1.17. The preparation scheme is shown in FIG. 6.
Example 15 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to aluminum content in the resin) of the aluminum porphyrin complex EC6 in example 6 and 75mmol of dried propylene oxide were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC6 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 15 was examined by 1 H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 51% and a polymer selectivity of 90%, and the TOF value of the catalyst system was calculated to be 72H -1, and the number average molecular weight of the polycarbonate obtained was 47700g/mol and the molecular weight distribution was 1.71 by GPC. The preparation scheme is shown in FIG. 6.
Example 16 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to aluminum content in the resin) of the aluminum porphyrin complex EC7 and 7mmol of dried propylene oxide in example 4 were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was then introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC7 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 16 was examined by 1 H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 92% and a polymer selectivity of 46%, and the TOF value of the catalyst system was 139H -1 as calculated, and the number average molecular weight of the polycarbonate obtained was 13200g/mol and the molecular weight distribution was 1.97 as measured by GPC. The preparation scheme is shown in FIG. 6.
Example 17 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to aluminum content in the resin) of the aluminum porphyrin complex EC8 and 210mmol of dried propylene oxide in example 5 were added to a 5mL autoclave which had been dehydrated and deoxygenated, and then the autoclave was taken out of the glove box, and carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement.
The reaction system is subjected to solid-liquid separation, and the solid part is reused for recycling for new polymerization reaction as a catalyst EC8 1 after being washed for 3 times by dichloromethane or acetone.
The product obtained in example 17 was examined by 1 H-NMR nuclear magnetism, which showed that PO had been completely converted to cyclic carbonate, and the TOF value of the catalytic system was calculated to be 583H -1. The preparation scheme is shown in FIG. 6.
Example 18 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to the aluminum content in the resin) of the aluminum porphyrin complex EC9 and 75mmol of dried propylene oxide in example 6 were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and the polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC9 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 18 was examined by 1 H-NMR nuclear magnetism, and as a result, it was found that the polycarbonate had a carbonate unit content of 65% and a polymer selectivity of 94%, the TOF value of the catalyst system was calculated to be 97H -1, and the number average molecular weight of the polycarbonate obtained by the examination by GPC was 64000g/mol and the molecular weight distribution was 1.47. The preparation scheme is shown in FIG. 6.
Example 19 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to aluminum content in the resin) of the aluminum porphyrin complex EC6 in example 6 and 75mmol of dried propylene oxide were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 50℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC6 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 19 was examined by 1 H-NMR nuclear magnetism, and the result showed that the polycarbonate had a carbonate unit content of 42% and a polymer selectivity of more than 99%, the TOF value of the catalyst system was calculated to be 15H -1, and the number average molecular weight of the polycarbonate obtained by GPC measurement was 26600g/mol and the molecular weight distribution was 1.32. The preparation scheme is shown in FIG. 6.
Example 20 preparation of polycarbonate
In a glove box, 0.015mmol (calculated as aluminum content in the resin) of the aluminum porphyrin complex EC6 in example 6, 0.0075mmol PPNCl and 75mmol of dried propylene oxide were added to a 5mL autoclave which had been dehydrated and deoxygenated, and then the autoclave was taken out of the glove box, and carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and the polymerization was carried out at a temperature of 70 ℃. 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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC6 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 20 was examined by 1 H-NMR nuclear magnetism, which showed that the polycarbonate had a carbonate unit content of 51% and a polymer selectivity of greater than 76%, the TOF value of the catalyst system was calculated to be 72H -1, and the number average molecular weight of the polycarbonate obtained was 39500g/mol and the molecular weight distribution was 1.65 as measured by GPC. The preparation scheme is shown in FIG. 6.
Example 21 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to aluminum content in the resin) of the aluminum porphyrin complex EC5 in example 5 and 210mmol of dried propylene oxide were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC5 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 21 was examined by 1 H-NMR nuclear magnetism, and the result showed that the polycarbonate had a carbonate unit content of 80% and a polymer selectivity of 44%, that the TOF value of the catalyst system was calculated to be 90H -1, and that the number average molecular weight of the polycarbonate obtained by GPC was 5300g/mol and the molecular weight distribution was 3.38. The preparation scheme is shown in FIG. 6.
Example 22 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to aluminum content in resin) of the aluminum porphyrin complex EC5 in example 5 and 420mmol 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 introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function, the pressure in the autoclave was brought to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC5 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 22 was examined by 1 H-NMR nuclear magnetism, and the result showed that the polycarbonate had a carbonate unit content of 94% and a polymer selectivity of 62%, that the TOF value of the catalyst system was calculated to be 76H -1, and that the number average molecular weight of the polycarbonate obtained by the measurement by GPC was 3400g/mol and that the molecular weight distribution was 2.13. The preparation scheme is shown in FIG. 6.
Example 23 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to aluminum content in the resin) of the aluminum porphyrin complex EC5 in example 5 and 150mmol of dried propylene oxide were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC5 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 23 was examined by 1 H-NMR nuclear magnetism, and the result showed that the polycarbonate had a carbonate unit content of 82% and a polymer selectivity of 55%, that the TOF value of the catalyst system was calculated to be 87H -1, that the number average molecular weight of the polycarbonate obtained by the examination by GPC was 15000 g/mol, and that the molecular weight distribution was 1.52. The preparation scheme is shown in FIG. 6.
Example 24 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to the aluminum content in the resin) of the recovered catalyst EC5 1 and 75mmol of the dried propylene oxide in example 4 were added to a 5mL autoclave which had been dehydrated and deoxygenated, and then the autoclave was taken out of the glove box, and further carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC5 2 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 24 was examined by 1 H-NMR nuclear magnetism, and it was found that the polycarbonate had a carbonate unit content of 73% and a polymer selectivity of 79%, that the TOF value of the catalyst system was 40H -1 by calculation, and that the number average molecular weight of the polycarbonate obtained by GPC measurement was 10700g/mol and the molecular weight distribution was 1.27. The preparation scheme is shown in FIG. 6.
Example 25 preparation of polycarbonate
In a glove box, 0.015mmol (calculated according to aluminum content in the resin) of the aluminum porphyrin complex EC10 and 75mmol of dried propylene oxide in example 6 were added to a 5mL autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and polymerization was carried out at a temperature of 70℃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 for nuclear magnetic measurement. Unreacted propylene oxide was removed in a vacuum oven at 45 ℃ to give a catalyst coated polycarbonate.
The polymer is fully dissolved by 10mL of dichloromethane, insoluble matters are used as catalysts, solid-liquid separation is carried out through extraction, the solid parts are repeatedly washed by acetone until the solids are mutually dispersed and no obvious polymer is wrapped in the solid parts, the solid parts are used as catalysts EC10 1 for catalyzing new polymerization reaction after being recovered, the liquid parts are dropwise added into methanol after being collected, and light-color or white polycarbonate is gradually precipitated and separated out.
The polycarbonate obtained in example 25 was examined by 1 H-NMR nuclear magnetism, and the result showed that the polycarbonate had a carbonate unit content of 64% and a polymer selectivity of 89%, that the TOF value of the catalyst system was calculated to be 87H -1, and that the number average molecular weight of the polycarbonate obtained by the measurement by GPC was 57900g/mol and the molecular weight distribution was 1.38. The preparation scheme 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 metalloporphyrin complex and tertiary amine monomer are loaded on a specific functionalized carrier to prepare the metalloporphyrin. Compared with the prior art, the complex has heterogeneous property as a catalyst, is easy to separate from a reaction system after reaction, realizes recycling, and simultaneously satisfies the multi-center metal synergistic effect and the Lewis acid-base synergistic effect between the metalloporphyrin complex and the quaternary ammonium salt monomer, and the interaction can be regulated 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 thereof, thereby improving the catalytic performance. The catalyst shows high polymer selectivity, high carbonate content, high activity and high recovery rate after being separated when catalyzing copolymerization of carbon dioxide and alkylene oxide.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The supported metalloporphyrin complex is characterized by having a structure shown in a formula I:
the Carrier is selected from chloromethyl functionalized crosslinked polystyrene resin;
the Linker 1 is a linking group with a structure shown in a formula II-a;
Wherein the N atom is Are connected;
the Linker 2 is a linking group with a structure shown in a formula II-c:
Wherein' is linked to R;
The range of x and y is 0< x <100%, and y is more than or equal to 0 and less than 100%;
R is selected from triethylammonium chloride or trihexylammonium chloride;
The said Is metalloporphyrin complex with a structure shown in a formula III-a;
In formula III-a, R 20 is selected from hydrogen, halogen, C1-C10 aliphatic;
X 1 is selected from halogen;
m is aluminum.
2. The supported metalloporphyrin complex according to claim 1, wherein R is selected from triethylammonium chloride.
3. The method for preparing the supported metalloporphyrin complex according to claim 1, comprising the steps of:
Reacting a porphyrin ligand with a structure of formula IV with an organic compound containing M and X groups to obtain a metalloporphyrin complex;
reacting metalloporphyrin complex and tertiary amine monomer with chloromethyl on crosslinked polystyrene resin to obtain supported metalloporphyrin complex with structure of formula I;
M is aluminum;
x is halogen;
R1 to R19 are independently selected from hydrogen;
In the structure of formula IV, is connected with NH 2.
4. Use of the supported metalloporphyrin complex according to claim 1 as a catalyst in the preparation of polycarbonate.
5. A process for producing a polycarbonate as defined in claim 4, comprising the steps of:
under the catalysis of the supported metalloporphyrin complex, the carbon dioxide and the epoxide are subjected to copolymerization reaction to obtain the polycarbonate.
6. The method for preparing polycarbonate according to claim 5, 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.
7. A process for producing a polycarbonate as defined in claim 5, wherein the epoxide is one or more selected from the group consisting of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.
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