Method for preparing supported multifunctional high-molecular catalyst by one-pot method and application of supported multifunctional high-molecular catalyst

Abstract

The invention provides a method for preparing a supported multifunctional high-molecular catalyst by a one-pot method. The supported multifunctional high-molecular catalyst is obtained by carrying out one-step polymerization on an alkenyl modified carrier and an alkenyl modified active component. In the method provided by the invention, the surface of the carrier and the active component are modified with polymerizable functional groups of the same type, so that the supported multifunctional polymer catalyst can be directly obtained through a one-step polymerization means. In order to verify the catalytic effect of the prepared supported catalyst, the prepared supported bifunctional polymer aluminum porphyrin is used for polymerization of epoxide and carbon dioxide, polymerization of epoxide and anhydride, self-polymerization of epoxide and ring-opening polymerization of lactone, and the performance of the supported bifunctional polymer aluminum porphyrin is equivalent to that of a catalyst prepared by a traditional multi-step method. The preparation method has the characteristics of simplicity, universality and high efficiency, and the prepared supported multifunctional aluminum porphyrin catalyst has excellent performance, is easy to separate and can be recycled.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and in particular relates to a method for preparing a supported multifunctional polymer catalyst by a one-pot method and an application thereof. Background Art

[0002] Catalysts can significantly accelerate chemical reactions and control product selectivity, playing an important role in industrial production and scientific research. Depending on whether the catalyst and substrate are in two phases, catalysts can be divided into two categories: heterogeneous catalysts and homogeneous catalysts. Traditional heterogeneous catalysts have the advantages of easy separation, recyclability, and can be used for continuous production. They are currently the most widely used catalysts in the industry. However, due to the uneven active sites, it is difficult to study the mechanism, and therefore it is difficult to further optimize the catalytic performance. Homogeneous catalysts have a clear and easily adjustable structure, which can be deeply optimized based on the structure-performance relationship, and are characterized by high activity and high selectivity. However, homogeneous catalysts are difficult to separate from the product, which limits the large-scale application of homogeneous catalysts.

[0003] In order to combine the advantages of easy separation of heterogeneous catalysts and high performance of homogeneous catalysts, it is an important trend in the development of catalysts to load homogeneous catalysts. The most commonly used loading method is to load homogeneous catalysts on the surface of a carrier using covalent bonds. This method retains the inherent structure of the homogeneous catalyst and has adjustability and predictability. In order to further improve the performance of the supported catalyst and increase the function of the supported catalyst, a variety of homogeneous catalysts can be loaded at the same time, but they are often only connected to the carrier through short organic chains. This causes the active sites to be restricted to the surface of the carrier, and due to the steric effect of the carrier, the active sites are difficult to fully contact with the substrate. Therefore, compared with homogeneous analogs, current supported catalysts often have poor performance and are still difficult to apply on a large scale.

[0004] In order to reduce the steric effect of the carrier, polymer chains are used to connect homogeneous catalysts and carriers, which can indeed significantly improve the performance of the catalyst. However, existing methods require multiple steps such as polymerization, modification, and loading, which is time-consuming and labor-intensive. Therefore, how to directly prepare supported multifunctional polymer catalysts through simple methods remains a challenge. Summary of the invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a method for preparing a supported multifunctional polymer catalyst in one pot and its application. The preparation method of the supported multifunctional polymer catalyst provided by the present invention is simple, efficient, and easy to control, eliminating the tedious multi-step synthesis.

[0006] The invention provides a one-pot method for preparing a supported multifunctional polymer catalyst, wherein an alkenyl-modified carrier and an alkenyl-modified active component are polymerized in one step to obtain the supported multifunctional polymer catalyst.

[0007] Preferably, the alkenyl-modified carrier and the alkenyl-modified active component are independently selected from one of the following groups:

[0008]

[0009] Preferably, the carrier in the alkenyl-modified carrier is selected from SiO 2 , Fe 2 O 3 , Fe 3 O 4 , MgO, ZnO, Al 2 O 3 、TiO 2 、ZrO 2 , Au, zeolite, graphene, cross-linked polystyrene, cross-linked polyamide, and cross-linked polyethylene-glycol resin.

[0010] Preferably, the active component in the alkenyl-modified active component includes at least one of a metal porphyrin complex and a metal thiophene complex;

[0011] Preferably, the active component also includes at least one of dimethylamino, methyl, and quaternary ammonium salt.

[0012] Preferably, the metal porphyrin complex has a structure shown in Formula I:

[0013]

[0014] The M is selected from aluminum, zinc, cobalt, iron, titanium, chromium, manganese, and magnesium;

[0015] The R 2 -R 19 independently selected from hydrogen, halogen, aliphatic, substituted aliphatic, substituted heteroaliphatic, aryl, substituted aryl or substituted heteroaryl;

[0016] The X is selected from halogen, nitrate ion, acetate ion, trifluoroacetate ion, trichloroacetate ion, perchlorate ion, azide ion, 2,4-dinitrophenoloxy anion, and pentafluorophenoloxy anion.

[0017] Preferably, the method comprises the following steps:

[0018] Under protective atmosphere conditions, the alkenyl-modified carrier and the alkenyl-modified active component are polymerized in the presence of an initiator to obtain a supported multifunctional polymer catalyst.

[0019] Preferably, the initiator includes azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile or potassium persulfate.

[0020] Preferably, the polymerization reaction temperature is 20 to 80° C. and the time is 24 to 96 hours.

[0021] The present invention also provides a supported multifunctional polymer catalyst prepared by the method.

[0022] The present invention also provides an application of the supported multifunctional polymer catalyst in catalyzing anionic ring-opening polymerization reaction.

[0023] Compared with the prior art, the present invention provides a one-pot method for preparing a supported multifunctional polymer catalyst, wherein an alkenyl-modified carrier and an alkenyl-modified active component are polymerized in one step to obtain a supported multifunctional polymer catalyst. In the method provided by the present invention, the surface of the carrier and the active component are modified with the same type of polymerizable functional groups, and the supported multifunctional polymer catalyst can be directly obtained by one-step polymerization. In order to verify the catalytic effect of the prepared supported catalyst, the prepared supported bifunctional polymer aluminum porphyrin is used for polymerization of epoxide and carbon dioxide, polymerization of epoxide and acid anhydride, self-polymerization of epoxide, and ring-opening polymerization of lactone, and its performance is comparable to that of the catalyst prepared by the traditional multi-step method. The present preparation method is simple, general, and efficient, and the prepared supported multifunctional aluminum porphyrin catalyst has excellent performance, is easy to separate, and can be recycled. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the infrared spectrum of double-bond functionalized nano-silica;

[0025] Figure 2 This is the H NMR spectrum of double-bond functionalized aluminum porphyrin;

[0026] Figure 3 This is the infrared spectrum of multifunctional aluminum porphyrin supported on silica;

[0027] Figure 4 Transmission electron microscopy of multifunctional aluminum porphyrin loaded on silica;

[0028] Figure 5 This is the H NMR spectrum of the copolymerization of propylene oxide and carbon dioxide catalyzed by multifunctional aluminum porphyrin supported on silica;

[0029] Figure 6 Flow chart for preparing double bond functionalized silica (350 nm) and double bond functionalized aluminum porphyrin for Example 1;

[0030] Figure 7 The preparation flow chart of double-bond functionalized SalenCo-Cl;

[0031] Figure 8 This is a flow chart of the multi-step synthesis method for preparing silica-supported polymer metalloporphyrin and its catalytic copolymerization of epoxides with carbon dioxide. DETAILED DESCRIPTION

[0032] The invention provides a one-pot method for preparing a supported multifunctional polymer catalyst, wherein an alkenyl-modified carrier and an alkenyl-modified active component are polymerized in one step to obtain the supported multifunctional polymer catalyst.

[0033] The present invention firstly performs alkenyl modification on the carrier and the active component respectively. Specifically, the alkenyl groups in the alkenyl-modified carrier and the alkenyl-modified active component are independently selected from one of the following groups:

[0034]

[0035] Preferably, the alkenyl group is selected from one of the following groups:

[0036]

[0037] In the present invention, the alkenyl-modified carrier carries one or more alkenyl groups, and the alkenyl-modified active component carries one or more alkenyl groups.

[0038] In the present invention, the carrier in the alkenyl-modified carrier is selected from SiO 2 , Fe 2 O 3 , Fe 3 O 4 , MgO, ZnO, Al 2 O 3 、TiO 2 、ZrO 2 , Au, zeolite, graphene, cross-linked polystyrene, cross-linked polyamide, cross-linked polyethylene glycol resin, preferably SiO 2 , Fe 2 O 3 , Fe 3 O 4 , MgO, ZnO, Al 2 O 3 、TiO 2 、ZrO 2 One of the above, more preferably SiO 2 , wherein the silicon dioxide is nano silicon dioxide, micro silicon dioxide, mesoporous silicon dioxide or silicon dioxide plate.

[0039] In the present invention, the particle size of the carrier is preferably 15 to 1000 nm, and can be 15, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, or any value between 15 and 1000 nm.

[0040] In the present invention, the specific type and proportion of the active component are selected according to the needs, and the active component is not limited to one type, and a multifunctional active component can be selected according to the needs.

[0041] Preferably, the active component in the alkenyl-modified active component includes at least one of a metal porphyrin complex and a metal thiophene complex; preferably a metal porphyrin complex. In the present invention, the metal porphyrin complex has a structure shown in Formula I:

[0042]

[0043] The M is selected from aluminum, zinc, cobalt, iron, titanium, chromium, manganese, and magnesium;

[0044] The R 2 -R 19 independently selected from hydrogen, halogen, aliphatic, substituted aliphatic, substituted heteroaliphatic, aryl, substituted aryl or substituted heteroaryl;

[0045] The X is selected from halogen, nitrate ion, acetate ion, trifluoroacetate ion, trichloroacetate ion, perchlorate ion, azide ion, 2,4-dinitrophenoloxy anion, and pentafluorophenoloxy anion.

[0046] Preferably, the active component also includes at least one of dimethylamino, methyl, and quaternary ammonium salt.

[0047] In the present invention, there is no particular limitation on the preparation methods of the alkenyl-modified carrier and the alkenyl-modified active component, and any alkenyl-modified method known to those skilled in the art can be used.

[0048] In the present invention, the one-pot method for preparing a supported multifunctional polymer catalyst comprises the following steps:

[0049] Under protective atmosphere conditions, the alkenyl-modified carrier and the alkenyl-modified active component are polymerized in the presence of an initiator to obtain a supported multifunctional polymer catalyst.

[0050] Specifically, the protective atmosphere condition is preferably a nitrogen atmosphere.

[0051] The invention dissolves the alkenyl-modified carrier and the alkenyl-modified active component in a solvent, and then adds an initiator to carry out a polymerization reaction.

[0052] Wherein, the solvent is selected from tetrahydrofuran, toluene, dichloromethane, dioxane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetonitrile, and ethyl acetate.

[0053] The initiator includes azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile or potassium persulfate.

[0054] The polymerization reaction temperature is 20-80°C, which can be 20, 30, 40, 50, 60, 70, 80, or any value between 20 and 80°C, and the reaction time is 24-96h, which can be 24, 48, 72, 96, or any value between 24 and 96h.

[0055] After the reaction is completed, dichloromethane is added for dilution, centrifugation is performed, and then washing is performed with a mixed solution of dichloromethane and methanol, and drying is performed to obtain a supported multifunctional polymer catalyst. Preferably, the volume ratio of dichloromethane to methanol is 10:1.

[0056] In the present invention, the polymerization method, carrier type and particle size, active component type and ratio, polymerization degree, bonding method, and loading amount are all adjustable variables. By selecting a suitable combination of variables, supported multifunctional polymer catalysts with different catalytic properties can be obtained to meet different application requirements.

[0057] The present invention also provides a supported multifunctional polymer catalyst prepared by the method.

[0058] The present invention also provides an application of the above-mentioned supported multifunctional polymer catalyst in catalyzing anionic ring-opening polymerization, and the specific anionic ring-opening polymerization reaction includes application in polycarbonate polyols, polyester polyols and / or polyether polyols. Wherein, the supported multifunctional polymer catalyst is preferably a supported multifunctional polymer metal porphyrin complex.

[0059] Specifically, the present invention provides a method for preparing a polycarbonate polyol, comprising:

[0060] Under the catalytic action of the supported multifunctional polymer metal porphyrin complex prepared by the above method, a chain transfer agent is added to carry out a telomerization reaction of epoxide and carbon dioxide to obtain a polycarbonate polyol.

[0061] Specifically, the epoxide is selected from one or more of ethylene oxide, propylene oxide, butylene oxide, cyclopentane oxide, cyclohexane oxide, epichlorohydrin, styrene oxide, allyl glycidyl ether, methacrylate glycidyl ether, and phenyl glycidyl ether;

[0062] The chain transfer agent is selected from one or more of amine compounds of water, alcohol, phenol, carboxylic acid, thiol, primary amine and secondary amine.

[0063] The polymerization reaction temperature is 20-150° C., the reaction time is 1-420 hours, the ratio of the supported multifunctional polymer catalyst to the monomer substance is 1:1000-4000000, and the ratio of the monomer to the chain transfer agent substance is ≥5.

[0064] The present invention provides a method for preparing a polyester polyol, comprising:

[0065] Under the catalytic action of the supported multifunctional polymer metal porphyrin complex prepared by the above method, a chain transfer agent is added to carry out epoxide and acid anhydride telomerization reaction or lactone ring-opening telomerization reaction to obtain polyester polyol.

[0066] The chain transfer agent is selected from amine compounds of water, alcohol, phenol, carboxylic acid, thiol, primary amine and secondary amine;

[0067] The acid anhydride is selected from one or more of phthalic anhydride, succinic anhydride, glutaric anhydride, camphoric anhydride, maleic anhydride, and cinnamic anhydride;

[0068] Specifically, the polymerization reaction temperature is 20-150° C., the reaction time is 1-420 hours, the ratio of the amount of supported multifunctional polymer catalyst to the amount of monomer is 1:1000-4000000, and the ratio of the amount of monomer to the amount of chain transfer agent is ≥5.

[0069] The present invention provides a method for preparing a polyether polyol, comprising:

[0070] Under the catalytic action of the supported multifunctional polymer metal porphyrin complex prepared by the above method, a chain transfer agent is added to carry out epoxide telomerization reaction to obtain polyether polyol.

[0071] The chain transfer agent is selected from amine compounds of water, alcohol, phenol, carboxylic acid, thiol, primary amine and secondary amine;

[0072] The epoxide is selected from one or more of propylene oxide, 1,2-butylene oxide, 1,2-pentene oxide, 1,2-hexene oxide, 1,2-heptane oxide, 1,2-octane oxide, cyclohexene oxide, cyclopentane oxide, styrene oxide, and epichlorohydrin;

[0073] Specifically, the polymerization reaction temperature is 20-150° C., the reaction time is 1-420 hours, the ratio of the amount of supported multifunctional polymer catalyst to the amount of monomer is 1:1000-4000000, and the ratio of the amount of monomer to the amount of chain transfer agent is ≥5.

[0074] After the reaction is completed, the catalyst can be separated from the reaction system and recycled.

[0075] The supported bifunctional polymer aluminum porphyrin prepared by the present invention can be used as a catalyst for the polymerization of epoxide and carbon dioxide, the polymerization of epoxide and acid anhydride, the self-polymerization of epoxide, and the ring-opening polymerization of lactone, and the catalyst is easy to separate and recycle, and the catalyst has stable performance and still has good catalytic performance after repeated use.

[0076] The present invention provides a one-pot method for preparing a supported multifunctional polymer catalyst and its application in catalyzing anionic ring-opening polymerization. The present invention can directly obtain a supported multifunctional polymer catalyst by one-step polymerization by modifying alkenyl groups on the surface of a carrier with an active component. The preparation method is simple, efficient, and easy to control, eliminating the need for cumbersome multi-step synthesis. The prepared supported bifunctional polymer porphyrin aluminum can be used as a catalyst for polymerization of epoxides and carbon dioxide, polymerization of epoxides and acid anhydrides, self-polymerization of epoxides, and ring-opening polymerization of lactones, showing excellent performance, and the catalyst is easy to separate and recycle.

[0077] Compared with the existing technology, this method is simple, efficient and easy to control.

[0078] In order to further understand the present invention, the one-pot method for preparing a supported multifunctional polymer catalyst and its application provided by the present invention are described below in conjunction with examples. The protection scope of the present invention is not limited by the following examples.

[0079] Example 1 One-pot preparation of silica-supported multifunctional polymer metalloporphyrin catalyst

[0080] according to Figure 6 The routes shown are for preparing double bond functionalized silica (350 nm) and double bond functionalized aluminum porphyrin:

[0081] The specific steps are: disperse 2g of silica (350nm) in ultra-dry toluene, add 0.2g of 3-(methacryloyloxy)propyltrimethoxysilane, reflux at 110°C for 12h, cool and centrifuge, wash with ethanol, and dry to obtain double-bond functionalized silica. The above route for preparing double-bond functionalized silica is only a schematic representation of its structure, and the modified double bonds are not limited to four. The infrared spectrum of the double-bond functionalized silica is as follows: Figure 1 shown.

[0082] Under nitrogen atmosphere, 20g of p-bromobenzaldehyde (112mmol) and 4.5g of p-hydroxybenzaldehyde (37mmol) were dissolved in 500mL of propionic acid and heated to 135°C. Then 10g of pyrrole (149mmol) was added dropwise, and after the addition was complete, the temperature was raised to 165°C and refluxed for 2h. After the reaction was completed, 1.5L of methanol was added, and the mixture was placed at 0°C overnight. The product was filtered and separated and purified by column chromatography (dichloromethane as mobile phase) to obtain the product TPP-OH with a yield of 6%. 1 H NMR (500 MHz, CDCl 3,δ,ppm):8.94-8.68(m,8H),8.21-8.01(m,8H),7.92(d,J=7.5Hz,6H),7.15(d,J=8.3Hz,2H),5.15(s,1H),-2.81(s,2H). Mass spectrum: 867 (m / z);

[0083] Under nitrogen atmosphere, 1g TPP-OH (1.1mmol) and 0.15g triethylamine (1.5mmol) were dissolved in 10mL ultra-dry dichloromethane, followed by slow addition of 0.14g methacryloyl chloride (1.3mmol), and stirred at room temperature overnight. After the reaction, the mixture was washed three times with brine and then three times with deionized water, the organic phase was separated, and the product was separated and purified by column chromatography (dichloromethane as mobile phase) to obtain a double-bond functionalized porphyrin ligand M-TPP with a yield of 95%. 1 H NMR (500 MHz, CDCl 3 ,δ,ppm):8.94-8.68(m,8H),8.21(d,J=7.5Hz,2H),8.06(d,J=8.4Hz,6H),7.90(d,J=7 .5Hz,6H),7.55(d,J=8.3Hz,2H),6.55(s,1H),5.91(s,1H),2.22(s,3H),-2.85(s,2H). Mass spectrum: 936 (m / z);

[0084] In a glove box, M-TPP was reacted with 1.2 equivalents of diethylaluminum chloride for 2 h. The product was purified by column chromatography (dichloromethane / methanol = 10 / 1, V / V) to obtain a double-bond functionalized aluminum porphyrin, whose NMR spectrum is shown in FIG. Figure 2 shown.

[0085] Under nitrogen protection, 1g of double-bond functionalized silica (15nm), 0.5g of double-bond functionalized aluminum porphyrin, 0.1g of dimethylaminoethyl methacrylate, and 0.1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile was added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain silica-supported multifunctional polymer aluminum porphyrin, the infrared spectrum of which is shown in the figure. Figure 3 Its transmission electron microscopy spectrum is shown in Figure 4 shown.

[0086] Example 2 One-pot preparation of silica-supported multifunctional polymer metalloporphyrin catalyst

[0087] Under nitrogen protection, 1g of double-bond functionalized silica (350nm), 0.5g of double-bond functionalized aluminum porphyrin, 0.1g of dimethylaminoethyl methacrylate, and 1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile was added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain silica-supported multifunctional polymer aluminum porphyrin.

[0088] Example 3 One-pot preparation of silica-supported multifunctional polymer metalloporphyrin catalyst

[0089] Under nitrogen protection, 1g of double-bond functionalized silica (350nm), 0.5g of double-bond functionalized aluminum porphyrin, 1g of dimethylaminoethyl methacrylate, and 1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile was added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain silica-supported multifunctional polymer aluminum porphyrin.

[0090] Example 4 One-pot preparation of silica-supported multifunctional polymer metalloporphyrin catalyst

[0091] Under nitrogen protection, 1g of double-bond functionalized silica (15nm), 0.5g of double-bond functionalized aluminum porphyrin, 0.1g of dimethylaminoethyl methacrylate, and 0.1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile was added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain silica-supported multifunctional polymer aluminum porphyrin.

[0092] Example 5 One-pot preparation of silica-supported multifunctional polymer metalloporphyrin catalyst

[0093] Under nitrogen protection, 1g of double-bond functionalized silica (15nm), 0.5g of double-bond functionalized aluminum porphyrin, 1g of dimethylaminoethyl methacrylate, and 1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile were added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain silica-supported multifunctional polymer aluminum porphyrin.

[0094] Example 6 One-pot preparation of ferric oxide-supported multifunctional polymer metalloporphyrin catalyst

[0095] 1 g of ferric oxide nanoparticles (50 nm) were dispersed in anhydrous ethanol, 0.2 g of 3-(methacryloyloxy)propyltrimethoxysilane was added, and the mixture was refluxed at 110° C. for 12 h. After cooling, the mixture was centrifuged, washed with ethanol, and dried to obtain double-bond functionalized ferric oxide nanoparticles.

[0096] Under nitrogen protection, 1g of double-bond functionalized ferric oxide, 0.5g of double-bond functionalized aluminum porphyrin, 1g of dimethylaminoethyl methacrylate, and 1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile were added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain ferric oxide-loaded multifunctional polymer aluminum porphyrin.

[0097] Example 7 One-pot preparation of ferroferric oxide supported multifunctional polymer metalloporphyrin catalyst

[0098] 1 g of ferroferric oxide nanoparticles (50 nm) were dispersed in anhydrous ethanol, 0.2 g of 3-(methacryloyloxy)propyltrimethoxysilane was added, and the mixture was refluxed at 110° C. for 12 h. After cooling, the mixture was centrifuged, washed with ethanol, and dried to obtain double-bond functionalized ferroferric oxide nanoparticles.

[0099] Under nitrogen protection, 1g of double-bond functionalized ferroferric oxide, 0.5g of double-bond functionalized aluminum porphyrin, 1g of dimethylaminoethyl methacrylate, and 1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile were added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain ferroferric oxide-loaded multifunctional polymer aluminum porphyrin.

[0100] Example 8 One-pot preparation of magnesium oxide-supported multifunctional polymer metalloporphyrin catalyst

[0101] 1 g of magnesium oxide nanoparticles (1000 nm) were dispersed in anhydrous ethanol, 0.1 g of 3-(methacryloyloxy)propyltrimethoxysilane was added, and the mixture was refluxed at 110° C. for 12 h. After cooling, the mixture was centrifuged, washed with ethanol, and dried to obtain double-bond functionalized magnesium oxide nanoparticles.

[0102] Under nitrogen protection, 1g of double-bond functionalized magnesium oxide, 0.5g of double-bond functionalized aluminum porphyrin, 1g of dimethylaminoethyl methacrylate, and 1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile were added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain magnesium oxide-supported multifunctional polymer aluminum porphyrin.

[0103] Example 9 One-pot preparation of zinc oxide-supported multifunctional polymer metalloporphyrin catalyst

[0104] 1 g of zinc oxide nanoparticles (100 nm) were dispersed in anhydrous ethanol, 0.2 g of 3-(methacryloyloxy)propyltrimethoxysilane was added, and the mixture was refluxed at 110° C. for 12 h. After cooling, the mixture was centrifuged, washed with ethanol, and dried to obtain double-bond functionalized zinc oxide nanoparticles.

[0105] Under nitrogen protection, 1g of double-bond functionalized zinc oxide, 0.5g of double-bond functionalized aluminum porphyrin, 1g of dimethylaminoethyl methacrylate, and 1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile were added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain zinc oxide-supported multifunctional polymer aluminum porphyrin.

[0106] Example 10 One-pot preparation of alumina-supported multifunctional polymer metalloporphyrin catalyst

[0107] 1 g of aluminum oxide nanoparticles (100 nm) were dispersed in anhydrous ethanol, 0.2 g of 3-(methacryloyloxy)propyltrimethoxysilane was added, and the mixture was refluxed at 110° C. for 12 h. After cooling, the mixture was centrifuged, washed with ethanol, and dried to obtain double-bond functionalized aluminum oxide nanoparticles.

[0108] Under nitrogen protection, 1g of double-bond functionalized alumina, 0.5g of double-bond functionalized aluminum porphyrin, 1g of dimethylaminoethyl methacrylate, and 1g of methyl methacrylate were dissolved in 10mL of tetrahydrofuran, and 20mg of azobisisobutyronitrile was added, and the mixture was reacted at 65°C for 48h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain alumina-supported multifunctional polymer aluminum porphyrin.

[0109] Example 11 One-pot preparation of titanium dioxide supported multifunctional polymer metalloporphyrin catalyst

[0110] Disperse 1 g of titanium dioxide nanoparticles (30 nm) in anhydrous ethanol, add 0.2 g of 3-(methacryloyloxy)propyltrimethoxysilane, reflux at 110 °C for 12 h, cool and then centrifuge, wash with ethanol and dry to obtain double bond-functionalized titanium dioxide nanoparticles.

[0111] Under nitrogen protection, dissolve 1 g of double bond-functionalized titanium dioxide, 0.5 g of double bond-functionalized aluminum porphyrin, 1 g of dimethylaminoethyl methacrylate, and 1 g of methyl methacrylate in 10 mL of tetrahydrofuran, add 20 mg of azobisisobutyronitrile, and react at 65 °C for 48 h. After the reaction, dilute with dichloromethane, centrifuge, and then wash with dichloromethane / methanol = 10 / 1 (V / V) and dry to obtain titanium dioxide-supported multifunctional polymer aluminum porphyrin.

[0112] Example 12 One-pot preparation of zirconia-supported multifunctional polymer metal porphyrin catalyst

[0113] Disperse 1 g of zirconia nanoparticles (30 nm) in anhydrous ethanol, add 0.2 g of 3-(methacryloyloxy)propyltrimethoxysilane, reflux at 110 °C for 12 h, cool and then centrifuge, wash with ethanol and dry to obtain double bond-functionalized zirconia nanoparticles.

[0114] Under nitrogen protection, dissolve 1 g of double bond-functionalized zirconia, 0.5 g of double bond-functionalized aluminum porphyrin, 1 g of dimethylaminoethyl methacrylate, and 1 g of methyl methacrylate in 10 mL of tetrahydrofuran, add 20 mg of azobisisobutyronitrile, and react at 65 °C for 48 h. After the reaction, dilute with dichloromethane, centrifuge, and then wash with dichloromethane / methanol = 10 / 1 (V / V) and dry to obtain zirconia-supported multifunctional polymer aluminum porphyrin.

[0115] Example 13 One-pot preparation of silica-supported multifunctional polymer metal porphyrin catalyst

[0116] Under nitrogen protection, dissolve 1 g of double bond-functionalized silica (15 nm), 0.5 g of double bond-functionalized aluminum porphyrin, 1 g of double bond-functionalized quaternary ammonium salt, and 1 g of methyl methacrylate in 10 mL of tetrahydrofuran, add 20 mg of azobisisobutyronitrile, and react at 65 °C for 48 h. After the reaction, dilute with dichloromethane, centrifuge, and then wash with dichloromethane / methanol = 10 / 1 (V / V) and dry to obtain silica-supported multifunctional polymer aluminum porphyrin.

[0117]

[0118] Example 14 One-pot preparation of silica-supported multifunctional polymer metal Salen catalyst

[0119] Under nitrogen protection, 1 g of double-bond functionalized silica (15 nm) and 0.5 g of double-bond functionalized SalenCo-Cl (preparation process as shown in Figure 7 As shown, Figure 7 Flow chart of the preparation of double-bond functionalized SalenCo-Cl), 0.1 g of dimethylaminoethyl methacrylate and 0.1 g of methyl methacrylate were dissolved in 10 mL of tetrahydrofuran, 20 mg of azobisisobutyronitrile was added, and the mixture was reacted at 65°C for 48 h. After the reaction, dichloromethane was added for dilution, centrifuged, washed with dichloromethane / methanol = 10 / 1 (V / V), and dried to obtain silica-supported multifunctional polymer SalenCo-Cl.

[0120] Example 15 Polymerization of Propylene Oxide and Carbon Dioxide Catalyzed by Multifunctional Aluminoporphyrin Supported by Silica

[0121] In a glove box, 0.285 μmol (calculated by the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst of Example 1 is added to a pre-dried 10 mL autoclave, 5.7 mmol of sebacic acid and 57 mmol of dried propylene oxide are added, and then the autoclave is taken out of the glove box, and carbon dioxide is flushed into the autoclave through a carbon dioxide supply line with a pressure regulating function, and the pressure is first made to be 1 MPa, and the autoclave is stabilized at 70 ° C for ten minutes, and then the pressure is adjusted to 3 MPa, and the reaction is carried out for 36 hours. After the reaction is completed, the autoclave is cooled to room temperature, carbon dioxide is slowly released, the autoclave is opened, and a small amount of sample is taken for nuclear magnetic resonance hydrogen spectrum analysis. The results show that the propylene oxide conversion rate is 44%, the polymer selectivity is 98%, the carbonate unit content is 63%, and the catalyst activity is 2450h -1 .

[0122] The remaining reaction mixture was diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst was repeatedly washed with acetone acidified with hydrochloric acid to obtain the recovered catalyst R-1. The liquid part was dripped into water and n-hexane, and the polycarbonate polyol was dispersed at the interface of water and n-hexane. The product was obtained by separating the water phase and the n-hexane phase, and drying to obtain a colorless and transparent polycarbonate polyol. The number average molecular weight of the obtained polycarbonate polyol was 0.9 kg / mol and the molecular weight distribution was 1.05 by GPC.

[0123] Example 16 Recovered silica-supported multifunctional aluminum porphyrin catalyzes the polymerization reaction of propylene oxide and carbon dioxide

[0124] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst R-1 recovered in Example 15 was added to a pre-dried 10 mL autoclave, 5.7 mmol of sebacic acid and 57 mmol of dried propylene oxide were added, and then the autoclave was taken out of the glove box, and carbon dioxide was flushed into the autoclave through a carbon dioxide supply line with a pressure regulating function, and the pressure was first made to be 1 MPa, and the autoclave was stabilized at 70 ° C for ten minutes, and then the pressure was adjusted to 3 MPa, and the reaction was carried out for 36 hours. After the reaction was completed, the autoclave was cooled to room temperature, carbon dioxide was slowly released, the autoclave was opened, and a small amount of sample was taken for nuclear magnetic resonance hydrogen spectrum analysis. The results showed that the propylene oxide conversion rate was 43%, the polymer selectivity was 98%, the carbonate unit content was 60%, and the catalyst activity was 2400h -1 .

[0125] The remaining reaction mixture was diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst was repeatedly washed with acetone acidified with hydrochloric acid to obtain the recovered catalyst R-2. The liquid part was dripped into water and n-hexane, and the polycarbonate polyol was dispersed at the interface of water and n-hexane. The product was obtained by separating the water phase and the n-hexane phase, and drying to obtain a colorless and transparent polycarbonate polyol. The number average molecular weight of the obtained polycarbonate polyol was 0.8 g / mol and the molecular weight distribution was 1.06 by GPC.

[0126] Example 17 Recovered silica-supported multifunctional aluminum porphyrin catalyzes the polymerization reaction of propylene oxide and carbon dioxide

[0127] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst R-2 recovered in Example 16 was added to a pre-dried 10 mL autoclave, 5.7 mmol of sebacic acid and 57 mmol of dried propylene oxide were added, and then the autoclave was taken out of the glove box, and carbon dioxide was flushed into the autoclave through a carbon dioxide supply line with a pressure regulating function, and the pressure was first made to be 1 MPa, and the autoclave was stabilized at 70 ° C for ten minutes, and then the pressure was adjusted to 3 MPa, and the reaction was carried out for 36 hours. After the reaction was completed, the autoclave was cooled to room temperature, carbon dioxide was slowly released, the autoclave was opened, and a small amount of sample was taken for nuclear magnetic resonance hydrogen spectrum analysis. The results showed that the propylene oxide conversion rate was 43%, the polymer selectivity was 97%, the carbonate unit content was 62%, and the catalyst activity was 2400h -1 .

[0128] The remaining reaction mixture was diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst was repeatedly washed with acetone acidified with hydrochloric acid to obtain the recovered catalyst R-3. The liquid part was dripped into water and n-hexane, and the polycarbonate polyol was dispersed at the interface of water and n-hexane. The product was obtained by separating the water phase and the n-hexane phase, and drying to obtain a colorless and transparent polycarbonate polyol. The number average molecular weight of the obtained polycarbonate polyol was 0.8 g / mol and the molecular weight distribution was 1.07 by GPC.

[0129] Example 18 Recovered silica-supported multifunctional aluminum porphyrin catalyzes the polymerization reaction of propylene oxide and carbon dioxide

[0130] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst R-3 recovered in Example 17 was added to a pre-dried 10 mL autoclave, 5.7 mmol of sebacic acid and 57 mmol of dried propylene oxide were added, and then the autoclave was taken out of the glove box, and carbon dioxide was flushed into the autoclave through a carbon dioxide supply line with a pressure regulating function, and the pressure was first made to be 1 MPa, and the autoclave was stabilized at 70 ° C for ten minutes, and then the pressure was adjusted to 3 MPa, and the reaction was carried out for 36 hours. After the reaction was completed, the autoclave was cooled to room temperature, carbon dioxide was slowly released, the autoclave was opened, and a small amount of sample was taken for nuclear magnetic resonance hydrogen spectrum analysis. The results showed that the propylene oxide conversion rate was 40%, the polymer selectivity was 98%, the carbonate unit content was 60%, and the catalyst activity was 2300h -1 .

[0131] The remaining reaction mixture was diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst was repeatedly washed with acetone acidified with hydrochloric acid to obtain the recovered catalyst R-4. The liquid part was dripped into water and n-hexane, and the polycarbonate polyol was dispersed at the interface of water and n-hexane. The product was obtained by separating the water phase and the n-hexane phase, and drying to obtain a colorless and transparent polycarbonate polyol. The number average molecular weight of the obtained polycarbonate polyol was 0.7 g / mol and the molecular weight distribution was 1.07 by GPC.

[0132] Example 19: Polymerization of Propylene Oxide and Carbon Dioxide Catalyzed by Supported Bifunctional Polymer Metalloporphyrin Complex

[0133] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst of Example 1 was added to a pre-dried 10 mL autoclave, 11.4 mmol of sebacic acid and 57 mmol of dried propylene oxide were added, and then the autoclave was taken out of the glove box, and carbon dioxide was flushed into the autoclave through a carbon dioxide supply line with a pressure regulating function, and the pressure was first made to be 1 MPa, and the autoclave was stabilized at 70°C for ten minutes, and then the pressure was adjusted to 3 MPa, and the reaction was carried out for 36 hours. After the reaction was completed, the autoclave was cooled to room temperature, carbon dioxide was slowly released, the autoclave was opened, and a small amount of sample was taken for nuclear magnetic resonance hydrogen spectrum analysis. The results showed that the propylene oxide conversion rate was 69%, the polymer selectivity was 99%, the carbonate unit content was 44%, and the catalyst activity was 3833h -1 .

[0134] The remaining reaction mixture is diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst is repeatedly washed with acetone acidified with hydrochloric acid to obtain a recovered catalyst. The liquid portion is dripped into water and n-hexane, and the polycarbonate polyol is dispersed at the interface of the water and n-hexane phases. The product can be obtained by separating the water phase and the n-hexane phase, and drying can obtain a colorless and transparent polycarbonate polyol. The number average molecular weight of the obtained polycarbonate polyol measured by GPC is 0.6 kg / mol, and the molecular weight distribution is 1.01.

[0135] Example 20 Polymerization of propylene oxide and carbon dioxide catalyzed by multifunctional aluminum porphyrin supported on silica

[0136] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst of Example 1 is added to a pre-dried 10 mL autoclave, 0.57 mmol bisphenol A and 57 mmol dry propylene oxide are added, and then the autoclave is taken out of the glove box, and carbon dioxide is flushed into the autoclave through a carbon dioxide supply line with a pressure regulating function, and the pressure is first made to be 1 MPa, and the autoclave is stabilized at 70 ° C for ten minutes, and then the pressure is adjusted to 3 MPa, and the reaction is carried out for 36 hours. After the reaction is completed, the autoclave is cooled to room temperature, carbon dioxide is slowly released, the autoclave is opened, and a small amount of sample is taken for nuclear magnetic resonance hydrogen spectrum analysis. The results show that the propylene oxide conversion rate is 47%, the polymer selectivity is 94%, the carbonate unit content is 40%, and the catalyst activity is 2630h -1 .

[0137] The remaining reaction mixture was diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst was repeatedly washed with acetone acidified with hydrochloric acid to obtain a recovered catalyst. The liquid portion was dripped into water and n-hexane, and the polycarbonate polyol was dispersed at the interface of the water and n-hexane phases. The product was obtained by separating the water phase and the n-hexane phase, and drying to obtain a colorless and transparent polycarbonate polyol. The number average molecular weight of the obtained polycarbonate polyol was 2.7 kg / mol and the molecular weight distribution was 1.05 by GPC.

[0138] Example 21…Silica-supported multifunctional aluminum porphyrin catalyzes the polymerization of propylene oxide and phthalic anhydride

[0139] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst of Example 1 was added to a pre-dried 50 mL autoclave, 1.14 mmol of sebacic acid, 57 mmol of phthalic anhydride and 285 mmol of dried propylene oxide were added, and then the autoclave was taken out of the glove box and stabilized at 70°C for 36 hours of reaction. After the reaction was completed, the autoclave was cooled to room temperature, the autoclave was opened, and a small amount of sample was taken for nuclear magnetic resonance hydrogen spectrum analysis. The results showed that the phthalic anhydride conversion rate was 47%, the polymer selectivity was 99%, the polyester unit content was 99%, and the catalyst activity was 2060h. -1 .

[0140] The remaining reaction mixture was diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst was repeatedly washed with acetone acidified with hydrochloric acid to obtain a recovered catalyst. The liquid portion was dripped into methanol, and the polyester polyol was precipitated in the methanol. The methanol was separated to obtain the product, and the white polyester polyol was obtained by drying. The number average molecular weight of the obtained polyester polyol was 4.4 kg / mol and the molecular weight distribution was 1.10 as measured by GPC.

[0141] Example 22…Silica-supported multifunctional aluminum porphyrin catalyzes propylene oxide polymerization

[0142] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst of Example 1 was added to a pre-dried 50 mL autoclave, 1.14 mmol of sebacic acid and 57 mmol of dry propylene oxide were added, and then the autoclave was taken out of the glove box and stabilized at 70°C for 60 hours of reaction. After the reaction was completed, the autoclave was cooled to room temperature, the autoclave was opened, and a small amount of sample was taken for nuclear magnetic resonance hydrogen spectrum analysis. The results showed that the propylene oxide conversion rate was 47%, the polymer selectivity was 99%, and the catalyst activity was 1500h. -1 .

[0143] The remaining reaction mixture was diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst was repeatedly washed with acetone acidified with hydrochloric acid to obtain a recovered catalyst. The liquid was rotary evaporated to obtain a colorless and transparent polyether polyol. The number average molecular weight of the obtained polyether polyol was 1.4 kg / mol and the molecular weight distribution was 1.07 as measured by GPC.

[0144] Example 23…Silica-supported multifunctional aluminum porphyrin catalyzes the polymerization of caprolactone

[0145] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the silica-supported multifunctional aluminum porphyrin catalyst of Example 1 was added to a pre-dried 50 mL polymerization tube, 1.14 mmol of sebacic acid and 57 mmol of dried caprolactone were added, and then the polymerization tube was taken out of the glove box, and the autoclave was stabilized at 100°C for 48 hours of reaction. After the reaction was completed, the autoclave was cooled to room temperature, the autoclave was opened, and a small amount of sample was taken for nuclear magnetic resonance hydrogen spectrum analysis. The results showed that the caprolactone conversion rate was 30%, the polymer selectivity was 99%, and the catalyst activity was 1250h. -1 .

[0146] The remaining reaction mixture was diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst was repeatedly washed with acetone acidified with hydrochloric acid to obtain a recovered catalyst. The liquid portion was rotary evaporated to obtain a white polyester polyol. The number average molecular weight of the obtained polyester polyol was measured by GPC to be 1.6 kg / mol and a molecular weight distribution of 1.09.

[0147] Comparative Example Preparation of Silica-supported Polymeric Metalloporphyrin by Multi-step Synthesis and Its Catalytic Copolymerization with Epoxide and Carbon Dioxide

[0148] The specific steps of the multi-step synthesis method are as follows Figure 8 As shown, a silane coupling agent with a specific structure is first prepared to modify the surface of silica, and then a RAFT agent with a specific structure is prepared to prepare a polymer catalyst precursor, and finally the polymer catalyst precursor is loaded on the surface of silica. The traditional multi-step synthesis method is cumbersome, time-consuming and labor-intensive.

[0149] In a glove box, 0.285 μmol (calculated according to the aluminum content in the loaded catalyst) of the comparative example of silica-supported multifunctional aluminum porphyrin catalyst was added to a pre-dried 10 mL autoclave, 5.7 mmol of sebacic acid and 57 mmol of dried propylene oxide were added, and then the autoclave was taken out of the glove box, and carbon dioxide was flushed into the autoclave through a carbon dioxide supply line with a pressure regulating function, and the pressure was first set to 1 MPa, and the autoclave was stabilized at 70 ° C for ten minutes, and then the pressure was adjusted to 3 MPa, and the reaction was carried out for 36 hours. After the reaction was completed, the autoclave was cooled to room temperature, carbon dioxide was slowly released, the autoclave was opened, and a small amount of sample was taken for nuclear magnetic resonance hydrogen spectrum analysis. The results showed that the propylene oxide conversion rate was 49%, the polymer selectivity was 95%, the carbonate unit content was 52%, and the catalyst activity was 2700h -1 The catalytic performance is equivalent to that of Example 15.

[0150] The remaining reaction mixture is diluted with acetone and centrifuged at 8000 rpm for 10 minutes to separate the catalyst. The catalyst is repeatedly washed with acetone acidified with hydrochloric acid to obtain a recovered catalyst. The liquid portion is dripped into water and n-hexane, and the polycarbonate polyol is dispersed at the interface of the water and n-hexane phases. The product can be obtained by separating the water phase and the n-hexane phase, and drying can obtain a colorless and transparent polycarbonate polyol. The number average molecular weight of the obtained polycarbonate polyol measured by GPC is 0.7 kg / mol, and the molecular weight distribution is 1.03.

[0151] As can be seen from the above embodiments, the present invention provides a method for preparing a supported multifunctional polymer catalyst by a one-pot method and its application in catalyzing anionic ring-opening polymerization. In the method provided by the present invention, the surface of the carrier and the active component are modified with the same type of polymerizable functional group alkenyl, and the supported multifunctional polymer catalyst can be directly obtained by a one-step polymerization method. In order to verify the catalytic effect of the prepared supported catalyst, the prepared supported bifunctional polymer porphyrin aluminum is used for polymerization of epoxide and carbon dioxide, polymerization of epoxide and acid anhydride, self-polymerization of epoxide, and ring-opening polymerization of lactone, and its performance is comparable to that of the catalyst prepared by the traditional multi-step method. The present preparation method is simple, general, and efficient, and the prepared supported multifunctional aluminum porphyrin catalyst has excellent performance, is easy to separate and can be recycled.

[0152] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A one-pot method for preparing a supported multifunctional polymer catalyst, characterized in that: The alkenyl-modified carrier and the alkenyl-modified active component are polymerized in one step to obtain a supported multifunctional polymer catalyst.

2. The method according to claim 1, characterized in that The alkenyl-modified carrier and the alkenyl-modified active component are independently selected from one of the following groups:

3. The method according to claim 1, characterized in that The carrier in the alkenyl-modified carrier is selected from one or more of SiO2, Fe2O3, Fe3O4, MgO, ZnO, Al2O3, TiO2, ZrO2, Au, zeolite, graphene, cross-linked polystyrene, cross-linked polyamide, and cross-linked polyethylene-glycol resin.

4. The method according to claim 1, characterized in that: The active component in the alkenyl-modified active component includes at least one of a metal porphyrin complex and a metal thiophene complex; Preferably, the active component also includes at least one of dimethylamino, methyl, and quaternary ammonium salt.

5. The method according to claim 4, characterized in that The metal porphyrin complex has a structure shown in Formula I: The M is selected from aluminum, zinc, cobalt, iron, titanium, chromium, manganese, and magnesium; The R2-R 19 independently selected from hydrogen, halogen, aliphatic, substituted aliphatic, substituted heteroaliphatic, aryl, substituted aryl or substituted heteroaryl; The X is selected from halogen, nitrate ion, acetate ion, trifluoroacetate ion, trichloroacetate ion, perchlorate ion, azide ion, 2,4-dinitrophenoloxy anion, and pentafluorophenoloxy anion.

6. The method according to claim 1, characterized in that The following steps are involved: Under protective atmosphere conditions, the alkenyl-modified carrier and the alkenyl-modified active component are polymerized in the presence of an initiator to obtain a supported multifunctional polymer catalyst.

7. The method according to claim 6, characterized in that The initiator includes azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile or potassium persulfate.

8. The method according to claim 6, characterized in that The polymerization reaction temperature is 20-80° C. and the reaction time is 24-96 hours.

9. A supported multifunctional polymer catalyst prepared by the method according to any one of claims 1 to 8.

10. Use of the supported multifunctional polymer catalyst as claimed in claim 9 in catalyzing anionic ring-opening polymerization.

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