Porphyrin immobilization polymer

Abstract

To provide a porphyrin immobilizing polymer capable of being used as a catalyst or a luminescent material in reaction of carbon dioxide with epoxide, and to provide a production method of the porphyrin immobilization polymer.SOLUTION: A production method of a porphyrin immobilization polymer includes: adding at a room temperature, a solution containing a porphyrin monomer having one or more vinyl groups, an azo polymerization initiator, at least one kind of monomer selected from the group consisting of a styrenic monomer, a (meth)acrylic acid monomer and a (meth)acrylic acid ester monomer, and an organic solvent to an aqueous solution containing Acacia gum, NaCl and water; and heating the product to generate and recover a porphyrin immobilization polymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to porphyrin-immobilized polymers. [Background technology]

[0002] Porphyrins and compounds having a porphyrin structure are known to be used as catalysts in chemical reactions and as materials that exhibit specific physical properties.

[0003] For example, Patent Document 1 describes a multifunctional bionic heterogeneous catalyst based on an organic porous copolymer obtained by copolymerizing an alkene-based metalloporphyrin with an alkenyl-group-containing quaternary phosphonium salt monomer, and its use as a catalyst in the coupling reaction of carbon dioxide with an epoxide. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Chinese Patent Application Publication No. 108440488 Summary of the Invention [Problem to be solved by the invention]

[0005] The organic porous copolymer-based multifunctional bionic heterogeneous catalyst described in Patent Document 1 has various demands, such as further improvement of its catalytic performance, ease of use as a catalyst, and ease of production.

[0006] In view of the above-mentioned state of the art, an object of the present invention is to provide a polymer to which a porphyrin is immobilized. [Means for solving the problem]

[0007] The present inventors have conducted extensive research into porphyrin-immobilized polymers and have completed the present invention. They have found that the porphyrin-immobilized polystyrene of the present invention can be used as a catalyst in the reaction of carbon dioxide with an epoxide, and that polyacrylic acid or polymethacrylic acid with immobilized porphyrin can be used as a light-emitting material.

[0008] That is, the present invention provides the following [1] to [4]. [1] The present invention relates to a porphyrin-immobilized polymer represented by the following formula (1).

[0009] [ka]

[0010] (The porphyrin-immobilized polymer represented by formula (1) may or may not contain M. In formula (1), when M is contained, p=1 and q=0, and M represents a metal atom of Group 2 or Group 7 of the periodic table, If M is not included, p=0 and q=1. R a1 , R a2 , R a3 and R a4 each independently represents a phenyl group, a carboxy group, or an ester group; R b1 , R b2 , R b3 and R b4 each independently represents a hydrogen atom or a methyl group, n1, n2, n3, and n4 each independently represent an integer of 10 to 10,000; X1, X2, X3, and X4 represent the proportion of structural units derived from the monomer in the formula, where n1, n2, n3, and n4 are each 1, and are independently a number of 0.01 to 0.99; R c1 , R c2 , R c3 and R c4each independently represents a divalent functional group having an oxygen atom and / or a carbonyl group at its terminal, m1, m2, m3 and m4 each independently represent 0 or 1.

[0011] [2] The present invention relates to a catalyst comprising a porphyrin-immobilized polymer represented by the formula (1).

[0012] [3] The present invention relates to a catalyst comprising a porphyrin-immobilized polymer represented by the formula (1), which is used in the synthesis of a cyclic carbonate by reacting carbon dioxide with an epoxide.

[0013] [4] The present invention relates to a light-emitting material comprising a porphyrin-immobilized polymer represented by the formula (1).

[0014] [5] The method for producing a porphyrin-immobilized polymer includes the following steps (1), (2), (3) and (4): Step (1): A porphyrin monomer having at least one alkylene group; an azo polymerization initiator; at least one monomer selected from the group consisting of styrene-based monomers, (meth)acrylic acid-based monomers, and (meth)acrylic acid ester-based monomers; an organic solvent; Obtaining a porphyrin monomer solution Step (2): Obtaining an aqueous solution containing gum acacia, NaCl, and water Step (3): adding the porphyrin monomer solution obtained in step (1) to the aqueous solution obtained in step (2) at room temperature, followed by heating to produce a porphyrin-immobilized polymer. Step (4): A step of recovering the porphyrin-immobilized polymer produced in the step (3).

[0015] [6] A method for producing a porphyrin-immobilized polymer, comprising: a porphyrin monomer having at least one alkylene group; an azo polymerization initiator; The present invention relates to a method for producing a porphyrin-immobilized polymer by heating at least one monomer selected from the group consisting of (meth)acrylic acid-based monomers and (meth)acrylic acid ester-based monomers.

[0016] [7] The method for producing the porphyrin-immobilized polymer represented by the formula (1) relates to the production method described in [5] or [6] above. [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a porphyrin-immobilized polymer that can be used as a catalyst in the reaction of carbon dioxide with an epoxide, and a porphyrin-immobilized polymer that can be used as a light-emitting material. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be specifically described below.

[0019] <Porphyrin-immobilized polymer> One embodiment of the present invention relates to a porphyrin-immobilized polymer represented by the following formula (1):

[0020] [ka]

[0021] (The porphyrin-immobilized polymer represented by formula (1) may or may not contain M. In formula (1), when M is contained, p=1 and q=0, and M represents a metal atom of Group 2 or Group 7 of the periodic table. When M is not contained, p=0 and q=1. R a1 , R a2 , R a3 and R a4each independently represents a phenyl group, a carboxy group, or an ester group, and R b1 , R b2 , R b3 and R b4 each independently represents a hydrogen atom or a methyl group; n1, n2, n3, and n4 each independently represent an integer of 10 to 10,000; X1, X2, X3, and X4 each independently represent a proportion of structural units derived from the monomer in the formula, with n1, n2, n3, and n4 each being 1, and each independently being a number of 0.01 to 0.99; R c1 , R c2 , R c3 and R c4 each independently represents a divalent functional group having an oxygen atom and / or a carbonyl group at its terminal, and m1, m2, m3, and m4 each independently represent 0 or 1.

[0022] In the formula (1), when M is contained, p=1 and q=0, and M represents a metal atom of Group 2 or Group 7 of the periodic table; when M is not contained, p=0 and q=1.

[0023] In the formula (1), when M is a Group 2 metal atom, examples of M include an Mg atom, a Ca atom, and an Sr atom, and preferably an Mg atom.

[0024] In the formula (1), when M is a Group 7 metal atom, examples of M include a Mn atom, a Tc atom, and a Re atom, and preferably a Mn atom.

[0025] In the formula (1), when M is contained, M is more preferably a Mg atom, which is a Group 2 metal atom.

[0026] In the formula (1), R a1 , R a2 , R a3 and R a4each independently represents a phenyl group, a carboxy group, or an ester group. Examples of the phenyl group include an unsubstituted phenyl group and a phenyl group in which a hydrogen atom is substituted with a hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group, and preferably a tertiary butyl group. Examples of the phenyl group in which a hydrogen atom is substituted with a hydrocarbon group include a 4-methyl-phenyl group, a 4-n-butyl-phenyl group, and a 4-tertiary butyl-phenyl group, and preferably a 4-tertiary butyl-phenyl group.

[0027] In the formula (1), the carboxy group is represented by —COOH.

[0028] In the formula (1), the ester group is -COOR d It is expressed as R d is a hydrocarbon group, and examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group, and preferably an n-butyl group.

[0029] In the formula (1), R b1 , R b2 , R b3 and R b4 each independently represents a hydrogen atom or a methyl group.

[0030] In the formula (1), n1, n2, n3, and n4 each independently represent an integer of 10 to 10,000, preferably 50 to 8,000, and more preferably 100 to 5,000.

[0031] In the formula (1), X1, X2, X3, and X4 represent the proportion of structural units derived from the monomers in the formula, where n1, n2, n3, and n4 are each 1, and are each independently a number from 0.01 to 0.99. Specifically, for the integer n1, the proportion of structural units derived from the monomer is X1%, and the proportion of structural units derived from other monomers is (1-X1)%. Each of X1, X2, X3, and X4 is preferably 0.50 to 0.99, more preferably 0.70 to 0.95, and even more preferably 0.80 to 0.90.

[0032] In the formula (1), R c1 , R c2 , R c3 and R c4 each independently represents a divalent functional group having an oxygen atom and / or a carbonyl group at its terminal. The divalent functional group is, for example, a functional group represented by the following formula (2).

[0033] [ka]

[0034] In the formula (1), m1, m2, m3 and m4 each independently represent 0 or 1.

[0035] Specific examples of the porphyrin-immobilized polymer represented by the formula (1) include the following: Porphyrin-immobilized polystyrene (polymer 1) represented by formula (3), Mg-porphyrin-immobilized polystyrene (polymer 2) represented by formula (4), Mn-porphyrin-immobilized polystyrene (polymer 3) represented by formula (5), Porphyrin-immobilized poly(n-butyl acrylate) (polymer 4) represented by formula (6), Porphyrin-immobilized polymethacrylic acid (polymer 5) represented by formula (7), Porphyrin-immobilized polymethacrylic acid (polymer 6) represented by formula (8), and Mg-porphyrin-immobilized poly(n-butyl acrylate) (polymer 7) represented by formula (9).

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] <Catalysts made from porphyrin-immobilized polymers> Another embodiment of the present invention relates to a catalyst comprising a porphyrin-immobilized polymer represented by the formula (1).

[0044] Another embodiment of the present invention relates to a catalyst comprising a porphyrin-immobilized polymer represented by the formula (1), which is used in the synthesis of a cyclic carbonate by reacting carbon dioxide with an epoxide.

[0045] The catalyst used in the synthesis of cyclic carbonates by reacting carbon dioxide with epoxide is preferably porphyrin-immobilized polystyrene (polymer 1) represented by the above formula (3) or Mg-porphyrin-immobilized poly(n-butyl acrylate) (polymer 7) represented by the above formula (9).

[0046] In the reaction of carbon dioxide with an epoxide represented by the following formula (10), a cyclic carbonate represented by the following formula (11) can be synthesized by using, as a catalyst, porphyrin-immobilized polystyrene represented by the above formula (3) (polymer 1) or Mg-porphyrin-immobilized polyn-butyl acrylate represented by the above formula (9) (polymer 7), and a quaternary ammonium halide or N,N'-dimethylaminopyridine.

[0047] [ka]

[0048] [ka]

[0049] Furthermore, in the reaction of carbon dioxide with an epoxide represented by the following formula (12), a cyclic carbonate represented by the following formula (13) can be synthesized by using, as a catalyst, Mg-porphyrin-immobilized polyn-butyl acrylate (polymer 7) represented by the above formula (9) and a quaternary ammonium halide or N,N'-dimethylaminopyridine.

[0050] [ka]

[0051] [ka]

[0052] <Light-emitting material made from porphyrin-immobilized polymer> Another embodiment of the present invention relates to a light-emitting material comprising a porphyrin-immobilized polymer represented by the formula (1).

[0053] A preferred example of the porphyrin-immobilized polymer represented by the formula (1) is porphyrin-immobilized polymethacrylic acid (polymer 6) represented by the formula (8). When an aqueous solution of porphyrin-immobilized polymethacrylic acid (polymer 6) represented by the formula (8) is irradiated with ultraviolet light of 365 nm, it emits yellow light.

[0054] Furthermore, when an aqueous solution of NaOH is added to an aqueous solution of porphyrin-immobilized polymethacrylic acid (polymer 6) represented by the formula (8), the luminescence changes from yellow to red, and when dilute hydrochloric acid is subsequently added, the luminescence returns to the original yellow color.

[0055] <Method for producing porphyrin-immobilized polymer-1> Another embodiment of the present invention relates to a method for producing a porphyrin-immobilized polymer, which comprises the following steps (1), (2), (3) and (4): Step (1): A step of obtaining a porphyrin monomer solution containing a porphyrin monomer having at least one alkylene group, an azo polymerization initiator, at least one monomer selected from the group consisting of a styrene-based monomer, a (meth)acrylic acid-based monomer, and a (meth)acrylic acid ester-based monomer, and an organic solvent. Step (2): Obtaining an aqueous solution containing gum acacia, NaCl, and water Step (3): Adding the porphyrin monomer solution obtained in step (1) to the aqueous solution obtained in step (2) at room temperature, followed by heating to form a porphyrin-immobilized polymer. Step (4): A step of recovering the porphyrin-immobilized polymer produced in step (3).

[0056] Another embodiment of the present invention relates to a method for producing a porphyrin-immobilized polymer represented by the formula (1), which comprises the steps (1), (2), (3), and (4).

[0057] The porphyrin-immobilized polymer produced by the above-mentioned production method-1 is porphyrin-immobilized polystyrene, porphyrin-immobilized poly(meth)acrylic acid, or porphyrin-immobilized poly(meth)acrylic acid ester.

[0058] Step (1) of the above-mentioned production method-1 is a step of obtaining a porphyrin monomer solution containing a porphyrin monomer having at least one alkylene group, an azo polymerization initiator, at least one monomer selected from the group consisting of a styrene-based monomer, a (meth)acrylic acid-based monomer, and a (meth)acrylic acid ester-based monomer, and an organic solvent. In this specification, "(meth)acrylic" means acrylic or methacrylic.

[0059] <Porphyrin Monomer> The porphyrin monomer used in step (1) of the above-mentioned production method-1 is a porphyrin monomer having at least one vinyl group, preferably a porphyrin monomer having four vinyl groups, represented by the following formula (14):

[0060] [ka]

[0061] The porphyrin monomer represented by formula (14) may or may not contain M. In formula (14), when M is contained, p=1 and q=0, and M represents a metal atom of Group 2 or Group 7 of the periodic table. When M is not contained, p=0 and q=1, and R c1 , R c2 , R c3 and R c4each independently represents a divalent functional group having an oxygen atom and / or a carbonyl group at its terminal, and m1, m2, m3, and m4 each independently represent 0 or 1.

[0062] In the formula (14), when M is a Group 2 metal atom, examples of M include an Mg atom, a Ca atom, and an Sr atom, and preferably an Mg atom.

[0063] In the formula (14), when M is a Group 7 metal atom, examples of M include a Mn atom, a Tc atom, and a Re atom, and preferably a Mn atom.

[0064] When the porphyrin monomer represented by the formula (14) contains M, M is more preferably an Mg atom, which is a Group 2 metal atom.

[0065] In the formula (14), R c1 , R c2 , R c3 and R c4 each independently represents a divalent functional group having an oxygen atom and / or a carbonyl group at its terminal. The divalent functional group is, for example, a functional group represented by the formula (2).

[0066] In the formula (14), m1, m2, m3 and m4 each independently represent 0 or 1.

[0067] Specific examples of the porphyrin monomer represented by the formula (14) include the following: Porphyrin (porphyrin 1) represented by formula (15), Mg-porphyrin (porphyrin 2) represented by formula (16), Mn-porphyrin (porphyrin 3) represented by formula (17), and porphyrin 4 represented by formula (18).

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] <Azo polymerization initiator> An example of the azo polymerization initiator used in step (1) of the above-mentioned production method-1 is 2,2'-azobis(2,4-dimethylvaleronitrile). As the azo polymerization initiator, V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. can be used.

[0073] <Styrene-based monomers> The styrene-based monomer used in step (1) of the above-mentioned Production Method-1 is a styrene-based monomer represented by the following formula (19).

[0074] [ka]

[0075] (In formula (19), R d are each independently a hydrocarbon group, and L is an integer of 0 to 5.

[0076] R d Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group, and preferably a tertiary butyl group.

[0077] Examples of the styrene-based monomer represented by formula (19) include styrene, 4-methylstyrene, 4-n-butyl-styrene, and 4-tert-butyl-styrene, with 4-tert-butyl-styrene being preferred.

[0078] <(Meth)acrylic acid-based monomer or (meth)acrylic acid ester-based monomer> The (meth)acrylic acid monomer or (meth)acrylic ester monomer used in step (1) of the above-mentioned Production Method-1 is a (meth)acrylic acid monomer or (meth)acrylic ester monomer represented by the following formula (20).

[0079] [ka]

[0080] In formula (20), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or an alkyl group.

[0081] In formula (20), R 1 is a hydrogen atom, and R 2 When R is a hydrogen atom, the formula (20) represents acrylic acid. 1 is a hydrogen atom, and R 2 When R is an alkyl group, the formula (20) represents an acrylate ester. 1 is a methyl group, and R 2 When R is a hydrogen atom, the formula (20) represents methacrylic acid. 1 is a methyl group, and R 2 When is an alkyl hydrogen atom, the formula (20) represents a methacrylate ester.

[0082] R 2 is an alkyl group, R 2 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group, and preferably an n-butyl group.

[0083] Examples of the (meth)acrylic acid monomer represented by formula (20) include acrylic acid and methacrylic acid. Examples of the (meth)acrylic acid ester monomer include n-butyl acrylate and n-butyl methacrylate. Preferred are methacrylic acid and n-butyl acrylate.

[0084] The organic solvent used in step (1) of the above-mentioned production method-1 is CH2Cl2, CHCl3, etc., preferably CHCl3.

[0085] Step (2) of the above-mentioned production method-1 is a step of obtaining an aqueous solution containing gum acacia, NaCl, and water. As the gum acacia, gum arabic manufactured by Nacalai Tesque, Inc. can be used. In step (2), it is preferable to add gum acacia and NaCl to water and stir until the solid disappears.

[0086] Step (3) of the above-mentioned production method-1 is a step of adding the porphyrin monomer solution obtained in step (1) to the aqueous solution obtained in step (2) at room temperature, followed by heating to produce a porphyrin-immobilized polymer.

[0087] Step (4) of the above-mentioned production method-1 is a step of recovering the porphyrin-immobilized polymer produced in step (3). Examples of the recovery method include filtering the solution obtained in step (3), washing the filtered solid, and drying the washed solid. Filtering is preferably performed by pressure filtration. Water, methanol, toluene, etc. can be used for washing, and washing is preferably performed in the order of water, methanol, toluene, and methanol. Drying is preferably performed by vacuum drying.

[0088] The above-mentioned production method-1 is preferred as a production method of porphyrin-immobilized polystyrene, and the porphyrin-immobilized polystyrene is obtained by copolymerizing a porphyrin monomer represented by the above-mentioned formula (14) with a styrene-based monomer represented by the above-mentioned formula (19).

[0089] The porphyrin-immobilized polystyrene can be produced by reacting the porphyrin monomer represented by the formula (14) with 4-tert-butyl-styrene, V-65 (2,2'-azobis(2,4-dimethylvaleronitrile) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), acacia gum (gum arabic manufactured by Nacalai Tesque, Inc.), and NaCl in a mixed solvent of CHCl and HO.

[0090] The amount of 4-tert-butyl-styrene used in the method for producing the porphyrin-immobilized polystyrene is 20 to 80 equivalents, preferably 30 to 60 equivalents, relative to 1 equivalent of the porphyrin monomer represented by the formula (14).

[0091] The amount of V-65 (2,2'-azobis(2,4-dimethylvaleronitrile)) used in the method for producing porphyrin-immobilized polystyrene is 1.0 to 2.0 equivalents, and preferably 1.1 to 1.3 equivalents, relative to 1 equivalent of the porphyrin monomer represented by formula (14).

[0092] The amount of gum acacia used in the above-mentioned method for producing porphyrin-immobilized polystyrene is 10 g to 40 g, preferably 20 g to 30 g, per 1 g of the porphyrin monomer represented by the formula (14).

[0093] The amount of NaCl used in the above-mentioned method for producing porphyrin-immobilized polystyrene is 10 g to 40 g, preferably 20 g to 30 g, per 1 g of the porphyrin monomer represented by the formula (14).

[0094] The mixing ratio of CHCl3 to H2O (CHCl3 / H2O (volume / volume)) in the CHCl3 and H2O mixed solvent used in the method for producing porphyrin-immobilized polystyrene is 1 / 5 to 1 / 20, preferably 1 / 8 to 1 / 11.

[0095] The reaction temperature in step (3) of the above-mentioned method for producing porphyrin-immobilized polystyrene is 50 to 65°C, and preferably 60 to 65°C.

[0096] The reaction time in step (3) of the method for producing porphyrin-immobilized polystyrene is 16 to 24 hours, and preferably 16 to 18 hours.

[0097] <Method for producing porphyrin-immobilized polymer-2> Another embodiment of the present invention is a method for producing a porphyrin-immobilized polymer, comprising the steps of: The present invention relates to a method for producing a porphyrin-immobilized polymer by heating a porphyrin monomer having at least one vinyl group, an azo polymerization initiator, and at least one monomer selected from the group consisting of (meth)acrylic acid-based monomers and (meth)acrylic acid ester-based monomers.

[0098] Another embodiment of the present invention relates to a method for producing a porphyrin-immobilized polymer represented by the formula (1) by the above <Production method 2 of a porphyrin-immobilized polymer>.

[0099] The porphyrin-immobilized polymer produced by the above-mentioned Production Method-2 is a porphyrin-immobilized poly(meth)acrylic acid or a porphyrin-immobilized poly(meth)acrylic acid ester.

[0100] The above-mentioned production method-2 is preferred as a method for producing a porphyrin-immobilized poly(meth)acrylic acid or a porphyrin-immobilized poly(meth)acrylic ester, and the porphyrin-immobilized poly(meth)acrylic acid or the porphyrin-immobilized poly(meth)acrylic ester is obtained by copolymerizing a porphyrin monomer represented by the above-mentioned formula (14) with a (meth)acrylic acid-based monomer or a (meth)acrylic ester-based monomer represented by the above-mentioned formula (20).

[0101] Examples of a method for producing the porphyrin-immobilized poly(meth)acrylic acid or porphyrin-immobilized poly(meth)acrylic acid ester include a method of heating and reacting a porphyrin monomer represented by the formula (14) with acrylic acid, an acrylic acid ester, methacrylic acid, or a methacrylic acid ester and V-65 (2,2'-azobis(2,4-dimethylvaleronitrile) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0102] The amount of acrylic acid, acrylic acid ester, methacrylic acid, or methacrylic acid ester used in the method for producing the porphyrin-immobilized poly(meth)acrylic acid or porphyrin-immobilized poly(meth)acrylic acid ester is 10,000 to 100,000 equivalents relative to 1 equivalent of the porphyrin monomer represented by formula (14).

[0103] The amount of V-65 (2,2'-azobis(2,4-dimethylvaleronitrile) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) used in the method for producing the porphyrin-immobilized poly(meth)acrylic acid or porphyrin-immobilized poly(meth)acrylic acid ester is 30 to 1200 equivalents relative to 1 equivalent of the porphyrin monomer represented by the formula (14). [Example]

[0104] Next, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

[0105] [Example 1] <Synthesis of porphyrin (porphyrin 1) represented by the following formula (15)>

[0106] [ka]

[0107] (1-1)<Synthesis of 4-vinylbenzaldehyde> A 300 mL four-neck flask was charged with 4.6 g (190 mmol) of magnesium and 100 g of THF, and then 25 g (181 mmol) of 4-chlorostyrene was added dropwise at room temperature under a nitrogen stream. After the addition was complete, the temperature was raised to 60°C and the mixture was stirred for 1 hour. After stirring was complete, the reaction mixture was cooled to room temperature, and 4.0 g (199 mmol) of DMF was added dropwise. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour, and toluene and dilute hydrochloric acid were added to separate the aqueous and organic layers. Water was added to the separated organic layer, and the mixture was separated again. The resulting organic layer was concentrated under reduced pressure, and the solvent was distilled off, yielding 21.00 g of 4-vinylbenzaldehyde (amount yield: 87.8%).

[0108] (1-2) <Synthesis of porphyrin 1> A 300 mL four-neck flask was charged with 4.0 g (30 mmol) of 4-vinylbenzaldehyde obtained in (1-1) above, 2.1 g (31 mmol) of pyrrole, and 150 mL of propionic acid, and the mixture was heated to 140°C under air. After heating, the reaction solution was stirred for 2 hours and then cooled to room temperature. The cooled reaction solution was transferred to a filter and filtered under pressure with nitrogen, and the solid remaining in the filter was washed with methanol. The washed solid was dried under reduced pressure to obtain 21.1 g of porphyrin 1 (as-is yield: 20.8%).

[0109] [Example 2] <Synthesis of Mg-porphyrin (porphyrin 2) represented by the following formula (16)>

[0110] [ka]

[0111] 2.0 g (2.8 mmol) of porphyrin 1 obtained in [Example 1] (1-2), 1.2 g (5.5 mmol) of Mg(OAc)2·4H2O, and 100 g of DMF were placed in a 180 mL three-neck flask and heated to 160°C under a nitrogen stream. After heating, the reaction solution was stirred for 16 hours and then cooled to room temperature. Water was added to the cooled reaction solution, which was then transferred to a filter and filtered under pressure with nitrogen. The solid remaining in the filter was washed with water. The washed solid was dried under reduced pressure to obtain 2.2 g of porphyrin 2 (as-reduced yield: 105.7%).

[0112] [Example 3] <Synthesis of Mn-porphyrin (porphyrin 3) represented by the following formula (17)>

[0113] [ka]

[0114] A 180 mL three-neck flask was charged with 1.5 g (2.1 mmol) of porphyrin 1 obtained in [Example 1] (1-2), 0.77 g (3.1 mmol) of Mn(OAc)2·4H2O, and 75.0 g of DMF, and the temperature was then raised to 160°C under a nitrogen stream. After heating, the reaction solution was stirred for 16 hours and then cooled to room temperature. Water was added to the cooled reaction solution, which was then transferred to a filter and filtered under pressure with nitrogen. The solid remaining in the filter was washed with water. The washed solid was dried under reduced pressure to obtain 1.7 g of porphyrin 3 (as-is yield: 104.8%).

[0115] [Example 4] <Synthesis of porphyrin-immobilized polystyrene (polymer 1) represented by the following formula (3)>

[0116] [ka]

[0117] A 50 mL three-neck flask was charged with 0.50 g of porphyrin 1 obtained in Example 1 (1-2), 0.22 g of V-65, 3.34 g of 4-tert-butyl-styrene, and 24 mL of chloroform, and the mixture was stirred under a nitrogen stream for 10 minutes to obtain a solution of porphyrin 1. A 500 mL four-neck flask was charged with 10.0 g of gum acacia, 12.5 g of NaCl, and 250 mL of water, and the mixture was stirred under a nitrogen stream until the solid disappeared, obtaining an aqueous solution. The porphyrin 1 solution was added dropwise to the resulting aqueous solution at room temperature while stirring under a nitrogen stream. After the addition was complete, the temperature was raised to 60°C and the mixture was stirred for 16 hours. After stirring, the reaction solution was cooled to room temperature and transferred to a filter. It was filtered under pressure with nitrogen, and the solid remaining in the filter was washed with water, methanol, toluene, and methanol, in that order. The washed solid was dried under reduced pressure to obtain 2.8 g of polymer 1.

[0118] [Example 5] <Synthesis of Mg-porphyrin-immobilized polystyrene (polymer 2) represented by the following formula (4)>

[0119] [ka]

[0120] A 50 mL three-neck flask was charged with 0.16 g of porphyrin 2 obtained in Example 2, 42 mg of V-65, 0.65 g of 4-tert-butyl-styrene, and 4 mL of chloroform, and the mixture was stirred for 10 minutes under a nitrogen stream to obtain a solution of porphyrin 2. A 50 mL three-neck flask was charged with 2.0 g of gum acacia, 2.5 g of NaCl, and 50 mL of water, and the mixture was stirred under a nitrogen stream until the solid disappeared, yielding an aqueous solution. The porphyrin 2 solution was added dropwise to the resulting aqueous solution at room temperature while stirring under a nitrogen stream. After the addition was complete, the temperature was raised to 60°C and the mixture was stirred for 16 hours. After stirring, the reaction solution was cooled to room temperature and transferred to a filter. Pressure-filtered with nitrogen, and the solid remaining in the filter was washed with water, methanol, toluene, and methanol, in that order. The washed solid was dried under reduced pressure to obtain 0.8 g of polymer 2.

[0121] [Example 6] <Synthesis of Mn-porphyrin-immobilized polystyrene (polymer 3) represented by the following formula (5)>

[0122] [ka]

[0123] A 50 mL three-neck flask was charged with 0.10 g of porphyrin 3 obtained in Example 3, 40 mg of V-65, 1.66 g of 4-tert-butyl-styrene, and 5 mL of chloroform, and the mixture was stirred under a nitrogen stream for 10 minutes to obtain a solution of porphyrin 3. A 180 mL three-neck flask was charged with 2.0 g of gum acacia, 2.5 g of NaCl, and 50 mL of water, and the mixture was stirred under a nitrogen stream until the solid disappeared, yielding an aqueous solution. The porphyrin 3 solution was added dropwise to the resulting aqueous solution at room temperature while stirring under a nitrogen stream. After the addition was complete, the temperature was raised to 60°C and the mixture was stirred for 16 hours. After stirring, the reaction solution was cooled to room temperature and transferred to a filter. It was filtered under pressure with nitrogen, and the solid remaining in the filter was washed with water, methanol, toluene, and methanol, in that order. The washed solid was dried under reduced pressure to obtain 0.6 g of polymer 3.

[0124] [Example 7] <Synthesis of cyclic carbonate using polymer 1 obtained in Example 4 as a catalyst> A 30 mL autoclave was charged with 59.2 mg of polymer 1 obtained in Example 4, 35.5 mg of tetrabutylammonium bromide, and 1.85 g of epoxydodecane, and the temperature was then raised to 120°C under nitrogen pressure (0.2 MPa). After heating, the nitrogen pressure was released and the reaction solution was stirred for 3 hours under CO2 pressure (0.8 MPa). NMR analysis was then performed on the reaction solution to confirm the degree of reaction progress (reaction progress rate) using the following formula, and it was confirmed that 100% of the epoxydodecane had been converted to cyclic carbonate.

[0125]

number

[0126] [Example 8] <Recycling experiment of catalyst (polymer 1) in synthesis of cyclic carbonate using polymer 1 obtained in Example 4 as a catalyst> Polymer 1 obtained in Example 4, tetrabutylammonium bromide, and epoxydodecane were placed in a 30 mL autoclave and heated to 120°C under nitrogen pressure (0.2 MPa). After heating, the nitrogen was removed and the reaction mixture was stirred for 3 hours under CO2 pressure (0.8 MPa), after which NMR analysis was performed on the reaction mixture. After analysis, the reaction mixture was cooled to room temperature, methanol was added, and the mixture was transferred to a filter. After vacuum filtration, the solid remaining in the filter was washed with methanol. The washed solid was dried under vacuum, and the resulting solid was used as a catalyst to synthesize cyclic carbonates twice. The results are shown in Table 1.

[0127] [Table 1]

[0128] [Example 9] <Synthesis of porphyrin 1-immobilized acrylate polymer (polymer 4) represented by the following formula (6)>

[0129] [ka]

[0130] 1.2 mg (1.7 μmol) of porphyrin 1 obtained in Example 1, 20 g (0.16 mol) of butyl acrylate, and 0.5 g (2.0 mmol) of V-65 were placed in an aluminum dish, and then heated in an oven heated to 65°C for 3 hours to obtain an acrylic acid-based polymer (polymer 4) with immobilized porphyrin 1. Polymer 4 was in a liquid state.

[0131] [Example 10] <Synthesis of methacrylic acid polymer (polymer 5) having porphyrin 1 immobilized thereon, represented by the following formula (7)>

[0132] [ka]

[0133] 3.8 mg (5.3 μmol) of porphyrin 1 obtained in Example 1, 5 g (0.06 mol) of methacrylic acid, and 50 mg (0.2 mmol) of V-65 were placed in an aluminum dish, and then heated in an oven heated to 65°C for 1 hour to obtain a methacrylic acid-based polymer (polymer 5) with immobilized porphyrin 1. Polymer 5 was a solid.

[0134] [Example 11] (11-1) Synthesis of 4-(11-hydroxyundecanoxy)benzaldehyde A 180 mL three-neck flask was charged with 5.0 g (41 mmol) of 4-hydroxybenzaldehyde, 9.3 g (37 mmol) of 11-bromo-1-undecanol, 6.2 g (45 mmol) of potassium carbonate, and 10 g of N,N'-dimethylacetamide, and the mixture was heated to 100 °C under a nitrogen stream. After heating, the reaction mixture was stirred for 3.5 hours and then cooled to room temperature. Toluene and water were added to the cooled reaction mixture, and the aqueous and organic layers were separated. Water was added to the separated organic layer, and this separation operation was repeated twice. Sodium sulfate was added to the resulting organic layer for dehydration. After dehydration, the sodium sulfate was filtered and washed with toluene. The resulting filtrate was concentrated under reduced pressure, and the solvent was removed by distillation to yield 10.5 g of 4-(11-hydroxyundecanoxy)benzaldehyde (as-obtained yield: 97.2%).

[0135] (11-2) Synthesis of 4-[[(1-oxo-2-propen-1-yl)oxy]undecanoxy]benzaldehyde 4.0 g (14 mmol) of 4-(11-hydroxyundecanoxy)benzaldehyde obtained in (11-1), 2.0 g (16 mmol) of N,N'-dimethylaniline, and 32 g of toluene were added and cooled to 0°C under a nitrogen stream. After cooling, 1.5 g (16 mmol) of acryloyl chloride was added dropwise over 1 hour, and the mixture was then heated to room temperature and stirred for 5 hours. Water was added to the resulting reaction solution and the temperature was raised to 60°C, after which the aqueous and organic layers were separated. Water was added to the separated organic layer, and the mixture was again separated at 60°C and cooled to room temperature. Sodium sulfate was added to the resulting organic layer for dehydration, and the sodium sulfate was filtered and washed with toluene. The resulting filtrate was concentrated under reduced pressure to remove the solvent, yielding 3.7 g of 4-[[(1-oxo-2-propen-1-yl)oxy]undecanoxy]benzaldehyde (as-obtained yield: 77.8%).

[0136] (11-3) <Synthesis of porphyrin (porphyrin 4) represented by the following formula (18)>

[0137] [ka]

[0138] 3.7 g (11 mmol) of 4-[[(1-oxo-2-propen-1-yl)oxy]undecanoxy]benzaldehyde obtained in (11-2), 0.7 g (10 mmol) of pyrrole, and 50 mL of propionic acid were placed in a 180 mL three-neck flask, and the mixture was heated to 140°C under air. After heating, the reaction solution was stirred for 1 hour and then cooled to room temperature. The cooled reaction solution was transferred to a filter and filtered under pressure with nitrogen. The solid remaining in the filter was washed with methanol. The washed solid was dried under reduced pressure to obtain 1.5 g of porphyrin 4 (as-is yield: 36.6%).

[0139] [Example 12] <Synthesis of methacrylic acid polymer (polymer 6) having porphyrin 4 immobilized thereon, represented by the following formula (8)>

[0140] [ka]

[0141] 3.8 mg (2.4 μmol) of porphyrin 4, 5 g (0.06 mol) of methacrylic acid, and 50 mg (0.2 mmol) of V-65 were placed in an aluminum dish, and then heated in an oven heated to 65°C for 1 hour to obtain a methacrylic acid-based polymer (polymer 6) with immobilized porphyrin 4.

[0142] [Example 13] <Change in luminescent color of polymer 6 obtained in Example 12> Polymer 6 obtained in Example 12 and water were placed in a vial and allowed to stand until the solid disappeared. When the resulting aqueous solution was irradiated with 365 nm ultraviolet light, it emitted yellow light, and when an aqueous NaOH solution was added, the emitted light color changed to red. When concentrated hydrochloric acid was added to the resulting aqueous solution, the emitted light color changed from red to the original yellow.

[0143] [Example 14] <Synthesis of Mg-porphyrin-immobilized polybutyl acrylate (polymer 7) represented by the following formula (9)>

[0144] [ka]

[0145] A 50 mL three-neck flask was charged with 0.51 g of the porphyrin 2 obtained in Example 2, 0.21 g of V-65, 2.60 g of butyl acrylate, and 5 mL of chloroform, and the mixture was stirred for 10 minutes under a nitrogen stream to obtain a solution of porphyrin 2. A 180 mL four-neck flask was charged with 2.0 g of gum acacia, 2.5 g of NaCl, and 50 mL of water, and the mixture was stirred under a nitrogen stream until the solid disappeared, obtaining an aqueous solution. The porphyrin 2 solution was added dropwise to the resulting aqueous solution at room temperature while stirring under a nitrogen stream. After the addition was complete, the temperature was raised to 60°C and the mixture was stirred for 5 hours. After stirring was complete, the reaction solution was cooled to room temperature and transferred to a filter. It was then filtered under pressure with nitrogen, and the solid remaining in the filter was washed with water and then methanol. The washed solid was dried under reduced pressure to obtain 0.84 g of polymer 7.

[0146] [Example 15] <Synthesis of cyclic carbonate using polymer 7 obtained in Example 14 as a catalyst> A 30 mL autoclave was charged with 48.4 mg of polymer 7 obtained in Example 14, 32.2 mg of tetrabutylammonium bromide, and 1.02 g of ethyl glycidyl ether, and the temperature was then raised to 120°C under nitrogen pressure (0.2 MPa). After heating, the nitrogen pressure was released and the reaction solution was stirred for 3 hours under CO pressure (0.8 MPa). NMR analysis was then performed on the reaction solution to confirm the degree of reaction progress (reaction progress rate) using the following formula, and it was confirmed that 94.5% of the ethyl glycidyl ether had been converted to cyclic carbonate.

[0147]

number

[0148] [Example 16] <Synthesis of cyclic carbonate using polymer 7 obtained in Example 14 as a catalyst> A 30 mL autoclave was charged with 48.4 mg of polymer 7 obtained in Example 14, 32.2 mg of tetrabutylammonium bromide, and 1.84 g of epoxydodecane, and the temperature was then raised to 120°C under nitrogen pressure (0.2 MPa). After heating, the nitrogen pressure was released and the reaction solution was stirred for 3 hours under CO pressure (0.8 MPa). NMR analysis was then performed on the reaction solution to confirm the degree of reaction progress (reaction progress rate) using the following formula, and it was confirmed that 46.2% of epoxydodecane had been converted to cyclic carbonate.

[0149]

number

[0150] According to the present invention, it is possible to provide a porphyrin-immobilized polymer that can be used as a catalyst in the reaction of carbon dioxide with an epoxide, and a porphyrin-immobilized polymer that can be used as a light-emitting material.

Claims

1. A porphyrin-immobilized polymer represented by the following formula (1): 【Chemical 1】 (The porphyrin-immobilized polymer represented by formula (1) may or may not contain M. In formula (1), when M is contained, p=1, q=0, and M represents a metal atom of Group 2 or Group 7 of the periodic table, If M is not included, then p=0 and q=1. R ａ１ , R ａ２ , R ａ３ and R ａ４ each independently represents a phenyl group, a carboxy group, or an ester group; R ｂ１ , R ｂ２ , R ｂ３ and R ｂ４ each independently represents a hydrogen atom or a methyl group, n1, n2, n3, and n4 each independently represent an integer of 10 to 10,000; X1, X2, X3, and X4 represent the proportion of structural units derived from monomers in the formula, where n1, n2, n3, and n4 are each 1, and are independently a number from 0.01 to 0.99; R ｃ１ , R ｃ２ , R ｃ３ and R ｃ４ each independently represents a divalent functional group having an oxygen atom and / or a carbonyl group at its terminal, m1, m2, m3 and m4 each independently represent 0 or 1.

2. A catalyst comprising the porphyrin-immobilized polymer according to claim 1.

3. A catalyst comprising the porphyrin-immobilized polymer of claim 1, which is used in the synthesis of cyclic carbonates by reacting carbon dioxide with an epoxide.

4. A light-emitting material comprising the porphyrin-immobilized polymer according to claim 1.

5. A method for producing a porphyrin-immobilized polymer, comprising the following steps (1), (2), (3) and (4): Step (1): A porphyrin monomer having at least one vinyl group; an azo polymerization initiator; at least one monomer selected from the group consisting of styrene-based monomers, (meth)acrylic acid-based monomers, and (meth)acrylic acid ester-based monomers; an organic solvent; Obtaining a porphyrin monomer solution Step (2): Obtaining an aqueous solution containing gum acacia, NaCl, and water Step (3): Adding the porphyrin monomer solution obtained in step (1) to the aqueous solution obtained in step (2) at room temperature, followed by heating to produce a porphyrin-immobilized polymer. Step (4): A step of recovering the porphyrin-immobilized polymer produced in the step (3).

6. A method for producing a porphyrin-immobilized polymer, comprising: a porphyrin monomer having at least one alkylene group; an azo polymerization initiator; and at least one monomer selected from the group consisting of (meth)acrylic acid-based monomers and (meth)acrylic acid ester-based monomers, to produce a porphyrin-immobilized polymer.

7. 7. A method for producing the porphyrin-immobilized polymer according to claim 1, wherein the method is a method for producing the porphyrin-immobilized polymer according to claim 5 or claim 6.

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