Polyurethane having a hyperbranched structure, its production method and polymer catalyst

Abstract

To provide: a novel hyperbranched polymer; an industrially advantageous method for producing the hyperbranched polymer; and a polymer catalyst using the hyperbranched polymer.SOLUTION: Provided is a polyurethane having a novel hyperbranched structure, comprising a structural unit including a 2,2'-bipyridyl group with which a metal can coordinate and a specific hyperbranched-type (branched-type) structural unit. Also provided are: a transition metal complex using as a ligand the polyurethane having the hyperbranched structure; and a polymer catalyst comprising the transition metal complex.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyurethane having a novel hyperbranched structure, a production method thereof, and a polymer catalyst using the same. [Background technology]

[0002] Polymer catalysts have industrial advantages in that they are easier to separate from a reaction system than monomolecular catalysts and can be reused.

[0003] However, it is known that catalytic activity is significantly reduced when a catalyst system that generally exhibits excellent properties as a low molecular weight system is polymerized. This is thought to be because the mobility of the catalyst molecules is reduced by polymerization, and because the steric hindrance around the catalytic site is increased by polymerization, making it difficult for the catalyst to interact with the substrate.

[0004] Previously, the present inventors have also proposed a polymer catalyst using a polymer ligand having a 2,2'-bipyridyl group in the main chain, which is represented by the following general formula (A) and has excellent catalytic activity (Non-Patent Document 1).

[0005] [ka]

[0006] Hyperbranched polymers, which are classified as dendritic polymers, have a unique structure in which branches are actively introduced. Hyperbranched polymers have a structure in which the molecular chains are branched in an extremely diverse manner, so that the entire polymer has a network structure. This makes it possible to support active ingredients inside and / or on the surface of the molecule. For this reason, this polymer is also expected to be used as a molecular capsule (see, for example, Patent Document 1, etc.). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2011-84601 A [Non-patent literature]

[0008] [Non-Patent Document 1] Polymer Chemistry,Vol.8,7406-7415p(2017) Summary of the Invention [Problem to be solved by the invention]

[0009] Hyperbranched polymers have the advantage that they are generally easier to synthesize than other dendrimers, which is particularly advantageous in industrial production. However, there are still only a few types of hyperbranched polymers that have been synthesized, and there is a demand for the development of new hyperbranched polymers to further expand their applications and functionalization.

[0010] Therefore, an object of the present invention is to provide a novel hyperbranched polymer. Another object of the present invention is to provide a method for producing the hyperbranched polymer in an industrially advantageous manner. A further object of the present invention is to provide a polymer catalyst using the hyperbranched polymer. [Means for solving the problem]

[0011] As a result of intensive research aimed at improving the catalytic performance of polymer catalysts using polymer ligands having 2,2'-bipyridyl groups in the main chain, the present inventors discovered a polyurethane having a novel hyperbranched structure, which has a structural unit having a 2,2'-bipyridyl group capable of coordinating with a metal and a specific hyperbranched (branched) structural unit. They also discovered that a transition metal complex using the polyurethane having the hyperbranched structure as a ligand has excellent catalytic performance, which led to the completion of the present invention.

[0012] A first invention provided by the present inventors is a polyurethane having a hyperbranched structure, which contains a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[0013] [ka] (In the formula, m1 represents an integer of 0 to 18. The dashed lines represent bonds in the polymer.)

[0014] [ka] (In the formula, n represents an integer of 0 to 5. The dashed lines represent bonds in the polymer.)

[0015] The second invention provided by the present inventors is a method for producing polyurethane having a hyperbranched structure, which comprises preparing a raw material mixture containing a bipyridine compound represented by the following general formula (3) and a triisocyanate compound represented by the following general formula (4), and then carrying out an addition polymerization reaction.

[0016] [ka] (In the formula, m1 represents an integer of 0 to 10.)

[0017] [ka] (In the formula, n represents an integer of 0 to 5.)

[0018] The third invention provided by the present inventors is a transition metal complex having the hyperbranched polyurethane of the first invention as a ligand.

[0019] The fourth invention provided by the present inventors is a polymer catalyst comprising the transition metal complex of the third invention. Effect of the Invention

[0020] According to the present invention, it is possible to provide a novel polyurethane having a hyperbranched structure, which has a structural unit having a 2,2'-bipyridyl group and a hyperbranched (branched) structural unit. Furthermore, according to the production method of the present invention, it is possible to provide the polyurethane having the hyperbranched structure in an industrially advantageous manner. Furthermore, the transition metal complex having the polyurethane having the hyperbranched structure of the present invention as a ligand has excellent catalytic ability and can also be suitably used as a polymer catalyst. [Brief description of the drawings]

[0021] [Figure 1] 1H NMR spectrum chart of the THF-soluble portion of the polyurethane sample having a hyperbranched structure obtained in Example 1. [Diagram 2] 3 is an IR spectrum chart of the THF insoluble part of the polyurethane sample having a hyperbranched structure obtained in Example 1. [Diagram 3] 1H NMR spectrum chart of the THF-soluble portion of the polyurethane sample having a hyperbranched structure obtained in Example 2. [Figure 4] IR spectrum chart of the THF insoluble part of the polyurethane sample having a hyperbranched structure obtained in Example 2. [Diagram 5] 1H NMR spectrum chart of the crude product obtained in Example 7. [Figure 6] 1 is a graph showing the relationship between the conversion rate of 4-bromotoluene to 4-methylbiphenyl and the reaction time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Hereinafter, the present invention will be described based on preferred embodiments. The polyurethane having a hyperbranched structure of the present invention is characterized by containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[0023] [ka] (In the formula, m1 represents an integer of 0 to 18. The dashed lines represent bonds in the polymer.)

[0024] [ka] (In the formula, n represents an integer of 0 to 5. The dashed lines represent bonds in the polymer.)

[0025] In the polyurethane having a hyperbranched structure of the present invention, the structural unit represented by general formula (1) is a structural unit having a site capable of coordinating to a metal.

[0026] In general formula (1), m1 represents an integer of 0 to 18, preferably 1 to 4, and more preferably 1 from the viewpoints of availability of raw materials and catalytic activity when made into a metal complex.

[0027] In the polyurethane having a hyperbranched structure according to the present invention, the structural unit of general formula (2) is a structural unit having a moiety that forms a hyperbranched (branched) structure.

[0028] In the general formula (2), n represents an integer of 0 to 5, preferably 0 to 3, and more preferably 0 or 1 from the viewpoints of availability of raw materials and catalytic activity when made into a metal complex.

[0029] In the polyurethane having a hyperbranched structure of the present invention, the content of the structural unit represented by the general formula (2) is preferably in a molar ratio of the structural unit represented by the general formula (2) to the structural unit represented by the general formula (1) (general formula (2) / general formula (1)) of 1 / 4 to 1 / 1, and more preferably in a molar ratio of 2 / 3 to 3 / 4, from the viewpoints of ease of synthesis of a polymerizable compound and catalytic activity when formed into a metal complex.

[0030] Furthermore, in the polyurethane having a hyperbranched structure of the present invention, structural units represented by the following general formula (5) and / or the following general formula (6) may be further contained as necessary for the purpose of imparting solvent affinity.

[0031] [ka] (In the formula, B represents an alkylene group having 1 to 18 carbon atoms. The dashed lines represent bonds in the polymer.)

[0032] [ka] (In the formula, Ar represents an arylene group, and A 2 represents an alkylene group having 0 to 18 carbon atoms, and m2 represents an integer of 0 or 1. The dashed lines represent bonds in the polymer.

[0033] Examples of the alkylene group represented by B in the general formula (5) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Among these, an alkylene group having 2 to 8 carbon atoms, particularly an alkylene group having 4 to 6 carbon atoms, is preferred from the viewpoints of ease of synthesis of a polymeric substance and catalytic activity when made into a metal complex.

[0034] In the polyurethane having a hyperbranched structure of the present invention, the content of the structural unit represented by the general formula (5) is preferably in a molar ratio of the structural unit represented by the general formula (5) to the structural unit represented by the general formula (1) (general formula (5) / general formula (1)) of 1 / 4 to 1 / 1, and more preferably in a molar ratio of 2 / 3 to 3 / 4, from the viewpoints of ease of synthesis of a polymerizable compound and catalytic activity when formed into a metal complex.

[0035] Examples of the arylene group represented by Ar in the general formula (6) include a phenylene group, a biphenylene group, a naphthylene group, a binaphthylene group, an anthrylene group, and a phenanthrylene group. Among these, the binaphthylene group is preferred from the viewpoints of ease of synthesis of a high molecular weight substance and catalytic activity when made into a metal complex.

[0036] A in general formula (6) 2 Examples of the alkylene group having 0 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0037] In the present invention, it is particularly preferred that m2 in general formula (6) is 0 from the viewpoints of availability of raw materials and catalytic activity when made into a metal complex.

[0038] In the polyurethane having a hyperbranched structure of the present invention, the content of the structural unit represented by the general formula (6) is preferably in a molar ratio of the structural unit represented by the general formula (6) to the structural unit represented by the general formula (1) (general formula (6) / general formula (1)) of 1 / 4 to 1 / 1, and from the viewpoints of ease of synthesis of a polymerizable substance and catalytic activity when formed into a metal complex, a molar ratio of 2 / 3 to 3 / 4 is more preferable.

[0039] The polyurethane having a hyperbranched structure of the present invention can contain a component that is soluble in organic solvents such as methanol and THF, and a component that is insoluble in these organic solvents. Hereinafter, the component that is soluble in THF will be referred to as the "soluble portion," and the component that is insoluble in THF will be referred to as the "insoluble portion."

[0040] The soluble portion of the polyurethane having a hyperbranched structure of the present invention preferably has a number average molecular weight (Mn) of 400 to 4,000,000, more preferably 1,000 to 100,000. Also, the weight average molecular weight (Mw) is preferably 600 to 600,000, more preferably 1,200 to 120,000. These molecular weights are molecular weights measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0041] The polyurethane having a hyperbranched structure of the present invention can be industrially advantageously produced by preparing a raw material mixture containing a bipyridine compound represented by the following general formula (3) and a triisocyanate compound represented by the following general formula (4), and then carrying out an addition polymerization reaction.

[0042] [ka] (In the formula, m1 represents an integer of 0 to 18.)

[0043] [ka] (In the formula, n represents an integer of 0 to 5.)

[0044] m1 in general formula (3) corresponds to m1 in general formula (1) in the polyurethane having a hyperbranched structure of the present invention. m1 in general formula (3) represents an integer of 0 to 18, preferably 1 to 4, and more preferably 1. In the present invention, 4,4'-bis(hydroxymethyl)-2,2'-bipyridine, which is a compound in which m1 in general formula (3) is 1, is particularly preferably used.

[0045] The bipyridine compound represented by the general formula (3) can be produced by a known method (see, for example, JP-A-62-129270 and JP-A-2019-194188, paragraphs 0030 to 0035, etc.). In addition, 4,4'-bis(hydroxymethyl)-2,2'-bipyridine is commercially available from Tokyo Chemical Industry Co., Ltd., Fujifilm Wako Pure Chemical Industries, Ltd., and the like.

[0046] In general formula (4), n corresponds to n in general formula (2) in the polyurethane having a hyperbranched structure of the present invention. In general formula (4), n represents an integer of 0 to 5, preferably 0 to 3, and more preferably 0 or 1.

[0047] The triisocyanate compound represented by the general formula (4) can be easily produced according to the following reaction scheme (1).

[0048] [ka] (In the formula, n represents an integer of 0 to 5.)

[0049] The amount of the triisocyanate compound of the general formula (4) in the raw material mixture is preferably such that the molar ratio of the triisocyanate compound of the general formula (4) to the bipyridine compound of the general formula (3) (general formula (4) / general formula (3)) is 1 / 1 to 1 / 4, and more preferably 3 / 4 to 2 / 3 from the viewpoint of suppressing side reactions.

[0050] The polyurethane having a hyperbranched structure of the present invention can be produced by subjecting a bipyridine compound represented by the general formula (3) to an addition polymerization reaction with a triisocyanate compound represented by the general formula (4) in a solvent in the presence of a catalyst.

[0051] Examples of solvents that can be used include ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and tetralin; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactopropane. Examples of the suitable organic solvent include esters such as N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and other amides; ureas such as N,N,N',N'-tetramethylurea (TMU), N,N'-dimethylpropyleneurea (DMPU), and other ureas; dimethyl sulfoxide (DMSO); and alcohols such as methanol, ethanol, isopropyl alcohol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol, and these may be mixed in any ratio for use.

[0052] Examples of the catalyst that can be used include known catalysts that are usually used in the reaction of an isocyanate group (NCO) with a hydroxyl group (OH), such as tertiary amines such as triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N',N''-pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl)ether, triethylenediamine, 1,5-diazabicyclo(4,3,0)nonene-5, 1,8-diaza-bicyclo(5,4,0)undecene-7, 1,2-dimethylimidazole, 1-butyl-2-methylimidazole, and 1,4-dimethylpiperazine, and organic acid salts thereof; and amino alcohols such as dimethylethanolamine, N-trioxyethylene-N,N-dimethylamine, and N,N-dimethyl-N-hexanolamine, and organic acid salts thereof.

[0053] The amount of the catalyst added is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the bipyridine compound represented by the general formula (3).

[0054] Furthermore, the raw material mixture may contain a diisocyanate compound represented by the following general formula (9) and / or a dihydroxy compound represented by the following general formula (10), if necessary.

[0055] [ka] (In the formula, B represents an alkylene group having 1 to 18 carbon atoms.)

[0056] [ka] (In the formula, Ar represents an arylene group, and A 2 represents an alkylene group having 0 to 18 carbon atoms, and m2 represents an integer of 0 or 1.

[0057] B in general formula (9) corresponds to B in the structural unit represented by general formula (5) that is optionally contained in the polyurethane having a hyperbranched structure of the present invention. Examples of the alkylene group represented by B in general formula (9) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Among these, an alkylene group having 2 to 8 carbon atoms, particularly preferably an alkylene group having 4 to 6 carbon atoms, is preferred.

[0058] The amount of the diisocyanate compound represented by the general formula (9) is preferably such that the molar ratio of the diisocyanate compound represented by the general formula (9) to the dipyridine compound represented by the general formula (3) (general formula (9) / general formula (3)) is 1 / 4 to 1 / 1, and from the viewpoint of suppressing side reactions, it is preferably 2 / 3 to 3 / 4.

[0059] Ar in general formula (10) corresponds to Ar in the structural unit represented by general formula (6) that is optionally contained in the polyurethane having a hyperbranched structure of the present invention. Examples of the arylene group represented by Ar in general formula (10) include a phenylene group, a biphenylene group, a naphthylene group, a binaphthylene group, an anthrylene group, and a phenanthrylene group, and among these, a binaphthylene group is preferred.

[0060] A in general formula (10) 2 represents A in the structural unit represented by general formula (6) which is optionally contained in the polyurethane having a hyperbranched structure of the present invention. 2 In general formula (10), A 2 Examples of the alkylene group having 0 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0061] In the general formula (10), m2 corresponds to m2 in the structural unit represented by the general formula (6) that is optionally contained in the polyurethane having a hyperbranched structure of the present invention. In the general formula (6), m2 is preferably 0.

[0062] The amount of the dihydroxy compound represented by the general formula (10) to be blended is preferably such that the molar ratio of the dihydroxy compound represented by the general formula (10) to the dipyridine compound represented by the general formula (3) (general formula (10) / general formula (3)) is 1 / 4 to 1 / 1, preferably 2 / 3 to 3 / 4, from the viewpoint of suppressing side reactions.

[0063] The reaction conditions for the addition polymerization reaction are preferably a reaction temperature of 0 to 60° C. and a reaction time of 1 to 100 hours, for example, at room temperature (25° C.) for 12 to 48 hours.

[0064] After the reaction is completed, purification such as extraction, recrystallization, centrifugation, and reprecipitation can be carried out as necessary to obtain the polyurethane having a hyperbranched structure of the present invention.

[0065] In particular, the polyurethane having a hyperbranched structure of the present invention is preferably obtained as a methanol-insoluble portion and a THF-insoluble portion from the viewpoint of ease of recovery when used as a catalyst.

[0066] The hyperbranched polyurethane of the present invention is expected to be used in applications such as separation materials, gas / low molecule separation materials, porous materials, and structural materials.

[0067] The polyurethane having a hyperbranched structure of the present invention can form a complex with a transition metal as a ligand. This transition metal complex is particularly useful as a polymer catalyst.

[0068] Examples of transition metals that can form a complex with the polyurethane having a hyperbranched structure of the present invention include rhodium, ruthenium, iridium, palladium, nickel, iron, and copper, and among these, iridium and palladium are preferred from the viewpoint of providing a polymer catalyst with high catalytic activity.

[0069] The transition metal complex can be easily obtained by mixing the polyurethane having a hyperbranched structure of the present invention with a desired transition metal compound in a solvent.

[0070] It is particularly preferable to use a palladium compound or an iridium compound as the transition metal compound from the viewpoint of obtaining a polymer catalyst having high catalytic activity.

[0071] Examples of palladium compounds include PdCl2, PdBr2, Pd(OAc)2, Pd(acac)2, PdCl2(NCMe), PdCl2(NCPh), PdCl2(PPh3)2, PdCl2(NH3)4, PdCl2(cod), Pd(OTf)2, [PdCl(π-allyl)]2, and the like.

[0072] Examples of iridium compounds include, for example, [Ir(cod)(CH3CN)2]BF4, [Ir(cod)Cl]2, [Ir(cod)2]BF4, [Ir(cod)2]ClO4, [Ir(cod)2]PF6, [Ir(cod)2]BPh4, [Ir(nbd)2]BF4, [Ir(nbd)2]ClO4, [Ir(nbd)2]PF6, [Ir(nbd)2]BPh4, and the like.

[0073] In the transition metal complex of the present invention, the molar ratio of the bipyridine group in the polyurethane having a hyperbranched structure to the transition metal compound is preferably bipyridine group:transition metal compound=1:1 to 1:0.5, and more preferably bipyridine group:transition metal compound=1:1 to 1:0.8.

[0074] Examples of the solvent used in preparing the transition metal complex of the present invention include ether solvents such as water, tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, 1,4-dioxane, methyl tert-butyl ether, 1,2-dimethoxyethane, etc., aliphatic hydrocarbon solvents such as pentane, hexane, cyclohexane, etc., aromatic hydrocarbon solvents such as o-xylene, m-xylene, p-xylene, toluene, benzene, etc. Furthermore, the solvent used may be a mixed solvent of these.

[0075] The transition metal complex of the present invention, after being prepared as described above, can be used as it is in a reaction as a catalyst without isolation, or it may be isolated after removing the solvent and, if necessary, purification.

[0076] The polymer catalyst of the present invention comprises the transition metal complex in which the polyurethane having a hyperbranched structure serves as a ligand and forms a complex together with a transition metal.

[0077] The polymer catalyst of the present invention is useful as a catalyst for the Suzuki-Miyaura coupling reaction, the boronation reaction of aromatic compounds, the oxidation reaction of benzyl alcohol, and the like, and can be particularly suitably used as a catalyst for the Suzuki-Miyaura coupling reaction.

[0078] The method for producing an organic compound of the present invention uses the polymer catalyst of the present invention as a catalyst in the production of an organic compound, which includes a step of carrying out the known Suzuki-Miyaura coupling reaction.

[0079] The Suzuki-Miyaura coupling reaction is generally a method for producing a biaryl compound by cross-coupling reaction of an organoboron compound with an aryl halide in the presence of a base using a catalyst. For example, an arylboronic acid compound represented by the general formula R1B(OR2) can be reacted with an aryl halide represented by the general formula R3X to produce a biaryl compound represented by the general formula R1-R3, where R1 represents an aryl group, R2 represents a hydrogen atom or an alkyl group, R3 represents an aryl group, and X represents a halogen atom.

[0080] The aryl group of R1 and R3 in the general formula includes a phenyl group, a naphthyl group, an anthranyl group, a pyridyl group, a pyrimidyl group, an indolyl group, a benzimidazolyl group, a quinolyl group, a benzofuranyl group, an indanyl group, an indenyl group, a dibenzofuranyl group, and a methylenedioxyphenyl group. The aryl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group such as a benzyl group or an acetyl group, a nitro group, an aldehyde group, an amide group such as acetamide, a carboxyl group, an amino group, an alkylamino group, a thiol group, an alkylthiol group, a chloro group, a bromo group, and an iodo group.

[0081] The alkyl group represented by R2 in the above general formula includes alkyl groups having 1 to 18 carbon atoms.

[0082] The amount of the polymer catalyst of the present invention used in the Suzuki-Miyaura coupling reaction is 0.01 to 10 mol %, preferably 0.1 to 5 mol %, based on the aryl halide. As the reaction solvent, a mixed solvent of water and an organic solvent can be used, and as the organic solvent, a hydrocarbon such as toluene is preferable, and ethers such as tetrahydrofuran and dimethoxyethane, ketones such as acetone, and nitriles such as acetonitrile can also be preferably used. If necessary, an alcohol such as ethanol can also be added.

[0083] Suitable bases to be added in the Suzuki-Miyaura coupling reaction include inorganic salts such as alkali metal carbonates, phosphates, and acetates, and organic salts such as triethylamine, pyridine, morpholine, quinoline, piperidine, DBU, anilines, and tetra-n-butylammonium acetate. The reaction temperature is 70° C. to 150° C., preferably 70 to 100° C., and the reaction time is 1 hour to 24 hours, depending on the substrate, and the reaction is usually completed in 3 to 20 hours.

[0084] After the reaction, the polymer catalyst of the present invention is removed and recovered by filtration or centrifugation, and the filtrate is subjected to extraction, concentration, and purification to obtain the target product. On the other hand, the recovered polymer catalyst can be reused by washing and drying. EXAMPLES

[0085] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0086] (Synthesis Example 1) 1,3,5-benzenetricarboxylic acid (1) (5.00 g, 23.8 mmol) and a stirrer tip were placed in a 50 mL bifurcated flask, and a reflux tube and a three-way cock were attached. Nitrogen replacement was performed three times. In order to capture the HCl and SO2 gases generated during the reaction, a tube was attached to the end of the reflux tube and connected to a bath of KOH aqueous solution, and nitrogen was made to flow. SOCl2 (15.0 mL, 206 mmol) was added to dissolve compound 1, and then five drops of DMF were added with a Pasteur pipette. The reaction solution was heated and reacted under reflux conditions for 5 hours. Unreacted SOCl2 was distilled off under reduced pressure, and then a white solid of 1,3,5-benzenetricarboxylic acid trichloride (2) was obtained by vacuum distillation. Yield: 82% (5.15g, 19.4mmol) IR (KBr, cm -1 ) 3089, 1755, 1592, 1432, 1154, 1025, 1006, 709, 701, 680; 1H NMR (400 MHz, CDCl3) δ 9.09 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 166.3, 138.4, 135.7.

[0087] A stirrer tip and sodium azide (858 mg, 13.2 mmol) were placed in a 100 mL recovery flask, and water (7.0 mL) was added to dissolve the azide. The flask was cooled in an ice bath, and a dichloroethane solution (15.0 mL) of 1,3,5-benzenetricarboxylic acid trichloride (2) (1.06 g, 4.00 mmol) was added dropwise. The mixture was allowed to warm to room temperature and stirred for 3 hours. The formation of 1,3,5-benzenetricarboxylic acid triazide (3) was confirmed by NMR ( 1 H NMR (400 MHz, CDCl3) δ 8.84 (s, 3H). The organic layer was collected, dried over MgSO4, filtered, and collected in a 100 mL bifurcated flask. A stirrer tip was placed in the bifurcated flask, and a three-way cock and reflux tube were attached. The mixture was purged with nitrogen three times and stirred under reflux for 3 hours. The solvent was removed under reduced pressure to obtain a white solid of 1,3,5-benzenetriisocyanate (4). Yield 96% (774mg, 3.85mmol) 1 H NMR (400 MHz, CDCl3) δ 6.68 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 135.8, 125.6, 118.8.

[0088] [ka]

[0089] (Synthesis Example 2) A stirrer tip, 1,3,5-tribromobenzene (5) (9.44 g, 30.0 mmol), 4-carboxyphenylboronic acid (6) (17.9 g, 108 mmol), and Pd(OAc)2 (673 mg, 3.00 mmol) were placed in a 2 L forked flask, and a reflux tube and a three-way cock were attached. Nitrogen replacement was performed three times. EtOH (500 mL) and an aqueous solution (500 mL) of Na2CO3 (47.7 g, 450 mmol) were added and stirred at 85 °C for 20 hours. The reaction solution was cooled to room temperature, filtered, and the solvent was distilled off. A 2N aqueous solution of HCl (300 mL) was added, and the precipitated white solid was collected by centrifugation. It was washed with water and methanol and dried in vacuum for 49 hours to obtain a white solid of 1,3,5-tris(4-carboxyphenyl)benzene (7). Yield 99% (13.0g, 29.7mmol) 1 H NMR (600 MHz, DMSO-d6) δ 8.10 (s, 3H), 8.07 (s, 12H); 13 C NMR (150 MHz, DMSO-d6) δ 167.3, 143.9, 140.9, 130.1, 130.0, 127.5, 125.7.

[0090] A stirrer tip and 1,3,5-tris(4-carboxyphenyl)benzene (7) (4.38 g, 10.0 mmol) were placed in a 500 mL bifurcated flask, and a reflux tube and a three-way cock were attached. Nitrogen replacement was performed three times. In order to capture the HCl and SO2 gases generated during the reaction, a tube was attached to the end of the reflux tube and connected to a bath of a KOH aqueous solution, and nitrogen was made to flow. The mixture was suspended in dehydrated THF (300 mL), and 10 drops of DMF were added using a Pasteur pipette. The reaction solution was heated and reacted under reflux conditions for 5 hours. Unreacted SOCl2 was distilled off under reduced pressure to obtain a white solid of 1,3,5-tris[(4-chlorocarbonyl)phenyl]benzene (8). The formation of compound 8 was confirmed by FTIR (IR(KBr, cm -1)1774,1735,1601,1394,1213,1179,902,895,836,818,738,672,651.) Compound 8 was suspended in dehydrated THF (300 mL) under nitrogen, and an aqueous solution (100 mL) of NaN3 (13.1 g, 200 mmol) was added thereto. After stirring at room temperature for 16 hours, water and chloroform were added and the layers were separated. The organic layer was washed with water and brine, and then filtered. The white solid collected by filtration was found to be the target compound 9 by FTIR and NMR. The filtrate was slowly evaporated in an evaporator, and the precipitated white solid was collected by filtration. The obtained solid was dried under vacuum for 3 hours to obtain a white solid of 1,3,5-tris[(4-azidocarbonyl)phenyl]benzene (9). Yield: 51% (2.63 g, 5.12 mmol) IR (KBr, cm -1 ) 2926, 2136, 1692, 1604, 1262, 1240, 1205, 1185, 988, 840, 822, 751, 686; 1 H NMR (600 MHz, CDCl3) δ 8.16 (d, J = 8.4 Hz, 6H), 7.87 (s, 3H), 7.78 (d, J = 8.4 Hz, 6H); 13 C NMR (150 MHz, CDCl3) δ 172.3, 146.3, 141.6, 130.4, 130.2, 127.7, 126.5.

[0091] A stirrer tip and 1,3,5-tris[(4-azidocarbonyl)phenyl]benzene (9) (503 mg, 0.98 mmol) were placed in a 100 mL recovery flask and a three-way cock was attached. The atmosphere was replaced with nitrogen three times, and dehydrated toluene (40 mL) was added and suspended. The mixture was stirred at 90°C for 3 hours. The solvent was distilled off under reduced pressure to obtain a white solid of 1,3,5-tris(4-isocyanatophenyl)benzene (10). Yield 98% (415mg, 0.97mmol) 113C NMR (100 MHz, CDCl3) δ 141.6, 138.5, 133.2, 128.5, 125.4, 125.1, 125.0.

[0092] [ka]

[0093] [Example 1] 1,3,5-Triisocyanatobenzene (TIB) (623 mg, 1 mmol) was added to a solution of 4,4'-bis(hydroxymethyl)-2,2'-bipyridine (BHMB) (1003 mg, 3.1 mmol) in THF (4.4 mL). After the reaction system was completely homogenized by stirring, Et3N (0.12 mL) was added to initiate the addition polymerization reaction, and the mixture was stirred at room temperature (25 °C) for 24 hours. The reaction was then quenched by adding methanol (2.0 mL). The crude product was then reprecipitated in methanol, and the methanol-insoluble portion was collected by centrifugation to obtain Poly(BHMB-TIB) (yield 1514 mg, 93%). The product was then separated into THF-soluble and insoluble portions by centrifugation using THF (yield 1367 mg, 84% of the THF-insoluble portion). About THF soluble parts 1 The product was analyzed by 1 H NMR, and the THF insoluble portion was analyzed by IR. 1 The 1 H NMR spectrum chart is shown in FIG. 1, and the IR spectrum chart is shown in FIG.

[0094] [ka]

[0095] [Example 2] 1,3,5-Tris(4-isocyanatophenyl)benzene (TIPB) (34.5 mg, 0.08 mmol) was added to a solution of 4,4'-bis(hydroxymethyl)-2,2'-bipyridine (BHMB) (26 mg, 0.12 mmol) in THF (1.2 mL). After the reaction system was completely homogenized by stirring, Et3N (0.02 mL) was added to start the polyaddition reaction, and the mixture was stirred at room temperature (25 °C) for 24 hours. The reaction was then quenched by adding methanol (2.0 mL). The crude product was then reprecipitated in methanol, and the methanol-insoluble portion was collected by centrifugation to obtain Poly(BHMB-TIPB) (yield 49 mg, 81%), which was then separated into THF-soluble and insoluble portions by centrifugation using THF (yield of THF-insoluble portion 36 mg, 60%). About THF soluble parts 1 The product was analyzed by 1 H NMR, and the THF insoluble portion was analyzed by IR. 1 The 1 H NMR spectrum chart is shown in FIG. 3, and the IR spectrum chart is shown in FIG.

[0096] [ka]

[0097] [Example 3] 1,3,5-Tris(4-isocyanatophenyl)benzene (TIPB) (20.78 mg, 0.1 mmol) and 1,6-diisocyanatohexane (DIH) (16.90 mg, 0.1 mmol) were added to a solution of 4,4'-bis(hydroxymethyl)-2,2'-bipyridine (BHMB) (32.5 mg, 0.15 mmol) in THF (2.0 mL). After the reaction system was completely homogenized by stirring, Et3N (0.11 mL) was added to initiate the polyaddition reaction, and the mixture was stirred at room temperature (25 °C) for 24 h. The reaction was then quenched by adding methanol (2.0 mL). The crude product was then reprecipitated in methanol, and the methanol-insoluble portion was collected by centrifugation to obtain Poly(BHMB-DIH-TIB). The mixture was then centrifuged using THF to separate the product into THF-soluble and insoluble parts (yield of the THF-insoluble part: 77 mg, 82%). About THF soluble parts 1 The product was analyzed by 1 H NMR, and the THF insoluble portion was analyzed by IR. 1 The 1 H NMR spectrum chart is shown in FIG. 3, and the IR spectrum chart is shown in FIG.

[0098] [ka]

[0099] (Molecular Weight Measurement) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the soluble portion of the polyurethane sample having a hyperbranched structure obtained in the examples were measured by gel permeation chromatography. The results are shown in Table 1. Mn and Mw are molecular weights calculated in terms of standard polystyrene.

[0100] [Table 1]

[0101] [Example 4] Poly(BHMB-TIB) (34.8 mg, 0.1 mmol) obtained in Example 1 and Pd(OAc)2 (11.2 mg, 0.05 mmol) were added to methanol (1 mL) and stirred at room temperature (25°C) for 24 hours. The insoluble matter was separated using a centrifuge, and a polymer catalyst in which palladium was coordinated to Poly(BHMB-TIB) was obtained as a dark brown solid (yield 34.4 mg, 85.1%). Hereinafter, the obtained polymer catalyst will be referred to as Poly(BHMB-TIB) / Pd(OAc)2.

[0102] [Example 5] Poly(BHMB-TIPB) (25.0 mg, 0.05 mmol) obtained in Example 2 and Pd(OAc)2 (11.2 mg, 0.05 mmol) were added to methanol (1 mL) and stirred at room temperature (25°C) for 24 hours. The insoluble matter was separated using a centrifuge, and a polymer catalyst in which palladium was coordinated to Poly(BHMB-TIPB) was obtained as a dark brown solid (yield 32.2 mg, 88.9%). Hereinafter, the obtained polymer catalyst will be referred to as Poly(BHMB-TIPB) / Pd(OAc)2.

[0103] [Example 6] A 30 mL flask equipped with a condenser was charged with 4-bromotoluene (0.12 mL, 1.0 mmol), phenylboronic acid (183 mg, 1.5 mmol), K2CO3 (276 mg, 2 mmol), Poly(BHMB-TIB) / Pd(OAc)2 (5.48 mg, 1.0 mol%), 1,2-dimethoxyethane (DME) (2.0 mL), and H2O (3.0 mL). The reaction was then heated at 80 °C with stirring for 17 h. The crude product was extracted with ethyl acetate (20 mL) and the organic layer was washed with brine, dried over MgSO4, and concentrated under vacuum to give the crude product.

[0104] [Example 7] The reaction was carried out in the same manner as in Example 6, except that Poly(BHMB-TIPB) / Pd(OAc)2 (7.48 mg, 1.0 mol%) was used instead of Poly(BHMB-TIB) / Pd(OAc)2.

[0105] [Reference example 1] 2,2'-Bipyridine (bpy) (156.2 mg, 1 mmol) and Pd(OAc)2 (224.5 mg, 1 mmol) were added to methanol (1 mL) and stirred at room temperature (25°C) for 24 hours to prepare a catalyst (bpy / Pd(OAc)2) in which palladium was coordinated to 2,2'-bipyridine (bpy). The reaction was carried out in the same manner as in Example 6, except that bpy / Pd(OAc)2 (3.8 mg, 1.0 mol%) was used instead of Poly(BHMB-TIB) / Pd(OAc)2.

[0106] [ka]

[0107] <Catalyst evaluation> 6 shows the relationship between the conversion rate from 4-bromotoluene to 4-methylbiphenyl and the reaction time in Examples 6 to 7 and Reference Example 1. Table 2 shows the yield of 4-methylbiphenyl. The conversion rate of 4-bromotoluene to 4-methylbiphenyl was 1 The results are shown in FIG. 6. 1 The 1 H NMR spectrum chart is shown in Figure 5. Conversion rate (%) = (spectral intensity of methyl group of 4-methylbiphenyl / spectral intensity of methyl group of 4-bromotoluene) × 100

[0108] The catalyst turnover number (TON) was calculated from the conversion rate (%), the amount of 4-bromotoluene used [4-bromotoluene]0 (mol), and the amount of palladium catalyst used [Pd]0 (mol) according to the following formula. The results are shown in Table 2. TON = Conversion rate (%) / ([4-bromotoluene]0 / [Pd]0)

[0109] [Table 2]

[0110] These results demonstrate that the transition metal complexes having the hyperbranched polyurethane structure of the present invention as a ligand have catalytic turnover numbers equivalent to those of transition metal complexes having low molecular weight compounds as ligands, and are therefore suitable as polymer catalysts.

Claims

1. A polyurethane having a hyperbranched structure, comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2): 【Chemistry 1】 (In the formula, m1 represents an integer of 0 to 18. The dashed lines represent bonds in the polymer.) 【Chemistry 2】 (In the formula, n is an integer of 0 to 5. The dashed lines represent bonds in the polymer.)

2. The polyurethane having a hyperbranched structure according to claim 1 , wherein m1 in the general formula (1) is 1.

3. 3. The polyurethane having a hyperbranched structure according to claim 1 or 2, wherein n in the general formula (2) is 0 or 1.

4. A method for producing polyurethane having a hyperbranched structure, comprising preparing a raw material mixture containing a bipyridine compound represented by the following general formula (3) and a triisocyanate compound represented by the following general formula (4), and then performing an addition polymerization reaction. 【Chemistry 3】 (In the formula, m1 represents an integer of 0 to 18.) 【Chemistry 4】 (In the formula, n represents an integer of 0 to 5.)

5. A transition metal complex having the polyurethane having a hyperbranched structure according to any one of claims 1 to 3 as a ligand.

6. 6. The transition metal complex according to claim 5, wherein the transition metal in the transition metal complex is iridium or palladium.

7. A polymer catalyst comprising the transition metal complex according to claim 6.

8. The polymer catalyst according to claim 7, which is a catalyst for Suzuki-Miyaura coupling reaction.

9. A method for producing an organic compound, comprising a step of carrying out a Suzuki-Miyaura coupling reaction using the polymer catalyst according to claim 8.

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