Curcumin polymer

Abstract

To provide a curcumin polymer which can be used in an industrial field such as an optical member.SOLUTION: The curcumin polymer has a structure represented by general formula (1). (In General Formula (1), R11's each independently represent a hydrogen atom or a methoxy group, R12 represents a single bond, a C2 to C6 alkenylene group, or a phenylene group, and n1 represents a number of 2 to 100.). ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curcumin polymer. More specifically, the present invention relates to a curcumin polymer that can be used for industrial applications such as optical components. [Background technology]

[0002] Conventionally, resin materials with a refractive index of 1.6 or higher are called high refractive index materials, and these high refractive index materials are widely used industrially for purposes such as increasing the brightness, resolution, and viewing angle of displays, improving functionality by miniaturizing lenses, and increasing the sensitivity of sensors (increasing light extraction efficiency).

[0003] More specifically, high refractive index materials are used in brightness enhancement films for liquid crystal displays, smartphone lens materials, various sensors such as CMOS area sensors, light extraction materials for OLEDs, diffractive optical elements, holographic optical element materials, etc.

[0004] Such high refractive index materials are required to have even higher performance (that is, a refractive index of more than 1.7), and various materials have been reported.

[0005] For example, Patent Document 1 reports a triazine ring-containing hyperbranched polymer that has a high refractive index of 1.790 due to the high electron density caused by the close packing of triazine rings and aryl moieties. It has also been reported that this hyperbranched polymer has high transparency and heat resistance, as well as excellent solubility in various solvents.

[0006] Non-Patent Document 1 reports a hydroxy-substituted polyphenylene sulfide (OHPPS) that has a high refractive index of n=1.80 and vD=20, due to high density caused by strong intermolecular hydrogen bonds between the rigid main chain PPS and the side chains. It is also reported that this hydroxy-substituted polyphenylene sulfide exhibits a high Abbe number, excellent light transmittance, and thermal stability.

[0007] Non-Patent Document 2 describes the synthesis of 2,4,6-triiodophenyl acrylate (TIPA) as an iodine-containing polyacrylate, and the synthesis of several types of polymers by radical copolymerization reaction with several types of acrylate monomers. Among the synthesized polymers, poly(TIPA85-co-EEA15) is reported to exhibit a high refractive index and Abbe number of n=1.85 and v=20.7.

[0008] Here, when attempting to improve the performance of high refractive index materials, materials in which inorganic materials such as titania and zirconia are nano-dispersed in resin are sometimes used.

[0009] However, materials with nano-dispersed inorganic materials have the problem of reduced transparency (total light transmittance) in the short wavelength region, and when used in lenses, they can cause problems such as reduced contrast due to Rayleigh scattering in the inorganic material nanocomposite layer.

[0010] Therefore, resins that do not contain inorganic materials but exhibit a high refractive index are also known, such as resins that contain halogens other than fluorine or sulfur in order to increase atomic refraction. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-110133 [Non-patent literature]

[0012] [Non-Patent Document 1] Kenichi Oyaizu,et al.Macromolecules,2022,55,2252-2259. [Non-patent document 2] Hiroyuki Maekawa, Hikaru Amano, Ikuko Nishina, and Hiroto Kudo, ChemistrySelect, 2022, July 28. Summary of the Invention [Problem to be solved by the invention]

[0013] There is a demand for the development of resin materials that exhibit high refractive indexes, but so far, there have been few reports other than triazine / benzoguanamine resins, etc. Therefore, the development of new resin materials is required.

[0014] Therefore, the problem to be solved by the present invention is to provide a curcumin polymer that has heat resistance and can be used as a raw material for a resin material having a high refractive index. [Means for solving the problem]

[0015] The applicants discovered that a resin material made from a polymer (curcumin polymer) of curcumin or a curcumin derivative with a specific monomer has heat resistance and also a high refractive index, leading to the completion of the present invention.

[0016] According to the present invention, there is provided a curcumin polymer as shown below.

[0017] [1] A curcumin polymer having a structure represented by the following general formula (1):

[0018] [ka] (In general formula (1), R 11 each independently represents a hydrogen atom or a methoxy group, and R 12 represents a single bond, a C2-C6 alkenylene group, or a phenylene group, and n1 represents a number from 2 to 100.

[0019] [2] A curcumin polymer having a structure represented by the following general formula (2):

[0020] [ka] (In general formula (2), R 21 each independently represents a hydrogen atom or a methoxy group, and R 22 represents a C1 to C6 alkylene group, and n2 represents a number from 2 to 100.

[0021] [3] A curcumin polymer having a structure represented by the following general formula (3):

[0022] [ka] (In general formula (3), R 31 each independently represents a hydrogen atom or a methoxy group, and R 32 represents a phenylene group, and n3 represents a number from 2 to 100.

[0023] [4] A curcumin polymer having a structure represented by the following general formula (4):

[0024] [ka] (In general formula (4), R 41 each independently represents a hydrogen atom or a methoxy group, and R 42 represents a group represented by the following general formula (5) or a group represented by the following general formula (6), and R 51 represents a C1 to C6 alkylene group, and n4 represents a number from 2 to 100.

[0025] [ka] (In general formula (5), R 43 each independently represents a hydrogen atom or a methoxy group, and the wavy line represents a bonding site.

[0026] [ka] (In general formula (6), R 44 represents a sulfur atom or a group represented by the following general formula (7), and X 1each independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and the wavy line represents a bonding site.

[0027] [ka] (In general formula (7), R 45 and R 46 each independently represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a trifluoromethyl group, or a methoxy group, and the wavy line represents a bonding site.

[0028] [5] The curcumin polymer according to any one of [1] to [4] above, which is used for optical components. [Effects of the Invention]

[0029] The curcumin polymer of the present invention (first to fourth inventions) exhibits the effect that a resin material made from the polymer has heat resistance and also has a high refractive index. DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0031] (1) Curcumin polymer of the first invention (ester-type curcumin polymer): (1-1) The curcumin polymer of the first invention has a structure represented by the following general formula (1):

[0032] [ka] (In general formula (1), R 11 each independently represents a hydrogen atom or a methoxy group, and R 12represents a single bond, a C2-C6 alkenylene group, or a phenylene group, and n1 represents a number from 2 to 100.

[0033] The curcumin polymer of the first invention is a resin material made from this polymer that has heat resistance and a high refractive index, and furthermore, this polymer does not contain any halogens other than fluorine and sulfur.

[0034] The refractive index of a resin material is generally about 1.3 to 1.6, and a resin material having a refractive index of 1.6 or higher can be said to have a high refractive index.

[0035] R in general formula (1) 11 each independently represents a hydrogen atom or a methoxy group. Either of these groups can provide a resin material having good heat resistance and refractive index.

[0036] R in general formula (1) 12 represents a single bond, a C2-C6 alkenylene group, or a phenylene group. Among these, by employing a phenylene group, a resin material having good heat resistance and refractive index can be obtained. Furthermore, a curcumin polymer having solubility in solvents and film-forming properties can be obtained.

[0037] In general formula (1), n1 represents a number from 2 to 100, and preferably a number from 10 to 100. Within this range, the number average molecular weight of the curcumin polymer becomes large, and a resin material having good heat resistance and refractive index can be obtained.

[0038] (1-2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) The number average molecular weight (Mn) of the curcumin polymer of the first invention is not particularly limited, but can be set to 1,000 to 50,000, and preferably 3,000 to 10,000. By setting the number average molecular weight (Mn) within the above range, a resin material having better heat resistance and refractive index can be obtained.

[0039] The molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)) of the curcumin polymer of the first invention is not particularly limited, but can be 1.0 to 5.0, preferably 1.0 to 4.0. By setting the molecular weight distribution within the above range, a resin material with better heat resistance and refractive index can be obtained.

[0040] In the present specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the curcumin polymer can be calculated by a standard polystyrene conversion method using size exclusion chromatography (SEC).

[0041] (1-3) Preparation of esterified curcumin polymer: There are no particular limitations on the method for producing the ester-type curcumin polymer, and it can be produced by polymerization using a monomer represented by the following general formula (1a) and a monomer represented by the following general formula (1b).

[0042] [ka] (In general formula (1a), R 11 each independently represents a hydrogen atom or a methoxy group.

[0043] [ka] (In general formula (1b), R 12 represents a single bond, a C2-C6 alkenylene group, or a phenylene group. 13 and R 14 each independently represents a halogen atom.

[0044] (1-3-1) Monomer represented by general formula (1a): The monomer represented by general formula (1a) is a monomer such as curcumin or a curcumin derivative. The curcumin derivative includes a monomer represented by general formula (1a) where R 11 Examples include "CCM-II," in which all atoms are hydrogen atoms.

[0045] In this way, the present invention can use curcumin (CCM) extracted from turmeric and the curcumin derivative (CCM-II) without the methoxy group. These are biomass raw materials, and their use has the advantage of being "carbon neutral" because no new carbon dioxide is emitted in the production of the raw materials.

[0046] In general formula (1a), R 11 is R in general formula (1). 11 is the same as

[0047] (1-3-2) Monomer represented by general formula (1b): Examples of the monomer represented by the general formula (1b) include oxalyl chloride, fumaric acid chloride, isophthalic acid dichloride, and terephthalic acid dichloride.

[0048] In general formula (1b), R 12 is R in general formula (1). 12 is the same as

[0049] The polymerization method is not particularly limited, and any conventionally known method can be appropriately employed. For example, various polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization are possible.

[0050] The organic solvent used in the polymerization reaction is not particularly limited, but examples thereof include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and dimethyl sulfoxide (DMSO).

[0051] The polymerization initiator is also not particularly limited, but examples thereof include cesium carbonate, triethylamine, dibutyltin (IV) dilaurate, and tetrabutylammonium bromide.

[0052] (1-4) Use of the curcumin polymer of the first invention: The uses of the curcumin polymer of the first invention are not particularly limited and can be used in a variety of industrial products, including, for example, optical components such as organic electroluminescence elements, optical waveguides, and high refractive index materials for microlenses.

[0053] (2) Curcumin polymer of the second invention (ether-type curcumin polymer): (2-1) The curcumin polymer of the second invention has a structure represented by the following general formula (2):

[0054] [ka] (In general formula (2), R 21 each independently represents a hydrogen atom or a methoxy group, and R 22 represents a C1 to C6 alkylene group, and n2 represents a number from 2 to 100.

[0055] The curcumin polymer of the second invention is a resin material made from this polymer that has heat resistance and a high refractive index. Furthermore, a curcumin polymer with solubility in solvents and film-forming properties can be obtained. Furthermore, this polymer does not contain any halogens other than fluorine or sulfur.

[0056] R in general formula (2) 21 each independently represents a hydrogen atom or a methoxy group. Either of these groups can provide a resin material having good heat resistance and refractive index.

[0057] In general formula (2), n2 represents a number from 2 to 100, and preferably a number from 10 to 100. Within this range, the number average molecular weight of the curcumin polymer becomes large, and a resin material having good heat resistance and refractive index can be obtained.

[0058] (2-2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) The number average molecular weight (Mn) of the curcumin polymer of the second invention is not particularly limited, but can be set to 1,000 to 50,000, and preferably 3,000 to 10,000. By setting the number average molecular weight (Mn) within the above range, a resin material having better heat resistance and refractive index can be obtained.

[0059] The molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)) of the curcumin polymer of the second invention is not particularly limited, but can be 1.0 to 10.0, preferably 1.0 to 4.0. By setting the molecular weight distribution within the above range, a resin material with better heat resistance and refractive index can be obtained.

[0060] (2-3) Preparation of ether-type curcumin polymer: There are no particular limitations on the method for producing the ether-type curcumin polymer, and it can be produced by polymerization using a monomer represented by the following general formula (2a) and a monomer represented by the following general formula (2b).

[0061] [ka] (In general formula (2a), R 21 each independently represents a hydrogen atom or a methoxy group.

[0062] [ka] (In general formula (2b), R 22 represents a C1 to C6 alkylene group. 23 and R 24 each independently represents a halogen atom.

[0063] (2-3-1) Monomer represented by general formula (2a): The monomer represented by the general formula (2a) is a monomer such as curcumin or a curcumin derivative, and is similar to the monomer represented by the general formula (1a).

[0064] In general formula (2a), R 21 is R in general formula (2) 21 is the same as

[0065] (2-3-2) Monomer represented by general formula (2b): Examples of the monomer represented by the general formula (2b) include ethylene bromide, 1,4-dibromobutane, and 1,6-dibromohexane.

[0066] In general formula (2b), R 22 is R in general formula (1). 22 is the same as

[0067] The polymerization method is not particularly limited, and any conventionally known method can be appropriately employed. For example, various polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization are possible.

[0068] The organic solvent used in the polymerization reaction is not particularly limited, but examples thereof include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and dimethyl sulfoxide (DMSO).

[0069] The polymerization initiator is also not particularly limited, and examples thereof include cesium carbonate, potassium carbonate, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), tetrabutylammonium bromide (TBAB), tetraphenylphosphonium bromide (TPPB), and tetraphenylphosphonium chloride (TPPC).

[0070] (2-4) Use of the curcumin polymer of the second invention: The uses of the curcumin polymer of the second invention are not particularly limited and can be used in a variety of industrial products, including, for example, optical components such as organic electroluminescence elements, optical waveguides, and high refractive index materials for microlenses.

[0071] (3) Curcumin polymer of the third invention (urethane-type curcumin polymer): (3-1) The curcumin polymer of the third invention has a structure represented by the following general formula (3):

[0072] [ka] (In general formula (3), R 31 each independently represents a hydrogen atom or a methoxy group, and R 32 represents a phenylene group, and n3 represents a number from 2 to 100.

[0073] The curcumin polymer of the third invention is a resin material made from this polymer that has heat resistance and a high refractive index, and furthermore, this polymer does not contain any halogens other than fluorine and sulfur.

[0074] R in general formula (3) 31 Each of the groups independently represents a hydrogen atom or a methoxy group. When the group is a methoxy group, a resin material having better heat resistance and refractive index can be obtained. Furthermore, a curcumin polymer having solubility in solvents and film-forming properties can be obtained.

[0075] R in general formula (3) 32 represents a phenylene group. Among these, when a phenylene group is used, a resin material having better heat resistance and refractive index can be obtained. Furthermore, a curcumin polymer having solubility in solvents and film-forming properties can be obtained.

[0076] In general formula (3), n3 represents a number from 2 to 100, and preferably a number from 10 to 100. Within this range, the number average molecular weight of the curcumin polymer becomes large, and a resin material having good heat resistance and refractive index can be obtained.

[0077] (3-2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) The number-average molecular weight (Mn) of the curcumin polymer of the third invention is not particularly limited, but can be 1,000 to 50,000, preferably 3,000 to 10,000. By setting the number-average molecular weight (Mn) within the above range, a resin material with better heat resistance and refractive index can be obtained. Furthermore, a curcumin polymer with solubility in solvents and film-forming properties can be obtained.

[0078] The molecular weight distribution (ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn)) of the curcumin polymer of the third invention is not particularly limited, but can be 1.0 to 5.0, preferably 1.0 to 4.0. By setting the molecular weight distribution within the above range, a resin material with better heat resistance and refractive index can be obtained. Furthermore, a curcumin polymer with solubility in solvents and film-forming properties can be obtained.

[0079] (3-3) Preparation of urethane-type curcumin polymer: There are no particular limitations on the method for producing the urethane-type curcumin polymer, and it can be produced by polymerization using a monomer represented by the following general formula (3a) and a monomer represented by the following general formula (3b).

[0080] [ka] (In general formula (3a), R 31 each independently represents a hydrogen atom or a methoxy group.

[0081] [ka] (In general formula (3b), R 32 represents a phenylene group.

[0082] (3-3-1) Monomer represented by general formula (3a): The monomer represented by the general formula (3a) is a monomer such as curcumin or a curcumin derivative, and is similar to the monomer represented by the general formula (1a).

[0083] In general formula (3a), R 31 is R in general formula (3). 31 is the same as

[0084] (3-3-2) Monomer represented by general formula (3b): The monomer represented by general formula (3b) is a diisocyanate compound, more specifically, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, etc.

[0085] In general formula (3b), R 32 is R in general formula (3). 32 is the same as

[0086] The polymerization method is not particularly limited, and any conventionally known method can be appropriately employed. For example, various polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization are possible.

[0087] The organic solvent used in the polymerization reaction is not particularly limited, but examples thereof include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and dimethyl sulfoxide (DMSO).

[0088] The polymerization initiator is also not particularly limited, but examples thereof include cesium carbonate, triethylamine, dibutyltin (IV) dilaurate, and tetrabutylammonium bromide.

[0089] (3-4) Use of the curcumin polymer of the third invention: The uses of the curcumin polymer of the third invention are not particularly limited and can be used in a variety of industrial products, including, for example, optical components such as organic electroluminescence elements, optical waveguides, and high refractive index materials for microlenses.

[0090] (4) Curcumin polymer of the fourth invention (ether ester type curcumin polymer): (4-1) The curcumin polymer of the fourth invention has a structure represented by the following general formula (4).

[0091] The curcumin polymer of the fourth invention is a resin material made from this polymer that has heat resistance and also has a high refractive index.

[0092] [ka] (In general formula (4), R 41 each independently represents a hydrogen atom or a methoxy group, and R 42 represents a group represented by the following general formula (5) or a group represented by the following general formula (6), and R 51 represents a C1 to C6 alkylene group, and n4 represents a number from 2 to 100.

[0093] [ka] (In general formula (5), R 43 each independently represents a hydrogen atom or a methoxy group, and the wavy line represents a bonding site.

[0094] [ka] (In general formula (6), R 44 represents a sulfur atom or a group represented by the following general formula (7), and X 1 each independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and the wavy line represents a bonding site.

[0095] [ka] (In general formula (7), R 45 and R 46 each independently represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a trifluoromethyl group, or a methoxy group, and the wavy line represents a bonding site.

[0096] R in general formula (4) 41 each independently represents a hydrogen atom or a methoxy group. Either of these groups can provide a resin material having good heat resistance and refractive index.

[0097] R in general formula (4) 42 represents a group represented by general formula (5) or a group represented by general formula (6). Either of these groups can provide a resin material with good heat resistance and refractive index.

[0098] In general formula (4), n4 represents a number from 2 to 100, and preferably a number from 10 to 100. Within this range, the number average molecular weight of the curcumin polymer becomes large, and a resin material having good heat resistance and refractive index can be obtained.

[0099] (4-2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) The number average molecular weight (Mn) of the curcumin polymer of the fourth invention is not particularly limited, but can be set to 1,000 to 50,000, and preferably 3,000 to 10,000. By setting the number average molecular weight (Mn) within the above range, a resin material having better heat resistance and refractive index can be obtained.

[0100] The molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)) of the curcumin polymer of the fourth invention is not particularly limited, but can be 1.0 to 6.0, preferably 1.0 to 4.0. By setting the molecular weight distribution within the above range, a resin material with better heat resistance and refractive index can be obtained.

[0101] (4-3) Preparation of ether ester curcumin polymer: The method for producing the ether ester type curcumin polymer is not particularly limited, but for example, the ether ester type curcumin polymer can be produced by a method comprising: a first step of reacting a monomer represented by the following general formula (4a) with a monomer represented by the following general formula (4b) to produce an ester type monomer; and a second step of polymerizing the obtained ester type monomer with a monomer represented by the following general formula (4c) or a monomer represented by the following general formula (4d).

[0102] [ka] (In general formula (4a), R 41 each independently represents a hydrogen atom or a methoxy group.

[0103] [ka] (In general formula (4b), R 51 represents a C1 to C6 alkylene group. 52 and R 53 each independently represents a halogen atom.

[0104] [ka] (In general formula (4c), R 43 each independently represents a hydrogen atom or a methoxy group.

[0105] [ka] (In general formula (4d), R 44 represents a sulfur atom or a group represented by the following general formula (4d-1), and X 1 each independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.

[0106] [ka] (In general formula (4d-1), R 45 and R46 each independently represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a trifluoromethyl group, or a methoxy group, and the wavy line represents a bonding site.

[0107] (4-3-1) First step: The monomer represented by general formula (4a) used in the first step is a monomer such as curcumin or a curcumin derivative, and is similar to the monomer represented by general formula (1a).

[0108] In general formula (4a), R 41 is R in general formula (4). 41 is the same as

[0109] Examples of the monomer represented by the general formula (4b) used in the first step include butylacetyl bromide and 3-bromopropionyl chloride.

[0110] In general formula (4b), R 51 is R in general formula (4). 51 is the same as

[0111] In this step, the method for producing the ester type monomer is not particularly limited, and any conventionally known method can be appropriately adopted.

[0112] (4-3-2) Second step: Examples of the monomer represented by general formula (4c) used in the second step include curcumin and bisdemethoxycurcumin.

[0113] In general formula (4c), R 43 is R in general formula (5) 43 is the same as

[0114] Examples of the monomer represented by general formula (4d) used in the second step include bisphenol A, tetraiodobisphenol A, and bis-4-hydroxyphenyl thioether.

[0115] In general formula (4d), R 44 is R in general formula (6) 44 is the same as

[0116] In this step, the method for polymerizing the ester-type monomer and each monomer is not particularly limited, and a conventionally known method can be appropriately adopted. For example, the polymerization form may be various methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization.

[0117] The organic solvent used in the polymerization reaction is not particularly limited, but examples thereof include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and dimethyl sulfoxide (DMSO).

[0118] The polymerization initiator is not particularly limited either, but examples thereof include cesium carbonate and tetraphenylphosphonium chloride (TPPC).

[0119] (4-4) Use of the curcumin polymer of the fourth invention: The uses of the curcumin polymer of the fourth invention are not particularly limited and can be used in a variety of industrial products, including, for example, optical components such as organic electroluminescence elements, optical waveguides, and high refractive index materials for microlenses. [Example]

[0120] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "%" is by mass unless otherwise specified.

[0121] <Ester-type curcumin polymer> The synthesis method of the ester-type curcumin polymer is shown below.

[0122] Example 1: Synthesis of poly(CCM-co-IPD): A test tube was charged with 0.184 g (0.5 mmol) of curcumin (hereinafter sometimes referred to as "CCM") and a stir bar, and the atmosphere was replaced with nitrogen. A mixed solution of 0.151 g (1.25 mmol) of triethylamine (TEA) as a catalyst and 1.0 mL of dimethylformamide (DMF) as a solvent was then added to the test tube with a syringe and stirred for 15 minutes in an ice bath. A mixed solution of 0.101 g (0.5 mmol) of isophthaloyl dichloride (IPD) and 0.5 mL of DMF was then added dropwise with a syringe and stirred at room temperature for 24 hours to obtain a reaction solution. The curcumin used was manufactured by Sanwa Chemical Co., Ltd.

[0123] The resulting reaction solution was diluted with DMF and added dropwise to a 1N HCl aqueous solution to cause reprecipitation, followed by membrane filtration. The residue was then washed with water, methanol, and diethyl ether, in that order. It was then dried overnight at 100°C using a vacuum oven to obtain 0.240 g of a yellow solid (yield: 95%).

[0124] The obtained yellow solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0125] IR (KBr, cm -1 ):543(ν,aromatic),721(ν,aromatic),1198(ν,C=O),1253(ν,C=O),1625(ν,C=C),1742(ν,C=O),3438(ν,C=O)

[0126] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.86(s),6.23(s),6.74-8.11(m),8.25-8.86(m),9.73(s)

[0127] IR analysis was performed using an FT / IR 4600 manufactured by JASCO Corporation. 1 For the H-NMR analysis, a 400 MHz-NMR (JOEL ECS-400K or JOEL ECZ-400K) manufactured by JEOL Ltd. was used, as in the following examples.

[0128] Example 2: Synthesis of poly(CCM-co-IPD): A test tube was charged with 0.184 g (0.5 mmol) of curcumin and a stir bar, and the atmosphere was replaced with nitrogen. A mixed solution of 0.151 g (1.25 mmol) of triethylamine (TEA) as a catalyst and 2.5 mL of NMP as a solvent was added to the test tube with a syringe and stirred in an ice bath for 15 minutes. A mixed solution of 0.101 g (0.5 mmol) of isophthaloyl dichloride (IPD) and 0.5 mL of NMP was then added dropwise with a syringe and stirred at room temperature for 24 hours to obtain a reaction solution.

[0129] The resulting reaction solution was diluted with DMF and added dropwise to a 1N HCl aqueous solution to reprecipitate, followed by membrane filtration. The residue was then washed with water, methanol, and diethyl ether, in that order. It was then dried overnight at 100°C using a vacuum oven to obtain 0.197 g of a yellow solid (yield: 79%).

[0130] The obtained yellow solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0131] IR (KBr, cm -1 ):547(ν,aromatic),720(ν,aromatic),1255(ν,C=O),1627(ν,C=C),1744(ν,C=O),3443(ν,C=O)

[0132] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.86(s),6.21(s),6.84-7.90(m),8.03-8.44(m),9.72(s),16.23(s)

[0133] Example 3: Synthesis of poly(CCM-co-TPD): A test tube was placed with 0.184 g (0.5 mmol) of curcumin and a stir bar, and the atmosphere was replaced with nitrogen. A mixed solution of 0.151 g (1.25 mmol) of triethylamine (TEA) as a catalyst and 1.0 mL of DMF as a solvent was added to the test tube with a syringe and stirred for 15 minutes in an ice bath. Subsequently, a mixed solution of 0.101 g (0.5 mmol) of terephthaloyl dichloride (TPD) and 0.5 mL of DMF was added dropwise with a syringe and stirred at room temperature for 24 hours to obtain a reaction solution.

[0134] The resulting reaction solution was diluted with DMF and reprecipitated by dropping it into a 1N HCl aqueous solution, followed by membrane filtration. The residue was then washed with water, methanol, and diethyl ether, in that order. It was then dried overnight at 100°C using a vacuum oven, yielding 0.210 g of a yellow solid (yield: 84%).

[0135] The obtained yellow solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0136] IR (KBr, cm -1 ):546(ν,aromatic),720(ν,aromatic),1253(ν,C=O),1625(ν,C=C),1744(ν,C=O),3444(ν,C=O)

[0137] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.86(s),6.21(s),6.70-7.76(m),8.03-8.44(m),9.72(s)

[0138] Example 4: Synthesis of poly(CCM-co-TPD): A test tube was charged with 0.184 g (0.5 mmol) of curcumin and a stir bar, and the atmosphere was replaced with nitrogen. A mixed solution of 0.151 g (1.25 mmol) of triethylamine (TEA) as a catalyst and 2.5 mL of NMP as a solvent was added to the test tube with a syringe and stirred in an ice bath for 15 minutes. Subsequently, a mixed solution of 0.101 g (0.5 mmol) of terephthaloyl dichloride (TPD) and 0.5 mL of NMP was added dropwise with a syringe and stirred at room temperature for 24 hours to obtain a reaction solution.

[0139] The resulting reaction solution was diluted with DMF and reprecipitated by dropping it into a 1N HCl aqueous solution, followed by membrane filtration. The residue was then washed with water, methanol, and diethyl ether, in that order. It was then dried overnight at 100°C using a vacuum oven, yielding 0.235 g of a yellow solid (yield: 94%).

[0140] The obtained yellow solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0141] IR (KBr, cm -1 ):545(ν,aromatic),722(ν,aromatic),1253(ν,C=O),1624(ν,C=C),1746(ν,C=O),3439(ν,C=O)

[0142] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.87(s),6.24(s),6.79-7.85(m),8.13-8.44(m),9.72(s),16.26(s)

[0143] Example 5: Synthesis of poly(CCM-co-OD): A test tube was charged with 0.184 g (0.5 mmol) of CCM, 0.126 g (1.25 mmol) of triethylamine (TEA) as a base, and 2.5 ml of N-methyl-2-pyrrolidone (NMP) (2.5 ml) dehydrated with molecular sieves as a solvent, and the mixture was purged with nitrogen. The mixture was stirred in an ice bath for 0.5 hours to obtain a reaction solution. Next, a solution of 0.063 g (0.5 mmol) of oxalyl chloride (OD) in 0.5 ml of NMP was added dropwise to the reaction solution, and the reaction was carried out at room temperature for 24 hours under a nitrogen atmosphere.

[0144] After the reaction was completed, the mixture was diluted with a small amount of NMP, and reprecipitated by adding dropwise 0.1N HCl. The precipitate (residue) was then filtered off by membrane filtration. The residue was then washed with water, methanol, and diethyl ether in that order, and dried under reduced pressure using a vacuum heating dryer to obtain 0.14 g of a brown solid (yield: 63%).

[0145] IR (KBr, cm -1 ):1113(ν,CO),1509(ν,C=C),1585(ν,C=O),1626(ν,C=C),1752(ν,C=O),2933(ν,CH)

[0146] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.83(s),6.05(s),6.73-7.56(m),9.66(s),16.41(s)

[0147] (Reference Example 1) Synthesis of poly(CCM-co-SD): A test tube was charged with 0.184 g (0.5 mmol) of CCM, 0.126 g (1.25 mmol) of TEA as a base, and 2.5 ml of NMP (dehydrated with molecular sieves) as a solvent. The atmosphere was replaced with nitrogen and the mixture was stirred in an ice bath for 0.5 hours to obtain a reaction solution. Next, a solution of 0.077 g (0.5 mmol) of succinic acid chloride (SD) in 0.5 ml of NMP was added dropwise to the reaction solution, and the reaction was carried out at room temperature for 24 hours under a nitrogen atmosphere.

[0148] After the reaction was completed, the mixture was diluted with a small amount of NMP, dropped into 0.1N HCl to reprecipitate, and the precipitate (residue) was separated by membrane filtration. The residue was then washed with water, methanol, and diethyl ether in that order, and dried under reduced pressure using a vacuum heating dryer to obtain 0.19 g of a yellow-green solid (yield: 88%).

[0149] IR (KBr, cm -1 ):1119(ν,CO),1416(ν,CH),1509(ν,C=C),1758(ν,C=O),2919(ν,CH)

[0150] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):2.97(s),3.83(s),6.27(s),6.71-7.88(m),9.70(s),16.19(s)

[0151] Example 6: Synthesis of poly(CCM-co-FD): A test tube was charged with 0.184 g (0.5 mmol) of CCM, 0.126 g (1.25 mmol) of TEA as a base, and 2.5 ml of NMP (dehydrated with molecular sieves) as a solvent. The mixture was then purged with nitrogen and stirred in an ice bath for 0.5 hours. Next, a solution of fumarolic acid chloride (FD) (0.5 mmol, 0.076 g) in 0.5 ml of NMP was added dropwise to the reaction solution, and the reaction was continued at room temperature for 24 hours under a nitrogen atmosphere to obtain a reaction solution.

[0152] After the reaction was completed, the mixture was diluted with a small amount of NMP, dropped into 0.1N HCl to reprecipitate, and the precipitate (residue) was separated by membrane filtration. The residue was then washed with water, methanol, and diethyl ether in that order, and dried under reduced pressure using a vacuum heating dryer to obtain 0.14 g of a brown solid (yield: 59%).

[0153] IR (KBr, cm -1 ):1121(ν,CO),1517(ν,C=C),1589(ν,C=C),1731(ν,C=O),2935(ν,CH)

[0154] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):2.97(s),3.83(s),6.27(s),6.71-7.88(m),9.70(s),16.19(s)

[0155] (Reference Example 2) Synthesis of poly(CCM-co-AD): A test tube was charged with 0.184 g (0.5 mmol) of CCM, 0.126 g (1.25 mmol) of TEA as a base, and 2.5 ml of NMP (dehydrated with molecular sieves) as a solvent. The mixture was then purged with nitrogen and stirred in an ice bath for 0.5 hours. Next, a solution of adipic acid chloride (AD) (0.5 mmol, 0.091 g) in 0.5 ml of NMP was added dropwise to the reaction solution, and the reaction was carried out at room temperature for 24 hours under a nitrogen atmosphere to obtain a reaction solution.

[0156] After the reaction was completed, the mixture was diluted with a small amount of NMP and reprecipitated by adding dropwise 0.1N HCl. The precipitate (residue) was then filtered off by membrane filtration. The residue was then washed with water, methanol, and diethyl ether in that order, and dried under reduced pressure using a vacuum heating dryer to obtain 0.20 g of an orange solid (yield: 80%).

[0157] IR (KBr, cm -1 ):1120(ν,CO),1416(ν,CH),1509(ν,C=C),1585(ν,C=O),1758(ν,C=O),2934(ν,CH)

[0158] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):1.77(quintet),2.66(t),3.84(s),6.13(s),6.71-7.79(m),9.71(s),16.21(s)

[0159] <Ether-type curcumin polymer> The synthesis method of the ether-type curcumin polymer is shown below.

[0160] Example 7: Synthesis of poly(CCM-co-EB): A test tube was charged with 0.184 g (0.5 mmol) of CCM, 0.407 g (1.25 mmol) of cesium carbonate as a base, 0.016 g (0.05 mmol) of tetrabutylammonium bromide (TBAB) as a catalyst, and a stir bar, and the atmosphere was replaced with nitrogen. Then, 1.0 mL of N-methyl-2-pyrrolidone (NMP) as a solvent was added to the test tube with a syringe and stirred at 80 °C for 2 hours. Then, a mixed solution of 0.094 g (0.5 mmol) of ethylene bromide and 0.5 mL of NMP was added dropwise with a syringe, and the mixture was stirred at 80 °C for 24 hours to obtain a reaction solution.

[0161] The resulting reaction solution was diluted with NMP, dropped into a 1N HCl aqueous solution to reprecipitate, and then filtered through a membrane. The residue was then washed with water and dried overnight at 100°C using a vacuum heating dryer to obtain 0.12 g of a brown solid (yield: 60%).

[0162] IR (KBr, cm -1 ):539(v,CH of aromatic),851(v,CH of aromatic),1022(v,OH),1,255(v,OC),1510(v,CH of aromatic),1658(v,C=C)

[0163] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.76(s),4.07-4.42(m),6.19-7.65(m)

[0164] Example 8: Synthesis of poly(CCM-II-co-EB): A test tube was charged with 0.154 g (0.5 mmol) of CCM-II (curcumin derivative, manufactured by Sanwa Chemical Co., Ltd.), 0.407 g (1.25 mmol) of cesium carbonate as a base, 0.016 g (0.05 mmol) of tetrabutylammonium bromide (TBAB) as a catalyst, and a stir bar, and the atmosphere was replaced with nitrogen. Then, 1.0 mL of N-methyl-2-pyrrolidone (NMP) as a solvent was added to the test tube with a syringe and stirred at 80 °C for 2 hours. A mixed solution of 0.094 g (0.5 mmol) of ethylene bromide and 0.5 mL of NMP was then added dropwise with a syringe and stirred at 80 °C for 24 hours to obtain a reaction solution.

[0165] The resulting reaction solution was diluted with NMP, dropped into 1N HCl aqueous solution to reprecipitate, and then filtered through a membrane. The residue was then washed with water and dried overnight at 100°C using a vacuum heating dryer to obtain 0.070g of a brown solid (yield: 42%).

[0166] The obtained brown solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0167] IR (KBr, cm -1 ):504(v,CH of aromatic),835(v,CH of aromatic),1026(v,OH),1,223(v,OC),1509(v,CH of aromatic),1625(v,C=C),3530(v,OH)

[0168] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):4.06-4.71(m),5.30-8.09(m),8.90-9.89(m)

[0169] <Ether ester type curcumin polymer> The synthesis method of the ether ester type curcumin polymer is shown below.

[0170] Example 9 Synthesis of poly(CCM-BAB-co-CCM): First, 1.84 g (5 mmol) of curcumin (CCM) was added to a 30 ml recovery flask and the atmosphere was replaced with nitrogen. Next, 1.09 g (15 mmol) of triethylamine (TEA) and 10 ml of tetrahydrofuran (THF) solvent dehydrated through molecular sieves were added to the recovery flask using a syringe, and the mixture was stirred in an ice bath under a nitrogen atmosphere for 1 hour. Then, 3.02 g (15 mmol) of bromoacetyl bromide (BAB) was added dropwise, and the mixture was allowed to react at room temperature for 24 hours under a nitrogen atmosphere.

[0171] After the reaction was completed, the reaction mixture was filtered, diluted with ethyl acetate, and washed with 0.1N aqueous HCl and saturated aqueous sodium bicarbonate in that order. The organic layer was dried with anhydrous magnesium sulfate and then concentrated with an evaporator.

[0172] The reaction solution was then analyzed by thin layer chromatography (TLC) using a 1:9 mixture of ethyl acetate and toluene. A spot was identified at an Rf value of approximately 0.5, indicating the target product. The product was then separated and concentrated by column chromatography using a 1:9 mixture of ethyl acetate and toluene as the developing solvent. The concentrate was then reprecipitated in hexane and filtered using a membrane filter. The product was then dried under reduced pressure at 70°C, yielding 3.04 g of a yellow powder (curcumin bromoacetyl bromide derivative (CCM-BAB)) (yield: 51%).

[0173] Next, 0.092 g (0.25 mmol) of CCM, 0.203 g (0.063 mmol) of cesium carbonate as a base, 0.009 g (0.025 mmol) of tetraphenylenephosphonium chloride (TPPC) as a catalyst, and 0.5 ml of dimethyl sulfoxide (DMSO) as a solvent were added to a test tube with a ground glass, and the mixture was stirred for 1 hour at 120°C under a nitrogen atmosphere. After that, a solution of curcumin bromoacetyl bromide derivative (CCM-BAB) in 0.25 ml of DMSO was added dropwise, and the reaction was carried out under a nitrogen atmosphere at 120°C.

[0174] After the reaction was completed, the product was reprecipitated in 1N HCl and filtered off using a membrane filtration system. The residue was then washed with water and dried under reduced pressure using a vacuum dryer, yielding 0.109 g of a brown solid (yield: 53%).

[0175] IR (KBr, cm -1 ):812(v,CH of aromatic),1029(v,OH),1,266(v,CO),1512(v,C=C ),1733(v,C=O)

[0176] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.60-3.88(m),4.53-4.74(m),6.19-7.70(m)

[0177] Example 10: Synthesis of poly(CCM-BAB-co-BPA): First, a curcumin bromoacetyl bromide derivative (CCM-BAB) was prepared in the same manner as in Example 9.

[0178] Next, 0.057 g (0.25 mmol) of bisphenol A (BPA), 0.203 g (0.063 mmol) of cesium carbonate as a base, 0.009 g (0.025 mmol) of TPPC as a catalyst, and 0.5 ml of DMSO as a solvent were added to a test tube with a ground glass, and the mixture was stirred for 1 hour at 120°C under a nitrogen atmosphere. After that, a solution of CCM-BAB in 0.25 ml of DMSO was added dropwise, and the reaction was carried out under a nitrogen atmosphere at 120°C.

[0179] After the reaction was completed, the product was reprecipitated in 1N HCl and filtered off using a membrane filtration system. The residue was then washed with water and dried under reduced pressure using a vacuum dryer to obtain 0.078 g of a brown solid (yield: 46%).

[0180] IR (KBr, cm -1 ):1,207(v,CO),1262(v,CH of aromatic),1511(v,C=C),1730(v,C=O)

[0181] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):1.52(s),3.63-3.88(m),4.40-4.84(m),6.48-7.64(m),9.10(s)

[0182] Example 11 Synthesis of poly(CCM-BAB-co-TIBPA): First, a curcumin bromoacetyl bromide derivative (CCM-BAB) was prepared in the same manner as in Example 9.

[0183] Next, 0.182 g (0.25 mmol) of tetraiodobisphenol A (TIBPA), 0.203 g (0.063 mmol) of cesium carbonate as a base, 0.009 g (0.025 mmol) of TPPC as a catalyst, and 0.5 ml of DMSO as a solvent were added to a ground test tube and stirred for 1 hour at 120°C under a nitrogen atmosphere. After that, a solution of CCM-BAB in 0.25 ml of DMSO was added dropwise, and the reaction was carried out under a nitrogen atmosphere at 120°C.

[0184] After the reaction was completed, the product was reprecipitated in 1N HCl and filtered using a membrane filtration system. The residue was then washed with water and then methanol, and dried under reduced pressure using a vacuum dryer to obtain 0.06 g of a brown solid (yield: 20%).

[0185] IR (KBr, cm -1 ):1169(v,CI)1,208(v,CO),1267(v,CH of aromatic),1512(v,C=C),1717(v,C=O)

[0186] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):1.53(s),3.53-3.88(m),4.39(s),6.60-7.06(m),7.55-7.67(m)9.25(s)

[0187] Example 12 Synthesis of poly(CCM-BAB-co-BHPS): First, a curcumin bromoacetyl bromide derivative (CCM-BAB) was prepared in the same manner as in Example 9.

[0188] Next, 0.054 g (0.25 mmol) of bis(4-hydroxyphenyl) sulfide (BHPS), 0.203 g (0.063 mmol) of cesium carbonate as a base, 0.009 g (0.025 mmol) of TPPC as a catalyst, and 0.5 ml of DMSO as a solvent were added to a test tube with a ground glass, and the mixture was stirred for 1 hour at 120°C under a nitrogen atmosphere. After that, a solution of CCM-BAB in 0.25 ml of DMSO was added dropwise, and the reaction was carried out under a nitrogen atmosphere at 120°C.

[0189] After the reaction was completed, the product was reprecipitated in 1N HCl and filtered off using a membrane filtration system. The residue was then washed with water and dried under reduced pressure using a vacuum dryer to obtain 0.110 g of a brown solid (yield: 64%).

[0190] IR (KBr, cm -1 ):1,213(v,CO),1262(v,CH of aromatic),1511(v,C=C),1729(v,C=O),2540(v,SH)

[0191] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.71-3.86(m),4.62(s),6.52-7.25(m),7.52-7.65(m)9.60(s)

[0192] <Urethane-type curcumin polymer> The synthesis method of the urethane-type curcumin polymer is shown below.

[0193] (Reference Example 3) Synthesis of poly(CCM-co-HDI): A test tube with a frosted surface was charged with 0.184 g (0.5 mmol) of curcumin (CCM) and a stir bar, and the inside of the tube was replaced with nitrogen. Then, a mixed solution of 0.84 g (0.5 mmol) of hexamethylene diisocyanate (HDI), 0.031 g (0.05 mmol) of dibutyltin dilaurate as a catalyst, and 1.0 mL of DMF as a solvent was added to the test tube with a syringe and stirred at 60°C for 24 hours to obtain a reaction solution.

[0194] The resulting reaction solution was diluted with DMF, then dropped into diethyl ether to reprecipitate, and filtered through a membrane. The residue was then washed with diethyl ether and dried overnight using a vacuum dryer to obtain 0.141 g of an orange solid (yield: 52%).

[0195] The obtained orange solid was subjected to IR analysis, and the results are shown below.

[0196] IR (KBr, cm -1 ):539(v,CH of aromatic),836(v,CH of aromatic),962(v,CH of aromatic),1031(v,CH),1123(v,CN),1202(v,C=O),1509(v,CH of aromatic),1625(v,NH),1725(v,C=O),2856(v,CH),2931(v,CH),3319(v,NH),3540(v,OH)

[0197] (Reference Example 4) Synthesis of poly(CCM-II-co-HDI): A test tube was charged with 0.154 g (0.5 mmol) of CCM-II (a curcumin derivative) and a stir bar, and the inside of the tube was replaced with nitrogen. A mixed solution of 0.84 g (0.5 mmol) of hexamethylene diisocyanate (HDI), 0.031 g (0.05 mmol) of dibutyltin dilaurate as a catalyst, and 1.0 mL of DMF as a solvent was added to the test tube with a syringe, and the mixture was stirred at 60°C for 24 hours to obtain a reaction solution.

[0198] The resulting reaction solution was diluted with DMF, then dropped into diethyl ether to reprecipitate, and filtered through a membrane. The residue was then washed with diethyl ether and dried overnight using a vacuum dryer to obtain 0.238 g of an orange solid (yield: 92%).

[0199] The obtained orange solid was subjected to IR analysis, and the results are shown below.

[0200] IR (KBr, cm -1 ):512(v,CH of aromatic),820(v,CH of aromatic),967(v,CH of aromatic),1113(v,CN),1215(v,C=O),1500(v,CH of aromatic),1628(v,NH),1702(v,C=O),2856(v,CH),2933(v,CH),3037(v,NH),3329(v,OH)

[0201] Example 13 Synthesis of poly(CCM-co-1,4-PDI) (II): A test tube with a frosted surface was charged with 0.184 g (0.5 mmol) of curcumin (CCM) and a stir bar, and the atmosphere was replaced with nitrogen. A mixed solution of 0.80 g (0.5 mmol) of 1,4-phenylenediisocyanate (1,4-PDI), 0.031 g (0.05 mmol) of dibutyltin dilaurate as a catalyst, and 1.0 mL of DMF as a solvent was then added to the test tube with a syringe and stirred at 80°C for 24 hours to obtain a reaction solution.

[0202] The resulting reaction solution was diluted with DMF, then dropped into diethyl ether to reprecipitate, and filtered through a membrane. The residue was then washed with diethyl ether and dried overnight using a vacuum dryer to obtain 0.112 g of an orange solid (yield: 42%).

[0203] The obtained orange solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0204] IR (KBr, cm -1 ):820(v,CH of aromatic),1193(v,C=O),1223(v,C=O),1296(v,CH),1508(v,CH of aromatic),1627(v,NH),1750(v,C=O),3290(v,NH),3520(v,OH)

[0205] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):3.83(s),6.10(s),6.73-7.36(m),7.54-7.69(m),8.30-8.66(m),10.12(s)

[0206] Example 14 Synthesis of poly(CCM-II-co-1,4-PDI): A test tube was charged with 0.154 g (0.5 mmol) of CCM-II (a curcumin derivative) and a stir bar, and the atmosphere was replaced with nitrogen. A mixed solution of 0.80 g (0.5 mmol) of 1,4-phenylenediisocyanate (1,4-PDI), 0.031 g (0.05 mmol) of dibutyltin dilaurate as a catalyst, and 1.0 mL of DMF as a solvent was added to the test tube with a syringe and stirred at 80°C for 24 hours to obtain a reaction solution.

[0207] The resulting reaction solution was diluted with DMF, then dropped into diethyl ether to reprecipitate, and filtered through a membrane. The residue was then washed with diethyl ether and dried overnight using a vacuum dryer to obtain 0.234 g of an orange solid (yield: 72%).

[0208] The obtained orange solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0209] IR (KBr, cm -1):518(v,CH of aromatic),829(v,CH of aromatic),1209(v,C=O),1302(v,C=O),1506(v,CH of aromatic),1631(v,NH),1778(v,C=O),3300(v,NH)

[0210] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):6.31(s),6.56-8.59(m),8.41(s),10.26(s)

[0211] Example 15 Synthesis of poly(CCM-co-1,3-PDI) (III): A test tube with a frosted rim was charged with 0.184 g (0.5 mmol) of curcumin (CCM) and a stir bar, and the atmosphere was replaced with nitrogen. A mixture of 0.80 g (0.5 mmol) of 1,3-phenylenediisocyanate (1,3-PDI), 0.005 g (0.05 mmol) of triethylamine (TEA) as a catalyst, and 1.5 mL of DMF as a solvent was then added to the test tube with a syringe and stirred at 80°C for 24 hours to obtain a reaction solution.

[0212] The resulting reaction solution was diluted with DMF, then dropped into 1N HCl aqueous solution to reprecipitate, and filtered through a membrane. The residue was then washed with water and dried overnight at 100°C using a vacuum heating dryer, yielding 0.250 g of a yellow solid (yield: 95%).

[0213] The obtained yellow solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0214] IR (KBr, cm -1 ):1512(v,CH of aromatic),1681(v,NH),1778(v,C=O),2843(v,CH),3336(v,NH)

[0215] 1H-NMR(DMSO-d6,400MHz,δ(ppm)):3.87(s),6.06(s),6.73-7.36(m),7.49-7.79(m),8.86(s),9.96(s)

[0216] Example 16 Synthesis of poly(CCM-II-co-1,3-PDI): A test tube was charged with 0.154 g (0.5 mmol) of CCM-II (a curcumin derivative) and a stir bar, and the atmosphere was replaced with nitrogen. A mixture of 0.80 g (0.5 mmol) of 1,3-phenylenediisocyanate (1,3-PDI), 0.005 g (0.05 mmol) of triethylamine (TEA) as a catalyst, and 1.5 mL of DMF as a solvent was added to the test tube with a syringe and stirred at 80°C for 24 hours to obtain a reaction solution.

[0217] The resulting reaction solution was diluted with DMF, then dropped into 1N HCl aqueous solution to reprecipitate, and filtered through a membrane. The residue was then washed with water and dried overnight at 100°C using a vacuum oven to obtain 0.203 g of a yellow solid (yield: 84%).

[0218] The obtained yellow solid was analyzed by IR and 1 H-NMR analysis was performed, and the results are shown below.

[0219] IR (KBr, cm -1 ):1512(v,CH of aromatic),1666(v,NH),1733(v,C=O),2810(v,CH),3301(v,NH)

[0220] 1 H-NMR(DMSO-d6,400MHz,δ(ppm)):6.06(s),6.54-7.89(m),8.62(s),10.11(s)

[0221] (Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)) The number average molecular weight (Mn) and weight average molecular weight (Mw) of each polymer in Examples 1 to 16 and Reference Examples 1 to 4 were measured using size exclusion chromatography (SEC), and the molecular weight distribution (Mw / Mn) was calculated. The measurements were performed using an HLC-8220 manufactured by Tosoh Corporation. The results are shown in Table 1.

[0222] Specifically, the analysis was carried out under the following conditions: Column: Showa Denko Shodex asahipak GF-510 HQ + GF-310 x 2 Standard: Polystyrene Eluent: 20 mM lithium bromide, 20 mM phosphate in dimethylformamide Detector: HLC-8220 built-in RI·UV-8220 (280nm)

[0223] (Heat resistance) For each of the polymers in Examples 1 to 16 and Reference Examples 1 to 4, the thermal decomposition onset temperature (T d i ), 5% weight loss temperature (T d 5% ), and 10% weight loss temperature (T d 10% ) was measured. For the measurement, a TGA-50 manufactured by Shimadzu Corporation was used.

[0224] Specifically, 3 mg of each polymer was placed in an aluminum pan and measured under a nitrogen atmosphere at a temperature increase rate of 10° C. / min. The results are shown in Table 1.

[0225] As shown in Table 1, it was confirmed that all the polymers of the examples had heat resistance.

[0226] [Table 1]

[0227] (Solubility) Of the synthesized polymers, the solubility in various solvents of each example shown in Table 2 was evaluated.

[0228] Specifically, approximately 1 mg of the synthesized polymer was placed in a sample tube, and 5 mL of each solvent was added, followed by evaluation according to the following criteria. In Table 2, "-" indicates "not soluble", "+-" indicates "partially soluble", and "+" indicates "soluble".

[0229] [Table 2]

[0230] In Table 2, "NMP" is N-methyl-2-pyrrolidone (manufactured by Wako), "DMF" is N,N-dimethylformamide (manufactured by Wako), "MeOH" is methanol (manufactured by Wako), "THF" is tetrahydrofuran (manufactured by Wako), "chloroform" is manufactured by Wako, and "PGME" is propylene glycol monomethyl ether (manufactured by TCI).

[0231] (Film formation test) Of the synthesized polymers, a film-forming test was carried out for each of the Examples and Reference Examples shown in Table 3, and the film-forming properties of each polymer were evaluated.

[0232] Specifically, the polymers of each Example and Reference Example were dissolved in DMF or PGME to prepare solutions, and uniform thin films were formed by spin coating using a spin coater. The film thickness of each thin film was measured using a spectroscopic ellipsometer (Photonic Lattice, Inc., Model No. SE-101).

[0233] As a result of this test, as shown in Table 3, it was possible to form a thin film in each of the Examples and Reference Examples, and it was found that the polymers of each of the Examples and Reference Examples have excellent film-forming properties.

[0234] (refractive index) Of the synthesized polymers, for each of the Examples and Reference Examples shown in Table 3, the refractive index at 636 nm of the thin films prepared in the above-mentioned film formation test was measured using a spectroscopic ellipsometer (manufactured by Photonic Lattice, Inc., model number SE-101).

[0235] The polymers of the Examples and Reference Examples shown in Table 3 have a refractive index of 1.70 or more at 636 nm, which is very high.

[0236] [Table 3]

[0237] As shown in Tables 1 and 3, it was found that the curcumin polymer of the present invention has heat resistance and can be used to prepare resin parts having a high refractive index. [Industrial Applicability]

[0238] The curcumin polymer of the present invention can be used in various industrial products, for example, in optical components such as organic electroluminescence elements, optical waveguides, and high refractive index materials for microlenses.

Claims

1. A curcumin polymer having a structure represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), R １１ each independently represents a hydrogen atom or a methoxy group, R １２ is a single bond, C ２ ~C ６ represents an alkenylene group or a phenylene group, and n1 represents a number from 2 to 100.

2. A curcumin polymer having a structure represented by the following general formula (2): 【Chemistry 2】 (In general formula (2), R ２１ each independently represents a hydrogen atom or a methoxy group, R ２２ is C １ ~C ６ and n2 is a number from 2 to 100.

3. A curcumin polymer having a structure represented by the following general formula (3): 【Transformation 3】 (In general formula (3), R ３１ each independently represents a hydrogen atom or a methoxy group, R ３２ represents a phenylene group, and n3 represents a number from 2 to 100.

4. A curcumin polymer having a structure represented by the following general formula (4): 【Chemistry 4】 (In general formula (4), R ４１ each independently represents a hydrogen atom or a methoxy group, R ４２ represents a group represented by the following general formula (5) or a group represented by the following general formula (6), and R ５１ is C １ ~C ６ and n4 represents a number from 2 to 100. 【Transformation 5】 (In general formula (5), R ４３ each independently represents a hydrogen atom or a methoxy group, and the wavy line represents a bonding site. 【Transformation 6】 (In general formula (6), R ４４ represents a sulfur atom or a group represented by the following general formula (7), and X １ each independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and the wavy line represents a bonding site. 【Transformation 7】 (In general formula (7), R ４５ and R ４６ each independently represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a trifluoromethyl group, or a methoxy group, and the wavy line represents a bonding site.

5. The curcumin polymer according to any one of claims 1 to 4, which is used for optical components.

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