Bismuth-containing polymer compound and method for producing same

Abstract

The present invention makes it possible to provide a method for producing a polymer compound that contains a repeating unit represented by formula (3), said method comprising a step for reacting, in the presence of an oxidizing agent, a bismuth compound represented by formula (1) and a dicarboxylic acid compound represented by formula (2). (In formula (1), X1-X3 may be the same or different and each represent a C6-14 aromatic hydrocarbon group.) (In formula (2), R represents a divalent organic group.) (In formula (3), X1-X3 and R are as defined above. n represents an integer of 2 or more.)

Description

Bismuth-containing polymer compounds and methods for producing the same

[0001] The present invention relates to optical materials such as filters, plastic lenses, prisms, and optical fibers, which are transparent components that need to shield from radiation, and to polymer compounds that are particularly suitable for use in filters and plastic lenses, as well as to methods for producing the same.

[0002] Generally, alpha rays can be easily shielded using thin materials such as paper, and beta rays using thin metal plates such as aluminum. However, gamma rays and X-rays can be weakened by using thick plates of lead or iron as shielding materials. On the other hand, these materials are not transparent, making it impossible to see what is on the other side of the shielding material.

[0003] In this context, in advanced medical settings where CT (computed tomography) and PET (positron emission tomography) equipment are used for medical treatment, and in nuclear power plants, it is necessary to transmit images visually or via cameras to confirm the situation at the site where radiation is being used, while adequately shielding from radiation. Therefore, materials that are transparent to visible light while adequately shielding from radiation are required.

[0004] Given such requirements, lead-containing glass is generally known as a transparent and radiation-shielding material (Patent Documents 1 and 2). However, unlike plastics, lead-containing glass has poor processability and moldability, and its high specific gravity makes it unsuitable for applications requiring lightweight materials.

[0005] On the other hand, rubber sheets filled with heavy metals such as barium sulfate, cerium oxide, and barium oxide are commonly known as radiation shielding plastics (Patent Document 3). However, because these rubber sheets are opaque, it is not possible to confirm the site where radiation is being used.

[0006] Therefore, there is a need for plastic materials that are lightweight, easy to process, and possess radiation shielding capabilities. In addition, there is a need for thermoplastic materials that can be bent and thermoformed.

[0007] Japanese Patent Publication No. 2016-008146, Japanese Patent Publication No. 2014-062863, Japanese Patent Publication No. 2015-224967

[0008] The present invention aims to solve at least one of the problems in the prior art described above. Furthermore, the present invention aims to provide a thermoplastic polymer compound that can be bent and thermoformed and provide a transparent optical material having radiation shielding capabilities.

[0009] In view of these circumstances, the present inventors have conducted extensive research and have found that the above problems can be solved by using a compound with a specific structure containing bismuth and a dicarboxylic acid compound. Specifically, the present invention includes the following embodiments: <1> A method for producing a polymer compound containing a repeating unit represented by the following formula (3), comprising the step of reacting a bismuth compound represented by the following formula (1) and a dicarboxylic acid compound represented by the following formula (2) in the presence of an oxidizing agent. (In formula (1), X １ ~X ３ (These may be the same or different groups, and represent aromatic hydrocarbon groups with 6 to 14 carbon atoms.) (In formula (2), R represents a divalent organic group.) (In formula (3), X １ ~X ３ R is the same as above. n represents an integer of 2 or more.) <2> The manufacturing method according to <1> above, wherein the bismuth compound is triphenylbismuth. <3> The manufacturing method according to <1> or <2> above, wherein the dicarboxylic acid compound is at least one selected from the group consisting of aromatic dicarboxylic acid compounds, methyl succinic acid, phenyl succinic acid, and spicrispolic acid. <4> The manufacturing method according to <3> above, wherein the aromatic dicarboxylic acid compound is a compound represented by the following formula (4) or (5). (In formula (4), A １ ~A ６ (These may be the same or different atoms, and represent either a hydrogen atom or a halogen atom.) (In formula (5), m represents an integer of 2 to 8.) <5> The production method according to any one of <1> to <4> above, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, m-chloroperbenzoic acid, peracetic acid, tert-butyl hydroperoxide, tert-butyl peroxide, sodium perborate, and iodobenzene diacetate. <6> A polymer compound containing a repeating unit represented by the following formula (6). (In formula (6), X １ ~X ３ may be the same or different and each represents an aromatic hydrocarbon group having 6 to 14 carbon atoms. Y represents a linking group represented by the following formula (7) or (8). n represents an integer of 2 or more.) (In formula (7), A １ ~A ６ may be the same or different and each represents a hydrogen atom or a halogen atom.) (In formula (8), m represents an integer of 2 to 8.) <7> The polymer compound according to <6> above, wherein in formula (6), X １ ~X ３ each independently represents a naphthyl group or a phenyl group. <8> The polymer compound according to <7> above, wherein in formula (6), X １ ~X ３ represents a phenyl group. <9> The polymer compound according to any one of <6> to <8> above, wherein in formula (7), A １ ~A ６ represents a fluorine atom. <10> The polymer compound according to any one of <6> to <8> above, wherein in formula (8), m is 6. <11> The polymer compound according to <6> above, wherein the repeating unit represented by formula (6) is a repeating unit represented by the following formula (9). (In formula (9), n represents an integer of 2 or more.) <12> The polymer compound according to <6> above, wherein the repeating unit represented by formula (6) is a repeating unit represented by the following formula (10). (In formula (10), n represents an integer of 2 or more.) <13> A polymer compound containing a repeating unit represented by any one of the following formulas (11) to (17). <14> It is an optical material containing the polymer compound described in any one of <6> to <13> above. <15> It is a color change material containing the polymer compound described in any one of <6> to <13> above.

[0010] By using the polymer compound of the preferred embodiment of the present invention, it is possible to provide a transparent optical material that can be bent or thermoformed and has radiation shielding ability.

[0011] The polymer compound obtained in Example 1 １ It is an H-NMR spectrum. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 1. It is an XPS spectrum of the polymer compound obtained in Example 1. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 2. It is a transmission spectrum of a film formed using the polymer compound obtained in Example 1 on a polyethylene terephthalate film. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 18. The polymer compound obtained in Example 19 １ It is an H-NMR spectrum. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 19. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 20. The polymer compound obtained in Example 21 １ It is an H-NMR spectrum. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 21. The polymer compound obtained in Example 22 １ It is an H-NMR spectrum. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 22. The polymer compound obtained in Example 23 １ It is an H-NMR spectrum. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 23. The polymer compound obtained in Example 24 １ It is an H-NMR spectrum. It is an IR spectrum (ATR method) of the polymer compound obtained in Example 24.

[0012] Hereinafter, the present invention will be described in detail by exemplifying production examples, examples, etc. However, the present invention is not limited to the exemplified production examples, examples, etc., and can be changed to any aspect as long as it does not deviate significantly from the content of the present invention.

[0013] One embodiment of the present invention includes a step of reacting a bismuth compound represented by the following formula (1) with a dicarboxylic acid compound represented by the following formula (2) in the presence of an oxidizing agent, and is a method for producing a polymer compound containing a repeating unit represented by the following formula (3). In formula (1), X １ to X ３ may be the same or different and each represents an aromatic hydrocarbon group having 6 to 14 carbon atoms. X １ to X ３ preferably each independently represents a naphthyl group or a phenyl group, and more preferably all of X １ to X ３ represent phenyl groups. In formula (2), R represents a divalent organic group. In formula (3), X １ to X ３ and R have the same meanings as described above. In formula (3), n represents an integer of 2 or more, preferably represents an integer of 3 to 200, and more preferably represents an integer of 5 to 30.

[0014] The present invention is characterized by using the dicarboxylic acid compound represented by the above formula (2). When a monocarboxylic acid compound is used instead of the dicarboxylic acid compound, no polymerization reaction occurs between the bismuth compound represented by the above formula (1), and only monomers can be obtained. On the other hand, the present inventors have found that when the dicarboxylic acid compound as described above is used, a polymerization reaction proceeds between the bismuth compound represented by the above formula (1), and a polymer compound can be obtained. Moreover, the obtained polymer compound can be bent and thermoformed, can provide a transparent optical material having radiation shielding ability, and has the advantage of being thermoplastic.

[0015] In the present invention, any dicarboxylic acid compound represented by formula (2) above can be used without particular limitation, but it is preferable that it be at least one selected from the group consisting of aromatic dicarboxylic acid compounds, methyl succinic acid, phenyl succinic acid, and spicrispolic acid. In particular, in formula (2), R preferably represents a divalent organic group having an aromatic ring. In the present invention, as described in Examples 19, 21, 23, and 24 below, two types of dicarboxylic acid compounds may be used, and three or more types may also be used. In the present invention, it is more preferable that the aromatic dicarboxylic acid compound is a compound represented by the following formula (4) or (5). In formula (4), A １ ~A ６ These may be the same or different atoms, and represent either a hydrogen atom or a halogen atom. A １ ~A ６ Preferably, represents a hydrogen atom or a fluorine atom, and more preferably A １ ~A ６ All of these represent fluorine atoms. In formula (5), m represents an integer from 2 to 8, preferably an integer from 3 to 7, and more preferably 6.

[0016] The oxidizing agent used in the present invention is not particularly limited, but is preferably selected from the group consisting of hydrogen peroxide, m-chloroperbenzoic acid, peracetic acid, tert-butyl hydroperoxide, tert-butyl peroxide, sodium perborate, and iodobenzene diacetic acid, and more preferably one or more selected from the group consisting of tert-butyl hydroperoxide and hydrogen peroxide. The amount of oxidizing agent used is preferably 1 to 50 times the number of moles of the dicarboxylic acid compound represented by formula (2) used, and more preferably 5 to 20 times the number of moles.

[0017] In the present invention, the reaction temperature may be at room temperature, while cooling, or while adding heat. The reaction temperature is preferably -20 to 50°C, and more preferably 0 to 30°C. Furthermore, in the present invention, it is preferable to react the bismuth compound represented by formula (1) with the dicarboxylic acid compound represented by formula (2) while stirring, and the stirring time is preferably 1 to 50 hours, and more preferably 2 to 24 hours.

[0018] In the present invention, it is preferable to add an organic solvent when reacting the bismuth compound represented by formula (1) with the dicarboxylic acid compound represented by formula (2). The organic solvent used is not particularly limited, but it is preferably one or more selected from the group consisting of chloroform, dichloromethane, tetrahydrofuran, toluene, methanol, 1,4-dioxane, and acetone, and more preferably one or more selected from the group consisting of chloroform and tetrahydrofuran. The amount of organic solvent used is preferably 1 to 200 mL, and more preferably 3 to 50 mL, per 1 mmol of triphenylbismutin.

[0019] In this invention, after the above reaction is complete, a solid polymer compound can be obtained by reprecipitation of the reaction solution with alcohol or by suction filtration. The polymer compound thus obtained is preferably transparent. Annealing the obtained polymer compound at a temperature of 50 to 150°C for about 10 minutes to 5 hours is a preferred treatment to remove strain. Furthermore, the obtained polymer compound may be subjected to surface treatments such as hard coating or anti-reflective coating as needed.

[0020] When manufacturing optical materials using the polymer compound of the present invention, the practicality of the resulting optical material can be further improved by adding additives such as ultraviolet absorbers, antioxidants, adhesion improvers, and mold release agents to the polymer compound.

[0021] Another embodiment of the present invention is a polymer compound comprising repeating units represented by the following formula (6). In formula (6), X１ ~X ３ These may be the same or different, and represent an aromatic hydrocarbon group having 6 to 14 carbon atoms. １ ~X ３ Preferably, each independently represents a naphthyl group or a phenyl group, and more preferably, X １ ~X ３ All of these represent a phenyl group. In formula (6), Y represents a linking group represented by the following formula (7) or (8). n represents an integer of 2 or more, preferably an integer from 3 to 200, and more preferably an integer from 5 to 30. In formula (7), A １ ~A ６ These may be the same or different atoms, and represent either a hydrogen atom or a halogen atom. A １ ~A ６ Preferably, represents a hydrogen atom or a fluorine atom, and more preferably A １ ~A ６ All of these represent fluorine atoms. In formula (8), m represents an integer from 2 to 8, preferably an integer from 3 to 7, and more preferably 6.

[0022] A preferred embodiment of the present invention is a polymer compound comprising repeating units represented by the following formula (9). In equation (9), n is equivalent to the above.

[0023] Another preferred embodiment of the present invention is a polymer compound comprising repeating units represented by the following formula (10). In equation (10), n is equivalent to the above.

[0024] Another preferred embodiment of the present invention is a polymer compound comprising a repeating unit represented by any of the following formulas (11) to (17).

[0025] One embodiment of the present invention is a molded article made using the polymer compound of the present invention. The molded article has applications in advanced medical settings, such as CT (computed tomography) and PET (positron emission tomography) equipment, and in nuclear power plants. It can be used as a radiation shielding plate or shielding filter, or directly as an optical material (component). For example, it can be used in a camera lens to protect the camera sensor from radiation damage and to transmit images with radiation noise removed. These applications include optical materials (components), mechanical parts materials, electrical and electronic parts materials, automotive parts materials, civil engineering and construction materials, molding materials, and various other applications such as paints and adhesives. In particular, optical materials such as lenses including eyeglass lenses, imaging lenses for (digital) cameras, light beam focusing lenses, and light diffusion lenses; transparent glass and cover glass such as LED encapsulants, optical adhesives, bonding materials for optical transmission, prisms, filters, diffraction gratings, watch glass, and cover glass for display devices; display device applications such as substrates for LCDs, organic EL displays, and PDPs, substrates for color filters, substrates for touch panels, display backlights, light guide plates, display protective films, anti-reflective films, and anti-fogging films; recording media such as optical memory and electronic paper; sensor materials such as ultraviolet checkers; light-adjusting materials such as window glass, sunglasses, and automobile window glass; textile products, cosmetic materials, photochromic materials, and other color-changing materials such as printed materials. Among the optical materials mentioned above, optical adhesives, prisms, and coating agents are particularly preferred.

[0026] The present invention will be specifically described by the following examples, but the present invention is not limited to these examples.

[0027] (Example 1) In a round-bottom flask, add triphenylbismutin (0.100 mmol, 0.0440 g) represented by the following structural formula (hereinafter referred to as "BiPh") ３(Sometimes described as "), 2,2-bis(4-carboxyphenyl)hexafluoropropane (0.100 mmol, 0.0392 g), represented by the following structural formula, chloroform (1 mL), and 35% hydrogen peroxide solution (0.2 mL) were added and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the reaction mixture was reprecipitated with methanol to obtain a white solid (yield 0.0305 g, yield 37%).

[0028] The obtained white solid １ The H-NMR spectrum is shown in Figure 1, the IR spectrum (ATR method) is shown in Figure 2, and the XPS spectrum is shown in Figure 3. １ The H-NMR spectrum was measured using an ECX-400 from JEOL Ltd., the diffusion coefficient used to calculate the molecular weight was measured using an ECX-500 from JEOL Ltd., the IR spectrum (ATR method) was measured using an FT / IR-460Plus from JASCO Corporation, and the XPS spectrum was measured using a JPS-9030 from JEOL Ltd. (X-ray: MgKα rays, X-ray intensity: 10kV, 10mA, neutralization gun: 5V, 5mA). Furthermore, the glass transition temperature, determined by differential scanning calorimetry using a DSC220 from Seiko Instruments Corporation (heating rate 10°C / min, under nitrogen atmosphere, second heating process), was 2°C. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula (weight-average molecular weight in polystyrene terms is 7900).

[0029] (Example 2) Triphenylbismutin (0.100 mmol, 0.0440 g), 1,6-bis(4-carboxyphenoxy)hexane (0.100 mmol, 0.0359 g) represented by the following structural formula, tetrahydrofuran (1 mL), and 35% hydrogen peroxide solution (0.2 mL) were added to a round-bottom flask and stirred at room temperature for 24 hours. After the reaction was complete, a white solid was obtained by suction filtration (yield 0.0105 g, yield 13%).

[0030] The IR spectrum (ATR method) of the obtained white solid is shown in Figure 4. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula.

[0031] The white solid obtained in Example 1 was soluble in chloroform. The solution was cast onto a 25 μm thick polyethylene terephthalate film and dried, resulting in a colorless, transparent, flexible thin film 2 μm thick. Figure 5 shows the transmission spectrum of this thin film, measured using the polyethylene terephthalate film support as the baseline. The transmittance above 420 nm exceeded 85%, indicating excellent visible light transmittance.

[0032] The white solid obtained in Example 1 was sandwiched between two 19 μm thick polyimide sheets and molded into pellets of 402 μm and 426 μm thickness using a JASCO MP-1 hand press. These pellets were attached to cellophane tape, and the X-ray transmittance to copper Kα rays (8.0 keV, accelerating voltage 40 kV, irradiation time 60 seconds) was measured using a Rigaku NanoViewer. The X-ray count for cellophane tape alone was 697,047, while the X-ray counts for cellophane tape with pellets obtained from the white solid obtained in Example 1 were 24,573 and 26,525, respectively. The X-ray shielding performance determined from these results was 96.5% and 96.2%, respectively.

[0033] (Examples 3-9) The solvent and oxidizing agent used in Example 1 are those shown in Table 1 below, the temperature and reaction (stirring) time are as shown in Table 1 below, and the oxidizing agent is pH ３ The polymer compound was synthesized in the same manner as in Example 1, except that 20 molar equivalents were used for polymerization relative to Bi. The yields are shown in Table 1 below. The weight-average molecular weight of the polymer compound obtained in Example 7, on a polystyrene basis, was 9200.

[0034]

[0035] (Examples 10-17) The solvent used in Example 1 was changed to chloroform, and the oxidizing agent was H ２ O２ The polymer compound was synthesized in the same manner as in Example 1, except that the equivalent amount of was changed as shown in Table 2 below. The yield is shown in Table 2 below. Note that Example 15 is the same as Example 6.

[0036]

[0037] (Example 18) Triphenylbismutin (0.0995 mmol, 0.0438 g), methylsuccinic acid represented by the following structural formula (0.0976 mmol, 12.9 mg), chloroform (1.0 mL), and 70% tert-butyl hydroperoxide (t-BuOOH) aqueous solution (0.200 mmol, 0.411 mL) were added to a round-bottom flask and stirred at room temperature for 3 hours. After the reaction was complete, the reaction mixture was poured into an excess amount of methanol to obtain 0.0489 g of a white solid precipitate in a yield of 86.2%.

[0038] The IR spectrum (ATR method) of the obtained white solid is shown in Figure 6. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula.

[0039]

[0040] (Example 19) Triphenylbismutin (0.101 mmol, 0.0446 g), methylsuccinic acid (0.0515 mmol, 6.80 mg), 2,2-bis(4-carboxyphenyl)hexafluoropropane (0.0487 mmol, 0.0191 g), chloroform (1.0 mL), and 70% t-BuOOH aqueous solution (0.200 mmol, 0.411 mL) were added to a round-bottom flask and stirred at 0°C under nitrogen for 3 hours. After the reaction was complete, the reaction mixture was poured into an excess amount of methanol to obtain 0.0394 g of a white solid precipitate in a yield of 55.9%.

[0041] The obtained white solid １The 1H-NMR spectrum is shown in Figure 7, and the IR spectrum (ATR method) is shown in Figure 8. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula. The unit ratio of methylsuccinic acid to 2,2-bis(4-carboxyphenyl)hexafluoropropane was found to be 41:59.

[0042]

[0043] (Example 20) Triphenylbismutin (0.999 mmol, 0.4400 g), phenylsuccinic acid represented by the following structural formula (0.998 mmol, 0.1938 g), chloroform (1.0 mL), and 70% t-BuOOH aqueous solution (2.00 mmol, 4.11 mL) were added to a round-bottom flask and stirred at 0°C under nitrogen for 3 hours. After the reaction was complete, the reaction mixture was poured into an excess amount of methanol to obtain 0.4871 g of a white solid precipitate in a yield of 76.3%.

[0044] The IR spectrum (ATR method) of the obtained white solid is shown in Figure 9. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula.

[0045]

[0046] (Example 21) Triphenylbismutin (0.100 mmol, 0.0442 g), phenylsuccinic acid (0.0520 mmol, 0.0101 g), 2,2-bis(4-carboxyphenyl)hexafluoropropane (0.0507 mmol, 0.0199 g), chloroform (1.0 mL), and 70% t-BuOOH aqueous solution (0.200 mmol, 0.411 mL) were added to a round-bottom flask and stirred at 0°C under nitrogen for 3 hours. After the reaction was complete, the reaction mixture was poured into an excess amount of methanol to obtain 0.0529 g of a white solid precipitate in a yield of 71.3%.

[0047] The obtained white solid １The 1H-NMR spectrum is shown in Figure 10, and the IR spectrum (ATR method) is shown in Figure 11. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula. The unit ratio of phenylsuccinic acid to 2,2-bis(4-carboxyphenyl)hexafluoropropane was found to be 32:68.

[0048]

[0049] (Example 22) In a round-bottom flask, triphenylbismutin (1.01 mmol, 0.4426 g), spicrispolic acid represented by the following structural formula (1.00 mmol, 0.3286 g), chloroform (1.0 mL), and 70% t-BuOOH aqueous solution (2.00 mmol, 4.11 mL) were added and the mixture was stirred at 0°C under nitrogen for 3 hours. After the reaction was complete, the reaction solution was poured into an excess amount of methanol, and 0.5501 g of a white solid precipitate was obtained in a yield of 71.3%.

[0050] The obtained white solid １ The 1H-NMR spectrum is shown in Figure 12, and the IR spectrum (ATR method) is shown in Figure 13. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula.

[0051]

[0052] (Example 23) Triphenylbismutin (0.101 mmol, 0.0445 g), spicrispolic acid (0.0515 mmol, 0.0169 g), 2,2-bis(4-carboxyphenyl)hexafluoropropane (0.0497 mmol, 0.0195 g), chloroform (1.0 mL), and 70% t-BuOOH aqueous solution (0.200 mmol, 0.411 mL) were added to a round-bottom flask and stirred at 0°C under nitrogen for 3 hours. After the reaction was complete, the reaction mixture was poured into an excess amount of methanol to obtain 0.0455 g of a white solid precipitate in a yield of 56.2%.

[0053] The obtained white solid １The 1H-NMR spectrum is shown in Figure 14, and the IR spectrum (ATR method) is shown in Figure 15. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula. The unit ratio of spicrispolic acid to 2,2-bis(4-carboxyphenyl)hexafluoropropane was found to be 60:40.

[0054]

[0055] (Example 24) Triphenylbismutin (0.999 mmol, 0.4400 g), 1,6-bis(4-carboxyphenoxy)hexane (0.500 mmol, 0.1791 g), 2,2-bis(4-carboxyphenyl)hexafluoropropane (0.499 mmol, 0.1958 g), chloroform (1.0 mL), and 70% t-BuOOH aqueous solution (0.200 mmol, 0.411 mL) were added to a round-bottom flask and stirred at 0°C under nitrogen for 3 hours. After the reaction was complete, the reaction mixture was poured into an excess amount of methanol to obtain 0.6163 g of a white solid precipitate in a yield of 75.4%.

[0056] The obtained white solid １ The 1H-NMR spectrum is shown in Figure 16, and the IR spectrum (ATR method) is shown in Figure 17. From these results, it was found that the obtained white solid is a polymer compound having repeating units represented by the following formula. The unit ratio of 1,6-bis(4-carboxyphenoxy)hexane to 2,2-bis(4-carboxyphenyl)hexafluoropropane was found to be 51:49.

[0057]

Claims

1. A method for producing a polymer compound containing a repeating unit represented by the following formula (3), comprising the step of reacting a bismuth compound represented by the following formula (1) with a dicarboxylic acid compound represented by the following formula (2) in the presence of an oxidizing agent. (In formula (1), X １ ~X ３ (These may be the same or different groups, and represent aromatic hydrocarbon groups with 6 to 14 carbon atoms.) (In formula (2), R represents a divalent organic group.) (In formula (3), X １ ~X ３ And R are equivalent to the above. n represents an integer greater than or equal to 2.

2. The manufacturing method according to claim 1, wherein the bismuth compound is triphenylbismuth.

3. The method for producing a product according to claim 1, wherein the dicarboxylic acid compound is at least one selected from the group consisting of aromatic dicarboxylic acid compounds, methyl succinic acid, phenyl succinic acid, and spicrispolic acid.

4. The manufacturing method according to claim 3, wherein the aromatic dicarboxylic acid compound is a compound represented by the following formula (4) or (5). (In formula (4), A １ ~A ６ (These may be the same or different atoms, and represent either a hydrogen atom or a halogen atom.) (In equation (5), m represents an integer between 2 and 8.) 5. The manufacturing method according to claim 1, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, m-chloroperbenzoic acid, peracetic acid, tert-butyl hydroperoxide, tert-butyl peroxide, sodium perborate, and iodobenzene diacetic acid.

6. A polymer compound containing a repeating unit represented by the following formula (6). (In formula (6), X １ to X ３ may be the same or different and each represents an aromatic hydrocarbon group having 6 to 14 carbon atoms. Y represents a linking group represented by the following formula (7) or (8). n represents an integer of 2 or more.) (In formula (7), A １ to A ６ may be the same or different and each represents a hydrogen atom or a halogen atom.) (In formula (8), m represents an integer of 2 to 8.) 7. In formula (6), X １ ~X ３ The polymer compound according to claim 6, wherein each of these independently represents a naphthyl group or a phenyl group.

8. In formula (6), X １ ~X ３ The polymer compound according to claim 7, wherein is a phenyl group.

9. In formula (7), A １ ~A ６ The polymer compound according to claim 6, wherein is a fluorine atom.

10. The polymer compound according to claim 6, wherein m is 6 in formula (8).

11. The polymer compound according to claim 6, wherein the repeating unit represented by formula (6) is the repeating unit represented by the following formula (9). (In equation (9), n represents an integer greater than or equal to 2.) 12. The polymer compound according to claim 6, wherein the repeating unit represented by formula (6) is the repeating unit represented by the following formula (10). (In equation (10), n represents an integer greater than or equal to 2.) 13. A polymer compound containing a repeating unit represented by any of the following formulas (11) to (17).

14. An optical material comprising the polymer compound described in any one of claims 6 to 13.

15. A color-changing material comprising the polymer compound described in any one of claims 6 to 13.

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