Bifunctionalized monomer of phenylpropanoid, polymer, production method of bifunctionalized monomer of phenylpropanoid, production method of polymer, and production method of bisphenol

Abstract

To provide a monomer capable of polymerizing by homopolymerization as a raw material of a biomass-derived constituent.SOLUTION: A bifunctionalized monomer of phenylpropanoid is expressed by formula (1a), (1b), or (1c). In the formulae (1a), (1b) and (1c), R1 to R5 each mutually independently express a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amide group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl groupe, an aralkyl group, or an aryl group, and L expresses a linker group.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a difunctionalized phenylpropanoid monomer, a polymer, a method for producing a difunctionalized phenylpropanoid monomer, a method for producing a polymer, and a method for producing a bisphenol. [Background technology]

[0002] From the viewpoint of realizing carbon neutrality, plastic production that does not depend on fossil resources is desired. Lignin-derived biomass is the most abundant aromatic compound on earth, and is expected to be an alternative raw material to petroleum in plastic production. Among lignin-derived biomass, many phenylpropanoids have a styrene-type structure and are suitable for polymerization. Phenylpropanoids are the main components of essential oils, and since the extraction and purification technology has been established, they are a group of raw material compounds that can be used in large quantities as plastic raw materials. Anethole, isoeugenol, etc. are known as phenylpropanoids contained in essential oils.

[0003] As polymerization reactions of phenylpropanoids, copolymerization by cationic polymerization (Non-Patent Document 1) and copolymerization by radical polymerization (Non-Patent Document 2) have been reported so far. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] JACS, 2007, 129, 9586; Polymer Journal, 2015, 47, 527 [Non-Patent Document 2] Herk, Jena et al. Polym. Chem. 2020, 11, 5630 Summary of the Invention [Problem to be solved by the invention]

[0005] As disclosed in Non-Patent Documents 1 and 2, there have been reports of polymer synthesis using anethole as a raw material for polymerization reactions of phenylpropanoids, but most of them are addition polymerization (cationic polymerization, radical polymerization) at double bond sites. Phenylpropanoids such as anethole have a β-substituted styrene skeleton, making homopolymerization by addition polymerization difficult. For this reason, anethole has not been homopolymerized in the past, and only copolymerization with other monomers has been reported.

[0006] However, polymerization by copolymerization of phenylpropanoids has a problem in that it reduces the phenylpropanoid content in the polymer, i.e., the biomass content, compared to polymerization by homopolymerization.

[0007] In order to solve such problems, an object of the present invention is to provide a monomer that can be produced from a biomass-derived component as a raw material and that can be polymerized by homopolymerization. Another object of the present invention is to provide a polymer obtained by homopolymerizing the monomer, a method for producing the monomer, a method for producing the polymer, and a method for producing bisphenol. [Means for solving the problem]

[0008] The above problems are solved by the present invention, which is specified as follows. 1. Bifunctional phenylpropanoid monomers represented by formula (1a), (1b) or (1c). [ka] (In formulas (1a), (1b) and (1c), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; L represents a linker group. 2. The bifunctional monomer of phenylpropanoid according to 1 above, wherein L in the formulas (1a), (1b) and (1c) is a linker group having a siloxane skeleton represented by formula (2a), a linker group having a phosphonate skeleton represented by formula (2b), >C=O, -S-, -SO-, -SO2-, -Se-, -Te-, or a linker group represented by any of formulas (2c) to (2n). [ka] [ka] [ka] (In formulas (2a) to (2n), R 20 ~R 29 , R 34 ~R 60 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; In formula (2b), E represents O, S or Se; In formulas (2m) and (2n), n represents a natural number. 3. A polymer represented by any one of formulas (4) to (6). [ka] (In formulas (4) to (6), R 1 , R 2 , R 18 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; L represents a linker group; n represents a natural number.) 4. The polymer according to 3 above, wherein L in the formulas (4) to (6) is a linker group having a siloxane skeleton represented by formula (2a), a linker group having a phosphonate skeleton represented by formula (2b), >C=O, -S-, -SO-, -SO2-, -Se-, -Te-, or a linker group represented by any of formulas (2c) to (2n). [ka] [ka] [ka] (In formulas (2a) to (2n), R 20 ~R 29 , R 34 ~R 60 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; In formula (2b), E represents O, S or Se; In formulas (2m) and (2n), n represents a natural number. 5. A method for producing a bifunctional monomer of phenylpropanoid according to 1 above, by reacting a hydroxyl group of a phenylpropanoid represented by formula (7a), (7b) or (7c) with a linker. [ka] (In formulas (7a), (7b) and (7c), R 1 ~R 5each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. 6. The method for producing a bifunctional monomer of phenylpropanoid according to 5 above, wherein the linker is a linker having a siloxane skeleton represented by formula (8) or a linker having a phosphonate skeleton represented by formula (9). [ka] (In formula (8), R 20 , R 21 , R 30 and R 31 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. In formula (9), E represents O, S or Se; R 22 , R 32 and R 33 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. 7. A method for producing the polymer described in 3 above by subjecting a bifunctional monomer of the phenylpropanoid described in 1 above to cycloaddition polymerization or metathesis polymerization. 8. Decomposing the polymer represented by the formula (4) described in 3 above to produce a bisphenol represented by the formula (10). Decomposing the polymer represented by the formula (5) to produce a bisphenol represented by the formula (11), or A method for producing a bisphenol represented by formula (12) by decomposing the polymer represented by formula (6). [ka] (In formulas (10) to (12), R 1 , R 2 , R 18 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. Effect of the Invention

[0009] According to the present invention, it is possible to provide a monomer that can be produced from a biomass-derived component as a raw material and that can be polymerized by homopolymerization. Furthermore, according to the present invention, it is possible to provide a polymer obtained by homopolymerizing the monomer, a method for producing the monomer, a method for producing the polymer, and a method for producing bisphenol. [Brief description of the drawings]

[0010] [Figure 1] 1 is a graph showing the results of TG measurement in Example 5. [Diagram 2] 1 is a graph showing the results of TG measurement in Example 6. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Next, the embodiments of the present invention will be described in detail with reference to the drawings. It should be understood that the present invention is not limited to the following embodiments, and that appropriate changes and improvements in the design may be made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention.

[0012] <Bifunctional phenylpropanoid monomer> The difunctionalized phenylpropanoid monomer according to this embodiment is represented by formula (1a), (1b) or (1c). [ka] (In formulas (1a), (1b) and (1c), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; L represents a linker group.

[0013] The bifunctional monomer of phenylpropanoid according to the present embodiment is produced using phenylpropanoid as the main component, and therefore can be produced using biomass-derived components as the raw material. In addition, as shown in formulas (1a), (1b) and (1c), the monomer has a structure in which two phenylpropanoids are linked by a linker group. Therefore, the content of phenylpropanoid in the monomer is high. In addition, the monomer, which will be described in detail later, can achieve sufficiently high reactivity even with a β-substituted styrene skeleton by using cyclic addition polymerization or metathesis polymerization instead of addition polymerization at the olefin site, and can be polymerized by homopolymerization. Therefore, the content of phenylpropanoid in the polymer is high. As a result, a polymer with a high biomass content can be produced.

[0014] R of the bifunctionalized phenylpropanoid monomer according to this embodiment 1 ~R 4 R is preferably, independently of the other, a hydrogen group, an alcohol group, or an alkoxy group (particularly a methoxy group) so that lignin-derived phenylpropanoids can be utilized. 5 is preferably a hydrogen group, an ester group, an ether group, or a carbonyl group.

[0015] The linker group (L) of the bifunctional monomer of phenylpropanoid according to the present embodiment is generated by the reaction of the linker described below with the hydroxyl group of the phenylpropanoid, and its structure depends on the structure of the raw material linker. The linker group (L) is preferably a linker group having a siloxane skeleton represented by formula (2a) or a linker group having a phosphonate skeleton represented by formula (2b). Since the siloxane skeleton has low toxicity, it is expected to create a plastic material with high biocompatibility. In addition, a polymer having a phosphonate skeleton is expected to become a flame-retardant material. In addition, a polymer having a phosphonate skeleton exhibits high birefringence, and it is expected to create a functional optical plastic material. In addition, the linker group (L) may be >C=O, -S-, -SO-, -SO2-, -Se-, -Te-, or a linker group represented by any of formulas (2c) to (2n). [ka] [ka] [ka] (In formulas (2a) to (2n), R 20 ~R 29 , R 34 ~R 60 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; In formula (2b), E represents O, S or Se; In formulas (2m) and (2n), n represents a natural number.

[0016] R of the linker group (L) of formula (2a) 20 and R 21From the viewpoints of monomer stability and ease of synthesis reaction, it is preferable that each of them independently represents an isopropyl group.

[0017] <Method for producing bifunctional phenylpropanoid monomers> The bifunctional monomer of phenylpropanoid according to the present embodiment can be produced by heating the phenylpropanoid represented by formula (7a), (7b) or (7c) and a linker in a basic solvent to react the hydroxyl group of the phenylpropanoid with the linker. With this configuration, the phenylpropanoid derived from essential oil can be converted into a monomer in a short process. [ka] (In formulas (7a), (7b) and (7c), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

[0018] The basic solvent is not particularly limited, but for example, a base such as sodium hydroxide, triethylamine, or N,N-dimethylaminopyridine can be added to an organic solvent such as NMP (N-methyl-2-pyrrolidone), ethyl acetate, or diethyl ether.

[0019] The heat treatment can be appropriately adjusted depending on the raw material used. The treatment temperature may be room temperature, or may be appropriately heated. The treatment time may be about 12 to 48 hours.

[0020] The linker used in the production of the bifunctional monomer of the phenylpropanoid according to the present embodiment is not particularly limited as long as it is a linker capable of binding two phenylpropanoids by reacting with the hydroxyl group of the phenylpropanoid. As the linker, a linker having a siloxane skeleton represented by formula (8) or a linker having a phosphonate skeleton represented by formula (9) can be used. [ka] (In formula (8), R 20 , R 21 , R 30 and R 31 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. In formula (9), E represents O, S or Se; R 22 , R 32 and R 33 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

[0021] R of a linker having a siloxane skeleton represented by formula (8) 30 and R 31 are preferably each independently a chlorine atom from the viewpoints of the availability of the precursor, reactivity, and stability with the reagent. In addition, formulas (13a), (13b), and (13c) show reaction formulas for the synthesis of bifunctional monomers of phenylpropanoids using dichlorosilane as a linker, respectively. [ka] [ka] [ka]

[0022] R of the linker having a phosphonate skeleton represented by formula (9) 32 and R 33 are preferably each independently a chlorine atom from the viewpoints of the availability of the precursor, reactivity, and stability with the reagent. In addition, formulas (14a), (14b), and (14c) show reaction formulas for the synthesis of bifunctional monomers of phenylpropanoids using (thio)phosphonic acid dichloride as a linker, respectively. [ka] [ka] [ka]

[0023] <Polymer> The polymer according to this embodiment is represented by any one of formulas (4) to (6). [ka] In formulas (4) to (6), R 1 , R 2 , R 18 and the linker group (L) are R in the above-mentioned bifunctional monomer of phenylpropanoid. 1 ~R 3 and the linker group (L). Furthermore, n represents a natural number, and may be, for example, an integer of 2 to 1,000.

[0024] The polymer according to the present embodiment is produced by homopolymerization of a difunctional monomer of phenylpropanoid, and has a high phenylpropanoid content in the polymer. Thus, the polymer according to the present embodiment can be a polymer with a high biomass content.

[0025] The polymer according to the present embodiment is characterized by thermal stability derived from the aromatic ring, structural specificity derived from having an alicyclic structure in the main chain, and electronic specificity derived from the elements, and is therefore particularly suitable for applications such as engineering plastics, optical films, and gas-permeable films.

[0026] <Polymer manufacturing method> The polymer according to this embodiment can be produced by cycloaddition polymerization or metathesis polymerization of a bifunctional monomer of phenylpropanoid. As an example, the synthesis reaction formula of the polymer according to this embodiment using the bifunctional monomer of phenylpropanoid shown in formula (1d) is shown in formula (15). [ka]

[0027] In this way, by using cycloaddition polymerization or metathesis polymerization instead of addition polymerization at the olefin site, sufficiently high reactivity can be achieved even with a β-substituted styrene skeleton, and polymerization by homopolymerization becomes possible. Here, the definitions of cycloaddition polymerization and metathesis polymerization in the present invention are shown below. Cycloaddition polymerization: A reaction induced by electron transfer or energy transfer in which two unsaturated bonds (double bonds) form a σ bond. This reaction does not involve oxidation-reduction when comparing the original bond formation system with the product system, and does not involve any elimination components. Metathesis polymerization: A reaction in which two double bonds rearrange via an olefin metathesis mechanism to form a new double bond with an elimination component.

[0028] Cycloaddition polymerization of a bifunctional monomer of phenylpropanoid can be selectively carried out under the following conditions. That is, first, a bifunctional monomer of phenylpropanoid and a polymerization initiator are charged into a reaction vessel, and an organic solvent is added to carry out the reaction under conditions of -10°C to room temperature to carry out cycloaddition polymerization. As the polymerization initiator, a catalytic amount of an oxidizing agent is used (e.g., tris(4-bromophenyl)aminium hexachloride antimonate, iodobenzene diacetate, iron(III) chloride, iron(III) perchlorate, etc.). It can also be carried out by adding a photoredox catalyst and irradiating light. As the photoredox catalyst, for example, iridium(III) bis[2-(2,4-difluorophenyl)-5-methylpyridine-N,C20]-4,40-di-tert-butyl-2,20-bipyridine hexafluorophosphate and the like can be mentioned. As the organic solvent, toluene, dichloromethane, acetonitrile, etc. can be mentioned.

[0029] The metathesis polymerization of the bifunctionalized phenylpropanoid monomer can be selectively carried out under the following conditions. That is, first, the bifunctionalized phenylpropanoid monomer and the catalyst are charged into a reaction vessel, and an organic solvent is added and reacted at room temperature to 100° C. to carry out the metathesis polymerization. Examples of the catalyst include Grubbs Catalyst (registered trademark) M204 and M300, and examples of the organic solvent include toluene, dichloromethane, and acetonitrile.

[0030] According to the method for producing a polymer according to the present embodiment, the synthesized novel monomer is rapidly polymerized by the addition of a catalytic amount of a polymerization initiator, so that the polymer can be obtained in a good yield.

[0031] <Bisphenol manufacturing method> In the method for producing bisphenol according to the present embodiment, the polymer represented by the above formula (4) is decomposed to produce bisphenol represented by formula (10). Alternatively, the polymer represented by the above formula (5) is decomposed to produce bisphenol represented by formula (11). Alternatively, the polymer represented by the above formula (6) is decomposed to produce bisphenol represented by formula (12). The decomposition reaction formula for these is shown in formula (16). According to this configuration, it becomes possible to decompose the main chain of the polymer by an acid or a base, and bisphenol can be produced efficiently. Furthermore, the bisphenol obtained in this manner can be used (upcycling) as a new monomer. [ka] R in formulas (10) to (12) 1 , R 2 , R 18 are R in formulas (4) to (6), respectively. 1 , R 2 , R 18 is the same as:

[0032] The decomposition reaction shown in formula (16) can be carried out at room temperature (20 to 25°C) by adding the polymer represented by formulas (4) to (6) to an organic solvent or water to which an acid or base has been added. The temperature of the decomposition reaction may be higher than room temperature. As the acid, hydrochloric acid, hydrogen bromide, etc. can be used. As the base, NaOH, KOH, Bu4NF, NHF, pyridine, etc. can be used. As the organic solvent, acetone, acetonitrile, DMSO, THF, etc. can be used. Water can also be used as a single solvent or as a mixed solvent with an organic solvent. According to the method for producing bisphenol according to this embodiment, since decomposition is possible at room temperature, the polymer can be decomposed under mild conditions, and bisphenol can be produced easily. EXAMPLES

[0033] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

[0034] <Example 1> Monomer synthesis (1) 5.9032 g (39.829 mmol) of trans-anethole, 0.178 g (0.374 mmol) of tri(pentafluorophenyl)borane, and 55 mL of dichloromethane were added to a two-neck flask. After cooling the solution to 0°C, 7.6 mL (48 mmol) of triethylsilane was added dropwise, and the mixture was allowed to react for 30 minutes while returning to room temperature. After adding 40 mL of a 1 M THF solution of tetrabutylammonium fluoride, the mixture was extracted with dichloromethane and subjected to a gradient column with hexane and ethyl acetate, and 3.945 g (29.40 mmol, 73% yield) of the target product was obtained as a pale yellow solid. The chemical formula of the product was confirmed by a gas chromatography / mass spectrometer (GCMS) and a nuclear magnetic resonance (NMR) device. The reaction formula is shown in formula (17). [ka]

[0035] Next, 1.80 g (13.4 mmol) of the demethylated trans-anethole obtained was added to a two-neck flask, and then nitrogen replacement was performed. Then, 30 mL of diethyl ether, 1.5022 g (14.845 mmol) of TEA (triethylamine), and 51.8 mg (0.423 mmol) of DMAP (4-dimethylaminopyridine) were added in this order. Next, 1.2786 g (6.905 mmol) of dichlorodiisopropylsilane was added dropwise, and the reaction was carried out at room temperature (RT) for 18 hours. After that, it was extracted with dichloromethane and subjected to a gradient column with hexane and ethyl acetate, and 1.9794 g (5.20 mmol, 75% yield) of a transparent liquid monomer was obtained. The chemical formula of the product was confirmed by a gas chromatography / mass spectrometer (GCMS) and a nuclear magnetic resonance (NMR) device. The reaction formula is shown in formula (18). [ka]

[0036] <Example 2> Monomer synthesis (2) After adding 3.0392 g (18.509 mmol) of isoeugenol to a two-neck flask, nitrogen replacement was performed. Then, 40 mL of diethyl ether, 1.8826 g (18.604 mmol) of TEA, and 40.5 mg (0.331 mmol) of DMAP were added in this order. Next, 1.2339 g (6.6639 mmol) of dichlorodiisopropylsilane was added dropwise, and the reaction was carried out at room temperature for 112 hours. After that, it was extracted with ethyl acetate and a gradient column was performed with hexane and ethyl acetate, and 2.7424 g (6.2233 mmol, 93% yield) of a transparent liquid monomer was obtained. The chemical formula of the product was confirmed by a gas chromatography / mass spectrometer (GCMS) and a nuclear magnetic resonance (NMR) device. The reaction formula is shown in formula (19). [ka]

[0037] <Example 3> Monomer synthesis (3) 1.0421g (4.6890mmol) of ethyl 4-hydroxy-3-methoxycinnamate was added to a two-neck flask, and then nitrogen replacement was performed. 25mL of diethyl ether, 0.5404g (5.340mmol) of TEA, and 31.7mg (0.259mmol) of DMAP were added in this order, and then 0.3968g (2.143mmol) of dichlorodiisopropylsilane was added dropwise to carry out the reaction. After the reaction, the mixture was extracted with dichloromethane and subjected to a gradient column with toluene and ethyl acetate, and 0.9652g (1.733mmol, 80% yield) of a white solid monomer was obtained. The chemical formula of the product was confirmed by a gas chromatography / mass spectrometer (GCMS) and a nuclear magnetic resonance (NMR) device. The reaction formula is shown in formula (20). [ka]

[0038] <Example 4> Monomer synthesis (4) After adding 1.9029g (10.68mmol) of trans-p-methyl coumarate to a two-neck flask, nitrogen replacement was performed. Then, 40mL of diethyl ether, 1.4914g (14.73mmol) of TEA, and 119.9mg (0.98mmol) of DMAP were added in this order. Next, 653.2g (3.53mmol) of dichlorodiisopropylsilane was added dropwise, and the reaction was performed at room temperature for 84 hours. After that, it was extracted with dichloromethane and a gradient column was performed with toluene and ethyl acetate, and 1.2232g (2.61mmol, 74% yield) of a white solid monomer was obtained. The chemical formula of the product was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (21). [ka]

[0039] <Example 5> Polymer synthesis (1) A 0.192M solution was prepared by dissolving 94.3mg (0.247mmol) of monomer in 1.3mL of dichloromethane. 5mol% of Magic Blue was added while nitrogen was simply sealed in to initiate polymerization. After the polymerization reaction proceeded for 60 minutes, the reaction mixture was dissolved in 1mL of dichloromethane and slowly dropped into 20mL of methanol for reprecipitation, yielding 81.1mg (86% yield) of a 4-membered ring-containing polymer. The physical properties of the polymer were Mn (number average molecular weight) = 6700, Mw (weight average molecular weight) = 73600, and PDI (polydisperse index) = 10.99. The chemical formula of the product (polymer) was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (22). In addition, the polymer was subjected to thermogravimetric analysis (TG measurement) using a thermogravimetric differential thermal analyzer (EXSTAR TG / DTA6200 manufactured by Seiko Instruments Inc. and STA7200RV manufactured by Hitachi High-Technologies Corporation). The results of the TG measurement are shown in Figure 1. Figure 1 shows that the polymer has good heat resistance. [ka]

[0040] <Example 6> Polymer synthesis (2) A 0.384M solution was prepared by dissolving 110.7mg (0.2512mmol) of monomer in 0.65mL of acetonitrile. 10mol% of Magic Blue was added while simply sealing in nitrogen to initiate polymerization. After the polymerization reaction proceeded for 60 minutes, the reaction mixture was dissolved in 1mL of dichloromethane and slowly dropped into 20mL of methanol for reprecipitation, yielding 41.2mg (37% yield) of a 5-membered ring-containing polymer. The physical properties of the polymer were Mn (number average molecular weight) = 6800, Mw (weight average molecular weight) = 42200, and PDI (polydisperse index) = 6.23. The chemical formula of the product (polymer) was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (23). In addition, the polymer was subjected to thermogravimetric analysis (TG measurement) using a thermogravimetric differential thermal analyzer (EXSTAR TG / DTA6200 manufactured by Seiko Instruments Inc. and STA7200RV manufactured by Hitachi High-Technologies Corporation). The results of the TG measurement are shown in Figure 2. Figure 2 shows that the polymer has good heat resistance. [ka]

[0041] <Example 7> Synthesis of bisphenol (1) Polymer ([Polymerization conditions] monomer concentration: 0.096M, dichloromethane: 2.60mL, Magic Blue: 5mol%, reaction time 60 minutes, room temperature): 88.5mg was dissolved in THF (tetrahydrofuran): 23mL to prepare a 10mM polymer solution. 0.930mL of 1M solution of TBAF (tetra-n-butylammonium fluoride) (2 equivalents relative to the number of siloxane bonds in the polymer) and 0.027mL of 2 equivalents of acetic acid as a proton source were added thereto to carry out a decomposition reaction. After reacting for 23 hours at room temperature, the solution was separated with 1M hydrochloric acid and ethyl acetate, and a column operation was carried out using hexane and ethyl acetate as the developing solvent. As a result, a 4-membered ring-containing dimer (bisphenol) was obtained with an isolation yield of 33% (repeating unit ratio). The chemical formula of the dimer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) device. In addition, 72.1 mg of the polymer ([Polymerization conditions] monomer concentration: 0.096 M, HFIP (1,1,1,3,3,3-hexafluoro-2-propanol): 2.60 mL, PIDA ((diacetoxyiodo)benzene): 10 mol%, reaction time: 60 minutes, room temperature): was dissolved in 19 mL of THF to prepare a 10 mM polymer solution. Two equivalents of TBAF (1 M solution: 0.757 mL) and two equivalents of acetic acid (0.043 mL) were added relative to the number of siloxane bonds in the polymer, and the decomposition reaction was carried out for 2 hours. As a result, a four-membered ring-containing dimer (bisphenol) was obtained with an NMR yield of 62% (polymer repeat unit ratio). The chemical formula of the dimer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (24). [ka]

[0042] <Example 8> Synthesis of bisphenol (2) 72.1 mg of polymer (polymerization conditions: monomer concentration 0.096 M, HFIP: 2.60 mL, PIDA: 10 mol%, reaction time 60 min, room temperature) was dissolved in 19 mL of THF to prepare a 10 mM polymer solution. 0.757 mL of a 1 M solution of TBAF (2 equivalents relative to the number of siloxane bonds in the polymer) and 0.043 mL of 2 equivalents of acetic acid as a proton source were added thereto to carry out a decomposition reaction. After reacting for 2 hours at room temperature, 1 equivalent of 1,3,5-trimethoxybenzene relative to the repeating unit was added as a standard substance and NMR measurement was performed. As a result, a dimer (bisphenol) was confirmed with an NMR yield of 62%. The reaction formula is the same as the above formula (24) except for the reaction time.

[0043] <Example 9> Synthesis of bisphenol (3) 40.3 mg of polymer (polymerization conditions: monomer concentration 0.384 M, acetonitrile: 1.95 mL, Magic Blue: 10 mol%, reaction time 60 min, room temperature) was dissolved in 9 mL of THF to prepare a 10 mM polymer solution. 0.360 mL of a 1 M solution of TBAF (2 equivalents relative to the number of siloxane bonds in the polymer) and 0.023 mL of 2 equivalents of acetic acid as a proton source were added thereto to carry out a decomposition reaction. After reacting for 25 hours at room temperature, a column operation was carried out using hexane and ethyl acetate as the developing solvent. As a result, a dimer (bisphenol) was isolated in an 88% yield (repeating unit ratio). The chemical formula of the dimer was confirmed by a gas chromatography / mass spectrometer (GCMS) and a nuclear magnetic resonance (NMR) device. The reaction formula is shown in formula (25). [ka]

[0044] <Example 10> Monomer synthesis (5) In a 200mL two-neck flask that had been purged with nitrogen, 6.1575g (37.5mmol) of isoeugenol, 5.23mL (37.5mmol) of TEA, and 50mL of ethyl acetate were added in that order. Then, 2.437g (12.5mmol) of phenylphosphonic dichloride was added dropwise, and the reaction was carried out at room temperature for 48 hours. After that, the reaction was quenched with about 100mL of saturated NaHCO3 aqueous solution, extracted with ethyl acetate, and run on a gradient column with hexane and ethyl acetate to obtain 5.0680g (11.3mmol, 90% yield) of monomer A as a white solid. The chemical formula of monomer A was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (26). [ka]

[0045] <Example 11> Monomer synthesis (6) 0.6709g (5mmol) of 4-propenylphenol, 0.693mL (5mmol) of TEA, and 10mL of ethyl acetate were added in this order to a 50mL two-neck flask that had been purged with nitrogen. Then, 0.355mL (2.5mmol) of phenylphosphonic acid dichloride was added dropwise at 0°C in an ice bath, and the reaction was carried out at room temperature for 48 hours. After that, the reaction was quenched with about 20mL of saturated NaHCO3 aqueous solution, extracted with ethyl acetate, and run on a gradient column with hexane and ethyl acetate to obtain 0.2903g (0.744mmol, 21% yield) of monomer B as a white solid. The chemical formula of monomer B was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (27). [ka]

[0046] <Example 12> Monomer synthesis (7) In a 200mL two-neck flask that had been purged with nitrogen, 4.18mL (27.5mmol) of isoeugenol, 3.82mL (27.5mmol) of TEA, and 25mL of ethyl acetate were added in that order. Then, 1.661g (12.5mmol) of methylphosphonic dichloride dissolved in 25mL of ethyl acetate was added dropwise at 0°C in an ice bath, and the reaction was carried out at room temperature for 48 hours. After that, the reaction was quenched with about 100mL of saturated NaHCO3 aqueous solution, extracted with ethyl acetate, and run on a gradient column with hexane and ethyl acetate to obtain 4.0668g (10.47mmol, 84% yield) of monomer C as a pale yellow transparent liquid. The chemical formula of the monomer C was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (28). [ka]

[0047] <Example 13> Monomer synthesis (8) 0.7179g (5.35mmol) of 4-propenylphenol, 0.742mL (5.35mmol) of TEA, and 6mL of ethyl acetate were added in this order to a 50mL two-neck flask that had been purged with nitrogen. Then, 0.3845g (2.89mmol) of methylphosphonic dichloride dissolved in 6mL of ethyl acetate was added dropwise at 0°C in an ice bath, and the reaction was carried out at room temperature for 48 hours. After that, the reaction was quenched with about 30mL of saturated NaHCO3 aqueous solution, extracted with ethyl acetate, and run on a gradient column with hexane and ethyl acetate to obtain 0.2581g (0.786mmol, 29% yield) of monomer D as a white solid. The chemical formula of monomer D was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (29). [ka]

[0048] <Example 14> Monomer synthesis (9) In a 50 mL two-neck flask that had been purged with nitrogen, 0.821 mL (5 mmol) of isoeugenol, 0.693 mL (5 mmol) of TEA, and 10 mL of ethyl acetate were added in that order. Then, 396 μL (2.5 mmol) of paramethoxyphenylphosphonic acid dichloride was added dropwise at 0°C in an ice bath, and the reaction was carried out at room temperature for 48 hours. After that, the reaction was quenched with about 20 mL of saturated NaHCO3 aqueous solution, extracted with ethyl acetate, and run on a gradient column with hexane and ethyl acetate to obtain 0.7069 g (1.47 mmol, 59% yield) of monomer E as a pale yellow transparent liquid. The chemical formula of the monomer E was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (30). [ka]

[0049] <Example 15> Polymerization of monomers (1) Monomer A: 90.1 mg (0.2 mmol) and CH3CN: 0.5 mL were placed in a 5 mL vial, and while simply sealing in nitrogen, Fe(ClO4)3·6H2O: 9.2 mg (0.02 mmol, 10 mol%) dissolved in CH3CN: 0.5 mL was added, and polymerization was started at room temperature. One hour after the start, the solvent was evaporated and reprecipitation was performed. The reaction mixture was dissolved in dichloromethane: 1 mL and slowly dropped into 20 mL of diethyl ether, and the formation of a compound that appeared to be a dimer was confirmed. The obtained compound had Mn = 850 and Mw = 960. The reaction formula is shown in formula (31). [ka]

[0050] <Example 16> Polymer synthesis (3) Monomer A and Grubs second generation catalyst (Grubbs II, 4.2 mg, 1 mol%) were placed in a 5 mL vial, and nitrogen flow was performed for about 30 minutes. Then, 0.5 mL of toluene was added to make the concentration of monomer A 0.25 M (0.25 mmol / 1 mL), and the reaction was performed at 80 ° C for 2 hours. After that, the solvent was evaporated and a reprecipitation operation was performed. The reaction mixture was dissolved in 1 mL of dichloromethane and slowly dropped into 20 mL of diethyl ether, and the production of a compound (polymer) that appeared to be an oligomer was confirmed. The obtained compound had Mn = 3800, Mw = 7200, and the yield was 60%. The chemical formula of the polymer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (32). [ka]

[0051] <Example 17> Monomer synthesis (10) (E)-4-(4-hydroxy-3-methoxyphenyl)-3-buten-2-one: 2.8949g (15.061mmol) was added to a two-neck flask, and then nitrogen replacement was performed. Diethyl ether: 50mL, TEA: 1.7851g (17.641mmol), DMAP: 79.4mg (0.649mmol) were added in this order, and then dichlorodiisopropylsilane: 1.1458g (17.641mmol) was dropped and reacted. After the reaction, it was extracted with ethyl acetate and a gradient column was performed with chloroform and ethyl acetate. As a result, 2.0468g (4.1209mmol, yield 66%) of a colorless, transparent, and highly viscous liquid monomer was obtained. The chemical formula of the monomer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (33). [ka]

[0052] <Example 18> Monomer synthesis (11) 0.9392g (5.790mmol) of 4-(4-hydroxyphenyl)-3-buten-2-one was added to a two-neck flask, and then nitrogen substitution was performed. 25mL of diethyl ether, 0.6336g (6.261mmol) of TEA, and 32.6mg (0.266mmol) of DMAP were added in this order, and then 0.4665g (2.519mmol) of dichlorodiisopropylsilane was added dropwise to carry out the reaction. After the reaction, the mixture was extracted with dichloromethane and subjected to a gradient column with toluene and ethyl acetate. As a result, 0.7620g (1.746mmol, 69% yield) of a pale yellow solid monomer was obtained. The chemical formula of the monomer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (34). [ka]

[0053] <Example 19> Monomer synthesis (12) 2.9607g (18.031mmol) of isoeugenol was added to a two-neck flask, followed by nitrogen replacement. 40mL of diethyl ether, 1.9437g (19.208mmol) of TEA, and 45.3mg (0.370mmol) of DMAP were added in this order, followed by dropwise addition of 1.1885g (7.5647mmol) of dichlorodiisopropylsilane, and the reaction was carried out for 21 hours. After the reaction, the mixture was extracted with ethyl acetate, and a gradient column was run with hexane and ethyl acetate. As a result, 2.5263g (6.1228mmol, 80% yield) of a transparent liquid monomer was obtained. The chemical formula of the monomer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (35). [ka]

[0054] <Example 20> Polymer synthesis (4) A 0.384M solution was prepared by dissolving 122.3mg (0.2462mmol) of monomer in 0.65mL of acetonitrile. While simply sealing in nitrogen, 1mol% of (Ir[dF(CF3)ppy]2(dtbpy))PF6 was added, and polymerization was initiated by irradiating blue light. After the polymerization reaction proceeded for 12 hours, the reaction mixture was dissolved in 1mL of dichloromethane, and slowly dropped into 20mL of hexane for reprecipitation. As a result, 86.2mg (70% yield) of a 4-membered ring-containing polymer was obtained. The physical properties of the polymer were Mn=2600, Mw=4200, and PDI=1.61. The chemical formula of the polymer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (36). [ka]

[0055] <Example 21> Polymer synthesis (5) A 0.192M solution was prepared by dissolving 118.1mg (0.2520mmol) of monomer in 1.3mL of acetonitrile. While simply sealing in nitrogen, 1mol% of (Ir[dF(CF3)ppy]2(dtbpy))PF6 was added, and polymerization was initiated by irradiating blue light. After the polymerization reaction was allowed to proceed for 60 hours, the reaction mixture was dissolved in 1mL of dichloromethane, and slowly dropped into 20mL of hexane for reprecipitation. As a result, 73.2mg (61% yield) of a 4-membered ring-containing polymer was obtained. The physical properties of the polymer were Mn=7600, Mw=17400, and PDI=2.27. The chemical formula of the polymer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (37). [ka]

[0056] <Example 22> Polymer synthesis (6) A 0.384M solution was prepared by dissolving 110.4mg (0.2530mmol) of monomer in 0.65mL of acetonitrile. While simply sealing in nitrogen, 1mol% of (Ir[dF(CF3)ppy]2(dtbpy))PF6 was added, and polymerization was initiated by irradiating blue light. After the polymerization reaction proceeded for 12 hours, the reaction mixture was dissolved in 1mL of dichloromethane, and slowly dropped into 20mL of hexane for reprecipitation. As a result, 39.7mg (35% yield) of a 4-membered ring-containing polymer was obtained. The physical properties of the polymer were Mn=1200, Mw=1957, and PDI=1.57. The chemical formula of the polymer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (38). [ka]

[0057] <Example 22> Polymer synthesis (7) Acetonitrile: 1.3mL was dissolved with 140.7mg (0.2527mmol) of monomer to make a 0.192M solution. While simply sealing in nitrogen, 1mol% of (Ir[dF(CF3)ppy]2(dtbpy))PF6 was added, and polymerization was started by irradiating blue light. After the polymerization reaction proceeded for 12 hours, the reaction mixture was dissolved in 1mL of dichloromethane, and slowly dropped into 20mL of hexane to perform reprecipitation. As a result, 58.1mg (yield 41%) of a 4-membered ring-containing polymer was obtained. The physical properties of the polymer were Mn=3700, Mw=9400, and PDI=2.49. The chemical formula of the polymer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (39). [ka]

[0058] <Example 23> Synthesis of bisphenol (4) Polymer ([Polymerization conditions] monomer concentration: 0.192 M, acetonitrile: 1.3 mL, (Ir[dF(CF3)ppy]2(dtbpy))PF6: 1 mol%, reaction time: 60 hours, room temperature): 73.2 mg was dissolved in THF: 19 mL to prepare a 10 mM polymer solution. Two equivalents of TBAF (1 M solution, 0.792 mL) and two equivalents of acetic acid (0.045 mL) relative to the number of siloxane bonds in the polymer were added to carry out a decomposition reaction. As a result, almost complete decomposition was confirmed, and a four-membered ring-containing dimer was confirmed. The chemical formula of the dimer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (40). [ka]

[0059] <Example 24> Monomer synthesis (13) In a 30 mL two-neck flask, 0.8138 g (6.06 mmol) of 4-propenylphenol and 0.836 mL (6 mmol) of TEA were dissolved in 12 mL of ethyl acetate under a nitrogen atmosphere, and 0.450 g (2 mmol) of 4-methoxyphenylphosphonic acid dichloride was added dropwise to the mixture and reacted at room temperature for 48 hours. The mixture was then quenched with approximately 30 mL of saturated NaHCO3aq., extracted with ethyl acetate, and subjected to a gradient column with hexane and ethyl acetate to obtain 0.3324 g (0.79 mmol, 40% yield) of colorless oily monomer F. The chemical formula of the monomer F was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) spectrometry. The reaction formula is shown in formula (41). [ka]

[0060] <Example 25> Monomer synthesis (14) In a 100mL two-neck flask, 2.0525g (12.5mmol) of isoeugenol and 1.74mL (12.5mmol) of TEA were dissolved in 20mL of ethyl acetate under a nitrogen atmosphere, and 0.7371g (5.0mmol) of ethylphosphonyl dichloride was added dropwise to the mixture and reacted at room temperature for 48 hours. After that, the mixture was quenched with about 50mL of saturated NaHCO3aq., extracted with ethyl acetate, and subjected to a gradient column with hexane and ethyl acetate to obtain 1.7617g (4.38mmol, 87% yield) of monomer G as a pale yellow oil. The chemical formula of the monomer G was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) apparatus. The reaction formula is shown in formula (42). [ka]

[0061] <Example 26> ·Synthesis of Monomers(15) In a 50mL two-neck flask, 1.0064g (7.5mmol) of 4-propenylphenol and 1.05mL (7.5mmol) of TEA were dissolved in 12mL of ethyl acetate under a nitrogen atmosphere, and 0.4407g (3.0mmol) of ethylphosphonyl dichloride was added dropwise to the mixture and reacted at room temperature for 48 hours. After quenching with about 30mL of saturated NaHCO3aq., the mixture was extracted with ethyl acetate and subjected to a gradient column with hexane and ethyl acetate to obtain 0.7784g (2.27mmol, 76% yield) of monomer H as a pale yellow oil. The chemical formula of the monomer H was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) spectrometry. The reaction formula is shown in formula (43). [ka]

[0062] <Example 27> ·Synthesis of Monomers(16) In a 200mL two-neck flask, 6.1575g (37.5mmol) of isoeugenol and 5.23mL (37.5mmol) of TEA were dissolved in 50mL of ethyl acetate under nitrogen atmosphere, and 2.6218g (12.4mmol) of phenylphosphonothioic acid dichloride was added dropwise and reacted at room temperature for 48 hours. After that, the reaction was quenched with about 100mL of saturated NaHCO3aq., extracted with ethyl acetate, and column-treated with toluene to obtain 4.6640g (10.0mmol, 80% yield) of monomer I as a white solid. The chemical formula of monomer I was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) spectrometry. The reaction formula is shown in formula (44). [ka]

[0063] <Example 28> Monomer synthesis (17) In a 50 mL two-neck flask, 1.2076 g (9 mmol) of 4-propenylphenol and 1.25 mL (9 mmol) of TEA were dissolved in 12 mL of ethyl acetate under a nitrogen atmosphere, and 0.6312 g (3.0 mmol) of phenylphosphonothioic acid dichloride was added dropwise to the mixture and reacted at room temperature for 48 hours. After that, the mixture was quenched with about 100 mL of saturated NaHCO3aq., extracted with ethyl acetate, and subjected to a gradient column with hexane and ethyl acetate to obtain 1.0196 g (2.51 mmol, 84% yield) of monomer J as a pale yellow oil. The chemical formula of monomer J was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (45). [ka]

[0064] <Example 29> ·Synthesis of Monomers(18) In a 30 mL two-neck flask, 0.7208 g (3.75 mmol) of (E)-4-(4-hydroxy-3-methoxyphenyl)-3-buten-2-one and 0.53 mL (3.75 mmol) of TEA were dissolved in 6 mL of ethyl acetate under a nitrogen atmosphere, and 0.2950 g (1.51 mmol) of phenylphosphonothioic acid dichloride was added dropwise to the flask and reacted at room temperature for 48 hours. The reaction was then quenched with approximately 50 mL of saturated NaHCO3aq., extracted with ethyl acetate, and then run on a gradient column with hexane and ethyl acetate to obtain 0.5990 g (1.18 mmol, 78% yield) of monomer K as a white solid. The chemical formula of monomer K was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) spectrometry. The reaction formula is shown in formula (46). [ka]

[0065] <Example 30> Monomer synthesis (19) In a 50 mL two-neck flask, 1.2164 g (7.5 mmol) of 4-(4-hydroxyphenyl)-3-buten-2-one and 1.05 mL (7.5 mmol) of TEA were dissolved in 12 mL of ethyl acetate under a nitrogen atmosphere, and 0.5833 g (2.99 mmol) of phenylphosphonothioic acid dichloride was added dropwise to the flask and reacted at room temperature for 48 hours. The reaction was then quenched with approximately 100 mL of saturated NaHCO3aq., extracted with ethyl acetate, and run on a gradient column with hexane and ethyl acetate to obtain 1.0117 g (2.27 mmol, 76% yield) of monomer L as a pale yellow solid. The chemical formula of monomer L was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) spectrometry. The reaction formula is shown in formula (47). [ka]

[0066] <Example 31> Monomer synthesis (20) In a 50mL two-neck flask, 1.3364g (7.5mmol) of trans-p-methyl coumarate and 1.05mL (7.5mmol) of TEA were dissolved in 12mL of ethyl acetate under nitrogen atmosphere, and 0.5822g (2.99mmol) of phenylphosphonothioic acid dichloride was added dropwise to the mixture and reacted at room temperature for 48 hours. After that, the mixture was quenched with about 100mL of saturated NaHCO3aq., extracted with ethyl acetate, and then run on a gradient column with hexane and ethyl acetate to obtain 1.1745g (2.45mmol, 82% yield) of monomer M as a white solid. The chemical formula of monomer M was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) spectrometry. The reaction formula is shown in formula (48). [ka]

[0067] <Example 32> Monomer synthesis (21) In a 30 mL two-neck flask, 0.6727 g (3.5 mmol) of (E)-4-(4-hydroxy-3-methoxyphenyl)-3-buten-2-one and 0.488 mL (3.5 mmol) of TEA were dissolved in 6 mL of ethyl acetate under a nitrogen atmosphere, and 0.2945 g (1.40 mmol) of phenylphosphonothioic acid dichloride was added dropwise to the flask and reacted at room temperature for 48 hours. The mixture was then quenched with approximately 60 mL of saturated NaHCO3aq., extracted with ethyl acetate, and then column-treated with toluene and methanol to obtain 49 mg (0.938 mmol, 7% yield) of monomer N as a white solid. The chemical formula of monomer N was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) spectrometry. The reaction formula is shown in formula (49). [ka]

[0068] <Example 33> ·Synthesis of Monomers(22) In a 30mL two-neck flask, 0.8110g (5mmol) of 4-(4-hydroxyphenyl)-3-buten-2-one and 0.697mL (5mmol) of TEA were dissolved in 8mL of ethyl acetate under a nitrogen atmosphere, and 0.4226g (2.0mmol) of phenylphosphonothioic acid dichloride was added dropwise to the mixture and reacted at room temperature for 48 hours. After that, the mixture was quenched with about 50mL of saturated NaHCO3aq., extracted with ethyl acetate, and then column-treated with toluene and ethyl acetate to obtain 0.7559g (1.63mmol, 82% yield) of monomer O as a pale yellow oil. The chemical formula of the monomer O was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) apparatus. The reaction formula is shown in formula (50). [ka]

[0069] <Example 34> Monomer synthesis (23) In a 30 mL two-neck flask, 0.8910 g (5 mmol) of trans-p-methyl coumarate and 0.697 mL (5 mmol) of TEA were dissolved in 8 mL of ethyl acetate under a nitrogen atmosphere, and 0.4216 g (2.0 mmol) of phenylphosphonothioic acid dichloride was added dropwise to the mixture and reacted at room temperature for 48 hours. After that, the mixture was quenched with about 50 mL of saturated NaHCO3aq., extracted with ethyl acetate, and column-treated with toluene and ethyl acetate to obtain 0.7703 g (1.56 mmol, 78% yield) of colorless oily monomer P. The chemical formula of the monomer P was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) spectrometry. The reaction formula is shown in formula (51). [ka]

[0070] <Example 35> Polymer synthesis (8) Monomer I: 96.7 mg (0.21 mmol) was dissolved in dichloromethane: 0.5 mL in a 5 mL vial. Tris(4-bromophenyl)ammoniumylhexachloroantimonate (magic blue: 16.33 mg (0.02 mmol, 0.1 equiv.)) dissolved in dichloromethane: 0.5 mL was added while flowing nitrogen, and the reaction was carried out at room temperature for 1 hour. After quenching with methanol, the solvent was evaporated and reprecipitation was performed (dichloromethane / methanol (v / v=1 / 20)), and 82.3 mg of polymer was obtained (yield 85%). The molecular weight of the polymer was evaluated by gel permeation chromatography (GPC), and it was found to be Mn=2242, Mw=5443.

[0071] <Example 36> Polymer synthesis (9) In a 5 mL vial, 95.9 mg (0.21 mmol) of monomer I was dissolved in 0.5 mL of HFIP. 6.44 mg (0.02 mmol, 0.1 equiv.) of PIDA dissolved in 0.5 mL of HFIP was added while flowing nitrogen, and the reaction was carried out at room temperature for 1 hour. After quenching with methanol, the solvent was evaporated and reprecipitation was performed (dichloromethane / methanol (v / v=1 / 20)), and 49.4 mg of crude polymer and monomer was obtained (yield 52%). The molecular weight of the polymer was evaluated by gel permeation chromatography (GPC), and it was found to be Mn=1333 and Mw=1498.

[0072] <Example 37> Polymer Synthesis (10) In a 5mL vial, 80.8mg (0.20mmol) of monomer J was dissolved in 0.5mL of dichloromethane. While flowing nitrogen, 16.33mg (0.02mmol, 0.1 equiv.) of magic blue dissolved in 0.5mL of dichloromethane was added and the reaction was carried out at room temperature for 1 hour. After quenching with methanol, the solvent was evaporated and reprecipitation was carried out (dichloromethane / methanol (v / v=1 / 20)), and 32.5mg of polymer and monomer crude was obtained (40% yield). The molecular weight was evaluated by gel permeation chromatography (GPC) and was found to be Mn=1515 and Mw=2022.

[0073] <Example 38> Synthesis of bisphenol (5) Polymer ([Polymerization conditions] monomer concentration: 0.384 M, acetonitrile: 0.650 mL, (Ir[dF(CF3)ppy]2(dtbpy))PF6: 1 mol%, reaction time 12 hours, room temperature): 86.2 mg was dissolved in THF: 17 mL to prepare a 10 mM polymer solution. Two equivalents of TBAF (1 M solution, 0.694 mL) and two equivalents of acetic acid (0.039 mL) relative to the number of siloxane bonds in the polymer were added to carry out a decomposition reaction. As a result, almost complete decomposition was confirmed, and a four-membered ring-containing dimer was confirmed with an isolated yield of 59% (polymer repeat unit ratio). The chemical formula of the dimer was confirmed by gas chromatography / mass spectrometry (GCMS) and nuclear magnetic resonance (NMR) equipment. The reaction formula is shown in formula (52). [ka]

Claims

1. A difunctionalized phenylpropanoid monomer represented by formula (1a), (1b) or (1c): 【Chemistry 1】 (In formulas (1a), (1b) and (1c), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; L represents a linker group.

2. L in the formulas (1a), (1b) and (1c) represents a linker group having a siloxane skeleton represented by the formula (2a), a linker group having a phosphonate skeleton represented by the formula (2b), >C═O, —S—, —SO—, —SO 2 The bifunctionalized monomer of phenylpropanoid according to claim 1, wherein the linker group is -, -Se-, -Te-, or any one of the linker groups represented by formulas (2c) to (2n). 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 (In formulas (2a) to (2n), R 20 ~R 29 , R 34 ~R 60 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; In formula (2b), E represents O, S or Se; In formulas (2m) and (2n), n represents a natural number.

3. A polymer represented by any one of formulas (4) to (6): 【Chemistry 5】 (In formulas (4) to (6), R 1 , R 2 , R 18 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; L represents a linker group; n represents a natural number.)

4. In the formulas (4) to (6), L is a linker group having a siloxane skeleton represented by formula (2a), a linker group having a phosphonate skeleton represented by formula (2b), >C═O, —S—, —SO—, —SO 2 The polymer according to claim 3, wherein the linker group is -, -Se-, -Te-, or any one of the linker groups represented by formulas (2c) to (2n). 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 (In formulas (2a) to (2n), R 20 ~R 29 , R 34 ~R 60 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; In formula (2b), E represents O, S or Se; In formulas (2m) and (2n), n represents a natural number.

5. A method for producing a bifunctional monomer of a phenylpropanoid according to claim 1, by reacting a hydroxyl group of a phenylpropanoid represented by formula (7a), (7b) or (7c) with a linker. 【Chemistry 9】 (In formulas (7a), (7b) and (7c), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

6. The method for producing a bifunctional monomer of phenylpropanoid according to claim 5, wherein the linker is a linker having a siloxane skeleton represented by formula (8) or a linker having a phosphonate skeleton represented by formula (9). 【Chemistry 10】 (In formula (8), R 20 , R 21 , R 30 and R 31 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. In formula (9), E represents O, S or Se; R 22 , R 32 and R 33 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

7. A method for producing the polymer of claim 3 by cycloaddition or metathesis polymerization of the difunctionalized phenylpropanoid monomer of claim 1.

8. The method of producing a bisphenol represented by formula (10) by decomposing the polymer represented by formula (4) according to claim 3. Decomposing the polymer represented by the formula (5) to produce a bisphenol represented by the formula (11), or A method for producing a bisphenol represented by formula (12) by decomposing the polymer represented by formula (6). 【Chemistry 11】 (In formulas (10) to (12), R 1 , R 2 , R 18 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

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