Method for producing cyclic polymers and cyclic polymers

Abstract

To provide a novel production method of a cyclic polymer and the cyclic polymer produced by the method.SOLUTION: A cyclic polymer is obtained by emitting light in the presence of a monomer compound represented by a general formula (2) below and a compound represented by a general formula (1) below. In the general formula (1) below, Z is a sulfur atom or an oxygen atom, and Ar is an aromatic ring that may have a substituent group, where the aromatic ring may be a condensed ring. In the general formula (2) below, R1 is a hydrogen atom or an alkyl group of 1-5 carbons, X is -(C=O)OR3, -OR3, a carboxy group, a hydrogen atom, an ethenyl group, a cyano group, an alkyl group of 1-6 carbons, a phenyl group having a substituent group, a halogen atom, an aminocarbonyl group, a monoalkylaminocarbonyl group, a dialkylaminocarbonyl group, an alkylcarbonyloxy group, or a nitro group. R2 is each independently a hydrogen atom or a halogen atom. R3 is an univalent organic group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a method for producing cyclic polymers and to cyclic polymers. [Background technology]

[0002] Cyclic polymers are polymer compounds that do not have molecular ends. Compared to linear polymers, cyclic polymers have less entanglement between polymer chains, and are known to have different physical properties such as viscosity, melting point, and glass transition temperature. As an example of utilizing the properties of cyclic polymers, Patent Document 1 discloses a hot-melt adhesive containing a hydrocarbon-based cyclic polymer. According to the same document, hot-melt adhesives using linear α-olefin polymers have limited applications because the time it takes to bond the adhesive to the substrate after application is very short, sometimes less than a few seconds, due to the high crystallinity and high melting point of the α-olefin polymer. However, by incorporating a hydrocarbon-based cyclic polymer, creep resistance at high temperatures is improved.

[0003] Two methods have been developed for synthesizing these cyclic polymers: end-linking and ring-expanding polymerization. End-linking involves synthesizing a linear polymer with reactive end groups, and then joining two reactive end groups by an intramolecular cyclization reaction. As an example of such a synthesis method, Patent Document 2 discloses a method for polymerizing ring-opening polymerizable monomers in a compressible fluid using an organic catalyst that does not contain metal atoms.

[0004] Ring expansion polymerization is a method of obtaining polymers by sequentially inserting monomers using a cyclic initiator. As an example of such a synthesis method, Patent Document 3 discloses a method for synthesizing macrocyclic polymers using a metal alkylidene complex as a catalyst for the ring insertion reaction of cyclic olefin monomers. Non-Patent Document 1 discloses cyclic alkoxytin as an initiator. The synthesis of cyclic polyesters by ring-expanding polymerization of cyclic γ-butyrolactone using [a specific method / technology] has been reported. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2018 / 012593 [Patent Document 2] Japanese Patent Publication No. 2017-39863 [Patent Document 3] Special Publication No. 2005-534777 [Non-patent literature]

[0006] [Non-Patent Document 1] Hans R. Kricheldop et. al., Macromol. Chem. Phys., 1998, 199, 273-282. [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] This invention has been made in view of the above circumstances, and aims to provide a novel method for producing cyclic polymers and a cyclic polymer obtained thereby. [Means for solving the problem]

[0008] The inventors, after diligent research to solve the above problems, have found that 3H-benzothiazole-2-thione (BTT) or 2(3H)-benzothiazolon (BTO) or derivatives having the same skeleton undergo uniform cleavage of the dithioester or thioester portion upon light irradiation, as shown in chemical formulas (A) and (B) below, generating a pair of radicals within the molecule. When these radicals act in the presence of a monomer compound having an ethylenically unsaturated bond, the monomer compound is inserted between the pair of radicals, causing ring closure and the formation of a cyclic polymer, as shown in chemical formula (C) below. In other words, the chemical species shown in chemical formulas (A) and (B) below act as photopolymerization initiators for cyclic polymer synthesis. This cyclic polymer undergoes repeated uniform cleavage and ring closure as long as light irradiation continues, and continues to polymerize in a living manner in the presence of the monomer compound. In the chemical formulas (A) to (C) below, 3H-benzothiazole-2-thione (BTT) or 2(3H)-benzothiazolone (BTO) are given as photopolymerization initiators, and methyl methacrylate (MMA) is given as a monomer compound. However, these are merely examples for illustrative purposes, and the present invention is not limited to these compounds.

[0009] [ka]

[0010] Specifically, the present invention provides the following:

[0011] (1) The present invention relates to the existence of a monomer compound represented by the following general formula (2) and a compound represented by the following general formula (1). Bottom, room temperature This method is characterized by light irradiation and is a method for producing a cyclic polymer in which the above monomer compound is incorporated as a repeating unit. [ka] (In the above general formula (1), Z is a sulfur atom or an oxygen atom, and Ar is an aromatic ring which may have substituents, and the aromatic ring may be a fused ring.) [ka] (In the above general formula (2), X is a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms, and X is -(C=O)OR 3 , -OR 3 or a carboxyl group, R 2 Each is independently a hydrogen atom or a halogen atom, and R 3 (This is a monovalent organic group.)

[0012] (2) The present invention also provides a method for producing the cyclic polymer described in item (1), wherein Z is a sulfur atom.

[0013] (3) The present invention also relates to a method for producing a cyclic polymer according to item (1) or (2), wherein the compound represented by the general formula (2) is a (meth)acrylic acid ester.

[0014] (4) The present invention further provides a method for producing a cyclic polymer according to any one of items (1) to (3), wherein the above light irradiation is performed in the presence of a thioxanthone compound, a xanthone compound, anthracene compound, or an anthraquinone compound.

[0015] (5) The present invention also relates to a method for producing the cyclic polymer described in item (4), wherein the thioxanthone compound is 2-isopropylthioxanthone.

[0016] (6) The present invention is also a cyclic polymer represented by the following general formula (3). [ka] (In the above general formula (3), Z is a sulfur atom or an oxygen atom, Ar is an aromatic ring which may have substituents, and the aromatic ring may be a fused ring, R 1 is a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms, and X is -(C=O)OR 3 , -OR 3 or Carboxy group and , R 2is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and R 3 is a monovalent organic group, and n is an integer of 1 or more.)

[0017] (7) The present invention also relates to the cyclic polymer described in item (6) represented by the following general formula (3a). [Chemical formula] (In the above general formula (3a), Z is a sulfur atom or an oxygen atom, Ar is an aromatic ring which may have a substituent, and the aromatic ring may be a condensed ring, and R 1 is a hydrogen atom or a methyl group, R 2 are each independently a hydrogen atom or a methyl group, R is a monovalent organic group, and n is an integer of 1 or more.)

[0018] (8) The present invention also relates to the cyclic polymer described in item (6) or (7) in which Z is a sulfur atom. [Advantages of the Invention]

[0019] According to the present invention, a novel method for producing a cyclic polymer and the cyclic polymer obtained thereby are provided. [Brief Description of the Drawings]

[0020] [Figure 1] FIG. 1 is a MALDI-TOF MS chart of the cyclic polymer (CP-MMA1) obtained in the examples. [Figure 2] FIG. 2 is a MALDI-TOF MS chart of the cyclic polymer (CP-MMA2) obtained in the examples. [Figure 3] FIG. 3 is a MALDI-TOF MS chart of the cyclic polymer (CP-CHMA) obtained in the examples. [Figure 4] FIG. 4 is a MALDI-TOF MS chart of the cyclic polymer (CP-BzMA) obtained in the examples. [Figure 5]Figure 5 shows the MALDI-TOF MS chart for the cyclic polymer (CP-MMA3) obtained in the examples. [Modes for carrying out the invention]

[0021] The following describes one embodiment of the method for producing the cyclic polymer of the present invention, and one embodiment of the cyclic polymer of the present invention. It should be noted that the present invention is not limited to the following embodiments or examples, and can be implemented with appropriate modifications within the scope of the present invention.

[0022] <Method for producing cyclic polymers> First, one embodiment of the method for producing the cyclic polymer of the present invention will be described. The method for producing the cyclic polymer of the present invention is characterized by irradiating with light in the presence of a monomer compound represented by the following general formula (2) and a compound represented by the following general formula (1). By carrying out this production method, a cyclic polymer in which the above monomer compound is incorporated as a repeating unit is obtained. As already explained, the compound represented by the following general formula (1) undergoes uniform cleavage between the CS bonds upon light irradiation, generating a pair of radicals within the molecule. These radicals act on the ethylenically unsaturated bonds of the (meth)acrylic acid ester, causing addition polymerization and increasing the molecular weight, while the pair of radicals present within the molecule bond together to cyclize the molecule. This uniform cleavage and cyclization are in equilibrium under light irradiation, and the compound represented by the following general formula (1) gradually increases its molecular weight by repeatedly going through the process of addition polymerization of the monomer compound after uniform cleavage and the process of cyclization to become a cyclic polymer. This polymerization process proceeds in a living manner and continues until all the monomer compounds in the system are consumed. The compound of the following general formula (1), which generates radicals upon light irradiation, acts as a photopolymerization initiator in the system of the present invention.

[0023] [ka]

[0024] In the above general formula (1), Z is either a sulfur atom or an oxygen atom. When Z is a sulfur atom, the compound represented by general formula (1) is 3H-arylthiazole-2-thion, and when Z is an oxygen atom... In this case, the compound represented by general formula (1) becomes 2(3H)-arylthiazolon, and in both cases, the compound represented by general formula (1) undergoes uniform cleavage between the CS bonds upon light irradiation, generating a pair of radicals within the molecule. As previously explained, these radicals polymerize the monomer compound.

[0025] In the general formula (1) above, Ar is an aromatic ring which may have substituents. Examples of aromatic rings include benzene rings and naphthalene rings. Examples of substituents which these aromatic rings may have include hydroxyl groups, amino groups, nitro groups, azi groups, halogen atoms, allyl groups, carboxyl groups, acyl groups, C2-C6 alkenyl groups, C2-C6 alkynyl groups, C1-C6 alkoxy groups, carboxyalkyl groups, alkyloxycarbonyl groups, 1-piperidylcarbonyl groups, and hydroxyalkyl groups. These substituents may be present one or more times.

[0026] Compounds represented by the above general formula (1) include 3H-benzothiazole-2-thion, 4-hydroxy-2(3H)-benzothiazolethion, 6-amino-2(3H)-benzothiazolethion, naphtho[1,2-d]thiazole-2(1H)-thion, naphtho[2,1-d]thiazole-2(3H)-thion, 6-hydroxymethyl-2(3H)-benzothiazolethion, naphtho[2,3-d]thiazole-2(3H)-thion, 6-ethynyl-2(3H)-benzothiazolethion, 5-amino-2(3H)-benzothiazolethion, 5 -Bromo-2(3H)-benzothiazolethion, 5-fluoro-2(3H)-benzothiazolethion, 2,3-dihydro-2-thioxo-6-benzothiazolecarbonitrine, 6-iodo-2(3H)-benzothiazolethion, 5-hydroxymethyl-2(3H)-benzothiazolethion, 5-ethenyl-2(3H)-benzothiazolethion, 7-amino-2(3H)-benzothiazolethion, 4-chloro-2(3H)-benzothiazolethion, 4-methoxy-2(3H)-benzothiazolethion, 4-bromo-2(3H) -Benzothiazolethion, 7-hydroxymethyl-2(3H)-benzothiazolethion, 7-bromo-2(3H)-benzothiazolethion, 2,3-dihydro-2-thioxo-6-benzothiazolecarboxylic acid, 2,3-dihydro-2-thioxo-6-benzothiazoleacetic acid, 6-nitro-2(3H)-benzothiazolethion, 4-phenyl-2(3H)-benzothiazolethion, 2,3-dihydro-2-thioxo-7-benzothiazolecarboxylic acid, 2,3-dihydro-2-thioxo-6-benzothiazolecarboxylic acid methyl ester Tel, (2,3-dihydro-2-thioxo-5-benzothiazolyl)-1-piperidinylmethanone, 6-hydroxy-2(3H)-benzothiazolon, 5-hydroxy-2(3H)-benzothiazolon, 4-hydroxy-2(3H)-benzothiazolon, 6-amino-2(3H)-benzothiazolon, 6-bromo-2(3H)-benzothiazolon, 6-fluoro-2(3H)-benzothiazolon, 5-bromo-2(3H)-benzothiazolon, 5-fluoro-2(3H)-benzothiazolon, 5-ethenyl-2(3H)-benzothiazolon, 2,Examples include 3-dihydro-2-oxo-6-benzothiazole carboxylic acid, 5-acetyl-2(3H)-benzothiazolon, 6-azido-2(3H)-benzothiazolon, 5-nitro-2(3H)-benzothiazolon, and among these, 3H-benzothiazole-2-thion is preferred.

[0027] A preferred example of the compound represented by the above general formula (1) is the one represented by the following general formula (1a). The compound represented by the following general formula (1a) is one of the compounds represented by the above general formula (1) in which Ar is a benzene ring. In the following general formula (1a), Z is either a sulfur atom or an oxygen atom, and among these, a sulfur atom is preferred as Z.

[0028] [ka]

[0029] The monomer compound is a component used to increase molecular weight by addition polymerization using radicals generated by the homogeneous cleavage of the above general formula (1), and is represented by the following general formula (2).

[0030] [ka]

[0031] In the above general formula (2), R 1 R is a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms, and among these, a hydrogen atom or a methyl group is preferred. In the above general formula (2), the two R 2 Each is independently a hydrogen atom. It is an alkyl group or halogen atom with 1 to 5 carbon atoms, and among these, two R 2 It can be preferably stated that both are hydrogen atoms. In the above general formula (2), X is -(C=O)OR 3 , -OR 3R is a carboxyl group, a hydrogen atom, an ethenyl group, a cyano group, a C1-C6 alkyl group, a substituted phenyl group, a halogen atom, an aminocarbonyl group, a monoalkylaminocarbonyl group, a dialkylaminocarbonyl group, an alkylcarbonyloxy group, or a nitro group. 3 This is a monovalent organic group, and examples of such monovalent organic groups include C1-C12 alkyl groups which may have branches, C1-C18 cycloalkyl groups which may be fused rings, aryl groups, aralkyl groups, aryloxy groups, alkylaryloxy groups, fluorenyl groups, carbazolyl groups, polysylsesquioxanyl groups, etc. These monomer compounds may be used individually or in combination of two or more.

[0032] (Meth)acrylic acid esters are preferred examples of monomers represented by the above general formula (2). In this invention, the term "(meth)acrylic acid ester" means acrylic acid ester and / or methacrylic acid ester. (Meth)acrylic acid esters are compounds also called (meth)acrylates. In this invention, the term "(meth)acrylate" means acrylate and / or methacrylate. Examples of such compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate. Examples include acrylates, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, etc. Among these, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, fluorenyl (meth)acrylate, carbazolyl (meth)acrylate, polysilsesquioxanyl (meth)acrylate, etc. These (meth)acrylates may be used individually or in combination of two or more.

[0033] Furthermore, when polymerizing monomer compounds represented by general formula (2) and compounds represented by general formula (1) by light irradiation, it is preferable to use a sensitizer. Examples of such sensitizers include thioxanthone compounds, xanthone compounds, anthracene compounds, and anthraquinone compounds. The presence of such sensitizers promotes the polymerization reaction by light irradiation, and compared to cases where no sensitizer is used, the conversion rate of the monomer compound can be increased even with the same reaction time.

[0034] Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Examples of xanthone compounds include 2-isopropylxanthone, 4-isopropylxanthone, 2,4-diethylxanthone, 2,4-dichloroxanthone, and 1-chloro-4-propoxyxanthone. Among these, 2-isopropylthioxanthone is a preferred example. These thioxanthone compounds and xanthone compounds may be used individually or in combination of two or more.

[0035] A polymerization reaction occurs when a solution containing a monomer compound represented by general formula (2) and a compound represented by general formula (1) is irradiated with light, thereby synthesizing a cyclic polymer. Examples of solvents that can be used in this process include toluene, tetrahydrofuran, 1,4-dioxane, acetonitrile, and N-methylpyrrolidone. Among these, 1,4-dioxane is preferred from the viewpoint of suppressing side reactions in which multiple compounds represented by general formula (1) are incorporated into a single cyclic monomer.

[0036] Light sources used for irradiation include those containing ultraviolet light at or below approximately 370 nm, which is the absorption wavelength of the compound represented by general formula (1). Examples of such light sources include ultraviolet light-emitting diodes (UV-LEDs), xenon lamps, metal halide lamps, and high-pressure mercury lamps.

[0037] The molar ratio of the monomer compound represented by general formula (2) and the compound represented by general formula (1) can be appropriately determined according to the desired molecular weight of the resulting cyclic polymer. Furthermore, since the cyclic polymer incorporating the compound represented by general formula (1) undergoes further uniform cleavage upon light irradiation, becoming radicals, further molecular weight increases can be achieved by adding more monomer compounds to the solution containing these radicals and irradiating with light. Moreover, by utilizing these properties, a cyclic block copolymer can be prepared by forming a cyclic polymer using only one monomer, stopping the light irradiation, adding another monomer, and then irradiating with light again.

[0038] <Cyclic polymer> Next, the cyclic polymer obtained by the method for producing the cyclic polymer of the present invention described above will be explained. This cyclic polymer is also one of the present inventions. The cyclic polymer of the present invention is a molecule that exhibits a cyclic shape rather than a linear shape like general polymers, and therefore exhibits unique properties not found in linear polymers, based on its molecular shape. Specifically, the cyclic polymer of the present invention has different physical properties such as viscosity, melting point, and glass transition temperature compared to linear polymers.

[0039] The cyclic polymer of the present invention is a compound represented by the following general formula (3). This cyclic polymer may be a cyclic polymer formed by the polymerization of a single monomer compound, or it may be a cyclic random copolymer or a cyclic block copolymer formed by the polymerization of two or more polymers. The method for preparing the cyclic block copolymer is as previously described.

[0040] [ka]

[0041] In the general formula (3) above, Ar is an aromatic ring which may have substituents. Examples of aromatic rings include benzene rings and naphthalene rings. Examples of substituents which these aromatic rings may have include hydroxyl groups, amino groups, nitro groups, azi groups, halogen atoms, allyl groups, carboxyl groups, acyl groups, C2-C6 alkenyl groups, C2-C6 alkynyl groups, C1-C6 alkoxy groups, carboxyalkyl groups, alkyloxycarbonyl groups, 1-piperidylcarbonyl groups, and hydroxyalkyl groups. These substituents may be present one or more times.

[0042] In the above general formula (3), Z is a sulfur atom or an oxygen atom, and among these, a sulfur atom is preferred as Z. Also, in the above general formula (3), R 1 R is a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms, and among these, a hydrogen atom or a methyl group is preferred. In the above general formula (3), the two R 2 Each of these is independently a hydrogen atom, a C1-C5 alkyl group, or a halogen atom. In the above general formula (3), X is -(C=O)OR 3 , -OR 3 R is a carboxyl group, a hydrogen atom, an ethenyl group, a cyano group, a C1-C6 alkyl group, a substituted phenyl group, a halogen atom, an aminocarbonyl group, a monoalkylaminocarbonyl group, a dialkylaminocarbonyl group, an alkylcarbonyloxy group, or a nitro group. 3 This is a monovalent organic group, and examples of such monovalent organic groups include C1-C12 alkyl groups which may have branches, C1-C18 cycloalkyl groups which may be fused rings, aryl groups, aralkyl groups, aryloxy groups, alkylaryloxy groups, etc.

[0043] In the general formula (3) above, n represents the number of repeats of the monomer structure, which is the repeating unit. n is an integer of 1 or more, preferably an integer of 5 or more.

[0044] A preferred example of the cyclic polymer represented by the above general formula (3) is the one represented by the following general formula (3a).

[0045] [ka]

[0046] In the above general formula (3a), R 1 , Z and n are the same as in the general formula (3) above, and the two R 2 Each of these is independently either a hydrogen atom or a methyl group. Also, in general formula (3a), R is a monovalent organic group. As an example of such a monovalent organic group, R in general formula (3) above is... 3 Similar examples can be given.

[0047] A more preferred example of the cyclic polymer represented by the above general formula (3) is the one represented by the following general formula (3b).

[0048] [ka]

[0049] The cyclic polymer represented by the above general formula (3b) is obtained by polymerizing (meth)acrylic acid ester using 3H-benzothiazole-2-thion as a photopolymerization initiator. In the above general formula (3b), R 1 , R and n are the same as those in the general formula (3a) above. [Examples]

[0050] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples.

[0051] • Synthesis of cyclic polymers by photopolymerization 1 (CP-MMA1) [ka]

[0052] Add 3H-benzothiazole-2-thion (BTT, 0.167g, 1.00 mmol), 1,4-dioxane (1.00 mL), and methyl methacrylate (MMA, 1.00 g, 10.0 mmol) to a 5 mm diameter screw-cap sample tube and stir to create a homogeneous solution. Then, perform four freeze-degassing cycles. Finally, place a UV-LED (805 mW / cm²) at a distance of approximately 1 cm from the solution. 2 The reaction was irradiated with light at 365 nm for 4 hours at room temperature. After light irradiation, the reaction solution was dried under reduced pressure to obtain the product, cyclic polymethyl methacrylate (CP-MMA1), as a transparent viscous solid (conversion rate 39%, yield 0.267 g, yield 23%).

[0053] The physical properties of the product are as follows: FT-IR(KBr,cm -1 ):2995(ν C-H芳香族 ),2950(ν C-Hアルカン ),1733(ν C=Oカルボニル ),1455(ν C=Sチオアミド ),731(ν C-Sスルフィド ). 1 H-NMR(500MHz,CDCl3) δ(ppm):8.03(br,1.00H,H a ),7.88(br,0.994H,H d ), 7.49(br,1.04H,H c ), 7.40(br,1.11H,H b ),3.76-3.27(br,13.72H,H h )1.88-1.56(br,32.46H,H f )1.13-0.837(br,17.41H,H g ). GPC(DMF,Polystyrene std,RI)Mn=1190,Mw / Mn=2.73

[0054] [ka]

[0055] Mass spectrometry was performed on CP-MMA1 obtained using the above procedure by MALDI-TOF MS (ionizing agent: silver trifluoroacetate). The results are shown in Figure 1. Figure 1 is a MALDI-TOF MS chart for the cyclic polymer (CP-MMA1) obtained in the example. In Figure 1, the peaks marked with circles represent the molecular weight of BTT + molecular weight of MMA × n + mass of silver ions [(BTT + nMMA) + Ag]. + It corresponds to.

[0056] As shown in Figure 1, each peak interval corresponds to the molecular weight of MMA (M MMA This matches (=100.12), and since each of these peaks corresponds to the molecular weight (+mass of silver ions) of the cyclic CP-MMA containing the BTT1 molecule, it can be seen that the product has a cyclic structure. Table 1 shows the degree of polymerization (n) and the MS result for each peak corresponding to the cyclic polymer with a degree of polymerization of 28-32 in Figure 1. + The measured values ​​and their calculated values ​​are shown below.

[0057] [Table 1]

[0058] • Synthesis of cyclic polymers by photopolymerization 2 (CP-MMA2) [ka]

[0059] Add BTT (0.167g, 1.00 mmol), 1,4-dioxane (1.00 mL), and methyl methacrylate (MMA, 1.00g, 10.0 mmol) to a 5 mm diameter screw-cap sample tube and stir to create a homogeneous solution. Then, perform four freeze-degassing cycles. After that, place a UV-LED (919 mW / cm²) at a distance of approximately 1 cm from the solution. 2 The reaction was irradiated with light at 365 nm for 6 hours at room temperature. After the light irradiation was complete, the reaction solution was dried under reduced pressure to obtain the product, cyclic polymethyl methacrylate (CP-MMA2), as a transparent viscous solid (conversion rate 65%, yield 1.01 g, yield 86%).

[0060] The physical properties of the product are as follows: FT-IR(KBr,cm -1 ):2996(ν C-H芳香族 ),2950(ν C-Hアルカン ),1733(ν C=Oカルボニル ),1486(ν C-C芳香族 ),1456(ν C=Sチオアミド ),758(ν C-Sスルフィド ). 1 H-NMR(500MHz,CDCl3) δ(ppm):8.03(br,1.00H,H a ),7.88(br,0.984H,H d ), 7.49(br,1.02H,H c ), 7.40(br,1.03H,H b ),3.76-3.27(br,22.50H,H h )1.88-1.57(br,25.31H,H f )1.02-0.837(br,11.54H,H g ). GPC(DMF,Polystyrene std,RI)Mn=1360,Mw / Mn=2.36

[0061] [ka]

[0062] Mass spectrometry was performed on the CP-MMA2 obtained using the above procedure by MALDI-TOF MS (ionizing agent: silver trifluoroacetate). The results are shown in Figure 2. Figure 2 is a MALDI-TOF MS chart for the cyclic polymer (CP-MMA2) obtained in the example. In Figure 2, the peaks marked with circles represent the molecular weight of BTT + molecular weight of MMA × n + mass of silver ions [(BTT + nMMA) + Ag]. + It corresponds to.

[0063] As shown in Figure 2, each peak interval corresponds to the molecular weight of MMA (M MMAThis matches (=100.12), and since each of these peaks corresponds to the molecular weight (+mass of silver ions) of the cyclic CP-MMA containing the BTT1 molecule, it can be seen that the product has a cyclic structure. Table 2 shows the degree of polymerization (n) and the MS result for each peak corresponding to the cyclic polymers with a degree of polymerization of 13-17 in Figure 2. + The measured values ​​and their calculated values ​​are shown below.

[0064] [Table 2]

[0065] • Synthesis of cyclic polymers by photopolymerization 3 (CP-CHMA) [ka]

[0066] Add BTT (0.167g, 1.00 mmol), 1,4-dioxane (1.00 mL), and cyclohexyl methacrylate (CHMA, 1.68g, 10.0 mmol) to a 5 mm diameter screw-cap sample tube and stir to create a homogeneous solution. Then, freeze-drain the solution four times, and place a UV-LED (907 mW / cm²) at a distance of approximately 1 cm from the solution. 2 The reaction was irradiated with light at 365 nm for 6 hours at room temperature. After the light irradiation was complete, the reaction solution was dried under reduced pressure to obtain the product, cyclic polycyclohexyl methacrylate (CP-CHMA), as a yellow viscous solid (conversion rate 92%, yield 0.775 g, yield 66%).

[0067] The physical properties of the product are as follows: FT-IR(KBr,cm -1 ):2936(ν C-H芳香族 ),2958(ν C-Hアルカン ),1725(ν C=Oカルボニル ),1450(ν C=Sチオアミド ),759(ν C-Sスルフィド ). 1H-NMR(500MHz,CDCl3) δ(ppm):8.01(br,1.00H,H a ),7.88(br,0.995H,H d ),7.47(br,1.07H,H c ), 7.38(br,1.07H,H b ),4.87-3.27(br,8.76H,H f ),2.50-0.924(br,103.27H,H g,h ). GPC(DMF,Polystyrene std,RI)Mn=1140,Mw / Mn=1.95

[0068] [ka]

[0069] Mass spectrometry was performed on the CP-CHMA obtained using the above procedure by MALDI-TOF MS (ionizing agent: silver trifluoroacetate). The results are shown in Figure 3. Figure 3 is a MALDI-TOF MS chart for the cyclic polymer (CP-CHMA) obtained in the example. In Figure 3, the peaks marked with circles represent the molecular weight of BTT + molecular weight of CHMA × n + mass of silver ions [(BTT+nCHMA)+Ag]. + It corresponds to.

[0070] As shown in Figure 3, each peak interval corresponds to the molecular weight of CHMA (M CHMA This matches (=168.24), and since each of these peaks corresponds to the molecular weight (+mass of silver ions) of the cyclic CP-CHMA containing the BTT1 molecule, it can be seen that the product has a cyclic structure. Table 3 shows the degree of polymerization (n) and the MS result for each peak corresponding to the cyclic polymers with a degree of polymerization of 8 to 12 in Figure 3. + The measured values ​​and their calculated values ​​are shown below.

[0071] [Table 3]

[0072] ·Synthesis of Cyclic Polymers by Photopolymerization 4 (CP-BzMA)

Chem.

[0073] BTT (0.167 g, 1.00 mmol), 1,4-dioxane (1.00 mL), and benzyl methacrylate (BzMA, 1.76 g, 10.0 mmol) were added to a screw sample tube with a diameter of 5 mm and stirred to form a homogeneous solution. After that, freeze-degassing was performed 4 times, and ultraviolet light-emitting diode (UV-LED, 918 mW / cm 2 at 365 nm) was used to irradiate the solution at room temperature for 6 hours with an interval of about 1 cm left in the solution. After the light irradiation was completed, the reaction solution was dried under reduced pressure to obtain the product, cyclic polybenzyl methacrylate (CP-BzMA), as a yellow viscous solid (conversion rate 81%, yield 0.526 g, yield 27%).

[0074] The physical property data of the product are as follows. FT-IR (KBr, cm -1 ): 2952 (ν C-H芳香族 ), 1728 (ν C=Oカルボニル ), 1455 (ν C=Sチオアミド ), 751 (ν C-Sスルフィド ). 1 H-NMR (500 MHz, CDCl3) δ (ppm): 7.98 (br, 1.00H, H a ), 7.83 (br, 1.30H, H d ), 7.46 (br, 2.03H, H c,b ), 7.28 (br, 46.93H, H i ), 5.16 - 4.87 (br, 26.23H, H h ) 1.89 - 1.40 (br, 34.39H, H f ) 1. 13 - 0 [0.837 (br, 34.48H, H g ). GPC (DMF, Polystyrene std, RI) Mn = 3120, Mw / Mn = 2.03

[0075]

Chem.

[0076] Mass spectrometry of the CP-BzMA obtained by the above procedure was performed using MALDI-TOF MS (ionizing agent: silver trifluoroacetate). The results are shown in Fig. 4. Fig. 4 is a chart of MALDI-TOF MS for the cyclic polymer (CP-BzMA) obtained in the examples. In Fig. 4, the peaks marked with circles correspond to the molecular weight of BTT + the molecular weight of BzMA × n + the mass of silver ions [(BTT + nBzMA) + Ag]. + corresponds to

[0077] As shown in Fig. 4, the interval between each peak coincides with the molecular weight of BzMA (M BzMA = 176.22), and since each of these peaks corresponds to the molecular weight of the cyclic CP-BzMA containing 1 molecule of BTT (+ the mass of silver ions), it can be seen that the product has a cyclic structure. Table 4 shows the degree of polymerization (n), the measured value of [(BTT + nBzMA) + Ag] by MS, and the calculated value for each peak corresponding to the cyclic polymer with a degree of polymerization of 5 - 9 in Fig. 4. + respectively.

[0078]

Table 4

[0079] ·Synthesis of cyclic polymer 5 (CP-MMA3) by photopolymerization

Chem.

[0080] BTT (0.167 g, 1.00 mmol), 1,4-dioxane (1.00 mL), 2-isopropylthioxanthone (ITX, 0.0128 g, 0.05 mmol), and methyl methacrylate (MMA, 1.00 g, 10.0 mmol) were added to a screw sample tube with a diameter of 5 mm and stirred to form a homogeneous solution. Then, freeze-degassing was performed 4 times, and an ultraviolet light-emitting diode (UV-LED, 939 mW / cm was placed at an interval of about 1 cm from the solution.2 The reaction was irradiated with light at 365 nm for 4 hours at room temperature. After light irradiation, the reaction solution was dried under reduced pressure to obtain the product, cyclic polymethyl methacrylate (CP-MMA3), as a transparent viscous solid (conversion rate 78%, yield 0.407 g, yield 35%).

[0081] The physical properties of the product are as follows: FT-IR(KBr,cm -1 ):2995(ν C-H芳香族 ),2950(ν C-Hアルカン ),1733(ν C=Oカルボニル ),1486(ν C-C芳香族 ),1456(ν C=Sチオアミド ),758(ν C-Sスルフィド ). 1 H-NMR(500MHz,CDCl3) δ(ppm):8.03(br,1.00H,H a ), 7.88(br,1.14H,H d ), 7.51(br,1.17H,H c ), 7.41(br,1.53H,H b ),3.76-3.29(br,32.17H,H h )2.18-1.56(br,20.45H,H f )1.44-0.837(br,46.35H,H h ). GPC(DMF,Polystyrene std,RI)Mn=1630,Mw / Mn=2.40

[0082] [ka]

[0083] Mass spectrometry was performed on the CP-MMA3 obtained using the above procedure by MALDI-TOF MS (ionizing agent: silver trifluoroacetate). The results are shown in Figure 5. Figure 5 is a MALDI-TOF MS chart for the cyclic polymer (CP-MMA3) obtained in the example. In Figure 5, the peaks marked with circles represent the molecular weight of BTT + molecular weight of MMA × n + mass of silver ions [(BTT + nMMA) + Ag].+ It corresponds to.

[0084] As shown in Figure 5, each peak interval corresponds to the molecular weight of MMA (M MMA This matches (=100.12), and since each of these peaks corresponds to the molecular weight (+mass of silver ions) of the cyclic CP-MMA containing the BTT1 molecule, it can be seen that the product has a cyclic structure. Table 5 shows the degree of polymerization (n) and the MS result for each peak corresponding to the cyclic polymers with a degree of polymerization of 5 to 9 in Figure 5. + The measured values ​​and their calculated values ​​are shown below.

[0085] [Table 5]

Claims

1. A method for producing a cyclic polymer in which the monomer compound is incorporated as a repeating unit, characterized by irradiating with light at room temperature in the presence of a monomer compound represented by the following general formula (2) and a compound represented by the following general formula (1). 【Chemistry 1】 (In the above general formula (1), Z is a sulfur atom or an oxygen atom, and Ar is an aromatic ring which may have substituents, and the aromatic ring may be a fused ring.) 【Chemistry 2】 (In the above general formula (2), R １ is a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 5 carbon atoms, and X is -(C=O) OR ３ , -OR ３ or a carboxyl group, R ２ Each of these is independently a hydrogen atom, a C1-C5 alkyl group, or a halogen atom, R ３ (This is a monovalent organic group.)

2. A method for producing a cyclic polymer according to claim 1, wherein Z is a sulfur atom.

3. A method for producing a cyclic polymer according to claim 1 or 2, wherein the compound represented by the general formula (2) is a (meth)acrylic acid ester.

4. Furthermore, the method for producing a cyclic polymer according to any one of claims 1 to 3, wherein the light irradiation is performed in the presence of a thioxanthone compound, a xanthone compound, anthracene compound, or an anthraquinone compound.

5. The method for producing a cyclic polymer according to claim 4, wherein the thioxanthone compound is 2-isopropylthioxanthone.

6. A cyclic polymer represented by the following general formula (3). 【Transformation 3】 (In the above general formula (3), Z is a sulfur atom or an oxygen atom, Ar is an aromatic ring which may have a substituent, and the aromatic ring may be a condensed ring, R １ is a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 5 carbon atoms, X is -(C=O)OR ３ , -OR ３ or a carboxy group, and each of R ２ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, R ３ is a monovalent organic group, and n is an integer of 1 or more.)

7. The cyclic polymer according to claim 6, represented by the following general formula (3a). 【Chemistry 4】 (In the above general formula (3a), Z is a sulfur atom or an oxygen atom, Ar is an aromatic ring which may have substituents, and the aromatic ring may be a fused ring, R １ R is a hydrogen atom or a methyl group, ２ Each of these is independently either a hydrogen atom or a methyl group, R is a monovalent organic group, and n is an integer greater than or equal to 1.

8. The cyclic polymer according to claim 6 or 7, wherein Z is a sulfur atom.

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