Compound, polymer, composition and crosslinked polymer using these, and method for producing novel compound

Abstract

The present disclosure provides: a novel compound having a novel multibranched structure and exhibiting small dielectric loss in a high frequency band of the Sub-THz band; and a method for producing the same. A compound according to the present disclosure is represented by general formula (1). (In general formula (1), R1 and R2 are each independently a hydrogen atom or an alkyl group, Ar1 to Ar4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, Cy1 to Cy4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms.)

Description

Compounds, polymers, compositions and crosslinked polymers using these compounds, and methods for producing novel compounds

[0001] The present invention relates to a novel compound and a method for producing the same. More specifically, the present invention relates to a novel compound having a multibranched structure, a polymer using the same, a composition and a crosslinked polymer using the same, and a method for producing the novel compound.

[0002] In recent years, the development of IoT technology has progressed toward the realization of Society 5.0, a new society expected in the 2030s that integrates cyberspace with the real world. Beyond 5G, the next generation of fifth-generation mobile communications systems (5G), has attracted attention as a system that will play a central role in supporting IoT technology, and further improvements in the performance of electronic devices are desired in order to commercialize Beyond 5G.

[0003] Beyond 5G aims to realize the next generation of information and communications infrastructure by using even higher frequency bands than the currently used radio wave signal frequency bands. For example, while the 3.7 GHz, 4.5 GHz, and 28 GHz bands have traditionally been allocated as frequencies for 5G in Japan, the use of the higher sub-THz band is being considered for next generation communication systems. However, the use of high frequency bands increases the transmission loss of radio wave signals inside devices. Therefore, there is a need to develop materials with low dielectric loss in the high frequency band of the sub-THz band.

[0004] Conventionally, as materials with small dielectric loss in the high frequency band, for example, multi-branched monomers having specific aromatic groups as substituents have been proposed (see Non-Patent Documents 1 to 3).

[0005] K. Matsumoto, T. Higashihara, M. Ueda, Macromolecules, 2009, 42, 1161-1166.Y. Hu, B. Wang, X. Li, D. Chen, W. Zhang, J. Power Sources, 2018, 387, 33-42.L. Xiong, Y. Hu, Z. Zheng, Z. Xie, D. Chen, Chin J Polym Sci, 2020, 38, 278-287.

[0006] An object of the present invention is to provide a novel compound having a novel multi-branched structure and exhibiting low dielectric loss in the high frequency band of the sub-THz band, as well as a method for producing the same, etc. Another object of the present invention is to provide the novel compound, a polymer obtained using the novel compound, and a composition, a crosslinked polymer, etc. using the novel compound or the polymer.

[0007] In addition to the objectives stated here, the present invention can also be positioned as another objective of achieving effects that cannot be obtained by conventional technologies, which are derived from the various components shown in the detailed description of the invention described below.

[0008] As a result of extensive research into new molecular designs for achieving low dielectric constants and low dielectric loss tangents, the present inventors synthesized novel compounds into which polycyclic hydrocarbon groups, in which aromatic hydrocarbons and alicyclic hydrocarbons are bonded, are introduced in a multi-branched manner, and discovered that the above-mentioned problems can be solved by using the novel compounds, leading to the completion of the present invention. That is, the present invention provides various specific embodiments as shown below.

[0009] [1] A compound represented by the following general formula (1): (In general formula (1), R 1 and R 2 are each independently a hydrogen atom or an alkyl group, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms.

[0010] [2] Ar in the general formula (1) 1 ~Ar 4 The compound according to [1], wherein the aromatic hydrocarbon group is selected from the group consisting of benzene, naphthalene, anthracene, pentalene, indene, as-indacene, biphenylene, acenaphthylene, fluorene, phenalene, heptalene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, and coronene.

[0011] [3] Cy in the general formula (1) 1 ~Cy 4 The compound according to [1] or [2], wherein the alicyclic hydrocarbon group is selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, and cycloicosane.

[0012] [4] A polymer containing at least a (co)polymerization unit A represented by the following general formula (1A): (In general formula (1A), Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms, and * is a bond.

[0013] [5] Ar in the general formula (1A) 1 ~Ar 4The polymer according to [4], wherein the aromatic hydrocarbon group is selected from the group consisting of benzene, naphthalene, anthracene, pentalene, indene, as-indacene, biphenylene, acenaphthylene, fluorene, phenalene, heptalene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, and coronene.

[0014] [6] Cy in the general formula (1A) 1 ~Cy 4 The polymer according to [4] or [5], wherein the alicyclic hydrocarbon group is selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, and cycloicosane.

[0015] [7] The polymer according to any one of [4] to [6], further comprising a copolymerization unit B, wherein the copolymerization unit B is one or more units represented by the following general formula group (11A):

[0016] [8] The polymer according to claim [7], containing the copolymerization units A and the copolymerization units B in a molar ratio of 45:55 to 55:45.

[0017] [9] The polymer according to any one of [4] to [6], further comprising a copolymerization unit B and a copolymerization unit C, wherein the copolymerization unit B is one or more units shown in the following general formula group (11A), and the copolymerization unit C is one or more units shown in the following general formula group (21A).

[0018]

[10] The polymer according to [9], containing the copolymerization unit A and the copolymerization unit B in a molar ratio of 1:99 to 99:1.

[0019]

[11] A composition comprising the compound according to any one of [1] to [3].

[0020]

[12] A composition comprising the polymer according to any one of [4] to

[10] .

[0021]

[13] A crosslinked polymer, which is a crosslinked product of the composition according to

[11] .

[0022]

[14] A crosslinked polymer, which is a crosslinked product of the composition according to

[12] .

[0023]

[15] A method for producing a compound, comprising reacting a compound represented by the following general formula (31A) with one or more compounds represented by the following general formula (41A) to synthesize a compound represented by the following general formula (1′): (In general formula (31A), R 11 and R 21 are each independently an alkyl group, and X 1 ~X 4 are each independently a halogen atom. (In the general formula (31A), Ar' is Ar in the general formula (1'). 1 ~Ar 4 is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy' is a group corresponding to Cy in general formula (1'). 1 ~Cy 4 and is a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms. (In general formula (1'), R 11 and R 21 are each independently an alkyl group, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms.

[0024]

[16] A method for producing a compound, comprising dealkylating a compound represented by the following general formula (1′) in the presence of an acid or a base to synthesize a compound represented by the following general formula (1″): (In general formula (1'), R 11 and R 21are each independently an alkyl group, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms. (In general formula (1''), R 31 and R 41 are each independently a hydrogen atom, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms.

[0025] According to the present invention, it is possible to realize a novel compound having a novel multi-branched structure and low dielectric loss in the high frequency band of the sub-THz band, and a method for producing the same. Furthermore, according to the present invention, it is possible to realize the novel compound, a polymer obtained using the novel compound, and a composition and a crosslinked polymer using the novel compound and the polymer. Furthermore, according to one aspect of the present invention, it is possible to realize a novel compound that not only has low dielectric loss in the high frequency band of the sub-THz band, but also has heat resistance of preferably 250°C or higher, more preferably 300°C or higher. Therefore, the present invention is useful as an insulating material, an interlayer insulating material, a rewiring insulating material, and the like, required in fifth-generation mobile communication systems or beyond 5G, etc.

[0026] FIG. 1 shows the structure of compound (1). 1 2 shows the H-NMR spectrum of compound (1). 19 FIG. 3 shows the F-NMR spectrum of compound (2). 1 4 shows the H-NMR spectrum of compound (2). 13 FIG. 5 shows the C-NMR spectrum of compound (3). 1 6 shows the H-NMR spectrum of compound (3). 13Figure 7 shows the C-NMR spectrum of compound (3). Figure 8 shows the FT-IR spectrum of polymer P4. 1 FIG. 11 shows a comparison of the physical properties of polymer P4 and comparative polymer P5. FIG. 12 shows TG curves of polymer P4 and comparative polymer P5. FIG. 13 shows the weight loss temperatures of polymer P4 and comparative polymer P5. FIG. 14 shows a DSC curve of polymer P4. FIG. 15 shows a DSC curve of comparative polymer P5. FIG. 16 shows the WAXD measurement results of polymer P4 and comparative polymer P5.

[0027] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The following embodiments are examples (typical examples) of the present invention, and the present invention is not limited thereto. In other words, the present invention can be implemented with any modifications within the scope of the gist thereof. In this specification, when a numerical value or physical property value is enclosed before and after the "-" symbol, the values ​​before and after the "-" symbol are used to include the values. For example, the expression "1 to 100" of a numerical range includes both the upper limit "100" and the lower limit "1". The same applies to the expression of other numerical ranges.

[0028] [Compound] The compound of this embodiment is a compound represented by the following general formula (1). (In general formula (1), R 1 and R 2 are each independently a hydrogen atom or an alkyl group, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms.

[0029] R in the above general formula (1) 1 and R 2is a hydrogen atom or an alkyl group. Suitable examples of the alkyl group include linear or branched alkyl groups, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is even more preferred.

[0030] Ar in the above general formula (1) 1 ~Ar 4 The aromatic hydrocarbon group of Ar in the above general formula (1) is not particularly limited as long as it is an aromatic hydrocarbon group having 6 to 24 carbon atoms. 1 ~Ar 4 The aromatic hydrocarbon group may be an aromatic ring having 6 to 24 carbon atoms, and specific examples thereof include benzene, naphthalene, anthracene, pentalene, indene, as-indacene, biphenylene, acenaphthylene, fluorene, phenalene, heptalene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, and coronene, but are not particularly limited thereto. 1 ~Ar 4 The aromatic hydrocarbon group is preferably benzene, naphthalene, or anthracene, more preferably benzene or naphthalene, and even more preferably benzene. 1 ~Ar 4 represents —O— and Cy in the above general formula (1). 1 ~Cy 4 It can also be said that —O— and Cy are divalent linking groups that bond to each other. 1 ~Cy 4 Ar for 1 ~Ar 4 The bonding position (substitution position) of Ar is not particularly limited. 1 ~Ar 4 The aromatic hydrocarbon group or aromatic ring may be at any position.

[0031] In addition, Ar 1 ~Ar 4The aromatic hydrocarbon group may further have a substituent on each aromatic ring, or may have no substituent. 1 ~Ar 4 Preferably, the aromatic hydrocarbon group of Ar does not further have such a substituent. 1 ~Ar 4 It is preferable that the aromatic hydrocarbon group further has such a substituent. Specific examples of the substituent include, but are not limited to, an alkyl group having 1 to 4 carbon atoms, a halogen atom (F, Cl, Br, etc.), etc. Among these, the substituent preferably has an alkyl group having 1 to 3 carbon atoms or a halogen atom, more preferably an alkyl group having 1 to 3 carbon atoms. The number of the substituents described here and the substitution positions thereof are not particularly limited. For example, the number of the substituents may be 0 or 1 to 3, and the substitution position of the substituent may be any position on the aromatic hydrocarbon group or aromatic ring. In this specification, Ar 1 ~Ar 4 When the aromatic hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in the calculation of the above "aromatic hydrocarbon group having 6 to 24 carbon atoms."

[0032] Cy in the above general formula (1) 1 ~Cy 4 The alicyclic hydrocarbon group of Cy in the above general formula (1) is not particularly limited as long as it is an alicyclic hydrocarbon group having 5 to 20 carbon atoms. 1 ~Cy 4 The alicyclic hydrocarbon group may be an alicyclic group having 6 to 24 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, and cycloicosane, but are not particularly limited thereto. 1 ~Cy 4The alicyclic hydrocarbon group is preferably cyclopentane, cyclohexane, cycloheptane, or cyclooctane, more preferably cyclopentane, cyclohexane, or cycloheptane, and even more preferably cyclohexane. 1 ~Cy 4 represents Ar in the general formula (1). 1 ~Ar 4 It can also be said that Ar is a monovalent substituent that bonds to Ar. 1 ~Ar 4 Cy 1 ~Cy 4 The bonding position (substitution position) of Ar is not particularly limited. 1 ~Ar 4 The aromatic hydrocarbon group or aromatic ring may be at any position.

[0033] In addition, Cy 1 ~Cy 4 The alicyclic hydrocarbon group may further have a substituent on each alicyclic ring, or may have no substituent. 1 ~Cy 4 Preferably, the alicyclic hydrocarbon group of the formula (I) does not further have such a substituent. 1 ~Cy 4 It is preferable that the alicyclic hydrocarbon group further has such a substituent. Specific examples of the substituent include, but are not limited to, an alkyl group having 1 to 4 carbon atoms, a halogen atom (F, Cl, Br, etc.), etc. Among these, the substituent preferably has an alkyl group having 1 to 3 carbon atoms or a halogen atom, more preferably an alkyl group having 1 to 3 carbon atoms. The number of the substituents described here and the substitution positions thereof are not particularly limited. For example, the number of substituents may be 0 or 1 to 3, and the substitution position of the substituent may be any position on the alicyclic hydrocarbon group or the alicyclic ring. In this specification, Cy 1 ~Cy 4 When the alicyclic hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in the calculation of the above "alicyclic hydrocarbon group having 5 to 20 carbon atoms."

[0034] The compound of the present embodiment described above is a compound having the following formula (1a) as a main skeleton, and X 1 ~X 4 It can also be said that this is a compound in which multiple branches have been introduced into the main skeleton. (In general formula (1a), R 11 and R 21 represents R in the above general formula (1). 1 and R 2 and X 1 ~X 4 are the following formulas (1b) to (1e), respectively. (In general formulas (1b) to (1e), Ar 1 ~Ar 4 are each independently the Ar in the general formula (1) above. 1 ~Ar 4 and Cy 1 ~Cy 4 are each independently a Cy in the general formula (1) above. 1 ~Cy 4 and * are equivalent to bonds.)

[0035] In a preferred embodiment, the compound represented by the general formula (1) may be represented by the following general formula (1-1): (In general formula (1-1), R 1 and R 2 are each independently a hydrogen atom or an alkyl group, and Cy 1 ~Cy 4 are each independently a Cy in the general formula (1) above. 1 ~Cy 4 are synonymous with

[0036] The compound of the present embodiment is molecularly designed to have a small molar polarizability and a large molar volume. 1 ~Cy 4Due to the relatively bulky structure of [Chemical Formula 1], the overall molecular structure has a rigid structure with low polarization of the functional groups and low mobility, such as rotation and vibration, of the molecular chain, thereby achieving both a low dielectric constant and a low dielectric loss tangent. Therefore, for example, by crosslinking the compound of this embodiment, or by polymerizing the compound of this embodiment alone, or by forming a copolymer using the compound of this embodiment as a copolymerization component, a material with a low dielectric constant and a low dielectric loss tangent can be obtained. Furthermore, due to its molecular design, the compound of this embodiment inherently has high heat resistance. Therefore, the compound of this embodiment is useful as an insulating material, an interlayer insulating material, a rewiring insulating material, etc., required for fifth-generation mobile communication systems or Beyond 5G, etc.

[0037] (Production Method) The compound of the present embodiment described above can be produced by a known synthesis route, and the production method is not particularly limited. In a preferred aspect of the present embodiment, the compound of the present embodiment described above can be synthesized by synthesizing an alkoxy compound according to the following scheme, and then carrying out a deprotection reaction of the alkyl group by a dealkylation reaction to hydroxylate the compound.

[0038] <Synthesis of Alkoxy Compound> A compound represented by the following general formula (31A) can be reacted with one or more compounds represented by the following general formula (41A) to synthesize a compound represented by the following general formula (1′) (alkoxy compound). (In general formula (31A), R 11 and R 21 are each independently an alkyl group, and X 1 ~X 4 are each independently a halogen atom. (In the general formula (41A), Ar' is Ar in the general formula (1'). 1 ~Ar 4 is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy' is a group corresponding to Cy in general formula (1'). 1 ~Cy 4 and is a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms. (In general formula (1'), R11 and R 21 are each independently an alkyl group, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms.

[0039] Here, Ar in general formulas (1') and (41) 1 ~Ar 4 are each independently the Ar in the general formula (1) above. 1 ~Ar 4 and Cy 1 ~Cy 4 are each independently a Cy in the general formula (1) above. 1 ~Cy 4 The same applies to the preferred examples, so a duplicated explanation will be omitted here.

[0040] <Synthesis Conditions for Alkoxy Compound> The compound (alkoxy compound) represented by the general formula (31A) above may be commercially available or may be appropriately synthesized by a known synthesis route. In addition, for example, the compound represented by the general formula (31A) above can also be synthesized by carrying out an aromatic nucleophilic substitution reaction between a commercially available aryl halide (haloarene) and an alkoxyphenol.

[0041] The synthesis of the alkoxy compound can be carried out according to a conventional method, and the synthesis method is not particularly limited. For example, the synthesis can be carried out in the presence of a base, a solvent, or the like. The solvent may be appropriately selected depending on the reaction temperature, the reactants, and the like, and is not particularly limited. Examples of the solvent include aromatic hydrocarbon solvents such as benzene and toluene; amide solvents such as acetonitrile, N,N-dimethylacetamide, and N,N-dimethylformamide; aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl-3-methyl-2-pyrrolidone; ether solvents such as tetrahydrofuran (hereinafter also referred to as THF), diethyl ether, and 1,2-dimethoxyethane; alcohol solvents such as methanol, ethanol, and isopropanol; and halogenated solvents such as dichloromethane, dichloroethane, and chloroform. These solvents can be used alone or in any combination and ratio of two or more. The base may be appropriately selected depending on the reaction temperature, reactants, etc., and is not particularly limited. Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; and alkaline earth metal bicarbonates such as calcium hydrogen carbonate and barium hydrogen carbonate. These may be used alone or in any combination and ratio of two or more. Among these, alkali metal carbonates and alkali metal bicarbonates are preferred, potassium carbonate and potassium hydrogen carbonate are more preferred, and potassium carbonate is even more preferred. The alkali is preferably used in the form of an anhydride, but can also be used as a hydrate, etc. The reaction temperature is not particularly limited, but may be preferably room temperature (25°C to 250°C), more preferably 120 to 240°C, and even more preferably 150 to 230°C.The reaction time can be adjusted appropriately by monitoring the progress of the reaction using, for example, GC-MS, and is not particularly limited, but is preferably 5 minutes to 100 hours, preferably 0.5 hours to 70 hours, and more preferably 1 hour to 60 hours. After completion of the reaction, the reaction solution may be subjected to known post-treatments as necessary. Examples of known post-treatments include washing with water, precipitation, filtration, drying, extraction, distillation, recrystallization, and chromatography. Two or more of these methods may be combined.

[0042] <Synthesis of Hydroxy Compound> A compound (alkoxy compound) represented by the following general formula (1′) can be dealkylated in the presence of an acid or a base to synthesize a compound (hydroxy compound) represented by the following general formula (1″). (In general formula (1'), R 11 and R 21 are each independently an alkyl group, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms. (In general formula (1''), R 31 and R 41 are each independently a hydrogen atom, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms.

[0043] Here, Ar in general formula (1″) 1 ~Ar 4 are each independently the Ar in the general formula (1) above. 1 ~Ar 4 and Cy 1 ~Cy 4are each independently a Cy in the general formula (1) above. 1 ~Cy 4 The same applies to the preferred examples, so a duplicated explanation will be omitted here.

[0044] <Synthesis Conditions for Hydroxy Compound> The synthesis of a hydroxy compound can be carried out according to a conventional method, and the synthesis method is not particularly limited. For example, the synthesis can be carried out in the presence of a Lewis acid, a Bronsted acid, a solvent, or the like. The solvent can be appropriately selected depending on the reaction temperature, the reactants, and the like, and is not particularly limited. Examples of the solvent include aromatic hydrocarbon solvents such as benzene and toluene; amide solvents such as acetonitrile, N,N-dimethylacetamide, and N,N-dimethylformamide; aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl-3-methyl-2-pyrrolidone; ether solvents such as tetrahydrofuran (hereinafter also referred to as THF), diethyl ether, and 1,2-dimethoxyethane; alcohol solvents such as methanol, ethanol, and isopropanol; and halogenated solvents such as dichloromethane, dichloroethane, and chloroform. These solvents can be used alone or in any combination and ratio of two or more. Furthermore, the Lewis acid or Bronsted acid may be appropriately selected depending on the reaction temperature, reactants, etc., and is not particularly limited. Examples include, but are not limited to, boron tribromide (BBr), aluminum chloride (AlCl), and hydrobromic acid (HBr). These may be used alone or in any combination and ratio of two or more. Among these, boron tribromide is preferred. The reaction temperature is not particularly limited, but is preferably −85°C to 100°C, more preferably −80°C to 50°C. The reaction time can be adjusted appropriately by monitoring the progress of the reaction using, for example, GC-MS, and is not particularly limited, but is preferably 5 minutes to 100 hours, preferably 0.5 hours to 70 hours, and more preferably 1 hour to 60 hours. After the reaction is completed, the reaction solution may be subjected to known post-treatments as necessary. For example, known methods such as water washing, precipitation, filtration, drying, extraction, distillation, recrystallization, and chromatography can be used. Two or more of these methods may be combined.

[0045] [Polymer] The polymer of this embodiment is a (co)polymer containing the compound represented by the above general formula (1) as a (co)polymerizable monomer. That is, the polymer of this embodiment contains at least a (co)polymerized unit A represented by the following general formula (1A): (In general formula (1A), Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms, and * is a bond.

[0046] Ar in the above general formula (1A) 1 ~Ar 4 The aromatic hydrocarbon group of Ar in the above general formula (1A) is not particularly limited as long as it is an aromatic hydrocarbon group having 6 to 24 carbon atoms. 1 ~Ar 4 The aromatic hydrocarbon group may be an aromatic ring having 6 to 24 carbon atoms, and specific examples thereof include benzene, naphthalene, anthracene, pentalene, indene, as-indacene, biphenylene, acenaphthylene, fluorene, phenalene, heptalene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, and coronene, but are not particularly limited thereto. 1 ~Ar 4 The aromatic hydrocarbon group is preferably benzene, naphthalene, or anthracene, more preferably benzene or naphthalene, and even more preferably benzene. 1 ~Ar 4 represents —O— and Cy in the above general formula (1A). 1 ~Cy 4 It can also be said that —O— and Cy are divalent linking groups that bond to each other. 1 ~Cy 4 Ar for 1 ~Ar 4 The bonding position (substitution position) of Ar is not particularly limited. 1 ~Ar 4The aromatic hydrocarbon group or aromatic ring may be at any position.

[0047] In addition, Ar 1 ~Ar 4 The aromatic hydrocarbon group may further have a substituent on each aromatic ring, or may have no substituent. 1 ~Ar 4 Preferably, the aromatic hydrocarbon group of Ar does not further have such a substituent. 1 ~Ar 4 It is preferable that the aromatic hydrocarbon group further has such a substituent. Specific examples of the substituent include, but are not limited to, an alkyl group having 1 to 4 carbon atoms, a halogen atom (F, Cl, Br, etc.), etc. Among these, the substituent preferably has an alkyl group having 1 to 3 carbon atoms or a halogen atom, more preferably an alkyl group having 1 to 3 carbon atoms. The number of the substituents described here and the substitution positions thereof are not particularly limited. For example, the number of the substituents may be 0 or 1 to 3, and the substitution position of the substituent may be any position on the aromatic hydrocarbon group or aromatic ring. In this specification, Ar 1 ~Ar 4 When the aromatic hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in the calculation of the above "aromatic hydrocarbon group having 6 to 24 carbon atoms."

[0048] Cy in the above general formula (1A) 1 ~Cy 4 The alicyclic hydrocarbon group of Cy in the above general formula (1A) is not particularly limited as long as it is an alicyclic hydrocarbon group having 5 to 20 carbon atoms. 1 ~Cy 4The alicyclic hydrocarbon group may be an alicyclic group having 6 to 24 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, and cycloicosane, but are not particularly limited thereto. 1 ~Cy 4 The alicyclic hydrocarbon group is preferably cyclopentane, cyclohexane, cycloheptane, or cyclooctane, more preferably cyclopentane, cyclohexane, or cycloheptane, and even more preferably cyclohexane. 1 ~Cy 4 represents Ar in the general formula (1A). 1 ~Ar 4 It can also be said that Ar is a monovalent substituent that bonds to Ar. 1 ~Ar 4 Cy 1 ~Cy 4 The bonding position (substitution position) of Ar is not particularly limited. 1 ~Ar 4 The aromatic hydrocarbon group or aromatic ring may be at any position.

[0049] In addition, Cy 1 ~Cy 4 The alicyclic hydrocarbon group may further have a substituent on each alicyclic ring, or may have no substituent. 1 ~Cy 4 Preferably, the alicyclic hydrocarbon group of the formula (I) does not further have such a substituent. 1 ~Cy 4It is preferable that the alicyclic hydrocarbon group further has such a substituent. Specific examples of the substituent include, but are not limited to, an alkyl group having 1 to 4 carbon atoms, a halogen atom (F, Cl, Br, etc.), etc. Among these, the substituent preferably has an alkyl group having 1 to 3 carbon atoms or a halogen atom, more preferably an alkyl group having 1 to 3 carbon atoms. The number of the substituents described here and the substitution positions thereof are not particularly limited. For example, the number of substituents may be 0 or 1 to 3, and the substitution position of the substituent may be any position on the alicyclic hydrocarbon group or the alicyclic ring. In this specification, Cy 1 ~Cy 4 When the alicyclic hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in the calculation of the above "alicyclic hydrocarbon group having 5 to 20 carbon atoms."

[0050] The polymer of this embodiment may be a homopolymer of the compound (monomer) represented by the general formula (1) above, or may be a copolymer with another copolymerization component (another monomer). When the polymer of this embodiment is a copolymer with another copolymerization component, the type of the other copolymerization component (another monomer) is not particularly limited, and known copolymerization components (another monomers) can be used.

[0051] In a preferred aspect of the present embodiment, the polymer may contain a compound (monomer) represented by the above general formula (1) as copolymerization unit A and further contain one or more copolymerization units B represented by the following general formula group (11A):

[0052] The content ratio of the copolymerization units A and B is not particularly limited and can be appropriately set depending on the desired performance. In one embodiment, the content ratio of the copolymerization units A and B may be a molar ratio of 45:55 to 55:45, 47:53 to 53:47, 49:51 to 51:49, or 50:50.

[0053] In a preferred aspect of the present embodiment, the polymer may contain a compound (monomer) represented by the above general formula (1) as copolymerization unit A, and further contain one or more copolymerization units B represented by the above general formula group (11A) and one or more copolymerization units C represented by the following general formula group (21A):

[0054] The content ratio of the copolymerization units A, B, and C can be appropriately set depending on the desired performance and is not particularly limited. The content ratio of the copolymerization units A and B can be set over a wide range by blending the copolymerization units C. In one aspect, the content ratio of the copolymerization units A and B may be a molar ratio of 1:99 to 99:1, 10:90 to 90:10, 20:80 to 80:20, or 30:70 to 70:30. The polymer of this embodiment may further contain other copolymerization components in addition to the copolymerization units A, B, and C described above.

[0055] <Polymer Synthesis Conditions> The synthesis of the polymer of this embodiment can be carried out according to a conventional method, and the synthesis method is not particularly limited. For example, the synthesis can be carried out in the presence of a base, a solvent, or the like. The solvent may be appropriately selected depending on the reaction temperature, reactants, and the like, and is not particularly limited. Examples of the solvent include aromatic hydrocarbon solvents such as benzene and toluene; amide solvents such as acetonitrile, N,N-dimethylacetamide, and N,N-dimethylformamide; aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl-3-methyl-2-pyrrolidone; ether solvents such as tetrahydrofuran (hereinafter also referred to as THF), diethyl ether, and 1,2-dimethoxyethane; alcohol solvents such as methanol, ethanol, and isopropanol; and halogenated solvents such as dichloromethane, dichloroethane, and chloroform. These solvents can be used alone or in any combination and ratio of two or more. The base may be appropriately selected depending on the reaction temperature, reactants, etc., and is not particularly limited. Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; and alkaline earth metal bicarbonates such as calcium hydrogen carbonate and barium hydrogen carbonate. These may be used alone or in any combination and ratio of two or more. Among these, alkali metal carbonates and alkali metal bicarbonates are preferred, potassium carbonate and potassium hydrogen carbonate are more preferred, and potassium carbonate is even more preferred. The alkali is preferably used in the form of an anhydride, but can also be used as a hydrate, etc. The reaction temperature is not particularly limited, but may be preferably room temperature (25°C to 250°C), more preferably 120 to 220°C, and even more preferably 150 to 200°C.The reaction time can be adjusted appropriately by monitoring the progress of the reaction using, for example, GC-MS, and is not particularly limited, but is preferably 5 minutes to 100 hours, preferably 0.5 hours to 70 hours, and more preferably 1 hour to 60 hours. After completion of the reaction, the reaction solution may be subjected to known post-treatments as necessary. Examples of known post-treatments include washing with water, precipitation, filtration, drying, extraction, distillation, recrystallization, and chromatography. Two or more of these methods may be combined.

[0056] [Composition] One aspect of the composition of this embodiment contains at least a compound represented by the general formula (1) above as an essential component. Another aspect of the composition of this embodiment contains at least a polymer containing at least a (co)polymerization unit A represented by the general formula (1A) above as an essential component. Needless to say, the composition of this embodiment may contain a compound represented by the general formula (1) above and a polymer containing at least a (co)polymerization unit A represented by the general formula (1A) above.

[0057] In addition, in any of the compositions described above, in addition to the essential components described above, additives known in the art may be included, to the extent that they do not excessively impair the effects of the present invention. For example, release modifiers such as higher fatty acids having 10 to 25 carbon atoms, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts, polysiloxanes, and fluororesins; dyes, pigments, colorants; organic fillers; inorganic fillers; lubricants; plasticizers; antioxidants; heat stabilizers; light stabilizers; UV absorbers; flame retardants; antistatic agents; surfactants; rust inhibitors; foaming agents; antifoaming agents; and fluorescent agents. These additives may be used alone or in combination of two or more. The content of the additives is not particularly limited, but from the viewpoints of moldability and thermal stability, it is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, and even more preferably 0.5 to 5% by mass, relative to the total amount of the polymer of this embodiment. The composition of this embodiment may also include the above-mentioned bases, Lewis acids, Bronsted acids, and solvents. For example, when the composition of this embodiment contains a solvent, the composition of this embodiment may exhibit the properties of a solution or dispersion. Furthermore, the composition of this embodiment may further contain other resin components, such as a thermosetting resin or a thermoplastic resin, in addition to the above-mentioned monomers and polymers. For example, when the composition of this embodiment further contains other resin components, the composition of this embodiment may exhibit the properties of a granular or pellet-like shape by mixing, kneading, melt-kneading, or the like, and processing it with a strand-cut or hot-cut pelletizer.

[0058] The composition of the present embodiment may be prepared by a conventional method, and is not particularly limited. The above-mentioned components can be produced and processed by known methods such as dissolving, dispersing, mixing, kneading, melt-kneading, granulating, extrusion molding, pressing, or injection molding. When melt-kneading, commonly used kneading devices such as single-screw or twin-screw extruders and various kneaders can be used. When supplying the components to these melt-kneading devices, the liquid crystal polyester, polymer materials, etc. may be dry-blended in advance using a mixing device such as a tumbler or Henschel mixer.

[0059] [Crosslinked Polymer] The crosslinked polymer of this embodiment is a crosslinked product obtained by crosslinking the composition of this embodiment described above. This crosslinked product may be a crosslinked product of a compound represented by the general formula (1) above, or a crosslinked product of a polymer containing at least the (co)polymerization unit A represented by the general formula (1A) above as an essential component. Furthermore, although it goes without saying, the crosslinked polymer of this embodiment may be a crosslinked product obtained by crosslinking a compound represented by the general formula (1) above with a polymer containing at least the (co)polymerization unit A represented by the general formula (1A) above. Furthermore, the crosslinked polymer of this embodiment may be a crosslinked product of a compound represented by the general formula (1) above and / or a polymer containing at least the (co)polymerization unit A represented by the general formula (1A) above with another component capable of forming a crosslinked structure. These other components capable of forming a crosslinked structure may be those known in the art and are not particularly limited, but examples thereof include crosslinking agents, crosslinkable monomers, crosslinkable polymers, etc.

[0060] The features of the present invention will be explained in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. That is, the materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Furthermore, the values ​​of various production conditions and evaluation results in the following examples represent preferred upper or lower limits in the embodiments of the present invention, and preferred ranges may be defined by combining the above-mentioned upper or lower limits with the values ​​in the following examples or values ​​between the examples.

[0061] [Nuclear magnetic resonance spectrum ( 1 H-NMR, 13 C-NMR, 19 NMR measurements of the obtained compounds were carried out using a JNM-ECS-400 NMR apparatus (manufactured by JEOL Ltd.) CDCl3 and DMSO-d6 were used as deuterated solvents, respectively. 1 Samples for H-NMR measurement and 19 A sample for F-NMR measurement was prepared by dissolving about 10 mg of the sample in 0.6 ml of a heavy solvent. 13A sample for C-NMR measurement was prepared by dissolving about 100 mg of the sample in 0.6 ml of a deuterated solvent.

[0062] [Fourier Infrared Absorption Spectroscopy (FT-IR) Measurement] FT-IR measurement of the obtained compound was carried out using a Fourier transform infrared spectrophotometer FT / IR-4100 (manufactured by JASCO Corporation). Solid samples were measured by the KBr tablet method.

[0063] Synthesis Example 1: 4.594 ml (40 mmol) of hexafluorobenzene (Hexafluorobenzene, manufactured by Tokyo Chemical Industry Co., Ltd.), 10.4278 g (84 mmol) of 4-methoxyphenol (4-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.), 13.8205 g (100 mmol) of potassium carbonate (K2CO3, manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), and 80 ml of N,N-dimethylacetamide (DMAc, manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) were placed in a recovery flask and stirred for 30 minutes at room temperature under an argon atmosphere, followed by stirring for 1 hour at 60°C and 2 hours at 80°C, and then overnight at 100°C. After completion of the reaction, the resulting reaction solution was poured into 600 ml of hydrochloric acid (10 wt%), and the precipitated white solid was filtered. The resulting residue was then dried under reduced pressure to remove the solvent, yielding a white solid. The resulting white solid was then purified by recrystallization from a mixed solvent of ethanol and chloroform to obtain 8.6750 g of the target compound (1), i.e., 4,4'-((perfluoro-1,4-phenylene)bis(oxy))bis(methoxybenzene) (yield: 55%).

[0064] The obtained compound (1) 1 H-NMR and 19 The F-NMR is shown below. 1 The H-NMR spectrum is shown in FIG. 19The F-NMR spectra are shown below. The peaks were clearly assigned, and the chemical shifts of the peaks were also in good agreement. These findings indicate that the target compound (1) was obtained by the aromatic nucleophilic substitution reaction between hexafluorobenzene and 4-methoxyphenol. 20 H 14 O4F4(394.32 g / mol) 1 H-NMR (400 MHz, CDCl3): δ 6.96 (d, J = 9.2 Hz, 4H), 6.86 (d, J = 9.2 Hz, 4H), 3.79 (s, 6H) ppm. 19 F-NMR (376 MHz, CDCl3): δ -156.21

[0065] A recovery flask equipped with a Dean-Stark apparatus was charged with 3.9432 g (10 mmol) of compound (1) synthesized by the above method, 10.5756 g (60 mmol) of 4-cyclohexylphenol (Tokyo Chemical Industry Co., Ltd.), 13.8205 g (100 mmol) of potassium carbonate (KCO, Fujifilm Wako Pure Chemical Industries, Ltd.), 40 ml of 1,3-dimethyl-2-imidazolidinone (DMI, Kanto Chemical Co., Inc.), and 25 ml of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.). The mixture was stirred at room temperature for 30 minutes under an argon atmosphere, followed by stirring at 150°C for 2 hours. The toluene was then distilled off, and the mixture was stirred at 165°C for 21 hours and then at 220°C for an additional hour. After completion of the reaction, the resulting reaction solution was poured into 600 ml of a 5 wt% aqueous sodium hydroxide solution, and the precipitated white solid was filtered. The residue was then dried under reduced pressure to remove the solvent, yielding a white solid. The resulting white solid was then purified by silica gel column chromatography (silica mesh, using a 1:2 mixture of methylene chloride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and hexane (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as the developing solvent). This gave 2.2925 g of the target compound (2), i.e., 4,4',4'',4'''-((3,6-bis(4-methoxyphenoxy)benzene-1,2,4,5-tetrayl)tetrakis(oxy))tetrakis(cyclohexylbenzene) (4,4',4'',4'''-((3,6-bis(4-methoxyphenoxy)benzene-1,2,4,5-tetrayl)tetrakis(oxy))tetrakis(cyclohexylbenzene)) (yield: 56%).

[0066] The obtained compound (2) 1 H-NMR and 13 The C-NMR is shown below. 1 The H-NMR spectrum is shown in FIG. 13The C-NMR spectra are shown below. The peaks were clearly assigned, and the chemical shifts of the peaks were also in good agreement. These results indicate that the target compound (2) was obtained by the aromatic nucleophilic substitution reaction of the compound (1) with 4-cyclohexylphenol. 68 H 74 O8 (1019.31 g / mol) 1 H-NMR (400 MHz, CDCl3): δ 6.94 (d, J = 8.8 Hz, 8H), 6.63 (m, J = 21.2 Hz, 16H), 3.71 (s, 6H), 2.37 (m, J = 26 Hz, 4H), 1.76 (m, J = 45.6 Hz, 20H), 1.28 (m, J = 98.8 Hz, 20H) ppm. 13 C-NMR (100 MHz, CDCl3): δ 155.5, 154.7, 151.2, 142.0, 140.7, 140.4, 127.2, 116.7, 115.5, 114.0, 55.5, 43.7, 34.6, 26.9, 26.1 ppm.

[0067] A two-necked flask equipped with a calcium chloride tube and a nitrogen inlet tube was thoroughly heated with a heat gun and purged with nitrogen. After returning to room temperature, 0.4 mmol (0.4077 g) of compound (2) synthesized by the above method and 8 ml of ultra-dehydrated dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd., dry dichloromethane) were added to the two-necked flask. Under a nitrogen atmosphere, 1.6 ml (1.6 mmol) of boron tribromide (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise to the two-necked flask while stirring at -78 °C. The reaction was allowed to proceed at -78 °C for 1 hour, followed by an additional 12 hours at room temperature. After completion of the reaction, water was added to the resulting reaction solution, which was then extracted with ethyl acetate (Fujifilm Wako Pure Chemical Industries, Ltd.) and dried with magnesium sulfate (Fujifilm Wako Pure Chemical Industries, Ltd.). The obtained white solid was washed with chloroform and purified by recrystallization from toluene (Fujifilm Wako Pure Chemical Industries, Ltd.), to obtain 0.2373 g of the target compound (3), i.e., 4,4'-((2,3,5,6-tetrakis(4-cyclohexylphenoxy)-1,4-phenylene)bis(oxy))diphenol (yield: 60%).

[0068] The obtained compound (3) 1 H-NMR and 13 The C-NMR and FT-IR are shown below. 1 The H-NMR spectrum is shown in FIG. 13 The C-NMR spectrum is shown in Figure 1, and the FT-IR spectrum is shown in Figure 7. The assignment of each peak in the NMR spectrum is clear, and the chemical shifts of each peak are also in good agreement. In the FT-IR spectrum, a peak derived from a hydroxy group was confirmed. These facts indicate that the target compound (3) can be obtained by deprotecting the methoxy group of the above compound (2) using boron tribromide. 66 H 70 O8 (991.25 g / mol) 1H-NMR (400 MHz, DMSO-d6): δ 9.07 (s, 2H), 7.01 (d, J = 8.8 Hz, 8H), 6.66 (d, J = 8.8 Hz, 8H), 6.55 (s, 8H), 2.39 (m, J = 18.8 Hz, 20H), 1.70 (m, J = 30.8 Hz, 20H), 1.27 (m, J = 81.6 Hz, 20H)ppm. 13 C-NMR (100 MHz, DMSO-d6): δ 155.2, 152.5, 150.0, 141.5, 140.2, 139.8, 127.3, 116.2, 115.5, 115.0, 42.9, 34.1, 26.4, 25.6 ppm. FT-IR (KBr): 3278, 3031, 2923, 2850, 2670, 2360, 1884, 1608, 1506, 1448, 1364, 1222, 1208, 1171, 1097, 1015, 996, 816, 776cm -1 .

[0069] Example 1: 0.4956 g (0.5 mmol) of compound (3) synthesized by the above method, 0.1271 g (0.5 mmol) of bis(4-fluorophenyl)sulfone (Tokyo Chemical Industry Co., Ltd., Bis(4-fluorophenyl)sulfone recrystallized with chloroform / hexane), 0.2073 g (1.5 mmol) of potassium carbonate (KCO, Fujifilm Wako Pure Chemical Industries, Ltd.), 3.6 ml of N,N-dimethylacetamide (DMAc, Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.6 ml of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a recovery flask equipped with a Dean-Stark apparatus. The mixture was stirred at room temperature for 30 minutes under an argon atmosphere, followed by stirring at 150°C for 2 hours. The toluene was then distilled off, and the mixture was further stirred at 165°C for 16 hours. After completion of the reaction, the resulting reaction solution was poured into 100 ml of water, and the precipitated white solid was filtered. The resulting residue was then dried under reduced pressure to remove the solvent, yielding the target product, a white solid of polymer P4.

[0070] FIG. 8 shows the polymer P4 obtained.1 The H-NMR spectrum and the FT-IR spectrum of the obtained polymer P4 are shown in FIG. 1 The chemical shifts of the peaks observed in the H-NMR spectrum were clearly assigned, and the peaks derived from the hydroxyl groups disappeared and the peaks derived from the sulfonyl groups were confirmed in the FT-IR spectrum. These facts indicate that the target polymer P4 was obtained by the aromatic nucleophilic substitution polymerization of the compound (3) and bis(4-fluorophenyl)sulfone.

[0071] Comparative Example 1: A recovery flask equipped with a Dean-Stark apparatus was charged with 0.3424 g (1.5 mmol) of bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd., Bisphenol A recrystallized with toluene), 0.3814 g (1.5 mmol) of bis(4-fluorophenyl)sulfone (manufactured by Tokyo Chemical Industry Co., Ltd., Bis(4-fluorophenyl)sulfone recrystallized with chloroform / hexane), 0.6219 g (4.5 mmol) of potassium carbonate (KCO, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4.2 ml of N,N-dimethylacetamide (DMAc, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.9 ml of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The mixture was stirred at room temperature for 30 minutes under an argon atmosphere, and then stirred at 150°C for 2 hours. The toluene was then distilled off, and the mixture was further stirred at 165°C for 16 hours. After the reaction was completed, the reaction solution was poured into 300 ml of water, and the precipitated white solid was filtered. The filtered substance was then dried under reduced pressure to remove the solvent, thereby obtaining the target white solid of Comparative Polymer P5.

[0072] To confirm the progress of the polymerization reaction and obtain an index of molecular weight, SEC measurement and viscosity measurement were performed on the synthesized polymer P4 and comparative polymer P5. The SEC curves are shown in Figure 10 and the results of each measurement are shown in Figure 11. These results indicated that the polymerization reaction proceeded sufficiently and a high molecular weight polymer was obtained.

[0073] [Size Exclusion Chromatography (SEC) Measurement] SEC measurement of the obtained polymer was carried out using a Prominence 501 (manufactured by Shimadzu Corporation) as the liquid delivery system, sampler, and column oven. Refractive index measurement was carried out using a differential refractive index detector for high performance liquid chromatography RI501 (manufactured by Showa Science Co., Ltd.). Tetrahydrofuran (THF) was used as the developing solvent, and a GPC LF-804 (manufactured by Shodex) was used as the column. The SEC solution was prepared by dissolving 2 mg of polymer in 2 ml of THF. In addition, a calibration curve was created using standard polystyrene (PS Standard), and measurements were carried out under conditions of a column temperature of 40°C and a flow rate of 1 ml / min. In addition, the number average molecular weight Mn, weight average molecular weight Mw, and polydispersity Mw / Mn were also measured.

[0074] [Viscosity η Measurement] The viscosity of the obtained polymer was measured by dissolving it in N,N-dimethylacetamide (DMAc, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to a sample concentration of 0.5 g / dL, and measuring it using an Ostwald viscometer in a water bath at 30°C.

[0075] To clarify the thermal properties of the obtained polymers, thermogravimetry (TG) measurement and differential scanning calorimetry (DSC) measurement were carried out for the synthesized polymer P4 and the comparative polymer P5. Figures 12 and 13 show the results of the TG measurement, and Figures 14 and 15 show the results of the DSC measurement. The 5% weight loss temperature T d-5 and 10% weight loss temperature T d-10 The glass transition temperature (T g ) was 112°C.

[0076] [Thermogravimetry (TG) Measurement] The TG measurement of the obtained compound was carried out using a thermogravimetry / differential thermal analyzer TG / DTA7300 (manufactured by Hitachi High-Tech Science Corp.) Here, the measurement was carried out in a nitrogen gas flow in the range of 30°C to 550°C at a temperature increase rate of 10°C / min.

[0077] [Differential Scanning Calorimetry (DSC) Measurement] The DSC measurement of the obtained compound was carried out using a differential scanning calorimeter DSC7020 (manufactured by Hitachi High-Tech Science Corp.) Here, the measurement was carried out under a nitrogen gas flow at a temperature increase and decrease rate of 10°C / min.

[0078] WAXD measurement was performed to clarify the higher-order structure of the obtained polymer. The measurement results are shown in Figure 16. For the synthesized polymer P4, a peak was observed around 2θ = 5 °C, confirming a change in the higher-order structure.

[0079] [Wide-Angle X-ray Diffraction (WAXD) Measurement] WAXD measurement of the obtained polymer was carried out using a New D8 DISCOVER (output: 40 kV, 40 mA) manufactured by BRUKER. The detector used was a VANTEC 500 manufactured by the same company. CuKα rays (wavelength: 1.5418 Å (A)) were used as X-rays.

[0080] (Preparation Example 1, Comparative Preparation Example 1) Prior to measuring the dielectric constant and dielectric loss tangent, 5 cm square film samples for measurement were prepared using the synthesized polymer P4 and the comparative polymer P5, respectively. Here, a THF solution of each polymer was dropped onto a glass plate and dried at room temperature to form a film, which was then heated stepwise to 30 ° C, 40 ° C, 50 ° C, and 60 ° C on a hot plate, and finally vacuum dried at 40 ° C. The film was then peeled off from the glass plate in water. The sample films prepared using both the synthesized polymer P4 and the comparative polymer P5 were tough and self-supporting. The film using the synthesized polymer P4 was colorless and transparent, while the film using the comparative polymer P5, which used bisphenol A, was cloudy.

[0081] (Preparation Example 1, Comparative Preparation Example 1) The dielectric constant and dielectric loss tangent at 10 GHz and 20 GHz were measured using each of the prepared film samples. The measurement results are shown in Table 1. The dielectric constant and dielectric loss tangent values ​​of Polymer P4 at each frequency were both smaller than those of Comparative Polymer P5, and the dielectric loss was successfully reduced.

[0082]

[0083] [Measurement of Dielectric Constant and Dielectric Loss Tangent] The dielectric constant and dielectric loss tangent were measured using a vector network analyzer MS46122B manufactured by Anritsu Corp. Here, the analyzer was connected to a TE mode AET cavity resonator and measurements were made at 10 GHz and 20 GHz.

[0084] The compounds of the present invention have a novel multi-branched structure and exhibit small dielectric loss in the high frequency band of the sub-THz band, and therefore can be widely and effectively used as insulating materials, interlayer insulating materials, rewiring insulating materials, and the like, which are required in fifth-generation mobile communication systems or Beyond 5G, etc.

Claims

1. A compound represented by the following general formula (1): (In general formula (1), R 1 and R 2 are each independently a hydrogen atom or an alkyl group, and Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms.

2. Ar in the general formula (1) 1 ~Ar 4 2. The compound according to claim 1, wherein the aromatic hydrocarbon group is selected from the group consisting of benzene, naphthalene, anthracene, pentalene, indene, as-indacene, biphenylene, acenaphthylene, fluorene, phenalene, heptalene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, and coronene.

3. Cy in the general formula (1) 1 ~Cy 4 2. The compound of claim 1, wherein the alicyclic hydrocarbon group is selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, and cycloicosane.

4. A polymer containing at least a (co)polymerization unit A represented by the following general formula (1A): (In general formula (1A), Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and Cy 1 ~Cy 4 are each independently a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 20 carbon atoms, and * is a bond.

5. Ar in the general formula (1A) 1 ~Ar 4 5. The polymer of claim 4, wherein the aromatic hydrocarbon group is selected from the group consisting of benzene, naphthalene, anthracene, pentalene, indene, as-indacene, biphenylene, acenaphthylene, fluorene, phenalene, heptalene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, and coronene.

6. Cy in the general formula (1A) 1 ~Cy 4 5. The polymer of claim 4, wherein the alicyclic hydrocarbon group is selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, and cycloicosane.

7. The polymer according to claim 4, further comprising copolymerized units B, wherein the copolymerized units B are one or more of the copolymerized units shown in the following general formula group (11A):

8. The polymer according to claim 7, comprising the copolymerized units A and the copolymerized units B in a molar ratio of 45:55 to 55:

45.

9. The polymer according to claim 4, further comprising copolymerized units B and copolymerized units C, wherein the copolymerized units B are one or more of the copolymerized units shown in the following general formula group (11A), and the copolymerized units C are one or more of the copolymerized units shown in the following general formula group (21A).

10. The polymer according to claim 9, comprising the copolymerized units A and the copolymerized units B in a molar ratio of 1:99 to 99:

1.

11. A composition comprising the compound of claim 1.

12. A composition comprising the polymer of claim 4.

13. A crosslinked polymer which is a crosslinked product of the composition according to claim 11.

14. A crosslinked polymer which is a crosslinked product of the composition according to claim 12.

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