Fluorine-containing compound, fluorine-containing polymer, and production method for fluorine-containing compound

Abstract

The present invention provides a fluorine-containing compound that is represented by formula (M1) or formula (M2). X, R1a–R1d, m1, and m2 in formula (M1) and R2a–R2d and m3 in formula (M2) are as defined in the description.

Description

Fluorine-containing compound, fluorine-containing polymer, and method for producing fluorine-containing compound

[0001] The present disclosure relates to a fluorine-containing compound, a fluorine-containing polymer, and a method for producing a fluorine-containing compound.

[0002] A known method for producing a fluorine-containing compound is a Diels-Alder reaction between a fluorine-containing alkene and a cyclic polyene. For example, Patent Document 1 discloses a production method for obtaining a target fluorine-containing compound with high selectivity.

[0003] Fluorine-containing polymers produced using fluorine-containing compounds as raw materials are used as coating materials for optical systems, etc. For example, Patent Document 2 discloses a fluorine-containing polymer that is excellent in heat resistance, light resistance, and light transmittance and is used as a material for semiconductor microfabrication using vacuum ultraviolet light.

[0004] JP 2019-89714 A International Publication No. 2002 / 088216

[0005] However, it is difficult to produce fluorine-containing compounds having specific structures by the known Diels-Alder reaction due to the reactivity of the substrates, and fluorine-containing compounds and fluorine-containing polymers exhibiting desired physical properties have not been obtained.

[0006] The present disclosure has been made in view of the above, and relates to providing a novel fluorine-containing compound, a fluorine-containing polymer, and a method for producing a fluorine-containing compound.

[0007] The present disclosure includes the following aspects: <1> A fluorine-containing compound represented by the following formula (M1) or formula (M2): (In formula (M1), m1 is 0 or 1; when m1 is 0 in formula (M1), m2 is an integer of 0 to 4; each X independently represents -O-, -S-, or -NR-; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom; R １ａ ~R １ｄeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom; １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure, in formula (M1), when m1 is 1, m2 is an integer of 0 to 4, each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom; １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure or are not bonded to each other, in formula (M2), m3 is an integer of 0 to 4, ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄany two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom.) <2> In the formula (M1), m1 is 1, m2 is an integer of 0 to 4, and R １ａ ~R １ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R １ａ ~R １ｄ At least one of R is a group having a fluorine atom or a fluorine atom, １ａ ~R １ｄ are not bonded to each other. <3> The fluorine-containing compound according to <1>, represented by the following formula (M12), formula (M13), formula (M22), or formula (M23): (In formula (M12), m1 is 0 or 1, m2 is an integer of 0 to 4, each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a heteroatom, R １２ａ ~R １２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T １ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, in formula (M13), m1 is 0 or 1, m2 is an integer of 0 to 4, each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, and R １３ａ ~R １３ｂeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ２ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, and in formula (M22), m3 represents an integer of 0 to 4, and R ２２ａ ~R ２２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ３ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom, and in formula (M23), m3 is an integer of 0 to 4, and R ２３ａ ~R ２３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ４ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom.) <4> A fluorine-containing polymer represented by the following formula (P1a), formula (P1b), formula (P1c) or formula (P2): (In formulas (P1a) to (P1c), each X independently represents -O-, -S-, or -NR-; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom; R １ａ ~R １ｄeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom, p1 is an integer of 2 to 10,000, and in formula (P1a), R １ａ ~R １ｄ Any two of R are bonded to each other to form a ring structure, and in formula (P1b), １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure, m2b is an integer of 0 to 3, and in formula (P1c), R １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure or are not bonded to each other, m2c is an integer of 0 to 4, in formula (P2), m3 is an integer of 0 to 4, R ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄ any two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom; and p2 is an integer of 2 to 10,000. <5> In the formula (P1c), m2c is an integer of 0 to 4; １ａ ~R １ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R１ａ ~R １ｄ At least one of R is a group having a fluorine atom or a fluorine atom, １ａ ~R １ｄ are not bonded to each other. <6> The fluorine-containing polymer according to <4>, which is represented by the following formula (P12a), formula (P12b), formula (P12c), formula (P13a), formula (P13b), formula (P13c), formula (P22), or formula (P23): (In formulas (P12a) to (P12c), each X independently represents —O—, —S—, or —NR—; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom; R １２ａ ~R １２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T １ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, p1 is an integer of 2 to 10,000, in formulas (P13a) to (P13c), each X independently represents —O—, —S—, or —NR—, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, and R １３ａ ~R １３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ２represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, p1 is an integer of 2 to 10,000, in formulas (P12b) and (P13b), m2b is an integer of 0 to 3, in formulas (P12c) and (P13c), m2c is an integer of 0 to 4, in formula (P22), R ２２ａ ~R ２２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ３ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom, m3 is an integer of 0 to 4, p2 is an integer of 2 to 10,000, and in formula (P23), R ２３ａ ~R ２３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ４ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom, m3 is an integer of 0 to 4, and p2 is an integer of 2 to 10,000.) <7> A fluorine-containing polymer represented by the following formula (H1a), formula (H1b), formula (H1c) or formula (H2). (In formulas (H1a) to (H1c), each X independently represents -O-, -S-, or -NR-; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom; R １ａ ~R １ｄeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom, p1 is an integer of 2 to 10,000, and in formula (H1a), １ａ ~R １ｄ Any two of R are bonded to each other to form a ring structure, and in formula (H1b), １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure, m2b is an integer of 0 to 3, and in formula (H1c), R １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure or are not bonded to each other, m2c is an integer of 0 to 4, in formula (H2), m3 is an integer of 0 to 4, R ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄany two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom, and p2 is an integer of 2 to 10,000. <8> A method for producing a fluorine-containing compound, comprising reacting a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom, a fluorine-containing cyclic alkene, and a cyclopentadiene in the same reaction system. <9> A method for producing a fluorine-containing compound, comprising reacting a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom, and a fluorine-containing heterocyclic alkene having an oxygen atom as a heteroatom. <10> The method for producing a fluorine-containing compound according to <8> or <9>, wherein the cyclic heterodiene is furan. <11> The method for producing a fluorine-containing compound according to any one of <8> to <10>, wherein the reaction is a Diels-Alder reaction.

[0008] According to the present disclosure, a novel fluorine-containing compound, a fluorine-containing polymer, and a method for producing a fluorine-containing compound are provided.

[0009] An embodiment of the present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiment. In the following disclosure, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0010] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the lower and upper limits, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another staged numerical range. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, when multiple substances corresponding to each component are present in the composition, the content of each component refers to the total content of those multiple substances present in the composition, unless otherwise specified. In the present disclosure, when multiple elements are listed using "or," this does not exclude the selection of multiple elements in combination, unless otherwise specified, unless a technical contradiction occurs. In the present disclosure, even when an element is described in the singular, this does not exclude the presence of multiple elements, unless otherwise specified, unless a technical contradiction occurs. In the present disclosure, multiple exemplary embodiments described separately may be combined with each other to form a new embodiment, unless mutually contradictory. In the present disclosure, a "compound represented by formula (X)" is also referred to as a "compound (X)," and a "polymer represented by formula (X)" is also referred to as a "polymer (X)."

[0011] <Fluorine-Containing Compound> The fluorine-containing compound of the present disclosure is represented by the following formula (M1) or formula (M2).

[0012]

[0013] In formula (M1), m1 is 0 or 1; when m1 is 0 in formula (M1), m2 is an integer of 0 to 4; each X independently represents -O-, -S-, or -NR-; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a heteroatom; R １ａ ~R １ｄeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom; １ａ ~R １ｄ Any two of these are bonded to each other to form a ring structure.

[0014] In formula (M1), when m1 is 1, m2 is an integer of 0 to 4, each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a heteroatom, and R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom; １ａ ~R １ｄ Any two of these may be bonded to each other to form a ring structure or may not be bonded to each other.

[0015] In formula (M2), m3 is an integer of 0 to 4, and R ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄAny two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom.

[0016] In this disclosure, R Ｘ (For example, R １ａ ~R １ｄ , R ２ａ ~R ２ｄ ) forms a group having a fluorine atom or a ring structure having a fluorine atom as a substituent, specifically, for example, when the ring structure is a ring T １ ~T ４ When the ring T １ ~T ４ The fluorine atom-containing group in R may or may not further form a ring structure. Ｘ The ring structure formed by the formula (I) may or may not further include a ring in the form of a spiro structure. However, from the viewpoint of ease of synthesis, separation and purification, it is preferable that the number of further formed ring structures be up to one. Furthermore, it is preferable that the further formed ring structure be a 4- to 6-membered ring.

[0017] The compounds (M1) and (M2) are novel compounds. The stereoisomers of the compounds (M1) and (M2) can be easily separated and purified, and the compounds (M1) and (M2) are soluble in polymerization solvents and known organic solvents. The fluorine-containing polymers obtained using the compounds (M1) and (M2) are excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0018] [In formula (M1), when m1 is 0] <m2> m2 is an integer of 0 to 4. From the viewpoint of ease of separation and purification and solubility, m2 is preferably 0 or 1, and from the viewpoint of high heat resistance (for example, a high glass transition point) of the obtained polymer, m2 is preferably 1. <X> Xs each independently represent -O-, -S-, or -NR-, and R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a heteroatom.

[0019] From the viewpoint of synthesis, with less steric repulsion and ease of deprotection, R in -NR- is preferably an aralkyl group, and more preferably a benzyl group or a benzyl group having a substituent (for example, a benzyl group, a p-methoxybenzyl group, etc.). The aromatic ring of the aralkyl group may be a heterocycle, and examples of heteroatoms of the heterocycle include an oxygen atom and / or a nitrogen atom. Examples of such heterocycles include a pyridine ring. From the viewpoint that the polymer obtained using compound (M1) has excellent water repellency, oil repellency, solubility, and a low refractive index, X is preferably -O-. When the polymer obtained using compound (M1) has a CO ２ In view of excellent separation and adsorption of X, X is preferably —NR—. In view of the high refractive index of the polymer obtained by using the compound (M1), X is preferably —S—.

[0020] <R １ａ ~R １ｄ > R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ At least one of the groups is a group having a fluorine atom or a fluorine atom.

[0021] From the viewpoint of oil repellency of the polymer obtained by using the compound (M1), R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ At least two of the groups preferably contain a fluorine atom or a fluorine atom.

[0022] R １ａ ~R １ｄand are each independently more preferably a fluorine atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, an alkoxy group having 1 to 10 carbon atoms and a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms and a fluorine atom, from the viewpoint of oil repellency.

[0023] Compared with an alkoxyalkyl group, a polymer obtained by using a fluorine-containing compound has high heat resistance (for example, a high glass transition point), and therefore, R １ａ ~R １ｄ are each independently more preferably a fluorine atom-containing alkyl group having 1 to 10 carbon atoms or a fluorine atom, still more preferably a fluorine atom-containing alkyl group having 1 to 5 carbon atoms or a fluorine atom, and particularly preferably a fluorine atom-containing alkyl group having 1 to 3 carbon atoms.

[0024] Since the fluorine atom contributes to oil repellency, as described above, R １ａ ~R １ｄ is preferably a group having a fluorine atom or a fluorine atom.

[0025] R １ａ ~R １ｄ Any two of these are bonded to each other to form a ring structure. From the viewpoint of oil repellency, the ring structure preferably has at least one fluorine atom or a group having a fluorine atom as a substituent, and more preferably has at least one fluorine atom. From the viewpoint of ease of synthesis, the ring structure is preferably a 4- to 6-membered ring, and more preferably a 5-membered ring. Furthermore, since the water and oil repellency of the resulting polymer is improved and the refractive index of the resulting polymer is further reduced, the ring structure is preferably a 5-membered heterocycle having a fluorine atom or a group having a fluorine atom as a substituent and an oxygen atom as a heteroatom, and a trifluoromethyl group (-CF ３ ) or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom is more preferred.

[0026] [In formula (M1), when m1 is 1] <m2> m2 is an integer of 0 to 4. From the viewpoints of ease of separation and purification and solubility, m2 is preferably 0 or 1, and from the viewpoint of high heat resistance (for example, a high glass transition point) of the obtained polymer, m2 is preferably 1. <X> Xs each independently represent -O-, -S-, or -NR-, and R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a heteroatom.

[0027] From the viewpoint of synthesis, with less steric repulsion and ease of deprotection, R in -NR- is preferably an aralkyl group, and more preferably a benzyl group or a benzyl group having a substituent (for example, a benzyl group, a p-methoxybenzyl group, etc.). The aromatic ring of the aralkyl group may be a heterocycle, and examples of heteroatoms of the heterocycle include an oxygen atom and / or a nitrogen atom. Examples of such heterocycles include a pyridine ring. From the viewpoint that the polymer obtained using compound (M1) has excellent water repellency, oil repellency, solubility, and a low refractive index, X is preferably -O-. When the polymer obtained using compound (M1) has a CO ２ In view of excellent separation and adsorption of X, X is preferably —NR—. In view of the high refractive index of the polymer obtained by using the compound (M1), X is preferably —S—.

[0028] <R １ａ ~R １ｄ > R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ At least one of the groups is a group having a fluorine atom or a fluorine atom.

[0029] From the viewpoint of oil repellency of the polymer obtained by using the compound (M1), R １ａ ~R １ｄeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ At least two of the groups preferably contain a fluorine atom or a fluorine atom.

[0030] R １ａ ~R １ｄ and are each independently more preferably a fluorine atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, an alkoxy group having 1 to 10 carbon atoms and a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms and a fluorine atom, from the viewpoint of oil repellency.

[0031] Compared with an alkoxyalkyl group, a polymer obtained by using a fluorine-containing compound has high heat resistance (for example, a high glass transition point), and therefore, R １ａ ~R １ｄ are each independently more preferably a fluorine atom-containing alkyl group having 1 to 10 carbon atoms or a fluorine atom, still more preferably a fluorine atom-containing alkyl group having 1 to 5 carbon atoms or a fluorine atom, and particularly preferably a fluorine atom-containing alkyl group having 1 to 3 carbon atoms.

[0032] Since the fluorine atom contributes to oil repellency, as described above, R １ａ ~R １ｄ is preferably a group having a fluorine atom or a fluorine atom.

[0033] R １ａ ~R １ｄ Any two of R may be bonded to each other to form a ring structure. １ａ ~R １ｄmay not be bonded to each other, that is, may not form a ring structure. From the viewpoint of oil repellency, the ring structure preferably has at least one fluorine atom or a group having a fluorine atom as a substituent, more preferably at least one fluorine atom. The ring structure is preferably a 4- to 6-membered ring, more preferably a 5-membered ring. Furthermore, since the water and oil repellency of the resulting polymer is improved and the refractive index of the resulting polymer is further reduced, the ring structure is preferably a 5-membered heterocycle having a fluorine atom or a group having a fluorine atom as a substituent and an oxygen atom as a heteroatom, and a trifluoromethyl group (-CF ３ ) or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom is more preferred. Note that, as the number of ring structures in the compound increases, the glass transition temperature of the polymer obtained using the compound increases, the thermal stability improves, and the oil repellency also improves. On the other hand, separation and purification of the compound tends to become difficult, and the solubility tends to decrease. From the above viewpoint, in formula (M1), m1 is 1, m2 is 0, and R １ａ ~R １ｄ It is preferred that any two of these form a ring structure.

[0034] [In the case of formula (M2)] <m3> m3 is an integer of 0 to 4. From the viewpoint of ease of separation and purification and solubility, m3 is preferably 0 or 1, and from the viewpoint of high heat resistance (for example, high glass transition point) of the obtained polymer, m3 is preferably 1.

[0035] <R ２ａ ~R ２ｄ > R ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ At least one of the groups is a group having a fluorine atom or a fluorine atom.

[0036] From the viewpoint of oil repellency of the polymer obtained by using the compound (M2), R ２ａ ~R２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ At least two of the groups preferably contain a fluorine atom or a fluorine atom.

[0037] R ２ａ ~R ２ｄ and are each independently more preferably a fluorine atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, an alkoxy group having 1 to 10 carbon atoms and a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms and a fluorine atom, from the viewpoint of oil repellency.

[0038] Compared with an alkoxyalkyl group, a polymer obtained by using a fluorine-containing compound has high heat resistance (for example, a high glass transition point), and therefore, R ２ａ ~R ２ｄ are each independently more preferably a fluorine atom-containing alkyl group having 1 to 10 carbon atoms or a fluorine atom, still more preferably a fluorine atom-containing alkyl group having 1 to 5 carbon atoms or a fluorine atom, and particularly preferably a fluorine atom-containing alkyl group having 1 to 3 carbon atoms.

[0039] Since the fluorine atom contributes to oil repellency, as described above, R ２ａ ~R ２ｄ is preferably a group having a fluorine atom or a fluorine atom.

[0040] R ２ａ ~R ２ｄAny two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom. From the viewpoint of oil repellency, the ring structure preferably has at least one fluorine atom or a group having a fluorine atom as a substituent, and more preferably has at least one fluorine atom. The ring structure is preferably a 4- to 6-membered ring, and more preferably a 5-membered ring. Furthermore, since the water and oil repellency of the resulting polymer is improved and the refractive index of the resulting polymer is further reduced, the ring structure is preferably a 5-membered heterocycle having a fluorine atom or a group having a fluorine atom as a substituent and an oxygen atom as a heteroatom, and a trifluoromethyl group (-CF ３ ) or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom is more preferred.

[0041] [Fluorine-Containing Compound of First Embodiment] The fluorine-containing compound of the first embodiment of the present disclosure is represented by the following formula (M11): In formula (M11), m1 is 1, m2 is an integer of 0 to 4, and R １１ａ ~R １１ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R １１ａ ~R １１ｄ At least one of R is a group having a fluorine atom or a fluorine atom, １１ａ ~R １１ｄ are not bonded to each other (i.e., R １１ａ ~R １１ｄ does not form a ring structure).

[0042] In formula (M11), m2 is preferably 0 or 1, more preferably 0. In formula (M11), the explanation of X is the same as the explanation of X in formula (M1), including definitions, examples, preferred embodiments, etc. In formula (M11), R １１ａ ~R １１ｄ The description of R includes definitions, examples, and preferred embodiments. １１ａ ~R １１ｄ R in formula (M1) except that １ａ~R １ｄ The explanations are the same as those given above.

[0043]

[0044] That is, the fluorine-containing compound of the first embodiment of the present disclosure is represented by the formula (M1) above, wherein m1 is 1, m2 is an integer of 0 to 4, and R １ａ ~R １ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R １ａ ~R １ｄ At least one of R is a group having a fluorine atom or a fluorine atom, １ａ ~R １ｄ are not connected to each other.

[0045] The fluorine-containing compound of the first embodiment is a novel compound. A polymer obtained by using the fluorine-containing compound of the first embodiment is excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0046] <Specific Examples> Specific examples of the fluorine-containing compound of the first embodiment in which m1 is 1 and m2 is 0 include the following formulae (M11-1) to (M11-14).

[0047]

[0048] [Fluorine-Containing Compound of Second Embodiment] A fluorine-containing compound of a second embodiment of the present disclosure is represented by the following formula (M12).

[0049]

[0050] In formula (M12), m1 is 0 or 1, m2 is an integer of 0 to 4, each X independently represents —O—, —S—, or —NR—, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, and R １２ａ ~R １２ｂeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T １ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom.

[0051] The fluorine-containing compound of the second embodiment is a novel compound. A polymer obtained by using the fluorine-containing compound of the second embodiment is particularly excellent in transparency, thermal stability, water repellency, and oil repellency.

[0052] In formula (M12), the explanations of X, m1, and m2, including definitions, examples, preferred embodiments, etc., are the same as the explanations of X, m1, and m2 in formula (M1), respectively.

[0053] <R １２ａ ~R １２ｂ > R １２ａ ~R １２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １２ａ ~R １２ｂ From the viewpoint of oil repellency, R are each independently more preferably a fluorine atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, an alkoxy group having 1 to 10 carbon atoms and a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms and a fluorine atom. １２ａ ~R １２ｂ are each independently more preferably a fluorine atom-containing alkyl group having 1 to 10 carbon atoms or a fluorine atom, even more preferably a fluorine atom-containing alkyl group having 1 to 5 carbon atoms or a fluorine atom, and particularly preferably a fluorine atom.

[0054] <T １ > T １represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom. The ring may be a carbon ring or a hetero ring. The hetero atom contained in the hetero ring is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. From the viewpoint that the polymer obtained by using the fluorine-containing compound of the second embodiment is excellent in transparency, thermal stability, water repellency, and oil repellency, T １ is preferably a group having a fluorine atom or a five-membered ring having at least one fluorine atom as a substituent, more preferably a five-membered ring having a fluorine atom as a substituent, and even more preferably a five-membered carbon ring having a fluorine atom as a substituent. １ is preferably a group having a fluorine atom as a substituent or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom, and more preferably a 5-membered heterocycle having a fluorine atom or a trifluoromethyl group as a substituent and an oxygen atom as a heteroatom.

[0055] When m1 is 0 and m2 is 0 among the fluorine-containing compounds of the second embodiment of the present disclosure, they are represented by the following formula (M12a): When m1 is 0 and m2 is 1 to 4 among the fluorine-containing compounds of the second embodiment of the present disclosure, they are represented by the following formula (M12b): When m1 is 1 among the fluorine-containing compounds of the second embodiment of the present disclosure, they are represented by the following formula (M12c):

[0056]

[0057] From the viewpoint of ease of synthesis and a low refractive index, the fluorine-containing compound of the second embodiment is preferably a compound (M12c) in which m1 is 1, m2 is an integer of 0 to 4, X is —O—, and T １ is preferably a compound in which m1 is 1, m2 is 1, X is —O—, and T is a group having a fluorine atom or a five-membered ring having at least one fluorine atom as a substituent, １is a 5-membered heterocyclic ring having at least one fluorine atom and an oxygen atom as a heteroatom. １ is a 5-membered heterocyclic ring having at least one fluorine atom or trifluoromethyl group and an oxygen atom as a heteroatom. From the viewpoint of ease of synthesis, high heat resistance, and oil repellency, the compound (M12b) is preferably a compound in which m2 is 1, X is —O—, and T １ is a five-membered heterocycle having at least one fluorine atom or trifluoromethyl group and an oxygen atom as a heteroatom.

[0058] <Specific Examples> Specific examples of the fluorine-containing compound of the second embodiment include the following formulae (M12-1) to (M12-29).

[0059]

[0060]

[0061] [Fluorine-Containing Compound of Third Embodiment] A fluorine-containing compound of a third embodiment of the present disclosure is represented by the following formula (M13).

[0062]

[0063] In formula (M13), m1 is 0 or 1, m2 is an integer of 0 to 4, each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, and R １３ａ ~R １３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ２ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom.

[0064] The fluorine-containing compound of the third embodiment is a novel compound. A polymer obtained by using the fluorine-containing compound of the third embodiment is particularly excellent in transparency, thermal stability, water repellency, and oil repellency.

[0065] In formula (M13), the explanations of X, m1, and m2, including definitions, examples, preferred embodiments, etc., are the same as the explanations of X, m1, and m2 in formula (M1), respectively.

[0066] <R １３ａ ~R １３ｂ > R １３ａ ~R １３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, from the viewpoint of oil repellency; R １３ａ ~R １３ｂ are each independently preferably a fluorine atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, an alkoxy group having 1 to 10 carbon atoms and a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms and a fluorine atom. １３ａ ~R １３ｂ are each independently more preferably a fluorine atom-containing alkyl group having 1 to 10 carbon atoms or a fluorine atom, even more preferably a fluorine atom-containing alkyl group having 1 to 5 carbon atoms or a fluorine atom, and particularly preferably a fluorine atom.

[0067] <T ２ > T ２ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom. The ring may be a carbon ring or a hetero ring. The hetero atom contained in the hetero ring is an oxygen atom from the viewpoint of a low refractive index, a sulfur atom from the viewpoint of a high refractive index, or CO ２ A nitrogen atom is preferred from the viewpoint of excellent separation and adsorption of T. ２is preferably a group having a fluorine atom as a substituent or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom, and more preferably a 5-membered heterocycle having a fluorine atom or a trifluoromethyl group as a substituent and an oxygen atom as a heteroatom.

[0068] Among the fluorine-containing compounds of the third embodiment of the present disclosure, when m1 is 0 and m2 is 0, they are represented by the following formula (M13a). Among the fluorine-containing compounds of the third embodiment of the present disclosure, when m1 is 0 and m2 is 1 to 4, they are represented by the following formula (M13b). Among the fluorine-containing compounds of the third embodiment of the present disclosure, when m1 is 1, they are represented by the following formula (M13c).

[0069]

[0070] From the viewpoint of ease of synthesis, low refractive index, and oil repellency, the polymer obtained by using the fluorine-containing compound of the third embodiment is preferably a compound (M13c). In formula (M13), m1 is 1, m2 is an integer of 0 to 4, X is —O—, and T ２ is preferably a compound in which m1 is 1, m2 is 1, X is —O—, and T is a group having a fluorine atom or a five-membered ring having at least one fluorine atom as a substituent, ２ is a 5-membered heterocycle having at least one fluorine atom. ２ is a 5-membered heterocyclic ring having at least one fluorine atom or trifluoromethyl group and an oxygen atom as a heteroatom. From the viewpoint of ease of synthesis, high heat resistance, and oil repellency, the compound (M13b) is preferably a compound in which m2 is 1, X is —O—, and T ２ is a five-membered heterocycle having at least one fluorine atom or trifluoromethyl group and an oxygen atom as a heteroatom.

[0071] <Specific Examples> Specific examples of the fluorine-containing compound of the third embodiment include the following formulae (M13-1) to (M13-18).

[0072]

[0073] [Fluorine-Containing Compound of Fourth Embodiment] A fluorine-containing compound of a fourth embodiment of the present disclosure is represented by the following formula (M22).

[0074]

[0075] In formula (M22), m3 is an integer of 0 to 4, and R ２２ａ ~R ２２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ３ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom.

[0076] The fluorine-containing compound of the fourth embodiment is a novel compound. A polymer obtained by using the fluorine-containing compound of the fourth embodiment is particularly excellent in transparency, thermal stability, water repellency, and oil repellency.

[0077] In formula (M22), the explanation of m3, including definitions, examples, preferred embodiments, etc., is the same as the explanation of m3 in formula (M2) above.

[0078] <R ２２ａ ~R ２２ｂ > R ２２ａ ~R ２２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, from the viewpoint of oil repellency; R ２２ａ ~R ２２ｂare each independently preferably a fluorine atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, an alkoxy group having 1 to 10 carbon atoms and a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms and a fluorine atom. ２２ａ ~R ２２ｂ are each independently more preferably a fluorine atom-containing alkyl group having 1 to 10 carbon atoms or a fluorine atom, even more preferably a fluorine atom-containing alkyl group having 1 to 5 carbon atoms or a fluorine atom, and particularly preferably a fluorine atom.

[0079] <T ３ > T ３ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom. The oxygen-containing heterocycle is a heterocycle having an oxygen atom as a heteroatom. From the viewpoint that the polymer obtained by using the fluorine-containing compound of the fourth embodiment is excellent in transparency, thermal stability, water repellency, and oil repellency, T ３ is preferably a group having a fluorine atom or a five-membered ring having at least one fluorine atom as a substituent, more preferably a five-membered ring having a fluorine atom as a substituent, and even more preferably a five-membered carbon ring having a fluorine atom as a substituent. ３ is preferably a group having a fluorine atom as a substituent or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom, and more preferably a 5-membered heterocycle having a fluorine atom or a trifluoromethyl group as a substituent and an oxygen atom as a heteroatom.

[0080] <Specific Example> From the viewpoint that the polymer obtained by using the fluorine-containing compound of the fourth embodiment has excellent transparency, thermal stability, water repellency, and oil repellency, in formula (M22), m3 is an integer of 0 to 4, and T ３ is a group having a fluorine atom or a 5-membered heterocycle having at least one fluorine atom as a substituent and an oxygen atom as a heteroatom, ３is a five-membered heterocyclic ring having at least one fluorine atom or trifluoromethyl group and an oxygen atom as a heteroatom.

[0081] <Specific Examples> Specific examples of the fluorine-containing compound of the fourth embodiment include the following formulae (M22-1) to (M22-12).

[0082]

[0083] [Fluorine-Containing Compound of Fifth Embodiment] A fluorine-containing compound of a fifth embodiment of the present disclosure is represented by the following formula (M23).

[0084]

[0085] In formula (M23), m3 is an integer of 0 to 4, and R ２３ａ ~R ２３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ４ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom.

[0086] The fluorine-containing compound of the fifth embodiment is a novel compound. A polymer obtained by using the fluorine-containing compound of the fifth embodiment is particularly excellent in transparency, thermal stability, water repellency, and oil repellency.

[0087] In formula (M23), the explanation of m3, including definitions, examples, preferred embodiments, etc., is the same as the explanation of m3 in formula (M2) above.

[0088] <R ２３ａ ~R ２３ｂ > R ２３ａ ~R ２３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, from the viewpoint of oil repellency; R ２３ａ~R ２３ｂ are each independently preferably a fluorine atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, an alkoxy group having 1 to 10 carbon atoms and a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms and a fluorine atom. ２３ａ ~R ２３ｂ are each independently more preferably a fluorine atom-containing alkyl group having 1 to 10 carbon atoms or a fluorine atom, even more preferably a fluorine atom-containing alkyl group having 1 to 5 carbon atoms or a fluorine atom, and particularly preferably a fluorine atom.

[0089] <T ４ > T ４ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom. The water and oil repellency of the polymer obtained by using the fluorine-containing compound of the fifth embodiment is improved, and the refractive index can be further reduced. Therefore, T ４ is preferably a group having a fluorine atom as a substituent or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom, and more preferably a 5-membered heterocycle having a fluorine atom or a trifluoromethyl group as a substituent and an oxygen atom as a heteroatom.

[0090] In view of the fact that the polymer obtained by using the fluorine-containing compound of the fifth embodiment has excellent transparency, thermal stability, water repellency, and oil repellency, it is preferable that in formula (M23), m3 is an integer of 0 to 4, and T ４ is a group having a fluorine atom as a substituent or a 5-membered heterocycle having at least one fluorine atom and an oxygen atom as a heteroatom, ４ is a five-membered heterocycle having at least one fluorine atom or trifluoromethyl group is more preferred.

[0091] <Specific Examples> Specific examples of the fluorine-containing compound of the fifth embodiment include the following formulae (M23-1) to (M23-12).

[0092]

[0093] <<First Fluorine-Containing Polymer>> The first fluorine-containing polymer of the present disclosure is represented by the following formula (P1a), formula (P1b), formula (P1c) or formula (P2).

[0094]

[0095] In formula (P1a) to formula (P1c), X's each independently represent -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ At least one of the groups is a group having a fluorine atom or a fluorine atom, and p1 is an integer of 2 to 10,000.

[0096] In formula (P1a), R １ａ ~R １ｄ In formula (P1b), any two of R are bonded to each other to form a ring structure. １ａ ~R １ｄ Any two of R are bonded to each other to form a ring structure, and m2b is an integer of 0 to 3. １ａ ~R １ｄ any two of these may be bonded to each other to form a ring structure or may not be bonded to each other; and m2c is an integer of 0 to 4.

[0097] In formula (P2), m3 is an integer of 0 to 4, and R ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄ Any two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom; and p2 is an integer of 2 to 10,000.

[0098] The polymers (P1a) to (P1c) and the polymer (P2) are novel polymers, and are excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0099] The weight-average molecular weight (Mw) of polymers (P1a) to (P1c) and polymer (P2) is preferably from 10,000 to 1,000,000, more preferably from 10,000 to 500,000, and even more preferably from 10,000 to 250,000, from the viewpoint of moldability. In the present disclosure, the weight-average molecular weight is measured using gel permeation chromatography (GPC, manufactured by Spectris Inc., Viscotek GPCmax (VE-2001)) using tetrahydrofuran as a solvent and calculated in terms of polystyrene.

[0100] [In the case of formulae (P1a) to (P1c)] <m2b, m2c> In view of ease of synthesis and separation and purification, in formula (P1b), m2b is preferably 0 or 1, more preferably 0. In formula (P1c), m2c is preferably 0 or 1, more preferably 0. <X> In formulae (P1a) to (P1c), the explanation of X is the same as the explanation of X in formula (M1) above, including definitions, examples, preferred embodiments, etc. <R １ａ ~R １ｄ > In formulas (P1a) to (P1b), R １ａ ~R １ｄ The explanation of R in the above [when m1 is 0 in formula (M1)], including definitions, examples, and preferred embodiments, is １ａ ~R １ｄ In formula (P1c), R １ａ ~R １ｄ The explanation of R in the above [when m1 is 1 in formula (M1)], including definitions, examples, and preferred embodiments, is １ａ ~R １ｄ The explanations are the same as those given above.

[0101] <p1> p1 is an integer of 2 to 10,000. From the viewpoint of molding processability, p1 is preferably 2 to 8,000, and more preferably 2 to 5,000.

[0102] [In the case of formula (P2)] In formula (P2), m3 and R ２ａ ~R ２ｄ The description of m3 and R in formula (M2) includes definitions, examples, and preferred embodiments. ２ａ ~R ２ｄ The explanations are the same as those given above.

[0103] <p2> p2 is an integer of 2 to 10,000. From the viewpoint of molding processability, p2 is preferably 2 to 8,000, and more preferably 2 to 5,000.

[0104] [First Fluorine-Containing Polymer of First Embodiment] The first fluorine-containing polymer of the first embodiment of the present disclosure is represented by the following formula (P11): In formula (P11), m2 is an integer of 0 to 4, and R １１ａ ~R １１ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R １１ａ ~R １１ｄ are not bonded to each other (i.e., R １１ａ ~R １１ｄ does not form a ring structure).

[0105] In formula (P11), the descriptions of m2, p1, and X, including definitions, examples, and preferred embodiments, are the same as the descriptions of m2c, p1, and X in formula (P1c), respectively. １１ａ ~R １１ｄ The description of R includes definitions, examples, and preferred embodiments. １１ａ ~R １１ｄ R in formula (P1c) except that １ａ ~R １ｄ The explanations are the same as those given above.

[0106]

[0107] That is, the first fluorinated polymer of the first embodiment of the present disclosure is a polymer represented by the formula (P1c), wherein m2c is an integer of 0 to 4, and R １ａ ~R １ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R １ａ ~R １ｄ At least one of R is a group having a fluorine atom or a fluorine atom, １ａ ~R １ｄ are not connected to each other.

[0108] The first fluorine-containing polymer of the first embodiment is a novel polymer. The first fluorine-containing polymer of the first embodiment is excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0109] <Specific Examples> Specific examples of the first fluorinated polymer of the first embodiment in which m2 is 0 include the following formulae (P11-1) to (P11-14): In formulae (P11-1) to (P11-14), p1 is an integer of 2 to 10,000.

[0110]

[0111] [First Fluorine-Containing Polymer of Second Embodiment] The first fluorine-containing polymer of the second embodiment of the present disclosure is represented by the following formula (P12a), formula (P12b) or formula (P12c).

[0112]

[0113] In formulae (P12a) to (P12c), X's each independently represent -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a heteroatom, and R １２ａ ~R １２ｂeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T １ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, p1 is an integer of 2 to 10,000, in formula (P12b), m2b is an integer of 0 to 3, and in formula (P12c), m2c is an integer of 0 to 4.

[0114] The first fluorine-containing polymer of the second embodiment is a novel polymer, and is particularly excellent in transparency, thermal stability, water repellency, and oil repellency.

[0115] In formula (P12a) to formula (P12c), the explanations of X and p1, including definitions, examples, preferred embodiments, etc., are the same as the explanations of X and p1 in formula (P1c). １２ａ ~R １２ｂ and T １ The explanation of R in formula (M12a) including definitions, examples, and preferred embodiments is １２ａ ~R １２ｂ and T １ In formula (P12b), m2b and R １２ａ ~R １２ｂ and T １ The explanation of m2, R in the formula (M12b) includes definitions, examples, and preferred embodiments. １２ａ ~R １２ｂ and T １ In formula (P12c), m2c and R １２ａ ~R １２ｂ and T １ The explanation of m2, R in the formula (M12c) includes definitions, examples, and preferred embodiments. １２ａ ~R １２ｂ and T １ The explanations are the same as those given above.

[0116] <Specific Examples> From the viewpoint that the first fluorine-containing polymer of the second embodiment is excellent in transparency, thermal stability, water repellency, oil repellency, moldability, and high heat resistance (for example, high glass transition point), in formula (P12b), m2b is an integer of 0 to 3, in formula (P12c), m2c is an integer of 0 to 4, in formulae (P12a) to (P12c), X is —O—, and T １ is a group having a fluorine atom or a 5-membered ring having at least one fluorine atom as a substituent, and p1 is an integer of 2 to 8,000; m2b in formula (P12b) and m2c in formula (P12c) are 0; X in formulas (P12a) to (P12c) is —O—; and T １ is a five-membered carbon ring having at least one fluorine atom, and p1 is an integer of 2 to 5,000.

[0117] From the viewpoint of excellent transparency, low refractive index, water repellency, and oil repellency, the first fluorinated polymer of the second embodiment is preferably selected from the group consisting of: m2b in formula (P12b) and m2c in formula (P12c) being 0; X in formulas (P12a) to (P12c) being —O—; and T １ is a group having a fluorine atom as a substituent or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom, and p1 is an integer of 2 to 8,000; m2b in formula (P12b) and m2c in formula (P12c) are 0; X in formulas (P12a) to (P12c) is —O—; and T １ is a trifluoromethyl group or a 5-membered heterocycle having a fluorine atom and an oxygen atom as a heteroatom, and p1 is an integer of 2 to 5,000.

[0118] Specific examples of the first fluorine-containing polymer of the second embodiment include the following formulae (P12-1) to (P12-30): In formulae (P12-1) to (P12-30), p1 represents an integer of 2 to 10,000.

[0119]

[0120]

[0121] [First Fluorine-Containing Polymer of Third Embodiment] The first fluorine-containing polymer of the third embodiment of the present disclosure is represented by the following formula (P13a), formula (P13b) or formula (P13c).

[0122]

[0123] In formulae (P13a) to (P13c), X's each independently represent -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a heteroatom, and R １３ａ ~R １３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ２ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, p1 is an integer of 2 to 10,000, in formula (P13b), m2b is an integer of 0 to 3, and in formula (P13c), m2c is an integer of 0 to 4.

[0124] The first fluorine-containing polymer of the third embodiment is a novel polymer, and is particularly excellent in transparency, thermal stability, water repellency, and oil repellency.

[0125] In formula (P13a) to formula (P13c), the explanations of X and p1, including definitions, examples, preferred embodiments, etc., are the same as the explanations of X and p1 in formula (P1c). １３ａ ~R １３ｂ and T ２ The explanation of R in formula (M13a) includes definitions, examples, and preferred embodiments. １３ａ ~R １３ｂ and T ２ In formula (P13b), m2b and R １３ａ ~R １３ｂ and T ２The explanation of m2, R in formula (M13b) includes definitions, examples, and preferred embodiments. １３ａ ~R １３ｂ and T ２ In formula (P13c), m2c and R １３ａ ~R １３ｂ and T ２ The explanation of m2, R in the formula (M13c) includes definitions, examples, and preferred embodiments. １３ａ ~R １３ｂ and T ２ The explanations are the same as those given above.

[0126] In the third embodiment, from the viewpoint of excellent transparency, moldability, water repellency, and oil repellency, the first fluorinated polymer preferably has a structure in which, in formula (P13b), m2b is an integer of 0 to 3, in formula (P13c), m2c is an integer of 0 to 4, in formulae (P13a) to (P13c), X is —O—, and T ２ is a group having a fluorine atom or a 5-membered heterocycle having at least one fluorine atom as a substituent and an oxygen atom as a heteroatom, and p1 is an integer of 2 to 8,000, and m2b in formula (P13b) and m2c in formula (P13c) are 0, X is —O—, and T ２ is a five-membered heterocycle having at least one fluorine atom or trifluoromethyl group and an oxygen atom as a heteroatom, and p1 is an integer of 2 to 5,000, is more preferred.

[0127] Specific examples of the first fluorine-containing polymer of the third embodiment include the following formulae (P13-1) to (P13-18): In formulae (P13-1) to (P13-18), p1 represents an integer of 2 to 10,000.

[0128]

[0129] [First Fluorine-Containing Polymer of Fourth Embodiment] The first fluorine-containing polymer of the fourth embodiment of the present disclosure is represented by the following formula (P22).

[0130]

[0131] In formula (P22), R ２２ａ ~R ２２ｂeach independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ３ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom; m3 is an integer of 0 to 4; and p2 is an integer of 2 to 10,000.

[0132] The first fluorine-containing polymer of the fourth embodiment is a novel polymer, and is particularly excellent in transparency, thermal stability, water repellency, and oil repellency.

[0133] In formula (P22), the explanations of m3 and p2, including definitions, examples, preferred embodiments, etc., are the same as the explanations of m3 and p2 in formula (P2) above. ２２ａ ~R ２２ｂ and T ３ The explanation of R in formula (M22) including definitions, examples, and preferred embodiments is ２２ａ ~R ２２ｂ and T ３ The explanations are the same as those given above.

[0134] In view of the fact that the first fluorinated polymer of the fourth embodiment is excellent in transparency, thermal stability, water repellency, and oil repellency, it is preferable that, in formula (P22), m3 is an integer of 0 to 4, and T ３ is a group having a fluorine atom or a 5-membered heterocycle having at least one fluorine atom as a substituent and an oxygen atom as a heteroatom, and p2 is an integer of 2 to 8,000; ３ is a five-membered heterocycle having at least one fluorine atom or trifluoromethyl group and an oxygen atom as a heteroatom, and p2 is an integer of 2 to 5,000, is more preferred.

[0135] Specific examples of the first fluorine-containing polymer of the fourth embodiment include the following formulae (P22-1) to (P22-12): In formulae (P22-1) to (P22-12), p2 represents an integer of 2 to 10,000.

[0136]

[0137] [First Fluorine-Containing Polymer of Fifth Embodiment] The first fluorine-containing polymer of the fifth embodiment of the present disclosure is represented by the following formula (P23).

[0138]

[0139] In formula (P23), R ２３ａ ~R ２３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ４ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom; m3 is an integer of 0 to 4; and p2 is an integer of 2 to 10,000.

[0140] The first fluorine-containing polymer of the fifth embodiment is a novel polymer, and is particularly excellent in transparency, thermal stability, water repellency, and oil repellency.

[0141] In formula (P23), the explanations of m3 and p2, including definitions, examples, preferred embodiments, etc., are the same as the explanations of m3 and p2 in formula (P2). ２３ａ ~R ２３ｂ and T ４ The explanation of R in formula (M23) includes definitions, examples, and preferred embodiments. ２３ａ ~R ２３ｂ and T ４ The explanations are the same as those given above.

[0142] In view of the fact that the first fluorinated polymer of the fifth embodiment is excellent in transparency, thermal stability, moldability, water repellency, and oil repellency, it is preferable that, in formula (P23), m3 is an integer of 0 to 4, and T ４is a group having a fluorine atom or a 5-membered heterocycle having at least one fluorine atom as a substituent and an oxygen atom as a heteroatom, and p2 is an integer of 2 to 8,000; ４ is a five-membered heterocycle having at least one fluorine atom or trifluoromethyl group and an oxygen atom as a heteroatom, and p2 is an integer of 2 to 5,000, is more preferred.

[0143] Specific examples of the first fluorine-containing polymer of the fifth embodiment include the following formulae (P23-1) to (P23-12): In formulae (P23-1) to (P23-12), p2 represents an integer of 2 to 10,000.

[0144]

[0145] <<Second Fluorine-Containing Polymer>> The second fluorine-containing polymer of the present disclosure is represented by the following formula (H1a), (H1b), (H1c) or (H2): The second fluorine-containing polymer of the present disclosure is obtained, for example, by hydrogenation.

[0146]

[0147] In formula (H1a) to formula (H1c), each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ At least one of R is a group having a fluorine atom or a fluorine atom, and p1 is an integer of 2 to 10,000. １ａ ~R １ｄ In formula (H1b), any two of R are bonded to each other to form a ring structure. １ａ ~R １ｄany two of R are bonded to each other to form a ring structure, and m2b is an integer of 0 to 3. １ａ ~R １ｄ any two of these may be bonded to each other to form a ring structure or may not be bonded to each other; and m2c is an integer of 0 to 4.

[0148] In formula (H2), m3 is an integer of 0 to 4, and R ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄ Any two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom; and p2 is an integer of 2 to 10,000.

[0149] The polymers (H1a) to (H1c) and the polymer (H2) are novel polymers. The polymers (H1a) to (H1c) and the polymer (H2) are excellent in light transmittance, thermal stability, water repellency, and oil repellency. The second fluorine-containing polymer is preferable compared to the first fluorine-containing polymer from the viewpoints of light stability and improved handleability due to a lower glass transition temperature.

[0150] The weight average molecular weight (Mw) of the polymers (H1a) to (H1c) and the polymer (H2) is preferably from 10,000 to 1,000,000, more preferably from 10,000 to 500,000, and even more preferably from 10,000 to 250,000, from the viewpoint of moldability.

[0151] In formula (H1a) to formula (H1c), the explanations of X and p1, including definitions, examples, preferred embodiments, etc., are the same as the explanations of X and p1 in formula (P1c). １ａ ~R １ｄ The explanation of R in formula (P1a) including definitions, examples, and preferred embodiments is １ａ~R １ｄ In formula (H1b), m2b and R １ａ ~R １ｄ The description of m2b and R in formula (P1b) includes definitions, examples, and preferred embodiments. １ａ ~R １ｄ In formula (H1c), m2c and R １ａ ~R １ｄ The description of m2c and R in formula (P1c) includes definitions, examples, and preferred embodiments. １ａ ~R １ｄ The explanations are the same as those given above.

[0152] m3, R in polymer (H2) ２ａ ~R ２ｄ The explanation of m3, R and p2, including definitions, examples, preferred embodiments, etc., is based on the same as that of m3, R in the polymer (P2) described in the above <<First fluorine-containing polymer>>. ２ａ ~R ２ｄ , and p2 respectively.

[0153] [Second Fluorine-Containing Polymer of First Embodiment] The second fluorine-containing polymer of the first embodiment is represented by the following formula (H11): In formula (H11), m2 is an integer of 0 to 4, and R １１ａ ~R １１ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R １１ａ ~R １１ｄ are not bonded to each other (i.e., R １１ａ ~R １１ｄ does not form a ring structure).

[0154] In formula (H11), the descriptions of m2, p1, and X, including definitions, examples, and preferred embodiments, are the same as the descriptions of m2c, p1, and X in formula (H1c), respectively. １１ａ ~R １１ｄ The description of R includes definitions, examples, and preferred embodiments. １１ａ ~R１１ｄ R in formula (H1c) except that １ａ ~R １ｄ The explanations are the same as those given above.

[0155]

[0156] The second fluorine-containing polymer of the first embodiment is a novel polymer. The second fluorine-containing polymer of the first embodiment is excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0157] <Specific Examples> Specific examples of the second fluorinated polymer of the first embodiment in which m2 is 0 include the following formulae (H1-1) to (H1-14): In formulae (H1-1) to (H1-14), p1 is an integer of 2 to 10,000.

[0158]

[0159] [Second Fluorine-Containing Polymer of Second Embodiment] The second fluorine-containing polymer of the second embodiment of the present disclosure is represented by the following formula (H12a), formula (H12b) or formula (H12c).

[0160]

[0161] In formulae (H12a) to (H12c), X's each independently represent -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, and R １２ａ ~R １２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T １ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, and p1 is an integer of 2 to 10,000.

[0162] The second fluorine-containing polymer of the second embodiment is a novel polymer, and is excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0163] In formula (H12a) to formula (H12c), the explanations of X and p1, including definitions, examples, preferred embodiments, etc., are the same as the explanations of X and p1 in formula (H1c) above. １２ａ ~R １２ｂ and T １ The explanation of R in formula (P12a) including definitions, examples, and preferred embodiments is as follows. １２ａ ~R １２ｂ and T １ In formula (H12b), m2b and R １２ａ ~R １２ｂ and T １ The explanation of m2b, R in formula (P12b) includes definitions, examples, and preferred embodiments. １２ａ ~R １２ｂ and T １ In formula (H12c), m2c and R １２ａ ~R １２ｂ and T １ The explanation of m2c, R in formula (P12c) includes definitions, examples, and preferred embodiments. １２ａ ~R １２ｂ and T １ The explanations are the same as those given above.

[0164] <Specific Examples> Specific examples of the second fluorinated polymer of the second embodiment include the following formulae (H12-1) to (H12-30): In formulae (H12-1) to (H12-30), p1 represents an integer of 2 to 10,000.

[0165]

[0166]

[0167] [Second Fluorinated Polymer of Third Embodiment] The second fluorinated polymer of the third embodiment of the present disclosure is represented by the following formula (H13a), formula (H13b) or formula (H13c).

[0168]

[0169] The second fluorine-containing polymer of the third embodiment is a novel polymer, and is particularly excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0170] In formula (H13a) to formula (H13c), the explanations of X and p1, including definitions, examples, preferred embodiments, etc., are the same as the explanations of X and p1 in formula (H1c). １３ａ ~R １３ｂ and T ２ The explanation of R in formula (P13a) including definitions, examples, and preferred embodiments is １３ａ ~R １３ｂ and T ２ In formula (H13b), m2b and R １３ａ ~R １３ｂ and T ２ The explanation of m2b, R in formula (P13b) includes definitions, examples, and preferred embodiments. １３ａ ~R １３ｂ and T ２ In formula (H13c), m2c and R １３ａ ~R １３ｂ and T ２ The explanation of m2c, R in formula (P13c) includes definitions, examples, and preferred embodiments. １３ａ ~R １３ｂ and T ２ The explanations are the same as those given above.

[0171] Specific examples of the second fluorine-containing polymer of the third embodiment include the following formulae (H13-1) to (H13-18): In formulae (H13-1) to (H13-18), p1 represents an integer of 2 to 10,000.

[0172]

[0173] [Second Fluorine-Containing Polymer of Fourth Embodiment] The second fluorine-containing polymer of the fourth embodiment of the present disclosure is represented by the following formula (H22).

[0174]

[0175] The second fluorine-containing polymer of the fourth embodiment is a novel polymer, and is particularly excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0176] In formula (H22), R ２２ａ ~R ２２ｂ , m3, T ３ The description of p2 includes definitions, examples, and preferred embodiments, etc., and is based on R in the formula (P22). ２２ａ ~R ２２ｂ , m3, T ３ , and p2 respectively.

[0177] Specific examples of the second fluorine-containing polymer of the fourth embodiment include the following formulae (H22-1) to (H22-12): In formulae (H22-1) to (H22-12), p2 represents an integer of 2 to 10,000.

[0178]

[0179] [Second Fluorine-Containing Polymer of Fifth Embodiment] The second fluorine-containing polymer of the fifth embodiment of the present disclosure is represented by the following formula (H23).

[0180]

[0181] The second fluorine-containing polymer of the fifth embodiment is a novel polymer, and is particularly excellent in light transmittance, thermal stability, water repellency, and oil repellency.

[0182] In formula (H23), R ２３ａ ~R ２３ｂ , m3, T ４ The description of p2 includes definitions, examples, and preferred embodiments, etc., and is based on R ２３ａ ~R ２３ｂ , m3, T ４ , and p2 respectively.

[0183] Specific examples of the second fluorine-containing polymer of the fifth embodiment include the following formulae (H23-1) to (H23-12): In formulae (H23-1) to (H23-12), p2 represents an integer of 2 to 10,000.

[0184]

[0185] <<First embodiment of method for producing a fluorine-containing compound>> The first embodiment of the method for producing a fluorine-containing compound of the present disclosure includes reacting a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom, a fluorine-containing cyclic alkene, and cyclopentadiene in the same reaction system to obtain a fluorine-containing compound.

[0186] For example, a method for producing a specific fluorine-containing compound by reacting furan with a fluorine-containing cyclic alkene (e.g., octafluorocyclopentene) has been known. However, in the method for producing a fluorine-containing compound of the first embodiment, cyclopentadiene is further present in the same reaction system and the reaction is carried out. This produces a fluorine-containing compound having a specific structure that has not been obtained before. The coexistence of cyclopentadiene in the same reaction system makes it easier to form a structure in which a ring structure is added to the reaction intermediate, and also makes it easier to add a ring structure derived from a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom as a heteroatom, making it possible to produce a fluorine-containing compound having a specific structure that has not been obtained before.

[0187] <<Method for Producing Fluorine-Containing Compound of Second Embodiment>> A method for producing a fluorine-containing compound of a second embodiment of the present disclosure includes reacting a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom with a fluorine-containing heterocyclic alkene having an oxygen atom as a heteroatom, thereby obtaining a fluorine-containing compound having an oxygen atom as a heteroatom.

[0188] As described above, for example, methods for producing specific fluorine-containing compounds by reacting furan with a fluorine-containing cyclic alkene have been known. However, in the method for producing a fluorine-containing compound of the second embodiment, a fluorine-containing heterocyclic alkene having an oxygen atom as a heteroatom is used as a raw material and reacted. This produces a fluorine-containing compound having a specific structure that has not been obtained before. By using a fluorine-containing heterocyclic alkene having an oxygen atom as a heteroatom as a raw material, a structure in which a ring structure is added to the reaction intermediate is easily formed, and a ring structure derived from a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom as a heteroatom is also easily added, thereby producing a fluorine-containing compound having a specific structure that has not been obtained before.

[0189] <Heterodiene A> Hereinafter, a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom will also be referred to as "heterodiene A."

[0190] In the first and second embodiments of the production method of the present disclosure, the heterodiene A is preferably a cyclic heterodiene having an oxygen atom, more preferably a cyclic heterodiene having 4 to 6 carbon atoms and having an oxygen atom, and even more preferably furan, from the viewpoint of ease of synthesis. The heterodiene A may be used alone or in combination of two or more types.

[0191] <Fluorinated Cyclic Alkene> In the first embodiment of the production method of the present disclosure, from the viewpoint of ease of synthesis, the fluorinated cyclic alkene is preferably a fluorinated cyclic alkene having 4 to 10 carbon atoms, more preferably a fluorinated cyclic alkene having 4 to 6 carbon atoms. The fluorinated cyclic alkene may be a carbocyclic ring or a heterocyclic ring, but a heterocyclic ring is preferred. In the case of a heterocyclic ring, an oxygen atom is preferred as the heteroatom. A specific example of the fluorinated cyclic alkene is octafluorocyclopentene 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole.

[0192] In a second embodiment of the production method of the present disclosure, the fluorine-containing heterocyclic alkene is a fluorine-containing heterocyclic alkene having an oxygen atom as a heteroatom, and from the viewpoints of ease of synthesis and availability of raw materials, a fluorine-containing heterocyclic alkene having 4 to 10 carbon atoms and having an oxygen atom as a heteroatom is preferred, a fluorine-containing heterocyclic alkene having 4 to 6 carbon atoms and having an oxygen atom as a heteroatom is more preferred, and from the viewpoint of reactivity, a 5-membered heterocyclic compound having a trifluoromethyl group and an oxygen atom as a heteroatom is even more preferred. One type of fluorine-containing heterocyclic alkene may be used alone, or two or more types may be used in combination.

[0193] <Cyclopentadiene> In the first embodiment of the production method of the present disclosure, the cyclopentadiene used may be a cyclopentadiene produced by decomposition of dicyclopentadiene, or a cyclopentadiene produced by thermal decomposition of dicyclopentadiene. The heat may be heat for reacting the heterodiene A, the fluorinated cyclic alkene, and the cyclopentadiene in the first embodiment of the production method of the present disclosure. That is, the first embodiment of the production method of the present disclosure may include obtaining a fluorine-containing compound by heating and reacting the heterodiene A, the fluorinated cyclic alkene, and the dicyclopentadiene.

[0194] <Reaction> In the first and second embodiments of the production method of the present disclosure, the reaction is preferably a Diels-Alder reaction from the viewpoint of ease of synthesis. The detailed conditions for the Diels-Alder reaction are not particularly limited, and known conditions may be used.

[0195] In the first embodiment of the production method of the present disclosure, the molar ratio of heterodiene A, fluorinated cyclic alkene, and cyclopentadiene in the reactor before the reaction is not particularly limited. From the viewpoint of improving the yield, the molar ratio of heterodiene A to cyclopentadiene (heterodiene A / cyclopentadiene) in the reactor before the reaction is preferably 0.1 to 20, more preferably 0.5 to 15, and even more preferably 1.0 to 10. The molar ratio of fluorinated cyclic alkene to cyclopentadiene in the reactor before the reaction (fluorinated cyclic alkene / cyclopentadiene) is preferably 0.1 to 5.0, more preferably 0.2 to 2.0, and even more preferably 0.3 to 1.0.

[0196] In the second embodiment of the production method of the present disclosure, the molar ratio of heterodiene A to the fluorinated heterocyclic alkene having an oxygen atom as a heteroatom in the reactor before the reaction is not particularly limited. From the viewpoint of improving the yield, the molar ratio of heterodiene A to the fluorinated heterocyclic alkene in the reactor before the reaction (heterodiene A / fluorinated heterocyclic alkene) is preferably 0.1 to 20, more preferably 0.2 to 10, and even more preferably 0.5 to 2.0.

[0197] There are no particular limitations on the concentrations of the heterodiene A, the fluorinated cyclic alkene, and the cyclopentadiene in the reactor before the reaction.

[0198] In the first and second embodiments of the production method of the present disclosure, the heterodiene A, the fluorinated cyclic alkene, and, if necessary, cyclopentadiene may be continuously or intermittently supplied to the reactor.

[0199] In the first and second embodiments of the production method of the present disclosure, the heterodiene A, the fluorinated cyclic alkene, and, if necessary, the cyclopentadiene are preferably degassed and / or dehydrated in advance from the viewpoint of improving yield. The degassing method is not particularly limited, and examples thereof include ultrasonic degassing, vacuum decompression degassing, and freeze degassing. The dehydration method is also not particularly limited, and examples thereof include a method in which the heterodiene A is contacted with a dehydrating agent such as a molecular sieve.

[0200] In the first and second embodiments of the production method of the present disclosure, the reaction temperature can be set appropriately depending on the target fluorine-containing compound. From the viewpoint of reaction rate, the reaction temperature is preferably 50 to 300°C, more preferably 100 to 200°C, and even more preferably 130 to 180°C. The reaction time can also be set appropriately depending on the target fluorine-containing compound. From the viewpoint of improving the yield and productivity, the reaction time is preferably 1 to 50 hours, more preferably 5 to 20 hours, and even more preferably 10 to 15 hours.

[0201] The reaction pressure can also be appropriately set depending on the target fluorine-containing compound, and the reaction pressure may be either normal pressure or elevated pressure.

[0202] The type of reactor is not particularly limited. The reactor may be a batch-type reactor without stirring, a complete mixing type stirred tank reactor, or a piston flow type tubular reactor. Materials for the reactor, stirring blades, piping, etc. may be stainless steel such as SUS304, SUS304L, SUS316, or SUS316L, a Hastelloy alloy, or glass. Materials that are not susceptible to corrosion by the fluorine-containing cyclic alkene are suitably selected in consideration of reaction conditions such as heating temperature and pressure.

[0203] In the first and second embodiments of the production method of the present disclosure, the target fluorine-containing compound may be isolated by a known method, such as distillation, column chromatography, and recycle preparative HPLC, and these may be used alone or in combination as necessary.

[0204] The resulting fluorine-containing compound can be identified by a commonly known method. Examples of analytical methods include: １ H-NMR (proton nuclear magnetic resonance), １９ F-NMR (fluorine-19 nuclear magnetic resonance), １３ Examples of such spectroscopy include C-NMR (carbon-13 nuclear magnetic resonance) and GC-MS (gas chromatography mass spectrometry), and these may be used alone or in combination as needed.

[0205] The content of the fluorine-containing compound in the product obtained by the first and second embodiments of the production method of the present disclosure (i.e., the target product production rate) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of productivity. According to the first embodiment of the production method of the present disclosure, as described above, by adding cyclopentadiene, it is possible to make a fluorine-containing compound having a specific structure that has not been obtainable in the past, at a level not lower than the lower limit of the target product production rate. The content of the fluorine-containing compound in the product obtained by the first and second embodiments of the production method of the present disclosure is １９ It can be measured by F-NMR. When the obtained fluorine-containing compound has a plurality of isomers, the total content of the plurality of isomers is defined as the content of the fluorine-containing compound.

[0206] According to the first and second embodiments of the production method of the present disclosure, a fluorine-containing compound represented by the following formula (M12), formula (M13), formula (M22), or formula (M23) is preferably produced.

[0207]

[0208] The explanations of formula (M12), formula (M13), formula (M22), and formula (M23) in the first and second embodiments of the production method of the present disclosure, including definitions, examples, preferred aspects, and the like, are the same as the explanations of formula (M12), formula (M13), formula (M22), and formula (M23) in <Fluorine-Containing Compound>, respectively.

[0209] <<Method for Producing First Fluorine-Containing Polymer>> The method for producing the first fluorine-containing polymer of the present disclosure can be carried out by a conventionally known method using the fluorine-containing compound obtained by the first or second embodiment of the production method of the present disclosure as a raw material. For example, ring-opening metathesis polymerization of the fluorine-containing compound of the present disclosure can be used. More specifically, the fluorine-containing compound is dissolved in tetrahydrofuran, and a Grubbs second-generation ruthenium catalyst (dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II)) is added, followed by stirring at room temperature for 19 hours. Thereafter, n-butyl vinyl ether is added to terminate the polymerization reaction. The resulting solution is reprecipitated using methanol, and the solid is recovered by centrifugation followed by filtration. The same reprecipitation procedure is carried out again, and the resulting solid is vacuum-dried to obtain the first fluorine-containing polymer.

[0210] <<Method for producing second fluoropolymer>> The method for producing the second fluoropolymer of the present disclosure can be carried out by a conventionally known method using the first fluoropolymer obtained by the method for producing the first fluoropolymer of the present disclosure as a raw material. For example, the method includes a hydrogenation reaction of the first fluoropolymer. More specifically, p-toluenesulfonyl hydrazide is added to the first fluoropolymer and nitrogen is substituted. Thereafter, dehydrated dimethylformamide and dehydrated tetrahydrofuran are added and the mixture is stirred at room temperature to dissolve the solid matter. Thereafter, the mixture is heated to 130°C and stirred for 16 hours. Thereafter, the mixture is cooled to room temperature and reprecipitation is carried out twice using methanol to obtain the second fluoropolymer.

[0211] <Transparency, Thermal Stability, Water Repellency, and Oil Repellency> <Light Transmittance> In the present disclosure, light transmittance is measured by the following method. A 5% by mass solution of a fluororesin is dissolved in tetrahydrofuran, and the solution is applied to a glass substrate in a glove box under an Ar atmosphere. After drying at room temperature for 12 hours, the solution is vacuum dried at 200°C, and then the film is peeled off from the glass substrate to produce a free-standing film. The light transmittance of the obtained free-standing film over a wavelength range of 250 to 2000 nm is measured using a UV-Vis-Near-Infrared Spectrophotometer (V-770, manufactured by JASCO Corporation).

[0212] The higher the light transmittance (%), the more transparent the compound. In the fluorine-containing compound, first fluorine-containing polymer, and second fluorine-containing polymer of the present disclosure, from the viewpoint of high transparency in the near-infrared region, which is considered important in optical fibers and optical waveguides, the light transmittance at 1750 nm is preferably 92% or more, more preferably 93% or more, and even more preferably 94% or more. The light transmittance may be 100% or less.

[0213] <10% Thermal Decomposition Temperature> In the present disclosure, a thermogravimetric analyzer TG / DTA6200 (manufactured by Hitachi High-Tech Corporation) is used to measure the 10% thermal decomposition temperature by increasing the temperature at a rate of 10° C. per minute.

[0214] The higher the 10% thermal decomposition temperature (°C), the more excellent the thermal stability of the compound. In the fluorine-containing compound, first fluorine-containing polymer, and second fluorine-containing polymer of the present disclosure, the 10% thermal decomposition temperature is preferably 401°C or higher, more preferably 410°C or higher, even more preferably 420°C or higher, and particularly preferably 430°C or higher, from the viewpoint of the temperature conditions during use and molding of the compound. The 10% thermal decomposition temperature may be 500°C or lower, or 450°C or lower.

[0215] <Glass Transition Point> In the present disclosure, the glass transition point is measured using a differential scanning calorimeter DSC-2500 (manufactured by TA Instruments) by increasing the temperature at a rate of 10° C. per minute.

[0216] The higher the glass transition temperature, the more excellent the thermal stability of the dimensions and mechanical properties of the molded article. In the fluorine-containing compound, first fluorine-containing polymer, and second fluorine-containing polymer of the present disclosure, the glass transition point is preferably 200°C or higher, more preferably 220°C or higher, and even more preferably 240°C or higher, from the viewpoint of the temperature conditions during use of the compound and molding processing. The glass transition point may be 500°C or lower, 450°C or lower, or 400°C or lower.

[0217] <Water Contact Angle and Diiodomethane Contact Angle> In the present disclosure, the water contact angle and diiodomethane contact angle are measured by the following method. A 5% by mass solution of a fluororesin is prepared by dissolving a fluororesin in tetrahydrofuran, and the solution is applied to a piranha-treated Si substrate using a spin coater at 1000 rpm for 30 seconds, followed by vacuum drying at 200°C for 12 hours to produce a Si wafer surface-treated with the fluororesin. The contact angle of the obtained substrate is measured using a contact angle meter (DMo-502KTT, manufactured by Kyowa Interface Science Co., Ltd.) when 1 μL each of distilled water and diiodomethane is dropped onto the substrate.

[0218] The larger the water contact angle (degrees), the better the water repellency of the compound. The larger the diiodomethane contact angle (degrees), the better the oil repellency of the compound. In the fluorine-containing compound, first fluorine-containing polymer, and second fluorine-containing polymer of the present disclosure, the water contact angle is preferably 90 degrees or more, more preferably 95 degrees or more, and even more preferably 100 degrees or more, from the viewpoint of preventing adsorption of moisture and dust. The diiodomethane contact angle is preferably 55 degrees or more, more preferably 60 degrees or more, and even more preferably 70 degrees or more, from the viewpoint of preventing adsorption of oil and dust. The diiodomethane contact angle may be 150 degrees or less, 140 degrees or less, or 130 degrees or less.

[0219] <Surface Free Energy> In the present disclosure, the surface free energy is calculated from the contact angle results of water and diiodomethane, for which the dispersion component, hydrogen bond, and dipole-dipole interaction are known, using the Owens and Wendt equation.

[0220] The surface free energy (mJ / m ２ In the fluorine-containing compound, the first fluorine-containing polymer, and the second fluorine-containing polymer of the present disclosure, the surface free energy is 30 mJ / m or less from the viewpoint of preventing adsorption of moisture, oil, and dust. ２ Preferably, 25 mJ / m or less ２ More preferably, 20 mJ / m or less ２ More preferably, the surface free energy is 3 mJ / m or less. ２ Above, 4mJ / m ２ or more, or 5 mJ / m ２ More than that is fine.

[0221] <Refractive Index> In the present disclosure, the refractive index is measured using a rotary compensator type high-speed spectroscopic ellipsometer M-2000 (manufactured by J.A. Woollam) in a wavelength range of 300 to 1600 nm and at angles of incidence of 65 degrees, 70 degrees, and 75 degrees. The obtained results are analyzed using Cauchy's dispersion equation, and the refractive index at 633 nm is recorded. The refractive index at 633 nm is preferably 1.20 or more, more preferably 1.23 or more, and even more preferably 1.25 or more. The refractive index is preferably 1.50 or less, more preferably 1.48 or less, and even more preferably 1.46 or less.

[0222] Low refractive index materials are used as core materials for optical fibers because they reduce Rayleigh scattering, while high refractive index materials are used as lens materials because they can reduce the thickness of lenses.

[0223] <<Uses>> The fluorine-containing compound, first fluorine-containing polymer and second fluorine-containing polymer of the present disclosure can be used as a coating agent or a film.

[0224] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure. Examples 1 to 6 and Examples 11 to 19 are examples, and Examples 7 to 10 are comparative examples.

[0225] In the present disclosure, the identification of the synthetic monomers is carried out by subjecting the purified product to: １ H-NMR, １９ The analysis was carried out by F-NMR (JEOL, JNM-ECZ400S / L1) spectrum analysis.

[0226] In the present disclosure, the weight average molecular weight (Mw) of the synthesized polymer was measured using gel permeation chromatography (GPC, manufactured by Spectris Inc., Viscotek GPCmax (VE-2001)) using tetrahydrofuran as the solvent and calculated in terms of polystyrene.

[0227] Example 1: Synthesis of Compound A 3.0 g of cyclopentadiene (Tokyo Chemical Industry Co., Ltd., 23 mmol) and 1.9 g of 5,5,6-trifluoro-6-(trifluoromethyl)-7-oxabicyclo[2.2.1]-2-heptene (synthesized by the method described in JP 2007-63351 A, 9 mmol) were added to an autoclave, and freeze-degassing was carried out three times. The autoclave was then heated to 150°C and reacted for 12 hours. The resulting product was purified by column chromatography (hexane solvent) to obtain 2.3 g (8 mmol) of a colorless, transparent target product. The resulting Compound A was a mixture of isomers, and each of Isomer 1 and Isomer 2 １ H-NMR and １９ The F-NMR is as follows:

[0228] Isomer 1 １ H-NMR (399.8MHz, Solvent: CDCl3)δ(ppm):6.09 - 5.94 (2H,m), 4.39 (1H,dd, J = 13.2, 3.6 Hz), 4.25 (1H,d, J = 9.2 Hz), 3.02 (2H,ddq, J = 6.6, 3.2, 1.6 Hz, 1H),2.92 (1H,dtd, J = 8.2, 4.2, 1.2 Hz, 0H), 2.84 - 2.71 (1H,m), 1.49 - 1.21 (2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -71.77 (3F, dd, J = 15.4, 7.3 Hz), -115.97--116.61 (1F, m), -122.45--123.09 (1F, m), -174.93 (1F, dp, J = 22.0, 7.2 Hz)

[0229] Isomer 2 １H-NMR (399.8MHz, Solvent: CDCl3) δ (ppm): δ 6.09 - 5.94 (2H,m), 4.51 (1H,d, J = 2.2 Hz), 4.25 (1H,d, J = 9.2 Hz), 3.02 (2H,ddq, J = 6.6, 3.2, 1.6 Hz), 2.84 - 2.71 (2H,m), 1.49 - 1.21 (2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -76.25 - -76.44 (3F, m), -116.22 - -116.45 (1F, m), , -117.91-118.55 (1F, m), -183.05 (1F, dp, J = 11.7, 4.0 Hz).

[0230] Example 2: Ring-opening metathesis polymerization of compound A In a glove box filled with an argon atmosphere, 1.2 g (4 mmol) of compound A obtained in Example 1 was dissolved in 20 mL of tetrahydrofuran, and 20 mg of Grubbs second-generation ruthenium catalyst (Sigma-Aldrich, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 0.02 mmol) was added, followed by stirring at room temperature for 19 hours. Then, 0.5 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.) was added to terminate the polymerization reaction. The resulting solution was reprecipitated using 200 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was repeated, and the resulting solid was dried in vacuo to obtain 1.0 g of the target white solid (Mw=52,000, Mw / Mn=2.3). １ H-NMR and １９ The F-NMR is as follows:

[0231] １ H-NMR (399.8MHz, solvent: THF-δ8) δ (ppm): δ 5.89-5.53 (2H,m), 5.05-4.50 (2H,m), 3.28-2.67 (4H,m), 1.70 (2H,m) １９ ​F-NMR (376.2 MHz, solvent: THF-δ8, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -73.30 (1.1 F, m), -77.23 (1.9 F, m), -116.53--118.96 (1.6 F, m), -120.84-123.14 (0.4 F, m), -176.52 - -177.72 (0.4 F, m), -180.15 - -181.37 (0.6 F, m).

[0232] Example 3: Synthesis of Compound B and Compound C 8.0 g of dicyclopentadiene (Tokyo Chemical Industry Co., Ltd., 60 mmol), 63.0 g of furan (Tokyo Chemical Industry Co., Ltd., 93 mmol), and 16.0 g of octafluorocyclopentene (Tokyo Chemical Industry Co., Ltd., 80 mmol) were added to a stainless steel autoclave (internal volume 600 mL), and freeze-degassing was performed three times. The reactor was then heated at 150°C for 12 hours. Dicyclopentadiene decomposes at 150°C, producing two equivalents of cyclopentadiene. The resulting reaction solution was purified by column chromatography (hexane solvent) to obtain 10.6 g (30 mmol) of Compound B and 1.7 g (5 mmol) of Compound C. Both the obtained compounds were white solids, and Compounds B and C were stereoisomers. １ H-NMR and １９ The F-NMR is as follows:

[0233] Compound B １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): δ 6.05 (2H,t,J=1.7Hz), 4.61 (2H,s), 3.09-2.92 (4H,m), 1.48-1.29 (2H,m) １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -128.05--128.20 (2F, m), -133.46-135.77 (4F, m), -186.73 (2F, d, J = 3.0 Hz)

[0234] Compound C １H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): δ 6.23 (2H,t,J=2.1Hz), 4.70 (2H,s), 2.90 (2H,p,J=1.7), 2.37 (2H,dt,J=2.9,1.4Hz),2.20 (1H,dt,J=8.9,1.8Hz), 1.14 (1H,dt,J=8.9,1.5Hz) １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -127.16--129.32 (2F, m), -133.12-135.91 (4F, m), -184.77 (2F, d, J = 4.0 Hz)

[0235] Example 4: Ring-opening metathesis polymerization of compound B In a glove box filled with an argon atmosphere, 520 mg (1.5 mmol) of compound B obtained in Example 3 was dissolved in 8 mL of tetrahydrofuran, and 9 mg of Grubbs' first-generation ruthenium catalyst (Sigma-Aldrich, dichloro(benzylidene)bis(tricyclohexylphosphine)ruthenium(II), 0.01 mmol) was added, followed by stirring at room temperature for 19 hours. Then, 0.1 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.) was added to terminate the polymerization reaction. The resulting solution was reprecipitated using 100 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was carried out again, and the resulting solid was dried in vacuo to obtain 420 mg of the target white solid (Mw=54,000, Mw / Mn=2.6). １ H-NMR and １９ The F-NMR is as follows:

[0236] １ H-NMR (399.8MHz, solvent: THF-δ8)δ(ppm):δ 5.77(2H,m), 4.90 (2H,m), 2.98(4H,m), 1.69(2H,m) １９ F-NMR (376.2 MHz, solvent: THF-δ8, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -128.05--130.59 (4F, m), -134.65-137.49 (2F, m), -185.01 (2F, m) ​

[0237] Example 5: Ring-opening metathesis polymerization of compound C In a glove box filled with an argon atmosphere, 180 mg (0.5 mmol) of compound B obtained in Example 3 was dissolved in 3 mL of tetrahydrofuran, and 3 mg of Grubbs second-generation ruthenium catalyst (Sigma-Aldrich, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 0.004 mmol) was added, followed by stirring at room temperature for 19 hours. Then, 0.1 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.) was added to terminate the polymerization reaction. The resulting solution was reprecipitated using 100 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was carried out again, and the resulting solid was dried in vacuo to obtain 180 mg of the target white solid (Mw=48,000, Mw / Mn=2.6). １ H-NMR and １９ The F-NMR is as follows:

[0238] １ H-NMR (399.8MHz, solvent: THF-δ8)δ(ppm):δ 5.22(2H,m), 4.32 (2H,m), 2.61-1.97(4H,m), 1.69(2H,m) １９ F-NMR (376.2 MHz, solvent: THF-δ8, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -129.33 (4F, m), -134.32-137.56 (2F, m), -184.65-187.18 (2F, m)

[0239] ​Example 6: Hydrogenation reaction of ring-opening metathesis polymer A 50 mL two-neck flask was charged with 200 mg (0.6 mmol) of the white solid obtained in Example 4 and 1.2 g (6.5 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of p-toluenesulfonylhydrazide, and the atmosphere was replaced with nitrogen. Then, 10 mL of dehydrated dimethylformamide (manufactured by Kanto Chemical Industry Co., Ltd.) and 10 mL of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Industry Co., Ltd.) were added and stirred at room temperature to dissolve the solid. The mixture was then heated to 130°C and stirred for 16 hours. The mixture was then cooled to room temperature, and reprecipitation was carried out twice using 50 mL of methanol, yielding 198 mg of a white solid. １ H-NMR and １９ The F-NMR is as follows:

[0240] １ H-NMR (399.8 MHz, solvent: pentafluoroanisole) δ (ppm): δ 4.83 (2H, m), 2.86 (2H, m), 2.30-1.90 (4H, m), 1.65-1.40 (4H, m) １９ F-NMR (376.2 MHz, solvent: pentafluoroanisole, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -130.75--132.37 (4F, m), -137.17--139.25 (2F, m), -187.44--187.54 (2F, m)

[0241] Example 7 A ZEONOR film ZF014-023 (manufactured by Zeon Corporation) was prepared.

[0242] Example 8 A compound was synthesized by the method described in JP-A-2007-63351. Mw = 100,000, Mw / Mn = 2.7

[0243] Example 9 A compound was synthesized by the method described in JP 2010-132600 A. Mw = 121,000, Mw / Mn = 3.6

[0244] ​Example 10: 11.7 g of cyclopentadiene (Tokyo Chemical Industry Co., Ltd., 180 mmol) and 2.5 g of (+)-limonene (Tokyo Chemical Industry Co., Ltd., 18 mmol) were added to a stainless steel autoclave (internal volume 600 mL), and freeze-degassing was performed three times. Then, 40.0 g of hexafluoropropene (AGC Corporation, 270 mmol) was added to the reactor, and the mixture was heated at 200°C for 22 hours. The resulting reaction solution was purified by distillation, yielding 36.5 g (169 mmol) of compound X. 4.0 g (19 mmol) of the resulting compound X and 1.5 g (12 mmol) of dicyclopentadiene were added to a stainless steel autoclave (internal volume 20 mL), and freeze-degassing was performed three times. The reactor was then heated at 150°C for 24 hours. The resulting compound was purified by column chromatography, yielding 1.4 g (5 mmol) of compound Y. In a glove box filled with an argon atmosphere, 1.1 g (4.0 mmol) of the obtained compound Y was dissolved in 20 mL of tetrahydrofuran, and 18 mg of Grubbs' second-generation ruthenium catalyst (Sigma-Aldrich, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 0.004 mmol) was added, followed by stirring at room temperature for 27 hours. Subsequently, 0.5 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.) was added to terminate the polymerization reaction. The resulting solution was reprecipitated using 100 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was repeated, and the resulting solid was dried under vacuum to obtain 1.0 g of the desired white solid (Mw=126,000, Mw / Mn=3.1).

[0245] [Evaluation] Each of the obtained compounds was evaluated as follows.

[0246] <Light Transmittance> A 5% by mass solution of fluororesin was dissolved in tetrahydrofuran and applied to a glass substrate in a glove box under an Ar atmosphere. After drying at room temperature for 12 hours, the solution was vacuum dried at 200°C, and then the film was peeled off from the glass substrate to prepare a free-standing film. The light transmittance of the obtained free-standing film over the wavelength range of 250 to 2000 nm was measured using a UV-Vis-Near-Infrared Spectrophotometer (V-770, manufactured by JASCO Corporation), and the light transmittances at 450, 750, 1050, 1350, and 1750 nm were recorded.

[0247] <10% Thermal Decomposition Temperature> Measurement was carried out using a thermogravimetric analyzer TG / DTA6200 (manufactured by Hitachi High-Technologies Corporation) by increasing the temperature at a rate of 10° C. per minute.

[0248] <Glass Transition Point> The glass transition point was measured using a differential scanning calorimeter DSC-2500 (manufactured by TA Instruments) by increasing the temperature at a rate of 10° C. per minute.

[0249] <Water Contact Angle and Diiodomethane Contact Angle> A 5% by mass solution of a fluororesin was prepared by dissolving the fluororesin in tetrahydrofuran, and the solution was applied to a piranha-treated Si substrate using a spin coater at 1000 rpm for 30 seconds, followed by vacuum drying for 12 hours at 200° C. to produce a Si wafer surface-treated with the fluororesin. The contact angle of the obtained substrate was measured using a contact angle meter (DMo-502KTT, manufactured by Kyowa Interface Science Co., Ltd.) when 1 μL each of distilled water and diiodomethane was dropped onto the substrate.

[0250] <Surface Free Energy> The surface free energy was calculated from the contact angle results of water and diiodomethane, for which the dispersion component, hydrogen bond, and dipole-dipole interaction are known, using the Owens and Wendt equation.

[0251] <Refractive Index> The refractive index was measured using a rotary compensator type high-speed spectroscopic ellipsometer M-2000 (manufactured by J.A. Woollam) in the wavelength range of 300 to 1600 nm and at angles of incidence of 65 degrees, 70 degrees, and 75 degrees. The obtained results were analyzed using Cauchy's dispersion equation, and the refractive index at 633 nm was recorded.

[0252] The structural formulas of the compounds synthesized above in Examples 1 to 10 are shown below, and the evaluation results of each polymer (Examples 2, 4 to 10) are shown in Table 1. In the structural formula, n is an integer from 2 to 10,000. In Table 1, * indicates that a thin film could not be formed using THF (tetrahydrofuran) due to low solubility.

[0253]

[0254]

[0255] As described above, the compounds of Examples 1 to 6 were novel compounds, and the production methods of the compounds of Examples 3 to 6 were novel production methods. In particular, the compounds of Examples 4 and 5 were excellent in transparency, thermal stability, water repellency, and oil repellency.

[0256] Example 11 Synthesis of Compound D 1.4 g of cyclopentadiene (Tokyo Chemical Industry Co., Ltd., 21 mmol) and 4.0 g of 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole (AGC Corporation, 16 mmol) were added to an autoclave, and freeze-degassing was performed three times. The autoclave was then heated to 50°C and reacted for 16 hours. The resulting product was purified by column chromatography (hexane solvent) to obtain 1.3 g (4 mmol) of Compound D. The target product obtained was a mixture of isomers, and the proportions of each isomer were １ H-NMR and １９ The F-NMR is as follows:

[0257] Compound D Isomer 1 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.22 (2H, s), 3.16 (2H, tp, J=3.3, 1.7Hz), 2.53-2.26 (2H, m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -76.71 (3F, q, J = 9.8 Hz), -79.82 (3F, h, J = 9.4 Hz), -119.40--119.60 (2F, m)

[0258] Isomer 2 １H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.35 (2H,t,J=1.9Hz), 3.20 (2H,s),2.53-2.26(2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -78.11 (3F, q, J = 9.8 Hz), -79.19 (3F, h, J = 9.8 Hz), -116.75 (2F, qd, J = 11.6, 5.1 Hz)

[0259] Example 12 Synthesis of Compounds E and H 1.5 g of furan (Tokyo Chemical Industry Co., Ltd., 22 mmol) and 3.6 g of 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole (AGC Corporation, 15 mmol) were added to an autoclave, and freeze-degassing was performed three times. The autoclave was then heated to 100°C and reacted for 40 hours. The resulting product was purified by column chromatography (dichloromethane solvent) to obtain 2.2 g (6 mmol) of Compound E and 0.7 g (2 mmol) of Compound H. The target product obtained was a mixture of isomers, and the proportions of each isomer were １ H-NMR and １９ The F-NMR is as follows:

[0260] Compound E Isomer 1 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.64 (2H,s), 4.97-4.89 (2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -79.36 (3F, q, J = 8.7 Hz), -80.60 (3F, m), -119.85 (2F, q, J = 6.4 Hz)

[0261] Isomer 2 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.58 (2H,s), 5.03-4.97 (2H,m). １９F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -76.79 (3F, q, J = 9.5 Hz), -80.14 (3F, m), -127.73 (2F, q, J = 9.8 Hz)

[0262] Compound H Isomer 1 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.47 (2H,t,J=0.9Hz), 5.07-4.98 (2H,m), 4.62 (2H,d,J = 1.2 Hz), 2.41-2.36 (2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -79.34 (3F, m), -80.12 (3F, m), -130.59 (2F, q, J = 6.8 Hz)

[0263] Isomer 2 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.33 (2H,t,J=1.0Hz), 5.07-4.98 (2H,m),4.29-4.19 (2H,m), 3.00 (2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -79.34 (3F, m), -80.12 (3F, m), -131.71 (2F, q, J = 6.9 Hz)

[0264] Isomer 3 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.30 (2H,t,J=1.0Hz), 5.07-4.98 (2H,m),4.29-4.19 (2H,m), 3.00 (2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -77.74 (3F, q, J = 9.6 Hz), -80.12 (3F, m), -124.73 (2F, m)

[0265] Isomer 4 １H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.48 (2H,t,J=1.0Hz), 5.02 (2H,s), 4.64 (2H,dd,5.9,3.8Hz), 2.39 (2H,s). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -77.81 (3F, q, J = 9.4 Hz), -79.49 (3F, h, J = 10.1 Hz), -125.00 (2F, m)

[0266] Example 13: Synthesis of Compound F 0.7 g of cyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd., 10 mmol) and 2.4 g of 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole (manufactured by AGC Inc., 10 mmol) were added to an autoclave, and freeze-degassing was carried out three times. The autoclave was then heated to 50°C, and the reaction was carried out for 18 hours. 1.7 g of cyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd., 25 mmol) was added to the obtained product, and freeze-degassing was carried out three times. The autoclave was then heated to 150°C, and the reaction was carried out for 29 hours. The obtained product was purified by column chromatography (hexane solvent) to obtain 1.0 g (3 mmol) of Compound F. The obtained target product was a mixture of isomers, and the relative proportions of each isomer were １ H-NMR and １９ The F-NMR is as follows:

[0267] Compound F isomer 1 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.06 (2H,t,J=2.0Hz), 3.04-2.94 (2H,m),2.80(1H,dt,J=12.4,1.9Hz),2.66-2.48(4H,m),1.76(1H,d,J=12.4Hz),1.47-1.39(1H,m),1.25(1H,d,J=8.2Hz). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -77.40 (3F, q, J = 9.8 Hz), -78.99 (3F, tq, J = 13.7, 10.1 Hz), -120.59 (2F, m)

[0268] Isomer 2 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.06 (2H,t,J=2.0Hz), 3.04-2.94 (2H,m),2.63-2.48(5H,m),1.47-1.39(1H,m),1.34(1H,d,J=8.2Hz),1.23-1.17(1H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -77.57 (3F, q, J = 10.1 Hz), -78.60 (3F, tq, J = 13.0, 9.8 Hz), -130.17 (2F, m)f

[0269] Example 14: Synthesis of Compound G 0.7 g of dicyclopentadiene (Tokyo Chemical Industry Co., Ltd., 10 mmol), 0.7 g of furan (Tokyo Chemical Industry Co., Ltd., 11 mmol), and 2.9 g of 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole (AGC Inc., 12 mmol) were added to an autoclave, and freeze-degassing was performed three times. The autoclave was then heated to 150°C and reacted for 23 hours. The resulting product was purified by column chromatography (hexane / ethyl acetate mixed solvent) to obtain 1.0 g (3 mmol) of colorless, transparent, crystalline Compound G. The target product obtained was a mixture of isomers, and the isomers were separated. １ H-NMR and １９ The F-NMR is as follows:

[0270] Compound G isomer 1 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 6.03 (2H,t,J=1.9Hz), 4.28 (2H,m), 3.01 (2H,p, J = 1.9 Hz), 2.81 (2H,dq,J=2.7,1.4Hz), 1.48-1.32(2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -79.32 (3F, q, J = 8.7 Hz), -80.09 (3F, h, J = 10.1 Hz), -132.09 (2F, q, J = 7.2 Hz)

[0271] Isomer 2 １ H-NMR (399.8MHz, solvent: CDCl3) δ (ppm): 5.99 (2H,t,J=1.9Hz), 4.32-4.28(2H,m),3.01 (2H,p, J = 1.9 Hz), 2.83 (2H,q,J=1.5Hz), 1.46-1.26(2H,m). １９ F-NMR (376.2 MHz, solvent: CDCl3, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -77.76 (3F, q, J = 9.8 Hz), -79.50 (3F, h, J = 10.1 Hz), -125.37 (2F, tq, J = 11.6, 5.8 Hz)

[0272] Example 15: Ring-Opening Metathesis Polymerization of Compound D In a glove box filled with an argon atmosphere, 260 mg (0.8 mmol) of Compound D obtained in Example 11 was dissolved in 3 mL of tetrahydrofuran, and 4 mg of Grubbs' second-generation ruthenium catalyst (Sigma-Aldrich, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 0.004 mmol) was added, followed by stirring at 50°C for 13 hours. The polymerization reaction was then terminated by adding 0.1 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.). The resulting solution was reprecipitated using 100 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was repeated, and the resulting solid was dried under vacuum to obtain 260 mg of the target white solid (Mw=21,000, Mw / Mn=1.3).

[0273] １ H-NMR (399.8MHz, solvent: THF-δ8)δ(ppm):δ 5.95-5.56(2H,m), 3.53-2.83 (2H,m),2.40-1.77(1H,m),1.650-1.35(1H,m). １９ ​F-NMR (376.2 MHz, solvent: THF-δ8, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -79.72--82.16 (6F, m), -107.34--111.12 (1.8F, m), -122.31--125.32 (0.2F, m)

[0274] Example 16: Ring-Opening Metathesis Polymerization of Compound E In a glove box filled with an argon atmosphere, 240 mg (0.8 mmol) of Compound E obtained in Example 12 was dissolved in 3 mL of tetrahydrofuran, and 4 mg of Grubbs' second-generation ruthenium catalyst (Sigma-Aldrich, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 0.004 mmol) was added, followed by stirring at 50°C for 13 hours. The polymerization reaction was then terminated by adding 0.1 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.). The resulting solution was reprecipitated using 100 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was repeated, and the resulting solid was dried under vacuum to obtain 140 mg of the target white solid (Mw=100,000, Mw / Mn=1.3).

[0275] １ H-NMR (399.8MHz, solvent: THF-δ8)δ(ppm):δ 6.36-5.77(2H,m), 5.25-4.46 (2H,m). １９ F-NMR (376.2 MHz, solvent: THF-δ8, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -76.98--84.73 (6F, m), -119.31--123.87 (1F, m), -125.22--131.13 (1F, m)

[0276] ​Example 17: Ring-opening metathesis polymerization of compound F In a glove box filled with an argon atmosphere, 260 mg (0.8 mmol) of compound F obtained in Example 13 was dissolved in 3 mL of tetrahydrofuran, and 4 mg of Grubbs second-generation ruthenium catalyst (Sigma-Aldrich, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 0.004 mmol) was added, followed by stirring at 50°C for 13 hours. The polymerization reaction was then terminated by adding 0.1 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.). The resulting solution was reprecipitated using 100 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was repeated, and the resulting solid was dried under vacuum to obtain 260 mg of the target white solid (Mw=61,000, Mw / Mn=1.5).

[0277] １ H-NMR (399.8MHz, solvent: THF-δ8)δ(ppm):δ 5.91-5.27(2H,m), 3.41-2.52 (6H,m),2.32-1.39(4H,m). １９ F-NMR (376.2 MHz, solvent: THF-δ8, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -76.55--81.20 (6F, m), -119.67--129.45 (2F, m).

[0278] ​Example 18: Ring-Opening Metathesis Polymerization of Compound G In a glove box filled with an argon atmosphere, 250 mg (0.7 mmol) of Compound G obtained in Example 14 was dissolved in 3 mL of tetrahydrofuran, and 4 mg of Grubbs' second-generation ruthenium catalyst (Sigma-Aldrich, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 0.004 mmol) was added, followed by stirring at 50°C for 13 hours. The polymerization reaction was then terminated by adding 0.1 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.). The resulting solution was reprecipitated using 100 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was repeated, and the resulting solid was dried under vacuum to obtain 200 mg of the target white solid (Mw=74,000, Mw / Mn=1.6).

[0279] １ H-NMR (399.8MHz, solvent: THF-δ8)δ(ppm):δ 5.82-5.39(2H,m), 5.02-4.28 (2H,m),3.33-2.56(4H,m),1.98-1.43(2H,m). １９ F-NMR (376.2 MHz, solvent: THF-δ8, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -78.31--81.95 (6F, m), -125.89--132.39 (2F, m).

[0280] ​Example 19: Ring-Opening Metathesis Polymerization of Compound H In a glove box filled with an argon atmosphere, 230 mg (0.6 mmol) of Compound H obtained in Example 12 was dissolved in 3 mL of tetrahydrofuran, and 4 mg of Grubbs' second-generation ruthenium catalyst (Sigma-Aldrich, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 0.004 mmol) was added, followed by stirring at 50°C for 13 hours. The polymerization reaction was then terminated by adding 0.1 mL of n-butyl vinyl ether (Tokyo Chemical Industry Co., Ltd.). The resulting solution was reprecipitated using 100 mL of methanol, and the solid was recovered by centrifugation followed by filtration. The same reprecipitation procedure was repeated, and the resulting solid was dried under vacuum to obtain 210 mg of the target white solid (Mw=27,000, Mw / Mn=1.4).

[0281] １ H-NMR (399.8MHz, solvent: THF-δ8)δ(ppm):δ 6.25-5.51(2H,m), 5.24-4.14 (4H,m),3.32-2.55(2H,m). １９ F-NMR (376.2 MHz, solvent: THF-δ8, standard: 1,4-bistrifluoromethylbenzene) δ (ppm): -77.93--82.13 (6F, m), -124.90--133.78 (2F, m).

[0282] [Evaluation] Each of the obtained compounds was evaluated for light transmittance, 10% thermal decomposition temperature, glass transition point, water contact angle, diiodomethane contact angle, surface free energy, and refractive index as described above.

[0283] The structural formulae of the compounds synthesized above in Examples 11 to 19 are shown below, and the evaluation results of each polymer (Examples 15 to 19) are shown in Table 2. In the structural formulae, n is an integer of 2 to 10,000.

[0284]

[0285]

[0286] ​As described above, the compounds and polymers of Examples 11 to 19 were novel compounds or novel polymers, and their production methods were also novel. The polymers of Examples 15 to 19 were excellent in transparency, thermal stability, water repellency, and oil repellency.

[0287] The disclosures of Japanese Patent Application No. 2024-070702 filed on April 24, 2024 and Japanese Patent Application No. 2024-153754 filed on September 6, 2024 are incorporated herein by reference in their entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A fluorine-containing compound represented by the following formula (M1) or formula (M2): (In formula (M1), m1 is 0 or 1; when m1 is 0 in formula (M1), m2 is an integer of 0 to 4; each X independently represents -O-, -S-, or -NR-; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom; R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom; １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure, in formula (M1), when m1 is 1, m2 is an integer of 0 to 4, each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom; １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure or are not bonded to each other, in formula (M2), m3 is an integer of 0 to 4, ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄ Any two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom.

2. In the formula (M1), m1 is 1, m2 is an integer of 0 to 4, and R １ａ ~R １ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R １ａ ~R １ｄ At least one of R is a group having a fluorine atom or a fluorine atom, １ａ ~R １ｄ The fluorine-containing compound according to claim 1 , wherein are not bonded to each other.

3. The fluorine-containing compound according to claim 1, which is represented by the following formula (M12), (M13), (M22), or (M23): (In formula (M12), m1 is 0 or 1, m2 is an integer of 0 to 4, each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a heteroatom, R １２ａ ~R １２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T １ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, in formula (M13), m1 is 0 or 1, m2 is an integer of 0 to 4, each X independently represents -O-, -S-, or -NR-, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, and R １３ａ ~R １３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ２ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, and in formula (M22), m3 represents an integer of 0 to 4, and R ２２ａ ~R ２２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ３ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom, and in formula (M23), m3 is an integer of 0 to 4, and R ２３ａ ~R ２３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ４ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom.

4. A fluorine-containing polymer represented by the following formula (P1a), formula (P1b), formula (P1c) or formula (P2): (In formulas (P1a) to (P1c), each X independently represents -O-, -S-, or -NR-; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom; R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom, p1 is an integer of 2 to 10,000, and in formula (P1a), R １ａ ~R １ｄ Any two of R are bonded to each other to form a ring structure, and in formula (P1b), １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure, m2b is an integer of 0 to 3, and in formula (P1c), R １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure or are not bonded to each other, m2c is an integer of 0 to 4, in formula (P2), m3 is an integer of 0 to 4, R ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄ any two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom; and p2 is an integer of 2 to 10,000.

5. In the formula (P1c), m2c is an integer of 0 to 4, and R １ａ ~R １ｄ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom, and R １ａ ~R １ｄ At least one of R is a group having a fluorine atom or a fluorine atom, １ａ ~R １ｄ The fluorine-containing polymer according to claim 4, wherein are not bonded to each other.

6. The fluorine-containing polymer according to claim 4, which is represented by the following formula (P12a), (P12b), (P12c), (P13a), (P13b), (P13c), (P22) or (P23). (In formulas (P12a) to (P12c), each X independently represents —O—, —S—, or —NR—; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom; R １２ａ ~R １２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T １ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, p1 is an integer of 2 to 10,000, in formulas (P13a) to (P13c), each X independently represents —O—, —S—, or —NR—, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom, and R １３ａ ~R １３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ２ represents a group having a fluorine atom or a 4- to 6-membered ring having at least one fluorine atom, p1 is an integer of 2 to 10,000, in formulas (P12b) and (P13b), m2b is an integer of 0 to 3, in formulas (P12c) and (P13c), m2c is an integer of 0 to 4, in formula (P22), R ２２ａ ~R ２２ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ３ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom, m3 is an integer of 0 to 4, p2 is an integer of 2 to 10,000, and in formula (P23), R ２３ａ ~R ２３ｂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; T ４ represents a group having a fluorine atom or a 4- to 6-membered oxygen-containing heterocycle having at least one fluorine atom, m3 is an integer of 0 to 4, and p2 is an integer of 2 to 10,000.

7. A fluorine-containing polymer represented by the following formula (H1a), (H1b), (H1c) or (H2): (In formulas (H1a) to (H1c), each X independently represents -O-, -S-, or -NR-; R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aralkyl group having 6 to 20 carbon atoms which may or may not have a hetero atom; R １ａ ~R １ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R １ａ ~R １ｄ at least one of R is a group having a fluorine atom or a fluorine atom, p1 is an integer of 2 to 10,000, and in formula (H1a), １ａ ~R １ｄ Any two of R are bonded to each other to form a ring structure, and in formula (H1b), １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure, m2b is an integer of 0 to 3, and in formula (H1c), R １ａ ~R １ｄ any two of these are bonded to each other to form a ring structure or are not bonded to each other, m2c is an integer of 0 to 4, in formula (H2), m3 is an integer of 0 to 4, R ２ａ ~R ２ｄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may or may not have a fluorine atom, an alkoxy group having 1 to 10 carbon atoms which may or may not have a fluorine atom, or an alkoxyalkyl group having 2 to 10 carbon atoms which may or may not have a fluorine atom; R ２ａ ~R ２ｄ at least one of R is a group having a fluorine atom or a fluorine atom; ２ａ ~R ２ｄ any two of these are bonded to each other to form a ring structure, and the ring structure has an oxygen atom, and p2 is an integer of 2 to 10,000.

8. A method for producing a fluorine-containing compound, comprising reacting a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom, a fluorine-containing cyclic alkene, and cyclopentadiene in the same reaction system.

9. A method for producing a fluorine-containing compound, comprising reacting a cyclic heterodiene having an oxygen atom, a sulfur atom, or a nitrogen atom with a fluorine-containing heterocyclic alkene having an oxygen atom as a heteroatom.

10. The method for producing a fluorine-containing compound according to claim 8 or 9, wherein the cyclic heterodiene is furan.

11. The method for producing a fluorine-containing compound according to claim 8 or 9, wherein the reaction is a Diels-Alder reaction.

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