JP4900688B2 - Optically active polymer compound - Google Patents

Description

  The present invention relates to an optically active polymer compound.

で表される、３個の芳香環が共役した側鎖がポリエチレン主鎖に直接結合した光学活性な高分子化合物（非特許文献２）が提案されているが、側鎖どうしが立体的に混み合っており、光学活性な開始剤を用いて主鎖を光学活性ならせん構造にすることが難しい。 Examples of the optically active polymer compound include a polymer compound having an optically active side chain obtained by polymerizing an optically active monomer, and an optically active helical structure in which the main chain is formed using an optically active initiator. Molecular compounds and the like are known. More specifically, an optically active polymer compound in which a bulky side chain containing about 3 non-conjugated aromatic rings is bonded to a polyethylene main chain via an oxygen atom or —C (O) O— group (non-patented) Document 1) has been proposed, but the side chain conjugation is short, and functions such as luminescence cannot be sufficiently exhibited. Also, the following formula:

An optically active polymer compound (Non-patent Document 2) in which a side chain conjugated with three aromatic rings is directly bonded to a polyethylene main chain has been proposed, but the side chains are sterically crowded. It is difficult to make the main chain into an optically active helical structure using an optically active initiator.

Chem. Rev. 101, 4013 (2001) Chem. Commun. 974 (2003)

  Accordingly, an object of the present invention is to provide a novel optically active polymer compound having excellent light emitting properties and having an optically active helical structure in the main chain.

（I）
（式中、Ａｒは芳香環を含む３価の有機基であり、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴はそれぞれ独立に、直接結合、置換イミノ基、エテニレン基又はエチニレン基である。但し、Ｒ¹及びＲ²はＡｒ中の芳香環に結合する。Ａｒ¹及びＡｒ²はそれぞれ独立に、芳香環を含む２価の有機基である。但し、Ｒ¹及びＲ³はＡｒ¹中の芳香環に結合し、Ｒ²及びＲ⁴はＡｒ²中の芳香環に結合する。ｎ¹及びｎ²はそれぞれ独立に、１以上の整数である。Ｒ⁵及びＲ⁶はそれぞれ独立に、水素原子、ハロゲン原子、１価の炭化水素基、ヒドロカルビルオキシ基、ヒドロカルビル二置換アミノ基又はヒドロカルビルメルカプト基である。Ｒ⁷は酸素原子、硫黄原子、置換イミノ基、カルボニル基及び２価の炭化水素基からなる群から選ばれる１〜３個を組み合わせた２価の基である。Ｒ⁸、Ｒ⁹及びＲ¹⁰はそれぞれ独立に、水素原子又は１価の炭化水素基である。） In the present invention, first, an optically active polymer compound having a repeating unit represented by the following general formula (I) (that is, a side chain conjugated with three or more aromatic rings is indirectly bonded to the main chain) An optically active polymer compound).

(I)
(In the formula, Ar is a trivalent organic group containing an aromatic ring, and R ¹ , R ² , R ³ and R ⁴ are each independently a direct bond, a substituted imino group, an ethenylene group or an ethynylene group. , R ¹ and R ² are bonded to the aromatic ring in Ar. Ar ¹ and Ar ² are each independently a divalent organic group containing an aromatic ring, provided that R ¹ and R ³ are in Ar ¹ . R ² and R ⁴ are bonded to the aromatic ring in Ar ^2. n ¹ and n ² are each independently an integer of 1 or more, R ⁵ and R ⁶ are each independently hydrogen. An atom, a halogen atom, a monovalent hydrocarbon group, a hydrocarbyloxy group, a hydrocarbyl disubstituted amino group or a hydrocarbyl mercapto group, wherein R ⁷ is an oxygen atom, a sulfur atom, a substituted imino group, a carbonyl group and a divalent hydrocarbon group; 2 combining 1 to 3 selected from the group consisting of R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a monovalent hydrocarbon group.)

（III）
（式中、Ａｒ、Ａｒ¹、Ａｒ²、Ｒ¹〜Ｒ¹⁰、ｎ¹及びｎ²は、それぞれ独立に、前記と同じである。） Secondly, the present invention provides a method for producing the polymer compound, which comprises a step of polymerizing a compound represented by the following general formula (III) using an optically active polymerization initiator.

(III)
(In the formula, Ar, Ar ¹ , Ar ² , R ^{1 to} R ¹⁰ , n ¹ and n ² are each independently the same as described above.)

（IV）
（式中、Ａｒ¹、Ａｒ²、Ｒ¹〜Ｒ¹¹、ｎ¹及びｎ²は、それぞれ独立に、前記と同じである。） Thirdly, the present invention provides a compound represented by the following general formula (IV).

(IV)
(In the formula, Ar ¹ , Ar ² , R ^{1 to} R ¹¹ , n ¹ and n ² are each independently the same as described above.)

  Fourth, the present invention provides the polymer compound used for chiral separation (polymer compound for chiral separation), the polymer compound used for chiral identification (polymer compound for chiral identification), and the high compound used for polarized light emission. Provided are a polymer compound used for a molecular compound (polymer compound for polarized light emission) and a polarizing filter (polymer compound for polarizing filter).

  The polymer compound of the present invention is optically active and has a side chain formed by conjugating three or more aromatic rings, and the side chain and the main chain are indirectly (that is, a spacer such as a carbonyloxy group). Via). In addition, when the production method of the present invention is applied, the polymer compound can be synthesized by developing an optically active helical structure by using a small amount of an optically active polymerization initiator during polymerization.

  Furthermore, the polymer compound of the present invention can be provided with functions such as molecular recognition, light-emitting property, charge transporting property, optical property, and liquid crystallinity by selecting the type of conjugated side chain. Therefore, the compounds of the present invention are particularly useful for chiral separation materials, chiral identification materials, polarized light emitting materials, polarizing filter materials and the like.

  Hereinafter, the present invention will be described in detail. In the present specification, “room temperature” means 10 to 40 ° C. Further, in this specification, the number of aromatic rings is 1 for a benzene ring, thiophene ring, etc., and 2 for a naphthalene ring, fluorene ring, etc. Count as one.

<Polymer compound>
The polymer compound of the present invention is optically active and has a repeating unit represented by the general formula (I). In the polymer compound of the present invention, two or more repeating units are linked.

  In the general formula (I), Ar is a trivalent organic group containing an aromatic ring. The “trivalent organic group containing an aromatic ring” is a residue obtained by removing three hydrogen atoms from an aromatic ring serving as a basic skeleton. Examples of the aromatic ring serving as the basic skeleton include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, and a furan ring. , A pyrrole ring, a thiophene ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring and the like; a condensed aromatic ring obtained by condensing two or more selected from the monocyclic aromatic rings; Two or more selected from the monocyclic aromatic ring and / or the condensed aromatic ring are a single bond, methylene group, ethylene group, ethenylene group, ethynylene group, oxygen atom, sulfur atom, imino group, carbonyl Group, a polycyclic aromatic ring linked by a sulfonyl group; a structure in which the condensed aromatic ring or two adjacent aromatic rings of the polycyclic aromatic ring are crossed by a methylene group, an ethylene group, a carbonyl group, or a sulfonyl group Have one or more Transannular aromatic rings, and the like.

  In the condensed aromatic ring, the number of monocyclic aromatic rings to be condensed is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2. In the polycyclic aromatic ring, the number (total) of the monocyclic aromatic ring and the condensed aromatic ring to be connected is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2. In the transannular aromatic ring, the number (total) of monocyclic aromatic rings and condensed aromatic rings that have been translocated is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1.

Examples of the monocyclic aromatic ring include the following.

Examples of the condensed aromatic ring include the following.

Examples of the polycyclic aromatic ring include the following.

Examples of the transannular aromatic ring include the following.

  As the basic skeleton, a monocyclic aromatic ring, a condensed aromatic ring and a transannular aromatic ring are preferable, a monocyclic aromatic ring and a transannular aromatic ring are more preferable, and a transannular aromatic ring is more preferable. Fluorene is particularly preferred.

  In the aromatic ring serving as the basic skeleton, by removing one hydrogen atom from each of three carbon atoms and / or nitrogen atoms to which hydrogen atoms are bonded, a trivalent organic group containing an aromatic ring is obtained. However, at least two of the three carbon atoms and / or nitrogen atoms that remove hydrogen atoms are carbon atoms and / or nitrogen atoms that constitute the aromatic ring.

  In the trivalent organic group containing the aromatic ring, a hydrogen atom bonded to a carbon atom is substituted with a substituent such as a halogen atom, a monovalent hydrocarbon group, a hydrocarbyloxy group, a hydrocarbyl disubstituted amino group, or a hydrocarbyl mercapto group. The hydrogen atom bonded to the nitrogen atom may be substituted with a substituent such as a monovalent hydrocarbon group. When two or more substituents are present, any two substituents may be linked to form a ring.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a fluorine atom, a chlorine atom, and a bromine atom are preferable, a fluorine atom and a chlorine atom are more preferable, and a fluorine atom is further preferable.

  Examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, pentyl group, octyl group, nonyl group, Alkyl groups such as dodecyl group, pentadecyl group, octadecyl group, docosyl group (for example, about 1 to 50 carbon atoms); cyclopropyl group, cyclobutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group Cyclic saturated hydrocarbon groups such as cycloalkyl groups, norbornyl groups, adamantyl groups and the like (for example, about 3 to 50 carbon atoms); ethenyl groups, propenyl groups, 3-butenyl groups, 2-butenyl groups, 2-pentenyl groups, Alkenyl groups such as 2-hexenyl group, 2-nonenyl group, 2-dodecenyl group (for example, 2 to About 0); phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropyl Aryl groups such as phenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group, 4-phenylphenyl group (for example, carbon number 6 About 50)); phenylmethyl group, 1-phenyleneethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3- Phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, etc. An aralkyl group (for example, about 7 to 50 carbon atoms) and the like, monovalent hydrocarbon groups having 1 to 20 carbon atoms are preferable, monovalent hydrocarbon groups having 1 to 15 carbon atoms are more preferable, 10 monovalent hydrocarbon groups are more preferred.

  The hydrocarbyloxy group is a group formed by bonding one monovalent hydrocarbon group to an oxy group.

  The hydrocarbyl mercapto group is a group formed by bonding one monovalent hydrocarbon group to a mercapto group.

  The hydrocarbyl disubstituted amino group is a group in which two hydrogen atoms in an amino group are substituted with the two monovalent hydrocarbon groups.

  The substituent in the trivalent organic group containing an aromatic ring is preferably a monovalent hydrocarbon group, hydrocarbyloxy group, or hydrocarbyl disubstituted amino group for a hydrogen atom bonded to a carbon atom, and a monovalent hydrocarbon group. A hydrocarbyloxy group is more preferable, and a monovalent hydrocarbon group is more preferable. As for the hydrogen atom bonded to the nitrogen atom, a monovalent hydrocarbon group is preferable.

In the general formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently a direct bond, a substituted imino group, an ethenylene group or an ethynylene group, preferably a direct bond, a substituted imino group or an ethenylene group. , A direct bond and a substituted imino group are more preferable, and a direct bond is more preferable. However, R ¹ and R ² are bonded to the aromatic ring in Ar (that is, when Ar is fluorene, the bonding positions of R ¹ and R ² may be the 1st to 8th positions). . A plurality of R ¹ , R ² , R ³ and R ⁴ present in the polymer compound may be the same or different.

  The substituted imino group is a group represented by —N (Q) — (Q represents a substituent). Examples of the substituent represented by Q include a monovalent hydrocarbon group. The monovalent hydrocarbon group represented by Q is the same as described and exemplified above, but an aryl group such as a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-propylphenyl group. Aralkyl groups such as 4-isopropylphenyl group, 4-butylphenyl group and 4-t-butylphenyl group are preferred.

In the general formula (I), Ar ¹ and Ar ² are each independently a divalent organic group containing an aromatic ring. The “divalent organic group containing an aromatic ring” is a residue obtained by removing two hydrogen atoms from an aromatic ring serving as a basic skeleton. A plurality of Ar ¹ and Ar ² present in the polymer compound may be the same or different. However, R ¹ and R ³ are bonded to the aromatic ring in Ar ¹ , and R ² and R ⁴ are bonded to the aromatic ring in Ar ² .

  The aromatic ring serving as the basic skeleton in the divalent organic group containing the aromatic ring is the same as that explained and exemplified as the aromatic ring serving as the basic skeleton in the section of the trivalent organic group containing the aromatic ring. In the aromatic ring serving as the basic skeleton, a hydrogen atom is removed from each of two carbon atoms and / or nitrogen atoms to which a hydrogen atom is bonded, whereby a divalent organic group containing an aromatic ring is obtained. The divalent organic group containing the aromatic ring is preferably a phenylene group.

In the general formula (I), n ¹ and n ² are each independently an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably 1 or 2, particularly Preferably it is 1. A plurality of n ¹ and n ² present in the polymer compound may be the same or different.

In the general formula (I), R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, a hydrocarbyloxy group, a hydrocarbyl disubstituted amino group, or a hydrocarbyl mercapto group. These atoms and groups are the same as those described and exemplified above, but are preferably a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or a hydrocarbyloxy group, more preferably a hydrogen atom, 1 A monovalent hydrocarbon group such as an alkyl group having 1 to 8 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, t -A butyl group, a hexyl group, a cyclohexyl group, and an octyl group. A plurality of R ⁵ and R ⁶ present in the polymer compound may be the same or different.

In the general formula (I), R ⁷ is 1 to 3 selected from the group consisting of an oxygen atom, a sulfur atom, a substituted imino group, a carbonyl group (—C (═O) —) and a divalent hydrocarbon group. Is a divalent group. The substituted imino group is the same as described and exemplified above. Examples of the divalent hydrocarbon group include an alkylene group such as a methylene group, an ethylene group, and a propylene group, and an arylene group such as a phenylene group. R ⁷ is preferably a divalent group in which 1 to 3 groups selected from the group consisting of an oxygen atom, a carbonyl group and a divalent hydrocarbon group are combined, and more preferably a carbonyloxy group (ie, A combination of a carbonyl group and an oxygen atom; —C (═O) O—, —OC (═O) —) and a divalent hydrocarbon group in combination with a divalent hydrocarbon group, a carbonyloxy group, Particularly preferred is a carbonyloxy group. A plurality of R ⁷ present in the polymer compound may be the same or different.

In the general formula (I), R ^{8 to} R ¹⁰ are each independently a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group is the same as described and exemplified above. R ⁸ is preferably a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are preferably a hydrogen atom. A plurality of R ⁸ , R ⁹ and R ¹⁰ present in the polymer compound may be the same or different.

（II）
（式中、Ｒ¹¹は水素原子又は１価の炭化水素基である。Ａｒ¹、Ａｒ²、Ｒ¹〜Ｒ¹⁰、ｎ¹及びｎ²は、それぞれ独立に、前記と同じである。）
で表される繰り返し単位であることが好ましい。 The repeating unit represented by the general formula (I) is represented by the following general formula (II):

(II)
(In the formula, R ¹¹ is a hydrogen atom or a monovalent hydrocarbon group. Ar ¹ , Ar ² , R ^{1 to} R ¹⁰ , n ¹ and n ² are each independently the same as described above.)
It is preferable that it is a repeating unit represented by these.

In the general formula (II), R ¹¹ is a hydrogen atom or a monovalent hydrocarbon group, preferably a hydrogen atom. The monovalent hydrocarbon group is the same as described and exemplified above. A plurality of R ¹¹ present in the polymer compound may be the same or different.

In the general formula (II), Ar ¹ , Ar ² , R ^{1 to} R ¹⁰ , n ¹ and n ² are each independently the same as described and exemplified above.

（V）
（式中、Ｒ⁸〜Ｒ¹⁰はそれぞれ独立に、前記と同じである。Ｒ¹²は、直接結合、酸素原子、硫黄原子、置換イミノ基、カルボニル基及び２価の炭化水素基からなる群から選ばれる１〜３個を組み合わせた２価の基である。Ｒ¹³は、水素原子又は１価の炭化水素基である。）
で表される繰り返し単位を有していてもよく、分岐構造及び／又は架橋構造を有していてもよい。 In the polymer compound of the present invention, the repeating unit represented by the general formula (I) may be included alone or in combination of two or more. In addition to the repeating unit represented by the general formula (I), the following general formula (V):

(V)
(Wherein R ^{8 to} R ¹⁰ are each independently the same as defined above. R ¹² is selected from the group consisting of a direct bond, an oxygen atom, a sulfur atom, a substituted imino group, a carbonyl group, and a divalent hydrocarbon group. (It is a divalent group in which 1 to 3 selected groups are combined. R ¹³ is a hydrogen atom or a monovalent hydrocarbon group.)
Or a branched structure and / or a crosslinked structure.

In the general formula (V), R ^{8 to} R ¹⁰ are each independently the same as described and exemplified above.

In the general formula (V), the substituted imino group and divalent hydrocarbon group represented by R ¹² are the same as those described and exemplified above. R ¹² is preferably a divalent group formed by combining 1 to 3 groups selected from the group consisting of a direct bond, an oxygen atom, a carbonyl group and a divalent hydrocarbon group, more preferably a direct bond, a carbonyl A divalent group obtained by combining an oxy group and a divalent hydrocarbon group, and a carbonyloxy group, more preferably a direct bond and a carbonyloxy group. A plurality of R ¹² present in the polymer compound may be the same or different.

In the general formula (V), the monovalent hydrocarbon group represented by R ¹³ is the same as described and exemplified above. R ¹³ is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, still more preferably. , Hydrogen atom, methyl group, ethyl group, and phenyl group. A plurality of R ¹³ present in the polymer compound may be the same or different.

  When the polymer compound of the present invention has a repeating unit other than the repeating unit represented by the general formula (I) (for example, the repeating unit represented by the general formula (V)), the content thereof is Although it is appropriately determined within the range not impairing the physical properties of the polymer compound, the repeating unit represented by the general formula (I) is 50 mol% or more with respect to all repeating units in the polymer compound. Preferably, it is 80 mol% or more, more preferably 90 mol% or more.

  The polymer compound of the present invention is optically active. In other words, a part of the repeating unit represented by the general formula (I) may be optically active, the terminal structure may be optically active, or may be optically active based on the helical structure of the main chain, and these A combination may be used.

  The polymer compound of the present invention preferably exhibits at least one of a circular dichroism spectrum and an optical rotatory power from the viewpoint of use in chiral separation / identification, polarized light emission / filter material, etc., and exhibits a circular dichroism spectrum. Is more preferable. The circular dichroism spectrum mainly corresponds to the difference in absorbance when the left and right circularly polarized light is absorbed by the chromophore constituting the helical polymer, and is based on the helical structure of the main chain. In general, the circular dichroism spectrum is often based on the helical structure of the main chain, and it is considered that the higher the intensity, the greater the left-right bias of the helical structure. On the other hand, the optical rotation is often based on the helical structure of the main chain, and is a phenomenon in which the polarization plane is rotated when linearly polarized light passes through the helical polymer, and the angle of rotation corresponds to the optical rotation. In general, it is considered that the greater the optical rotation, the greater the left-right bias of the helix.

The polymer compound of the present invention has a mole per repeating unit mole in the wavelength region of 200 to 500 nm of the circular dichroism spectrum from the viewpoint of sufficiently expressing the performance of chiral separation / identification, polarized light emission / filter material, etc. preferably the maximum value of the absolute value of the ellipticity is 100degree · cm ² · dmol ^-1 or more, more preferably 500degree · cm ² · dmol ^-1 or more, 1,000degree · cm ² · dmol ^-1 or More preferably. The upper limit of this value is not particularly limited, usually, a 1,000,000degree · cm ² · dmol ^-1, more preferably ^{100,000degree · cm 2 · dmol -1,} 50,000degree · cm 2 · dmol -1 More preferably. Here, by adopting the parameter of “absolute value of molar ellipticity per mole of repeating unit” in “in the wavelength region of 200 to 500 nm of the circular dichroism spectrum”, the molar ellipticity of the polymer compound is determined. Since it can be expressed not per mole but per mole of the repeating unit structure, the influence of the molecular weight of the polymer compound can be eliminated.

The molar ellipticity [θ] (degree · cm ² · dmol ⁻¹ ) per mole of repeating units in the optically active polymer compound having the repeating unit represented by the general formula (I) is determined as follows. In the circular dichroism spectrum, not the number of moles of the molecule, the solution concentration of the polymer compound is C (g / cm ³ ), and the weight per 1 decimole of the repeating unit represented by the above general formula (I) is [Θ] = θM / (CL) is calculated from the ellipticity θ (degree) when M (g / dmol) and the optical path length are L (cm).

  The polystyrene equivalent number average molecular weight Mn of the polymer compound of the present invention is usually 500 to 1,000,000, preferably 1,000 to 100,000, more preferably 2,000 to 50,000. The polymer compound of the present invention preferably has a molecular weight dispersity (namely defined by [weight average molecular weight Mw in terms of polystyrene] / [number average molecular weight Mn in terms of polystyrene]) of 1 to 4, more Preferably it is 1-3, More preferably, it is 1-2.

<Manufacturing method>
The production method of the polymer compound of the present invention is not particularly limited, but includes a step of polymerizing the compound represented by the general formula (III) (that is, the monomer compound) using an optically active polymerization initiator. The method of having is preferable. Furthermore, the compound represented by the general formula (III) is preferably a compound represented by the general formula (IV).

In the general formula (III), Ar, Ar ¹ , Ar ² , R ^{1 to} R ¹⁰ , n ¹ and n ² are the same as those described and exemplified in the section of the general formula (I). In the general formula (IV), Ar ¹ , Ar ² , R ^{1 to} R ¹¹ , n ¹ and n ² are the same as those described and exemplified in the section of the general formula (II).

  Examples of the optically active polymerization initiator include an optically active anionic polymerization initiator, an optically active cationic polymerization initiator, an optically active radical polymerization initiator, and the like, from the viewpoint of highly controlling optical selectivity. Therefore, an optically active anionic polymerization initiator is preferable, an anionic polymerization initiator having an optically active alkyl group, an anionic polymerization initiator having an optically active alkoxy group, and an optically active anionic polymerization initiator coordinated with a chiral ligand are more preferable. .

  As the anionic polymerization initiator having an optically active alkyl group, an optically active alkyl metal compound is preferable, and an optically active alkyl-alkali metal compound and an optically active alkyl-alkaline earth metal compound are preferable. As the anionic polymerization initiator having an optically active alkoxy group, an optically active alkoxy metal compound is preferable, and an optically active alkoxy-alkali metal compound and an optically active alkoxy-alkaline earth metal compound are preferable. Of these, optically active alkoxy-alkali metal compounds are particularly preferred, and specific examples thereof include (−)-menthoxy potassium, (+)-menthoxy potassium, and the like.

  In the anionic polymerization initiator coordinated with the chiral ligand, the chiral ligand is preferably a bidentate ligand having an optically active group (that is, an optically active group), more preferably an optically active diamino compound. Specific examples thereof include (+)-spartein, (−)-spartein, (+)-1,4-bis (dimethylamino) -2,3-dimethoxybutane, (−)-1,4. -Bis (dimethylamino) -2,3-dimethoxybutane, (+)-1- (2-pyrrolidinylmethyl) pyrrolidine, (-)-1- (2-pyrrolidinylmethyl) pyrrolidine, (+)- (4S) -2,2 ′-(1-ethylpropylidene) bis [4- (1-phenylethyl) -4,5-dihydrooxazole], (−)-(4S) -2,2 ′-( 1-ethylpropylidene) bis [4- (1-phenylethyl) -4,5-dihydrooxazole] and the like. Among these, (+)-sparteine, (−)-sparteine, (+)-1,4-bis (dimethylamino) -2,3-dimethoxybutane, (−)-1,4-bis (dimethyl) Amino) -2,3-dimethoxybutane, (+)-1- (2-pyrrolidinylmethyl) pyrrolidine, (-)-1- (2-pyrrolidinylmethyl) pyrrolidine are preferred.

  The amount of the optically active polymerization initiator used is not particularly limited, but the compound represented by the general formula (III) (for example, the general formula (IV)) with respect to 1 mol of the optically active polymerization initiator. Is preferably 2 to 5,000 mol, more preferably 5 to 500 mol, and even more preferably 10 to 200 mol. The optically active polymerization initiators may be used alone or in combination of two or more.

  The polymerization reaction may be performed without using a reaction solvent, but it is preferable to use a reaction solvent, and more preferably in an organic solvent when anionic polymerization is performed. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; chain aliphatic hydrocarbons such as heptane; cyclic aliphatic hydrocarbons such as cyclohexane; halogenated carbons such as chlorobenzene, dichlorobenzene, and dichloromethane. Hydrogen; Nitriles such as acetonitrile and benzonitrile; Ethers such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether; Amides such as N, N-dimethylformamide and N-methylpyrrolidone; Nitro compounds such as nitromethane and nitrobenzene Aromatic hydrocarbons and ethers are preferred. These organic solvents may be used alone or in combination of two or more.

  The amount of the organic solvent used is usually 0.01 to 10,000 L with respect to 1 mol of the compound represented by the general formula (III) (for example, the compound represented by the general formula (IV)). Preferably it is 0.1-1,000L, More preferably, it is 1-100L.

  The reaction temperature of the polymerization reaction is not particularly limited, but is preferably −150 to 150 ° C., more preferably −120 to 50 ° C., and further preferably −100 to 0 ° C.

  When terminating the polymerization reaction, it is preferable to add the alcohol, water or the like to stop the polymerization reaction, and then evaporate the organic solvent or add a poor solvent to precipitate the polymer compound for isolation. . As the poor solvent, a solvent that does not dissolve a polymer compound may be used. For example, chain aliphatic hydrocarbons such as heptane; cycloaliphatic hydrocarbons such as cyclohexane; methanol, ethanol, n-propyl alcohol, isopropyl alcohol Examples of such alcohols include water, and methanol is preferred.

（VI）
（式中、Ｒ⁸〜Ｒ¹⁰、Ｒ¹²及びＲ¹³はそれぞれ独立に、前記と同じである。）
で表される化合物とを共重合すればよいが、光学選択性を高度に制御する観点から、前記一般式(III)で表される化合物を重合した後に前記一般式(VI)で表される化合物をブロック共重合することが好ましい。それ以外の点については、上述の製造方法と同様にして、該高分子化合物を製造することができる。 When the polymer compound of the present invention has a repeating unit represented by the general formula (V), the compound represented by the general formula (III) and the following general formula (VI):

(VI)
(Wherein R ^{8 to} R ¹⁰ , R ¹² and R ¹³ are independently the same as described above.)
May be copolymerized with the compound represented by general formula (VI), but from the viewpoint of highly controlling optical selectivity, the compound represented by general formula (III) is represented by the general formula (III) after polymerization. It is preferable to block copolymerize the compound. About a point other than that, this polymer compound can be manufactured like the above-mentioned manufacturing method.

In the general formula (VI), R ^{8 to} R ¹⁰ , R ¹² and R ¹³ are each independently the same as described and exemplified above.

<Composition>
The polymer compound of the present invention can be used as it is, but may be used as a composition by mixing with other components. Examples of other components include polymer compounds other than the polymer compound of the present invention, modifiers, solvents, and the like. In the composition, the polymer compound of the present invention and other components may be used alone or in combination of two or more.

  Examples of the polymer compound other than the polymer compound of the present invention include polyolefins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, polyacrylonitrile, and copolymers thereof; Polyethers such as methylene, polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide), poly (2,5-dimethyl-1,4-phenylene oxide) and copolymers thereof; polyethylene terephthalate , Polyesters such as polybutylene terephthalate, poly (ethylene-2,6-dinaphthalate), poly (4-oxybenzoate), poly (2-oxy-6-naphthalate) and copolymers thereof; nylon 6, nylon Polyamides such as 66; poly Boneto; polyphenylene sulfide; polysulfone; polyether sulfone; polyether ether ketone; polyimide; polyetherimides; phenolic resins, urea resins, melamine resins, and thermosetting polymers such as epoxy resin. These may be used alone or in combination of two or more.

  Examples of the modifier include stabilizers such as 2,6-di-t-butylphenol derivatives and 2,2,6,6-tetramethylpiperidines; flame retardants such as polyhalides and phosphate esters; surface activity Agents; flow modifiers and the like. These modifiers may be used alone or in combination of two or more.

<Application>
The polymer compound of the present invention (including the case where it is prepared as a composition) is optically active. For example, chiral separation for separating an optically active compound, chiral discrimination for identifying an optically active compound, and light source It is useful for polarizing filters that transmit only polarized light, polarized light emission that the light source itself emits polarized light, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited at all by these Examples.

<Synthesis Example 1>
Synthesis of 2,7-bis (4-tert-butylphenyl) -9-fluorenone

  Magnesium (10.5 g, 0.432 mmol) and THF (500 ml) that had been dried over calcium hydride and distilled were added to a 1 L three-necked flask equipped with a reflux tube that was flame-dried and purged with nitrogen, and heated to reflux. To this was added 5 mg of iodine, and 1-bromo-4-tert-butylbenzene (62.4 ml) was added dropwise in small portions over 1 hour. During this time, the solution changed from colorless to green and then to black. Thereafter, the mixture was stirred at reflux temperature for 5 hours to obtain a THF solution of 4-tert-butylphenylmagnesium bromide.

Flame-dried, nitrogen-substituted 3L 4-neck flask with reflux tube, zinc chloride (60.2g, 442mmol) and N, N, N ', N'-tetramethylethylenediamine (TMEDA, dried with calcium hydride and distilled) 64.0 ml, 424 mmol), THF dried over calcium hydride (500 ml) and 4-tert-butylphenylmagnesium bromide in THF (0.64 M, 530 ml) were added and stirred for 20 minutes. Further, 2,7-dibromofluorenone (34.6 g, 102 mmol) and tetrakis (triphenylphosphine) palladium ((Pd (PPh ₃ ) ₄ , 12.1 g, 10.5 mmol) were added, and the mixture was heated to reflux for 17 hours. The system was heterogeneous and yellow, and then the reaction was stopped by adding water (100 ml) and 1N HCl (100 ml) little by little to the resulting reaction mixture. The solid component was washed with methanol (800 ml) and hexane (400 ml), and then the solid component was dissolved in methylene chloride, filtered through Florisil, and concentrated to obtain an orange solid. This solid was dissolved in a mixed solvent of chloroform (400 ml) and hexane (300 ml) with heating, and recrystallized at 4 ° C. to give orange crystals (2,7-bis (4-tert-butylphenyl) -9- Fluorenone, 39.9 g, yield 80.9%) was obtained.

<Synthesis Example 2>
Synthesis of 2,7-bis (4-tert-butylphenyl) -9-fluorenol

  Flame-dried and nitrogen-substituted 1 L three-necked flask was charged with 2,7-bis (4-tert-butylphenyl) -9-fluorenone (5.5015 g, 12.38 mmol) and sodium borohydride (468.5 mg, 12.38 mmol). , THF (1 L) was added and stirred at room temperature. After confirming that the raw materials were completely consumed after 3 hours by TLC, methanol was added to stop the reaction. 1N HCl was added in small portions until the reaction solution became acidic, and the product was extracted with chloroform. The obtained organic phase was washed first with a saturated aqueous sodium hydrogen carbonate solution and then with a saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The organic phase thus obtained was concentrated and dried in vacuo to give a flesh-colored solid (2,7-bis (4-tert-butylphenyl) -9-fluorenol, 5.5025 g, yield> 99%).

<Synthesis Example 3>
Synthesis of 2,7-bis (4-tert-butyl) phenylfluoren-9-yl methacrylate

  2,7-bis (4-tert-butylphenyl) -9-fluorenol (10.0 g, 22.4 mmol) was added to a 1 L three-necked flask equipped with a reflux tube that was flame-dried and purged with nitrogen, and after deaeration for 20 minutes, Replaced with nitrogen. Toluene (600 ml) dried and distilled over sodium wire, methacrylic acid chloride (3.75 ml, 33.6 mmol) dried over calcium hydride and distilled over calcium hydride. Triethylamine (3.12 ml, 22.4 ml) was added and stirred at 45 ° C. After 43 hours, a part of the reaction system was sampled and subjected to NMR analysis. After confirming that the starting alcohol was completely consumed, the system was returned to room temperature and the solvent was distilled off. The product was extracted with methylene chloride (300 ml), and the resulting organic phase was washed with a saturated aqueous sodium bicarbonate solution (200 ml × 3 times), a saturated aqueous sodium chloride solution (200 ml × 2 times), and water (200 ml × 1 time). did. The obtained organic phase was dried over anhydrous magnesium sulfate and then concentrated to obtain a crude product (yellow, 11.6 g). This crude product was first recrystallized with diethyl ether and further recrystallized with a mixed solvent of benzene-hexane (volume ratio: 1/1) to give a pale yellow solid (2,7-bis (4-tert-butyl). ) Phenylfluoren-9-yl methacrylate, 7.21 g, yield 62.7%, melting point 242.2-243.3 ° C.).

<Example 1>
Asymmetric anionic polymerization of 2,7-bis (4-tert-butylphenyl) fluoren-9-yl methacrylate

Place 2,7-bis (4-tert-butyl) phenylfluorenyl methacrylate (0.100 g, 0.194 mmol) in a 100 ml polymerization ampoule that has been frame-dried and substituted with dry nitrogen, vacuum degassed for 1 hour, and dry nitrogen. Replaced. To this was added 1.00 ml of toluene to dissolve all of the monomer (2,7-bis (4-tert-butyl) phenylfluorenyl methacrylate), and then the solution was cooled at −78 ° C. for 20 minutes. Then, 0.1M toluene of the complex of asymmetric ligand (+)-2,3-dimethoxy-1,4-bis (dimethylamino) butane ((+)-DDB) and 9-fluorenyllithium (FlLi) Solution (0.194 ml) was added as a polymerization initiator. After 24 hours, methanol (0.2 ml) was added to terminate the polymerization. A part of the reaction mixture was sampled, diluted with CDCl ₃ and subjected to ¹ H NMR measurement to obtain monomer conversion as shown in Table 1. The obtained product was reprecipitated in methanol, collected by centrifugation, dried in vacuum, and the methanol-insoluble part was further reprecipitated in a mixed solvent of diethyl ether: hexane = 8: 2 (volume ratio). Recovered by centrifugation. The product (polymer compound) thus obtained was poly (bis-2,7- (4-t-butylphenyl) fluorenyl methacrylate). Table 1 shows the polystyrene-reduced number average molecular weight Mn and dispersity Mw / Mn of the product (polymer compound) thus obtained.

<Examples 2 to 4>
In Example 1, the reaction scale was changed in proportion to the monomer weight so that the monomer concentration was the same, and the polymerization initiator, monomer / polymerization initiator (molar ratio), and reaction time were changed as shown in Table 1. Except for the above, a product (polymer compound) was obtained in the same manner as in Example 1. Table 1 shows the polystyrene-reduced number average molecular weight Mn and dispersity Mw / Mn of the product (polymer compound) thus obtained.

^aモノマー 0.1g(実施例１)、0.05g(実施例２、３)、1.0g(実施例４)
^b1H-NMRスペクトルにより決定。
^cゲルパーミエーションクロマトグラフィ（GPC）(vs.ポリスチレン)により決定。
^dポリマー重量により決定（収率）
^*表１中、Mnは高分子化合物のポリスチレン換算の数平均分子量を意味し、Mwは高分子化合物のポリスチレン換算の重量平均分子量を意味する。
^*表１中の重合開始剤の欄において、略語で表される構造は、以下のとおりである。

・FlLi ： 9-フルオレニルリチウム
・(+)-DDB ： (+)-2,3-ジメトキシ-1,4-ビス(ジメチルアミノ)ブタン
・(-)-Sp ： (-)-スパルテイン
・(+)-PMP ： (S)-(+)-1-(2-ピロリジニルメチル)ピロリジン <Table 1>
Asymmetric anionic polymerization of 2,7-bis (4-tert-butylphenyl) fluoren-9-yl methacrylate (-78 ^o C in toluene)

^a monomer 0.1 g (Example 1), 0.05 g (Examples 2 and 3), 1.0 g (Example 4)
Determined by ^b1 H-NMR spectrum.
^c Determined by gel permeation chromatography (GPC) (vs. polystyrene).
^d Determined by polymer weight (yield)
^{* In} Table 1, Mn means the polystyrene equivalent number average molecular weight of the polymer compound, and Mw means the polystyrene equivalent weight average molecular weight of the polymer compound.
^{* In} the column of the polymerization initiator in Table 1, the structures represented by abbreviations are as follows.

・ FlLi: 9-fluorenyllithium ・ (+)-DDB: (+)-2,3-dimethoxy-1,4-bis (dimethylamino) butane ・ (-)-Sp: (-)-spartein (+)-PMP: (S)-(+)-1- (2-pyrrolidinylmethyl) pyrrolidine

<Synthesis Example 4>
Synthesis of 2,7-bis (4-tert-butyl) phenylfluoren-9-yl acrylate

  2,7-bis (4-tert-butylphenyl) -9-fluorenol (5.00 g, 11.2 mmol) was placed in a 500 mL two-necked flask equipped with a reflux tube that was flame-dried and purged with nitrogen, and degassed for 15 minutes. And replaced with nitrogen. To this was added benzene (300 ml), triethylamine (1.56 ml, 11.2 mmol), and acrylic acid chloride (1.36 ml, 16.8 mmol), and the mixture was heated to reflux. The raw material alcohol was not completely dissolved in benzene, but the product was highly soluble, and the solid matter in the reaction system decreased with time. After 10 hours, TLC confirmed that the raw material was completely consumed, and then the reaction mixture was returned to room temperature. Next, the reaction solution was concentrated, and the resulting solid was washed with water (100 mL) and methanol (100 mL) on a glass filter and then vacuum-dried to give a light skin-colored solid (5.14 g, yield 91.6%) Got. This solid was recrystallized first with diethyl ether and then with a mixed solvent of benzene: hexane = 1: 1 (volume ratio) to give a pale skin-colored solid (2,7-bis (4-tert-butyl) phenylfluorene-9 -Yl acrylate, 3.23 g, yield 57.5%).

<Example 5>
Asymmetric anionic polymerization of 2,7-bis (4-tert-butylphenyl) fluoren-9-yl acrylate

  2,7-bis (4-tert-butylphenyl) fluoren-9-yl acrylate (200 mg, 0.400 mmol) was placed in a 25 mL polymerization ampoule that had been flame-dried and purged with dry nitrogen, and after vacuum degassing for 1 hour, The inside of the ampoule was replaced with dry nitrogen. To this was added dry toluene (3.7 ml) to dissolve all of the monomer (2,7-bis (4-tert-butylphenyl) fluoren-9-yl acrylate) and the solution was cooled at -78 ° C. for 20 minutes. In this solution, as an asymmetric ligand, (S)-(+)-1- (2-pyrrolidinylmethyl) pyrrolidine ((+)-PMP) and 9-fluorenyllithium (FlLi) complex 0.1M toluene solution (0.10 ml) was added as a polymerization initiator (monomer / polymerization initiator molar ratio was 40). The color of the solution changed from light yellow to light pink. The viscosity of the reaction solution gradually increased, and almost no fluidity was obtained after 4 hours. Forty hours after the start of polymerization, methanol (0.1 ml) was added to the reaction solution to terminate the polymerization. During the polymerization, the reaction solution was not fluid, but when the polymerization was stopped and the reaction solution was brought to room temperature, a uniform solution was obtained. Next, the product was poured into methanol for reprecipitation, and a product in an insoluble part (methanol insoluble part: 0.189 g, yield: 93.5%) was recovered by centrifugation. The product of the methanol insoluble part was dissolved in chloroform and THF. The product (polymer compound) thus obtained was poly (bis-2,7- (4-t-butylphenyl) fluorenyl acrylate). Table 2 shows the polystyrene-reduced number average molecular weight Mn and dispersity Mw / Mn of the product (polymer compound) thus obtained.

<Examples 6 and 7>
In Example 5, the product (polymer compound) was prepared in the same manner as in Example 5 except that the polymerization initiator, the monomer / polymerization initiator (molar ratio), and the reaction time were changed as shown in Table 2. Obtained. Table 2 shows the polystyrene-reduced number average molecular weight Mn and dispersity Mw / Mn of the product (polymer compound) thus obtained.

^aモノマー 200mg(実施例５〜７)
^b反応混合物の¹H NMR分析により決定。
^cゲルパーミエーションクロマトグラフィ（GPC）(vs.ポリスチレン)により決定。 <Table 2>
Asymmetric anionic polymerization of 2,7-bis (4-tert-butylphenyl) fluoren-9-yl acrylate (-78 ^o C in toluene)

^a Monomer 200mg (Examples 5-7)
^b Determined by ¹ H NMR analysis of the reaction mixture.
^c Determined by gel permeation chromatography (GPC) (vs. polystyrene).

<Characteristic evaluation>
-Circular dichroic spectrum and emission spectrum-
The circular dichroic spectrum was measured using a circular dichroism absorption spectrometer (J-820, manufactured by JASCO Corp., model J-820) at room temperature in THF, at a measured concentration of 2 × 10 ^-3 M (monomer unit conversion), cell length Measured at 0.1 mm. The circular dichroism spectra of the polymer compounds synthesized in Examples 1, 3, and 4 are shown in FIG. The circular dichroism spectra of the polymer compounds synthesized in Examples 5 and 6 are shown in FIG. The absorption spectrum (measured in THF at room temperature) and fluorescence spectrum (measured by excitation at 322 nm in THF at room temperature) (fluorescence quantum yield: 33%) of the polymer compound synthesized in Example 1 are shown in FIG. Show.
From the above, it can be seen that the polymer compound of the present invention has an optically active helical structure and has luminescent properties.

-Chiral quenching experiment-
The measurement of the emission spectrum was carried out by removing nitrogen by bubbling nitrogen gas for 10 minutes immediately before the measurement using a 1 cm four-sided quartz cell with a screw cap using spectral grade THF as a solvent.

3.24 mg of the optically active poly (bis-2,7- (4-t-butylphenyl) fluorenyl methacrylate) obtained in Example 4 was made into a 10 ml THF solution using a measuring flask (in monomer unit concentration). 6.30 × 10 ^-4 M). 0.3 ml of this THF solution was collected with a whole pipette into a 10 ml volumetric flask, and THF was added to make a 10 ml solution (monomer unit concentration: 1.89 × 10 ⁻⁵ M). 0.5 ml of this solution was collected with a whole pipette into a 5 ml volumetric flask, and (R)-(+)-N, N-dimethyl-1-phenylethylamine or (S)-(-)-N as a chiral quencher. N-dimethyl-1-phenylethylamine was added in an amount of 8.2 μl, 16.4 μl, or 24.6 μl, and THF was added thereto to make a solution with a total volume of 5 ml. The monomer unit concentration of the polymer (poly (bis-2,7- (4-t-butylphenyl) fluorenyl) methacrylate) in these samples is 1.89 × 10 ⁻⁶ M, and the concentration of the chiral quencher is It was 0.01M, 0.02M, or 0.03M.

  The sample was excited at 322 nm, and the difference in the degree of quenching due to the quencher was confirmed by comparing the peak area (intensity) of the emission spectrum. The emission spectrum intensity was normalized by the absorbance at an excitation wavelength of 322 nm.

The experimental result thus obtained is represented by the following formula (1):
I _o / I = 1 + k _q · τ _s [Q] (1)
Thus, I _o / I was plotted on the vertical axis and [Q] on the horizontal axis, and the Stern-Volmer constant for each quencher was determined. This figure is shown in FIG. In FIG. 4, black triangles and black circles correspond to (R) -body quencher and (S) -body quencher, respectively.

Here, I is the emission intensity, I _o is the emission intensity at a quencher concentration of 0 (M), k _q (value for _{q (R)} quencher, _{q q (R)} , value for (S) quencher. k _{q (S)} ) is the quenching constant, τ _s is the fluorescence lifetime, and [Q] is the quencher concentration (M). The slope k _q · τ _s of the plot in FIG. 4 is the Stern-Volmer constant. In calculating the Stern-Volmer constant, a point of zero quencher concentration (I _o / I = 1, [Q] = 0M) was added to 3 points of actual measurement data, and the data of 4 points was approximated by a first order. As a result, Stern-Volmer constants were calculated as k _{q (R)} · τ _s = 48.7 and k _{q (S)} · τ _s = 26.4 for both quenchers.

The selectivity in chiral quenching is evaluated by α = k _{q (R)} / k _{q (S)} . Therefore, it is assumed that the emission lifetime τ _s is the same for the R and S isomers, and from the above Stern-Volmer constant, α = k _{q (R)} / k _{q (S)} = k _{q (R)} · τ _{It was determined that s} / k _{q (S)} · τ _s = 48.7 / 26.4 = 1.84.

  As described above, the amount of decrease in the emission intensity of the R-form and the S-form is different due to the interaction between the polymer compound of the present invention and the other optically active compound. Or each can be quantified.

2 is a circular dichroism spectrum (measured in THF at room temperature) of the polymer compound synthesized in Examples 1, 3, and 4. It is a circular dichroism spectrum (measured in THF at room temperature) of the polymer compound synthesized in Examples 5 and 6. It is the absorption spectrum (measured at room temperature in THF at room temperature) and the fluorescence spectrum (measured by excitation at 322 nm in THF at room temperature) of the polymer synthesized in Example 4 (fluorescence quantum yield: 33%). In order to calculate the Stern-Volmer constant based on the data obtained in the chiral quenching experiment, the vertical axis represents the relative emission intensity I _o / I, and the horizontal axis represents the N, N-dimethyl-1-phenylethylamine concentration (M ) Is the plot created.

Claims (17)

An optically active polymer compound having a repeating unit represented by the following general formula (I).

(I)
(In the formula, Ar is a trivalent organic group containing an aromatic ring, and R ¹ , R ² , R ³ and R ⁴ are each independently a direct bond, a substituted imino group, an ethenylene group or an ethynylene group. , R ¹ and R ² are bonded to the aromatic ring in Ar. Ar ¹ and Ar ² are each independently a divalent organic group containing an aromatic ring, provided that R ¹ and R ³ are in Ar ¹ . R ² and R ⁴ are bonded to the aromatic ring in Ar ^2. n ¹ and n ² are each independently an integer of 1 or more, R ⁵ and R ⁶ are each independently hydrogen. An atom, a halogen atom, a monovalent hydrocarbon group, a hydrocarbyloxy group, a hydrocarbyl disubstituted amino group or a hydrocarbyl mercapto group, wherein R ⁷ is an oxygen atom, a sulfur atom, a substituted imino group, a carbonyl group and a divalent hydrocarbon group; 2 combining 1 to 3 selected from the group consisting of R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a monovalent hydrocarbon group.)   The high molecular compound of Claim 1 which shows a circular dichroism spectrum. 3. The high value according to claim ¹ , wherein the maximum value of the molar ellipticity per repeating unit mole is 100 degrees · cm ² · dmol ⁻¹ or more within a wavelength region of 200 to 500 nm of the circular dichroism spectrum. Molecular compound.   The polymer compound according to any one of claims 1 to 3, which has a polystyrene-reduced number average molecular weight of 500 to 1,000,000.   The polymer compound according to any one of claims 1 to 4, having a dispersity of 1 to 4. The polymer compound according to claim 1, wherein the repeating unit represented by the general formula (I) is a repeating unit represented by the following general formula (II).

(II)
(In the formula, R ¹¹ is a hydrogen atom or a monovalent hydrocarbon group. Ar ¹ , Ar ² , R ^{1 to} R ¹⁰ , n ¹ and n ² are each independently the same as described above.) The polymer compound according to claim 6, wherein Ar ¹ and Ar ² in the general formula (II) are phenylene groups. The polymer compound according to claim 6 or 7, wherein R ⁷ in the general formula (II) is a carbonyloxy group. The polymer compound according to any one of claims 6 to 8, wherein R ¹ , R ² , R ³ and R ^{4 in the} general formula (II) are a direct bond. The polymer compound according to claim 6, wherein R ⁸ in the general formula (II) is a methyl group, and R ⁹ and R ¹⁰ are hydrogen atoms. The manufacturing method of the high molecular compound as described in any one of Claims 1-10 which has the process of polymerizing the compound represented with the following general formula (III) using an optically active polymerization initiator.

(III)
(In the formula, Ar, Ar ¹ , Ar ² , R ^{1 to} R ¹⁰ , n ¹ and n ² are each independently the same as described above.) The production method according to claim 11, wherein the compound represented by the general formula (III) is represented by the following general formula (IV).

(IV)
(In the formula, Ar ¹ , Ar ² , R ^{1 to} R ¹¹ , n ¹ and n ² are each independently the same as described above.) Compound represented by the following general formula (IV).

(IV)
(Where
R ¹ , R ² , R ³ and R ⁴ are each independently a direct bond, a substituted imino group, an ethenylene group or an ethynylene group.
Ar ¹ and Ar ² are each independently a divalent organic group containing an aromatic ring. However, R ¹ and R ³ are bonded to the aromatic ring in Ar ¹ , and R ² and R ⁴ are bonded to the aromatic ring in Ar ² .
n ¹ and n ² are each independently an integer of 1 or more.
R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, a hydrocarbyloxy group, a hydrocarbyl disubstituted amino group, or a hydrocarbyl mercapto group.
R ⁷ is a divalent group in which 1 to 3 groups selected from the group consisting of an oxygen atom, a sulfur atom, a substituted imino group, a carbonyl group and a divalent hydrocarbon group are combined.
R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a monovalent hydrocarbon group. )   The polymer compound according to claim 1, which is used for chiral separation.   The polymer compound according to claim 1, which is used for chiral discrimination.   The polymer compound according to claim 1, which is used for polarized light emission.   The polymer compound according to claim 1, which is used for a polarizing filter.

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