WO2012147809A1 - Procédé pour la modification de composé polymère et procédé pour la production de film contenant le composé polymère modifié - Google Patents

Procédé pour la modification de composé polymère et procédé pour la production de film contenant le composé polymère modifié Download PDF

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WO2012147809A1
WO2012147809A1 PCT/JP2012/061119 JP2012061119W WO2012147809A1 WO 2012147809 A1 WO2012147809 A1 WO 2012147809A1 JP 2012061119 W JP2012061119 W JP 2012061119W WO 2012147809 A1 WO2012147809 A1 WO 2012147809A1
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東村　秀之
小林　憲史
中野　環
猛 坂本
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住友化学株式会社
国立大学法人北海道大学
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    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
    • C08G2261/3162—Arylamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state

Definitions

  • the present invention relates to a method for modifying a polymer compound and a method for producing a film containing the modified polymer compound.
  • an optically active polymer compound can be synthesized by introducing an optically active site into a unit structure or by forming an optically active helical structure in the main chain. Recently, there has been reported a method for obtaining an optically active substance by irradiating a circularly polarized light to a polymer compound into which an azobenzene unit that is a photosensitive site is introduced (Non-patent Document 1).
  • the present invention provides a method for easily obtaining a polymer compound having a wide range of applicable polymer compounds and imparted with optical activity.
  • the present inventors have intensively studied, and as a result, found that a polymer compound having a specific structure is modified into a polymer compound imparted with optical activity by irradiating circularly polarized light.
  • the present invention has been completed.
  • the present invention provides the following [1] to [7].
  • [1] A method for modifying a polymer compound, comprising irradiating a polymer compound having a repeating unit represented by the following formula (1) with circularly polarized light.
  • R 1 is a divalent aromatic group which may have a substituent or a divalent group represented by the following formula (2).
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom or a hydrocarbyl group optionally having a substituent.
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same or different.
  • m 1 is an integer of 1 or more
  • m 2 is an integer of 0 or more.
  • R 5 , R 6 and R 7 are each independently a hydrogen atom or a hydrocarbyl group optionally having a substituent.
  • R 8 is a direct bond or a group represented by —O—, a group represented by —S—, a group represented by —C ( ⁇ O) O—, —C ( ⁇ O) N (R 9 ).
  • a divalent group selected from the group consisting of a group represented by-, a hydrocarbylene group which may have a substituent, and a divalent group formed by combining two of these groups.
  • R 9 is a hydrogen atom or a hydrocarbyl group optionally having a substituent.
  • Ar 2 is a monovalent aromatic hydrocarbon group (that is, an aromatic hydrocarbyl group) which may have a substituent, and the monovalent aromatic hydrocarbon group contains 7 or more sp 2 carbon atoms. .
  • R 1 is a divalent aromatic group which may have a substituent, and the divalent aromatic group which may have a substituent may have a substituent.
  • R 1 is a divalent group represented by the formula (2)
  • R 5 , R 6 and R 7 are hydrogen atoms
  • R 8 is a group represented by —O—, —C ( The group represented by ⁇ O) O—, the group represented by —C ( ⁇ O) N (R 9 ) —, or the direct bond, the high group according to any one of the above [1] to [3] Modification method of molecular compounds.
  • [5] The method for modifying a polymer compound according to any one of [1] to [4] above, wherein the polymer compound is in the form of a film.
  • a method for producing a film containing a modified polymer compound comprising the following steps (a) and (b): (A) The process of forming the film
  • R 1 is a divalent aromatic group which may have a substituent or a divalent group represented by the following formula (2).
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom or a hydrocarbyl group optionally having a substituent.
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same or different.
  • m 1 is an integer of 1 or more
  • m 2 is an integer of 0 or more.
  • R 5 , R 6 and R 7 are each independently a hydrogen atom or a hydrocarbyl group optionally having a substituent.
  • R 8 is a direct bond or a group represented by —O—, a group represented by —S—, a group represented by —C ( ⁇ O) O—, —C ( ⁇ O) N (R 9 ).
  • a divalent group selected from the group consisting of a group represented by-, a hydrocarbylene group which may have a substituent, and a divalent group formed by combining two of these groups.
  • R 9 is a hydrogen atom or a hydrocarbyl group optionally having a substituent.
  • Ar 2 is a monovalent aromatic hydrocarbon group which may have a substituent, and the monovalent aromatic hydrocarbon group contains 7 or more sp 2 carbon atoms.
  • substituent means that part or all of the hydrogen atoms constituting the compound or group described immediately after that may be substituted with a substituent. means. Unless otherwise specified, examples of the substituent include a halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyl mercapto having 1 to 30 carbon atoms.
  • a halogen atom, a hydrocarbyl group having 1 to 18 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, or a hydrocarbyl mercapto group having 1 to 18 carbon atoms is preferable, and a halogen atom, A hydrocarbyl group having 1 to 12 carbon atoms or a hydrocarbyloxy group having 1 to 12 carbon atoms is more preferable, and a halogen atom or a hydrocarbyl group having 1 to 12 carbon atoms is particularly preferable.
  • the number of substituents is one or more, and when there are a plurality of substituents, each substituent may be the same or different.
  • the “repeating unit” means a structural unit contained in a compound by two or more.
  • modification as used for a polymer compound means that the polymer compound changes to a state exhibiting optical activity.
  • optical activity as referred to for a polymer compound means that the polymer compound has a bias in the right and left absorbances in the circular dichroism spectrum. Whether or not the right and left absorbances in the circular dichroism spectrum are biased can be confirmed by measuring the circular dichroism ratio of the specimen under the measurement conditions of the examples described later.
  • the polymer compound having the repeating unit represented by the formula (1) is irradiated with circularly polarized light.
  • R 1 is a divalent aromatic group which may have a substituent or a divalent group represented by the formula (2).
  • Examples of the divalent aromatic group represented by R 1 include a divalent aromatic hydrocarbon group (that is, an aromatic hydrocarbylene group) and a divalent aromatic heterocyclic group.
  • Examples of the divalent aromatic group represented by R 1 include a benzene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a 1,3,5-triazine ring, a 1,2,4-triazine ring, 1,2,4,5-tetrazine ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, isoxazole ring, 1,2,5-oxadiazole ring, 1,3,4 Oxadiazole ring, 2,3-diazafuran ring, thiazole ring, isothiazole ring, 2,4-diazafuran ring, 1,3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1,2,4- A divalent group in which two hydrogen atoms directly bonded to the atoms constituting
  • the divalent aromatic group represented by R 1 is a divalent group in which two hydrogen atoms directly bonded to atoms constituting the ring are removed from a monocyclic aromatic ring, a condensed polycyclic ring A divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the aromatic ring, or two hydrogen atoms directly bonded to the atoms constituting the ring from the bridged polycyclic aromatic ring.
  • the divalent group removed is preferable, and from the viewpoint of the rigidity of the polymer compound, the divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the condensed polycyclic aromatic ring.
  • a divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the bridged polycyclic aromatic ring is more preferable, and the atoms constituting the ring from the bridged polycyclic aromatic ring are more preferable. More preferred is a divalent group in which two directly bonded hydrogen atoms are removed.
  • the number of monocyclic aromatic rings to be condensed is usually 2 to 6, preferably 2 to 5, more preferably 2 to 4, and further 2 to 3 Two are particularly preferred.
  • the number of linked aromatic rings is usually 2 to 6, preferably 2 to 5, more preferably 2 to 4, more preferably 2 to 3, and more preferably 2 to 2.
  • the number of aromatic rings to be bridged is usually 2 to 6, preferably 2 to 5, more preferably 2 to 4, more preferably 2 to 3 Two are particularly preferred.
  • Examples of the monocyclic aromatic ring include the following rings (Formula 500 to Formula 526).
  • condensed polycyclic aromatic ring examples include the following rings (Formula 527 to Formula 575).
  • aromatic ring assembly examples include the following rings (Formula 576 to Formula 602).
  • bridged polycyclic aromatic ring examples include the following rings (Formula 603 to Formula 614).
  • the divalent aromatic group represented by R 1 is represented by formula 500 to formula 505, formula 508 to formula 514, formula 527 to formula 534, formula 543, formula 561 to formula 564, formula 568, formula 576 to formula 584, It is a divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the ring represented by any one of formulas 587 to 602, 603 to 608 and 611 Are preferably represented by any one of Formula 500 to Formula 505, Formula 508 to Formula 514, Formula 527 to Formula 534, Formula 543, Formula 561 to Formula 564, Formula 568, Formula 603 to Formula 608, and Formula 611.
  • a divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the ring including Formula 500, Formula 527 to Formula 534, Formula 543, Formula 561 to Formula 564, Formula 568 and Expression 603 to Expression 607 It is more preferable that the divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the ring represented by any one of formulas 527 to 530 and 603 to 607 A divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the ring represented by any of them is particularly preferable.
  • the two positions from which hydrogen atoms are removed are atoms bonded to H x when the two hydrogen atoms to be removed are H x and H y . and it is preferable to choose between atoms bonded with H y as the number of atoms increases which connects shortest. Further, the number of atoms connecting the atoms bonded to H x and the atoms bonded to H y at the shortest is preferably an even number because the conjugate length is further expanded.
  • the hydrogen atom when a hydrogen atom is removed at the para position, the minimum number of atoms between the carbon atoms bonded to the removed hydrogen atom is 4 atoms, and at the meta position, 3 atoms, 2 atoms in ortho position. For this reason, in the case of the benzene ring represented by Formula 500, it is preferable that a hydrogen atom be removed at the para position.
  • the number of atoms connected in the shortest is the largest (eight), so the 2,7-position It is preferred that the hydrogen atom be removed.
  • the following positions are also preferable as the two positions (that is, the positions of H x and H y ) from which hydrogen atoms are removed.
  • the naphthalene ring represented by the above formula 527 there are two positions of 1-position and 4-position.
  • the anthracene ring represented by the formula 528 there are two positions, 9-position and 10-position.
  • the tetracene ring represented by the formula 529 there are two positions, the 2-position and the 3-position.
  • the pyrene ring represented by the above formula 530 there are two positions of 1-position and 6-position.
  • the divalent aromatic group represented by R 1 may have a substituent.
  • the number of substituents contained in the divalent aromatic group represented by R 1 is preferably 0 to 4, more preferably 0 to 2, still more preferably 1 to 2, and particularly preferably 2.
  • Examples of the substituent that the divalent aromatic group represented by R 1 may have include a halogen atom, a hydroxy group, a hydrocarbyl group, a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbyl mercapto group, and a hydrocarbylcarbonyl group.
  • the hydrocarbyl group is a group represented by R— (specific examples will be described later), the hydrocarbyloxy group is a group represented by RO—, and the hydrocarbyl mercapto group is a group represented by RS—
  • the hydrocarbylcarbonyl group is a group represented by RC ( ⁇ O) —
  • the hydrocarbyloxycarbonyl group is a group represented by ROC ( ⁇ O) —
  • the hydrocarbylcarbonyloxy group is RC ( ⁇ O).
  • a dihydrocarbylamino group is a group represented by R 2 N—
  • a (dihydrocarbyl) aminocarbonyl group is a group represented by R 2 N—C ( ⁇ O) —. It is.
  • two R may be the same or different from each other, preferably the same as each other.
  • they may be bonded to each other to form a ring structure.
  • the substituent which the divalent aromatic group represented by R 1 may have is preferably a halogen atom, a hydroxy group, a hydrocarbyl group, a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylcarbonyl group, a hydrocarbyloxy group.
  • hydrocarbyl group represented by R examples include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n A linear alkyl group having 1 to 50 carbon atoms such as nonyl group and n-decyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methyl Pentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 2,
  • the hydrocarbyl group represented by R includes a linear alkyl group having 1 to 50 carbon atoms, a branched alkyl group having 3 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or a carbon atom.
  • An aralkyl group having 7 to 50 carbon atoms is preferable, a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms is preferable.
  • a linear alkyl group having 1 to 12 carbon atoms More preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 18 carbon atoms, or a linear alkyl group having 1 to 12 carbon atoms, or A phenyl group is particularly preferred.
  • X 1 is a group represented by —O—, a group represented by —S—, a group represented by —C ( ⁇ O) —, or —C ( ⁇ O) O—.
  • a group represented by —O— a group represented by —C ( ⁇ O) —, a group represented by —C ( ⁇ O) O—, —C ( ⁇ O) N (R 10 )
  • a group represented by — a group represented by —OC ( ⁇ O) O—, a group represented by —OC ( ⁇ O) N (R 11 ) —, and a group represented by —C (R 14 ) 2 —.
  • Examples of the divalent amine residue represented by X 1 include a divalent aromatic amine residue represented by the following formula (3).
  • Ar 3 , Ar 4 , Ar 5 and Ar 6 are each independently a divalent aromatic group which may have a substituent, and Ar 7 , Ar 8 and Ar 9 are These are each independently a monovalent aromatic group optionally having a substituent.
  • m 3 and m 4 are each independently 0 or 1.
  • Examples of the divalent aromatic group which may have a substituent represented by Ar 3 , Ar 4 , Ar 5 and Ar 6 may have a substituent represented by R 1. It is the same as a divalent aromatic group, and is preferably a phenylene group which may have a substituent.
  • Examples of the monovalent aromatic group which may have a substituent represented by Ar 7 , Ar 8 and Ar 9 are divalent which may have a substituent represented by R 1 .
  • the aromatic group it is a monovalent group formed by bonding one hydrogen atom out of two removed hydrogen atoms, and is preferably a phenyl group which may have a substituent.
  • the carbon atom in Ar 3 and the carbon atom in Ar 5 may be directly bonded, and a divalent group such as a group represented by —O— or a group represented by —S— It may be bonded via the group.
  • a divalent group such as a group represented by —O— or a group represented by —S— It may be bonded via the group.
  • the carbon atom in Ar 5 and the carbon atom in Ar 9 may be directly bonded to each other, and a group represented by —O— or a group represented by —S— And may be bonded via a divalent group such as
  • Examples of the divalent aromatic amine residue represented by the formula (3) include 2 hydrogen atoms directly bonded to the carbon atom constituting the ring from the aromatic amine represented by any of the following formulas 615 to 627. Exemplified groups are exemplified.
  • the divalent amine residue represented by the formula (3) is preferably an aromatic amine represented by any one of the formulas 615 to 621 and 627 among the aromatic amines represented by the formulas 615 to 627.
  • the ring is constituted from the aromatic amine represented by any one of the formulas 615 and 617 In which two hydrogen atoms directly bonded to the carbon atom to be removed are removed.
  • the positions of the two hydrogen atoms removed from the aromatic amine represented by the above formulas 615 to 627 are such that both of the two hydrogen atoms removed are each of the amine nitrogen atom with respect to the amine nitrogen atom.
  • the positions at which two hydrogen atoms are removed are H 2 and H 2 when the two hydrogen atoms to be removed are H x and H y. It is preferable to choose between atoms bonded with the atoms to H y which joins the x as the number of atoms connecting the shortest increases.
  • the 6-membered aryl group from which a hydrogen atom is removed is preferably a phenyl group.
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom or a hydrocarbyl group which may have a substituent.
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same or different.
  • Examples of the hydrocarbyl group in R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 include a linear alkyl group, a branched alkyl group, a cyclic saturated hydrocarbyl group, an alkenyl group, and an alkynyl group.
  • An aryl group, and an aralkyl group, a linear alkyl group, a branched alkyl group, an aryl group, or an aralkyl group is preferable, and a linear alkyl group, a branched alkyl group, or an aryl group is more preferable.
  • the number of carbon atoms of the hydrocarbyl group is usually 1 to 50, preferably 1 to 30, more preferably 1 to 18, still more preferably 1 to 8, and particularly preferably 4 to 8. is there.
  • Examples of the linear alkyl group, branched alkyl group, cyclic saturated hydrocarbyl group, alkenyl group, alkynyl group, aryl group, and aralkyl group are the same as those for R.
  • R 10 , R 11 , R 12 and R 13 are preferably hydrogen atoms.
  • R 14 , R 15 and R 16 are preferably hydrocarbyl groups which may have a substituent.
  • m 1 is an integer of 1 or more
  • m 2 is an integer of 0 or more.
  • m 1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1 or 2, and particularly preferably 1.
  • m 2 is preferably an integer of 0 to 10, more preferably an integer of 0 to 5, still more preferably 0 or 1, and particularly preferably 0.
  • the combination of m 1 and m 2 is preferably such that m 1 is 1 and m 2 is 0.
  • R 1 R x type X 1 is present X y type, so that the m 1 / R x, the ratio of m 2 / X y is minimized integer ratio Is done.
  • m 1 / R x 1.
  • R x is a number of 1 or more, preferably 1 or 2, and more preferably 1.
  • X y is a number of 1 or more, preferably 1 or 2, and more preferably 1.
  • R 5 , R 6 and R 7 are each independently a hydrogen atom or a hydrocarbyl group which may have a substituent.
  • the hydrocarbyl group represented by R 5 , R 6 and R 7 is the same as the hydrocarbyl group described above for R 10 .
  • the number of carbon atoms of the hydrocarbyl group represented by R 5 , R 6 and R 7 is preferably 1 to 18, more preferably 1 to 8, still more preferably 1 to 4, and particularly preferably 1 It is.
  • the hydrocarbyl group represented by R 5 , R 6 and R 7 is preferably a linear alkyl group, a branched alkyl group, an aryl group or an aralkyl group, more preferably a linear alkyl group or a branched group.
  • R 5 , R 6 and R 7 are preferably hydrogen atoms.
  • R 8 is preferably a group represented by —O—, a group represented by —S—, a group represented by —C ( ⁇ O) O—, —C ( ⁇ O) N (R 9 ).
  • a group represented by-, a hydrocarbylene group which may have a substituent, or a direct bond, more preferably a group represented by -O-, represented by -C ( O) O-.
  • An example of the hydrocarbylene group represented by R 8 is a divalent group in which one hydrogen atom is removed from the hydrocarbyl group described above for R 10 .
  • the number of carbon atoms of the hydrocarbylene group represented by R 8 is preferably 1 to 18, more preferably 1 to 10, and still more preferably 1 to 4.
  • the hydrocarbylene group represented by R 8 is preferably a linear alkylene group, a branched alkylene group, an arylene group, or an aralkylene group, and more preferably a linear alkylene group or an arylene group. More preferably, it is a linear alkylene group.
  • R 9 is a hydrogen atom or a hydrocarbyl group which may have a substituent, and is preferably a hydrocarbyl group.
  • Examples of the hydrocarbyl group represented by R 9 are the same as the hydrocarbyl group described above for R 10 .
  • the number of carbon atoms of the hydrocarbyl group represented by R 9 is preferably 1 to 18, more preferably 1 to 12, still more preferably 4 to 12, and particularly preferably 6 to 8.
  • the hydrocarbyl group represented by R 9 is preferably a linear alkyl group, a branched alkyl group, an aryl group, or an aralkyl group, more preferably a linear alkyl group or an aryl group, An aryl group is preferable.
  • Ar 2 is a monovalent aromatic hydrocarbon group which may have a substituent, and the monovalent aromatic hydrocarbon group contains 7 or more sp 2 carbon atoms.
  • An example of a monovalent aromatic hydrocarbon group in Ar 2 is obtained by bonding one hydrogen atom out of two hydrogen atoms removed in the divalent aromatic group represented by R 1.
  • the monovalent aromatic hydrocarbon group represented by Ar 2 is preferably represented by any one of Formulas 527 to 530, Formulas 576 to 579, Formulas 585 to 587, and Formulas 603 to 607.
  • the monovalent aromatic hydrocarbon group represented by Ar 2 may have a substituent.
  • the number of substituents possessed by the aromatic hydrocarbon group represented by Ar 2 is preferably 0 to 5, more preferably 0 to 4, further preferably 0 to 3, and particularly preferably. Is 0-2.
  • Examples of the substituent that the monovalent aromatic hydrocarbon group represented by Ar 2 may have include a halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms.
  • a hydrocarbyl mercapto group having 1 to 30 carbon atoms preferably a halogen atom, a hydrocarbyl group having 1 to 18 carbon atoms, or a hydrocarbyloxy group having 1 to 18 carbon atoms, more preferably Is a hydrocarbyl group having 1 to 12 carbon atoms or a hydrocarbyloxy group having 1 to 12 carbon atoms, more preferably a hydrocarbyl group having 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • a branched alkyl group having 1 to 8 carbon atoms particularly preferably a branched alkyl group having 1 to 6 carbon atoms. Kill group.
  • the monovalent aromatic hydrocarbon group represented by Ar 2 contains 7 or more sp 2 carbon atoms.
  • the sp 2 sp 2 carbon atoms of the substituents on the number of carbon atoms is not included. Since it is easy to maintain the molecular orientation, the monovalent aromatic hydrocarbon group in Ar 2 preferably contains 8 or more sp 2 carbon atoms, more preferably 10 or more, and particularly preferably 12 or more.
  • the sp 2 carbon atom contained in the entire Ar 2 is preferably 20% by weight or more, more preferably 40% by weight or more of the entire Ar 2 because the molecular arrangement of the polymer compound is fixed by stacking of the sp 2 carbon atoms. Is more preferable, 50% by weight or more is further preferable, and 60% by weight or more is particularly preferable.
  • R 1 is a divalent aromatic group which may have a substituent or a divalent group represented by the above formula (2).
  • the divalent aromatic group that may have a substituent may be a single group that may have a substituent.
  • a divalent group from which two are removed is preferable.
  • R 1 is a divalent group represented by the formula (2)
  • Ar 2 has one hydrogen atom directly bonded to an atom constituting the ring from an aromatic ring assembly which may have a substituent.
  • the monovalent group which is removed is preferable, and among them, the ring may be formed from the ring represented by any one of the formulas 576 to 579 and 585 to 587 which may have a substituent. It is preferably a group in which one hydrogen atom directly bonded to the atom to be removed is removed.
  • R 1 is a divalent group represented by the formula (2)
  • R 5 , R 6 and R 7 are hydrogen atoms
  • R 5 , R 6 and R 7 are hydrogen atoms.
  • R 8 is more preferably a group represented by —C ( ⁇ O) N (R 9 ) — or a direct bond.
  • Examples of the repeating unit represented by the formula (1) include the following repeating units (formula 100 to formula 128).
  • t-Bu represents a tert-butyl group
  • n-Hex represents an n-hexyl group
  • n-Oct represents an n-octyl group.
  • the repeating unit represented by formula (1) is preferably a repeating unit selected from formula 100 to formula 113, formula 118 to formula 121, and formula 125 to formula 128 among formula 100 to formula 128, Preferred is a repeating unit selected from Formula 100, Formula 103 to Formula 105, Formula 107, Formula 111, Formula 112, Formula 118 to Formula 121, and Formula 125 to Formula 128, and more preferably Formula 103, Formula 104, Formula 111, Formula 112, Formula 118, Formula 119, Formula 121, and a repeating unit selected from Formulas 126 to 128.
  • the polymer compound used in the present invention only needs to contain at least partially a repeating unit having one or more chemical structures selected from the repeating unit represented by the above formula (1). Since it is easy to control the degree of introduction of optical activity and a high optical activity polymer compound is obtained, the polymer compound used in the present invention is a repeating unit represented by the formula (1) with respect to the weight of the whole molecule. Is preferably 1% by weight or more, more preferably 5% by weight or more, further preferably 25% by weight or more, particularly preferably 80% by weight or more, and particularly preferably 100% by weight.
  • the polymer compound used in the present invention may be a homopolymer or a copolymer, but is preferably a homopolymer.
  • the polymer compound used in the present invention is a homopolymer means that the polymer compound contains only a repeating unit having a specific chemical structure selected from repeating units represented by the formula (1) in the molecule. It means to do.
  • the polymer compound used in the present invention is a copolymer, the polymer compound contains a repeating unit having two or more chemical structures selected from repeating units represented by the formula (1) in the molecule.
  • the polymer compound has a repeating unit having one or more chemical structures selected from the repeating unit represented by the formula (1) in the molecule, and a repeating unit other than the repeating unit represented by the formula (1). It means containing 1 or 2 or more repeating units.
  • the polymer compound used in the present invention is a copolymer, for example, a divalent group having a triarylamine skeleton, a divalent group having a triazine skeleton, or a divalent group having a cyclic hydrocarbyl group having an asymmetric carbon atom. It may further contain a group as a repeating unit, and preferably further contains a divalent group having a triarylamine skeleton or a divalent group having a triazine skeleton as a repeating unit.
  • the number average molecular weight (Mn) in terms of polystyrene of the polymer compound used in the present invention is usually 5 ⁇ 10 2 to 1 ⁇ 10 8 .
  • Mn of the polymer compound of the present invention is preferably 1 ⁇ 10 3 to 1 ⁇ 10 7 , since film forming property and solubility in a solvent can be improved to ensure good moldability. It is preferably 2 ⁇ 10 3 to 1 ⁇ 10 6 , more preferably 3 ⁇ 10 3 to 5 ⁇ 10 5 , particularly preferably 4 ⁇ 10 3 to 1 ⁇ 10 5 , and particularly preferably 1 ⁇ 10 6. 4 to 1 ⁇ 10 5 .
  • the polystyrene equivalent weight average molecular weight (Mw) of the polymer compound used in the present invention is usually 1 ⁇ 10 3 to 1 ⁇ 10 9 , preferably 2 ⁇ 10 3 to 1 ⁇ 10 8 , more It is preferably 5 ⁇ 10 3 to 1 ⁇ 10 7 , more preferably 1 ⁇ 10 4 to 5 ⁇ 10 6 , and particularly preferably 5 ⁇ 10 4 to 5 ⁇ 10 5 .
  • the polymer compound used in the present invention may be a polymer compound that exhibits optical activity before irradiation with circularly polarized light.
  • a polymer compound exhibiting optical activity before irradiation with circularly polarized light a polymer compound exhibiting stronger optical activity can be obtained by the modification method of the present invention.
  • the polymer compound used in the present invention can be synthesized by a conventionally known polymer compound synthesis method.
  • the polymer compound used in the present invention is produced, for example, by the method of the following example. In addition to the embodiment, it is also manufactured by the following method. For example, in a nitrogen atmosphere, a THF solution of 2,7-dibromo-9,9-di-n-octylfluorene is added to a suspension obtained by adding tetrahydrofuran and 1,2-dibromoethane to metal magnesium, while heating. Stir. Thereafter, [1,3-bis (diphenylphosphino) propane] dichloronickel (II) is added to the obtained reaction solution, and further stirred while heating. Next, the resulting reaction solution is extracted by adding dilute hydrochloric acid and chloroform, and washed with water. The obtained organic layer can be synthesized by drying over anhydrous magnesium sulfate, filtering and concentrating, dissolving in THF, dropping the resulting solution into methanol and reprecipitating.
  • the polymer compound having a repeating unit represented by the above formula (1) is also produced by the following method.
  • a styrene derivative and a chloroform solution of 2,2′-azobis (isobutyronitrile) are mixed and stirred while heating.
  • the solvent can be distilled off from the reaction solution, dissolved in chloroform, and the resulting solution can be synthesized by dropping into methanol and reprecipitating.
  • the polymer compound when the polymer compound is irradiated with circularly polarized light, the polymer compound may be in any shape / state such as a powder, a film, a molded body, a solution, and a dispersion.
  • the shape / state of the powder, film, molded body, or dispersion is preferable, and the shape / state of the film or dispersion is more preferable. Since the process load is light and the control of molecular orientation is easy, the polymer compound is more preferably in the form of a film.
  • the thickness of the film is usually 1 nm to 500 ⁇ m, preferably 2 nm to 100 ⁇ m, more preferably 3 nm to 20 ⁇ m, still more preferably 5 nm to 1 ⁇ m, and particularly preferably 10 nm to 200 nm.
  • the thin film may include pinholes or irregular shapes.
  • a method for producing the membrane for example, a suspension obtained by suspending or dissolving a polymer compound having a repeating unit represented by the above formula (1) and other components in a solvent at an arbitrary ratio.
  • the former method is used.
  • solvent used in the coating step examples include benzene, toluene, xylene, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4.
  • examples of the coating method include spin coating, casting, dip coating, gravure printing, bar coating, roll coating, spray coating, screen printing, flexographic printing, and inkjet printing. And an offset printing method, and a spin coating method, a casting method, a roll coating method, a spray coating method, a screen printing method, a flexographic printing method, an inkjet printing method or an offset printing method is preferable.
  • the above-described polymer compound may be used alone, or within the range where the effects of the present invention are not impaired, the polymer compound and other components are used in combination as a composition. Also good. When used as a composition, a better and better modification effect can be obtained. Therefore, the content of the polymer compound is preferably 1% by weight or more with respect to 100% by weight of the entire composition. % Or more, more preferably 50% by weight or more, and particularly preferably 90% by weight or more. Moreover, the upper limit is 99 weight% normally.
  • components other than the above-described polymer compound include, for example, a low-molecular organic material, a polymer organic material, and an organic inorganic material.
  • a composite material, an inorganic material, and a mixture thereof are mentioned, and can be arbitrarily selected depending on the application.
  • examples of the other components include the following.
  • anode material examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO); metals such as gold, silver, chromium, and nickel; the conductive metal oxides and the above Mixtures with metals; inorganic conductive materials such as copper iodide and copper sulfide; organic conductivity such as polyaniline and its derivatives, polythiophene and its derivatives [poly (3,4) ethylenedioxythiophene, etc.], polypyrrole and its derivatives Materials; and combinations thereof, preferably polyaniline and derivatives thereof, polythiophene and derivatives thereof, or polypyrrole and derivatives thereof. These are useful when the modified polymer compound obtained by the modification method of the present invention is used for an anode of a light emitting device.
  • conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO); metals such as gold, silver, chromium, and nickel
  • cathode materials examples include alkali metals (Li, Na, K, Cs, etc.) and their fluorides and oxides; alkaline earth metals (Mg, Ca, Ba, etc.) and their fluorides and oxides; gold, silver Metals such as lead, aluminum, etc .; sodium-potassium alloys, sodium-potassium mixed metals, lithium-aluminum alloys, lithium-aluminum mixed metals, magnesium-silver alloys, magnesium-silver mixed metals, and mixed metals; indium, ytterbium Rare earth metals; and combinations thereof. These are useful when the modified polymer compound obtained by the modification method of the present invention is used for the cathode of a light emitting device.
  • hole injection and hole transport materials examples include carbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, hydrazone derivatives, stilbene derivatives. , Silazane derivatives, porphyrin derivatives, polysilane derivatives, poly (N-vinylcarbazole) derivatives, and polymers containing residues of these derivatives; conductive polymer oligomers such as aniline copolymers, thiophene oligomers, polythiophenes, etc.
  • carbazole derivatives arylamine derivatives, or poly (N-vinylcarbazole) derivatives. These are useful when the modified polymer compound obtained by the modification method of the present invention is used for a light emitting layer, a hole injection and a hole transport layer of a light emitting device.
  • electron injection and electron transport materials examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, pyridine derivatives, pyrazine derivatives, triazine derivatives, imidazole derivatives, fluorene derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, Diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes (eg, 8-quinolinol derivatives) Metal complexes having metal phthalocyanine as a ligand, metal complexes having benzoxazole as a ligand, and metal complexes having benzothiazole as a
  • electrolyte material examples include a supporting salt (such as lithium trifluoromethanesulfonate, lithium perchlorate, tetrabutylammonium perchlorate, potassium hexafluorophosphate, tetra-n-butylammonium tetrafluoroborate) and a supporting salt.
  • a supporting salt such as lithium trifluoromethanesulfonate, lithium perchlorate, tetrabutylammonium perchlorate, potassium hexafluorophosphate, tetra-n-butylammonium tetrafluoroborate
  • a supporting salt such as lithium trifluoromethanesulfonate, lithium perchlorate, tetrabutylammonium perchlorate, potassium hexafluorophosphate, tetra-n-butylammonium tetrafluoroborate
  • Solvents that may be contained (propylene carbonate, acetonitrile, 2-methyltetrahydrofuran, 1,3-dioxofuran, nitrobenzene, N, N-dimethylformamide, dimethyl sulfoxide, glycerin, propyl alcohol, water, etc.) or swollen with the solvent Examples thereof include gel-like polymers (polyethylene oxide, polyacrylonitrile, a copolymer of vinylidene fluoride and propylene hexafluoride, and the like). These are useful when the modified polymer compound obtained by the modification method of the present invention is used in a light emitting layer of a light emitting device (for example, an electrochemiluminescent device) that forms an electric double layer.
  • a light emitting device for example, an electrochemiluminescent device
  • Examples of the light-emitting material include metal complexes using platinum group elements (such as iridium complexes coordinated with phenylpyridine derivatives), metal complexes using rare earth elements (such as europium complexes coordinated with phenanthroline derivatives), 8- Examples include aluminum complexes coordinated with quinolinol derivatives, naphthacene derivatives, dicyanoethylene derivatives, coumarin derivatives, quinacridone derivatives, anthracene derivatives, perylene derivatives, phenylene vinylene derivatives, fluorene derivatives, naphthalene derivatives, preferably iridium complexes or fluorene derivatives. is there. These may be used in combination when the optically active polymer compound obtained by the modification method of the present invention is used as the light emitting material of the light emitting device.
  • a resin that improves the film forming property can be used as other components.
  • the resin for improving the film forming property include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, and ethyl cellulose.
  • proteins In addition to these, proteins, antioxidants, refractive index adjusters, viscosity adjusters, heat insulating agents, light absorbers, and the like can be used.
  • irradiation with circularly polarized light can be performed using a general light source exhibiting circular polarization.
  • a general light source exhibiting circular polarization.
  • Examples of such a light source include an apparatus using an Ar + laser, a YAG laser, or the like.
  • the intensity of the circularly polarized light is preferably 1 ⁇ 1000mW / cm 2, more preferably 2 ⁇ 500mW / cm 2, more preferably 3 ⁇ 250mW / cm 2, particularly preferably 5 ⁇ 100mW / cm 2.
  • the irradiation time of the circularly polarized light is preferably 0.1 second to 72 hours, more preferably 1 second to 24 hours, further preferably 10 seconds to 12 hours, particularly preferably 1 minute to 6 hours, and 5 minutes to 2 hours. Especially preferred.
  • the irradiation environment of circularly polarized light may be in air or in an inert gas atmosphere such as nitrogen gas or argon gas, but is preferably in air because it is simple.
  • circularly polarized light is preferably irradiated at room temperature, the specimen may be heated by irradiation with circularly polarized light.
  • elliptically polarized light can be used as the circularly polarized light irradiated in the present invention.
  • the optically active polymer compound obtained by the modification method of the present invention is an electronic device (for example, a light emitting device (for example, an organic electroluminescent device, preferably an organic electroluminescent device emitting circularly polarized light), a solar cell, an organic It can be used for (transistor) materials, optical resolution, asymmetric field for asymmetric reactions, polarizing materials, refractive materials, pharmaceuticals, and the like.
  • a light emitting device for example, an organic electroluminescent device, preferably an organic electroluminescent device emitting circularly polarized light
  • a solar cell for example, a solar cell, an organic It can be used for (transistor) materials, optical resolution, asymmetric field for asymmetric reactions, polarizing materials, refractive materials, pharmaceuticals, and the like.
  • the method for producing a film containing a modified polymer compound according to the present invention includes the following steps (a) and (b).
  • Step (a) is a step of forming a film containing a polymer compound having a repeating unit represented by the above formula (1) on a substrate.
  • the high molecular compound which has a repeating unit represented by the said Formula (1) used for the manufacturing method of this invention is the same as what was demonstrated by the said ⁇ modification method of a high molecular compound>.
  • the substrate for example, quartz, glass, transparent or translucent resin, or the like may be used.
  • a film containing a polymer compound may be formed on an anode manufactured by a conventional method.
  • the anode functions as a “base material”.
  • a film containing a polymer compound may be formed on the hole injection and hole transport layer manufactured by a conventional method.
  • the hole injection and hole transport layer functions as a “substrate”. That is, the substrate may be arbitrarily selected according to the use of the membrane as long as the polymer compound can be received on the surface and the polymer compound can be physically supported.
  • a polymer compound having a repeating unit represented by the above formula (1) and other components may be arbitrarily selected.
  • a method of applying a suspension or solution obtained by suspending or dissolving in a solvent in a ratio to a substrate (hereinafter also simply referred to as an application method), and a repeating unit represented by the above formula (1)
  • a method of vapor-depositing a polymer compound and other components on a base material at an arbitrary ratio (hereinafter also simply referred to as vapor deposition method) can be mentioned.
  • vapor deposition method since the process can be simplified, it is preferable to form a coating by the former coating method.
  • the solvent contained in the suspension or solution is dried.
  • the method for drying the solvent include air drying, heat drying, reduced pressure drying, heat reduced pressure drying, and drying performed by blowing nitrogen gas. Air drying or heat drying is preferable, and heat drying is more preferable.
  • the atmosphere for drying the solvent is not particularly limited, but is preferably an inert gas atmosphere such as nitrogen gas or argon gas.
  • examples and preferred examples of the other components used in combination with the polymer compound having the repeating unit represented by the formula (1) are those described in the above ⁇ Modification method of polymer compound>. And can be selected according to the intended use of the resulting membrane.
  • the anode material described in the above ⁇ Method for modifying polymer compound> may be used as the other component.
  • the hole injection and hole transport layer of the light emitting device the hole injection and hole described in the above ⁇ Method for modifying polymer compound> are used as the other components.
  • a transport material may be used.
  • the other components are the hole injection and hole transporting materials described in the above ⁇ Method for modifying polymer compound>. Electron injection and electron transport materials, electrolyte materials, and luminescent materials may be used.
  • the content of the polymer compound having the repeating unit represented by the above formula (1) in the film formed in the step (a) can be determined according to the use of the film, but a more excellent modification effect is obtained. Therefore, it is preferably 1% by weight or more, more preferably 10% by weight or more, still more preferably 50% by weight or more, and 90% by weight or more, based on the total weight of the film. Is particularly preferred, with 100% by weight (excluding inevitable impurities) being particularly preferred.
  • the thickness of the film formed in the step (a) can be determined depending on the use of the film, but is usually 1 nm to 500 ⁇ m, preferably 2 nm to 100 ⁇ m, more preferably 3 nm to 20 ⁇ m, More preferably, it is 5 nm to 1 ⁇ m, and particularly preferably 10 nm to 200 nm.
  • Step (b) is a step of irradiating circularly polarized light on the film formed in step (a) and containing the polymer compound having the repeating unit represented by the above formula (1).
  • the polymer compound in the film is modified to exhibit optical activity by irradiating the film containing the polymer compound having the repeating unit represented by the formula (1) with circularly polarized light. be able to.
  • the circularly polarized light source, the intensity of the circularly polarized light, and the irradiation time are as described in the above ⁇ Method for modifying polymer compound>.
  • the intensity of the circularly polarized light and the irradiation time of the circularly polarized light to be irradiated in the step (b) can be adjusted so that the obtained film exhibits the desired optical activity.
  • the film containing a modified polymer compound obtained by the production method of the present invention can be used for the same applications as the optically active polymer compound described above.
  • the reaction vessel was filled with a nitrogen gas atmosphere, and then at room temperature, dibromoethane (1.37 g) was added to a mixture of magnesium metal (3.72 g, 153 mmol) and tetrahydrofuran (hereinafter referred to as “THF”) (20 mL). , 7.30 mmol) was added slowly. After bubbling ceased, a solution of 1-bromo-4-tert-butylbenzene (31.1 g, 146 mmol) in THF (100 mL) was added to the resulting reaction solution and refluxed at 60 ° C. for 1 hour.
  • THF tetrahydrofuran
  • reaction solution was added to a solution of zinc (II) chloride (19.9 g, 146 mmol) in THF (60 mL), and further, N, N, N ′, N′-tetramethylethylenediamine (16.9 g, 146 mmol) was added. And stirred at room temperature for 30 minutes. Thereafter, tetrakis (triphenylphosphine) palladium (0) (2.32 g, 2.01 mmol) was added thereto, and further, a solution of 2,5-dibromotoluene (9.12 g, 36.5 mmol) in THF (60 mL). Was slowly added over 20 minutes and stirred at 60 ° C. for 13 hours.
  • reaction liquid was returned to room temperature, added to ice-cooled 10% by weight hydrochloric acid (350 mL) and filtered, and the residue was extracted with chloroform.
  • the obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the solvent was distilled off, the filtrate was washed with methanol, and 2,5-bis (4-tert-butyl Phenyl) toluene was obtained (9.31 g, yield 73.0%).
  • reaction liquid was returned to room temperature, filtered, the solvent was distilled off, and the residue was washed with methanol to obtain 2,5-bis (4-tert-butylphenyl) benzyl bromide (20.6 g, Yield 84.4%).
  • the obtained reaction solution was extracted with dichloromethane, and the obtained organic layer was purified by silica gel column chromatography (developing solvent: dichloromethane) after evaporating the solvent, and [2,5-bis (4-tert-butylphenyl). ) Styrene (1.56 g, yield 94.4%) was obtained.
  • the polystyrene equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer compound 1 were measured by size exclusion chromatography (SEC).
  • SEC size exclusion chromatography
  • a case where the mobile phase is an organic solvent in SEC is referred to as “GPC”.
  • Measurement sample (polymer compound 1) was dissolved in tetrahydrofuran at a concentration of about 0.1% by weight, and 10 ⁇ L was injected into GPC (Hitachi L7100). The mobile phase of GPC was flowed at a flow rate of 1.0 mL / min using THF. As the columns, TOSOH TSK gel G3000HHR and TOSOH TSK gel G6000HHR were used. A UV-VIS detector (Hitachi L-7420 UV) and an RI detector (Hitachi L-7490 RI) were used as detectors.
  • N, N-dimethylaniline (2) was added to a solution of N-4-biphenylaniline (3.00 g, 12.2 mmol) obtained in (2) above in benzene (180 mL). .16 mL) and acryloyl chloride (1.20 mL, 14.7 mmol) were added, and the mixture was stirred at 23 ° C. for 20 hours. Distilled water and 0.1 M hydrochloric acid (100 mL) were added to the obtained reaction solution, and then toluene was added for extraction, and the resulting organic layer was washed with saturated brine.
  • Toluene (19 mL) was added to a solution of tert-butyllithium in n-pentane (1.77 M, 1.0 mL) to prepare a 8.9 ⁇ 10 ⁇ 2 M solution.
  • This prepared solution (470 ⁇ L) was added to toluene (6.25 mL) of N-4-biphenyl N-phenylacrylamide (250 mg, 0.835 mmol) obtained in (2) above at ⁇ 78 ° C. in a reaction vessel.
  • the solution was added dropwise to the solution, mixed and stirred for 14 hours while maintaining at -78 ° C.
  • polymer compound 3 was obtained in a yield of 62%.
  • Example 1 The film obtained in Film Production Example 1 was irradiated with right circularly polarized light for 120 minutes (film specimen 1-1). Separately, the film obtained in Film Production Example 1 was irradiated with left circularly polarized light for 120 minutes (film specimen 1-2).
  • the circular dichroism ratio of the membrane specimen 1-1 was measured, it showed a negative signal of 5.0 mdeg at a wavelength of 268 nm.
  • the circular dichroism ratio of the membrane specimen 1-2 When the circular dichroism ratio of the membrane specimen 1-2 was measured, it showed a positive signal of 5.0 mdeg at a wavelength of 268 nm.
  • the absorbance at 268 nm in the film obtained in Production Example 1 of the film was approximately 0.5.
  • the molar extinction coefficient per unit of the polymer compound 1 obtained in Synthesis Example 1 at 268 nm in THF was 4.2 ⁇ 10 4 L ⁇ cm ⁇ 1 ⁇ mol ⁇ 1 .
  • Example 2 The film obtained in Film Production Example 2 was irradiated with right circularly polarized light for 10 minutes (film specimen 2-1). Separately, the film obtained in Film Production Example 2 was irradiated with left circularly polarized light for 10 minutes (film specimen 2-2).
  • film specimen 2-1 When the circular dichroism ratio was measured at a wavelength of 280 nm, the membrane specimen 2-1 showed a negative circular dichroism signal, the membrane specimen 2-2 showed a positive circular dichroism signal, and each signal intensity The difference was 1.9 mdeg.
  • the membrane specimen 2-1 showed a positive circular dichroism signal
  • the membrane specimen 2-2 showed a negative circular dichroism signal
  • the difference in signal intensity was 1.7 mdeg.
  • the absorbance at 280 nm and 310 nm in the film obtained in Production Example 2 of the film was approximately 0.3 and 0.2, respectively.
  • the molar extinction coefficient per unit of the polymer compound 2 obtained in Synthesis Example 2 in THF is approximately 1.9 ⁇ 10 4 L ⁇ cm ⁇ 1 ⁇ mol ⁇ 1 and 1.2 at 280 nm and 310 nm, respectively. ⁇ 10 4 L ⁇ cm ⁇ 1 ⁇ mol ⁇ 1
  • Example 3 The film obtained in Film Production Example 3 was irradiated with right circular polarized light for 1.5 hours (film specimen 3-1). Separately, the film obtained in Film Production Example 3 was irradiated with left circularly polarized light for 1.5 hours (film specimen 3-2).
  • the circular dichroism ratio was measured at a wavelength of 390 nm
  • the membrane specimen 3-1 showed a negative circular dichroism signal
  • the membrane specimen 3-2 showed a positive circular dichroism signal.
  • the difference in strength was 20 mdeg.
  • the absorbance at 390 nm in the film obtained in Production Example 3 of the film was 0.35.
  • the molar extinction coefficient per unit of poly (9,9-di-n-octylfluorene-2,7-diyl) at 390 nm in THF is 4.0 ⁇ 10 4 L ⁇ cm ⁇ 1 ⁇ mol ⁇ 1 . there were.
  • Example 4 The film obtained in Film Production Example 3 was irradiated with left circularly polarized light for 6 minutes (film specimen 4-1).
  • the membrane specimen 4-1 showed a strong positive circular dichroism signal around 400 nm.
  • the film specimen 4-1 was irradiated with right circularly polarized light for 9.5 minutes (film specimen 4-2).
  • the circular dichroic signal almost disappeared.
  • the membrane specimen 4-2 was irradiated with right circularly polarized light for 25 minutes (membrane specimen 4-3).
  • negative absorption having a shape almost symmetrical to the circular dichroism spectrum of the membrane specimen 4-1 was observed.
  • Example 5 1.00 mg of poly (9,9-di-n-octylfluorene-2,7-diyl), which is a polymer compound having a repeating unit represented by the formula 111, is suspended in 8 mL of methylcyclohexane, and right-handed circularly polarized light was observed for 10 minutes, and a change was observed in the circular dichroism spectrum compared to before irradiation with right circularly polarized light.
  • poly (9,9-di-n-octylfluorene-2,7-diyl) which is a polymer compound having a repeating unit represented by the formula 111
  • Example 6 The film obtained in Film Production Example 4 was irradiated with left circularly polarized light for 45 minutes (film specimen 6-1).
  • the intensity of the positive circular dichroic signal before irradiation was 0.5 mdeg.
  • the absorbance at 290 nm of the film obtained in Film Production Example 4 was approximately 0.9.
  • the molar extinction coefficient per unit of the polymer compound 3 obtained in Synthesis Example 3 in THF was approximately 4.0 ⁇ 10 3 L ⁇ cm ⁇ 1 ⁇ mol ⁇ 1 at 290 nm.
  • Example 7 The film obtained in Film Production Example 5 was irradiated with right circularly polarized light for 1.5 hours (film specimen 7-1). Separately, the film obtained in Film Preparation Example 5 was irradiated with left circularly polarized light for 1.5 hours (film specimen 7-2).
  • the circular dichroism ratio was measured at a wavelength of 360 nm
  • the membrane specimen 7-1 showed a negative signal of 0.7 mdeg
  • the membrane specimen 7-2 showed a positive signal of 0.6 mdeg.
  • the absorbance at 360 nm in the film obtained in Membrane Preparation Example 5 was 0.35.
  • the molar extinction coefficient per unit of poly (2,5-di-n-octyloxy-1,4-phenylene) at 360 nm in chloroform is 3.0 ⁇ 10 3 L ⁇ cm ⁇ 1 ⁇ mol ⁇ 1 . there were.
  • Example 8> The film obtained in Film Production Example 6 was irradiated with right circularly polarized light for 100 minutes (film specimen 8-1). Separately, the film obtained in Film Production Example 6 was irradiated with left circularly polarized light for 100 minutes (film specimen 8-2).
  • the membrane specimen 8-1 showed a negative signal of 1.0 mdeg
  • the membrane specimen 8-2 showed a positive signal of 1.0 mdeg.
  • the absorbance at 360 nm in the film obtained in Production Example 6 of the film was 0.65.
  • Example 9 The film obtained in Film Production Example 7 was irradiated with right circularly polarized light for 100 minutes (film specimen 9-1). Separately, the film obtained in Film Production Example 7 was irradiated with left circularly polarized light for 210 minutes (film specimen 9-2).
  • the circular dichroism ratio was measured at a wavelength of 360 nm
  • the membrane specimen 9-1 showed a negative signal of 1.8 mdeg
  • the membrane specimen 9-2 showed a positive signal of 2.3 mdeg.
  • the absorbance at 360 nm in the film obtained in Production Example 6 of the film was 0.55.
  • Example 10 The film obtained in Film Production Example 7 was irradiated with left circularly polarized light for 10 minutes (film specimen 10-1).
  • the membrane specimen 10-1 showed a positive signal of 0.85 mdeg at a wavelength of 360 nm.
  • the membrane specimen 10-1 was irradiated with right circularly polarized light for 30 minutes (membrane specimen 10-2).
  • the circular dichroism signal at 360 nm almost disappeared.
  • the membrane specimen 10-2 was irradiated with right circular polarized light for 40 minutes (membrane specimen 10-3).
  • the membrane specimen 10-3 showed a negative signal of 0.85 mdeg at a wavelength of 360 nm.
  • an optically active polymer compound can be obtained by irradiating circularly polarized light without introducing a photosensitive site such as azobenzene.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur un procédé pour l'obtention d'un composé polymère avec lequel une large gamme de composés polymères peuvent être utilisés et avec lequel une activité optique est simplement conférée et sur un procédé pour la modification d'un composé polymère par exposition d'un composé polymère ayant des motifs répétés spécifiques à une polarisation circulaire de lumière.
PCT/JP2012/061119 2011-04-27 2012-04-25 Procédé pour la modification de composé polymère et procédé pour la production de film contenant le composé polymère modifié WO2012147809A1 (fr)

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WO2024005140A1 (fr) * 2022-06-30 2024-01-04 三菱ケミカル株式会社 Composé, composition polymérisable, polymère, support d'enregistrement holographique, matériau optique et composant optique

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JP6942717B2 (ja) * 2016-10-14 2021-09-29 日本曹達株式会社 接着性組成物

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WO2024005140A1 (fr) * 2022-06-30 2024-01-04 三菱ケミカル株式会社 Composé, composition polymérisable, polymère, support d'enregistrement holographique, matériau optique et composant optique

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