JP4422544B2 - Side chain conductive polymer - Google Patents

Description

  The present invention relates to a novel conductive polymer having both fluorescence and semiconductor properties in both the main chain and the side chain.

  A conductive polymer has a reversible transition from an insulator or a semiconductor state to a metal state when carriers generated by doping or photoexcitation of an appropriate electron acceptor or electron donor move on the polymer chain. Is possible. Conductive polymers also have unique properties such as easy interaction with light having energy in the visible range, and significant changes in optical properties due to doping. Conductive materials, electronics field, information recording・ Applied research in various fields such as memory, energy field and molecular level recognition and control.

  Such conductive polymers are insoluble and infusible due to their rigid main chain structure, lack of moldability, and are often not easily controlled for molecular orientation, so far, from the viewpoint of controlling molecular orientation, A conductive polymer liquid crystal in which a liquid crystal group is introduced into a side chain of a conductive polymer has been developed (see, for example, Patent Document 1 and Non-Patent Document 1).

  However, the liquid crystal group introduced into the conductive polymer liquid crystal is selected from the viewpoint of imparting autonomous alignment ability to the conductive polymer, and is intended to introduce functionality other than the alignment effect of the liquid crystal. It does not have optical or electronic functionality such as photoconductivity or hole / electron conductivity. Therefore, the optical and electronic characteristics of the conductive polymer greatly depend on the main chain portion, and there is no interaction such as energy transfer between the main chain and the side chain.

  On the other hand, liquid crystalline organic semiconductors having self-organizing ability have been reported as new functional materials (see, for example, Patent Document 2, Patent Document 3, and Patent Document 4). Therefore, it is difficult to develop materials such as free processability and thinning by itself, so a polymerizable group such as a vinyl group or a methacryloyl group is introduced at the end of the side chain so that it can be introduced between the same molecule or within the same molecule. Attempts have been made to form new bonds (see, for example, Patent Document 5).

However, although the liquid crystalline organic semiconductor having the polymerizable group introduced therein is polymerized, the processability is improved by polymerization, but the polymer main chain portion composed of a non-π conjugated system does not have semiconductor properties, so that the optical properties of the polymer are high. -The electronic characteristics depend largely on the side chain, and there is no optical / electronic interaction between the main chain and the side chain.
JP 2002-212548 A JP-A-9-59267 Japanese Patent Laid-Open No. 10-231260 Japanese Patent Laid-Open No. 2001-233872 Japanese Patent Laid-Open No. 11-209761 Yoshiharu Hirai, Polymer Proceedings, 55, 2, 66-73 (1998.2)

  The present invention provides optical / electrons between main chains or between side chains constituting a polymer or between main chains and side chains by selecting the light-emitting properties of the main chain and side chains and controlling the molecular orientation by liquid crystallinity. It is an object of the present invention to provide a novel optical / electronic functional polymer compound that can control the physical properties and is excellent in melt solubility, film formability and processability.

  As a result of intensive studies to obtain a conductive polymer having new optical and electronic functionality by the interaction between the main chain and the side chain, the main chain has a fluorescence emission characteristic and a semiconductor property. A conductive polymer composed of an aromatic π-conjugated compound having a rod-like semiconductor liquid crystalline group having a fluorescence emission property and a high charge transporting ability by hopping conduction in its side chain. Since energy transfer can be arbitrarily controlled by selecting the light-emitting properties of the chains or controlling the molecular orientation, new optical and electrical characteristics can be easily imparted, and processability such as solubility and meltability is also excellent. The present invention has been found to be useful as an optical / electronic functional material that can be used in photosensors, photoconductive materials, secondary batteries, fuel cells, thin film transistors, light emitting devices, and the like.

  That is, the present invention has a polyaromatic π-conjugated compound selected from the group consisting of polyfuran, polythiophene, polypyrrole and polyfluorene and substituted derivatives thereof as a main chain, and charge transport due to at least fluorescence emission characteristics and hopping conduction in the side chain. The present invention provides a side chain type conductive polymer characterized by having a rod-like semiconductor liquid crystal group having a function.

  Moreover, this invention provides the liquid crystalline composition containing the said side chain type conductive polymer.

  Moreover, this invention provides the compound used as the precursor monomer of the said side chain type conductive polymer.

  The side chain type conductive polymer of the present invention has a fluorescence emission characteristic and a semiconductor characteristic in both the main chain and the side chain in addition to the self-alignment ability by liquid crystallinity or the orientation ability by heat treatment, etc. Can be controlled by molecular orientation. Moreover, new optical and electrical characteristics can be easily imparted by selecting and combining the functionalities of the main chain and the side chain independent of each other. Therefore, it is useful as a photo / electronic functional material that can be used in many application fields such as photosensors, photoconductive materials, electroluminescent elements, spatial modulation elements, secondary batteries, fuel cells, temperature sensors, and thin film transistors. .

The side chain type conductive polymer of the present invention has a polyaromatic π-conjugated compound selected from the group consisting of polyfuran, polythiophene, polypyrrole, polyfluorene and substituted derivatives thereof as a main chain, and at least fluorescent light emission in the side chain It is formed by introducing a rod-like semiconductor liquid crystal group having characteristics and charge transporting ability by hopping conduction, but the polyaromatic π-conjugated compound constituting the main chain has conductivity and fluorescence characteristics. The rod-like semiconductor liquid crystal group constituting the side chain is a rod-like liquid crystal compound having fluorescence emission characteristics and charge transporting ability by hopping conduction.
Thus, a conductive polymer having fluorescent properties and semiconductor properties in both the main chain and the side chain and having an alignment ability has not been known so far.

  As a substituted derivative of polyfuran, polythiophene, polypyrrole or polyfluorene, a hydrogen atom present on the ring may have a substituent, an alkyl group having 1 to 25 carbon atoms, a cyano group, an amino group, a hydroxyl group, Examples thereof include polyaromatic π-conjugated compounds that are substituted with groups such as a mercapto group and a nitro group and have the same conductivity and fluorescence characteristics.

The side chain type conductive polymer according to the present invention is excellent in solubility and meltability, and can be easily formed into a thin film by a casting method, a spin coating method or the like, and further oriented by a rubbing method, an annealing method, an electric field, a magnetic field, or the like. Can do. In addition, this side chain type conductive polymer has photoconductivity due to photoexcitation in both the main chain and the side chain. In addition, light emission from the main chain direction and the side chain direction is possible. Further, even when there is no liquid crystallinity, the molecules can be aligned by heat treatment or the like, and light emission from the main chain direction and the side chain direction is possible.
Therefore, the energy transfer can be controlled by selecting the light-emitting properties of the main chain and the side chain, and the energy transfer can be controlled between the main chain and the side chain or individually by controlling the molecular orientation. it can.
Moreover, the side chain type conductive polymer of the present invention can promote the ion transport ability in the polymer by connecting the main chain and the side chain with a polyether group such as polyethylene oxide which is an ion conductive material.
Therefore, the side chain type conductive polymer of the present invention makes use of such characteristics to provide photo / electron that can be used for photosensors, photoconductive materials, secondary batteries, fuel cells, thin film transistors, light emitting devices, and the like. It is useful as a functional material.
On the other hand, in general, rod-like liquid crystalline organic semiconductors have been reported to improve charge mobility by nearly two orders of magnitude with ordering of molecular orientation compared with material systems with the same core structure (M & BE, Vol. .11, No. 1 (2000) 50). Accordingly, the compound serving as a precursor monomer for the side chain type conductive polymer of the present invention showing a high-order smectic phase at room temperature in addition to the fluorescence emission property is an unprecedented liquid crystalline organic semiconductor having high charge mobility at room temperature. It can be.

  A preferred structure of the side chain type conductive polymer of the present invention is shown in the following (1) or (2).

[In the formula, A represents an oxygen atom, a sulfur atom or NH; L represents a rod-like semiconductor liquid crystal group having fluorescence emission characteristics and photoconductivity which may be different from each other; M may be different from each other; An optionally substituted alkyl group having 1 to 25 carbon atoms, a cyano group, an amino group, a hydroxyl group, a mercapto group and a nitro group, n represents an integer of 2 to 10,000, and a represents an integer of 1 to 3 B represents an integer of 1 to 8, d represents an integer of 0 to 2, and e represents an integer of 0 to 7. ]

  In the formulas (1) and (2), the parentheses indicate a repeating unit, and n indicates an integer representing the degree of polymerization of the repeating unit. Such a degree of polymerization is 2 to 10,000, preferably 5 to 8,000, particularly preferably 5 to 5,000.

In the general formulas (1) and (2), “M” means a group capable of substituting for a hydrogen atom present on the ring, and d and e indicate the number of substituents.
The number of substitution of d is preferably 0 or 1, and is preferably substituted at the 3-position or 4-position.
The number of substitution of e is preferably 0 to 3, particularly preferably substituted at the 3-position, 6-position or 9-position.
Examples of the alkyl group having 1 to 25 carbon atoms which may have a substituent represented by M include linear or branched alkyl groups having 1 to 25 carbon atoms, preferably 2 to 20 carbon atoms. Include those similar to those exemplified in the linear or branched hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ described later, preferably 2 carbon atoms. -20 linear or branched alkyl groups, particularly a methyl group, an ethyl group, a butyl group and the like are preferable.
Examples of the group that can be substituted with the alkyl group include a hydroxyl group, a mercapto group, an amino group, a cyano group, a nitro group, a trifluoromethyl group, and a halogen atom.

In the general formulas (1) and (2), “L” is a group capable of substituting for a hydrogen atom present on the ring, and means a rod-like semiconductor liquid crystal group having fluorescence emission characteristics and charge transporting ability by hopping conduction. A and b indicate the number of substituents.
The number of substitution of a is preferably 1 or 2, and when A is an oxygen atom or sulfur atom, it is substituted at the 3-position or 4-position, and when A is a nitrogen atom, it is substituted at the 1-position and / or 3-position or 4-position Is preferred. The number of substitution of b is preferably 1 to 4, particularly preferably substituted at the 3-position, 6-position or 9-position, more preferably 1-substitution or 2-substitution at the 9-position.

  Such a rod-like semiconductor liquid crystal group is not particularly limited as long as it is a liquid crystalline group having fluorescence emission characteristics and charge transporting ability by hopping conduction. For example, a 6π electron aromatic benzene ring or thiophene in the core portion. Ring, pyrrole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, pyridine ring, pyridazine ring, oxadiazole ring, thiadiazole ring; 10π electron aromatic ring naphthalene ring, benzothiazole ring, benzimidazole ring, Benzothiazole ring, benzoxazole ring, benzooxadiazole ring, benzotriazole ring, benzothiadiazole ring, benzoselenadiazole ring, azulene ring, coumarin ring, etc .; 14π electron aromatic ring anthracene ring, phenanthrene ring, fluorene Aromatic rings such as rings and carbazole rings Having 2-5 ring system skeleton building the hydrocarbon same or in different combinations, and include rod-like liquid crystal group having a charge transport ability by fluorescence properties and hopping conduction.

  Among these, from the viewpoint of liquid crystallinity, fluorescence, and charge transport properties, a combination of a benzene ring, thiophene ring, naphthalene ring, benzothiazole ring, pyridine ring, thiadiazole ring, oxadiazole ring, thiazole ring in the core part 2 Preference is given to pentacyclic compounds, in particular benzene ring-naphthalene ring-benzene ring, benzene ring-benzothiazole ring, thiophene ring-thiophene ring-thiophene ring, benzene ring-thiazole ring-benzene ring, thiophene ring-thiadiazole ring-thiophene ring Benzene ring-thiadiazole ring-benzene ring, benzene ring-oxadiazole ring-benzene ring, thiophene ring-oxadiazole ring-thiophene ring, thiophene ring-thiazole ring-thiophene ring, thiophene ring-pyridine ring-thiophene ring, etc. Liquid crystalline compounds with a main skeleton Patent Documents 2 to 4, etc.) is preferable.

  Preferred groups as “L” are shown in the following formulas (3) to (7).

[In the formula, R ¹ is a linear or branched hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or a cyclic hydrocarbon having 3 to 30 carbon atoms which may have a substituent. An aromatic heterocyclic group having 2 to 30 carbon atoms which may have a group or a substituent, and R ² represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, a lower alkyl group or a lower alkoxy group; , W represents a single bond, an oxygen atom or a sulfur atom, B represents an oxygen atom or a sulfur atom, D and E represent a nitrogen atom or CH, Y may have a substituent, and —CH ₂ —, —O—, —S—, —C═C—, —C≡C—, —COO—, —OCO—, —CO—, —SO ₂ —, —SiR ³ R ⁴ , —GeR ⁵ R ⁶ 2 having 1 to 25 carbon atoms, including a group selected from —, —NR ⁷ —, —CH═N—, a cyclic alkylene group, an aromatic ring group, and a heterocyclic group. A valent group (wherein R ^{3 to} R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), Z represents a single bond, —CH ₂ CH ₂ —, —C = C-, -C≡C-, -COO-, -OCO-, -N≡N- or -CH = N-. ]

Here, the hydrocarbon group in the linear or branched hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ has 1 to 25 carbon atoms, preferably 2 carbon atoms. -20 linear or branched alkyl groups are mentioned.

  Examples of the linear or branched alkyl group having 1 to 25 carbon atoms include methyl, ethyl, n-propyl, n-pentyl, n-hexyl, n-peptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-henecosyl, n-docosyl, n- Tricosyl, n-tetracosyl, 1-methylethyl, 1-methylpropyl, 1-ethylpropyl, 1-n-propylpropyl, 1-methylbutyl, 1-ethylbutyl, 1-propylbutyl, 1-n-butylbutyl, 1-methyl Pentyl, 1-ethylpentyl, 1-n-propylpentyl, 1-n-pentylpentyl, 1-methyl Xyl, 1-ethylhexyl, 1-n-propylhexyl, 1-n-butylhexyl, 1-n-pentylhexyl, 1-n-hexylhexyl, 1-methylheptyl, 1-ethylheptyl, 1-n-propylheptyl 1-n-butylheptyl, 1-n-pentylheptyl, 1-n-heptylheptyl, 1-methyloctyl, 1-ethyloctyl, 1-n-propyloctyl, 1-n-butyloctyl, 1-n- Pentyloctyl, 1-n-hexyloctyl, 1-n-heptyloctyl, 1-n-octyloctyl, 1-methylnonyl, 1-ethylnonyl, 1-n-propylnonyl, 1-n-butylnonyl, 1-n-pentyl Nonyl, 1-n-hexylnonyl, 1-n-heptylnonyl, 1-n-octylnonyl, 1-n-nonylnonyl 1-methyldecyl, 2-methylbutyl, 2-ethylbutyl, 2-n-propylpentyl, 2-methylhexyl, 2-ethylhexyl, 2-n-propylhexyl, 2-n-butylhexyl, 2-methylheptyl, 2-ethyl Heptyl, 2-n-propylhexyl, 2-n-butylheptyl, 2-n-pentylheptyl, 2-methyloctyl, 2-ethyloctyl, 2-n-propyloctyl, 2-n-butyloctyl, 2-n -Pentyloctyl, 2-n-hexyloctyl, 2-methylnonyl, 2-ethylnonyl, 2-n-propylnonyl, 2-n-butylnonyl, 2-n-pentylnonyl, 2-n-hexylnonyl, 2-n- Heptylnonyl, 2-methyldecyl, 2,3-dimethylbutyl, 2,3,3-trimethylbutyl, 3-methylbutyl Til, 3-methylpentyl, 3-ethylpentyl, 4-methylpentyl, 4-ethylhexyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,4,4-trimethylpentyl, 2,3,3 4-tetramethylpentyl, 3-methylhexyl, 2,5-dimethylhexyl, 3-ethylhexyl, 3,5,5-trimethylhexyl, 4-methylhexyl, 6-methylheptyl, 3,7-dimethyloctyl, 6- Among them, methyl octyl and the like are mentioned, and among these, from the viewpoint of liquid crystallinity, a linear alkyl group having 4 to 15 carbon atoms and further 8 to 12 carbon atoms is preferable, and n-octyl and n-dodecyl are particularly preferable.

Examples of the cyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent represented by R ¹ include a cycloalkyl group having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl and cyclopentyl, and a cyclohexylphenyl group. And a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms such as biscyclohexyl group, biphenylenyl, triphenylenyl, indenyl, naphthyl, azulenyl, fluorenyl, acenaphthhienyl, phenalenyl, anthryl, phenanthryl and the like.

Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms which may have a substituent represented by R ¹ include thienyl, benzothienyl, furyl, benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidyl, pyridazinyl. , Pyrazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, quinolyl, isoquinolyl, carbazolyl, furfuryl and the like.

  Examples of the group that can be substituted with the linear or branched hydrocarbon group, cyclic hydrocarbon group, and aromatic heterocyclic group include a hydroxyl group, a mercapto group, an amino group, a cyano group, a nitro group, and a trifluoromethyl group. And halogen atoms.

Examples of the halogen atom represented by R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
Examples of the lower alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group. Examples of the lower alkoxy group include carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group. Examples thereof include 1 to 6 linear or branched alkoxy groups, and a methyl group, an ethyl group, a methoxy group, an ethoxy group, and the like are particularly preferable from the viewpoint of sufficiently exhibiting liquid crystallinity.

  W represents a single bond, an oxygen atom or a sulfur atom, and is preferably a sulfur atom or a single bond.

Z represents a single bond, —CH ₂ CH ₂ —, —C═C—, —C≡C—, —COO—, —OCO—, —N≡N— or —CH═N—. A single bond is preferred.

Y may have a substituent, —CH ₂ —, —O—, —S—, —C═C—, —C≡C—, —COO—, —OCO—, —CO—, ^{_{-SO 2 -, - SiR 3 R}} 4, -GeR 5 R 6 -, - NR 7 -, - CH = N-, 1 carbon atoms containing a group selected from cyclic alkylene group, aromatic ring group and the heterocyclic group To 25 divalent groups (wherein R ^{3 to} R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), the divalent group represented here is A plurality may be selected. Examples of the divalent group include a linear or branched alkylene group having 1 to 25 carbon atoms, a linear or branched alkyleneoxy group having 1 to 25 carbon atoms, and a linear or branched group having 1 to 25 carbon atoms. another of alkylenethio groups such as including _{-O-, -CH 2 O (CH 2} ) m -, - CH 2 (OCH 2 CH 2) m O -, - CH 2 O (CH 2 CH 2 O _{) m CH 2 CO -, -} (CH 2) m O -, - (CH 2) m CH 2 O -, - O (CH 2) m O -, - CH 2 O (CH 2 CH 2 O) m ( CH ₂ ) _m O— etc., including —S—, —CH ₂ S (CH ₂ ) _m , —CH ₂ (SCH ₂ CH ₂ ) _m S—, —CH ₂ S (CH ₂ CH ₂ S) _m CH ₂ CS-, etc., as containing _{-C = C-, -CH 2 CH =} CH (CH 2) m -, - CH 2 (CH = CHCH 2 CH 2) m CH = CH- _{-CH 2 CH = CH (CH 2} CH 2 CH = CH) m CH 2 CH = CH- and the like, as including _{-C≡C-, -CH 2 C≡C (CH 2} ) m -, - CH 2 _{(C≡CCH 2 CH 2) m C≡C} -, - CH 2 C≡C (CH 2 CH 2 C≡C) m CH 2 C≡C- , etc., as including -COO-, -CH ₂ COO _{(CH 2) m, -CH 2} (COOCH 2 CH 2) m COO -, - CH 2 COO (CH 2 CH 2 COO) m CH 2 COO- , etc., as including -OCO-, -CH ₂ OCO ( _{CH 2) m, -CH 2 (} OCOCH 2 CH 2) m OCO -, - CH 2 OCO (CH 2 CH 2 OCO) m CH 2 OCO- such as including a -CO-, -CH ₂ CO (CH _{2) m, -CH 2 (COCH} 2 CH 2) m CO -, - CH 2 CO (CH 2 CH 2 CO) m CH 2 C - etc., -SO ₂ - as _{including, -CH 2 SO 2 (CH 2} ) m, -CH 2 (SO 2 CH 2 CH 2) m SO 2 -, - CH 2 SO 2 (CH 2 CH 2 SO ₂ ) _m CH ₂ SO ₂ — and the like, including —CH═N—, —CH ₂ CH═N (CH ₂ ) _m , —CH ₂ (CH═NCH ₂ CH ₂ ) _m CH═N—, — _{CH 2 CH = N (CH 2} CH 2 CH = N) m CH 2 CH = N- , and the like.
Examples of those containing a cyclic alkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, 1,4-dimethylenecyclohexane and the like, preferably cyclohexylene, 1,4-dimethylenecyclohexane, etc. Is mentioned. Examples of those containing an aromatic ring group include phenylene, 1,4-dimethylenebenzene, biphenylenylene, triphenylenylene, indenylene, naphthylene, azulenylene, fluorenylene, acenaphthylene, phenalylene, anthrylene, phenanthrylene, and the like. Preferably, phenylene, naphthylene, 1,4-dimethylenebenzene and the like are mentioned. Those containing a heterocyclic group include thienylene, benzothienylene, furylene, benzofurylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, pyrimidylene, pyridazinylene, pyrazinylene, oxazolylene, isoxazolylene, thiazolylene, isothiazolylene, benzoxazolylene, benzoxazolylene, Thiazolylene, benzimidazolylene, quinolylene, isoquinolylene, carbazolylene, furfurylene, and the like are preferable, and thienylene, pyridylene, carbazolylene, and the like are preferable.
When Y includes a cyclic alkylene group, an aromatic ring group or a heterocyclic group, a linear or branched alkylene group having 1 to 25 carbon atoms or a linear or branched alkylene group having 1 to 25 carbon atoms What further contains an oxy group etc. is more preferable.
In the above formula, m represents an integer of 0 to 10, preferably 2 to 10.
Moreover, as a C1-C8 alkyl group shown by R < ³ > -R < ⁷ >, a methyl group, an ethyl group, a propyl group, etc. are preferable.

  Specific examples of the linear or branched alkylene group having 1 to 25 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, peptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, Pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene, heneicosylene, docosylene, tricosylene, tetracosylene, 1-methylethylene, 1-methylpropylene, 1-ethylpropylene, 1-n-propylpropylene, 1-methylbutylene, 1- Ethylbutylene, 1-n-propylbutylene, 1-n-butylbutyl, 1-methylpentylene, 1-ethylpentylylene, 1-n-propylpentylylene, 1-n-pentylpentyl 1-methylhexylene, 1-ethylhexylene, 1-n-propylhexylene, 1-n-butylhexylene, 1-n-pentylhexylene, 1-n-hexylhexylene, 1-methylheptylene, 1-ethylheptylene, 1-n-propylheptylene, 1-n-butylheptylene, 1-n-pentylheptylene, 1-n-heptylheptylene, 1-methyloctylene, 1-ethyloctylene, 1 -N-propyloctylene, 1-n-butyloctylene, 1-n-pentyloctylene, 1-n-hexyloctylene, 1-n-heptyloctylene, 1-n-octyloctylene, 1-methylnonylene 1-ethylnonylene, 1-n-propylnonylene, 1-n-butylnonylene, 1-n-pentylnonylene, 1-n-hexylnonylene 1-n-heptylnonylene, 1-n-octylnonylene, 1-n-nonylnonylene, 1-methyldecylene, 2-methylbutylene, 2-ethylbutylene, 2-n-propylpentylene, 2-methylhexylene, 2-ethylhexylene, 2-n-propylhexylene, 2-n-butylhexylene, 2-methylheptylene, 2-ethylheptylene, 2-n-propylhexylene, 2-n-butylheptylene, 2-n-pentylhe Butylene, 2-methyloctylene, 2-ethyloctylene, 2-n-propyloctylene, 2-n-butyloctylene, 2-n-pentyloctylene, 2-n-hexyloctylene, 2-methylnonylene 2-ethylnonylene, 2-n-propylnonylene, 2-n-butylnonylene, 2-n-pentylnonylene, 2-n- Hexylnonylene, 2-n-heptylnonylene, 2-methyldecylene, 2,3-dimethylbutylene, 2,3,3-trimethylbutylene, 3-methylbutylene, 3-methylpentylene, 3-ethylpentylene, 4 -Methylpentylene, 4-ethylhexylene, 2,3-dimethylpentylene, 2,4-dimethylpentylene, 2,4,4-trimethylpentylene, 2,3,3,4-tetramethylpentylene, 3-methylhexylene, 2,5-dimethylhexylene, 3-ethylhexylene, 3,5,5-trimethylhexylene, 4-methylhexylene, 6-methylheptylene, 3,7-dimethyloctylene, 6- And methyl octylene. Among these, from a liquid crystalline viewpoint, a C4-C15 alkylene group is preferable and a decylene and undecylene are more preferable.

  Examples of the linear or branched alkyleneoxy group having 1 to 25 carbon atoms include methyleneoxy, ethyleneoxy, butyleneoxy, hexyleneoxy, octyleneoxy, decyleneoxy, and undecyleneoxy. From the viewpoint of liquid crystallinity, carbon An alkyleneoxy group of 4 to 15 is preferable, and decyleneoxy and undecyleneoxy are more preferable.

  Examples of the linear or branched alkylenethio group having 1 to 25 carbon atoms include methyleneoxy, ethyleneoxy, butyleneoxy, hexyleneoxy, octyleneoxy, decyleneoxy, and undecyleneoxy. From the viewpoint of liquid crystallinity, carbon An alkylenethio group of 4 to 15 is preferable, and decylenethio and undecylenethio are more preferable.

  In addition, examples of the group that can be substituted with such a divalent group include a halogen atom, a nitro group, a mercapto group, a cyano group, and an amino group.

  B represents an oxygen atom or a sulfur atom, preferably a sulfur atom.

The side chain type conductive polymer of the present invention is a combination of a reactive derivative of an aromatic π-conjugated compound constituting a main chain portion and a reactive derivative constituting a corresponding side chain portion liquid crystal group. By performing etherification, esterification reaction, and carbon-carbon bonding reaction, a precursor monomer can be produced, and this can be produced by polymerizing it by a known method such as the Suzuki coupling method or the Yamamoto method.
Below, the synthesis example of a typical thing is shown among the compounds shown by General formula (1) or (2).

[Wherein, X ¹ represents a hydrogen atom, a halogen atom, a benzenesulfonyl group, a p-toluenesulfonyl group, a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group, X ² represents a halogen atom, and L is the same as defined above. L ′ is the following (3 ′) to (7 ′):

(Wherein R ¹ , R ² , W, B, D, E, and Z are the same as those described above). ]

In the above formula, X ¹ varies depending on the polymerization method used, but is preferably a halogen atom when using the Suzuki coupling method or the Yamamoto method.

  As etherification reaction, Williamson reaction of alkyl halide and alcohol (amide type such as DMF, ether type such as tetrahydrofuran or ketone type solvent such as acetone, methyl ethyl ketone, cyclohexanone, potassium carbonate, sodium hydroxide, hydrogenation) Reaction in the presence of an alkali such as sodium, sodium methylate, natylium ethylate, t-butoxypotassium), or Mitsunobu reaction reported in Bull, Chem, Soc, Jpn 40 (1967) 2380 (in tetrahydrofuran, azodicarbon And the like in the presence of ethyl acid and triphenylphosphine).

  As the esterification reaction, an acid chloride and an alcohol are reacted in the presence of a base such as pyridine or triethylamine, or a dehydration condensation reaction using dicyclohexylcarbodiimide and 4-dimethylaminopyridine is used.

  As a carbon-carbon bond formation reaction, an organic halide is reacted with a Grignard reagent or a boron compound under a Ni or Pd catalyst, or sodium hydroxide, potassium-t-butoxide, sodium hydride, lithium diisopropylamide, or the like. Reaction of a metallated organic compound with an organic halide or the like is used due to the strong base.

  The reactive derivative (for example, (a) to (f)) of the aromatic π-conjugated compound as a raw material can be synthesized by a known method. For example, By Peter Bauerle, Angew.Chem.Int.Ed.Engl.29 (1990) 4,419-420, Denise R. Rutherford., Marcomolecules, 1992, 25, 2294-2306, Claudius D'Silva, J. Org. ., 1998,63,6715-6718, Masashi kijima, Mol.Cryst and Liq.Cryst., 2001,364,911-918, Mazime, Ranger., Macromolecules, 1997, 30, 7686, Dirk, Marsitzky., J. Am. It may be synthesized according to the method described in Chem. Soc., 2001, 123, 6965.

  Moreover, the reactive derivative of the compound which comprises a side chain part liquid crystal group is also compoundable by a well-known method. For example, in the methods described in JP-A-10-231260, JP-A-9-59267, Chung K. Lai, Liquid Crystals, 2002, 29, 7, 915-920, Wenjie Li, Chem. Mater. 1999, 11, 458-465. According to this, synthesis may be performed.

  L is a rod-like semiconductor liquid crystal group represented by the above formulas (3) to (7), and Y is a divalent group containing at least a group selected from a cyclic alkylene group, an aromatic ring group and a heterocyclic group. An example of a method for synthesizing the compound represented by the general formula (2) when it is a group is as follows.

[Wherein, G represents an aromatic ring group, and X ¹ , X ² , L ′ and m represent the same as described above. ]

  That is, by reacting a reaction mixture of 2,7-dihalogen-substituted fluorenone (i) and G-OH such as phenol in methanesulfonic acid at 140 ° C. for 6 hours, compound (j) is obtained (Gang Yu, et al. Adv, Mater, 2002, 14, No11, June 5, Chia Hung, et. al. Macromolcules 2002, 35, 9673), and the obtained compound (j) is subjected to the etherification reaction or esterification reaction described above. The precursor monomer body (2b) or (2c) can be obtained by introducing a side chain liquid crystal group.

By polymerizing the precursor monomers ((1a), (2a), (2b), (2c)) obtained as described above, the side chain type conductive polymer of the present invention can be obtained. As the polymerization method, when X ¹ is a halogen atom in the precursor monomer, the Rieke method (Macromolecules 1993, 26, 3462), Still coupling (Macromolecules 2000, 133, 3634), Suzuki coupling (Chem. Mater 1998). , 10, 1052), McCullough method (J. Org. Chem 1993, 58, 904 and Adv. Mater 1999, 11, 250), Yamamoto coupling (Macromolecules 1992, 25, 1214), etc., X ¹ is a hydrogen atom In this case, the polymer is obtained by a polymerization method using an oxidizing agent such as FeCl ₃ (Synth. Met 1989, 28, C349), an electrochemical oxidation polymerization method (J. Chem. Soc., ChemCommum 1986, 873), etc. Can be obtained.

  The side chain type conductive polymer thus obtained preferably has a number average molecular weight of 1,000 to 10,000,000, particularly preferably 1,000 to 500,000.

  Examples of the film forming method for the side chain type conductive polymer of the present invention include chlorine solvents such as chloroform, methylene chloride, dichlorotan and dichlorobenzene, ether solvents such as tetrahydrofuran, t-butyl methyl ether and diisopropyl ether, and benzene. The polymer was dissolved in an appropriate solvent such as an aromatic hydrocarbon solvent such as toluene or xylene, a ketone solvent such as acetone or methyl ethyl ketone (MEK), or an ester solvent such as ethyl acetate or butyl acetate. Form a film from a solution by spin coating, casting, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, ink jet printing, etc. Can do.

  Further, a macroscopically oriented state can be formed by an external stress such as an electric field, a magnetic field, a shear stress, or rubbing, and electrical and optical anisotropy can be expressed.

  The side chain type conductive polymer of the present invention is low in the conventional polymer compound such as polyethylene, other main chain type conductive polymer and side chain type conductive polymer, and so as not to weaken the film strength. By mixing molecular liquid crystal or the like, a liquid crystalline composition, a fluorescent composition, a charge transporting composition, or the like can be obtained.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the scope of these examples. In addition, the measurement of ¹ H-NMR was measured in deuterated chloroform solvent using tetramethylsilane as a reference substance. The phase transition temperature was measured by increasing the temperature at 3 ° C./min on a Mettler hot stage and observing it under a polarizing microscope. Each liquid crystal phase is indicated by the following abbreviations.
Iso: isotropic liquid, Ne: nematic phase, Sm: smectic phase, SmA: smectic A phase, SmB: smectic B phase, SmE: smectic E phase, SmF: smectic F phase, SmX: smectic X phase, Cry: crystal , G: Glass transition

Example 1 Synthesis of Polymer 1 below

Example 1-1

  To a solution of 47.2 g of 10-bromodecanol in 300 ml of methylene chloride, 19.3 g of 3,4-dihydro-2H-pyran was added. Next, 2.0 ml of 35% hydrochloric acid was added little by little at 0 ° C., followed by stirring for 3 hours while maintaining the temperature at 0 ° C. The obtained reaction solution was added to a saturated aqueous sodium hydrogen carbonate solution to stop the reaction, and the methylene chloride layer was separated, washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off to give 2- 69.7 g of (10-bromodecyloxy) tetrahydropyran was obtained.

Example 1-2

  In an argon atmosphere, 1/5 volume of a solution prepared by dissolving 45.0 g of 2- (10-bromodecyloxy) tetrahydropyran in 3.75 g of metal magnesium in a solution of 150 ml of diethyl ether and 45 ml of anhydrous tetrahydrofuran was added and heated. did. After the start of the reaction, the remaining solution was added dropwise at such a rate that the reflux did not stop. Subsequently, the mixture was refluxed and stirred for 4 hours to prepare a Grignard reagent.

A mixture composed of 26.0 g of 3-bromothiophene and 0.3 g of 1,3-bis (diphenylphosphino) propanenickel (II) chloride Ni (dppp) Cl ₂ was cooled to 0 ° C., and the above Grignard reagent was added dropwise. . After the dropwise addition, the mixture was further stirred at reflux for 9 hours. The reaction mixture was poured into a saturated aqueous ammonium chloride solution, and the organic layer was separated. Further, the aqueous layer was extracted with diethyl ether, combined with the previously separated organic layer, and washed successively with a saturated aqueous ammonium chloride solution and saturated brine. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography using hexane-methylene chloride (10: 1 to 2: 1) as an eluent. , 41.2 g of 3- (10-tetrahydropyran-2-yloxydecyl) thiophene was obtained.

Example 1-3

  To a solution of 39.2 g of 3- (10-tetrahydropyran-2-yloxydecyl) thiophene in 390 ml of methanol, 1.15 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 20 hours. . 4.0 g of sodium bicarbonate was added to the reaction solution to stop the reaction, insoluble materials were removed, the solvent was distilled off, and the resulting crude product was treated with hexane-methylene chloride (6: 1 to 0: 1). After purification by silica gel column chromatography as an eluent, recrystallization was performed with hexane to obtain 17.7 g of 3-thiophenedecanol.

¹ H-NMR (CDCl ₃ / TMS) δ: 7.24 ppm (dd, 1H), 6.93 (dd, 1H), 6.92 (dd, 1H), 3.64 (t, 2H), 2.62 (t, 2H), 1.58 ( m, 4H), 1.30 (m, 12H), no proton at the hydroxyl group was detected

Example 1-4

  To a solution obtained by dissolving 10.4 g of 3-thiophendecanol in 100 ml of dimethylformamide, a solution obtained by dissolving 19.3 g of N-bromosuccinimide in 80 ml of dimethylformamide at −15 ° C. was dropped and kept at −15 ° C. Stir for 48 hours. The reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with hexane. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate and water in that order, dried over anhydrous sodium sulfate, the solvent was distilled off, and 2,5-dibromo-3- (10-hydroxydecan-1-yl was obtained as a crude product. ) -Thiophene 16.5g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 6.77 (s, 1H), 3.64 (t, 2H), 2.50 (t, 2H), 1.56 (m, 4H), 1.29 (m, 12H), hydroxyl proton Was not detected

Example 1-5

  Under an argon atmosphere, 1/5 of a solution prepared by dissolving 41.0 g of p-bromooctylbenzene in 150 ml of anhydrous THF in 4.1 g of metal magnesium was added and heated. After the start of the reaction, the remaining solution was added dropwise at a rate at which reflux did not stop, and the mixture was further refluxed for 2 hours to prepare a Grignard reagent. The obtained Grignard reagent was cooled to −50 ° C., and then a solution obtained by dissolving 18.6 g of trimethyl borate in 20 ml of anhydrous THF was added dropwise. After dropping, the mixture was stirred overnight at -30 to -15 ° C. The reaction mixture was poured into ice water, 35% hydrochloric acid was added dropwise to make the mixture acidic, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was extracted with benzene, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting crude product was recrystallized from hexane to obtain 26.4 g of p-octylphenylboric acid.

Example 1-6

Under an argon atmosphere, it consists of 15.0 g of p-octylphenylboric acid, 11.7 g of 2-bromo-6-methoxynaphthalene, 1.14 g of tetrakistriphenylphosphine palladium (0) Pd (PPh) ₄ and 110 ml of dimethoxyethane. A solution prepared by dissolving 6.8 g of sodium carbonate in 54 ml of water was added to the mixed solution, and the mixture was heated and stirred at 65 to 70 ° C. for 8 hours. The reaction mixture was extracted with toluene, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography using hexane-toluene (1: 0 to 2: 1) as an eluent to give 2- (4′-octylphenyl) -6- 15.5 g of methoxynaphthalene was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.96 (d, 1H), 7.80 (d, 1H), 7.78 (d, 1H), 7.71 (dd, 1H), 7.62 (d, 2H), 7.28 (d , 2H), 7.17 (dd, 1H), 7.15 (s, 1H), 3.94 (s, 3H), 2.66 (t, 3H), 1.66 (m, 2H), 1.28 to 1.43 (m, 10H), 0.89 ( t, 3H)

Example 1-7

Under an argon atmosphere, 18.6 g of 1M BBr ₃ · methylene chloride solution was added dropwise at 0 ° C. to a solution of 15.3 g of 2- (4′-octylphenyl) -6-methoxynaphthalene in 150 ml of methylene chloride. The mixture was warmed to room temperature and stirred for 48 hours. The reaction solution was poured into ice water, and the resulting white precipitate was dissolved in diethyl ether, and then the organic layer was separated, washed with a dilute sodium bicarbonate aqueous solution and water in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 14.6 g of 2- (4′-octylphenyl) -6-hydroxynaphthalene as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.96 (s, 1H), 7.80 (d, 1H), 7.74 (d, 1H), 7.70 (dd, 1H), 7.61 (d, 1H), 7.28 (d , 1H), 7.17 (d, 1H), 7.12 (dd, 1H), 4.86 (s, 1H), 2.66 (t, 2H), 1.65 (m, 2H), 1.28 to 1.45 (m, 10H), 0.89 ( t, 3H)

Example 1-8

  2.39 g of 2,5-dibromo-3- (10-hydroxydecan-1-yl) -thiophene obtained in Example 1-4, 2- (4′-octylphenyl) obtained in Example 1-7 ) 2.88 g of 40% ethyl azodicarboxylate / toluene solution was added dropwise at 0 ° C. to a mixed solution consisting of 2.0 g of -6-hydroxynaphthalene, 1.89 g of triphenylphosphine and 60 ml of THF, and the mixture was raised to room temperature. Stir for hours. The reaction mixture was concentrated, and the resulting residue was purified by silica gel column chromatography using hexane-toluene (9: 1) as an eluent, then recrystallized from acetone to give 2,5-dibromo-3- { 2.87 g of 10- [2- (4′-octylphenyl) naphthalen-6-yl] oxydecan-1-yl} thiophene was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.95 (d, 1H), 7.77 (d, 2H), 7.69 (dd, 1H), 7.61 (d, 2H), 7.28 (d, 2H), 7.16 (dd , 1H), 7.15 (s, 1H), 6.77 (s, 1H), 4.09 (t, 2H), 2.66 (t, 2H), 2.50 (t, 2H), 1.85 (m, 2H), 1.65 (m, 2H), 1.50 (m, 2H), 1.32 (m, 22H), 0.89 (t, 3H)
Phase transition temperature Cry ・ SmE 59.0 ℃ SmA 71.6 ℃ Iso

Example 1-9

Under an argon atmosphere, 0.13 g of bipyridine and 2.0 ml of DMF are added to 0.33 g of bis (1,5-cyclooctadiene) nickel (0) (hereinafter abbreviated as Ni (cod) ₂ ), and the mixture is stirred at room temperature for 10 minutes. After stirring, 2,5-dibromo-3- {10- [2- (4′-octylphenyl) -naphthalen-6-yl] -oxydecan-1-yl} -thiophene obtained in Example 1-8 A solution consisting of 0.70 g and 5 ml of DMF was added dropwise, and the mixture was heated and stirred at 90 ° C. for 45 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and the precipitated polymer was collected by filtration. The obtained polymer was again dissolved in 10 ml of chloroform, dropped into methanol (500 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration, and poly-3- {10- [2- (4′-octylphenyl) -naphthalen-6-yl] -oxydecan-1-yl} -2,5-thiophene (Polymer 1). 52 g was obtained. The phase transition temperature of this polymer was G · Sm · 171 ° C. (148 ° C.) · Iso, and the transition temperature of G and Sm could not be specified. The value in () indicates the phase transition temperature when the temperature is lowered. Further, the chemical structure of the obtained polymer 1 was determined by ¹ H-NMR measurement.

¹ H-NMR (CDCl _{3 /} TMS) δ 7.91 (1H), 7.4 to 7.8 (5H), 6.79 to 7.35 (6H), 4.0 (2H), 2.64 (4H), 1.79 (2H), 1.64 (2H) 1.15 ~ 1.55 (24H), 0.88 (3H)

The molecular weight of the polymer 1 obtained above was determined as a polystyrene conversion by gel permeation chromatography (hereinafter abbreviated as GPC) measurement. As a result, the weight average molecular weight (hereinafter abbreviated as Mw) 9800, the number average molecular weight (hereinafter, 7200 and a molecular weight distribution (hereinafter abbreviated as Mw / Mn) 1.4. Furthermore, for a film prepared by a cast method in a solution of this polymer or on a quartz plate, by absorption wavelength band and fluorescence spectrum (hereinafter abbreviated as PL) measurement by ultraviolet-visible spectrum (hereinafter abbreviated as UV-Vis) measurement. The emission wavelength band is shown below.
UV-Vis (chloroform solution); 258, 295, 394 nm
PL (chloroform solution, excitation wavelength 266 nm); 374, 536 nm
(Film, excitation wavelength 300 nm); 418, 539 nm
(Ψ = 0.18 vs fluorescein quantum efficiency)

Example 1-10

2,5-Dibromo-3- {10- [2- (4′-octylphenyl) -naphthalen-6-yl] -oxydecan-1-yl} -thiophene obtained in Example 1-8 under argon atmosphere After 0.71 g is dissolved in 20 ml of DMF by heating, 0.61 g of bis (pinacolato) diboron, 0.59 g of potassium acetate and [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) · PdCl ₂ (dppf) was added and stirred at 80 ° C. for 24 hours. The reaction solution was poured into water, extracted with diethyl ether, the organic layer was separated, and then the solvent was distilled off to obtain a crude thiophene borate product.

Furthermore, the 2,5-dibromo-3- {10- [2- (4′-octylphenyl) -naphthalene-6 obtained in Example 1-8] was added to the thiophene borate obtained above under an argon atmosphere. -Il] -oxydecan-1-yl} -thiophene 0.88 g, Pd (PPh) ₄ 0.023 g, 1 M aqueous sodium carbonate solution 10 ml and toluene 10 ml were added, and the mixture was refluxed and stirred at 100 ° C. for 4 days. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and the precipitated polymer was collected by filtration. The obtained polymer was again dissolved in 10 ml of chloroform, dropped into methanol (500 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration to obtain 0.75 g of polymer 1. The phase transition temperature of this polymer was G · Sm · 161 ° C. (144 ° C.) · Iso, and the transition temperature of G and Sm could not be specified. The value in () indicates the phase transition temperature when the temperature is lowered. Further, the chemical structure of the obtained polymer 1 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

The molecular weight of the polymer 1 obtained above was Mw6800, Mn5400, and Mw / Mn1.3 as determined by polystyrene conversion by GPC measurement. Furthermore, the absorption wavelength band by UV-Vis measurement in this polymer solution and the emission wavelength band by PL measurement are shown below.
UV-Vis (chloroform solution); 256, 297, 340 (sh), 394 (sh) nm
PL (chloroform solution, excitation wavelength 396 nm); 374, 536 (sh) nm
(Ψ = 0.3 vs fluorescein quantum efficiency)

Example 2 Synthesis of Polymer 2 below

Example 2-1

  A solution prepared by dissolving 30.2 g of p-methoxybenzaldehyde and 38.4 g of o-aminobenzenethiol in 190 ml of dimethyl sulfoxide was heated and stirred at 140 ° C. for 15 hours while the generated water was distilled off with a test tube. After pouring the reaction solution into ice water, the precipitated crude crystals were collected by filtration and then washed with ethanol to obtain 45.8 g of 2- (4'-methoxyphenyl) benzothiazole.

Example 2-2

  To a solution prepared by dissolving 45.8 g of 2- (4'-methoxyphenyl) benzothiazole in 930 ml of acetic acid, 36.5 g of bromine was added dropwise at room temperature over 30 minutes. After stirring at the same temperature for 40 minutes, 450 ml of water was added, and further heated and stirred at 80 ° C. for 10 hours. After allowing to cool, the deposited precipitate was collected by filtration and washed with water, a saturated aqueous sodium hydrogen carbonate solution, water and ethanol in this order. The obtained crude crystals were recrystallized from ethyl acetate to obtain 24.3 g of 2- (4'-methoxyphenyl) -6-bromobenzothiazole.

Example 2-3

  A suspension composed of 28.2 g of 2- (4'-methoxyphenyl) -6-bromobenzothiazole, 840 ml of 47% hydrobromic acid and 420 ml of acetic acid was heated and stirred at 100 to 115 ° C for 54 hours. After allowing to cool, the reaction mixture was poured into ice water, and the deposited precipitate was collected by filtration. The obtained crude crystals were washed with water and recrystallized with ethyl acetate to obtain 15.4 g of 2- (4'-hydroxyphenyl) -6-bromobenzothiazole.

Example 2-4

  To a solution obtained by dissolving 15.0 g of 2- (4′-hydroxyphenyl) -6-bromobenzothiazole in THF, 2.6 g of 60% sodium hydride was added little by little at 0 ° C., and the mixture was stirred at the same temperature for 30 minutes. To this suspension, 8.5 g of β-methoxyethoxymethoxychloride was added dropwise, and the mixture was further raised to room temperature and stirred for 15 hours. The reaction mixture was poured into ice water, and the deposited precipitate was collected by filtration. The obtained crude crystals were washed with methanol and hexane in this order to give 2- [4 ′-(β-methoxyethoxymethoxy) phenyl]- 17.5 g of 6-bromobenzothiazole was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.00 (d, 2H), 7.99 (d, 1H), 7.87 (d, 1H), 7.56 (dd, 1H), 7.16 (d, 2H), 5.34 (s , 2H), 3.85 (t, 2H), 3.57 (t, 2H)

Example 2-5

  Under ice-cooling, 4.57 g of 60% sodium hydride was suspended in diethyl ether, and 23.1 g of 1-dodecanethiol was added dropwise to this suspension, followed by stirring under reflux for 2 hours. Subsequently, ether was distilled off, 160 ml of N, N'-dimethylimidazolidinone was added to the obtained residue, and the mixture was heated to 60 ° C. To this suspension, 15 g of 2- [4 '-(β-methoxyethoxymethoxy) phenyl] -6-bromobenzothiazole was added, and the mixture was heated and stirred at the same temperature for 10 hours. After allowing to cool, the reaction mixture was poured into water and neutralized by adding a saturated aqueous ammonium chloride solution. The deposited precipitate was collected, washed with water and dried, and then 1.0 liter of methanol and 2.3 g of p-toluenesulfonic acid monohydrate were added and stirred under reflux for 26 hours. Subsequently, the reaction mixture was filtered while hot to remove methanol insolubles, and the obtained filtrate was concentrated to dryness to give 2- (4-hydroxyphenyl) -6-dodecylthiobenzothiazole as a crude product. 5 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.92 (d, 2H), 7.91 (d, 1H), 7.79 (s, 1H), 7.42 (d, 1H), 6.92 (d, 2H), 2.97 (t , 2H), 1.66 (m, 2H), 1.43 (m, 2H), 1.25 (m, 16H), 0.87 (t, 3H), no hydroxyl proton was detected.

Example 2-6

  2.80 g of 2,5-dibromo-3- (10-hydroxydecan-1-yl) thiophene obtained in Example 1-4, 2- (4-hydroxyphenyl)-obtained in Example 2-5 To a mixed solution consisting of 3.0 g of 6-dodecylthiobenzothiazole, 2.21 g of triphenylphosphine and 80 ml of THF, 3.67 g of 40% ethyl azodicarboxylate / toluene solution was added dropwise at 0 ° C. Stir for hours. The reaction mixture was concentrated, and the resulting residue was purified by silica gel column chromatography using hexane-toluene (6: 1 to 5: 1) as an eluent, and then recrystallized from acetone to give 2,5-dibromo. 0.82 g of -3- {10- [1- (6-dodecylthiobenzothiazol-2-yl) -phenyl] -oxydecan-1-yl} -thiophene was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.04 (d, 2H), 7.97 (d, 1H), 7.81 (d, 1H), 7.45 (dd, 1H), 6.99 (d, 2H), 6.78 (s , 1H), 4.03 (t, 2H), 2.98 (t, 2H), 2.50 (t, 2H), 1.81 (m, 2H), 1.67 (m, 2H), 1.25 to 1.54 (m, 32H), 0.88 ( t, 3H)
Phase transition temperature Cry 77.1 ℃ (SmX 63.1 ℃) Iso

Example 2-7

Under an argon atmosphere, 0.16 g of bipyridine and 2 ml of DMF were added to 0.28 g of Ni (cod) ₂ , stirred for 10 minutes at room temperature, and then 2,5-dibromo-3- {obtained in Example 2-6. A solution consisting of 0.63 g of 10- [1- (6-dodecylthiobenzothiazol-2-yl) -phenyl] -oxydecan-1-yl} -thiophene and 5 ml of DMF was added dropwise and stirred at 65 ° C. for 45 hours. . The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and the precipitated polymer was collected by filtration. The obtained polymer was again dissolved in 10 ml of chloroform, dropped into methanol (500 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration, and poly-3- {10- [1- (6-dodecylthiobenzothiazol-2-yl) phenyl] -oxydecan-1-yl} -2,5-thiophene (Polymer 2). 48 g was obtained. The phase transition temperature of this polymer is G · 113 ° C. · Sm · 137 ° C. (124 ° C.) · Iso, and the value in () indicates the phase transition temperature when the temperature is lowered. Further, the chemical structure of the obtained polymer 2 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

The molecular weight of the polymer 2 obtained above was Mw9874, Mn6210, and Mw / Mn1.6 as determined by polystyrene conversion by GPC measurement. Furthermore, the absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement are shown below about the film created by the casting method in the polymer solution or on the quartz plate.
UV-Vis (chloroform solution) 333, 400 nm
PL (chloroform solution, excitation light 352 nm) 407, 538 nm
(Film, excitation light 365 nm) 404,548 nm

Example 3 Synthesis of Polymer 3 below

Example 3-1

A solution consisting of 155 g of 11-aminoundecanoic acid, 102 g of 2,5-dimethoxytetrahydrofuran, 1.0 kg of pyridine, 770 g of acetic acid and 410 ml of water was heated and stirred at 100 ° C. for 48 hours, and then the reaction solution was concentrated to dryness. Next, the residue thus obtained was dissolved in 800 ml of methanol, 10 ml of concentrated sulfuric acid was added, and the mixture was stirred at reflux for 26 hours. The reaction solution was concentrated to dryness, poured into water, and extracted with diethyl ether. The separated organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting crude product was purified by distillation under reduced pressure to obtain 175.9 g (bp) of methyl 11- (1-pyrrolyl) undecanoate.
134-137 ° C./0.1 torr).

Example 3-2

  To a solution obtained by dissolving 111 g of methyl 11- (1-pyrrolyl) undecanoate in toluene, 260 g of a 65% sodium bis (2-methoxyethoxy) aluminum hydride / toluene solution was added dropwise at 0 ° C. Stir for 24 hours. After pouring the reaction solution into ice water, 35% hydrochloric acid was added to dissolve the gel. Further, the separated toluene layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain 103.7 g of 11- (1-pyrrolyl) undecanol as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 6.64 (t, 2H), 6.13 (t, 2H), 3.85 (t, 2H), 3.64 (t, 2H), 1.75 (m, 2H), 1.56 (m , 2H), 1.27 (m, 14H)

Example 3-3

  To a solution obtained by dissolving 10.0 g of 11- (1-pyrrolyl) undecanol in 120 ml of dimethylformamide, a solution obtained by dissolving 13.8 g of N-bromosuccinimide in 60 ml of dimethylformamide was added dropwise at -30 ° C. It stirred for 48 hours, keeping. The reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with hexane. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate and water in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 15.4 g of 11- (2,5-dibromopyrrolyl) undecanol as a crude product. It was.

¹ H-NMR (CDCl _{3 /} TMS) δ: 6.14 (s, 2H), 3.93 (t, 2H), 3.62 (t, 2H), 1.65 (m, 2H), 1.54 (m, 2H), 1.23 to 1.30 (m, 14H)

Example 3-4

  2.62 g of 11- (2,5-dibromopyrrolyl) undecanol obtained in Example 3-3 and 2- (4′-octylphenyl) -6-hydroxynaphthalene obtained in Example 1-7. To a mixed solution consisting of 0 g, 1.89 g of triphenylphosphine and 60 ml of THF, 3.16 g of 40% ethyl azodicarboxylate / toluene solution was added dropwise at 0 ° C., and the mixture was warmed to room temperature and stirred for 48 hours. The reaction mixture was concentrated, and the resulting residue was purified by silica gel column chromatography using hexane-toluene (9: 1) as an eluent, then recrystallized from acetone to give 2,5-dibromo-1- { 11- [2- (4′-octylphenyl) naphthalen-6-yl] oxyundecyl} pyrrole 2.69 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.95 (d, 1H), 7.77 (d, 2H), 7.69 (dd, 1H), 7.61 (d, 2H), 7.28 (d, 2H), 7.16 (dd , 1H), 7.15 (s, 2H), 6.16 (s, 2H), 4.08 (t, 2H), 3.95 (t, 2H), 2.66 (t, 2H), 1.85 (m, 2H), 1.65 (m, 2H), 1.50 (m, 2H), 1.28 (m, 24H), 0.89 (t, 3H)
Phase transition temperature Cry ・ SmX 48.6 ℃ SmA 73.5 ℃ Iso

Example 3-5

Under an argon atmosphere, 0.13 g of bipyridine and 2 ml of DMF were added to 0.33 g of Ni (cod) ₂ and stirred at room temperature for 10 minutes, and then 2,5-dibromo-1- {obtained in Example 3-4 was used. A solution consisting of 0.35 g of 11- [2- (4′-octylphenyl) -naphthalen-6-yl] -oxyundecyl} pyrrole and 5 ml of THF was added dropwise, and the mixture was heated and stirred at 65 ° C. for 3 days. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and the precipitated polymer was collected by filtration. Again, the obtained polymer was dissolved in 10 ml of THF, dropped into methanol (500 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration, and 0.27 g of poly-1- {11- [2-4′-octylphenyl) -naphthalen-6-yl] -oxyundecyl} -2,5-pyrrole (Polymer 3) was obtained. Obtained. The phase transition temperature of this polymer is G · 145 ° C. Sm · 183 ° C. (170 ° C.) · Iso, and the value in () indicates the phase transition temperature when the temperature is lowered. Further, the chemical structure of the obtained polymer 3 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

The molecular weight of the polymer 3 obtained above was Mw8652, Mn7392, and Mw / Mn1.17 as determined by polystyrene conversion by GPC measurement. Furthermore, the absorption wavelength band by the UV-Vis measurement and the emission wavelength band by the PL measurement of the film prepared by the casting method on the polymer solution or on the quartz plate are shown below.
UV-Vis (chloroform solution) 258, 294 nm
PL (chloroform solution, excitation light 310 nm) 375, 509 nm
(Film, excitation light 250 nm) 451 nm

Example 4 Synthesis of Polymer 4 below

Example 4-1

  2.0 g of 11- (2,5-dibromopyrrolyl) undecanol obtained in Example 3-3, 2- (4-hydroxyphenyl) -6-dodecylthiobenzothiazole 2 obtained in Example 2-5 To a mixed solution consisting of 0.0 g, 1.47 g of triphenylphosphine and 60 ml of THF, 2.46 g of 40% ethyl azodicarboxylate / toluene solution was added dropwise at 0 ° C., and the mixture was warmed to room temperature and stirred for 68 hours. The reaction mixture was concentrated, and the resulting residue was purified by silica gel column chromatography using hexane-toluene (8: 1 to 5: 1) as an eluent, and then with an acetone-methanol (2: 1) mixture. Recrystallization yielded 1.71 g of 2,5-dibromo-1- {11- [1- (6-dodecylthiobenzothiazol-2-yl) phenyl] oxyundecyl} pyrrole.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.01 (d, 2H), 7.93 (d, 1H), 7.81 (d, 1H), 7.44 (dd, 1H), 6.99 (d, 2H), 6.16 (s , 2H), 4.03 (t, 2H), 3.95 (t, 2H), 2.97 (t, 2H), 1.81 (m, 2H), 1.67 (m, 2H), 1.25 to 1.53 (m, 34H), 0.88 ( t, 3H)
Phase transition temperature Cry 69.3 ℃ (SmB 65.0 ℃) Iso

Example 4-2

Under an argon atmosphere, 0.13 g of bipyridine and 2 ml of DMF were added to 0.33 g of Ni (cod) ₂ and stirred at room temperature for 10 minutes, and then 2,5-dibromo-1- {obtained in Example 4-1 was used. A solution comprising 0.81 g of 11- [1- (6-dodecylthiobenzothiazol-2-yl) -phenyl] -oxyundecyl} pyrrole, 2 ml of THF and 5 ml of DMF was added dropwise, and the mixture was heated and stirred at 75 ° C. for 24 hours. . The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and then neutralized with aqueous ammonia. Further, the precipitated polymer was collected by filtration, extracted with chloroform, washed with water, dried over sodium carbonate, and then the solvent was distilled off to remove poly-1- {11- [1- (6-dodecylthiobenzothiazole-2- Yl) -phenyl] -oxyundecyl} -2,5-pyrrole (polymer 4) 0.47 g was obtained. The phase transition temperature of this polymer was G · Sm · 109 ° C. (101 ° C.) · Iso, and the transition temperature of G and Sm could not be specified. The value in () indicates the phase transition temperature when the temperature is lowered. Further, the chemical structure of the obtained polymer 4 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

The molecular weight of the polymer 4 obtained above was Mw5600, Mn4100, and Mw / Mn1.4 as determined by polystyrene conversion by GPC measurement. Furthermore, the absorption wavelength band by UV-Vis measurement in this polymer solution and the emission wavelength band by PL measurement are shown below.
UV-Vis (chloroform solution) 333 nm
PL (chloroform solution, excitation light 370 nm) 408 nm

Example 5 Synthesis of Polymer 5 below

Example 5-1

  In a mixed solution consisting of 12.2 g of sodium hydroxide, 12.2 ml of water and 120 ml of toluene, 8.0 g of 2,7-dibromofluorene, 1.6 g of tetrabutylammonium bromide, and 2- (10-bromodecyloxy) A solution consisting of 18.2 g of tetrahydropyran and 30 ml of toluene was sequentially added and stirred at 60 ° C. for 16 hours. The organic layer was separated from the reaction solution, washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain 9,9′-bis (10-tetrahydropyran-2-yloxydecyl) as a crude product. ) -2,7-dibromofluorene 29.7 g was obtained.

Example 5-2

  29.7 g of a crude product of 9,9′-bis (10-tetrahydropyran-2-yloxydecyl) -2,7-dibromofluorene obtained in Example 5-1 was dissolved in 250 ml of methanol, 2.0 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 2 days. The solvent was distilled off from the reaction solution, and the resulting concentrate was purified by silica gel column chromatography using ethyl acetate-hexane (1:10 to 1: 1) as an eluent to obtain 9,9′-bis (10 -Hydroxydecyl) -2,7-dibromofluorene 11.1 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.52 (d, 2H), 7.45 (dd, 2H), 7.43 (s, 2H), 3.61 (t, 4H), 1.90 (m, 4H), 1.53 (m , 4H), 1.05-1.34 (m, 24H), 0.58 (m, 4H), and no proton of a hydroxyl group was detected.

Example 5-3

  Under an argon atmosphere, 9.0 g of 9,9′-bis (10-hydroxydecyl) -2,7-dibromofluorene obtained in Example 5-2, 12.0 milliliters of triethylamine, 0.69 g of dimethylaminopyridine, and After cooling a solution consisting of 45.0 ml of methylene chloride to −5 ° C., 5.4 g of p-toluenesulfonic acid chloride was added and stirred at the same temperature for 21 hours. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed with water, dilute hydrochloric acid, and water in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 11.6 g of 9,9'-bis [10- (4-toluenesulfonyl) oxydecan-1-yl] -2,7-dibromofluorene as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.78 (d, 4H), 7.52 (d, 2H), 7.45 (dd, 1H), 7.43 (m, 2H), 7.32 (d, 2H), 3.99 (t , 4H), 2.43 (s, 6H), 1.90 (m, 4H), 1.59 (m, 4H), 1.02-1.23 (m, 24H), 0.56 (m, 4H)

Example 5-4

  9,9′-bis [10- (4-toluenesulfonyl) oxydecan-1-yl] -2,7-dibromofluorene obtained in Example 5-3, 10.2 g, sodium iodide 6.5 g, and acetone A mixture consisting of 175 ml was stirred under reflux for 8 hours. The reaction mixture was concentrated, poured into water, and extracted with diethyl ether. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 7.49 g of 9,9'-bis (10-iododecyloxy) -2,7-dibromofluorene as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.52 (d, 2H), 7.46 (dd, 2H), 7.45 (d, 2H), 3.16 (t, 4H), 1.91 (m, 4H), 1.78 (m , 4H), 05 to 1.35 (m, 24H), 0.57 (m, 4H)

Example 5-5

  1.92 g of 9,9′-bis (10-iododecyloxy) -2,7-dibromofluorene obtained in Example 5-4, 2- (4′-octylphenyl) obtained in Example 1-7 ) A mixture consisting of 1.5 g of -6-hydroxynaphthalene, 1.24 g of potassium carbonate and 30 ml of cyclohexanone was stirred under reflux for 10 hours. The solvent was distilled off from the reaction solution, water was added to the obtained residue, and the mixture was extracted with diethyl ether. The organic layer was washed with water and dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography using hexane-benzene (10: 1 to 3: 1) as an eluent, and then hexane. -Recrystallized with a mixture of acetone and 9,9'-bis {10- [2- (4'-octylphenyl) naphthalen-6-yl] oxydecan-1-yl} -2,7-dibromofluorene. 98 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.94 (d, 2H), 7.76 (d, 4H), 7.69 (dd, 2H), 7.61 (4H), 7.51 (d, 2H), 7.45 (dd, 2H ), 7.44 (s, 2H), 7.28 (d, 4H), 7.14 (dd, 2H), 7.13 (s, 2H), 4.06 (t, 4H), 2.65 (t, 4H), 1.91 (m, 4H) , 1.81 (m, 4H), 1.66 (m, 4H), 0.98 to 1.58 (m, 44H), 0.88 (t, 6H), 58 (m, 4H)
Phase transition temperature Cry ・ SmE 76.4 ℃ SmB 108.6 ℃ Iso

Example 5-6

Under an argon atmosphere, 0.19 g of bipyridine and 2.0 ml of DMF were added to 0.33 g of Ni (cod) ₂ , and the mixture was stirred at room temperature for 10 minutes, and then the 9,9′-bis { A solution consisting of 0.64 g of 10- [2- (4′-octylphenyl) naphthalen-6-yl] oxydecan-1-yl} -2,7-dibromofluorene and 5 ml of THF was added dropwise and stirred at 65 ° C. for 45 hours. did. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and the precipitated polymer was collected by filtration. The obtained polymer was again dissolved in 10 ml of chloroform, dropped into methanol (500 ml), and then stirred and washed at room temperature for 24 hours. The precipitate was collected by filtration, and poly-9,9′-bis {10- [2- (4′-octylphenyl) naphthalen-6-yl] oxydecan-1-yl} -2,7-fluorene (polymer 5). 0.46 g was obtained. The phase transition temperature of this polymer was C · 185 ° C. (Sm 165 ° C.) · Iso. The value in () indicates the phase transition temperature when the temperature is lowered. Further, the chemical structure of the obtained polymer 5 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.
Elemental analysis value Theoretical value C, 87.67; H, 9.49
Measurement C, 87.29; H, 9.42

It was Mw116100, Mn21800, and Mw / Mn5.3 when the molecular weight of the polymer 5 obtained above was determined as polystyrene conversion by GPC measurement. Furthermore, the absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement are shown below about the film created by the casting method in the polymer solution or on the quartz plate.
UV-Vis (chloroform solution) 298, 390 nm
(Film) 300, 394 nm
PL (chloroform solution, excitation light 390 nm) 420, 441 nm
(Film, excitation light 369 nm) 425, 450 nm

Example 6 Synthesis of Polymer 6 below

Example 6-1

  A mixture consisting of 4.0 g of 2- (4-hydroxyphenyl) -6-dodecylthiobenzothiazole obtained in Example 2-5, 2.44 g of 10-bromodecanol, 2.59 g of potassium carbonate, and 50 ml of DMF was used. Stir at 100 ° C. for 20 hours. The reaction mixture was poured into water and acidified with dilute hydrochloric acid, and the precipitated crude crystals were collected by filtration. The obtained crude crystals were washed with water and dried to obtain 3.76 g of 2- [4- (10-hydroxydecan-1-yl) oxyphenyl] -6-dodecylthiobenzothiazole as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.01 (d, 2H), 7.93 (d, 1H), 7.81 (d, 1H), 7.44 (dd, 1H), 6.98 (d, 2H), 4.03 (t , 2H), 3.64 (t, 2H), 2.97 (t, 2H), 1.2 to 1.9 (m, 36H), 0.88 (t, 3H), hydroxyl protons were not detected.

Example 6-2

  Under an argon atmosphere, 2.16 g of 2- [4- (10-hydroxydecan-1-yl) oxyphenyl] -6-dodecylthiobenzothiazole obtained in Example 6-1 1.6 ml of triethylamine, dimethylamino A solution consisting of 0.09 g of pyridine and 50 ml of methylene chloride was cooled to 0 ° C. To this, 1.06 g of p-toluenesulfonic acid chloride was added, and the mixture was warmed to room temperature and stirred for 24 hours. The reaction solution was poured into water and the organic layer was separated, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 2.48 g of 2- {4- [10- (4-toluenesulfonyl) oxydecan-1-yl] oxyphenyl} -6-dodecylthiobenzothiazole as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.99 (d, 2H), 7.91 (d, 1H), 7.81 (d, 1H), 7.79 (d, 2H), 7.43 (dd, 1H), 7.34 (d , 2H), 6.98 (d, 2H), 4.02 (t, 4H), 2.97 (t, 2H), 2.44 (s, 3H), 1.15 to 1.90 (m, 36H), 0.87 (t, 3H)

Example 6-3

  2.48 g of 2- {4- [10- (4-toluenesulfonyl) oxydecan-1-yl] oxyphenyl} -6-dodecylthiobenzothiazole obtained in Example 6-2, sodium iodide 1. A reaction solution consisting of 4 g and 60 ml of acetone was stirred for 10 hours under reflux. The reaction solution was poured into water, extracted with toluene, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography using methylene chloride-hexane (1: 1 to 1: 0) as an eluent to give 2- [4- (10-iododecan-1-yl) oxy. 1.03 g of phenyl] -6-dodecylthiobenzothiazole was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.99 (d, 2H), 7.90 (d, 1H), 7.82 (d, 1H), 7.43 (dd, 1H), 6.98 (d, 2H), 4.03 (t , 2H), 3.19 (t, 2H), 2.97 (t, 2H), 1.82 (m, 4H), 1.67 (m, 2H), 1.2 to 1.55 (m, 30H), 0.88 (t, 3H)

Example 6-4

  0.22 g of 2,5-dibromofluorene, 1.0 g of 2- [4- (10-iododecan-1-yl) oxyphenyl] -6-dodecylthiobenzothiazole obtained in Example 6-3, benzyltriethylamine chloride A mixture consisting of 49 mg, 1.75 ml of a 50 wt% aqueous sodium hydroxide solution and 10 ml of DMSO was stirred at 60 ° C. for 2 hours. The reaction mixture was poured into water and extracted with methylene chloride, and then the organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography using methylene chloride-hexane (1: 3 to 2: 1) as an eluent, and 9,9′-bis {10- [1- 0.76-g of (6-dodecylthiobenzothiazol-2-yl) benzene-4-yl] oxydecan-1-yl} -2,7-dibromofluorene was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.98 (d, 4H), 7.90 (d, 2H), 7.82 (d, 2H), 7.52 (d, 2H), 7.44 (dd, 2H), 7.44 (s , 2H), 6.97 (d, 4H), 4.00 (t, 4H), 2.97 (t, 4H), 1.91 (m, 4H), 77 (m, 4H), 1.66 (m, 4H), 1.50 to 0.98 ( m,), 0.87 (t, 6H), 0.57 (m, 4H)
Phase transition temperature Cry · 108.0 (SmC 63.6 ℃) · Iso

Example 6-5

Under an argon atmosphere, 0.19 g of bipyridine and 2.0 ml of DMF were added to 0.33 g of Ni (cod) ₂ , and the mixture was stirred at room temperature for 10 minutes, and then 9,9′-bis { A solution consisting of 0.65 g of 10- [1- (6-dodecylthiobenzothiazol-2-yl) benzene-4-yl] oxydecan-1-yl} -2,7-dibromofluorene and 5 ml of THF was added dropwise. Stir at 48 ° C. for 48 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and the precipitated polymer was collected by filtration. The obtained polymer was again dissolved in 10 ml of chloroform, dropped into methanol (500 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration, and poly-9,9′-bis {10- [1- (6-dodecylthiobenzothiazol-2-yl) benzene-4-yl] oxydecan-1-yl} -2,7- 0.5 g of fluorene (polymer 6) was obtained. The polymer phase transition was from a crystal to an isotropic liquid at 200 ° C. when the temperature was raised, and an intermediate phase in which a nematic or polygonal phase could not be clearly identified at 60 ° C. when the temperature was lowered was observed. Further, the chemical structure of the obtained polymer 6 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.
Elemental analysis value Theoretical value C, 76.68; H, 8.84
Measurement C, 76.03; H, 8.87

It was Mw116100, Mn21800, and Mw / Mn5.3 when the molecular weight of the polymer 6 obtained above was calculated | required as polystyrene conversion by GPC measurement. Furthermore, the absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement are shown below about the film created by the casting method in the polymer solution or on the quartz plate.
UV-Vis (chloroform solution) 336 nm
(Film) 289, 333nm
PL (chloroform solution, excitation light 358 nm) 416 nm
(Film, excitation light 320 nm) 423, 545 nm

Example 7 Synthesis of Polymer 7 below

Example 7-1

  A solution consisting of 8.1 g of ethyl 4-methoxybenzoate, 80% hydrazine monohydrate, and 60 ml of ethanol was stirred at reflux for 18 hours. The reaction solution was concentrated to dryness to obtain 7.53 g of 4-methoxybenzoylhydrazine.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.73 (d, 2H), 7.69 (br s, 1H), 6.93 (d, 2H), 4.13 (br s, 2H), 3.85 (s, 3H)

Example 7-2

  After 10 g of 4-octylbenzoic acid was dissolved in 50 ml of benzene, 27 g of thionyl chloride was added and stirred for 16 hours under reflux. The reaction solution was concentrated to dryness to obtain 12.1 g of 4-octylbenzoyl chloride.

Example 7-3

  7.53 g of 4-methoxybenzoylhydrazine obtained in Example 7-1 was dissolved in 90 ml of tetrahydrofuran and cooled to 0 ° C. A solution consisting of 14.3 g of pyridine and 12.1 g of 4-octylbenzoyl chloride obtained in Example 7-2 and 20 ml of tetrahydrofuran was successively added dropwise thereto, and the mixture was warmed to room temperature and stirred for 24 hours. After the solvent was distilled off from the reaction mixture, water was added and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and then sufficiently dried to obtain 16.2 g of N- (4-methoxybenzoyl) -N ′-(4-octylbenzoyl) -hydrazine.

¹ H-NMR (CDCl _{3 /} TMS) δ: 9.60 (d, 2H), 7.84 (d, 2H), 7.77 (d, 2H), 7.22 (d, 2H), 6.90 (d, 2H), 3.84 (t , 3H), 2.64 (t, 2H), 1.61 (m, 2H), 1.2 to 1.48 (m, 10H), 0.88 (t, 3H)

Example 7-4

  A suspension of 9.1 g of N- (4′-methoxybenzoyl) -N ′-(4-octylbenzoyl) -hydrazine obtained in Example 7-3 and 100 ml of phosphoryl chloride was stirred under reflux for 12 hours. did. The reaction solution was poured into ice water, neutralized with sodium carbonate, and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and then sufficiently dried to obtain 10.2 g of 2- (4'-methoxyphenyl) -5- (4-octylphenyl) -1,3,4-oxadiazole.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.08 (d, 2H), 8.03 (d, 2H), 7.33 (d, 2H), 7.03 (d, 2H), 3.90 (s, 3H), 2.68 (t , 2H), 1.65 (m, 2H), 1.2-1.4 (m, 10H), 0.88 (t, 3H)

Example 7-5

  10.2 g of 2- (4′-methoxyphenyl) -5- (4-octylphenyl) -1,3,4-oxadiazole obtained in Example 7-4 was dissolved in 150 ml of methylene chloride, and 0 ° C. Then, a solution consisting of 25.5 g of boron tribromide and 100 ml of methylene chloride was added dropwise. After the addition, the reaction solution was warmed to room temperature and stirred for 24 hours. The reaction solution was poured into ice water and extracted with diethyl ether, and then the organic layer was washed with water, a saturated aqueous sodium hydrogen carbonate solution, and water in this order. After drying over anhydrous sodium sulfate, the mixture was concentrated to dryness to obtain 9.8 g of 2- (4'-hydroxyphenyl) -5- (4-octylphenyl) -1,3,5-oxadiazole.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.04 (d, 2H), 8.03 (d, 2H), 7.34 (d, 2H), 7.04 (d, 2H), 2.68 (t, 2H), 1.65 (m , 2H), 1.2 to 1,42 (m, 10H), 0.88 (t, 3H), and no proton of a hydroxyl group was detected.

Example 7-6

  1.5 g of 9,9′-bis (10-hydroxydecyl) -2,7-dibromofluorene obtained in Example 5-2, 1.3 g of triphenylphosphine, 2− obtained in Example 7-5 A mixture of (4′-hydroxyphenyl) -5- (4-octylphenyl) -1,3,5-oxadiazole (1.74 g) and tetrahydrofuran (50 ml) was cooled to 0 ° C. and then diethyl azodicarboxylate. 2.68 ml of a 40% toluene solution was added dropwise and stirred at the same temperature for 24 hours. The solvent was distilled off from the reaction mixture, and the resulting residue was purified by silica gel column chromatography using ethyl acetate-hexane (1: 4) as an eluent, and then recrystallized with an acetone-methylene chloride mixed solvent. 9′-bis {10- [1- (2- (4′-octylbenzene-1-yl) -1,3,4-oxadiazol-5-yl) -benzene-4-yl] -oxythecan-1 2.1 g of -yl} -2,7-dibromofluorene was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.04 (t, 8H), 7.52 (d, 2H), 7.45 (dd, 2H), 7.44 (s, 2H), 7.33 (d, 4H), 7.00 (d , 4H), 4.01 (t, 4H), 2.68 (t, 4H), 1.90 (m, 4H), 1.76 (m, 4H), 1.0 to 1.72 (m, 48H), 0.88 (t, 6H), 0.58 ( m, 4H)
Phase transition temperature Cry ・ 58.7 ℃ ・ Iso

Example 7-7

Under an argon atmosphere, 0.19 g of bipyridine and 2.0 ml of DMF were added to 0.33 g of Ni (cod) ₂ , stirred for 10 minutes at room temperature, and then 9,9′-bis { 10- [1- (2- (4′-octylbenzene-1-yl) 1,3,4-oxadiazo-5-yl) -benzene-4-yl] oxydecan-1-yl} -2,7-dibromo A solution consisting of 0.65 g of fluorene and 5 ml of THF was added dropwise and stirred at 65 ° C. for 48 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and the precipitated polymer was collected by filtration. The obtained polymer was again dissolved in 10 ml of chloroform, dropped into methanol (500 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration and poly-9,9′-bis {10- [1- (2- (4′-octylbenzene-1-yl) -1,3,4-oxadiazol-5-yl). -Benzene-4-yl] -oxytecan-1-yl} -2,7-fluorene (0.53 g, polymer 7) was obtained. This polymer phase transition changed from a crystal to an isotropic liquid at 200 ° C. when the temperature was raised, and solidified in an intermediate phase where a nematic or polygonal-like phase could not be clearly identified when the temperature was lowered. Further, the chemical structure of the obtained polymer 7 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.
Elemental analysis value Theoretical value C, 80.73; H, 8.80
Measurement C, 80.38; H, 8.89

It was Mw178200, Mn13000, and Mw / Mn13.7 when the molecular weight of the polymer 7 obtained above was determined as polystyrene conversion by GPC measurement. Furthermore, the absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement are shown below about the film created by the casting method in the polymer solution or on the quartz plate.
UV-Vis (chloroform solution) 300, 391 nm
(Film) 298, 393 nm
PL (chloroform solution, excitation light 277, 390 nm) 420, 441 nm
(Film, excitation light 376 nm) 427, 453, 525 nm

Example 8 Synthesis of Polymer 8 below

Example 8-1

  Under an argon atmosphere, 20 g of thiophene was dissolved in 200 ml of tetrahydrofuran, cooled to −50 ° C., and 152 ml of a 1.56 M n-butyllithium / n-hexane solution was added dropwise. After stirring at the same temperature for 6 hours, 45.9 g of n-octyl bromide was added dropwise, and the reaction solution was warmed to room temperature and stirred for 14 hours. The reaction solution was poured into ice water and extracted with diethyl ether, and then the organic layer was separated and washed with water. After drying over anhydrous sodium sulfate, the solvent was distilled off, and the resulting residue was purified by distillation under reduced pressure to obtain 29.4 g of 2-octylthiophene (bp 111 ° C./9 mmHg).

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.10 (dd, 1H), 6.91 (dd, 1H), 6.77 (dd, 1H), 2.81 (t, 2H), 1.67 (m, 2H), 1.2-1.4 (m, 10H), 0.88 (t, 3H)

Example 8-2

  Under an argon atmosphere, 14 g of 2-octylthiophene obtained in Example 8-1 was dissolved in diethyl ether and cooled to −70 ° C., and then 54.5 ml of a 1.56 M n-butyllithium / hexane solution was added dropwise. . The reaction solution was heated to 0 ° C., stirred for 90 minutes, and then cooled to −70 ° C. again. To this was added 10.1 ml of trimethyl borate, and the mixture was stirred for 12 hours while raising the temperature to room temperature. The reaction solution was filtered through Celite, and the obtained filtrate was concentrated to dryness to obtain 20.7 g of 2-octyl-5-boron dimethoxide thiophene.

Example 8-3

  In an argon atmosphere, 10 g of 2,2′-bithiophene was dissolved in 50 ml of tetrahydrofuran, cooled to −50 ° C., and 39.7 ml of a 1.56 M n-butyllithium / n-hexane solution was added dropwise at the same temperature. Stir for 2 hours. A solution consisting of 2- (10-bromodecyloxy) tetrahydropyran obtained in Example 1-1 and 25 ml of tetrahydrofuran was added dropwise thereto and stirred for 19 hours while raising the temperature to room temperature. The reaction solution was poured into ice water and extracted with diethyl ether. The organic layer was separated, washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and the obtained residue was subjected to silica gel column chromatography using hexane-methylene chloride (8: 1 to 1: 1) as an eluent. Purification by chromatography gave 13.7 g of 5- (10-tetrahydropyran-2-yloxydecyl) -2,2′-bithiophene.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.16 (dd, 1H), 7.09 (dd, 1H), 6.95 to 7.02 (m, 2H), 6.67 (d, 2H), 4.57 (t, 1H), 3.84 (m, 1H), 3,73 (m, 1H), 3.51 (m, 1H), 3.38 (m, 1H), 2.78 (t, 2H), 1.24 to 1.90 (m, 22H)

Example 8-4

  Under an argon atmosphere, a solution consisting of 3.6 ml of diisopropylamine and 50 ml of tetrahydrofuran was cooled to -70 ° C., 15.5 ml of a 1.59 M n-butyllithium / n-hexane solution was added dropwise, and the temperature was raised to room temperature. Warmed and stirred for 1 hour. After cooling again to −70 ° C., 12.5 g of 5- (10-tetrahydropyran-2-yloxydecyl) -2,2′-bithiophene obtained in Example 8-3 and tetrahydrofuran 62. A solution consisting of 5 milliliters was added dropwise and stirred for 10 minutes, after which 6.26 g of iodine was added. The reaction mixture was further stirred at the same temperature for 5 minutes, then warmed to room temperature and stirred for 18 hours. The reaction mixture was poured into ice water and extracted with diethyl ether. The obtained organic layer was washed with a dilute aqueous sodium hydrogen carbonate solution, saturated brine and water in this order, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The obtained residue was recrystallized with an acetone-methanol mixed solvent to obtain 12.3 g of 5- (10-tetrahydropyran-2-yloxydecyl) -5'-iodo-2,2'-bithiophene.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.12 (d, 1H), 6.92 (d, 1H), 6.75 (d, 1H), 6.66 (d, 1H), 4.57 (t, 1H), 3.87 (m , 1H), 73 (m, 1H), 3.50 (m, 1H), 3.37 (m, 1H), 2.77 (t, 2H), 1.52-1.72 (m, 10H), 1.29 (m, 12H)

Example 8-5

Under argon atmosphere, 9.5 g of 5- (10-tetrahydropyran-2-yloxydecyl) -5′-iodo-2,2′-bithiophene obtained in Example 8-4, obtained in Example 8-2. Of 2-octyl-5-boron dimethoxide thiophene, 3.17 g sodium carbonate, 3.78 g sodium carbonate, 0.62 g Pd (PPh ₃ ) ₄ , 95 ml 1,2-dimethoxyethane, and 26.5 ml water. Was stirred under reflux for 7 hours. The reaction mixture was extracted with diethyl ether, and the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was recrystallized from an acetone-methanol mixed solvent to give 5- (10-tetrahydropyran-2-yloxy) -5 ″ -octyl-2,2 ′, 5 ′, 2 10.4 g of ″ -terthiophene was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 6.96 (s, 2H), 6.95 (d, 2H), 6.67 (d, 2H), 4.56 (t, 1H), 3.87 (m, 1H), 3.73 (m , 1H), 3.51 (m, 1H), 3.38 (m, 1H), 2.78 (t, 4H), 1.54-1.83 (m, 10H), 1.29 (m, 24H), 0.88 (t, 3H)

Example 8-6

  From 8.81 g of 5- (10-tetrahydropyran-2-yloxy) -5 ″ -octyl-2, 2 ′, 5 ′, 2 ″ -terthiophene obtained in Example 8-5 and 220 ml of methanol. To this suspension, 0.43 g of p-toluenesulfonic acid monohydrate was added and stirred for 5 hours under reflux. After allowing to cool, the precipitated crystals were collected by filtration to obtain 7.36 g of 5- (10-hydroxydecyl) -5 ″ -octyl-2,2 ′, 5 ′, 2 ″ -terthiophene.

¹ H-NMR (CDCl _{3 /} TMS) δ: 6.97 (s, 2H), 6.95 (d, 2H), 6.67 (d, 2H), 3.64 (t, 2H), 2.78 (t, 4H), 1.67 (m , 4H), 1.55 (m, 2H), 1.29 (m, 22H), 0.88 (t, 3H)

Example 8-7

  Under argon atmosphere, 5.94 g of 5- (10-hydroxydecyl) -5 ″ -octyl-2, 2 ′, 5 ′, 2 ″ -terthiophene obtained in Example 8-6, 4.82 triethylamine. A solution consisting of milliliters, 0.28 g of dimethylaminopyridine, and 356 ml of methylene chloride was cooled to 0 ° C. To this, 2.41 g of p-toluenesulfonic acid chloride was added, and the mixture was warmed to room temperature and stirred for 24 hours. The reaction solution was poured into water and the organic layer was separated, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 7.8 g of 5- [10- (4-toluenesulfonyl) oxydecyl] -5 ″ -octyl-2,2 ′, 5 ′, 2 ″ -terthiophene as a crude product. .

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.78 (d, 2H), 7.33 (d, 2H), 6.96 (s, 2H), 6.95 (d, 2H), 6.66 (d, 2H), 4.01 (t , 2H), 2.78 (t, 4H), 2.44 (s, 3H), 1.59 to 1.67 (m, 6H), 1.22 to 1.35 (m, 22H), 0.88 (t, 3H)

Example 8-8

  7.78 g of 5- [10- (4-toluenesulfonyl) oxydecyl] -5 ″ -octyl-2,2 ′, 5 ′, 2 ″ -terthiophene obtained in Example 8-7, iodine A reaction solution consisting of 1.87 g of sodium chloride and 233 ml of acetone was stirred at 55 ° C. for 5 hours. The reaction solution was allowed to cool, and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and methanol to give 5- (10-iododecyl) -5 ″ -octyl-2,2 ′, 5 ′. , 2 ″ -terthiophene 6.45 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 6.97 (s, 2H), 6.96 (d, 2H), 6.67 (d, 2H), 3.19 (t, 2H), 2.78 (t, 4H), 1.80 (m , 2H), 1.66 (m, 4H), 1.29 (m, 22H), 0.88 (t, 3H)

Example 8-9

  0.49 g of 2,5-dibromofluorene, 1.98 g of 5- (10-iododecyl) -5 ″ -octyl-2,2 ′, 5 ′, 2 ″ -terthiophene obtained in Example 8-8 A mixture of 48 mg of benzyltriethylamine chloride, 3.5 ml of a 50 wt% aqueous sodium hydroxide solution, 20 ml of toluene and 20 ml of DMSO was stirred at 60 ° C. for 1 hour. The reaction mixture was poured into water and extracted with methylene chloride, and then the organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was recrystallized with a diethyl ether-methanol mixed solvent to obtain 9,9′-bis {10- [5 ″ -octyl-2,2 ′, 5 ′, 2 ′. 1.60 g of '-terthiophen-5-yl] decan-1-yl} -2,7-dibromofluorene was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.43 to 7.52 (m, 6H), 6.96 (s, 4H), 6.94 (d, 4H), 6.66 (d, 2H), 6.65 (d, 2H), 2.73 ~ 2.80 (m, 8H), 1.88-1.92 (m, 4H), 1.64-1.68 (m, 8H), 1.04-1.29 (m, 4H), 0.88 (t, 6H), 0.57 (m, 4H)
Phase transition temperature Cry ・ SmF ・ 58.9 ・ Iso

Example 8-10

Under an argon atmosphere, 0.19 g of bipyridine and 2.0 ml of DMF were added to 0.33 g of Ni (cod) ₂ , and the mixture was stirred at room temperature for 10 minutes, and then obtained in Example 8-9, 9,9′-bis {10− [5 ″ -octyl-2,2 ′, 5 ′, 2 ″ -terthiophen-5-yl] decan-1-yl} -2,7-dibromofluorene (0.66 g) and THF (5 ml) were added dropwise. And stirred at 65 ° C. for 72 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 1 hour, and the precipitated polymer was collected by filtration. Again, the obtained polymer was dissolved in 10 ml of chloroform and dropped into methanol (900 ml), followed by stirring and washing for 24 hours. The precipitate was collected by filtration, and poly-9,9′-bis {10- [5 ″ -octyl-2,2 ′, 5 ′, 2 ″ -terthiophen-5-yl] decan-1-yl} -2,7-fluorene (polymer 8) 0.55g was obtained. This polymer phase transition was from a crystal to an isotropic liquid at 94 ° C. when the temperature was raised, and polarization was observed at 90 ° C. when the temperature was lowered. Further, the chemical structure of the obtained polymer 8 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.
Elemental analysis value Theoretical value C, 75.20; H, 8.30
Measurement C, 75.22; H, 8.28

It was Mw113200, Mn23900, and Mw / Mn4.7 when the molecular weight of the polymer 8 obtained above was obtained by polystyrene conversion by GPC measurement. Furthermore, the absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement are shown below about the film created by the casting method in the polymer solution or on the quartz plate.
UV-Vis (chloroform solution) 375 nm
(Film) 255, 370 nm
PL (chloroform solution, excitation light 365 nm) 502 nm
(Film, excitation light 369 nm) 518 nm

Example 9 Synthesis of the following polymer 9

Example 9-1

6.58 g of 2-bromo-1,3-thiazole, 11.3 g of 2-octyl-5-boron dimethoxide thiophene obtained in Example 8-2, 2.32 g of Pd (PPh ₃ ) ₄ , 8. A mixture consisting of 50 g, 66 ml 1,2-dimethoxyethane, and 60 ml water was stirred at 90 ° C. for 2 hours. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was separated, washed with saturated brine and water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography using ethyl acetate-hexane (1:20) as an eluent to give 2- (5′-octylthiophen-2′-yl) -1. , 3-thiazole 5.68 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.72 (d, 1H), 7.34 (d, 1H), 7.19 (d, 1H), 6.75 (d, 1H), 2.82 (t, 2H), 1.70 (m , 2H), 1.27 to 1.38 (m, 10H), 0.88 (t, 3H)

Example 9-2

  In an argon atmosphere, 5.68 g of 2- (5′-octylthiophen-2′-yl) -1,3-thiazole obtained in Example 9-1 was dissolved in 57 ml of tetrahydrofuran and cooled to −80 ° C. 12.95 ml of a 1.57 M n-butyllithium / hexane solution was added dropwise. After the addition, the reaction mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was cooled again to −80 ° C., and 4.90 g of iodine was added thereto, followed by stirring at room temperature for 12 hours. The reaction mixture was poured into water, extracted with diethyl ether, and the organic layer was separated. The organic layer was washed with saturated brine and water and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was recrystallized with an acetone-methanol mixed solvent to give 5.2 g of 2- (5′-octylthiophen-2′-yl) -5-iodo-1,3-thiazole. Got.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.71 (s, 1H), 7.27 (d, 1H), 6.74 (d, 1H), 2.82 (t, 2H), 1.69 (m, 2H), 1.27 to 1.38 (m, 10H), 0.88 (t, 3H)

Example 9-3

  Under an argon atmosphere, 3.33 g of thiophene was dissolved in 33 ml of tetrahydrofuran, cooled to −70 ° C., and then 25.3 ml of a 1.56 M n-butyllithium / hexane solution was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then the reaction solution was again cooled to -70 ° C, and 12.7 g of 2- (10-bromodecyloxy) tetrahydropyran obtained in Example 1-1 was added. The reaction solution was warmed to room temperature and stirred for 12 hours. The reaction solution was poured into water and extracted with chloroform, and then the organic layer was washed with saturated brine and water. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography using methylene chloride as an eluent to obtain 6.57 g of 2- (10-tetrahydropyran-2-yloxydecyl) -thiophene.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.10 (d, 1H), 6.91 (t, 1H), 6.77 (d, 1H), 4.57 (t, 1H), 3.85 to 3.42 (m, 1H), 3.70 ~ 3.76 (m, 1H), 3.48-3.51 (m, 1H), 3.35-3.42 (m, 1H), 2.81 (t, 2H), 1.54-1.87 (m, 10H), 1.29 (m, 12H)

Example 9-4

  6.57 g of 2- (10-tetrahydropyran-2-yloxydecyl) -thiophene obtained in Example 9-3 was dissolved in 65 ml of diethyl ether, cooled to -70 ° C, and then 1.56M n- 12.3 ml of butyllithium / hexane solution was added dropwise. After the dropwise addition, the reaction solution was warmed to room temperature and stirred for 1.5 hours. The reaction solution was cooled again to -70 ° C., 2.27 ml of trimethyl borate was added, and the mixture was stirred at room temperature for 12 hours. The reaction solution was filtered through Celite, and the obtained filtrate was concentrated to dryness to obtain 6.76 g of 2- (10-tetrahydropyran-2-yl-oxydecyl) -5-borondimethoxidethiophene.

Example 9-5

3.77 g of 2- (5′-octylthiophen-2′-yl) -5-iodo-1,3-thiazole obtained in Example 9-2, 2- (10 -Tetrahydropyran-2-yl-oxydecyl) -5-borondimethoxidethiophene 3.87 g, Pd (PPh ₃ ) ₄ 1.07 g, sodium carbonate 1.97 g, 1,2-dimethoxyethane 37.7 ml, and water The mixture consisting of 13.8 ml was stirred at 90 ° C. for 2 hours. The reaction mixture was poured into water and extracted with diethyl ether, and then the organic layer was separated and washed with saturated brine and water. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off. The obtained residue was recrystallized with an acetone-methanol mixed solvent to give 2- (5′-octylthiophen-2′-yl) -5- [5 ″-(10-tetrahydropyran-2-yl-oxydecyl). ) -Thiophen-2 ″ -yl] -1,3-thiazole 3.94 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.68 (s, 1H), 7.34 (d, 1H), 6.99 (d, 1H), 6.76 (d, 1H), 6.70 (d, 1H), 4.57 (s , 1H), 87 (m, 1H), 3.73 (m, 1H), 3.49 (m, 1H), 3.38 (m, 1H), 2.78-2.85 (m, 4H), 1.83 (m, 1H), 1.69 ( m, 4H), 1.54-1.59 (m, 10H), 1.29 (m, 22H), 0.88 (t, 3H)

Example 9-6

  2- (5′-octylthiophen-2′-yl) -5- [5 ″-(10-tetrahydropyran-2-yl-oxydecyl) -thiophene-2 ″-obtained in Example 9-5 Yl] -1,3-thiazole (4.31 g) and methanol (108 ml) were added with p-toluenesulfonic acid monohydrate (0.21 g) and stirred under reflux for 4 hours. The reaction mixture was cooled to 0 ° C., and the precipitated crystals were collected by filtration and washed with methanol. Further, recrystallization from a mixed solvent of methylene chloride and methanol gave 2- (5′-octylthiophen-2′-yl) -5- [5 ″-(10-hydroxydecyl) -thiophen-2 ″ -yl. ] 3,3-thiazole 3.27g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.68 (s, 1H), 7.31 (d, 1H), 6.98 (d, 1H), 6.75 (d, 1H), 6.70 (d, 1H), 3.64 (t , 2H), 2.78 (m, 4H), 1.69 (m, 4H), 1.56 (m, 2H), 1.23-1.38 (m, 22H), 0.88 (t, 3H)

Example 9-7

  2- (5′-octylthiophen-2′-yl) -5- [5 ″-(10-hydroxydecyl) -thiophen-2 ″ -yl] obtained in Example 9-6 under argon atmosphere A solution consisting of 2.0 g of -1,3-thiazole, 1.62 ml of triethylamine, 94 mg of dimethylaminopyridine, and 120 ml of methylene chloride was cooled to -5 ° C. To this, 0.77 g of p-toluenesulfonic acid chloride was added, and the mixture was warmed to room temperature and stirred for 12 hours. The reaction solution was poured into water, and the organic layer was separated, washed with dilute hydrochloric acid aqueous solution, saturated brine and water, and dried over anhydrous sodium sulfate. After the solvent was distilled off, the obtained residue was recrystallized with an acetone-methanol mixed solvent to give 2- (5′-octylthiophen-2′-yl) -5- {5 ″-[10- ( p-Toluenesulfonyl) oxydecyl] -thiophen-2 ″ -yl} -1,3-thiazole 2.16 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.78 (d, 2H), 7.76 (s, 1H), 7.33 (d, 2H), 7.29 (d, 1H), 6.98 (d, 1H), 6.75 (d , 1H), 6.70 (d, 1H), 4.02 (t, 2H), 2.81 (m, 4H), 2.44 (s, 3H), 1.65 (m, 6H), 1.23-1.38 (m, 12H), 0.88 ( t, 3H)

Example 9-8

  2- (5′-octylthiophen-2′-yl) -5- {5 ″-[10- (p-toluenesulfonyl) oxydecyl] -thiophen-2 ″ -yl obtained in Example 9-7 } -1,3-thiazole 2.16 g, sodium iodide 0.51 g, and acetone 64.8 ml were stirred at 55 ° C. for 5 hours. The reaction mixture was allowed to cool and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and methanol to give 2- (5′-octylthiophen-2′-yl) -5- [5 ″. -(10-Iododecyl) -thiophen-2 "-yl] -1,3-thiazole (1.55 g) was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.68 (s, 1H), 7.30 (d, 1H), 6.98 (d, 1H), 6.75 (d, 1H), 6.70 (d, 1H), 3.19 (t , 2H), 2.81 (q, 4H), 1.82 (m, 2H), 1.68 (m, 4H), 1.23-1.38 (m, 22H), 0.88 (t, 3H)

Example 9-9

  0.147 g of 2,5-dibromofluorene, 2- (5′-octylthiophen-2′-yl) -5- [5 ″-(10-iododecyl) -thiophene-2 obtained in Example 9-8 ”-Yl] -1,3-thiazole 0.6 g, benzyltriethylamine chloride 14 mg, 50 wt% aqueous sodium hydroxide solution 1.0 ml, toluene 6.0 ml and DMSO 6.0 ml 90 ° C. Stir for minutes. The reaction mixture was poured into water and extracted with methylene chloride, and then the organic layer was separated and washed with water. After drying over anhydrous sodium sulfate, the solvent was distilled off, and the resulting residue was recrystallized from a mixed solvent of diethyl ether-methanol to give 9,9′-bis {10- [2 ″ (2- (5 '-Octylthiophen-2'-yl) -1,3-thiazol-5-yl) -thiophen-5' '-yl] -decan-1-yl} -2,7-dibromofluorene was obtained in an amount of 0.52 g. .

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.67 (s, 2H), 7.50 to 7.52 (m, 2H), 7.43 to 7.46 (m, 4H), 7.31 (d, 2H), 6.97 (d, 2H) , 6.75 (d, 2H), 6.68 (d, 2H), 2.80 (m, 8H), 1.90 (m, 4H), 1.66 (m, 8H), 1.05-1.27 (m, 44H), 0.88 (t, 6H) ), 0.57 (m, 4H)

Examples 9-10

Under an argon atmosphere, 0.13 g of bipyridine and 1.4 ml of DMF were added to 0.23 g of Ni (cod) ₂ , stirred for 10 minutes at room temperature, and then 9,9′-bis { 10- [2 ″ (2- (5′-octylthiophen-2′-yl) -1,3-thiazol-5-yl) -thiophen-5 ″ -yl] -decan-1-yl} -2 , 7-Dibromofluorene 0.47g and THF 3.5ml was added dropwise and stirred at 65 ° C for 72 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 24 hours, and the precipitated polymer was collected by filtration. The obtained polymer was again dissolved in 50 ml of tetrahydrofuran, dropped into methanol (900 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration, washed with a mixed solution of methanol and aqueous ammonia, and water, and then sufficiently dried to obtain poly-9,9′-bis {10- [2 ″ (2- (5 ′ -Octylthiophen-2'-yl) -1,3-thiazol-5-yl) -thiophen-5 "-yl] -decan-1-yl} -2,7-fluorene (Polymer 9) 0.30 g Obtained. The chemical structure of the obtained polymer 9 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

The absorption wavelength band by UV-Vis measurement is shown below about the film produced in the solution of the polymer 9 obtained above, or on the quartz plate by the casting method.
UV-Vis (chloroform solution) 370 nm
(Film) 381nm

Example 10 Synthesis of Polymer 10 below

Example 10-1

  Under ice cooling, 44.0 g of 3,4-dihydro-2H-pyran was added to a solution of 23 g of 2- [2- (2-chloroethoxy) ethoxy] ethanol dissolved in 150 ml of methylene chloride. Next, 1.0 ml of 35% hydrochloric acid was added little by little, and the mixture was stirred overnight while maintaining at 0 ° C. Saturated aqueous sodium hydrogen carbonate solution was added to the resulting reaction solution to stop the reaction, methylene chloride was separated and washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and the title compound (1 ) 32.5 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 4.64 (t, 1H), 3.83 to 3.93 (m, 2H), 3.77 (t, 2H), 3.69 (t, 2H), 3.69 (s, 4H), 3.57 ~ 3.66 (m, 3H), 3.55-3.45 (m, 1H), 1.95-1.45 (m, 6H)

Example 10-2

  32.5 g of the compound (1) obtained in Example 10-1 was dissolved in 150 ml of acetone, then 30.4 g of sodium iodide was added, and the mixture was stirred at reflux for 24 hours. After completion of the reaction, the reaction mixture was poured into water, extracted with ether, washed with water, and dried over anhydrous sodium sulfate. Further, the solvent was distilled off to obtain 41.0 g of the title compound (2) as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 4.64 (t, 1H), 3.93 to 3.83 (m, 2H), 3.77 (t, 2H), 3.72 to 3.66 (t, 2H), 3.68 (s, 4H) 3.65 to 3.57 (m, 1H), 3.55 to 3.45 (m, 1H), 3.26 (t, 2H) 1.95 to 1.45 (m, 6H)

Example 10-3

  After dissolving 10 g of 3-thiophene methanol in 200 ml of dimethylformamide, 34.4 g of N-bromosuccinimide was added under ice cooling, and the mixture was stirred at the same temperature all day and night. After completion of the reaction, the reaction mixture was poured into water, extracted with methylene chloride, washed with water, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography using hexane-methylene chloride (3: 1 to 0: 1) as an eluent to obtain 20.9 g of the title compound (3). Obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.02 (s, 1H), 4.56 (s, 2H)

Example 10-4

  9.5 g of the compound (3) obtained in Example 10-3, 4.0 g of tetrabutylammonium bromide, 1.0 g of potassium iodide, 24 g of the compound (2) obtained in Example 10-2, potassium hydroxide A mixture of 15 g / 80 ml of water and 300 ml of tetrahydrofuran was stirred at reflux for 4 days. After completion of the reaction, the reaction mixture was poured into water, extracted with toluene, washed with water, and dried over anhydrous sodium sulfate. Then, after distilling off the solvent, the obtained crude product was purified by silica gel column chromatography using hexane-toluene (3: 2 to 0: 2) as an eluent to obtain 9.6 g of the title compound (4). Obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.0 (s, 1H), 4.67 to 4.6 (m, 1H), 4.44 (s, 2H), 3.92 to 3.82 (m, 2H), 3.8 to 3.55 (m, 11H), 3.55 to 3.45 (m, 1H), 1.95 to 1.45 (m, 6H)

Example 10-5

  After dissolving 5.0 g of the compound (4) obtained in Example 10-4 in 50 ml of methanol, 0.5 ml of 35% hydrochloric acid was added and stirred at room temperature all day and night. After completion of the reaction, sodium hydrogen carbonate was added to the reaction mixture and stirred for 1 hour. Then, after removing insolubles, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography using hexane-ethyl acetate (2: 1 to 0: 1) as an eluent to obtain 3.5 g of the title compound (5).

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.01 (s, 1H), 4.44 (s, 2H), 3.74 (t, 2H), 3.71 to 3.64 (m, 7H), 3.64 to 3.59 (m, 4H)

Example 10-6

  1.1 g of the compound (5) obtained in Example 10-5, 0.92 g of 2- (4′-octylphenyl) -6-hydroxynaphthalene obtained in Example 1-7, 0. To a mixed solution consisting of 87 g and 30 mL of THF, 1.44 g of a 40% ethyl azodicarboxylate / toluene solution was added dropwise at 0 ° C., and the mixture was warmed to room temperature and stirred for 48 hours. The reaction mixture was concentrated, and the resulting residue was purified by silica gel column chromatography using hexane-ethyl acetate (8: 1) as an eluent to obtain 1.1 g of a monomer compound (6).

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.94 (d, 1H), 7.77 (d, 2H), 7.70 (dd, 1H), 7.61 (d, 2H), 7.28 (d, 2H), 7.18 (dd , 1H), 7.15 (d, 1H), 6.99 (s, 1H), 4.43 (s, 2H), 4.27 (t, 2H), 3.94 (t, 2H), 3.82 to 3.75 (m, 2H), 3.75 to 3.65 (m, 4H), 3.65 to 3.58 (m, 2H), 2.66 (t, 2H), 1.73 to 1.61 (m, 2H), 1.45 to 1.2 (m, 10H), 0.89 (t, 3H)
Phase transition temperature Cry ・ 59.5〜60 ℃ ・ Iso

Example 10-7

Under an argon atmosphere, 0.13 g of bipyridine and 2.0 ml of DMF were added to 0.33 g of bis (1,5-cyclooctadiene) nickel (0) (hereinafter abbreviated as Ni (cod) ₂ ), and the mixture was stirred for 10 minutes at room temperature After stirring, a solution consisting of 0.33 g of the monomer compound obtained in Example 10-6 and 5.0 ml of THF was added dropwise, and the mixture was heated and stirred at 60 ° C. for 45 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 24 hours, and the precipitated polymer was collected by filtration. Again, the obtained polymer was dissolved in 5.0 ml of THF, dropped into a methanol / water mixed solvent (500 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration to obtain 0.24 g of polymer 10. Regarding the phase transition of this polymer, after raising the crystal to around 158 ° C. to an isotropic liquid, when the temperature is lowered, a polygonal-like intermediate phase appears at around 143 ° C. The mesophase remained. The chemical structure of the obtained polymer was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

It was Mn12580, Mw16042, Mw / Mn1.28 when the molecular weight of the polymer 10 obtained above was calculated | required as polystyrene conversion by GPC measurement. The absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement in the polymer 10 solution are shown below.
UV-Vis (chloroform solution) 257.5, 295.5, 404.5 nm
PL (chloroform solution, excitation light 404 nm) 542 nm

Example 11 Synthesis of Polymer 11 below

Example 11-1

  1.2 g of the compound (5) obtained in Example 10-5 and 2- (4′-hydroxyphenyl) -5- (4-octylphenyl) -1,3,5 obtained in Example 7-5 -To a mixed solution consisting of 0.92 g of oxadiazole, 0.87 g of triphenylphosphine and 30 ml of THF, 1.44 g of 40% ethyl azodicarboxylate / toluene solution was added dropwise at 0 ° C., and the mixture was warmed to room temperature and stirred for 48 hours. did. The reaction solution was concentrated, and the resulting residue was purified by silica gel column chromatography using hexane-ethyl acetate (2: 1) as an eluent to obtain 1.89 g of a monomer compound (7).

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.06 (d, 2H), 8.03 (d, 2H), 7.33 (d, 2H), 7.04 (d, 2H), 6.99 (s, 1H), 4.44 (s , 2H), 4.22 (t, 2H), 3.91 (t, 2H), 3.78 to 3.73 (m, 2H), 3.73 to 3.65 (m, 4H), 3.65 to 3.6 (m, 2H), 2.68 (t, 2H) ), 1.7-1.6 (m, 2H), 1.4-1.2 (m, 10H), 0.88 (t, 3H)
Phase transition temperature Cry ・ 34 ℃ ・ Iso

Example 11-2

Under an argon atmosphere, 0.19 g of bipyridine and 2.0 ml of DMF were added to 0.33 g of Ni (cod) ₂ , and the mixture was stirred at room temperature for 10 minutes, and then 0.37 g of the monomer (7) obtained in Example 11-1. And a solution consisting of 5.0 ml of THF was added dropwise and stirred at 60 ° C. for 45 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 24 hours, and the precipitated polymer was collected by filtration. Again, the obtained polymer was dissolved in 5.0 ml of THF, dropped into a methanol / water mixed solvent (500 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration to obtain 0.19 g of polymer 11. Regarding the phase transition of this polymer, it was transformed into an isotropic liquid when the temperature was raised to around 86 ° C., and further solidified in a glass state when the temperature was lowered.

The chemical structure of the obtained polymer was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

It was Mn8238, Mw9822, Mw / Mn1.19 when the molecular weight of the polymer 11 obtained above was calculated | required as polystyrene conversion by GPC measurement. The absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement in the polymer 11 solution are shown below.
UV-Vis (chloroform solution) 299.5, 399.5 nm
PL (chloroform solution, excitation light 392 nm) 535 nm

Example 12 Synthesis of Polymer 12 below

Example 12-1

5.9 g of 2,5-dibromopyridine, 5.1 g of 2-octyl-5-boron dimethoxide thiophene obtained in Example 8-2, 0.37 g of Pd (PPh ₃ ) ₄ , 2.9 g of sodium carbonate, 1 , 2-dimethoxyethane 50 ml and water 20 ml were stirred at reflux for 16 hours. The reaction mixture was poured into water and extracted with methylene chloride. The organic layer was separated, washed with saturated brine and water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography using hexane-methylene chloride (6: 1) as an eluent to obtain 5.6 g of the title compound (8).

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.56 (d, 1H), 7.75 (dd, 1H), 7.47 (d, 1H), 7.38 (d, 1H), 6.77 (d, 1H), 2.82 (t , 2H), 75 to 1.65 (m, 2H), 1.42 to 1.2 (m, 10H), 0.88 (t, 3H)

Example 12-2

3.9 g of the compound (8) obtained in Example 12-1 and 6.4 g of 2- (10-tetrahydropyran-2-yl-oxydecyl) -5-boron dimethoxide thiophene obtained in Example 9-4 , Pd (PPh ₃ ) ₄ 0.52 g, sodium carbonate 2.4 g, 1,2-dimethoxyethane 70 ml, and water 25 ml were stirred at reflux for 10 hours. The reaction mixture was poured into water and extracted with chloroform, and then the organic layer was separated and washed with saturated brine and water. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off. The obtained residue was purified by silica gel chromatography using hexane-ethyl acetate (8: 1) as an eluent, and then recrystallized from acetone to obtain 7.5 g of the title compound (9).

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.75 (d, 1H), 7.78 (dd, 1H), 7.57 (d, 1H), 7.40 (d, 1H), 7.17 (d, 1H), 6.78 (t , 2H), 4.57 (t, 1H), 3.9 to 3.82 (m, 1H), 3.76 to 3.69 (m, 1H), 3.53 to 3.46 (m, 1H), 3.41 to 3.33 (m, 1H), 2.89 to 2.78 (m, 4H), 1.8-1.45 (m, 12H), 1.45-1.15 (m, 22H), 0.88 (t, 3H)

Example 12-3

  After dissolving in 7.2 g of the compound (9) obtained in Example 12-2, 100 ml of methanol and 120 ml of THF, 1.0 ml of 35% hydrochloric acid was added dropwise and stirred at room temperature for 2 days. After completion of the reaction, sodium hydrogen carbonate and water were added to the reaction mixture, extracted with methylene chloride, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 6.2 g of the title compound (10) as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.75 (d, 1H), 7.77 (dd, 1H), 7.57 (d, 1H), 7.39 (d, 1H), 7.16 (d, 1H), 6.77 (t , 2H), 3.64 (t, 2H), 2.89 to 2.78 (m, 4H), 1.77 to 1.63 (m, 4H), 1.61 to 1.5 (m, 2H), 1.44 to 1.2 (m, 22H), 0.88 (t , 3H)

Example 12-4

  Under an argon atmosphere, a solution consisting of 2.6 g of the compound (10) obtained in Example 12-3, 2.2 ml of triethylamine, 0.12 g of dimethylaminopyridine, and 50 ml of methylene chloride was cooled to −5 ° C. To this, 1.46 g of p-toluenesulfonic acid chloride was added, and the mixture was warmed to room temperature and stirred for 3 days. The reaction solution was poured into water, the organic layer was separated, washed with a saturated aqueous ammonium chloride solution and water, and dried over anhydrous sodium sulfate. After the solvent was distilled off, 2.6 g of sodium iodide and 160 ml of methyl ethyl ketone were added to the obtained residue, and the mixture was stirred for 16 hours under reflux. The reaction solution was poured into water, extracted with methylene chloride, washed with water, and dried over anhydrous sodium sulfate. After the solvent was distilled off, the obtained residue was purified by silica gel column chromatography using hexane-methylene chloride (9: 1 to 2: 1) as an eluent to obtain 1.55 g of the title compound (11). .

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.75 (d, 1H), 7.77 (dd, 1H), 7.57 (d, 1H), 7.39 (d, 1H), 7.16 (d, 1H), 6.78 (t , 2H), 3.19 (t, 2H), 2.9 to 2.8 (m, 4H), 1.9 to 1.64 (m, 6H), 1.5 to 1.2 (m, 22H), 0.88 (t, 3H)

Example 12-5

  To a solution consisting of 0.88 g of the compound (3) obtained in Example 10-3, 3.3 mg of 18-crown-6-ether and 45 ml of tetrahydrofuran, 0.13 g of 60% sodium hydride was added with stirring at room temperature. Stir for 10 minutes.

Thereto was added dropwise a 10 ml tetrahydrofuran solution of 1.5 g of the compound (11) obtained in Example 12-4, and the mixture was stirred for 14 hours under reflux. After completion of the reaction, the reaction mixture was poured into water, extracted with methylene chloride, washed with dilute hydrochloric acid aqueous solution and water, and the organic layer was dried over sodium sulfate. After the solvent was distilled off, the obtained residue was purified by silica gel column chromatography using hexane-methylene chloride (2: 1) as an eluent to obtain monomer compound (12).
0.62 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 8.75 (d, 1H), 7.77 (dd, 1H), 7.57 (d, 1H), 7.39 (d, 1H), 7.16 (d, 1H), 6.97 (s , 1H) 6.78 (t, 2H), 4.43 (s, 2H), 3.43 (t, 2H), 2.88-2.78 (m, 4H), 1.76-1.66 (m, 4H), 1.63-1.5 (m, 2H) 1.44-1.2 (m, 22H), 0.88 (t, 3H)
Phase transition temperature Cry ・ 78 ℃ ・ SmA ・ 83.5 ℃ ・ Iso

Example 12-6

Under an argon atmosphere, 0.19 g of bipyridine and 2.0 ml of DMF were added to 0.33 g of Ni (cod) ₂ , and the mixture was stirred at room temperature for 10 minutes, and then 0.38 g of the monomer (12) obtained in Example 12-5. And a solution consisting of 5.0 ml of THF was added dropwise and stirred at 60 ° C. for 45 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (500 ml), stirred at room temperature for 24 hours, and the precipitated polymer was collected by filtration. The obtained polymer was washed with water and methanol, then suspended in a methanol / triethylamine mixed solvent (100 ml) and stirred at 50 ° C. for 1 hour. Further, the precipitate was collected by filtration and washed with water and methanol to obtain 0.2 g of polymer 12. Regarding the phase transition of this polymer, the crystal was heated to around 140 ° C. to make an isotropic liquid, and when the temperature was lowered, a polygonal-like intermediate phase appeared at around 123 ° C. The mesophase remained.

Further, the chemical structure of the obtained polymer 12 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

It was Mn6770, Mw7436, Mw / Mn1.10 when the molecular weight of the polymer 12 obtained above was calculated | required as polystyrene conversion by GPC measurement. The absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement in the polymer 12 solution are shown below.
UV-Vis (chloroform solution) 353 nm
PL (film, excitation light 353 nm) 531 nm

Example 13 Synthesis of Polymer 13 below

Example 13-1

  Under an argon atmosphere, a mixture of 3.0 g of 2,7-dibromo-9-fluorenone, 11.8 g of phenol and 0.85 g of methylsulfonic acid was heated and stirred at 140 ° C. for 16 hours. After completion of the reaction, the reaction mixture was diluted with methylene chloride, washed with saturated brine, and dried over anhydrous sodium sulfate. Next, the solvent was distilled off, and the obtained residue was purified by silica gel column chromatography using hexane-ethyl acetate (6: 1-3: 1) as an eluent to obtain 0.96 g of the title compound (13). .

¹ H-NMR (DMSO-d6 / TMS) δ: 9.41 (s, 2H), 7.90 (d, 2H), 7.58 (dd, 2H), 7.48 (s, 2H), 6.89 (d, 4H), 6.66 ( d, 4H)

Example 13-2

  7.8 g of 2- (10-bromodecyloxy) tetrahydropyran obtained in Example 1-1, 7.0 g of 2- (4′-octylphenyl) -6-hydroxynaphthalene obtained in Example 1-7 , 5.8 g of potassium carbonate, and 150 ml of methyl ethyl ketone were stirred at reflux for 24 hours. The reaction mixture was poured into water, and the precipitated crude crystals were collected by filtration. The obtained crude crystals were dissolved in acetone and recrystallized to obtain 8.5 g of the title compound (14).

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.94 (d, 1H), 7.77 (d, 2H), 7.70 (dd, 1H), 7.61 (d, 2H), 7.28 (d, 2H), 7.16 (dd , 1H), 7.14 (s, 1H), 4.63 to 4.5 (m, 1H), 4.08 (t, 2H), 3.92 to 3.8 (m, 1H), 3.8 to 3.67 (m, 1H), 3.55 to 3.45 (m , 1H), 3.43 to 3.32 (m, 1H) 2.66 (t, 2H), 1.92 to 1.2 (m, 34H), 0.89 (t, 3H)

Example 13-3

  After dissolving 5.1 g of the compound (14) obtained in Example 13-2 in a mixed solvent consisting of 130 ml of methanol and 150 ml of THF, 0.5 ml of 35% hydrochloric acid was added and stirred at room temperature for a whole day and night. After completion of the reaction, the reaction mixture was poured into water, extracted with methylene chloride, washed with water, and dried over anhydrous sodium sulfate. Subsequently, the solvent was distilled off to obtain 4.4 g of the title compound (15) as a crude product.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.95 (d, 1H), 7.77 (d, 2H), 7.70 (dd, 1H), 7.62 (d, 2H), 7.28 (d, 2H), 7.16 (dd 1H), 7.15 (s, 1H), 4.09 (t, 2H), 3.64 (t, 2H), 2.66 (t, 2H), 1.92 to 1.8 (m, 2H), 1.75 to 1.2 (m, 26H), 0.89 (t, 3H)

Example 13-4

  Under an argon atmosphere, a solution consisting of 1.58 g of the compound (15) obtained in Example 13-3, 1.4 ml of triethylamine, 0.08 g of dimethylaminopyridine, and 50 ml of methylene chloride was cooled to 0 ° C. To this, 0.93 g of p-toluenesulfonic acid chloride was added, and the mixture was warmed to room temperature and stirred for 24 hours. The reaction solution was poured into water and the organic layer was separated, washed with water, and dried over anhydrous sodium sulfate. After the solvent was distilled off, 2.6 g of sodium iodide and 60 ml of acetone were added to the obtained residue, and the mixture was stirred for 16 hours under reflux. The reaction solution was poured into water and the precipitate was collected by filtration. The resulting crude crystals were purified by silica gel column chromatography using hexane-methylene chloride (5: 1) as an eluent to give the title compound (16). 1.48 g was obtained.

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.95 (s, 1H), 7.77 (d, 2H), 7.70 (d, 1H), 7.62 (d, 2H), 7.28 (d, 2H), 7.16 (dd 1H), 7.15 (s, 1H), 4.09 (t, 2H), 3.19 (t, 2H), 2.66 (t, 2H), 1.89 to 1.79 (m, 4H), 1.7 to 1.62 (m, 2H), 1.55-1.46 (m, 2H), 1.44-1.2 (m, 20H), 0.89 (t, 3H)

Example 13-5

  A mixture comprising 0.28 g of the compound (13) obtained in Example 13-1, 0.67 g of the compound (16) obtained in Example 13-4, 0.28 g of potassium carbonate and 30 ml of methyl ethyl ketone was refluxed. Stir for 12 hours. After completion of the reaction, the reaction mixture was poured into water, extracted with methylene chloride, washed with water, and dried over anhydrous sodium sulfate. Subsequently, after distilling off the solvent, the obtained residue was purified by column chromatography using hexane-toluene (3: 1 to 1: 1) as an eluent to obtain 0.57 g of a monomer compound (17). .

¹ H-NMR (CDCl _{3 /} TMS) δ: 7.94 (s, 2H), 7.76 (d, 4H), 7.69 (dd, 2H), 7.61 (d, 4H), 7.55 (d, 2H), 7.46 (s , 2H), 7.45 (d, 2H), 7.28 (d, 4H), 7.15 (dd, 2H), 7.14 (s, 2H), 7.04 (d, 4H), 6.76 (4H), 4.08 (t, 4H) 3.90 (t, 4H), 2.66 (t, 4H), 1.9 to 1.8 (m, 4H), 1.8 to 1.6 (m, 8H), 1.53 to 1.2 (m, 44H), 0.88 (t, 6H)
Phase transition temperature Cry ・ 91.5 ℃ ・ Iso

Example 13-6

Under an argon atmosphere, 0.11 g of bipyridine and 2.0 ml of DMF were added to 0.18 g of Ni (cod) ₂ , stirred for 10 minutes at room temperature, and then 0.4 g of the monomer (17) obtained in Example 13-5. And a solution consisting of 3.0 ml of THF was added dropwise and stirred at 60 ° C. for 45 hours. The reaction solution was added to a methanol / hydrochloric acid mixed solvent (800 ml), stirred at room temperature for 24 hours, and the precipitated polymer was collected by filtration. The obtained polymer was again dissolved in 10 ml of chloroform, dropped into methanol (800 ml), and then washed with stirring for 24 hours. The precipitate was collected by filtration to obtain 0.35 g of polymer 13. The polymer phase transition melted around 200 ° C. when the temperature was raised, and an intermediate phase having polarized light that could not be clearly identified was developed. The temperature was raised to 280 ° C., but this intermediate phase remained.

Further, the chemical structure of the obtained polymer 13 was determined by ¹ H-NMR measurement in the same manner as in Example 1-9.

It was Mn69997, Mw368340, and Mw / Mn5.3 when the molecular weight of the polymer 13 obtained above was obtained by polystyrene conversion by GPC measurement. The absorption wavelength band by UV-Vis measurement and the emission wavelength band by PL measurement are shown below for the polymer 13 film cast on a quartz plate.
UV-Vis (film) 247, 290, 393 nm
PL (film, excitation light 262 nm) 425 nm

Test example 1
The polymer 1 obtained in Example 1-9 was rubbed in the liquid crystal state (125 ° C.), and then the polarized fluorescence spectrum in the alignment state was measured. The liquid crystal side chain groups were aligned parallel to the rubbing direction and the main chain was aligned vertically, and the emission dichroism ratio was 1.83. The result is shown in FIG.

Test example 2
The conductivity of the polymer 1 obtained in Example 1-9 was measured by the 4-terminal method. The sample was obtained by dissolving the polymer in chloroform and casting it on a slide glass, followed by iodine doping at room temperature in a nitrogen atmosphere. As a result, the conductivity was 9 × 10 ⁸ (S / cm) in the non-oriented state.

Test example 3
Test Example 3-1
A film was prepared from a chloroform solution of polymer 1 obtained in Example 1-9 by a casting method on a quartz plate, then heat-treated at a temperature showing a liquid crystal phase for 1 hour, and then gradually returned to room temperature. The fluorescence spectrum was measured. The light emission wavelength band was compared with that in the chloroform solution of these polymers and in the case of an untreated film. The result is shown in FIG.

The polymer 1 obtained in Example 1-9 emits light yellowish green with visual observation when irradiated with ultraviolet light in a chloroform solution, and shows maximum values at 374 nm and 536 nm in its fluorescence spectrum. The maximum light emission of 374 nm is light emission from the side chain naphthalene moiety, and the maximum light emission of 536 nm is light emission derived from the conjugated system of the main chain polythiophene. The polymer main chain and side chain light-emitting sites are linked via a methylene spacer (-(CH ₂ ) _10- ), and in the solution, the main chain site and the side chain site are sufficiently separated from each other. And emits fluorescence, and its relative intensity is approximately 1: 2.

  Generally, in the solid state, the fluorescence emission intensity is smaller than that of a dilute solution due to concentration quenching. In the solid thin polymer film prepared by the casting method, the emission intensity ratio around 374 nm and 536 nm changes to about 1: 8. This indicates that energy transfer from the side-chain naphthalene moiety to the main-chain polythiophene moiety has occurred or that concentration quenching of the naphthalene side-chain moiety has occurred preferentially by forming a solid thin film. Further, in the heat-treated polymer film, the emission intensity ratio is about 1:35. On the other hand, the polymer undergoes smectic liquid crystal alignment by heat treatment, and then the glass transitions and maintains the alignment state. Therefore, side chains are closely arranged, and excimer emission is observed at around 420 nm. The emission intensity ratio in the vicinity of 370 nm and 420 nm of the side chain site was about 1:10, which indicates that excimer emission at the side chain site preferentially occurred by heat treatment.

Test Example 3-2
A film was prepared on a quartz plate by a casting method from the polymer 2 chloroform solution obtained in Example 2-7, and then heat treated at a temperature showing a liquid crystal phase for 1 hour and then gradually returned to room temperature. The spectrum was measured. The light emission wavelength band was compared with that in the chloroform solution of these polymers and in the case of an untreated film. The result is shown in FIG.

  In the chloroform solution of polymer 2, by irradiating with ultraviolet light, a fluorescence spectrum having an emission maximum in the vicinity of 407 nm and 540 nm is obtained, and the emission intensity ratio is about 3: 1. The former is luminescence due to the side chain thiazole moiety, and the latter is luminescence derived from the conjugated system of the main chain polythiophene. In the polymer film formed into a solid thin film by the casting method, light emission at the side chain site was hardly observed, and only light emission around 540 nm was mainly observed. This indicates an efficient energy transfer from the side chain light emitting site to the main chain light emitting site. However, when this polymer film was heat-treated, the intensity ratio of light emission derived from the polymer main chain conjugated system near 540 nm was reduced by about 15 times. This indicates that the charge mobility between the main chain and the side chain is increased by making the smectic liquid crystal alignment state by heat treatment.

  That is, a conductive polymer having luminescence (photosensitivity) and charge transportability in the side chain is appropriately selected from the main chain conjugated system and the side chain luminescence (photosensitivity) / charge transport site, and the molecular orientation (amorphous and By changing the (liquid crystal) state, the selective sensitization of the main chain site using energy transfer from the side chain site (selective sensitization of the side chain site using energy transfer from the main chain site), the main Independent light emission of the chain part and side chain part, selective excimer light emission of the side chain part (selective excimer light emission of the main chain part), and selective quenching by molecular orientation are possible. Utilizing these facts, application as a new light energy conversion element material capable of controlling the energy mobility and charge transportability of the main chain part and the side chain part becomes possible.

Test Example 3-3
Using the polymer 5 obtained in Example 5-6 and the comparative compound 2- (4′-n-octylphenyl) -6-decyloxy-naphthalene (18) shown below, each of the compounds was cast by the casting method. FIG. 4 shows the fluorescence spectrum measurement results when the films were excited and then excited at the maximum excitation wavelength (269 nm) of the liquid crystal side chain portion of the polymer 5.

  As a result, the solid thin film of polymer 5 obtained in Example 5-6 showed no emission of the liquid crystal side chain portion having a light emitting region at about 378 nm as in the comparative compound, and had a maximum emission wavelength at 425 nm. Only light emission from the fluorene main chain site was observed. This indicates that a very efficient energy transfer from the liquid crystal side chain site to the polyfluorene main chain site occurred by thinning the solid film.

Test example 4
A dilute chloroform solution (0.05 μM) of polymer 5 obtained in Example 5-6 and poly-9,9-dioctylfluorene (19) and 2- (4′-n-octylphenyl) -6-6 shown below A dilute chloroform solution {(19); 0.05 μM, (18); 0.1 μM} of a mixture consisting of decyloxy-naphthalene (18) was prepared at the same concentration, and the UV-visible absorption spectrum and the fluorescence spectrum were measured. . The results are shown in FIGS.

  The polymer 5 obtained in Example 5-6 has a large overlap between the light emitting region of the liquid crystal side chain site and the absorption region of the polyfluorene main chain site in the chloroform solution. In the light emission behavior in the dilute solution, the polymer side Light emission corresponding to the polyfluorene main chain site having an emission intensity of 4947 and quenching of the liquid crystal side chain site were observed at 419 nm by photoexcitation at 262 nm which is the maximum excitation wavelength of the chain site. On the other hand, in the mixture of (18) and (19), when photoexcitation is performed at 262 nm, which is also the maximum excitation wavelength of (18), in the chloroform solution, (18) and (19) become 372 nm and emission intensities 822 and 418 nm, respectively. Light emission with a light emission intensity of 562 was observed. The results obtained when (18) and (19) were individually measured at the same concentration showed values almost in agreement with the results of these mixtures, and between (18) and (19) in a dilute solution. Was confirmed to have no interaction.

  The above results show that, in the polymer 5, excitons generated at the liquid crystal side chain site are transferred to the polyfluorene main chain site by resonance energy within the molecule.

Test Example 5
The fluorescence spectrum of an untreated film prepared by a casting method from the chloroform solution of polymer 13 obtained in Example 13-6 and a film obtained by heat-treating this film at about 200 ° C. for 1 hour or more in air were measured. It was compared with the fluorescence spectra of a chloroform solution of poly 9,9-dioctylfluorene (19), an untreated film, and a heat-treated film that efficiently emitted blue light. The result is shown in FIG.

Poly-9,9-dioctylfluorene (19) exhibits high-efficiency blue light emission in the chloroform solution at around 420 nm, but association and excimer are formed by thinning of the solid film, resulting in longer wavelength shift and broadening of the emission band. The color purity of luminescence was significantly reduced. On the other hand, the polymer 13 obtained in Example 13-6 exhibits high-efficiency blue light emission around 420 nm even when the solid film is thinned and heat-treated, and the light emission peak hardly changes before and after the heat-treatment. It is a polymer having excellent properties such as color purity and thermal stability.

The polarization fluorescence spectrum of polymer 1 obtained in Example 1-9 is shown. The fluorescence spectrum of the chloroform solution of the polymer 1 obtained in Example 1-9, an untreated film, and the heat-processed film is shown. The fluorescence spectrum of the chloroform solution of the polymer 2 obtained in Example 2-7, an untreated film, and the heat-processed film is shown. The fluorescence spectrum of the solid thin film of the polymer 5 obtained in Example 5-6 and the comparative compound 2- (4'-n-octylphenyl) -6-decyloxy-naphthalene (18) is shown. The ultraviolet-visible absorption spectrum and fluorescence spectrum of the chloroform solution of the polymer 5 obtained in Example 5-6 and the comparative compound (18) are shown. The fluorescence spectrum of the chloroform solution of the polymer 5 obtained in Example 5-6, the comparative compound (18), and the mixture of poly-9,9-dioctylfluorene (19) is shown. The fluorescence spectrum of the untreated film of polymer 13 obtained in Example 13-6 and the heat-treated film, and the fluorescence spectrum of poly-9,9-dioctylfluorene (19) in chloroform, untreated film and heat-treated film are as follows. Show.

Claims (4)

The following general formula (1) or (2):

Wherein, A represents an oxygen atom, a sulfur atom or NH, L is rather good also different from each other, the following general formula (3) to (7):

[In the formula, R ¹ is a linear or branched hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or a cyclic hydrocarbon having 3 to 30 carbon atoms which may have a substituent. An aromatic heterocyclic group having 2 to 30 carbon atoms which may have a group or a substituent, and R ² represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, a lower alkyl group or a lower alkoxy group; , W represents a single bond, an oxygen atom or a sulfur atom, B represents an oxygen atom or a sulfur atom, D and E represent a nitrogen atom or CH, Y may have a substituent, and —CH ₂ —, —O—, —S—, —C═C—, —C≡C—, —COO—, —OCO—, —CO— , —SO ₂ — , —SiR ³ R ⁴ , —GeR ⁵ R ⁶ -, -NR < ⁷ >-, -CH = N-, C1-C25 bivalent containing the group chosen from a cyclic alkyl group, an aromatic ring group, and a heterocyclic group Wherein R ^{3 to} R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Z represents a single bond, —CH ₂ CH ₂ —, —C═. C—, —C≡C—, —COO—, —OCO—, —N≡N— or —CH═N— is shown. ]
M represents a group selected from the following , M may be different from each other, and may be an optionally substituted alkyl group having 1 to 25 carbon atoms, a cyano group, an amino group, a hydroxyl group, a mercapto group, a nitro group, and n represents an integer of 2 to 10,000, a represents an integer of 1 to 3, b is indicates an integer of 1 to 8, d is an integer of 0 to 2, e is an integer of 0 to 7 Show. ]
A side chain type conductive polymer represented by A is a sulfur atom or a nitrogen atom, L is the general formula (3) or (4) the side chain of claim 1, wherein the rod-shaped semiconductor crystal group represented by type conductive polymer. A liquid crystalline composition containing the side chain type conductive polymer according to claim 1 . The following general formula (1a) or (2a):

Wherein, A represents an oxygen atom, a sulfur atom or NH, L is rather good also different from each other, the following general formula (3) to (7):

[In the formula, R ¹ is a linear or branched hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or a cyclic hydrocarbon having 3 to 30 carbon atoms which may have a substituent. An aromatic heterocyclic group having 2 to 30 carbon atoms which may have a group or a substituent, and R ² represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, a lower alkyl group or a lower alkoxy group; , W represents a single bond, an oxygen atom or a sulfur atom, B represents an oxygen atom or a sulfur atom, D and E represent a nitrogen atom or CH, Y may have a substituent, and —CH ₂ —, —O—, —S—, —C═C—, —C≡C—, —COO—, —OCO—, —CO— , —SO ₂ — , —SiR ³ R ⁴ , —GeR ⁵ R ⁶ -, -NR < ⁷ >-, -CH = N-, C1-C25 bivalent containing the group chosen from a cyclic alkyl group, an aromatic ring group, and a heterocyclic group Wherein R ^{3 to} R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Z represents a single bond, —CH ₂ CH ₂ —, —C═. C—, —C≡C—, —COO—, —OCO—, —N≡N— or —CH═N— is shown. ]
M represents a group selected from the above , M may be different from each other, and may have a substituent, an alkyl group having 1 to 25 carbon atoms, a cyano group, an amino group, a hydroxyl group, a mercapto group, or a nitro group; ¹ represents a hydrogen atom, a halogen atom, a benzenesulfonyl group, a p-toluenesulfonyl group, a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group, a represents an integer of 1 to 3, and b represents an integer of 1 to 8. D represents an integer of 0 to 2, and e represents an integer of 0 to 7. ]
A compound represented by

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