WO2008016090A1 - Procédé de production d'un composé polymère - Google Patents

Procédé de production d'un composé polymère Download PDF

Info

Publication number
WO2008016090A1
WO2008016090A1 PCT/JP2007/065107 JP2007065107W WO2008016090A1 WO 2008016090 A1 WO2008016090 A1 WO 2008016090A1 JP 2007065107 W JP2007065107 W JP 2007065107W WO 2008016090 A1 WO2008016090 A1 WO 2008016090A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
ring
represented
aryl
formula
Prior art date
Application number
PCT/JP2007/065107
Other languages
English (en)
Japanese (ja)
Inventor
Takanobu Noguchi
Tomoyuki Suzuki
Makoto Anryu
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO2008016090A1 publication Critical patent/WO2008016090A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1475—Heterocyclic containing nitrogen and oxygen as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Definitions

  • the present invention relates to a method for producing a polymer compound.
  • High molecular weight light-emitting materials have been studied in various ways because they are useful as materials used in the light-emitting layer of light-emitting elements.
  • poly (arylene vinylene) -based polymer compounds represented by poly (phenylene vinylene) have been developed from an early stage as materials for organic electoluminescence, conductive materials, transistor materials, solar cell materials, etc. ing.
  • a method for producing a poly (arylene vinylene) -based polymer compound for example, [1] polymerization by a Wittig reaction between a compound having an aldehyde group and a compound having a group derived from a phosphonium salt (J. Am. Chem.
  • An object of the present invention is to provide a novel method for producing a poly (arylene vinylene) -based polymer compound and the like.
  • the present invention provides the following formula (1):
  • Ai and A 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group.
  • ⁇ and X 2 are each independently Represents a group or a borate residue.
  • Art represents an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a divalent aromatic which may have a substituent.
  • ⁇ beauty Upsilon 2 each independently represent a halogen atom, alkyl sulfonate group, ⁇ Li one Rusuruho sulfonate group or ⁇ reel alkylsulfonate group.
  • the compound represented by the following formula (3a) has the step of reacting with one or more compounds represented by the following formula in the presence of a palladium catalyst and a base:
  • the production method of the present invention comprises at least one compound represented by the formula (1) and one or more compounds represented by the formula (2) in a solvent in the presence of a palladium catalyst and a base.
  • the compound represented by the formula (1) and the compound represented by the formula (2) may be used alone or in combination of two or more.
  • the total of one or more compounds represented by the formula (2) with respect to 1 mol of the total of one or more compounds represented by the formula (1) is usually 0. 7 to 1.3 moles, preferably 0.9 to 1.1 moles, more preferably 0.95. ⁇ 1.05 mol.
  • Ai and A 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group. From the viewpoint of ease of synthesis, a hydrogen atom, an alkyl group, and an aryl group are preferable, and an alkyl group and an aryl group are more preferable.
  • At least one of the Ai and A 2 is an alkyl group or an aryl group, one of the Ai and A 2 is an alkyl group or an aryl group, and the other is a hydrogen atom.
  • the resulting polymer compound is excellent in solubility in an organic solvent, and when it is an aryl group, the solubility and heat resistance of the resulting polymer compound are excellent. Excellent in properties.
  • the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group.
  • Octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, etc. from the viewpoint of the solubility of the polymer compound, propyl group, butyl group, pentyl group A hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and a 3,7-dimethyloctyl group are preferable.
  • the aryl group usually has about 6 to 60 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a substituted phenyl group, a 1-naphthyl group, a substituted 1-naphthyl group, a 2-naphthyl group, a substituted 2-naphthyl group, and the like.
  • a phenyl group and a substituted phenyl group are preferred.
  • substituents examples include an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryloxy group, an arylalkyl group, an arylalkyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, 1 Valent heterocyclic group, acyl group, acyloxy group, substituted carboxyl group, cyano group and the like.
  • phenyl group C t C alkoxyphenyl group
  • ⁇ “Alkoxy” means that the alkoxy moiety has 1 to 12 carbon atoms, and the same shall apply hereinafter.
  • C i C alkylphenyl group “Ji! ⁇ Ji ⁇ alkyl” indicates that the alkyl moiety has 1 to 12 carbon atoms, and so on. )
  • a substituted carboxyl group is preferred. When a plurality of the substituents are present, they may be the same or different.
  • Alkyl phenyl group is a phenyl group in which an alkyl group having 1 to 12 carbon atoms is introduced as a substituent on the phenyl ring.
  • the number of substituents on the phenyl ring is preferably 1 to 5, more preferably 1 to 3, particularly preferably 1.
  • the 1 2 alkyl moiety (group) may be linear, branched or cyclic, and may further have a substituent.
  • Examples of the C 1 -C 12 alkyl moiety (group) include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, a pentyl group, and hexyl.
  • the C i C alkoxyphenyl group is a phenyl group in which an alkoxy group having 1 to 12 carbon atoms is introduced as a substituent on the phenyl ring.
  • the number of substituents on the phenyl ring is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
  • alkoxy moiety (group) examples include, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentyloxy group, A xyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, a lauryloxy group, and the like.
  • the alkoxy group having a substituent may be a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexoxy group, or a perfluoro group.
  • Oloctyloxy group, methoxymethyl Examples include a ruoxy group and a 2-methoxyethyloxy group.
  • the ⁇ to alkoxy moiety (group) is a butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, A octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, and a lauryloxy group are preferred.
  • the substituent isacyl group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Specific examples include a acetyl group, propionyl group, and propylyl group. , Isoptyryl group, bivaloyl group, trifluoroacetyl group and the like.
  • the asiloxy group as the substituent is usually about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Specific examples include acetoxy group, propionyloxy group, Examples include a butylyloxy group, an isoptyryloxy group, a bivalyloxy group, and a trifluoroacetyloxy group.
  • the substituted carboxyl group which is the substituent, usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms.
  • Specific examples include alkyl groups, aryl groups,
  • a force lpoxyl group substituted with an alkyl group is preferred.
  • methoxycarbonyl is substituted with an alkyl group or a monovalent heterocyclic group.
  • the monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound.
  • the carbon number of the monovalent heterocyclic group is usually about 4 to 60. Carbon number does not include the carbon number of the substituent.
  • Heterocyclic compounds are organic compounds with a cyclic structure. The constituent atoms include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. As the monovalent cyclic group, a monovalent aromatic heterocyclic group is preferable.
  • the monovalent heterocyclic group examples include a chenyl group, a C 1, a C 1 to C 2 alkyl enyl group, a pyraryl group, a furyl group, a pyridyl group, a cis-alkyl pyridyl group, and the like.
  • Group, same, ⁇ . , 2 alkyl enyl groups, pyridyl groups, C 1 , to C 1 2 alkyl pyridyl groups are preferred.
  • Monovalent heterocyclic groups also include monovalent complex residues such as groups derived from triplet luminescent complexes.
  • the monovalent complex residue means the remaining atomic group obtained by removing one hydrogen atom from a metal complex.
  • Specific examples of the monovalent complex residue include the following monovalent metal complex residues.
  • the monovalent aromatic amine group means a remaining atomic group obtained by removing one hydrogen atom from an aromatic amine.
  • the carbon number of the monovalent aromatic amine group is usually about 4 to 60. The carbon number does not include the carbon number of the substituent.
  • Specific examples of the monovalent aromatic amine group include groups represented by the following formulas 1 2 3 to 1 2 7.
  • R in the examples of these monovalent aromatic amine groups (the above formulas 123 to 127) is specifically described and exemplified as R in the examples of the arylene groups described below (the following formulas 1 to 38, A to K). It is the same as that.
  • a plurality of R may be the same or different.
  • ⁇ and X 2 each independently represent a boric acid residue (— ⁇ ( ⁇ ) 2 ) or a boric acid ester residue.
  • Ra independently represents an alkyl group or an aryl group.
  • the alkyl group and aryl group represented by Ra are the same as those described and exemplified as the alkyl group and aryl group represented by Ai and A 2 .
  • a ri has an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. Represents a divalent aromatic amine group.
  • ⁇ ⁇ ⁇ is an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an aryl alkyl group, an aryl alkyl group, an aryl alkenyl group, an aryl alkynyl group, an aryl amino group, It may have a substituent such as a monovalent heterocyclic group, an acyl group, an acyloxy group, a substitution force lpoxyl group or a cyano group. When A has a plurality of substituents, they may be the same or different from each other.
  • the arylene group means an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon.
  • the carbon number of the arylene group is usually about 6 to 60. The carbon number does not include the carbon number of the substituent.
  • Aromatic hydrocarbons include those having a condensed ring and those in which two or more independent benzene rings or condensed rings are bonded directly or via a group such as a vinylene group.
  • arylene group examples include a phenylene group (the following formulas 1 to 3), a naphthalene diyl group (the following formulas 4 to 13), an anthracenylene group (the following formulas 14 to 19), a biphenylene group ( The following formula 20 to 2 5), the triphenylene group (the following formula 26 to 28), the condensed ring compound group (the following formula 29 to 3 8), the stilbene diyl group (the following formula A to D), the distilbene Examples thereof include a diyl group (formula E, F) and a benzofluorene-diyl group (formula G, H, I, K).
  • each R is independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl.
  • one structural formula has a plurality of Rs, but they may be the same or different.
  • R the group represented by R will be described.
  • a plurality of R may be the same or different.
  • Two Rs may be bonded to each other to form a ring.
  • alkyl group, Ariru group is in the Ai, the A 2 terms are the same as those described and exemplified.
  • the alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group.
  • the alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, i-propylpropyl group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group.
  • octylthio group 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, etc.
  • pentylthio group, hexylthio group, octylthio group, 2-ethyl A xylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferred.
  • the alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms.
  • Specific examples of the alkylsilyl group include a methylsilyl group, an ethylsilyl group, a propylsilyl group, an i-propylsilyl group, a butylsilyl group, an i-butylsilyl group, a t-butylsilyl group, a pentylsilyl group, a hexylsilyl group, and a cyclohexylsilyl group.
  • the alkylamino group may be linear, branched or cyclic, and may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms.
  • Archi Specific examples of the ruamino group include a methylamino group, a dimethylamino group, an ethylamino group, a jetylamino group, a propylamino group, a propylamino group, a ptylamino group, an i-butylamino group, a t-butylamino group, a pentylamino group, a hexylamino group, Examples include cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group,
  • the aryloxy group usually has about 6 to 60 carbon atoms.
  • the tool body Examples of Ariruokishi group, phenoxy group, ⁇ ⁇ 12 alkoxy phenoxyethanol group, ⁇ Ji alkyl phenoxy group, 1-Nafuchiruokishi group, 2-Nafuchiruokishi group and the like, Ci ⁇ C 12 alkoxy phenoxyethanol group , C i ⁇ C i 2 alkylphenoxy group are preferable.
  • the aryl alkyl group usually has about 7 to 60 carbon atoms.
  • aryl alkyl groups include phenyl Ci C alkyl groups, d to C 12 alkoxy phenyl—Ci C alkyl groups, Ci C alkyl phenyl Ci C alkyl groups, 1-naphthyl Ci C alkyl groups, 2—naphthyl— ⁇ ⁇ . 12 alkyl groups and the like, d -C 12 alkoxy phenylalanine - C 1 -C 12 alkyl group, Ci C alkylphenyl - d ⁇ C i 2 alkyl groups are preferred.
  • the aryl group is usually about 7 to 60 carbon atoms.
  • Specific examples of aryloxy groups include phenyl-d Cu alkoxy groups and Ci C alkoxy groups.
  • ⁇ Ji alkoxy group, ⁇ ⁇ ⁇ 12 Arukirufue two Lu Ci C alkoxy group, 1-naphthyl - ⁇ ⁇ . 12 alkoxy group, 2-naphthyl-d to C 12 alkoxy group and the like can be mentioned, Ci C alkoxy phenyl Ci C alkoxy group, C 1 to C 12 alkyl phenyl Ci d 2 alkoxy group are preferable.
  • the aryl alkenyl group usually has about 8 to 60 carbon atoms.
  • arylalkenyl groups include phenyl C 2 -C 12 alkenyl groups (“C 2 -C 12 alkenyl J indicates that the alkenyl moiety has 2 to 12 carbon atoms, and the same.), d ⁇ C 12 Arukokishifue two Lou C 2 -C 12 alkenyl group, C 1 -C 12 Arukirufue two Lou C 2 ⁇ C 12 alkenyl group, 1-Nafuchiru C 2 -C 12 alkenyl group, 2-naphthyl - C 2 ⁇ d 2 alkenyl groups and the like, Ci C Arukokishifue two Lou C 2 -C 12 alkenyl group, -C 12 Arukirufue two Lou C 2 -C 12 alkenyl groups are preferred.
  • the arylene alkynyl group usually has about 8 to 60 carbon atoms.
  • ⁇ Li one Rua Rukiniru group, phenylene Lou C 2 to d 2 alkynyl group ( "C 2 ⁇ C 12 alkynyl” means that the carbon number of the alkynyl moiety is 2 to 12, less The same applies to the following:), cis-alkoxyphenyl—C 2 -C 12 alkynyl group, Ci C alkylphenyl relay C 2 -C 12 alkynyl group, 1-naphthyl-C 2 -C 12 alkynyl group, 2-naphthyl-C 2 -C 12 alkynyl groups and the like, Ci C alkoxy phenylalanine - C 2 -C 12 al Kiniru group, d C alkylphenyl - C 2 ⁇ C 12 alkynyl group are preferable.
  • the arylamine group usually has about 6 to 60 carbon atoms.
  • arylamino groups include phenylamino groups, diphenylamino groups, Ci C alkoxyphenylamino groups, di (Ci C alkoxyphenyl) amino groups, di (Ci C alkylphenyl) amino groups, 1-naphthylamino groups, 2— A naphthylamino group and the like, and d to C 12 alkylphenylamino groups and di (Ci C alkylphenyl) amino groups are preferred.
  • the asil group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Specific examples thereof include an acetyl group, a propionyl group, a petityl group, an isobutyryl group, and a bivaloyl group. A benzoyl group, a trifluoroacetyl group, a pentafluorobenzoyl group, and the like.
  • the asiloxy group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms, and specific examples thereof include an acetoxy group, a propionyloxy group, a butylyloxy group, an isoptyryloxy group. Examples thereof include a xyl group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.
  • the substitution force lpoxyl group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Specific examples thereof include an alkyl group, an aryl group, an arylalkyl group, or a monovalent alkyl group.
  • a methoxycarbonyl group for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an i-propoxy group, and the like.
  • Xoxycarbonyl group butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexoxycarbonyl group, heptyloxycarbonyl group, o Ctyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group , Pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, PA R NI fluorhexoxycarbony
  • the monovalent heterocyclic group, with the Ai, the A 2 terms are the same as those described and exemplified.
  • the alkyl chain may be interrupted by a group containing a hetero atom or a hetero atom.
  • this hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • the group containing a hetero atom or a hetero atom include the following.
  • R ′ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, or 4 to 4 carbon atoms.
  • 60 is a monovalent heterocyclic group. When there are multiple R's, they may be the same or different.
  • the alkyl group, aryl group, and monovalent heterocyclic group represented by R ′ are examples of the above arylene group.
  • the A ring and the B ring each independently represent an aromatic hydrocarbon ring which may have a substituent.
  • Two bonds are present on the A ring and the Z or B ring, respectively, and are independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group.
  • the groups represented by Rw and Rx are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an aryl group.
  • the valent heterocyclic group, the acyl group, and the substitution force lpoxyl group are described and exemplified as the substituent represented by R in the above examples of the arylene group (the above formulas 1 to 38, A to K). Is the same. From the viewpoint of ease of synthesis of the monomer, it is preferable that Rw and Rx in the above formula (60) are the same group.
  • At least one of the A ring and the B ring is an aromatic hydrocarbon ring in which a plurality of benzene rings are condensed.
  • the aromatic hydrocarbon ring is preferably a benzene ring alone or a condensed benzene ring, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentocene ring, and a pyrene ring.
  • an aromatic hydrocarbon ring such as a phenanthrene ring, preferably a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring.
  • a combination of the A ring and the B ring is preferably a benzene ring, a benzene ring, or a benzene ring.
  • Rg independently represents a hydrogen atom, an alkyl group or an aryl group.
  • a plurality of Rg may be the same or different.
  • Two R g s may be bonded to each other to form a ring. :) Those represented by any of the above are particularly preferred.
  • the alkyl group represented by Rg, Ariru group, with the Ai, the A 2 terms are the same as those described and exemplified. From the viewpoint of solubility of the polymer compound in an organic solvent, a group containing an alkyl chain such as an alkyl group is preferred.
  • Examples of the arylene group which may have a substituent include those represented by the above formula (60) and the above formulas (2 A) to (2D). ), Naphthalene diyl group (formula 4 to 13), biphenylene group (formula 20 to 25), fluorene-zyl group (formula 36 to 38), stilbene diyl (formula A to D), Distilbene-zyl (formula E, F), benzofluorene diyl (formula G, H, I, K) and the like are preferred from the viewpoint of ease of synthesis of the compound represented by formula (2).
  • the divalent heterocyclic group means an atomic group remaining after removing two hydrogen atoms from the heterocyclic compound.
  • the divalent heterocyclic group usually has about 4 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent.
  • a heterocyclic compound is an organic compound having a cyclic structure in which not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, and fluorine are included in the ring. Say things.
  • a divalent aromatic heterocyclic group that is, a divalent heterocyclic group having aromaticity
  • Examples of the divalent heterocyclic group include the following.
  • Fluorene structure containing hetero atoms such as silicon, nitrogen, oxygen, sulfur, selenium, etc. ie, one of the carbon atoms constituting the 5-membered ring in the fluorene ring is silicon, nitrogen, oxygen
  • 5-membered heterocyclic groups containing atoms such as silicon, nitrogen, oxygen, sulfur, selenium as heteroatoms (94 to 98 below).
  • 5-membered condensed heterocyclic groups containing atoms such as silicon, nitrogen, oxygen, sulfur, selenium as hetero atoms (the following formulas 99 to 108).
  • each R is independently in the term of the arylene group (the above formulas 1 to 38, A to K Same as explained and exemplified).
  • a plurality of R may be the same or different.
  • C ring and D ring each independently represent an aromatic ring.
  • C ring and D ring are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, aryl alkyl group, aryl alkoxy group, arylalkyl group, aryl It may have a substituent selected from the group consisting of an alkynyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, an acyloxy group, a substitution force lpoxyl group and a cyano group.
  • E is O or S.
  • the thing represented by these is preferable.
  • Aromatic rings represented by C ring and D ring are aromatic hydrocarbon rings such as benzene ring, naphthenic ring, anthracene ring, tetracene ring, pennantene ring, pyrene ring, phenanthrene ring; pyridine ring, biviridine Heteroaromatic rings such as a ring, a phenantol ring, a quinoline ring, an isoquinoline ring, a thiophene ring, a furan ring and a pyrrole ring. From the viewpoint of ease of synthesis of the compound represented by the formula (2) Is preferably a benzene ring.
  • the divalent heterocyclic group optionally having a substituent represented by the formula (70) is represented by the following formula (2) from the viewpoint of ease of synthesis of the compound represented by the formula (2).
  • Rj and Rk each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group.
  • Rj and Rk are the same (ie, both are a hydrogen atom, an alkyl group, an alkoxy group or an alkyl group) because of the ease of synthesis of the compound represented by the formula (2).
  • a aryl group and preferably an alkoxy group.
  • Rj and Rk Alkyl group Ariru group, the Ai, in terms of A 2, to be the same as to those described and illustrated.
  • alkoxy group represented by Rj and Rk from the viewpoint of solubility of the obtained polymer compound in an organic solvent, a butoxy group, an i-butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, Heptyloxy group, octyloxy group, 2-ethyl hexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group are preferred, pentyloxy group, hexyloxy group, octyloxy group, 2-ethyl More preferred are a hexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group.
  • Ra, Rb, Rc and Rd each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • m 'and n' are each independently 1 or 2)
  • one or more of Ra, Rb, Rc and Rd are preferably alkyl groups from the viewpoint of solubility of the resulting polymer compound in an organic solvent.
  • the divalent aromatic amine group means the remaining atomic group obtained by removing two hydrogen atoms from the aromatic amine.
  • the divalent aromatic amine group usually has about 4 to 60 carbon atoms. Carbon number does not include the carbon number of the substituent.
  • Examples of the divalent aromatic amine group include a group represented by the following formula (3).
  • a r 6 and A r 8 are each independently an arylene group optionally having a substituent, A group represented by the following formula (4) or a group represented by the following formula (5) is represented, Ar 7 is an aryl group which may have a substituent, a group represented by the following formula (6) or a group represented by the following formula (7), 1 '6 and eight between, 1 "6 and eight 1" 8 during, or form a ring between the a r 7 and a r 8 Also good.
  • Ar 14 represents an arylene group which may have a substituent
  • Ar 17 and Ar 18 each independently represent an aryl group which may have a substituent
  • a ring may be formed between 14 and 1 " 17 , between 8 1 to 14 and 8 1" 18 , or between A r 17 and A r 18 .
  • Ar 15 represents an arylene group which may have a substituent
  • Ar 16 represents an aryl group which may have a substituent
  • Rii and Ri 2 are each independently Represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group.
  • the arylene group optionally having a substituent represented by Ar 6 , Ar 8 to Ar 12 , Ar 14 and Ar 15 is represented by the formula (2): In the term, it is the same as the arylene group described and exemplified as 8 ⁇ . In view of ease of synthesis of the formula (2), a phenylene group is preferable.
  • the aryl group which may have a substituent represented by Ar 7 , Ar 13 and Ar 16 to Ar 18 is the term of the arylene group.
  • the alkyl group, aryl group, and monovalent heterocyclic group represented by R9 to Ri2 are the same as those in the above-mentioned arylene group (the above formulas 1 to 38, A to The same as the alkyl group, aryl group, and monovalent heterocyclic group described and exemplified as R) of K.
  • Ar 6 to Ar 18 are an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an aryl alkyl group, an aryl alkyl group.
  • a substituent such as a group, an aryl alkenyl group, an aryl alkynyl group, an aryl amino group, a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group, and a cyano group.
  • divalent aromatic amine group examples include the following groups.
  • R is the term of the arylene group (the above formulas 1 to 38, as R in A to K) Same as described and illustrated.
  • a plurality of R may be the same or different.
  • ⁇ and Y 2 each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group, and the synthesis of the formula (2) From the viewpoint of easiness, a halogen atom is preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a bromine atom and an iodine atom are preferable, and a bromine atom is more preferable.
  • alkyl sulfonate group examples include a methane sulfonate group, an ether sulfonate group, a trifluoromethane sulfonate group, and the like.
  • aryl sulfonate groups examples include benzene sulfonate groups and ⁇ -toluene sulfonate groups.
  • arylsulfonate groups examples include benzyl sulfonate groups.
  • Rb is independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkyl group, an aryl group.
  • An alkynyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, an acyloxy group, and a substituent lpoxyl group are the above arylene groups (the above formulas 1 to 38, A to K). This is the same as described and exemplified as the substituent represented.
  • a plurality of Rb may be the same or different.
  • Examples of the palladium catalyst used in the production method of the present invention include palladium [tetrakis (triphenylphosphine)], paradimacetates, dichlorobis (including the Pd (0) catalyst, Pd (II) catalyst, etc.).
  • Triphenylphosphine) Palladium (II) and the like are exemplified, but dichlorobis (triphenylphosphine) palladium ( ⁇ ) is preferred from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate.
  • the addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst. Usually, 0.0001 mol to 0.5 mol is preferable with respect to 1 mol of the compound represented by the formula (1). Is 0.0003 mol to 0.1 mol.
  • the base used in the production method of the present invention is an inorganic base, an organic base, an inorganic salt, or the like.
  • the inorganic base include potassium carbonate, sodium carbonate, barium hydroxide and the like.
  • the organic base include trytylamine, tryptylamine and the like.
  • the inorganic salt include cesium fluoride.
  • the amount of the base added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 0.9 mol to 10 mol, and more preferably 1 mol of the compound represented by the formula (1). Is from 1 mol to 10 mol, particularly preferably from 1 mol to 5 mol.
  • a phosphorus compound such as triphenylphosphine, tri ( ⁇ -tolyl) phosphine, tri ( ⁇ -methoxyphenyl) phosphine can be added as a ligand.
  • the addition amount of the ligand is usually 0.5 mol to 100 mol, preferably 0.9 mol 20 mol, more preferably 1 mol to 10 mol with respect to 1 mol of the palladium catalyst.
  • the reaction is usually performed in a solvent.
  • the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. From the viewpoint of the solubility of the poly (arylenvinylene) polymer compound, toluene and tetrahydrofuran are preferred.
  • the base may be added as an aqueous solution and reacted in a two-phase system.
  • an inorganic salt is used as a base, it is usually added as an aqueous solution and reacted in a two-phase system from the viewpoint of solubility of the inorganic salt.
  • a phase transfer catalyst such as a quaternary ammonium salt may be added as necessary.
  • the temperature at which the reaction is carried out depends on the solvent, but is usually about 50 to 160, and is preferably 60 to 120 from the viewpoint of the high molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
  • reaction time may be the end point when the desired degree of polymerization is reached, but is usually about 0.1 to 200 hours, and about 0.5 to 30 hours is efficient and preferable. More preferably, the time is about 30 hours.
  • the reaction is carried out in a reaction system in which the P d (0) catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas.
  • an inert atmosphere such as argon gas or nitrogen gas.
  • argon gas or nitrogen gas for example, in a system that has been sufficiently degassed with argon gas or nitrogen gas.
  • the compound represented by the above formula (1) and the above formula (2) are contained in this polymerization container.
  • a palladium catalyst for example, dicyclobis (triphenylphosphine) palladium (II) catalyst
  • 10 to 20 weights of a base such as sodium carbonate
  • a 1% aqueous solution 1 to 20 moles (typically 1 to 10 moles) of 1 to 20 moles of the compound represented by the formula (1).
  • a phase transfer catalyst adding a phase transfer catalyst, and reacting at reflux temperature for 1 to 30 hours under an inert atmosphere.
  • R is the same as explained and exemplified in the above-mentioned arylene group (as R in the above formulas 1 to 38, A to K).
  • Ai and A 2 are the same as those described and exemplified as Ai and A 2 in the formula (1).
  • a plurality of R may be the same or different.
  • R is the same as described and exemplified in the above-mentioned arylene group (as R in the above formulas 1 to 38, AK). Multiple Rs are the same but different It may be.
  • the polymer compound obtained from the production method of the present invention has a polystyrene-equivalent number average molecular weight of typically 1 ⁇ 10 3 to: 1 ⁇ 10 8, more typically 2 ⁇ 10 3 ⁇ 1 X 1 0 7.
  • the polymer compound obtained by the production method of the present invention when a group (usually referred to as a polymerization active group) that is involved in polymerization remains in a group located at the molecular chain terminal (that is, terminal group),
  • a molecular compound is used in a light-emitting element, the light emission characteristics and lifetime may be reduced, and therefore, it may be protected with a stable group that does not participate in polymerization.
  • the terminal group preferably has a conjugated bond continuous with the substantial conjugated structure of the molecular chain main chain. Further, for example, it may be a structure bonded to an aryl group or a heterocyclic group via a vinylene group.
  • substituents described in Chemical formula 10 of JP-A-9-45478 are exemplified.
  • the molecular chain main chain is usually substantially conjugated.
  • substantially conjugated means usually 50 to 100 mol%, preferably 80 to 100 mol%, based on all repeating units constituting the molecular chain main chain.
  • the repeating unit may be linked with a non-conjugated part, or the repeating unit may contain a non-shared part.
  • Examples of the bonding structure including the non-conjugated portion include those shown below, in which two or more of the following are combined.
  • R * represents the same group as R ′.
  • Ar represents a hydrocarbon group having 6 to 60 carbon atoms.
  • the hydrocarbon group represented by Ar is specifically a group in which a hydrogen atom such as benzene, biphenyl, evening phenyl, naphthalene, anthracene, or the like is a bond.
  • the polymer compound obtained by the production method of the present invention may be any of an alternating copolymer, a random copolymer, a block copolymer, or a graft copolymer, or a high molecular weight intermediate structure thereof. It may be a molecule, for example, a random copolymer with block properties. From the viewpoint of obtaining a polymer compound having high fluorescence intensity, a random copolymer having block properties, a block copolymer or a graft copolymer is preferable to a complete random copolymer.
  • the polymer compound of the present invention includes a dendrimer when the main chain is branched and there are three or more terminal portions.
  • the polymer compound obtained from the production method of the present invention can be partially or wholly dissolved or dispersed in a solvent as necessary.
  • the good solvent for the polymer compound include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene.
  • it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.
  • the polymer compound obtained by the production method of the present invention is useful, for example, as a material for an organic electoluminescence light emitting material, an optical material, a thin film, an organic semiconductor (such as an organic transistor), and a solar cell.
  • EXAMPLES Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
  • the molecular weights of the compounds determined in Examples are the number average molecular weight and the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
  • polymer compound 1 a polymer (hereinafter, this polymer is referred to as “polymer compound 1”).
  • the polystyrene equivalent weight average molecular weight of the polymer compound 1 was 7. OX 10 3 , and the polystyrene equivalent number average molecular weight was 4.2 ⁇ 10 3 .
  • the structure of the repeating unit contained in polymer compound 1 deduced from the preparation is as follows.
  • Monomer (2) 0. 676 g, said monomer (100) 0.356 g, methyl trioctyl ammonium chloride (trade name: aliquat336, made by Aldrich,
  • polymer compound 2 The weight average molecular weight in terms of polystyrene of the polymer compound 2 is 8. 0 X 103, number average molecular weight of Po polystyrene-equivalent 4. was 9X 1 0 3.
  • the structure of the repeating unit contained in polymer compound 2 deduced from the preparation is as follows.
  • polymer compound 3 The weight average molecular weight in terms of polystyrene of the polymer compound 3 7. a 5X 1 0 3, the number average molecular weight of polystyrene-equivalent 4. was 6X 1 0 3.
  • the structure of the repeating unit contained in polymer compound 3 deduced from the preparation is as follows.
  • Monomer (3) 0.127 g, the monomer (1) 0.44 lg, the monomer (1 00) 0.352 g, and methyltrioctyl ammonium chloride.
  • dichlorobis (triphenylphosphine) palladium (II) 1. 6 mg was charged into the reaction vessel, and the inside of the reaction vessel was thoroughly replaced with argon gas. To this reaction vessel was added 15 ml of toluene that had been degassed by publishing with argon gas in advance.
  • polymer compound 4 This polymer was referred to as “polymer compound 4”).
  • the polymer compound 4 had a polystyrene equivalent weight average molecular weight of 1.1 ⁇ 10 4 and a polystyrene equivalent number average molecular weight of 6.0 ⁇ 103.
  • Monomer (1) 0.440 g, Monomer (3) 0.126 g, Monomer (200) 0.357 g, Methyltrioctyl ammonium chloride (trade name) : Aliquat336, manufactured by Aldrich, CH 3 N [(CH 2 ) 7 CH 3 ] 3 C1, density 0.884g / ml, 25t: trademark of Henkel Corporation) 0.13 g and diclonal bis (triphenylphosphine) palladium (II ) 1. 6 mg was charged into a reaction vessel, and the reaction vessel was thoroughly replaced with argon gas. To this reaction vessel, 15 ml of toluene which had been degassed by publishing with argon gas in advance was added.
  • this solution is pre-published with argon gas.
  • Degassed 16.7 wt% aqueous sodium carbonate solution 5 ml 1 was added dropwise over several minutes, and then the temperature was raised and refluxed for 11 hours. The reaction was performed in an argon gas atmosphere.
  • the reaction solution was cooled to near room temperature, and then 40 g of toluene was added to the reaction solution. Next, this reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, the obtained toluene solution was filtered to remove insoluble matters, and then the toluene solution was purified by passing through an alumina column. Next, the obtained toluene solution was concentrated under reduced pressure, poured into methanol, re-precipitated, and the generated precipitate was collected. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain 0.3 g of a polymer (hereinafter, this polymer is referred to as “polymer compound 5”).
  • the polymer compound 5 had a polystyrene equivalent weight average molecular weight of 8.7 ⁇ 103 and a polystyrene equivalent number average molecular weight of 4.8 ⁇ 10 3 .
  • Repeat unit C ⁇ Repeat unit C ' Monomer (5) 0.144 g, the monomer (200) 0.356 g, methyltrioctylmonum chloride (trade name: aliquat336, made by Aldricli,
  • the reaction solution was cooled to near room temperature, and 15 ml of toluene was added to the reaction solution. Next, this reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, the obtained toluene solution was filtered to remove insoluble matters, and then the toluene solution was poured into methanol and re-precipitated, and the generated precipitate was recovered. The obtained precipitate was dried under reduced pressure and then dissolved in toluene. Next, the obtained toluene solution was purified by passing through an alumina column. Next, the obtained toluene solution was concentrated under reduced pressure, poured into methanol, re-precipitated, and the generated precipitate was collected.
  • polymer compound 6 The polymer compound 6 had a polystyrene equivalent weight average molecular weight of 5.5 ⁇ 10 3 and a polystyrene equivalent number average molecular weight of 3.8 ⁇ 103.
  • the monomer represented by (6) 0.826 g, the monomer (100) 0.355 g, methyl trioctylammonium chloride (trade name: aliquat336, made by Aldrich,
  • reaction solution was cooled to near room temperature, and toluene 30 was added to the reaction solution. Next, this reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, the obtained toluene solution was filtered to remove insoluble matters, and then the toluene solution was purified by passing through an alumina column. Next, the obtained toluene solution was poured into methanol and reprecipitated, and the generated precipitate was recovered. The obtained precipitate was dried under reduced pressure and then dissolved in toluene. The obtained toluene solution was poured into methanol and re-precipitated, and the generated precipitate was recovered.
  • polymer compound 7 a polymer (hereinafter, this polymer is referred to as “polymer compound 7”).
  • High molecular compound 7 polystyrene equivalent The weight average molecular weight was 7.3 ⁇ 10 3 and the number average molecular weight in terms of polystyrene was 6.0 ⁇ 10 03.
  • the structure of the repeating unit contained in polymer compound 7 deduced from the preparation is as follows.
  • Monomer (8) 0.1 18 g and the monomer (200) 0.445 g, methyl trioctyl ammonium chloride (trade name: aliquat336, made by Aldrich,
  • reaction solution After completion of the reaction, the reaction solution is cooled to near room temperature, and then toluene is added to this reaction solution. Was added. Next, this reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, the obtained toluene solution was filtered to remove insoluble matters, and then the toluene solution was poured into methanol and re-precipitated, and the generated precipitate was recovered. The obtained precipitate was dried under reduced pressure and then dissolved in toluene. Next, the obtained toluene solution was purified by passing through an alumina column. Next, the obtained toluene solution was concentrated under reduced pressure, poured into methanol, re-precipitated, and the generated precipitate was collected.
  • polymer compound 8 The polymer compound 8 had a polystyrene equivalent weight average molecular weight of 6. IX 10 3 and a polystyrene equivalent number average molecular weight of 4.0X 103.
  • the reaction solution was cooled to near room temperature, and 30 ml of toluene was added to the reaction solution. Next, this reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, the obtained toluene solution was filtered to remove insoluble matters, and then the toluene solution was poured into methanol and re-precipitated, and the generated precipitate was recovered. The obtained precipitate was dried under reduced pressure and then dissolved in toluene. Next, the obtained toluene solution was purified by passing through an alumina column. Next, the obtained toluene solution was concentrated under reduced pressure, poured into methanol, re-precipitated, and the generated precipitate was collected.
  • polymer compound 9 a polymer (hereinafter, this polymer is referred to as “polymer compound 9”).
  • the polymer compound 9 had a polystyrene equivalent weight average molecular weight of 7.5 ⁇ 10 3 and a polystyrene equivalent number average molecular weight of 4.6 ⁇ 103.
  • a polymer compound such as a poly (arylene vinylene) -based polymer compound and a polymer compound having a substituent on the vinylene group can be easily produced.
  • the polymer compound thus obtained is useful for electronic materials, particularly polymer light emitting devices, segment display devices, dot matrix display devices, backlights for liquid crystal display devices, organic solar cells, solar cells, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un procédé de production d'un composé polymère contenant un motif répété répondant à la formule (3a) et/ou un motif répété répondant à la formule (3b), ledit procédé comprenant une étape consistant à faire réagir un ou plusieurs composés de formule (1) avec un ou plusieurs composés de formule (2), en présence d'un catalyseur au palladium et d'une base. (1) : X1-C(A1)=C(A2)-X2 ; (2) : Y1-Ar1-Y2 ; (3a) : -C(A1)=C(A2)-Ar1- ; (3b) : -C(A2)=C(A1)-Ar1-. Dans ces formules, A1 et A2 représentent un atome d'hydrogène, un groupe alkyle, un groupe aryle ou similaire ; X1 et X2 représentent un résidu acide borique ou un résidu ester d'acide borique ; Ar1 représente un groupe arylène, un groupe hétérocyclique divalent ou un groupe amine aromatique divalent ; enfin Y1 et Y2 représentent un atome d'halogène ou similaire.
PCT/JP2007/065107 2006-07-31 2007-07-26 Procédé de production d'un composé polymère WO2008016090A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006207728 2006-07-31
JP2006-207728 2006-07-31

Publications (1)

Publication Number Publication Date
WO2008016090A1 true WO2008016090A1 (fr) 2008-02-07

Family

ID=38997265

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/065107 WO2008016090A1 (fr) 2006-07-31 2007-07-26 Procédé de production d'un composé polymère

Country Status (1)

Country Link
WO (1) WO2008016090A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012076836A1 (fr) 2010-12-06 2012-06-14 Cambridge Display Technology Limited Couche d'injection de trous
US9054328B2 (en) 2011-06-24 2015-06-09 Cambridge Display Technology Limited Process for controlling the acceptor strength of solution-processed transition metal oxides for OLED applications
US9390921B2 (en) 2010-12-06 2016-07-12 Cambridge Display Technology Limited Adhesion layer for solution-processed transition metal oxides on inert metal contacts
US10205108B2 (en) 2012-09-13 2019-02-12 Cambridge Display Technology Limited Compound

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001247861A (ja) * 1999-12-20 2001-09-14 Sumitomo Chem Co Ltd 高分子蛍光体、その製造方法および高分子発光素子
JP2001515909A (ja) * 1997-09-08 2001-09-25 コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション ジボロン酸を使用する有機ボロン酸誘導体の製造方法
JP2002527443A (ja) * 1998-10-14 2002-08-27 コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション 有機ホウ素誘導体、及び有機化合物をカップリングさせる方法
JP2004168999A (ja) * 2002-10-30 2004-06-17 Sumitomo Chem Co Ltd 高分子化合物およびそれを用いた高分子発光素子
JP2005506418A (ja) * 2001-10-25 2005-03-03 ケンブリッジ ディスプレイ テクノロジー リミテッド エマルジョンのスズキカップリングによる共役ポリマーの製法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001515909A (ja) * 1997-09-08 2001-09-25 コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション ジボロン酸を使用する有機ボロン酸誘導体の製造方法
JP2002527443A (ja) * 1998-10-14 2002-08-27 コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション 有機ホウ素誘導体、及び有機化合物をカップリングさせる方法
JP2001247861A (ja) * 1999-12-20 2001-09-14 Sumitomo Chem Co Ltd 高分子蛍光体、その製造方法および高分子発光素子
JP2005506418A (ja) * 2001-10-25 2005-03-03 ケンブリッジ ディスプレイ テクノロジー リミテッド エマルジョンのスズキカップリングによる共役ポリマーの製法
JP2004168999A (ja) * 2002-10-30 2004-06-17 Sumitomo Chem Co Ltd 高分子化合物およびそれを用いた高分子発光素子

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAKAKAZU YAMAMOTO ET AL.: "Preparation of Polyacetylenes via Organometallic C-C Coupling Reactions", POLYMER BULLETIN, vol. 52, 2004, pages 315 - 319, XP003021022 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012076836A1 (fr) 2010-12-06 2012-06-14 Cambridge Display Technology Limited Couche d'injection de trous
DE112011104040T5 (de) 2010-12-06 2013-09-12 Cambridge Display Technology Limited Lochinjektionsschichten
US9390921B2 (en) 2010-12-06 2016-07-12 Cambridge Display Technology Limited Adhesion layer for solution-processed transition metal oxides on inert metal contacts
US9054328B2 (en) 2011-06-24 2015-06-09 Cambridge Display Technology Limited Process for controlling the acceptor strength of solution-processed transition metal oxides for OLED applications
US10205108B2 (en) 2012-09-13 2019-02-12 Cambridge Display Technology Limited Compound

Similar Documents

Publication Publication Date Title
JP5867489B2 (ja) 高分子材料およびそれを用いた素子
KR101215745B1 (ko) 고분자 화합물 및 그것을 이용한 고분자 발광 소자
KR101235971B1 (ko) 고분자 화합물 및 이를 이용한 고분자 발광 소자
US20030168656A1 (en) New polymer and polymer light-emitting device using the same
US20030068527A1 (en) Polymeric fluorescent substrate and polymer light-emitting device using the same
DE10392453T5 (de) Metallkomplex und organische elektrolumineszierende Vorrichtung
WO2007043495A1 (fr) Dispositifs électroluminescents à base de copolymères et de polymères fabriqués en utilisant ces derniers
EP2325226A1 (fr) Composés de copolymère d'aryle et dispositif électroluminescents à polymère fabriqués à partir de ceux-ci
GB2442655A (en) Polymeric material and polymeric luminescent element
JP4635528B2 (ja) 発光材料およびそれを用いた発光素子
WO2007081058A1 (fr) Compose polymere et dispositif electroluminescent polymere associe
JP2001342459A (ja) 高分子蛍光体、その製造方法、およびそれを用いた高分子発光素子
WO2008016090A1 (fr) Procédé de production d'un composé polymère
JP2003147347A (ja) 高分子蛍光体およびそれを用いた高分子発光素子
US20070103059A1 (en) Composition and polymer light-emitting device
JP5405797B2 (ja) 高分子化合物の製造方法
JP4752192B2 (ja) 組成物および高分子発光素子
JP2008056911A (ja) 高分子化合物の製造方法
JP5217633B2 (ja) 高分子化合物の製造方法
JP5059345B2 (ja) 反応性芳香族高分子化合物の製造方法
JP3762998B2 (ja) フッ素イオン検出用剤及びその製造方法
JP2005248092A (ja) ジベンゾジシラアゼピン系重合体、その製造方法、それを利用した蛍光材料及びそれを利用した電子素子、並びにジベンゾジシラアゾシン系重合体、その製造方法、それを利用した蛍光材料及びそれを利用した電子素子
JP4196736B2 (ja) 高分子化合物およびそれを用いた高分子発光素子
JP2004083637A (ja) 重合法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07791787

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 07791787

Country of ref document: EP

Kind code of ref document: A1