WO2008016090A1 - Method for producing polymer compound - Google Patents

Abstract

Disclosed is a method for producing a polymer compound containing a repeating unit represented by the formula (3a) below and/or a repeating unit represented by the formula (3b) below, which comprises a step for reacting one or more compounds represented by the formula (1) below and one or more compounds represented by the formula (2) below in the presence of a palladium catalyst and a base. X1-C(A1)=C(A2)-X2 (1) Y1-Ar1-Y2 (2) -C(A1)=C(A2)-Ar1- (3a) -C(A2)=C(A1)-Ar1- (3b) (In the formulae, A1 and A2 represent a hydrogen atom, an alkyl group, an aryl group or the like; X1 and X2 represent a boric acid residue or a boric acid ester residue; Ar1 represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; and Y1 and Y2 represent a halogen atom or the like.)

Description

 TECHNICAL FIELD Technical Field

 The present invention relates to a method for producing a polymer compound.

Background art

 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. Among them, 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. As 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. Soc., Vol.82, 4669-4671 (I960)), [2] Polymerization by Heck reaction of a compound having a vinyl group and a compound having a halogen atom (MakromoLChem. 189, 119-127 (1988)) [3] Polymerization by the Heck reaction between ethylene and a compound having a halogen atom (MakromoLChem. 192, 967-979 (1991)), [4] Heavy compounding of a compound having a methyl halide group by the deoctagonal hydrogenation method. Condensation (J. Poly. Sci. A-1, Vol. 4, 1337-1349 (1966)), [5] Polymerization of aldehyde-containing compounds by McMurry reaction (Makromol. Chem. Rapid Commun. 11, 375-379 (1990)) has been proposed.

Disclosure of the invention

 An object of the present invention is to provide a novel method for producing a poly (arylene vinylene) -based polymer compound and the like.

 As a result of intensive studies, the present inventors have made the present invention. That is, the present invention provides the following formula (1):

[Wherein, 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. Χΐ and X ² are each independently Represents a group or a borate residue. ]

And one or more compounds represented by the following formula (2):

[In the formula, 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. Represents an amine group. Υΐ及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:

 C (AO = C (A2) -A r i-(3 a)

[Wherein, Ari, Ai and A ² each independently have the same meaning as described above. ] A repeating unit represented by Z or the following formula (3b):

[Wherein, Α _{Γ ι} , Ai and A ² each independently have the same meaning as described above. ] The manufacturing method of the high molecular compound which has a repeating unit represented by these. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the production method of the present invention will be described in detail. In the present specification, when a vinylene moiety is present in the structure, the moiety may be a cis or trans structure. 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. A polymer compound having a repeating unit represented by the formula (3a) and a repeating unit represented by Z or the formula (3b). . 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.

In the production method of the present invention, 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.

 • Compound represented by formula (1)

In the above 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. 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.

It is preferable that 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. When at least one of Ai and A ² is an alkyl group, 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. Examples of the substituent 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. From the viewpoint of ease of monomer synthesis, 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.

^ ~ O _{1 2} 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.

^ ~ Ji ^ ~ in the alkylphenyl group. _{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. Group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, Perfluorobutyl group, perfluorinated hexyl group, perfluorooctyl group, etc., but from the viewpoint of solubility of the polymer compound in the solvent, butyl group, i-butyl group, t-butyl group , Pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group are preferred, hexyl group, heptyl group, o Butyl group, a cyclohexyl group 2 Echiru, 3, 7-Jimechiruokuchiru group is more preferable.

 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.

Examples of the alkoxy moiety (group) 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. From the viewpoint of the solubility of the polymer compound in the solvent, 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, For example, from the viewpoint of ease of synthesis, a force lpoxyl group substituted with an alkyl group is preferred. More specifically, methoxycarbonyl is substituted with an alkyl group or a monovalent heterocyclic group. Group, ethoxycarbonyl group, propoxycarbonyl group, i-propyloxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclo Hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl Group, nonyloxycarbonyl group, decoxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group Group

—Fluorobutoxycarbonyl group, perfluorohexoxycarbonyl group, perfluoropolyoctylcarbonyl group, phenoxy group, etc.

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. Specific examples of the monovalent heterocyclic group 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. In the above formula (1), Χΐ and X ² each independently represent a boric acid residue (—Β (ΟΗ) ₂ ) or a boric acid ester residue.

As a boric acid ester residue, the following formula:

 (In the formula, Me represents a methyl group, and Et represents an ethyl group.)

The group etc. which are represented by these are illustrated.

Specific examples of the compound represented by the formula (1) include the following formula:

 (In the formula, Ra independently represents an alkyl group or an aryl group.)

And more specifically, and more specifically,

The thing etc. which are represented by are mentioned.

In the above formula, 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 .

• Compound represented by formula (2)

 In the above formula (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.

Ι ι ^ 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. These substituents are the same as those specifically described and exemplified as R in the examples of the arylene group described below (the following formulas 1 to 38 and Α to Κ). In the above formula (2), 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.

 Examples of the arylene group 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). Among these, from the ease of synthesis of the monomer, phenylene group, naphthalene diyl group, biphenylene group, fluorene monozyl group (the following formulas 3 6 to 3 8), stilbene diyl group (below) Preferred are formulas A to D), a distilbene-diyl group (formulas E and F) and a benzofluorene-diyl group (formulas G, H, I and K).

.0TS90 / .00Zdf / X3d 0609 Difficult OOZ OAV

In the examples of arylene groups (the above formulas 1 to 38, A to 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. Represents a group, an aryloxy group, an arylalkyl group, an arylalkyl group, an arylalkylene group, an arylalkylinyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, an acyloxy group, a substitution force loxyl group or a cyano group. . In these examples of arylene groups, one structural formula has a plurality of Rs, but they may be the same or different. Next, 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.

The 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. Group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, etc., pentyloxy group Hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, and 3,7-dimethyloctyloxy group are preferable.

 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. 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. Group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, laurylsilyl group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group I-propyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethyl Xylous Michi Examples include silyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, pentylsilyl group, hexylsilyl group, octylsilyl group, 2- Ethylhexylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, decyldimethylsilyl group, 3,7- A dimethyloctyl-dimethylsilyl group is preferred.

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, laurylamino group, pentylamino group, hexylamino group, An octylamino group, a 2-ethylhexylamino group, a decylamino group, and a 3,7-dimethyloctylamino group are preferred.

The aryloxy group usually has about 6 to 60 carbon atoms. The tool body Examples of Ariruokishi group, phenoxy group, ^ ～〇 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. Specific examples of 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, ^ ~ 〇 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. Specific examples of 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. Examples of § 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. Specific examples of 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. 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 fluorhexoxycarbonyl group, perfluorate octyloxycarbonyl group, phenoxycarbonyl group , Naphthoxycarbonyl group, pyridyloxycarbonyl Etc. The. The alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent. -R NI.

The monovalent heterocyclic group, with the Ai, the A ² terms are the same as those described and exemplified.

When the substituent is a group containing an alkyl chain, the alkyl chain may be interrupted by a group containing a hetero atom or a hetero atom. Examples of this hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the group containing a hetero atom or a hetero atom include the following.

0 0

 II II

 — C one 0— -0-C- one

In the examples of the hetero atom or the hetero atom-containing group, 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. In the description (formula 1 to 38, A to K), the same as those explained and exemplified as the substituent represented by R.

From the viewpoint of the solubility of the resulting polymer compound in an organic solvent, among the arylene groups which may have a substituent, the following formula (60):

Is particularly preferred.

 In the above formula (60), 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. Represents an arylalkyl group, an arylalkyl group, an arylalkylene group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, a substituted carboxyl group or a cyano group, and Rw and Rx represent each other It may combine to form a ring.

 From the viewpoint of ease of synthesis of the compound represented by the formula (2), it is preferable that one of the two bonds is present on the A ring and the other is present on the B ring.

 In the formula (60), 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. Represents an alkyl group, an aryloxy group, an arylalkylenyl group, an arylalkylinyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, a substituted forceloxyl group or a cyano group, and Rw and Rx are bonded to each other. Form a ring.

Where, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, aryl alkyl group, aryl alkoxy group, aryl alkenyl group, aryl alkynyl group, aryl amino group, 1 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.

 Furthermore, from the viewpoint of heat resistance of the polymer compound, it is preferable that 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. And 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. And naphthenol ring, benzene ring and anthracene ring, benzene ring and phenanthrene ring, naphthalene ring and anthracene ring, naphthalene ring and phenanthrene ring, anthracene ring and phenanthrene ring, and the like. Easiness of synthesis of the compound represented, presence of the resulting polymer compound From the viewpoint of solubility in a solvent, benzene ring and benzene ring, a combination of a benzene ring and a naphthalene ring is more preferable.

 Among the arylene groups optionally having a substituent represented by the formula (60), from the viewpoint of ease of synthesis of the compound represented by the formula (2), the following formula (2 A) to (2D):

[Wherein 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.

In the formula (2A) ~ (2D), 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).

 In the above 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. As the divalent heterocyclic group, a divalent aromatic heterocyclic group (that is, a divalent heterocyclic group having aromaticity) is preferable. Examples of the divalent heterocyclic group include the following.

 a) Groups containing nitrogen atoms as heteroatoms

 Pyridine monodyl group (Formula 39-44), Diazaphenylene group (Formula 45-48), Quinoline dil group (Formula 49-63), Quinoxaline dil group (Formula 64-68), Acridine dil group (Bottom Formula 69 ~ 72), bibilidyl group (Formula 73 ~ 75), phenantine lindyl group (Formula 76 ~ 78) etc.

 b) 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 A group having a structure substituted by an atom such as sulfur or selenium or a group containing these atoms (the following formulas 79-93).

c) 5-membered heterocyclic groups containing atoms such as silicon, nitrogen, oxygen, sulfur, selenium as heteroatoms (94 to 98 below). d) 5-membered condensed heterocyclic groups containing atoms such as silicon, nitrogen, oxygen, sulfur, selenium as hetero atoms (the following formulas 99 to 108).

 e) A 5-membered heterocyclic group containing sulfur as a heteroatom and bonded at the α-position of the heteroatom to form a dimer or oligomer (the following formulas 109 to 110).

 f) A 5-membered heterocyclic group containing atoms such as silicon, nitrogen, oxygen, sulfur, selenium, etc. as heteroatoms, which are bonded to the phenyl group at the α-position of the heteroatom (the following formulas 111 to 117) g) A heterocyclic group containing nitrogen, sulfur, etc. as a heteroatom, and bonded to the cenyl group at the benzene ring (Formula 150).

.0TS90 / .00Zdf / X3d 0609 Difficult OOZ OAV

.OlS90 / Z.OOZdf / X3d 060910 / 800Z OAV

 150

 In the examples of the divalent heterocyclic group (the above formulas 39 to 1 17 and 15 50), 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.

As the divalent heterocyclic group, from the viewpoint of ease of synthesis of the compound represented by the formula (2) and solubility of the resulting polymer compound in an organic solvent, the following formula (70):

[Wherein, 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. In addition, when there are a plurality of substituents, they may be the same or different. 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.

 In the above formula (70), the substituents that the C ring and D ring may have are an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, and an aryloxy group. An aryl alkyl group, an aryl alkoxy 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 or a cyano group.

 Here, 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 arylamino group Group, monovalent heterocyclic group, acyl group, acyloxy group, and substitution force lpoxyl group described and exemplified as the substituent represented by R in the above examples of the arylene group (formula 1 to 38, AK). Is the same.

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). E):

 [Wherein Y represents O or S. Rj and Rk each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. ]

Is particularly preferred.

In the above formula (2E), 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. Expressed as Rj and Rk Alkyl group, Ariru group, the Ai, in terms of A ^2, to be the same as to those described and illustrated. In addition, as the 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.

In addition, the divalent heterocyclic group which may have a substituent represented by the above A is obtained from the viewpoint of the emission wavelength of the resulting polymer compound (light emission in the red region with good deep redness). Formula (1 a):

 [Wherein, 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)

It is preferable that it is represented by these.

In the formula (la), Ra, Rb, the alkyl group represented by R _C and Rd, Ariru group, before Symbol Ai, the A ² terms are the same as those described and exemplified. In the formula (la), 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.

In the above formula (2), 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).

[Wherein, 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.

(Wherein 8 1 " ₉ and 8 1" ₁₀ each independently represents an optionally substituted arylene group, and R ⁹ and Rio each independently represent a hydrogen atom, an alkyl group, or an aryl. Represents a monovalent heterocyclic group or cyan group.) Arn— N—— Ar ₁₂

Ar ₁₃

(In the formula, 8! ^! And 8! ^ Each independently represents an arylene group which may have a substituent, and Ar ₁₃ represents an aryl group which may have a substituent. And a ring may be formed between Arn and Ar ₁₃ , between eight and eight! ^^, or between A r ₁₂ and A r _13. )

(Wherein 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 .

II ( ⁷ )

R ¹¹ R ¹²

(In the formula, Ar ₁₅ represents an arylene group which may have a substituent, Ar ₁₆ represents an aryl group which may have a substituent, and 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.) In the above formulas (3) to (7), 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.

In the above formulas (3) to (7), 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. In the formula (1 to 38, A to K above) and the same as the aryl group in the examples described and exemplified as R.

In the above formulas (3) to (7), 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. In the above formulas (3) to (7), 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. And may have 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. These groups are the same as those described and exemplified as R (in the above formulas 1 to 38, A to K) in the above-mentioned arylene group.

 Specific examples of the divalent aromatic amine group include the following groups.

In the examples of divalent aromatic amine groups (the above formulas 1 1 8 to 1 2 2), 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.

In the formula (2), Υΐ 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.

 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In view of ease of synthesis of the polymer compound, a bromine atom and an iodine atom are preferable, and a bromine atom is more preferable.

 Examples of the alkyl sulfonate group include a methane sulfonate group, an ether sulfonate group, a trifluoromethane sulfonate group, and the like. Examples of aryl sulfonate groups include benzene sulfonate groups and ρ-toluene sulfonate groups. Examples of arylsulfonate groups include benzyl sulfonate groups.

 Specific examples of the compound represented by the formula (2) include the following formula:

(In the formula, 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. Represents an alkenyl group, an arylalkynyl group, an arylamine group, a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group or a cyano group, and two R ^b 's bonded together to form a ring. And those represented by).

 In the above formula, represented by Rb, 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 alkoxy group, an aryl alkenyl group, an aryl 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.

• Palladium catalyst

 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 (Π) 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.

'base The base used in the production method of the present invention is an inorganic base, an organic base, an inorganic salt, or the like. Examples of the inorganic base include potassium carbonate, sodium carbonate, barium hydroxide and the like. Examples of the organic base include trytylamine, tryptylamine and the like. Examples of 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.

 • Other ingredients

 When palladium acetate is used as the palladium catalyst, for example, a phosphorus compound such as triphenylphosphine, tri (ο-tolyl) phosphine, tri (ο-methoxyphenyl) phosphine can be added as a ligand. . In this case, 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.

 In the production method of the present invention, the reaction is usually performed in a solvent. Examples of 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. When 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. When the base is added as an aqueous solution and reacted in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added as necessary.

 • Reaction conditions

 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.

The time for carrying out the reaction (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. For example, in a system that has been sufficiently degassed with argon gas or nitrogen gas. Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the compound represented by the above formula (1) and the above formula (2) are contained in this polymerization container. Compound, dichlorobis

(Triphenylphosphine) Palladium catalyst such as palladium (Π) (Note that if a base is added later as an aqueous solution and reacted in a two-phase system, the quaternary ammonium salt, etc. In addition, the polymerization vessel is sufficiently replaced with nitrogen gas and degassed, and then degassed by publishing with nitrogen gas in advance, for example, toluene is added. Thereafter, a base degassed by publishing with nitrogen gas in advance, for example, an aqueous sodium carbonate solution, is dropped into this solution, and then heated and heated. For example, while maintaining an inert atmosphere at the reflux temperature for 8 hours. Polymerize.

 As a specific example of the production method of the present invention, the compound represented by the formula (1)

⁰ヽ.ヽ / 0-

B— C = CH B— C = C— B

 / 0 / 丄 / (丄 丄 One or more compounds represented by NT are selected, and the compound represented by the formula (2) is represented by the following formula:

In the presence of a palladium catalyst, for example, dicyclobis (triphenylphosphine) palladium (II) catalyst, 10 to 20 weights of a base such as sodium carbonate is selected. As 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). And adding a phase transfer catalyst), and reacting at reflux temperature for 1 to 30 hours under an inert atmosphere.

• Polymer compound having a repeating unit represented by the formula (3 a) or formula (3 b) The repeating unit represented by the formula (3 a) obtained by the production method of the present invention and Z or the above formula As the polymer compound having a repeating unit represented by (3 b), the following formula:

^-

And a polymer compound containing at least one repeating unit represented by the formula:

Here, 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.

As a more specific example of the polymer compound obtained by the production method of the present invention, the following formula:

The high molecular compound which has a repeating unit represented by these is mentioned.

In the above examples, 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.

 • Features of polymer compounds

 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.

 In 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), When 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. Specifically, substituents described in Chemical formula 10 of JP-A-9-45478 are exemplified.

 In the polymer compound obtained by the production method of the present invention, the molecular chain main chain is usually substantially conjugated. In the present specification, “substantially conjugated” means usually 50 to 100 mol%, preferably 80 to 100 mol%, based on all repeating units constituting the molecular chain main chain. Preferably 90 to: 100 mol% of repeating units constitute a conjugated system of the molecular chain main chain.

Further, 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.

In the examples of the bond structure containing these non-conjugated moieties, 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. Examples of the good solvent for the polymer compound include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. Although depending on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more. • Applications of polymer compounds

 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.

 <Example 1> (Synthesis of polymer compound 1)

Following formula:

The monomer represented by (1) 0.553 g and the following formula:

Monomer represented by (100) {[l-cis-l, 2-Bis (4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yDheptene] Wako Pure Chemical Industries, Ltd. ) Made} 0. 342 g, methyl trioctyl ammonium chloride (trade name: aliquat336, made by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884g / ml, 25 "C, (trademark of Henkel Corporation) 0.37 g and dichlorobis (triphenylphosphine) palladium (II) 2 mg were charged into a reaction vessel, and the reaction vessel was thoroughly replaced with argon gas. Next, 20 ml of toluene deaerated by bubbling was added to the solution, and then 10 ml of a 16.7 wt% aqueous sodium carbonate solution previously deaerated by bubbling with argon gas was added to the solution in a few minutes. The reaction was carried out under an argon gas atmosphere After the reaction was completed, the reaction solution was cooled to near room temperature. Then, 30 g of toluene was added to the reaction solution, and the separated toluene solution was recovered after allowing the reaction solution to stand. The toluene solution thus obtained was filtered to remove insoluble matters, and then the toluene solution was passed through an alumina column for purification. Next, the obtained toluene solution was concentrated under reduced pressure, poured into methanol, re-precipitated, and the generated precipitate was recovered. The precipitate was washed with methanol and then dried under reduced pressure to obtain 0.17 g of 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.

<Example 2> (Synthesis of polymer compound 2)

Following formula:

 Monomer (2) 0. 676 g, said monomer (100) 0.356 g, methyl trioctyl ammonium chloride (trade name: aliquat336, made by Aldrich,

CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ C1, density 0.884g / ml, 25, trademark of Henkel

 Corporation) 0.16 g and dichlorobis (triphenylphosphine) palladium (II) 1. lmg were charged into a reaction vessel, and the inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 15 ml of toluene deaerated in advance by bubbling argon gas was added. Next, 5 ml of a 16.7% by weight aqueous sodium carbonate solution which had been degassed by publishing argon gas in advance was added dropwise to the solution over several minutes, and then the temperature was raised and the mixture was refluxed for 11 hours. The reaction was performed under an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and 40 g of toluene was added to the reaction solution. The obtained reaction solution was allowed to stand, and the separated toluene solution was recovered. Then The obtained toluene solution was filtered to remove insoluble matters, and then the toluene solution was purified by passing through an alumina power ram. Next, the obtained toluene solution was concentrated under reduced pressure, poured into methanol, reprecipitated, and the generated precipitate was collected. The 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 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.

<Example 3> (Synthesis of polymer compound 3)

Following formula:

(200) {[cis-l, 2-Bis (4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yDstyrene] Aldrich} 0. 356 g The monomer (2) 0. 676 g, methyl trioctyl ammonium chloride (trade name: aliquat336, made by Aldrich,

CH ₃ N [(CH ₂ ) 7 CH ₃ ] ₃ CL density 0.884g / ml, 25, trademark of Henkel

Corporation) 0.13 g and dichlorobis (triphenylphosphine) palladium (Π) 1. 3 mg were charged into a reaction vessel, and the inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 15 ml of toluene deaerated in advance by publishing argon gas was added. Next, 16.7 wt% aqueous sodium carbonate solution (5 ml) deaerated in advance by bubbling with an argon gas was dropped into this solution in several minutes, and then the temperature was raised and refluxed for 11 hours. The reaction was performed under an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and then 40 g of toluene was added to the reaction solution. added. The obtained 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 precipitate was washed with methanol and then dried under reduced pressure to obtain 0.34 g of a polymer (hereinafter, this polymer is referred to as “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.

Example 4> (Synthesis of Polymer Compound 4)

Following formula:

Monomer (3) 0.127 g, the monomer (1) 0.44 lg, the monomer (1 00) 0.352 g, and methyltrioctyl ammonium chloride. (Product name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) 7 CH ₃ ] ₃ Cl, density 0.884 g / ml, 25, trademark of Henkel Corporation) 0.13 g, 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. Next, 5 ml of a 16.7% by weight aqueous sodium carbonate solution deaerated by bubbling with argon gas in advance was dropped into this solution in several minutes, and then the temperature was raised and the mixture was refluxed for 11 hours. The reaction was performed in an argon gas atmosphere. After completion of the reaction, the reaction solution was cooled to near room temperature, and then 40 g of toluene was added to the reaction solution. The 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 toluene solution was concentrated under reduced pressure, poured into methanol, re-precipitated, and the generated precipitate was recovered. The precipitate was washed with methanol and then dried under reduced pressure to obtain 0.3 g of a polymer (this polymer is 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.

 The structure of the repeating unit contained in polymer compound 4 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit A + repeating unit A ′): (repeating unit B + repeating) Unit B ′) = 4: 1.

'Repeat unit A' Repeat unit A,

<Example 5> (Synthesis of polymer compound 5)

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. Next, 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.

After completion of the reaction, 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 .

 The structure of the repeating unit contained in polymer compound 5 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit C + repeating unit C ′): (repeating unit D + repeating unit) D ′) = 4: 1.

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,

CH ₃ N [(CH ₂ ) 7CH ₃ ] ₃ C1, density 0.884g / ml, 25, trademark of Henkel Corporation) 0.19 g and diclonal bis (triphenylphosphine) palladium (Π) 2. Omg The reaction vessel was charged and the inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 15 ml of toluene deaerated in advance by bubbling with argon gas was added. Next, 16.7 wt% aqueous sodium carbonate solution 5 ml 1 deaerated by bubbling with argon gas in advance was dropped into this solution in several minutes, and then the temperature was raised and the mixture was refluxed for 12 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, 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. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain 0.32 g of a polymer (hereinafter, this polymer is referred to as “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 structure of the repeating unit contained in polymer compound 6 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit E + repeating unit E ′): (repeating unit F + repeating unit) F ′) = 4: 1.

Repeating unit E · Repeating unit E '

• Repeating unit F • Repeating unit F '

<Example 7> (Synthesis of polymer compound 7)

Following formula:

The monomer represented by (6) 0.826 g, the monomer (100) 0.355 g, methyl trioctylammonium chloride (trade name: aliquat336, made by Aldrich,

CH ₃ N [(CH ₂ ) 7CH3] 3C1, density 0.884 g / ml, 25, trademark of Henkel Corporation) 0.16 g and diclonal bis (triphenylphosphine) palladium (II) 1.6 mg The reaction vessel was charged and the inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 15 ml of toluene deaerated in advance by bubbling with argon gas was added. Next, 5 ml of a 16.7 wt% aqueous sodium carbonate solution previously deaerated by publishing with argon gas was dropped into the solution over several minutes, and then the temperature was raised and refluxed for 12 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, the 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. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain 0.21 g of 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.

Example 8> (Synthesis of Polymer Compound 8)

Monomer represented by (7) 0.5 4 g and the following formula:

Monomer (8) 0.1 18 g and the monomer (200) 0.445 g, methyl trioctyl ammonium chloride (trade name: aliquat336, made by Aldrich,

CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ C1, density 0.884g / ml, 25, trademark of Henkel Corporation) 0.23 g and diclonal bis (triphenylphosphine) palladium (II) 2.7 mg Were placed in a reaction vessel, and the inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 20 ml of toluene deaerated in advance by bubbling with argon gas was added. Next, 8 ml of a 16.7 wt% aqueous sodium carbonate solution deaerated in advance by bubbling with argon gas was added dropwise to the solution, and then the temperature was raised and refluxed for 12 hours. The reaction was performed in an argon gas atmosphere.

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. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain 0.14 g of a polymer (hereinafter, this polymer is referred to as “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 structure of the repeating unit contained in polymer compound 8 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit G + repeating unit G ′): (repeating unit H + Repeating unit H ′) = 4: 1.

 Repeat unit G · Repeat unit G '

'Repeat unit H · Repeat unit H'

The monomer represented by (9) 0.295 g and the monomer (2) 0.95 Og and the monomer. (3) 0.125 g and the above monomer (200) 0.7 1 2 g and methyltrioctylanmonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] 3 Cl, density 0.884g / ml, 25 ^< C> trademark of Henkel Corporation) 0. 30 g and dichlorobis (triphenylphosphine) palladium (II) 3.6 mg are charged into the reaction vessel. Was sufficiently replaced with argon gas. To this reaction vessel, 30 ml of toluene that had been deaerated in advance by publishing with argon gas was added. Next, 10 ml of a 16.7 wt% aqueous sodium carbonate solution that had been degassed by publishing with argon gas in advance was added dropwise to the solution, and then the temperature was raised and refluxed for 10 hours. The reaction was performed under an argon gas atmosphere.

After completion of the reaction, 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. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain 0.57 g of 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.

 The structure of the repeating unit in polymer compound 9 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit I + repeating unit Γ): (repeating unit J + repeating Unit J ′): (repeating unit K + repeating unit K ′) = 7: 2: 1.

 Repeat unit I Repeat unit I '

Repeat unit J · Repeat unit J '

Industrial applicability

 By the production method of the present invention, 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.

Claims

The scope of the claims

1. One or more compounds represented by the following formula (1),

[Wherein, 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. Χΐ and X ² each independently represent a boric acid residue or a boric acid ester residue. ]

One or more compounds represented by the following formula (2):

[In the formula, _{Γ Γι} may have an arylene group which may have a substituent, may have a divalent heterocyclic group or a substituent. Represents a divalent aromatic amine group. Υΐ及beauty Upsilon ² each independently represent a halogen atom, alkyl sulfonate group, Arirusuruho sulfonate group or § reel alkyl sulfonates one preparative group. ]

Production of a polymer compound having a repeating unit represented by the following formula (3a) having a step of reacting in the presence of a palladium catalyst and a base and having a repeating unit represented by Z and the following formula (3b) Method.

[Wherein, A r ^ Ai and A ² independently have the same meaning as described above. ]

2. The method according to claim 1 wherein Y ¹ and Y ² is a halogen atom.

 3. The production method according to claim 1 or 2, wherein the arylene group which may have a substituent represented by A 1 ^ is represented by the following formula (6 0).

[Wherein, A ring and B ring each independently represents an aromatic hydrocarbon ring which may have a substituent. The two bonds are on the A ring or B ring, respectively. 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 arylalkoxy group, an arylalkenyl group, an aryl group. It represents an alkynyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, a substituted carboxyl group or a cyano group, and Rw and Rx may be bonded to each other to form a ring. ]

 4. The arylene group which may have a substituent represented by the above formula (60) is represented by any one of the following formulas (2A)-(2D) Item 4. The manufacturing method according to Item 3.

 [In the formula, is independently 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. ]

 5. The production method according to claim 1 or 2, wherein the divalent heterocyclic group optionally having a substituent represented by A is represented by the following formula (70).

~ ¾_iS-(70) [wherein, 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, aryl alkyl group, aryl group. 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 substituted carboxyl group and a cyano group. In addition, when there are multiple substituents, they may be the same or different. Yes. E is O or S. ]

6. The production method according to claim 5, wherein the divalent heterocyclic group optionally having a substituent represented by the formula (70) is represented by the following formula (2E): .

[Wherein Y represents O or S. Rj and R ^k each independently represent a hydrogen atom, an alkyl group, an alkoxy group or an Ariru group. ]

7. The production method according to claim 1 or 2, wherein the divalent heterocyclic group optionally having a substituent represented by A is represented by the following formula (1a).

 [Wherein, 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)

8. The process according to any one of the Ai and claims 1-7, at least one of an alkyl group or Ariru group A ^2.

9. The production method according to claim 8, wherein ^one of A ¹ and A ² is an alkyl group or an aryl group, and the other is a hydrogen atom.

 10. The production method according to any one of claims 1 to 9, wherein the palladium catalyst is dichlorobis (triphenylphosphine) palladium (II).