JP6558146B2 - Polymer compound having high triple high level, production method thereof and use thereof - Google Patents

Description

  The present invention relates to a polymer compound having a high triple high level, a production method thereof, and an application thereof.

  An organic EL (electroluminescence) element usually has a structure in which a plurality of organic thin films are sandwiched between a pair of electrodes, and has recently been used in various applications such as portable displays and lighting fixtures. Low molecular weight compounds are the current mainstream materials used for the organic thin film layer, but the production cost is high because vacuum deposition is generally used to form the organic thin film layer of the low molecular weight compound. There was a problem. For this reason, there is a demand for the development of high-molecular materials that can be applied and formed at low manufacturing costs.

Moreover, in an organic EL element, it is industrially strongly desired to use a phosphorescent material having excellent luminous efficiency. In such phosphorescent organic EL devices, it is generally known that it is necessary to use peripheral materials (a hole transport material and an electron transport material) having a high excited triplet level (T ₁ ).

Examples of the polymer hole injection material, hole transport material, and light emitting host material include poly- (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine). An arylamine polymer typified by, for example (see, for example, Patent Documents 1 to 4), an arylamine polymer having a heteroaromatic group as a main skeleton (for example, Patent Document 5), and the like have been proposed. With respect to these materials, since T ₁ is not sufficiently high, the phosphorescent organic EL device has not yet exhibited sufficient performance.

JP-A-11-292828 Japanese Patent Laid-Open No. 13-98023 JP 2004-292882 A JP-T-2001-527102 JP 2004-93798 A

The present invention has been made in view of the above-described background art, and an object of the present invention is to provide a high molecular weight compound having a high T ₁ which is indispensable for increasing the luminous efficiency of a phosphorescent light-emitting device compared to conventionally known ones. It is another object of the present invention to provide a manufacturing method thereof and a material for an organic electroluminescence device containing the same.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polymer compound having a partial structure represented by the following general formula (1) in a repetitive structure has T ₁ as compared with a conventionally known material. In order to complete the present invention, it is found that the phosphorescent light emitting device has a remarkable effect that the light emitting efficiency of the phosphorescent light emitting device is superior to that of a conventionally known material and a different effect that the voltage of the phosphorescent light emitting device can be lowered. It came.

  That is, the present invention relates to a polymer compound having a partial structure represented by the following general formula (1) in a repeating structure (hereinafter referred to as “polymer compound (1)” as appropriate), a production method thereof, and use thereof.

(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 18 carbon atoms.
Ar ¹ is an aromatic group that may be linked or condensed with 4 to 60 carbon atoms (the group may have an alkyl group with 1 to 18 carbon atoms or an alkoxy group with 1 to 18 carbon atoms). ). )
In addition, it is preferable that the high molecular compound which has the partial structure represented by the said General formula (1) in a repeating structure contains the structure represented by the following General formula (2) as a repeating structure.

(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 18 carbon atoms.
Ar ¹ and Ar ² are each independently an aromatic group optionally having 4 to 60 carbon atoms or a condensed ring (these groups are each independently an alkyl group having 1 to 18 carbon atoms or Which may have an alkoxy group having 1 to 18 carbon atoms). )
The polymer compound containing the structure represented by the general formula (2) in the repeating structure is hereinafter appropriately referred to as “polymer compound (2)”.

  The polymer compound (1) of the present invention has a higher excited triplet level than a conventionally known polymer compound. For this reason, the organic EL device using the polymer compound (1) of the present invention is expected to be excellent in luminous efficiency and current efficiency. Therefore, the polymer compound of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

  The present invention is described in detail below.

  The polymer compound (1) of the present invention has a partial structure represented by the general formula (1) in a repeating structure. The polymer compound (1) is preferably a polymer compound (2) containing the structure represented by the general formula (2) as a repeating structure.

In the polymer compound (1) and the polymer compound (2), R ¹ and R ² each independently represents an alkyl group having 1 to 18 carbon atoms.

  The alkyl group having 1 to 18 carbon atoms means a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and is not particularly limited. For example, a methyl group, an ethyl group, n- Propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, cyclohexadienyl group, octyl group, trifluoromethyl group, benzyl group, or phenethyl group Etc.

R ¹ and R ² are preferably a methyl group, an ethyl group, an n-butyl group, or a tert-butyl group, and more preferably a methyl group, from the viewpoint of excellent production efficiency of the polymer compound.

In the polymer compounds (1) and (2), each Ar ¹ is independently an aromatic group that may be linked or condensed with 4 to 60 carbon atoms (these groups are each independently Which may have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms).

In the polymer compound (2), Ar ² is an aromatic group optionally having 4 to 60 carbon atoms or a condensed ring (these groups are each independently an alkyl group having 1 to 18 carbon atoms or Which may have an alkoxy group having 1 to 18 carbon atoms).

In Ar ¹ and Ar ² , the aromatic group that may be connected or condensed with 4 to 60 carbon atoms may be an aromatic hydrocarbon group that may be connected or condensed with 6 to 60 carbon atoms, or This is a superordinate concept of a heteroaromatic group which may be linked or condensed with 4 to 60 carbon atoms.

  The aromatic hydrocarbon group which may be linked or condensed with 6 to 60 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthalenyl group, a phenyl- Naphthalenyl group, naphthalenyl-phenyl group, anthracenyl group, phenyl-anthracenyl group, anthracenyl-phenyl group, pyrenyl group, terphenylenyl group, phenanthracenyl group, triphenylenyl group and the like can be mentioned.

  The heteroaromatic group having 4 to 60 carbon atoms which may be linked or condensed is not particularly limited, and examples thereof include a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienylenyl group, and a benzothiee group. Nylenyl group, dibenzothienyl group, carbazolyl group, pyridylenyl-phenyl group, dibenzothienylenyl-phenyl group, dibenzofuranyl-phenyl group, biphenyl-carbazolyl group, dibenzothienyl-carbazolyl group, pyridylenyl group, pyrimidinyl group, pyrazinyl Group, quinolinyl group, isoquinolinyl group, acridinyl group, benzothiazolyl group, quinazolyl group, quinoxalyl group, 1,6-naphthyridinyl group, 1,8-naphthyridinyl group and the like.

Alkyl group having 1 to 18 carbon atoms in Ar ¹ and Ar ² are the same definition as ^{R 1} and ^{R 2,} is not particularly limited, exemplified the same as those shown by ^{R 1} and ^{R 2} be able to. The same applies to the preferred range.

The alkoxy group having 1 to 18 carbon atoms in Ar ¹ and Ar ² means a linear, branched, or cyclic alkoxy group having 1 to 18 carbon atoms, and is not particularly limited. Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, cyclohexadienyloxy group, octyloxy group, tri Examples thereof include a fluoromethyloxy group, a benzyloxy group, and a phenethyloxy group.

Ar ¹ and Ar ² are each independently one or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring in that the polymer compound is excellent in hole transport properties. Are independently linked and / or condensed and formed with an aromatic group having 4 to 60 carbon atoms (which are each independently an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms). It may preferably have). The group is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a benzofluorenyl group, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, and a thienyl group. Benzothienyl group, dibenzothienyl group, dibenzothienylphenyl group, carbazolyl group, phenyl-carbazolyl group, biphenyl-carbazolyl group, dibenzothienyl-carbazolyl group and the like.

  Among these, one or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are independently formed and connected and / or condensed and / or an aromatic group having 4 to 40 carbon atoms. More preferably, it is a group (this group may have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms).

  Among these, one or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are independently formed and connected and / or condensed and / or an aromatic group having 4 to 20 carbon atoms. More preferably, it is a group (this group may have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms).

Furthermore, Ar ¹ and Ar ² are each independently a phenyl group, a biphenylyl group, a fluorenyl group, a carbazolyl group, a dibenzothienyl group, a dibenzothienylphenyl group, or in terms of excellent hole transport properties of the polymer compound Preferably an N-dibenzothienylcarbazolyl group (which may each independently have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms as a substituent), A phenyl group, a biphenylyl group, a fluorenyl group, a carbazolyl group, a dibenzothienyl group, a dibenzothienylphenyl group, or an N-dibenzothienylcarbazolyl group (which are each independently a methyl group, an ethyl group, an n-butyl group, t-butyl group, methoxy group, ethoxy group, n-butoxy group, or t-butoxy group as a substituent And more preferably may also be).

Ar ¹ and Ar ² are each independently selected from the group consisting of phenyl group, 4-methylphenyl group, 4-n-butylphenyl group, 4-t-butylphenyl group, 4-methoxyphenyl group, and dibenzothienyl. Group, dibenzothienylphenyl group, or N-dibenzothienylcarbazolyl group is more preferable.

  The polymer compound (2) of the present invention is more preferably a polymer compound having a repeating structure represented by the following general formula (3) (also referred to as “polymer compound (3)”).

(Where
R ¹ and R ² have the same definition as the polymer compound (2).
Ar ¹ and Ar ² have the same definition as the polymer compound (2).
Ar ⁴ is a C 4-60 aromatic group which may be linked or condensed (these groups are each independently an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms). May be included).
Ar ³ is a divalent valence having 4 to 60 carbon atoms formed by linking and / or condensing one or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring. (They may each independently have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms).
n represents 0-4.
When n is 2 to 4, Ar ³ and Ar ⁴ may be the same or different at each occurrence. )
Aromatic groups optionally having 4 to 60 carbon atoms or condensed rings in Ar ⁴ (these groups are each independently an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms). As for Ar ¹ , Ar ¹ , and Ar ² , an aromatic group which may be linked or condensed with 4 to 60 carbon atoms (these groups are each independently a carbon number). The same substituents as in the case of Ar ¹ and Ar ² may be exemplified. It is.

One or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring in Ar ³ are formed by linking and / or condensing a divalent C 4-60 divalent ring. The aromatic group is not particularly limited. For example, phenylene group (o-phenylene group, p-phenylene group, m-phenylene group), biphenyldiyl group, phenyl-phenylene group, terphenyldiyl group, naphthalene. Diyl group, anthracene diyl group, pyrene diyl group, terphenylene group, phenanthracene diyl group, perylene diyl group, triphenylene diyl group, frangyl group, benzofurandyl group, dibenzofurandyl group, carbazolyl group, thienylene group, benzothienylene group, or dibenzo Examples include thienylene group.

Ar ³ is one in which one or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are independently connected and / or condensed in terms of excellent hole transport properties of the polymer compound. A divalent aromatic group having 4 to 40 carbon atoms (which may each independently have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms). 4), wherein one or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are independently connected and / or condensed and have 4 to 20 carbon atoms. It is more preferable that they are each a bivalent aromatic group (which may each independently have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms).

Furthermore, as Ar ³ , in terms of excellent hole transport properties of the polymer compound, a phenylene group (o-phenylene group, p-phenylene group, m-phenylene group), biphenylylene group, fluorenylene group, dibenzothienylene group, Or a dibenzofurandiyl group (which may each independently have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms as a substituent), and is preferably a phenylene group (o -Phenylene group, p-phenylene group, m-phenylene group), biphenylylene group, fluorenylene group, dibenzothienylene group, or dibenzofurandiyl group (these are each independently a methyl group, an ethyl group, an n-butyl group, (It may have t-butyl group, methoxy group, ethoxy group, n-butoxy group, or t-butoxy group as a substituent) It is more preferable that

Ar ³ is more preferably a phenylene group, a tolylene group, a dimethylphenylene group, a dibenzothienylene group, or a dibenzofurandiyl group.

In general formula (3), when n is 2 to 4, Ar ³ and Ar ⁴ may be the same or different at each occurrence.

  Moreover, about the high molecular compounds (1), (2), and (3), the terminal is a substituent represented by following General formula (4) from the point of the luminescent property as an organic electroluminescent element, and durability. Preferably there is.

(In the formula, Ar ⁵ is an aromatic group which may be linked or condensed with 4 to 60 carbon atoms (the group has an alkyl group with 1 to 18 carbon atoms or an alkoxy group with 1 to 18 carbon atoms). It may be)
Aromatic groups optionally having 4 to 60 carbon atoms or condensed rings in Ar ⁵ (these groups are each independently an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms). As for Ar ¹ , Ar ¹ , and Ar ² , an aromatic group which may be linked or condensed with 4 to 60 carbon atoms (these groups are each independently a carbon number). The same substituents as in the case of Ar ¹ and Ar ² may be exemplified. It is.

Note that Ar ^5, regardless of the description of the above preferred ranges, the polymer compound (1), (2), or from the viewpoint of excellent production efficiency of (3), each independently, a phenyl group (those groups Each independently may have one or more substituents selected from the group consisting of a phenyl group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. More preferably, each independently represents an o-tolyl group, an m-tolyl group, a p-tolyl group, or a phenyl group.

  That is, the polymer compound (3) is preferably a polymer compound represented by the following general formula (5).

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , and n each independently represent the same definition as in the general formula (3). Ar ⁵ is independently Then, it represents the same definition as in the general formula (4), and when n is 2 to 4, Ar ³ and Ar ⁴ may be the same or different at each occurrence.
m represents an integer of 2 or more. )
The polymer compound of the present invention is not particularly limited as long as it falls under the above definition, but the following general formulas (9) to (15) are used from the viewpoint of physical properties such as luminous efficiency and lifetime of the organic electroluminescence device. What is represented in any of these can be illustrated as a preferable thing.

(In the above general formulas (9) to (12), (12-1), (12-2), and (13) to (15),
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. Represents a group.
m represents an integer of 2 or more. q represents an integer of 1 to 4. )
The alkyl group having 1 to 18 carbon atoms or the alkoxy group having 1 to 18 carbon atoms represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is represented by Ar ¹ . The same substituents as those of the alkyl group having 1 to 18 carbon atoms and the alkoxy group having 1 to 18 carbon atoms can be exemplified.

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, from the viewpoint of excellent production efficiency of the polymer compound. And each independently more preferably a hydrogen atom, a methyl group, or a butyl group (for example, an n-butyl group, a t-butyl group, etc.).

R ⁸ , R ⁹ , and R ¹⁰ are more preferably each independently a hydrogen atom or a methyl group from the viewpoint of excellent production efficiency of the polymer compound.

  Next, the manufacturing method of the high molecular compound (3) of this invention is demonstrated.

  The polymer compound (3) of the present invention is not particularly limited, but various arylene halides and aryleneamines or arylene halides and arylenediamines, trialkylphosphine and / or palladium as shown in the following reaction formula. It can be synthesized by polymerization in the presence of a catalyst comprising a compound and a base.

(In Reaction Formulas 1-3, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² and n represent the same definition as in the general formula (3). X ² , X ³ and X ⁴ are each Independently represents a chlorine atom, a bromine atom, or an iodine atom, and m represents an integer of 2 or more.)
As a raw material for producing the polymer compound (3), a dihalogen compound represented by the following general formula (8) can be used.

(In the formula, Ar ¹ , R ¹ and R ² each independently represent the same definition as in the general formula (1). X ¹ represents a chlorine atom, a bromine atom or an iodine atom.)
The dihalogen compound represented by the general formula (8) is preferably one represented by any one of the following general formulas (8-1) to (8-5) from the viewpoint that the luminous efficiency of the device is increased.

(In the above general formulas (8-1) to (8-5),
R ¹ , R ² and X ¹ represent the same definition as in the general formula (8). R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. )
Furthermore, the above general formula (8-1) or (8-2) is more preferable from the viewpoint of easy synthesis.

  The compound having a structure represented by the general formula (16) obtained from the polymerization step is usually a secondary amino group or a halogen group, or both a secondary amino group and a halogen group.

  The protection step includes a compound having a structure represented by the general formula (16) obtained in the polymerization step and an aromatic halogen compound represented by the following general formula (6) or the following general formula in the presence of a palladium catalyst and a base. It is carried out by reaction with an aromatic amine compound represented by the formula (7) or both.

(In the formula, Ar ⁵ has the same definition as Ar ⁵ in the general formula (4). X represents a chlorine atom, a bromine atom, or an iodine atom.)

(In the formula, Ar ⁵ is independently the same definition as Ar ⁵ in the general formula (4).)
As a product of the protection step, a polymer compound (3) having a reaction terminal protected, that is, a polymer compound represented by the following general formula (5) can be obtained.

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , and n each independently represent the same definition as in the general formula (3). Ar ⁵ is independently And m represents an integer greater than or equal to 2. When n is 1 to 4, Ar ³ and Ar ⁴ may be the same for each occurrence. , May be different.)
The protection step may be carried out in one pot following the polymerization step, or once the polymer compound of the general formula (16), which is a product of the polymerization step, is isolated, a palladium catalyst and a base are separately prepared. It may be performed in the presence.

  In the protection step, the reaction can be carried out by simultaneously using the aromatic halogen compound represented by the general formula (6) and the aromatic amine compound represented by the general formula (7). In terms of reaction efficiency, the reaction with the aromatic halogen compound and the reaction with the aromatic amine compound are preferably performed separately. In the case of performing the reaction separately, either the reaction using an aromatic halogen compound or the reaction using an aromatic amine compound may be performed first.

  In the protection step, the reaction using the aromatic halogen compound and the reaction using the aromatic amine compound can be carried out continuously in one pot. After one reaction, the reaction product is isolated and separated in a separate batch. The other reaction can also be performed.

  The aromatic halogen compound represented by the general formula (6) is not particularly limited. For example, bromobenzenes which may have a substituent [specifically, bromobenzene, 2-bromotoluene] 3-bromotoluene, 4-bromotoluene, 2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene , 5-bromo-m-xylene, 1-bromo-2-ethylbenzene, 1-bromo-4-ethylbenzene, 1-bromo-4-propylbenzene, 1-bromo-4-n-butylbenzene, 1-bromo-4 -Tert-butylbenzene, 1-bromo-5- (trifluoromethoxy) benzene, 2-bromoanisole, 3-bromoanisole, 4-bromoanisole, 1- Lomonaphthalene, 2-bromonaphthalene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 9-bromoanthracene, 9-bromophenanthrene, N-methyl-3-bromocarbazole, N-ethyl-3- Bromocarbazole, N-propyl-3-bromocarbazole, N-butyl-3-bromocarbazole, 2-bromofluorene, 2-bromo-9,9-dimethylfluorene, 2-bromo-9,9-diethylfluorene, 2- Bromo-9,9-diisopropylfluorene, 2-bromo-9,9-di-n-butylfluorene, 2-bromo-9,9-di-tert-butylfluorene, 2-bromo-9,9-di-sec -Butylfluorene, 2-bromo-9,9-di-n-hexylfluorene, 2-bromo-9,9- -N-octylfluorene, 2-bromodibenzothiophene, 2-bromodibenzofuran, etc.], chlorobenzenes optionally having a substituent [specifically, chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chloro Toluene, 2-chloro-m-xylene, 2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene, 5-chloro-m-xylene, 1-chloro-2-ethylbenzene, 1-chloro-4-ethylbenzene, 1-chloro-4-propylbenzene, 1-chloro-4-n-butylbenzene, 1-chloro-4-tert-butylbenzene, 1-chloro -5- (trifluoromethoxy) benzene, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, Loronaphthalene, 2-chloronaphthalene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 9-chloroanthracene, 9-chlorophenanthrene, N-methyl-3-chlorocarbazole, N-ethyl-3- Chlorocarbazole, N-propyl-3-chlorocarbazole, N-butyl-3-chlorocarbazole, 2-chlorofluorene, 2-chloro-9,9-dimethylfluorene, 2-chloro-9,9-diethylfluorene, 2- Chloro-9,9-diisopropylfluorene, 2-chloro-9,9-di-n-butylfluorene, 2-chloro-9,9-di-tert-butylfluorene, 2-chloro-9,9-di-sec -Butyl fluorene, 2-chloro-9,9-di-n-hexyl fluorene, 2-chloro-9,9-di n-octylfluorene, 2-chlorodibenzothiophene, 2-chlorodibenzofuran, etc.] and iodobenzenes which may have a substituent [specifically, iodobenzene, 2-iodotoluene, 3-iodotoluene, 4-iodotoluene, 2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o-xylene, 4-iodo-m-xylene, 5-iodo-m -Xylene, 1-iodo-2-ethylbenzene, 1-iodo-4-ethylbenzene, 1-iodo-4-propylbenzene, 1-iodo-4-n-butylbenzene, 1-iodo-4-tert-butylbenzene, 1-iodo-5- (trifluoromethoxy) benzene, 2-iodoanisole, 3-iodoanisole, 4-iodoanisole, -Iodonaphthalene, 2-iodonaphthalene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 9-iodoanthracene, 9-iodophenanthrene, N-methyl-3-iodocarbazole, N-ethyl-3 -Iodocarbazole, N-propyl-3-iodocarbazole, N-butyl-3-iodocarbazole, 2-iodofluorene, 2-iodo-9,9-dimethylfluorene, 2-iodo-9,9-diethylfluorene, 2 -Iodo-9,9-diisopropylfluorene, 2-iodo-9,9-di-n-butylfluorene, 2-iodo-9,9-di-tert-butylfluorene, 2-iodo-9,9-di- sec-Butylfluorene, 2-iodo-9,9-di-n-hexylfluorene, 2-iodo-9,9 -Di-n-octylfluorene, 2-iododibenzothiophene, 2-iododibenzofuran, etc.].

  The aromatic amine compound represented by the general formula (7) is not particularly limited. For example, diphenylamine, di-p-tolylamine, di (biphenyl) amine, N-phenyl-N- (1- Naphthyl) amine, N-phenyl-N- (2-naphthyl) amine and the like.

  The polymerization step and the protection step are both carried out in the presence of a palladium catalyst and a base, and the reaction conditions are not particularly limited, but the following may be used. it can. The palladium catalyst usually comprises a palladium compound and a ligand.

  Although it does not specifically limit as a palladium compound which is a structural component of a palladium catalyst, For example, tetravalent palladium compounds [Specifically, sodium hexachloro palladium (IV) acid tetrahydrate, hexachloro palladium (IV Potassium diacid), divalent palladium compounds (for example, palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II ), Dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroa Tate etc.], and zero-valent palladium compounds [specifically, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0) etc.].

  The ligand that is a constituent component of the palladium catalyst is not particularly limited, but may be any ligand that can coordinate to palladium, such as trialkylphosphines, arylphosphines, carbene-based ligands, and the like. Is mentioned.

  Although it does not specifically limit as trialkyl phosphine, For example, a triethyl phosphine, a tricyclohexyl phosphine, a triisopropyl phosphine, a tri-n-butyl phosphine, a triisobutyl phosphine, a tri-sec-butyl phosphine, a tri-tert- And butylphosphine. Of these, tri-tert-butylphosphine is preferably used because of its particularly high reaction activity as a catalyst.

  The aryl phosphines are not particularly limited, and examples thereof include triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, and 2,2′-bis. (Diphenylphosphino) -1,1′-binaphthyl (BINAP), trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene and the like.

  Examples of the carbene-based ligand include 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene hydrochloride.

  The amount of the ligand used in the palladium catalyst is not particularly limited, but it may be used usually in the range of 0.01 to 10000 times mol of 1 mol of palladium atom in the palladium compound, and expensive trialkyl. Since phosphines, arylphosphines, and carbene-based ligands are used, the range of 0.1 to 10 moles per mole of palladium atom in the palladium compound is preferable.

  The amount of the palladium catalyst used in the polymerization step is not particularly limited. For example, in the polymerization step of the reaction formula (1), the reaction formula (2), and the reaction formula (3), 1 mol of the starting halogen atom On the other hand, it is preferably within a range of usually 0.0000001 to 0.20 moles in terms of palladium atoms. Of these, from the viewpoint of catalytic activity and the use of an expensive palladium compound, it is usually more preferably in the range of 0.00001 to 0.05 times mole.

  Although the usage-amount of the palladium catalyst in a protection process is not specifically limited, The halogen atom 1 of the aromatic halogen compound represented by General formula (6), or the polymer represented by General formula (16) It is preferably within a range of usually 0.0000001 to 0.20 times moles in terms of palladium atoms with respect to moles. Of these, from the viewpoint of catalytic activity and the use of expensive palladium compounds, it is usually more preferably in the range of 0.00001 to 0.10 times mole.

  The method for adding the palladium catalyst in the polymerization step and the protection step is not particularly limited, but a palladium compound, a ligand, and other components may be added individually to the reaction system in the polymerization step or the protection step. The catalyst components may be added in advance and mixed in the form of a palladium complex.

  Although it does not specifically limit as a base used for a superposition | polymerization process and a protection process, For example, inorganic bases, such as a hydroxide of alkali metals (specifically sodium, potassium, etc.), carbonate, an alkoxide, or Organic bases such as tertiary amines can be mentioned. Of these, preferred are alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, and the like. It can be added as it is to the system, or it can be prepared in situ by subjecting an alkali metal, alkali metal hydride or alkali metal hydroxide and alcohol to the reaction system. More preferred is a method in which an alkali metal tertiary alkoxide such as lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide or the like is added to the reaction system as it is.

  The amount of base used in the polymerization step is not particularly limited, but is not particularly limited. For example, in the polymerization step of Reaction Formula (1), Reaction Formula (2), and Reaction Formula (3), It is selected from the range of 1 to 1000 times mol per mol of the halogen atom of the raw material. Among these, the range of 1 to 20 times mol is more preferable in consideration of the post-treatment operation after completion of the reaction.

  The amount of the base used in the protection step is not particularly limited, but is usually in the range of 1 to 1000 times mol, preferably 1 to 1000 times mol of the halogen atom of the aromatic halogen compound represented by the general formula (6). Is in the range of 1 to 20 times mol, or in the range of 1 to 100000 times mol, preferably in the range of 1 to 1000 times mol for 1 mol of the halogen atom of the polymer having the structure represented by the general formula (16). To be elected.

  Both the polymerization step and the protection step are usually preferably carried out in the presence of an inert solvent. The solvent used is not particularly limited as long as it does not significantly inhibit this reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane. A solvent, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide, etc. can be mentioned. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferred.

  The polymerization step and the protection step are preferably carried out under normal pressure and in an inert gas atmosphere such as nitrogen or argon, but can be carried out even under pressurized conditions.

  The reaction temperature in the polymerization step and the protection step is not particularly limited as long as the reaction proceeds at an economically acceptable rate, but is usually 20 to 300 ° C., preferably 50 to 200 ° C. Preferably it is the range of 100-150 degreeC.

  The reaction time in the polymerization step and the protection step is not particularly limited because it is not constant depending on the polymer compound, palladium catalyst, reaction temperature, etc. to be produced, but in many cases, it ranges from several minutes to 72 hours. Just choose. Preferably it is less than 24 hours.

  The polymer compound (5) produced by the polymerization step and the protection step is preferably separated and purified from unreacted low molecular weight compounds by reprecipitation or the like. Moreover, it is preferable to perform adsorption treatment with silica gel, activated alumina or the like in order to remove impurities such as a palladium catalyst.

  The polymer compound of the present invention (any of polymer compounds (1) to (5)) is a conductive polymer material in an electronic device such as a field effect transistor, an optical functional device, a dye-sensitized solar cell, or an organic EL device. Used as. In particular, it is extremely useful as a hole transport material, a light emitting material and a buffer material of an organic EL device.

  Further, the polymer compound of the present invention may be used by mixing a further polymer compound and a low-molecular compound. Moreover, conductive ink can be manufactured by adding a solvent, a viscosity modifier, a filler, etc.

  If the organic EL element of this invention is equipped with the organic layer containing the polymer compound of this invention, element structure will not be specifically limited.

  Since the polymer compound of the present invention is excellent in solubility, for example, a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method using a solution, a mixed solution, or a melt of these materials. The element can be easily produced by a conventionally known coating method such as the above. It can also be easily produced by an inkjet method, a Langmuir Blodget method, or the like.

  Examples of the present invention are shown below, but the present invention is not construed as being limited to these examples.

  Polymer molecular weight: THF GPC [HLC-8220 (manufactured by Tosoh Corporation). The columns were TSKgel-SuperH4000, TSKgel-SuperH3000, and TSKgel-SuperH2000 (all manufactured by Tosoh Corporation). ], The molecular weight of the synthesized polymer was measured. The molecular weight is shown in terms of standard polystyrene.

  Glass transition temperature: Measured using DSC200F3 (manufactured by Netch).

  HOMO level: Measured using an atmospheric photoelectron spectrometer measuring apparatus AC-3 (manufactured by Riken Keiki Co., Ltd.).

  LUMO level: The energy gap (Eg) was calculated from the absorption edge of the UV-vis absorption spectrum and subtracted from HOMO.

  Elemental analysis: Analysis was performed using a fully automatic elemental analyzer 2400II (Perkin Elmer).

Example 1
Into a 1 L four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, 36.8 g (192 mmol) of p-bromochlorobenzene, 10.0 g (93.3 mmol) of p-toluidine, sodium tert-butoxide 46. 2 g (481 mmol) and 440 g of o-xylene were charged. To this mixed solution, a solution of 0.84 g (3.73 mmol) of palladium (II) acetate and 2.27 g (11.2 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (15.0 g) solution. Was added. Next, the temperature was raised to 100 ° C. in a nitrogen atmosphere, and the mixture was aged for 20 hours while heating and stirring at 100 ° C. Subsequently, 41.2 g of p-toluidine was added, and the reaction was performed at 120 ° C. for 20 hours. Next, when the mixture was allowed to cool to 80 ° C., 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. Subsequently, extraction operation was performed by adding 200 mL of toluene. The extracted organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. Purification was performed by a recrystallization operation using toluene as a solvent to obtain 55.3 g of compound (17a).

  A 1 L three-necked round bottom flask equipped with a condenser and a thermometer was charged with 20.0 g (92.6 mmol) of 3-nitro-4-bromotoluene and 13.8 g of 4-methylphenylboronic acid under a nitrogen atmosphere at room temperature. (102 mmol), 1.07 g (0.93 mmol) of tetrakis (triphenylphosphine) palladium, 175 g of a 20% aqueous potassium carbonate solution, and 300 g of toluene were mixed. The inside of the reaction vessel was purged with nitrogen, and then stirred at a temperature of 110 ° C. for 18 hours. After allowing to cool to room temperature, 300 g of pure water and 100 g of toluene were added to the reaction solution for extraction. The extracted organic layer was passed through silica gel chromatography, and then toluene was removed by distillation under reduced pressure to obtain 21.8 g of compound (17b).

  A 1 L three-necked round bottom flask equipped with a condenser and a thermometer was mixed with 21.0 g (92.4 mmol) of compound (17b), 60.6 g (231 mmol) of triphenylphosphine and 105 g of o-dichlorobenzene, The mixture was stirred at 160 ° C. for 24 hours. After allowing to cool to room temperature, the reaction solution was passed through silica gel chromatography, and then the solvent was distilled off under reduced pressure to obtain a residue. Purification by recrystallization using toluene as a solvent gave 10.3 g of compound (17c).

  A 100 mL four-necked round bottom flask equipped with a condenser and a thermometer was charged with 6.16 g (31.5 mmol) of compound (17c), 5.20 g (33.1 mmol) of bromobenzene and xylene under a nitrogen atmosphere at room temperature. .6 g was charged. To this mixed solution, a solution of 74.4 mg (0.33 mmol) of palladium acetate and 0.201 g (0.99 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in xylene (5.0 g) was added. Thereafter, 9.15 g (66.2 mmol) of potassium carbonate and 0.26 g (0.99 mmol) of 18-crown-6 were further added. Thereafter, the temperature was raised to 140 ° C. in a nitrogen atmosphere and stirred for 16 hours. Next, when the mixture was allowed to cool to 80 ° C., 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. Subsequently, extraction operation was performed by adding 100 mL of toluene. The extracted organic layer was passed through silica gel column chromatography, and then the solvent was distilled off under reduced pressure to obtain a residue. The product was purified by recrystallization using hexane as a solvent to obtain 6.06 g of compound (17d).

  A 500 mL four-necked round bottom flask equipped with a condenser and a thermometer was charged with 6.00 g (21.2 mmol) of compound (17d) and 120 g of N, N-dimethylformamide (hereinafter abbreviated as DMF) at room temperature. And cooled to 0 ° C. To this mixture, a solution of 8.10 g (44.6 mmol) of N-bromosuccinimide in DMF (65 g) was slowly added dropwise over 20 minutes with stirring. Subsequently, after stirring at 0 degreeC for 1 hour, it heated up gradually to room temperature, and also stirred for 2 hours. Next, 200 g of a 10% aqueous sodium thiosulfate solution was added and stirred for 30 minutes. Subsequently, extraction operation was performed by adding 500 mL of toluene. Next, after passing through silica gel column chromatography, toluene was distilled off by distillation under reduced pressure to obtain a residue. The product was purified by recrystallization using toluene as a solvent to obtain 5.12 g of compound (17e).

  In a 100 mL four-necked round bottom flask equipped with a condenser and a thermometer, 0.44 g (0.93 mmol) of compound (17a), 0.40 g (0.93 mmol) of compound (17e) at room temperature under a nitrogen atmosphere, Sodium-tert-butoxide 0.36 g (3.73 mmol) and o-xylene 7.8 g were mixed. Nitrogen was allowed to flow through the reaction vessel for about 20 minutes, and then 8.5 mg (9.32 μmol) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and tri-tert-butylphosphine in this mixed solution were used. An additional 54 mg (37.3 μmol) of o-xylene (2.0 mL) solution was added. Subsequently, it stirred at the temperature of 130 degreeC for 3 hours. Subsequently, 73.2 mg (0.47 mmol) of bromobenzene was added, and the mixture was further stirred at 130 ° C. for 3 hours. Next, 0.16 g (0.93 mmol) of diphenylamine was further added, and the mixture was further stirred at 130 ° C. for 17 hours. The reaction mixture was then cooled to about 60 ° C., after which 2 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (100 mL). The precipitated solid was collected by filtration, washed in the order of acetone, water and acetone, and then dried under reduced pressure to obtain 0.44 g of a light yellow powdery polymer compound (17).

The obtained polymer compound (17) had a weight average molecular weight of 18,000 and a number average molecular weight of 8,2000 (dispersity of 2.2) in terms of polystyrene.

  The glass transition temperature was 298 ° C.

  The HOMO level was 5.06 eV and the LUMO level was 1.90 eV.

  Table 1 shows the results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 2
In a 100 mL four-necked round bottom flask equipped with a condenser and a thermometer, 4.01 g (20.6 mmol) of compound (17c) and 4.60 g of 4-n-butylbromobenzene at room temperature and under a nitrogen atmosphere (21. 6 mmol) and 36.8 g of xylene. To this mixed solution, a solution of 48.5 mg (0.22 mmol) of palladium acetate and 87.3 mg (0.43 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in xylene (2.0 g) was added. Subsequently, 5.97 g (43.2 mmol) of potassium carbonate and 0.17 g (0.65 mmol) of 18-crown-6 were added. Next, the temperature was raised to 140 ° C. in a nitrogen atmosphere and stirred for 15 hours. Next, when the mixture was allowed to cool to 80 ° C., 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. Subsequently, extraction operation was performed by adding 100 mL of toluene. The extracted organic layer was passed through silica gel column chromatography, and then the solvent was removed by distillation under reduced pressure to obtain 6.60 g of compound (18a).

  A 500 mL four-necked round bottom flask equipped with a condenser and a thermometer was charged with 6.60 g (19.3 mmol) of compound (18a) and 160 g of N, N-dimethylformamide (hereinafter abbreviated as DMF) at room temperature. And cooled to 0 ° C. A DMF (60 g) solution of 7.38 g (40.6 mmol) of N-bromosuccinimide was slowly added dropwise to this mixture over 20 minutes with stirring. Subsequently, after stirring at 0 degreeC for 1 hour, it heated up gradually to room temperature, and also stirred for 2 hours. Next, 200 g of a 10% aqueous sodium thiosulfate solution was added and stirred for 30 minutes, and then 500 mL of toluene was added for extraction. Then, after passing through silica gel column chromatography, toluene was removed by distillation under reduced pressure to obtain a residue. The product was purified by recrystallization using toluene as a solvent to obtain 5.26 g of compound (18b).

  In a 100 mL four-necked round bottom flask equipped with a condenser and a thermometer, 1.00 g (2.06 mmol) of compound (18b) and 0.31 g (2.06 mmol) of 4-n-butylaniline at room temperature under a nitrogen atmosphere ), 0.79 g (8.24 mmol) of sodium-tert-butoxide and 12.0 g of o-xylene were mixed. After circulating nitrogen for about 20 minutes inside the reaction vessel, 18.9 mg (20.6 μmol) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and tri-tert-butylphosphine in the mixed solution were used. A 7 mg (82.4 μmol) solution of o-xylene (2.0 mL) was added. Subsequently, it stirred at the temperature of 130 degreeC for 3 hours. Next, 0.16 g (1.03 mmol) of bromobenzene was added, and the mixture was further stirred at 130 ° C. for 3 hours. Next, 0.35 g (2.06 mmol) of diphenylamine was further added, and the mixture was further stirred at 130 ° C. for 15 hours. The reaction mixture was then cooled to about 60 ° C., after which 2 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (200 mL). The precipitated solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.74 g of a light yellow powdery polymer compound (18).

The obtained polymer compound (18) had a weight average molecular weight of 6,500 and a number average molecular weight of 4,300 (dispersity of 1.5) in terms of polystyrene.

  The glass transition temperature was not detected up to 350 ° C.

  The HOMO level was 5.19 eV and the LUMO level was 2.18 eV.

  Table 1 shows the results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 3
The same operation as in Example 2, except that 0.95 g (2.06 mmol) of N, N′-bis (4-n-butylphenylene) dibenzofuranylene-2,8-diamine was used instead of 4-butylaniline. Then, 1.02 g of a polymer compound (19) was obtained.

The obtained polymer compound (19) had a weight average molecular weight of 65,000 and a number average molecular weight of 9,300 (dispersion degree 7.0) in terms of polystyrene.

  The glass transition temperature was not detected up to 350 ° C.

  The HOMO level was 5.30 eV, and the LUMO level was 2.28 eV.

  Table 3 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 4
In a 200 mL four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, 4.40 g (10.3 mmol) of compound (17e), 4.39 g (41.0 mmol) of p-toluidine, sodium-tert-butoxide 2.36 g (24.6 mmol) and 49.4 g of o-xylene were charged. To this mixed solution, a solution of 46.0 mg (0.21 mmol) of palladium (II) acetate and 0.12 g (0.62 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (2.0 g) solution. Was added. Next, the mixture was aged at 140 ° C. for 17 hours in a nitrogen atmosphere. Next, when the mixture was allowed to cool to 60 ° C., 50 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. Subsequently, extraction operation was performed by adding 200 mL of toluene. The extracted organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure, and slowly added to a stirred solution of hexane (300 mL). The precipitated solid was collected by filtration to obtain 4.45 g of the compound (20a).

  In a 100 mL four-necked round bottom flask equipped with a condenser and a thermometer, 0.61 g (1.27 mmol) of compound (20a), 0.30 g (1.27 mmol) of m-dibromobenzene under a nitrogen atmosphere at room temperature, Sodium-tert-butoxide 0.49 g (5.09 mmol) and o-xylene 8.14 g were mixed. After flowing nitrogen through the reaction vessel for about 20 minutes, 11.6 mg (12.7 μmol) of tris (dibenzylideneacetone) dipalladium and tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere were added to this mixed solution. An additional 3 mg (50.9 μmol) of o-xylene (2.0 mL) solution was added. Subsequently, it stirred at the temperature of 130 degreeC for 19 hours. Subsequently, 0.10 g (0.64 mmol) of bromobenzene was added, and the mixture was further stirred at 130 ° C. for 3 hours. Next, 0.22 g (1.27 mmol) of diphenylamine was further added, and the mixture was further stirred at 130 ° C. for 3 hours. The reaction mixture was then cooled to about 60 ° C. and 1 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (110 mL). The precipitated solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.33 g of a light yellow powdery polymer compound (20).

  The obtained polymer compound (20) had a weight average molecular weight of 24,000 and a number average molecular weight of 16,000 (dispersity of 1.5) in terms of polystyrene.

  The glass transition temperature was 268 ° C.

  The HOMO level was 5.35 eV, and the LUMO level was 2.25 eV.

  Table 4 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 5
The same operation as Example 4 was carried out except that 0.32 g (1.27 mmol) of 3,5-dibromotoluene was used instead of m-dibromobenzene to obtain 0.29 g of a polymer compound (21).

  The obtained polymer compound (21) had a weight average molecular weight of 35,000 and a number average molecular weight of 18,000 (dispersity 1.9) in terms of polystyrene.

  The glass transition temperature was 281 ° C.

  The HOMO level was 5.24 eV and the LUMO level was 2.01 eV.

  Table 5 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 6
The same operation as in Example 4 was carried out except that 5.05 g (41.0 mmol) of p-anisidine was used instead of p-toluidine to obtain 4.32 g of compound (22a).

  Furthermore, the same operation was carried out except that 0.65 g (1.27 mmol) of the compound (22a) was used instead of the compound (20a) in Example 4, and 0.35 g of the polymer compound (22) was obtained.

  The obtained polymer compound (22) had a weight average molecular weight of 22,000 and a number average molecular weight of 17,000 (dispersity of 1.3) in terms of polystyrene.

  The glass transition temperature was 264 ° C.

  The HOMO level was 5.29 eV, and the LUMO level was 2.10 eV.

  Table 6 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 7
The same operation as in Example 1 was performed except that 0.35 g (0.93 mmol) of N, N′-bis (4-tert-butylphenyl) phenylene-1,3-diamine was used instead of the compound (17a). 0.10 g of a polymer compound (23) was obtained.

  The obtained polymer compound (23) had a weight average molecular weight of 24,000 and a number average molecular weight of 19,000 (dispersion degree 1.3) in terms of polystyrene.

  The glass transition temperature was 258 ° C.

The HOMO level was 5.36 eV and the LUMO level was 2.27 eV.
Table 7 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 8
The same operation as Example 4 was carried out except that 0.32 g (1.27 mmol) of 2,6-dibromotoluene was used instead of m-dibromobenzene to obtain 0.23 g of a polymer compound (24).

  The obtained polymer compound (24) had a weight average molecular weight of 9,700 and a number average molecular weight of 7,100 (dispersion degree of 1.4) in terms of polystyrene.

  The glass transition temperature was 260 ° C.

  The HOMO level was 5.40 eV and the LUMO level was 2.17 eV.

  Table 8 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 9
The same as Example 1 except that 0.30 g (0.93 mmol) of N, N′-bis (4-tolyl) -2,5-dimethylphenylene-1,4-diamine was used instead of the compound (17a). Operation was performed to obtain 0.11 g of a polymer compound (25).

  The obtained polymer compound (25) had a weight average molecular weight of 17,000 and a number average molecular weight of 8,900 (dispersity 1.9) in terms of polystyrene.

  The glass transition temperature was 260 ° C.

The HOMO level was 5.17 eV and the LUMO level was 2.07 eV.
Table 9 shows the results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Comparative Example 1
To a 50 mL four-necked round bottom flask equipped with a condenser and a thermometer, 1.30 g (2.84 mmol) of 3,6-dibromo-9- (4-n-butylphenyl) carbazole at room temperature under a nitrogen atmosphere, 0.42 g (2.84 mmol) of 4-n-butylaniline, 1.09 g (11.4 mmol) of sodium-tert-butoxide and 15.2 g of o-xylene were mixed. After allowing nitrogen to flow for about 20 minutes inside the reaction vessel, 26.0 mg (28.4 μmol) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and tri-tert-butylphosphine 34. An additional 5 mg (0.17 mmol) of o-xylene (3.0 mL) solution was added. Subsequently, it stirred at the temperature of 120 degreeC for 18 hours. Subsequently, 0.27 g (1.71 mmol) of bromobenzene was added, and the mixture was further stirred at 120 ° C. for 3 hours. Thereafter, 0.58 g (3.41 mmol) of diphenylamine was further added, and the mixture was further stirred at 120 ° C. for 3 hours. The reaction mixture was then cooled to about 60 ° C., after which 3 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (200 mL). The precipitated solid was collected by filtration, washed in the order of acetone, water and acetone, and then dried under reduced pressure to obtain 0.58 g of a light yellow powdery polymer compound (100).

The obtained polymer compound (100) had a weight average molecular weight of 37,000 and a number average molecular weight of 10,000 (dispersion degree 3.7) in terms of polystyrene.

  The glass transition temperature was not detected up to 300 ° C.

  The HOMO level was 4.98 eV, and the LUMO level was 2.27 eV.

  Table 10 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 10 Measurement of Triplet Level of Polymer Compound (17) 1 mg of polymer compound (17) and 1 mL of 2-methyltetrahydrofuran were mixed well in a sample tube to prepare a uniform solution. The solution was degassed by bubbling with nitrogen gas for 10 minutes, and then the sample tube was sealed and the phosphorescence spectrum was measured. The triplet level of the polymer compound (17) calculated from the obtained phosphorescence spectrum was 2.60 eV.

Example 11 Measurement of Triplet Level of Polymer Compound (18) The same operation as in Example 10 was performed except that polymer compound (18) was used instead of polymer compound (17) in Example 10. The phosphorescence spectrum was measured. The triplet level of the polymer compound (18) calculated from the obtained phosphorescence spectrum was 2.68 eV.

Example 12 Measurement of Triplet Level of Polymer Compound (19) The same operation as in Example 10 was performed except that polymer compound (19) was used instead of polymer compound (17) in Example 10. The phosphorescence spectrum was measured. The triplet level of the polymer compound (19) calculated from the obtained phosphorescence spectrum was 2.68 eV.

Example 13 Measurement of Triplet Level of Polymer Compound (20) The same operation as in Example 10 was performed except that polymer compound (20) was used instead of polymer compound (17) in Example 10. The phosphorescence spectrum was measured. The triplet level of the polymer compound (20) calculated from the obtained phosphorescence spectrum was 2.76 eV.

Example 14 Measurement of Triplet Level of Polymer Compound (21) The same operation as in Example 10 was performed except that polymer compound (21) was used instead of polymer compound (17) in Example 10. The phosphorescence spectrum was measured. The triplet level of the polymer compound (21) calculated from the obtained phosphorescence spectrum was 2.74 eV.

Example 15 Measurement of Triplet Level of Polymer Compound (22) The same operation as in Example 10 was performed except that polymer compound (22) was used instead of polymer compound (17) in Example 10. The phosphorescence spectrum was measured. The triplet level of the polymer compound (22) calculated from the obtained phosphorescence spectrum was 2.71 eV.

Example 16 Measurement of Triplet Level of Polymer Compound (23) The same operation as in Example 10 was performed except that polymer compound (23) was used instead of polymer compound (17) in Example 10. The phosphorescence spectrum was measured. The triplet level of the polymer compound (23) calculated from the obtained phosphorescence spectrum was 2.76 eV.

Example 17 Measurement of triplet level of polymer compound (24) The same operation as in Example 10 was performed except that polymer compound (24) was used instead of polymer compound (17) in Example 10. The phosphorescence spectrum was measured. The triplet level of the polymer compound (24) calculated from the obtained phosphorescence spectrum was 2.73 eV.

Example 18 Measurement of Triplet Level of Polymer Compound (25) The same operation as in Example 10 was performed except that polymer compound (25) was used instead of polymer compound (17) in Example 10. The phosphorescence spectrum was measured. The triplet level of the polymer compound (25) calculated from the obtained phosphorescence spectrum was 2.70 eV.

Comparative Example 2 Measurement of Triplet Level of Polymer Compound (100) The same operation as in Example 10 was performed except that polymer compound (100) was used instead of polymer compound (17) in Example 10. When the phosphorescence spectrum was measured, the triplet level of the polymer compound (100) calculated from the obtained phosphorescence spectrum was 2.48 eV.

Comparative Example 3 Measurement of Triplet Level of Arylamine Polymer (101) Poly- (N, N′bis (4-butylphenyl) -N, N′-bis instead of polymer compound (17) in Example 10 (Phenyl) benzidine (ADS254BE: manufactured by American Die Source) (101) was used, and the phosphorescence spectrum was measured in the same manner as in Example 10, and was calculated from the obtained phosphorescence spectrum. The triplet level of the arylamine polymer (101) was 2.35 eV.

Example 19 (Production and Evaluation of Device)
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Further, ultraviolet ozone cleaning was performed.

On this substrate, a suspension of poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (manufactured by Bayer, Baytron P CH8000) was applied by spin coating, and dried at 200 ° C. for 1 hour. As a result, a hole injection layer having a thickness of 80 nm was formed.

  Next, a 0.5 wt% chlorobenzene solution of the polymer compound (17) obtained in Example 1 was applied by spin coating, and dried at 160 ° C. for 3 hours. As a result, a 20 nm hole transport layer of the polymer compound (17) was formed.

Subsequently, after installing in a vacuum evaporation apparatus, it exhausted with the vacuum pump until it became 5x10 <^-4> Pa or less. Subsequently, 2- (4,6-difluorophenyl) pyridinate-N, C2 ′] iridium (III) picolinate (FIrpic)) as a phosphorescent dopant material and 4,4′-bis (N-carbazolyl) as a host material Biphenyl (CBP) was co-evaporated at a deposition rate of 0.25 nm / second so that the weight ratio was 1:10, thereby forming a 30 nm light-emitting layer.

Next, BAlq (bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum) was deposited at a deposition rate of 0.3 nm / second to form a 5 nm exciton block layer, and then Alq ₃ (Tris). (8-quinolinolato) aluminum) was deposited at 0.3 nm / second to form a 45 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer to a thickness of 0.5 nm at a deposition rate of 0.01 nm / second, and aluminum was further deposited to a thickness of 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation.
A current of 20 mA / cm ² was applied to the device thus fabricated, and driving voltage and current efficiency were measured. The results are shown in Table 11.
Example 20 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the polymer compound (18) synthesized in Example 2 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Example 21 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the polymer compound (19) synthesized in Example 3 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Example 22 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the polymer compound (20) synthesized in Example 4 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Example 23 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the polymer compound (21) synthesized in Example 5 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Example 24 (Production and Evaluation of Device)
A device was fabricated in the same manner as in Example 19 except that the polymer compound (22) synthesized in Example 6 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Example 25 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the polymer compound (23) synthesized in Example 7 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Example 26 (Production and Evaluation of Device)
A device was fabricated in the same manner as in Example 19 except that the polymer compound (24) synthesized in Example 8 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Example 27 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the polymer compound (25) synthesized in Example 9 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Comparative Example 4 (device fabrication and evaluation)
A device was fabricated in the same manner as in Example 19 except that the polymer compound (100) synthesized in Comparative Example 1 was used instead of the polymer compound (17), and the light emission characteristics were measured. The results are shown in Table 11.

Comparative Example 5 (device fabrication and evaluation)
Instead of the polymer compound (17), poly- (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine) (ADS254BE: manufactured by American Dye Source) (101) The device was fabricated in the same manner as in Example 19 except that was used, and the emission characteristics were measured. The results are shown in Table 11.

  In Table 11, the measurement results of Examples 19 to 27 and Comparative Example 4 are shown as relative values obtained by standardizing the measured values of driving voltage and luminous efficiency of Comparative Example 5 to 100.

  The lower the drive voltage (relative value), the better, and the higher the current efficiency (relative value), the better.

  Therefore, the polymer compound of the present invention has a higher triplet level than the conventional polymer compound, and the brightness is higher than that of the conventional polymer compound due to the higher excited triplet level. A phosphorescent or fluorescent organic EL element which is high and consumes little power can be provided.

  The polymer compound of the present invention has a high excited triplet level as compared with conventionally known polymer compounds. Therefore, when the polymer compound of the present invention is used, it is possible to provide an organic electroluminescence device having excellent luminous efficiency and current efficiency. Therefore, the polymer compound of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

Claims (5)

The high molecular compound represented by following General formula (5).
(Where
R ¹ And R ² Each independently represents an alkyl group having 1 to 18 carbon atoms.
Ar ¹ , Ar ² And Ar ⁴ Are each independently an aromatic group optionally having 4 to 60 carbon atoms connected or condensed (these groups are each independently an alkyl group having 1 to 18 carbon atoms or 1 to 18 carbon atoms). Which may have an alkoxy group of
Ar ³ Is a divalent fragrance having 4 to 60 carbon atoms formed by linking and / or condensing one or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring. Group group (these may each independently have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms).
Ar ⁵ Are each independently an aromatic group optionally having 4 to 60 carbon atoms or a condensed ring (the group has an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms). May be present).
n represents 0-4. When n is 2 to 4, Ar ³ And Ar ⁴ May be the same or different.
m represents an integer of 2 or more. ) A high molecular compound having a skeleton in which at least two repeating structures represented by the following general formula (3) are linked, and the terminal is a secondary amino group, a halogen atom, or both a secondary amino group and a halogen atom On the other hand, in the presence of a palladium catalyst and a base, an aryl halide represented by the following general formula (6), an arylamine represented by the following general formula (7), or an aryl halide represented by the general formula (6) And the arylamine represented by the general formula (7) are reacted. The method for producing a polymer compound according to claim 1 .
(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 18 carbon atoms.
Ar ¹ , Ar ² and Ar ⁴ are each independently an aromatic group optionally having 4 to 60 carbon atoms or a condensed ring (these groups are each independently having 1 to 18 carbon atoms). An alkyl group or an alkoxy group having 1 to 18 carbon atoms).
Ar ³ is a divalent valence having 4 to 60 carbon atoms formed by linking and / or condensing one or more ring structures selected from the group consisting of a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring. (They may each independently have an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms).
n represents 0-4.
When n is 2 to 4, Ar ³ and Ar ⁴ may be the same or different. )
(Where
Ar ⁵ is an aromatic group which may be linked or condensed with 4 to 60 carbon atoms (this group may have an alkyl group with 1 to 18 carbon atoms or an alkoxy group with 1 to 18 carbon atoms). ).
X represents a chlorine atom, a bromine atom, or an iodine atom. )
(In the formula, each of Ar ⁵ is independently an aromatic group optionally having 4 to 60 carbon atoms or a condensed ring (the group is an alkyl group having 1 to 18 carbon atoms or 1 to 18 carbon atoms). Which may have an alkoxy group of A conductive material comprising the polymer compound according to claim 1 . A conductive material for an organic EL device comprising the polymer compound according to claim 1 . A hole transport material for an organic EL device comprising the polymer compound according to claim 1 .