KR20140015837A - Norbornene-based styrene derivative and hole transporting polymer prepared by using the same - Google Patents

Abstract

The present invention relates to a norbornene-based styrene derivative represented by chemical formula 1 and a hole transport polymer prepared using the same, and more specifically, to a norbornene-based styrene derivative enabling thermal cross-linking of a hole transport polymer, and a hole transport polymer prepared by using the same.

Description

Norbornene-based styrene derivatives and hole-transport polymers prepared using the same {NORBORNENE-BASED STYRENE DERIVATIVE AND HOLE TRANSPORTING POLYMER PREPARED BY USING THE SAME}

The present invention relates to a norbornene-based styrene derivative and a hole transporting polymer prepared using the same. More specifically, the present invention relates to a norbornene-based styrene derivative that enables thermal crosslinking of a hole transport polymer and a hole transport polymer prepared using the same.

The hole transport material is a material used for facilitating the movement of holes. Recently, it is widely used in various optoelectronic devices such as organic light emitting diodes and solar cells. These hole transport materials can be broadly classified into amines, hydrazones, star bursts, and the like, and diamines, triamines, and tetraamine derivatives mainly containing triarylamine groups are frequently used.

The hole transport capacity of triarylamine groups in triarylamine derivatives originates from the fact that the single-electron pairs present in the nitrogen atom can be easily oxidized to form stable cationic radicals and provide holes therefrom. The hole transport material can be largely divided into a single molecule form and a polymer form.

The monomolecular form has been actively studied in the Shirota group, and the representative example is N, N'-Diphenyl-N, N'-di (m-tolyl) -benzidine (TPD), but the glass transition temperature Has a disadvantage in that the efficiency is lowered due to low crystallization due to low operation for a long time and high current driving, and thus, research into a material for replacing the same is being conducted.

On the other hand, the polymer material may be a compound designed to retain the excellent electrical and optical properties of the conjugated polymer by introducing such a monomolecular triarylamine derivative into the conjugated polymer skeleton. It is attracting attention because of its ability to be formed and its solution process, but there is a concern that the polymer is very rigid and the conjugate structure is formed in the polymer's main chain, thereby degrading the photoelectric stability and adversely affecting device life.

Another example of a polymeric material is that the polymer backbone is unconjugated, that is, a branched polymer. Although less studied than conjugated polymer systems, many studies have recently been conducted because there are advantages in controlling the type and amount of triarylamine functional groups and molecular weight through various polymerization methods. Moreover, it is known that such a branched polymer material can increase device life due to the excellent thermal stability of the polymer skeleton. Such a branched polymer can be prepared by a radical polymerization method using an acrylic monomer containing a triarylamine derivative, a radical and anion polymerization method using a styrene monomer, and a ring-opening polymerization method using a cyclic monomer.

Japanese Patent Publication No. 4004635 discloses an example in which an arylamine-containing polystyrene polymer obtained by polymerizing a styrene triarylamine monomer by a radical polymerization method is applied to an organic light emitting device, but the polystyrene polymer does not have high thermal stability and is broken. The disadvantage is that it has less flexibility because of its easy brittle nature.

In addition, US Patent Publication No. 2001-0017155 discloses a polymer having a structure in which a triphenylamine group is directly connected to a polyolefin main chain by side chain, but this is also a polystyrene-based polymer, which is brittle and has low flexibility, thereby providing a flexible substrate. It was difficult to apply to.

On the other hand, the conventional hole transport polymer has a problem that damage caused by the solvent occurs during the solution process when forming a thin film.

Patent Document 1: Japanese Patent No. 4004635 Patent Document 2: US Patent Publication No. 2001-0017155

An object of the present invention is to provide a monomer which enables thermal crosslinking of a hole transporting polymer and a method for producing the same.

In addition, an object of the present invention is to provide a hole transporting polymer that can be thermally crosslinked and is not damaged even in a solution process and a method of manufacturing the same.

In addition, an object of the present invention is to provide a hole transport polymer applicable to a flexible substrate and a method of manufacturing the same because it has excellent thermal stability, hole transport capacity and flexibility.

In addition, an object of the present invention is to provide a hole transport layer made of the hole transport polymer and an electronic device having the same.

1. Norbornene-based styrene derivative represented by the following formula (1):

Wherein n is an integer from 1 to 15.

2. A process for preparing the norbornene-based styrene derivative of 1 above, comprising reacting styrene substituted with alkyl halide and halogenated alkyl magnesium halide substituted with norbornene.

3. A hole transport polymer comprising a repeating unit of Formula 2 below:

Wherein n is an integer from 1 to 15.

4. A hole transport polymer represented by the following formula (3) or (4):

In Formula 3 and Formula 4,

로 이루어진 군에서 선택되는 어느 하나이고, 여기서 Ar₄ 내지 Ar₆은 서로 독립적으로 탄소수 6 내지 40의 아릴기, 아릴알킬기, 알킬아릴기, 아릴실릴기, 아릴알킬실릴기, 할로아릴기, 아릴옥시기, 아릴옥소알킬기, 티오아릴옥소알킬기, 아릴옥소아릴기, 아릴실록시기, 아릴알킬실록시기, 아릴실록소알킬기, 아릴실록소아릴기, 아릴아미노기, 아릴아미노 알킬기, 아릴아미노아릴기, 아릴포스피노알킬기, 디아릴아미도기 및 트리아릴아미도기로 이루어진 군에서 선택되는 어느 하나임.n is an integer from 1 to 15, m1 is an integer from 1 to 20, m2 is an integer from 0 to 20, p and q are mole fractions satisfying p + q = 1 (0 <p, q <1) , Z is any one selected from the group consisting of methylene group, methyl ether group and carboxyl group, Ar ₁ and Ar ₂ are independently of each other an aryl group, arylalkyl group, alkylaryl group, arylsilyl group, aryl having 6 to 40 carbon atoms Alkyl silyl group, haloaryl group, aryloxy group, aryl oxoalkyl group, thioaryl oxoalkyl group, aryl oxoaryl group, arylsiloxy group, arylalkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino Any one selected from the group consisting of an alkyl group, an arylaminoaryl group, an arylphosphinoalkyl group, a diarylamido group and a triarylamido group, Ar ₃ is an aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, aryl Silyl group, arylalkylsilyl group, haloaryl group, aryl jade Group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, arylsiloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxaneolic group, arylamino group, arylamino alkyl group, arylaminoaryl group, arylphosphino Alkyl groups, diarylamido groups, triarylamido groups, and

It is any one selected from the group consisting of, wherein Ar _{4 To} Ar ₆ Independently of each other an aryl group, arylalkyl group, alkylaryl group having 6 to 40 carbon atoms, arylsilyl group, arylalkylsilyl group, haloaryl group, aryljade Period, aryl oxo alkyl group, thioaryl oxo alkyl group, aryl oxo aryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, aryl phosphino Any one selected from the group consisting of an alkyl group, a diarylamido group and a triarylamido group.

5. The hole transport of 4 above prepared by adding at least one organometallic catalyst selected from the group consisting of compounds represented by the following Formula 5 to a mixture of the norbornene-based styrene derivative and the hole transporting polymer forming monomer of the above 1 Polymer preparation method:

Wherein Ma is a transition metal element of Groups 3 to 10 on the periodic table, and L ₁ , L ₂ are cyclopentadienyl derivatives which are Π- ligands or consist of phosphine, amine, imine, amide, oxide and heterocyclocarbine groups Any σ-ligand selected from the group may be the same or different within the same formula, Y is an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a cycloalkyl group, a cycloalkylsilyl group, an aryl group having 6 to 40 carbon atoms, alkyl Aryl group, arylalkyl group, arylsilyl group, alkylarylsilyl group, cycloalkylaryl group and any one selected from the group consisting of cycloalkylarylsilyl group, Xa to Xc as σ- ligand independently of each other hydrogen atom, halogen group, Hydroxy group, alkyl group having 1 to 20 carbon atoms, alkylallyl group, alkoxy group, thioalkoxy group, amide group, carboxyl group, acetylacetonato group, sulfonyl group, aryl group having 6 to 40 carbon atoms, alkyl Any one selected from the group consisting of aryl group, allylaryl group, arylalkyl group, haloaryl group, aryloxy group, arylalkoxy group, thioaryloxy group, arylamide group, aryl alkylamide group and arylaminoaryloxy group.

6. In the above 5, wherein the cyclopentadienyl derivative is any one selected from the group consisting of compounds represented by the following formula (6) A method for producing a hole transporting polymer:

In the formula, r1, r2, r3, r4, r5, r6, r7, r8 and r9 are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an alkylsilyl group, a haloalkyl group, Alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkyl Silyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, arylsiloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxaneoxy group, arylamino group, arylaminoalkyl group , An arylaminoaryl group and an arylphosphinoalkyl group.

7. In the above 5, the method of preparing a hole transporting polymer further adding at least one cocatalyst selected from the group consisting of compounds represented by the formula (7):

Expression from, R ₃ is unsubstituted or substituted with a hydrogen atom, a C 1 -C 20 substituted alkyl, optionally substituted 3 to 20 carbon atoms, or consisting of an unsubstituted cycloalkyl group, an aryl group, an alkylaryl group and an arylalkyl group having 6 to 40 carbon atoms P is an integer of 1 to 100, Ar ₇ is any one selected from the group consisting of aryl, haloaryl and haloalkylaryl groups having 6 to 40 carbon atoms, and Mb is 1 to 2 on the periodic table. Or a metal element ion of Groups 11 to 14, Q being a weakly coordinated anion promoter.

8. Electronic device having a hole transport layer made of the hole transport polymer of the above 4.

9. The electronic device of claim 8, wherein the electronic device is a solar cell or an organic light emitting diode.

When the norbornene-based styrene derivative of the present invention is mixed with a conventional hole transporting polymer-forming monomer to form a hole transporting polymer, thermally crosslinking is possible without degrading other physical properties of the hole transporting polymer of the polymer and thus, Damage caused by this can be prevented.

The hole transport polymer of the present invention can be prepared by a polymerization method using an organometallic catalyst, and can be applied to a flexible substrate because it has excellent thermal stability, hole transport capacity, and flexibility.

The organic light emitting diode and the solar cell manufactured using the hole transport polymer of the present invention as the hole transport layer material have high efficiency and stability.

The present invention relates to a norbornene-based styrene derivative represented by Formula 1 and a hole transporting polymer prepared by using the same, and to a norbornene-based styrene derivative which enables thermal crosslinking of a hole transporting polymer and a hole transporting polymer prepared using the same. will be.

Hereinafter, the present invention will be described in detail.

Norbornene-based styrene derivatives of the present invention are represented by the following formula (1).

[Formula 1]

In formula, n is an integer of 1-15.

When the norbornene-based styrene derivative of the present invention is used as a monomer of the polymer, the norbornene portion is easily decomposed by energy such as heat or ultraviolet rays, so that the polymer is polymerized to form a main chain, and the styrene portion is formed on the side chain. It will exist.

Since the styrene side chains also have unsaturated double bonds, when heat is applied after the polymerization of the polymer is completed, the styrene side chains bind to each other and crosslinking proceeds. In this respect, the norbornene-based styrene derivatives of the present invention are useful as comonomers that allow thermal crosslinking of polymers.

The alkylene chain linking norbornene and styrene preferably has 1 to 15 carbon atoms (an integer of 1 to 15). In consideration of the flexibility of the polymer chain, the efficiency of the crosslinking reaction and the like, n is more preferably 3 to 12.

One embodiment of the method for producing a norbornene-based styrene derivative of the present invention includes the step of reacting styrene substituted with halogenated alkyl and halogenated alkylmagnesium substituted with norbornene.

More specifically, styrene substituted with halogenated alkyl and halogenated alkyl magnesium substituted with norbornene are mixed in a state dissolved in a suitable organic solvent such as tetrahydrofuran (THF), respectively. Mixing is carried out at a low temperature of about -50 to -10 ℃, after the mixing is slowly heated to room temperature to proceed with the reaction. The reaction may be performed using a catalyst such as Li ₂ CuCl _4, and after completion of the reaction, the organic layer may be extracted to remove the solvent to obtain a norbornene-based styrene derivative according to the present invention.

Norbornene-based styrene derivatives of the present invention can be used as a comonomer of the hole transport polymer. The hole transport polymer using the norbornene-based styrene derivative of the present invention as a comonomer includes a repeating unit represented by the following Chemical Formula 2.

(2)

In formula, n is an integer of 1-15.

As mentioned above, the styrene of the side chain performs a thermal crosslinking reaction, and n is an integer which is more preferably 3 to 10.

One embodiment of the hole transport polymer of the present invention is represented by the following formula (3) or (4):

(3)

[Chemical Formula 4]

In Formula 3 and Formula 4,

n is an integer from 1 to 15, m1 is an integer from 1 to 20, m2 is an integer from 0 to 20,

p and q are mole fractions satisfying p + q = 1 (0 <p, q <1),

Z is any one selected from the group consisting of a methylene group, a methyl ether group and a carboxyl group,

Ar ₁ and Ar ₂ are each independently an aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, Aryl oxoaryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, arylphosphinoalkyl group, diarylamido group and triarylamido group Any one selected from the group consisting of,

로 이루어진 군에서 선택되는 어느 하나이고, 여기서 Ar₄ 내지 Ar₆은 서로 독립적으로 탄소수 6 내지 40의 아릴기, 아릴알킬기, 알킬아릴기, 아릴실릴기, 아릴알킬실릴기, 할로아릴기, 아릴옥시기, 아릴옥소알킬기, 티오아릴옥소알킬기, 아릴옥소아릴기, 아릴실록시기, 아릴알킬실록시기, 아릴실록소알킬기, 아릴실록소아릴기, 아릴아미노기, 아릴아미노 알킬기, 아릴아미노아릴기, 아릴포스피노알킬기, 디아릴아미도기 및 트리아릴아미도기로 이루어진 군에서 선택되는 어느 하나이다.Ar ₃ is an aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, aryl having 6 to 40 carbon atoms Siloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxanearyl group, arylamino group, arylamino alkyl group, arylaminoaryl group, arylphosphinoalkyl group, diarylamido group, triarylamido group and

It is any one selected from the group consisting of, wherein Ar _{4 To} Ar ₆ Independently of each other an aryl group, arylalkyl group, alkylaryl group having 6 to 40 carbon atoms, arylsilyl group, arylalkylsilyl group, haloaryl group, aryljade Period, aryl oxo alkyl group, thioaryl oxo alkyl group, aryl oxo aryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, aryl phosphino It is any one selected from the group consisting of an alkyl group, a diarylamido group and a triarylamido group.

In the hole transport polymer of the present invention, preferably p is 0.7 to 0.999, q is 0.001 to 0.3 is preferable in terms of crosslinking and hole transport capacity.

In addition, the weight average molecular weight is preferably 5,000 to 1,000,000 g / mol. If the molecular weight is less than 5,000g / mol, the physical properties of the polymer is lowered, if it is more than 1,000,000g / mol solubility of the polymer is lowered, it may be difficult to apply the solution process.

The hole transport polymer of the present invention is a monomer for forming a hole transport polymer, and may be prepared by copolymerizing a compound of Formula A or Formula B together with a norbornene-based styrene derivative according to the present invention.

(A)

[Formula B]

In Formula A and Formula B, m1 is an integer of 1 to 20, m2 is an integer of 0 to 20, Z is any one selected from the group consisting of methylene group, methyl ether group and carboxyl group, Ar ₁ and Ar ₂ Are independently of each other an aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, Arylsiloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxanearyl group, arylamino group, arylamino alkyl group, arylaminoaryl group, arylphosphinoalkyl group, diarylamido group and triarylamido group Which one is,

로 이루어진 군에서 선택되는 어느 하나이고, 여기서 Ar₄ 내지 Ar₆은 서로 독립적으로 탄소수 6 내지 40의 아릴기, 아릴알킬기, 알킬아릴기, 아릴실릴기, 아릴알킬실릴기, 할로아릴기, 아릴옥시기, 아릴옥소알킬기, 티오아릴옥소알킬기, 아릴옥소아릴기, 아릴실록시기, 아릴알킬실록시기, 아릴실록소알킬기, 아릴실록소아릴기, 아릴아미노기, 아릴아미노 알킬기, 아릴아미노아릴기, 아릴포스피노알킬기, 디아릴아미도기 및 트리아릴아미도기로 이루어진 군에서 선택되는 어느 하나이다.Ar ₃ is an aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, aryl having 6 to 40 carbon atoms Siloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxanearyl group, arylamino group, arylamino alkyl group, arylaminoaryl group, arylphosphinoalkyl group, diarylamido group, triarylamido group and

It is any one selected from the group consisting of, wherein Ar _{4 To} Ar ₆ Independently of each other an aryl group, arylalkyl group, alkylaryl group having 6 to 40 carbon atoms, arylsilyl group, arylalkylsilyl group, haloaryl group, aryljade Period, aryl oxo alkyl group, thioaryl oxo alkyl group, aryl oxo aryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, aryl phosphino It is any one selected from the group consisting of an alkyl group, a diarylamido group and a triarylamido group.

The olefin triarylamine monomers of Formulas A and B according to the present invention can form a polyolefin-based triarylamine polymer by a simple polymerization method, the polyolefin-based triarylamine polymer is a polyolefin main chain, Triarylamine groups are not directly connected to the main chain but exist in the form of side chains connected by alkyl chains. Unlike conventional polystyrene-based polymers, the polymers are highly flexible and can be applied to flexible substrates. It is excellent in that it can be usefully used in electronic devices using it as a hole transport material. In addition, since the main chain is a polyolefin, it is also an advantage that the optoelectronic stability is superior to the conventional conjugated polymer.

As the olefin-based triarylamine monomer according to the present invention represented by the formula (A) or (B), a triarylamine-substituted linear or cyclic olefin is suitable. Specific examples of the linear olefin include 4-triphenylamino-1-butene , 6-triphenylamino-1-hexene, 8-triphenylamino-1-octene, 10-triphenylamino-1-decene, vinyltolyldiphenylamine, 4-tolyldiphenylamino-1-butene, 6- Tolyldiphenylamino-1-hexene, 8-tolyldiphenylamino-1-octene, 10-tolyldiphenylamino-1-decene, vinylnaphthyldiphenylamine, 4-naphthyldiphenylamino-1-butene, 6- Naphthyldiphenylamino-1-hexene, 8-naphthyldiphenylamino-1-octene, 10-naphthyldiphenylamino-1-decene, etc. are mentioned.

On the other hand, specific examples of the cyclic olefin include 2-triphenylamino-5-norbornene, 2- (2-triphenylamino-1-ethyl) -5-norbornene, 2- (4-triphenylamino-1- Butyl) -5-norbornene, 2- (6-triphenylamino-1-hexyl) -5-norbornene, 2- (8-triphenylamino-1-octyl) -5-norbornene, 2- (10 -Triphenylamino-1-decyl) -5-norbornene, 2-tolidiphenylamino-5-norbornene, 2- (2-tolyldiphenylamino-1-ethyl) -5-norbornene, 2- ( 4-tolyldiphenylamino-1-butyl) -5-norbornene, 2- (6-tolyldiphenylamino-1-hexyl) -5-norbornene, 2- (8-tolyldiphenylamino-1-octyl ) -5-norbornene, 2-naphthyldiphenylamino-5-norbornene, 2- (2-naphthyldiphenylamino-1-ethyl) -5-norbornene, 2- (4-naphthyldiphenylamino-1 -Butyl) -5-norbornene, 2- (6-naphthyldiphenylamino-1-hexyl) -5-norbornene, 2- (8-naphthyldiphenylamino-1-octyl) -5-norbornene, 2 -(10-naphthyldiphenylamino-1-decyl) -5-norbornene, (5-norbornene-2-methyl) triphenylamine ether , (5-norbornene-2-methyl) (2-triphenylamino-1-ethyl) ether, (5-norbornene-2-methyl) (4-triphenylamino-1-butyl) ether, (5- Norbornene-2-methyl) (6-triphenylamino-1-hexyl) ether, (5-norbornene-2-methyl) (8-triphenylamino-1-octyl) ether, (5-norbornene-2 -Methyl) (2-tolyldiphenylamino-1-ethyl) ether, (5-norbornene-2-methyl) (4-tolyldiphenylamino-1-butyl) ether, (5-norbornene-2-methyl (6-tolyldiphenylamino-1-hexyl) ether, (5-norbornene-2-methyl) (8-tolyldiphenylamino-1-octyl) ether, (5-norbornene-2-methyl) ( 2-naphthyldiphenylamino-1-ethyl) ether, (5-norbornene-2-methyl) (4-naphthyldiphenylamino-1-butyl) ether, (5-norbornene-2-methyl) (6- Naphthyldiphenylamino-1-hexyl) ether, (5-norbornene-2-methyl) (8-naphthyldiphenylamino-1-octyl) ether, (5-norbornene-2-methyl) (10-naphthyldi Phenylamino-1-decyl) ether, (5-norbornene-2-carboxylic acid) triphenylamine S Le, (5-norbornene-2-carboxylic acid) (2-triphenylamino-1-ethyl) ester, (5-norbornene-2-carboxylic acid) (4-triphenylamino-1-butyl) Ester, (5-norbornene-2-carboxylic acid) (6-triphenylamino-1-hexyl) ester, (5-norbornene-2-carboxylic acid) (2-tolyldiphenylamino-1-ethyl ) Ester, (5-norbornene-2-carboxylic acid) (4-tolyldiphenylamino-1-butyl) ester, (5-norbornene-2-carboxylic acid) (6-tolyldiphenylamino-1 -Hexyl) ester, (5-norbornene-2-carboxylic acid) (8-tolyldiphenylamino-1-octyl) ester, (5-norbornene-2-carboxylic acid) (2-naphthyldiphenylamino -1-ethyl) ester, (5-norbornene-2-carboxylic acid) (4-naphthyldiphenylamino-1-butyl) ester, (5-norbornene-2-carboxylic acid) (6-naphthyldi Phenylamino-1-hexyl) ester, (5-norbornene-2-carboxylic acid) (8-naphthyldiphenylamino-1-octyl) ester, (5-norbornene-2-carboxylic acid) (10- Naphthyldiphenylamino -1-decyl) ester, etc. are mentioned.

Specific examples of the olefinic triarylamine monomer according to the present invention are shown in the following Chemical Formula 8, but are not limited thereto.

One embodiment of the method for producing a hole transporting polymer of the present invention, at least one organometal selected from the group consisting of compounds represented by the following formula (5) in a mixture of a norbornene-based styrene derivative of Formula 1 and a monomer for forming a hole transporting polymer Adding a catalyst to polymerize.

[Chemical Formula 5]

Wherein Ma is a transition metal element of Groups 3 to 10 on the periodic table, and L ₁ , L ₂ are cyclopentadienyl derivatives which are Π- ligands or consist of phosphine, amine, imine, amide, oxide and heterocyclocarbine groups Any σ-ligand selected from the group may be the same or different within the same formula, Y is an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a cycloalkyl group, a cycloalkylsilyl group, an aryl group having 6 to 40 carbon atoms, alkyl Aryl group, arylalkyl group, arylsilyl group, alkylarylsilyl group, cycloalkylaryl group and any one selected from the group consisting of cycloalkylarylsilyl group, Xa to Xc as σ- ligand independently of each other hydrogen atom, halogen group, Hydroxy group, alkyl group having 1 to 20 carbon atoms, alkylallyl group, alkoxy group, thioalkoxy group, amide group, carboxyl group, acetylacetonato group, sulfonyl group, aryl group having 6 to 40 carbon atoms, alkyl Any one selected from the group consisting of an aryl group, allylaryl group, arylalkyl group, haloaryl group, aryloxy group, arylalkoxy group, thioaryloxy group, arylamide group, aryl alkylamide group and arylaminoaryloxy group.

The organometallic catalyst represented by Chemical Formula 5 includes a transition metal element of Groups 3 to 10 on the periodic table, in which a ligand and a leaving group are bonded to the metal. Specific examples of transition metal elements include titanium, zirconium, hafnium, and Group 10 metals such as nickel and palladium. Specific examples of ligands (L ₁ and L ₂ ) include cyclopentadienyl derivatives, phosphines, and amines. , Imines, amides, oxides, heterocyclocarbine groups, and the like, and one or more in the same formula may be bonded to the metal. Can be used in connection.

The cyclopentadienyl derivative may be selected from the group consisting of compounds represented by the following formula (6).

[Chemical Formula 6]

In the formula, r1, r2, r3, r4, r5, r6, r7, r8 and r9 are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an alkylsilyl group, a haloalkyl group, Alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkyl Silyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, arylsiloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxaneoxy group, arylamino group, arylaminoalkyl group , Arylaminoaryl group and any one selected from the group consisting of arylphosphinoalkyl group, but is not limited thereto. More specific examples include cyclopentadienyl, indenyl, fluorenyl groups, and substituted forms thereof.

Specific examples of the phosphine group include triphenyl phosphine, trimethyl phosphine, triethyl phosphine, tricyclohexyl phosphine, tributyl butyl phosphine, bis diphenyl phosphinomethane, bis diphenyl phosphinoethane, bis di Phenylphosphinopropane, bisdiphenylphosphinoferrocene, and the like. Specific examples of the amine group include tertiary butylamine, isopropylamine, cyclohexylamine, aniline, dietary butylamine, diisopropylamine, dicyclohexylamine, diphenylamine, diaminobenzene, and the like. Specific examples of the above include (diisopropylphenyl) salicyl aldimine, bis (diisopropylphenyl) benzenediimine, bis (diisopropylphenyl) acenaphthalenequinonediimine and the like.

Specific examples of the amide group include a dimethylamide group, a diethylamide group, a diisopropylamide group, and the like, and specific examples of the oxide group include diphenylphosphineethylidine oxide, tertiary butyl amidate, and the like. Specific examples of the heterocyclocarbine include bis (diisopropylphenyl) imidazolidine, bis (diisopropylphenyl) dihydroimidazolidine and the like. In addition, specific examples of the bridging group (Y) include methylene, ethylene, dimethylsilyl, phenylene, isopropylidine, diphenylmethylidine and the like.

Specific examples of the leaving groups (Xa to Xc) include hydrogen, chlorine, bromine, fluorine, iodine, hydroxy, methyl, allyl, phenyl, benzyl, phenylallyl, methoxy, ethoxy and iso Propoxy group, phenoxy group, diisopropylphenoxy group, dimethylamide group, diethylamide group, diisopropylamide group, acetate group, benzoate group, acetylacetonato group, methanesulfonate group, trifluoromethanesulfo Nate group, toluenesulfonate group, etc. can be mentioned, These can combine with a metal each independently or simultaneously in the same formula.

In the preparation method according to the present invention, the organometallic catalyst represented by Chemical Formula 5 is preferably used together with a promoter represented by Chemical Formula 7.

[Formula 7]

Expression from, R ₃ is unsubstituted or substituted with a hydrogen atom, a C 1 -C 20 substituted alkyl, optionally substituted 3 to 20 carbon atoms, or consisting of an unsubstituted cycloalkyl group, an aryl group, an alkylaryl group and an arylalkyl group having 6 to 40 carbon atoms P is an integer of 1 to 100, Ar ₇ is any one selected from the group consisting of aryl, haloaryl and haloalkylaryl groups having 6 to 40 carbon atoms, and Mb is 1 to 2 on the periodic table. Or a metal element ion of group 11 to 14, and Q is a weakly coordinated anion promoter.

The cocatalyst of Formula 7 may be any one selected from the group consisting of an alkyl alumino acid compound, a weakly coordinating boron Lewis acid compound, and a weakly coordinating anion compound, wherein the alkyl alumino acid compound may be linear, cyclic or reticulated, Specifically, methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, hexyl aluminoxane, decyl aluminoxane and the like, and specific examples of the weakly coordinated boron Lewis acid compound, triphenyl borane , Tris (pentafluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, and the like, and specific examples of the weakly coordinated anion compound include trityl tetrakis (pentafluoro Rophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniyl Linium tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluoro antimonate, silver hexachloro antimonate, silver hexafluoro phosphate, etc. are mentioned.

These cocatalysts can also be preferably used with the aluminum compound of formula (9).

Wherein R ₄ , R 5 _, and R ₆ are each independently a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, or 6 to 40 carbon atoms It is any one selected from the group consisting of an aryl group, an alkylaryl group and an arylalkyl group, wherein at least one of R ₄ , R _{5 ,} and R ₆ includes an alkyl group.

The aluminum compound serves to alkylate the catalyst and to remove impurities in the reaction solution.

Specific examples of the aluminum compound include trimethylaluminum, dimethylaluminum chloride, dimethylaluminum methoxide, methylaluminum dichloride, triethylaluminum, diethylaluminum chloride, diethylaluminum methoxide, ethylaluminum dichloride, trinormal propylaluminum, dino Malpropyl aluminum chloride, normal propyl aluminum chloride, triisopropyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, diisobutyl aluminum hydride, etc. are mentioned.

In the copolymerization of the hole transporting polymer forming polymer and the norbornene-based styrene derivative according to the present invention using the organometallic catalyst system, the amount of the cocatalyst used together is not particularly limited, but may vary depending on the type. have. In the case of alkylaluminoxane, the molar ratio with the organometallic catalyst is mainly usable within the range of 1: 1 to 10 ⁶ : 1, and preferably used between 10: 1 and 10 ⁴ : 1. When the molar ratio of alkylaluminoxane and the organometallic catalyst is less than 10: 1, the catalytic activity is deteriorated, and it is difficult to expect a marked increase in activity even when used in excess of 10 ⁴ : 1. In addition, the amount of the alkyl aluminum that can be used with the alkylaluminoxane can be used in the range of 1: 1 to 10 ⁴ : 1 for the organometallic catalyst. In the case of the coordinating boron Lewis acid and the coordinating anion, the molar ratio of the organometallic catalyst can be used in the range of 0.1: 1 to 50: 1, wherein the amount of alkyl aluminum used together is 1: 1 to 3000: relative to the organometallic catalyst. 1, preferably within the range of 50: 1 to 1000: 1.

In the polymer production method according to the present invention, the polymerization temperature is -80 to 200 ° C, preferably 0 to 150 ° C. If the polymerization temperature is less than -80 ℃, the polymerization activity is significantly lowered, and if it exceeds 200 ℃, the activity degradation due to catalytic decomposition may occur. The polymerization pressure is suitably 1 to 1,000 atm, including the pressure of the comonomer, when copolymerizing the olefinic triarylamine monomer with the alpha olefin comonomer.

The process for preparing a polymer according to the present invention is largely performed by i) adding only a solvent and a monomer or monomer to a reactor and raising the temperature, followed by injection in the order of the cocatalyst and the organometallic compound as the main catalyst, or ii) the main catalyst is alkyl aluminum and a cocatalyst. After activation in advance, it may be achieved by injecting it into the reactor containing the monomer, or iii) pre-adding the alkylaluminum to the monomer and then injecting the main catalyst activated with the cocatalyst. In addition, the reaction for activating the main catalyst by contacting with the promoter is preferably performed for 30 seconds to 6 hours between -80 and 150 ° C.

The amount of the organometallic compound that is the main catalyst used in the polymer manufacturing process is not particularly limited, but the concentration of the central metal in the reaction system is appropriately 10 ^-8 to 1.0 M, ideally 10 ^-7 to 0.1 M concentration. Do.

The polyolefin-based trialkylamine polymer obtained from the polymerization reaction using the catalyst system has a molecular weight of 1,000 to 10 million, molecular weight distribution 1.1 to 100 by adjusting the type and amount of the main catalyst and the cocatalyst, the reaction temperature, the reaction pressure, and the concentration of the monomer. Various ranges can be adjusted.

The term electronic device used in the present invention is an electronic component using conduction of electrons in a solid state, and means a solar photovoltaic cell or an organic light emitting diode including an electron transporting material according to the present invention. The electronic device according to the present invention may be manufactured by applying the hole transport material according to the present invention to the hole transport layer by a conventional process known in the art.

The organic light emitting diode according to the present invention includes an organic emission layer (EML), an anode and a cathode, and a hole transport layer (HTL) including a hole transporting polymer according to the present invention between the anode and the organic light emitting layer. ) May be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic light emitting layer, and a hole injection layer (HIL) may be disposed below the hole transport layer. Can be further laminated.

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, and for example, CuPc, PEDOT: PSS, NPB which is a diamine, or TCTA which is a starburst type amine, mTA-MTDATA, etc. Can be used.

The electron transport layer used in the organic light emitting diode according to the present invention increases the chance of recombination in the light emitting layer by smoothly transporting the electrons supplied from the cathode to the organic light emitting layer and suppressing the movement of holes not bonded in the organic light emitting layer. It plays a role. The electron transport layer material may be used without particular limitation as long as it is commonly used in the art, and for example, an oxadiazole derivative such as PBD, BMD, BND, or Alq3 may be used.

Meanwhile, an electron injection layer (EIL) may be further stacked on the upper portion of the electron transport layer to facilitate electron injection from the cathode and ultimately improve power efficiency. The electron injection layer material may also be stacked. Any conventionally used in the art may be used without particular limitation, and for example, materials such as LiF, NaCl, CsF, Li 2 O, BaO, and the like may be used.

Looking at an embodiment of the organic light emitting diode and a method of manufacturing the same of the present invention. First, an anode is formed by coating an anode electrode material on the substrate. As the substrate, a substrate used in a conventional organic EL device is used, but an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, transparent and conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), and zinc oxide (ZnO) are used as the anode electrode material. The hole injection layer may be vacuum-heat-deposited or spin coated on the anode electrode to form a hole injection layer. Next, the hole transport layer material is spin coated on the upper portion of the hole injection layer by a solution method to form a hole transport layer. Subsequently, the organic light emitting layer may be stacked on the hole transport layer, and the hole blocking layer may be selectively formed on the organic light emitting layer by vacuum deposition or spin coating. The hole blocking layer serves to prevent such a problem by using a material having a very low HOMO level when the hole is introduced into the cathode through the organic light emitting layer to reduce the lifetime and efficiency of the device. In this case, the hole blocking material used is not particularly limited, but has an ion transporting potential and has a higher ionization potential than the light emitting compound, and BAlq, BCP, TPBI, etc. may be used. After depositing the electron transport layer on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer is formed thereon and a cathode electrode is vacuum-deposited on top of the electron injection layer to form a cathode electrode. The organic EL device is thereby completed. Here, the metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Manufacturing example  One: Norbornene  Preparation of Styrene Derivatives

Dissolve 1.30 g (5.12 mmol) of 1- (5-Bromopentyl) -4-vinylbenzene in 30 ml of THF and dissolve 1 mol% of Li ₂ CuCl ₄ at -20. It was added at ℃. 1 equivalent of the THF solution of norbornene methylmagnesium iodide was injected | maintained, and it heated up slowly to normal temperature. After stirring for 12 hours, the reaction was terminated with ammonium chloride. The organic layer was extracted with diethyl ether, the solvent was removed, and the residue was separated by column chromatography (silica gel, hexane), and then separated by 1- (5-norbornyl) -6- (4-vinylphenyl) hexane (1- (5-Norbornyl). ) -6- (4-vinylphenyl) -hexane) was obtained (yield: 0.43 g, 36%).

The NMR data of the prepared 1- (5-norbornyl) -6- (4-vinylphenyl) hexane are as follows.

¹ H NMR (CDCl ₃ , 300 MHz): δ 0.45-0.52 (m), 1.00-1.43 (m) (12H), 1.52-2.03 (m, 3H), 2.46-2.58 (m, 2H), 2.78 (s, 2H), 5.14-5.19 (d, 1H), 5.64-5.71 (d, 1H), 5.91 (dd, H _endo ), 6.01 (dd, H _exo ), 6.07-6.09 (m, H _exo ), 6.10 (dd , H _endo ) (2H), 6.62-6.73 (dd, 1H), 7.10-7.13 (d, 2H), 7.29-7.32 (d, 2H)

Manufacturing example  2: Hole transportation  Manufacture of Polymers

A schematic diagram of the hole transport polymer production is as follows.

Specifically, chlorobenzene is added to a mixture of [(NHC) Pd (η ³ -allyl) Cl] as the main catalyst and 1.5 equivalents Li (B (C ₆ F ₅ ) ₄ .2.5Et ₂ O as the main catalyst and Stirred for 8 hours at to prepare an activated catalyst solution (2.0 μM).

After filtration of the activated catalyst solution, the filtered activated catalyst solution (2.46 μmol) was added with M1 monomer (0.49 mmol, [monomer] / [Pd] = 200) and M2 prepared in Preparation Example 1 (2, 5, 10). The polymerization was initiated by introducing into a chlorobenzene solution (5 mL) containing mol%). The polymerization was carried out at 25 ° C. for 20 hours. The mixture was placed in a large amount of oxidized methanol (5% v / v, 300 mL) to precipitate the polymer. After stirring for 1 hour, the precipitated polymer was collected by filtration and washed with methanol (3 x 50 mL). The polymer was dissolved in CHCl ₃ and purified by repeating the procedure of re-casting in methanol / acetone (v / v = 4/1) three times. Finally, the obtained polymer was put in a vacuum oven and dried to a content weight at 70 ° C. to obtain a hole transporting polymer. NMR data of the prepared hole transporting polymer is as follows, and the polymerization results are shown in Table 1 below.

¹ H NMR (CDCl ₃ , 300 MHz): δ 0.5-1.9 (br, 15H), 2.0-2.8 (br, 4h), 4.95 (br s), 5.45 (br s), 6.47 (br s), 6.81 (br s, 10h), 6.92 (br s, 3h), 7.07 (br s, 8H), 7.28 (br s, 4H), 7.63 (br s, 2H), 7.76 (br s, 2H), 7.84 (br s, 2H).

Polymer Catalyst (mmol) M1 (mol) M2 (mol%) Yield (%) M2 content (mol%) 1-1 2.46 0.49 2 57 3.5 1-2 2.46 0.49 5 65 7.5 1-3 2.46 0.49 10 59 12

Manufacturing example  3: Hole transportation  Thermal crosslinking of polymers

A schematic diagram of the thermal crosslinking mechanism of the hole transport polymer is as follows.

이다.In the schematic, NPB

to be.

Specifically, the hole transporting polymer prepared in Preparation Example 2 was dissolved in chlorobenzene to prepare a solution of 1 to 2% by weight. The solution was dropped onto a 1 inch by 1 inch quartz substrate and a thin film was prepared using a spin-coater (2000 rpm, 30 seconds). The resulting quartz substrate was heated on a 180 to 200 ° C. hotplate for 15 to 60 minutes to advance crosslinking. The degree of crosslinking was calculated by comparing UV spectra after washing the thin film before and after crosslinking in chlorobenzene, and when heated for 30 minutes or more, a crosslinkable polymer having 100% crosslinking degree for all polymers could be prepared.

Manufacturing example  4: Fabrication of Organic Light Emitting Diode

First, wash the glass substrate with Anode (ITO) deposited, and then wash it with UV-Ozone (NLE NL-UV253) to clean the ITO surface and adjust the work-function of ITO. Was carried out. Then, spin-coating the material shown in Table 2 below as a HTL material on the cleaned ITO substrate (Mikasa 1H-DX2), followed by EML material PVK (Sigma-Aldrich): TPD (Lumtec): PBD (Lumtec). Co., Ltd.: Ir (mppy) 3 (Lumtec Co., Ltd.) was dissolved in chlorobenzene in a ratio of 0.61: 0.09: 0.24: 0.06, respectively, to form a thin film by spin-coating (Mikasa 1H-DX2). After that, EIL (CsF; Sigma-Aldrich) and Cathode (Al; Sigma-Aldrich) were formed by vacuum evaporation method, and encapsulated using encapsulating glass and UV curable encapsulant in a nitrogen atmosphere in a glove box. The device was produced.

Example Comparative Example One 2 3 One 2 3 Anode ITO ITO ITO ITO ITO ITO HTL Polymer 1-3 Polymer 1-3 Polymer 1-3 PEDOT: PSS PEDOT: PSS
PEDOT: PSS
HTL layer thickness 20 nm 50nm 80 nm 20 nm 50nm 80 nm EML PVK: TPD: PBD: Ir (mppy) 3 PVK: TPD: PBD: Ir (mppy) 3 PVK: TPD: PBD: Ir (mppy) 3 PVK: TPD: PBD: Ir (mppy) 3 PVK: TPD: PBD: Ir (mppy) 3 PVK: TPD: PBD: Ir (mppy) 3 EIL CsF CsF CsF CsF CsF CsF Cathode Al Al Al Al Al Al

Test Example

1. Luminous efficiency ( CD / A)

 The device luminous efficiency according to the current-voltage-luminance of the manufactured OLED device was measured using a luminance meter (MINOLTA CHROMA METER CS-100A) and a current-voltage application measuring equipment (Keithley Keithley 237).

2. Initial drive voltage (V)

 The initial driving voltage of the prepared OLED device was measured using a luminance meter (CHINOLTA CHROMA METER CS-100A) and a current-voltage application measurement device (Keithley Corporation Keithley 237).

3. CIE Color coordinates

The CIE color coordinates of the OLED device prepared above were measured using a luminance meter (CHROMA METER CS-100A, MINOLTA).

Example Comparative Example One 2 3 One 2 3 Luminous Efficiency (Cd / A) 18.4 20.5 17.1 12.4 16.5 13.7 Initial drive voltage (V) 3.5 3.8 4.1 4.0 4.2 4.5 CIE color coordinates (x, y) (0.30,0.59) (0.30,0.59) (0.30,0.59) (0.30,0.59) (0.30,0.59) (0.30,0.59)

Referring to Table 3, it can be seen that the diodes of the embodiments are very excellent in terms of luminous efficiency and initial driving voltage compared to the comparative examples.

Claims (9)

Norbornene-based styrene derivatives represented by Formula 1 below:
[Chemical Formula 1]

Wherein n is an integer from 1 to 15.
A method for producing a norbornene-based styrene derivative of claim 1 comprising reacting styrene substituted with halogenated alkyl and halogenated alkyl magnesium halide substituted with norbornene.
A hole transport polymer comprising a repeating unit of Formula 2 below:
(2)

Wherein n is an integer from 1 to 15.
A hole transport polymer represented by the following formula (3) or (4):
(3)

[Chemical Formula 4]

In Formula 3 and Formula 4,
n is an integer from 1 to 15, m1 is an integer from 1 to 20, m2 is an integer from 0 to 20,
p and q are mole fractions satisfying p + q = 1 (0 <p, q <1),
Z is any one selected from the group consisting of a methylene group, a methyl ether group and a carboxyl group,
Ar ₁ and Ar ₂ are each independently an aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, Aryl oxoaryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, arylphosphinoalkyl group, diarylamido group and triarylamido group Any one selected from the group consisting of,
Ar ₃ is an aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, aryl having 6 to 40 carbon atoms Siloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxanearyl group, arylamino group, arylamino alkyl group, arylaminoaryl group, arylphosphinoalkyl group, diarylamido group, triarylamido group and

It is any one selected from the group consisting of, wherein Ar _{4 To} Ar ₆ Independently of each other an aryl group, arylalkyl group, alkylaryl group having 6 to 40 carbon atoms, arylsilyl group, arylalkylsilyl group, haloaryl group, aryljade Period, aryl oxo alkyl group, thioaryl oxo alkyl group, aryl oxo aryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, aryl phosphino Any one selected from the group consisting of an alkyl group, a diarylamido group and a triarylamido group.
The hole transporting polymer of claim 4 prepared by adding and polymerizing at least one organometallic catalyst selected from the group consisting of compounds represented by the following Formula 5 to a mixture of the norbornene-based styrene derivative and the monomer for forming the hole transport polymer Manufacturing Method:
[Chemical Formula 5]

Wherein Ma is a transition metal element of Groups 3 to 10 on the periodic table, and L ₁ , L ₂ are cyclopentadienyl derivatives which are Π- ligands or consist of phosphine, amine, imine, amide, oxide and heterocyclocarbine groups Any σ-ligand selected from the group may be the same or different within the same formula, Y is an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a cycloalkyl group, a cycloalkylsilyl group, an aryl group having 6 to 40 carbon atoms, alkyl Aryl group, arylalkyl group, arylsilyl group, alkylarylsilyl group, cycloalkylaryl group and any one selected from the group consisting of cycloalkylarylsilyl group, Xa to Xc as σ- ligand independently of each other hydrogen atom, halogen group, Hydroxy group, alkyl group having 1 to 20 carbon atoms, alkylallyl group, alkoxy group, thioalkoxy group, amide group, carboxyl group, acetylacetonato group, sulfonyl group, aryl group having 6 to 40 carbon atoms, alkyl Any one selected from the group consisting of aryl group, allylaryl group, arylalkyl group, haloaryl group, aryloxy group, arylalkoxy group, thioaryloxy group, arylamide group, arylalkylamide group and arylaminoaryloxy group.
The method of claim 5, wherein the cyclopentadienyl derivative is any one selected from the group consisting of compounds represented by the following formula (6):
[Chemical Formula 6]

In the formula, r1, r2, r3, r4, r5, r6, r7, r8 and r9 are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an alkylsilyl group, a haloalkyl group, Alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkyl Silyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, arylsiloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxaneoxy group, arylamino group, arylaminoalkyl group , An arylaminoaryl group and an arylphosphinoalkyl group.
The method of claim 5, further comprising adding at least one cocatalyst selected from the group consisting of compounds represented by the following Formula 7 in the polymerization reaction:
(7)

Expression from, R ₃ is unsubstituted or substituted with a hydrogen atom, a C 1 -C 20 substituted alkyl, optionally substituted 3 to 20 carbon atoms, or consisting of an unsubstituted cycloalkyl group, an aryl group, an alkylaryl group and an arylalkyl group having 6 to 40 carbon atoms P is an integer of 1 to 100, Ar ₇ is any one selected from the group consisting of aryl, haloaryl and haloalkylaryl groups having 6 to 40 carbon atoms, and Mb is 1 to 2 on the periodic table. Or a metal element ion of Groups 11 to 14, Q being a weakly coordinated anion promoter.
An electronic device comprising a hole transport layer made of the hole transport polymer of claim 4.
The electronic device of claim 8, wherein the electronic device is a solar cell or an organic light emitting diode.