CN101148508A - Tricarbazole Hyperbranched Polymer - Google Patents

Abstract

Tricarbazole hyperbranched polymers relate to a blue light-emitting polymer, more specifically to a blue light hyperbranched polymer, in which a tricarbazole unit is introduced into the polymer backbone, and thus a tricarbazole The three-dimensional hyperbranched structure polymer with carbazole unit as the node, which is represented by the following formula, has good charge transfer ability and improved blue light emission performance, and can be widely used as electroluminescent material or transport material in organic electroluminescence Display devices, especially pure blue light polymer electroluminescent devices.

Description

Tricarbazole Hyperbranched Polymer

technical field

The present invention relates to a blue light emitting polymer. More specifically, the present invention relates to a blue-light hyperbranched polymer, in which tricarbazole units are introduced into the polymer skeleton, and a polymer having a three-dimensional hyperbranched structure with tricarbazole units as nodes is thus constructed , belongs to the technical field of electroluminescent materials.

Background technique

When an appropriate metal electrode is plated on the surface of a film (~0.1 μm) composed of some special organic fluorescent substances and a DC voltage of 2-5 volts is applied, the film will emit light. This process is called Organic Electroluminescence (OEL, or OLEDs) is one of the electrical/optical conversion processes. The color of the emitted light can be controlled by changing the film material used.

Compared with other display technologies, OLED devices have many advantages, such as low start-up voltage, fast response speed, low energy consumption, wide viewing angle, low cost, self-illumination, high brightness, high efficiency, large-screen full-color display and Flexible display, etc., has become the most competitive and market potential technology in modern display technology.

According to the molecular weight of the selected film material, organic EL materials can be divided into small molecule materials and polymer materials. Small-molecule EL materials are usually prepared by vacuum evaporation, which conforms to the principle of lightness, thinness and shortness, and the current application range is small and medium-sized. However, polymer materials can be used as EL materials to form films by spin coating and inkjet printing, which simplifies the manufacturing process and reduces manufacturing costs, and the organic layer thus formed has good mechanical properties, and is suitable for various sizes, multiple Display devices for various purposes can realize large-screen flexible flat-panel display, and have received extensive attention and investment from academia and industry.

In order to realize polymer full-color display, it is urgent to develop stable and efficient red, green and blue three-color polymer EL materials. At present, red light and green light polymer materials have met the requirements for practical use, but practical blue light polymer materials are relatively scarce. Especially in terms of spectral stability, luminous efficiency, and device life, there is still a big gap from the practical requirements. This considerably restricts the industrialization process of polymer EL display devices. Therefore, it is very important to develop stable and efficient blue light polymer EL materials.

In order to solve the problem of blue light emission of polymer EL materials, many studies have been carried out. This is mainly focused on the research and development of linear polymers. For example, US Patent 5,728,801 discloses a class of poly(arylamines) with improved electroluminescent properties; US Patent 6,169,163 describes the copolymerization method of fluorene-containing polymers to improve the electroluminescent properties of high molecular weight organic EL devices. However, these methods are not satisfactory in overcoming the blue light problem. In a sense, it can be understood that linear polymers are difficult to effectively suppress the aggregation or molecular chain stacking caused by intermolecular interactions due to their rigid coplanar characteristics, and overcome the red shift of the emission spectrum caused by this.

On the other hand, we have described a class of monodisperse branched structure functional materials based on trioxacarbazole units in Chinese patent (application number: 200610024302.8) and published papers (Macromolecules, 2006, 39, 3707-3709), It shows that the functional material containing the tricarbazole unit has good thermal stability, a relatively wide band gap energy level and a relatively low oxidation potential, and the obtained functional material has good blue light-emitting properties and excellent hole transport It is a kind of organic EL material with application prospect. However, due to its monodisperse complex multi-arm chemical structure, its molecular weight is low, and it appears that there are many steps in the synthesis, so it is not easy to prepare.

Therefore, it is necessary to develop a polymer system with a special spatial structure based on tricarbazole units, simplify the synthesis method, and achieve the purpose of improving the spectral stability of blue light emission and improving its device performance.

Contents of the invention

Technical problem: The purpose of this invention is to provide a kind of tricarbazole hyperbranched polymer, which can be used for the preparation of pure blue light organic EL devices. More specifically, it has improved blue light emission properties and excellent spectral stability properties due to the trioxacarbazole unit contained therein and thereby constituting a three-dimensional hyperbranched structure.

Technical solution: The hyperbranched polymer containing tricarbazole units provided by the present invention has a structure of the following formula 1:

Wherein, Ar is one or a combination of several types selected from substituted or unsubstituted C6-C30 arylene groups and substituted or unsubstituted C2-C30 heteroarylene groups;

R ₁ to R ₁₂ are each independently selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted Or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aralkyl, substituted or unsubstituted C2-C30 heteroarylalkyl, substituted or unsubstituted C5-C30 aryloxy, Substituted or unsubstituted C2-C30 heteroaryloxy, substituted or unsubstituted C3-C30 cycloalkyl, and substituted or unsubstituted C2-C30 heterocycloalkyl;

n is the number of repeating units of tricarbazole units in the obtained polymer chain, which is a real number between 1 and 1000; 1≤m≤3000, and is a real number.

The Ar unit is one or a combination of several groups selected from the following formulas 1a to 1q:

In the formula, R ₁₃ to R ₂₀ are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 aryl , substituted or unsubstituted C2-C20 heteroaryl, substituted or unsubstituted C6-C20 aralkyl, substituted or unsubstituted C2-C20 heteroarylalkyl, substituted or unsubstituted C5-C20 aryloxy group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C3-C20 cycloalkyl group, and substituted or unsubstituted C2-C20 heterocycloalkyl group.

Tricarbazole polymers are polymers represented by one of Formula 2 or Formula 3 below:

Wherein, R ₁ to R ₃ are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 aryl , substituted or unsubstituted C2-C20 heteroaryl, substituted or unsubstituted C6-C20 aralkyl, substituted or unsubstituted C2-C20 heteroarylalkyl, substituted or unsubstituted C5-C20 aryloxy group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C3-C20 cycloalkyl group, and substituted or unsubstituted C2-C20 heterocycloalkyl group;

R ₁₃ to R ₂₀ are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, and Substituted or unsubstituted amino groups;

n is the number of repeating units of the tricarbazole unit in the obtained polymer chain, which is a real number between 1-1000; 1≤m≤3000, which is a real number; 0≤p≤3000, which is a real number.

Tricarbazole polymer is a compound shown in one of the following formula 4 or formula 5:

In the formula, 1≤n≤1000, and it is a real number; 1≤m≤3000, and it is a real number; 0≤p≤1000, and it is a real number.

The polymer has the characteristics of a three-dimensional space structure, which can suppress the aggregation of molecules or the accumulation of molecular chains to the greatest extent, so as to more effectively overcome the reduction of fluorescence emission efficiency and spectral red shift caused by aggregation or the formation of excimer associations The phenomenon. Therefore, the polymer has the prospect of being applied to pure blue light polymer EL devices.

Beneficial effects: the tricarbazole hyperbranched polymer proposed by the present invention has good charge transfer ability and improved blue light emission characteristics, and can be widely used in organic electroluminescent display devices as electroluminescent materials or transport materials. In addition, the polymer proposed by the present invention also has the characteristics of simple and convenient preparation method. By adopting the blue electroluminescence hyperbranched polymer of the invention as a light-emitting layer, an organic EL device with excellent electroluminescence brightness, efficiency, color purity and spectral stability can be prepared.

Description of drawings:

Fig. 1 is the ¹ H NMR figure of the polymkeric substance obtained in Synthetic Example 1;

Fig. 2 is a ¹³ C NMR chart of the polymer obtained in Synthesis Example 1.

Detailed ways

The above features and advantages of the present invention will be more readily understood by describing in detail an exemplary embodiment thereof with reference to the accompanying drawings.

The polymer represented by Formula 1 below contains a trioxacarbazole unit in its main chain skeleton. The trioxacarbazole unit has strong electron donating ability, excellent charge transport ability, especially hole transport ability, and excellent blue light emission performance. Moreover, the tricarbazole unit has C ₃ symmetry, and it is easy to form a monomer containing three active sites, which is an ideal unit for constructing a hyperbranched structure.

In the formula, Ar is one or a combination of substituted or unsubstituted C6-C30 arylene groups and substituted or unsubstituted C2-C30 heteroarylene groups;

R ₁ to R ₁₂ are each independently selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted Or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aralkyl, substituted or unsubstituted C2-C30 heteroarylalkyl, substituted or unsubstituted C5-C30 aryloxy, Substituted or unsubstituted C2-C30 heteroaryloxy, substituted or unsubstituted C3-C30 cycloalkyl, and substituted or unsubstituted C2-C30 heterocycloalkyl;

n is the number of repeating units of tricarbazole units in the obtained polymer chain, which is a real number between 1 and 1000; 1≤m≤3000, and is a real number.

The Ar unit of formula 1 can be selected from one or a combination of several groups shown in the following formula 1a to formula 1q:

In the formula, R ₁₃ to R ₂₀ are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 aryl , substituted or unsubstituted C2-C20 heteroaryl, substituted or unsubstituted C6-C20 aralkyl, substituted or unsubstituted C2-C20 heteroarylalkyl, substituted or unsubstituted C5-C20 aryloxy group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C3-C20 cycloalkyl group, and substituted or unsubstituted C2-C20 heterocycloalkyl group;

The hyperbranched polymer according to the present invention may contain Ar units in its main chain skeleton, and when the Ar units have a fluorene structure, a group as shown in the above formula 1n. This kind of polymer can have good luminescence performance and solubility performance. Since the molecular structure of the polymer contains a hyperbranched structure caused by the introduction of tricarbazole units, the interaction between molecular chains is effectively isolated, thereby effectively Inhibiting the formation of excited exciton associations results in the polymer having improved blue light emitting properties.

The compound shown in Formula 1 may be a polymer of Formula 2 below:

Wherein, R ₁ to R ₃ are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 aryl , substituted or unsubstituted C2-C20 heteroaryl, substituted or unsubstituted C6-C20 aralkyl, substituted or unsubstituted C2-C20 heteroarylalkyl, substituted or unsubstituted C5-C20 aryloxy group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C3-C20 cycloalkyl group, and substituted or unsubstituted C2-C20 heterocycloalkyl group;

R ₁₃ and R ₁₄ are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, and Substituted or unsubstituted amino groups.

n is the number of repeating units of tricarbazole units in the obtained polymer chain, which is a real number between 1 and 1000; 1≤m≤3000, and is a real number.

In the hyperbranched polymer shown in formula 1, when the Ar unit is selected from the combination of the two groups shown in the above formulas 1o and 1p, it can be a compound shown in the following formula 3. This kind of polymer is characterized by the substitution of aryl group at the 9-position of fluorene in the main chain, which can have high thermal stability, high oxidation resistance and more obvious steric hindrance, making it impossible for the resulting polymer to be compatible with adjacent The chains interact to form interchain aggregates or excimates, thereby improving their light-emitting properties, especially their brightness, efficiency, and color purity.

Wherein, R ₁ to R ₃ are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 aryl , substituted or unsubstituted C2-C20 heteroaryl, substituted or unsubstituted C6-C20 aralkyl, substituted or unsubstituted C2-C20 heteroarylalkyl, substituted or unsubstituted C5-C20 aryloxy group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C3-C20 cycloalkyl group, and substituted or unsubstituted C2-C20 heterocycloalkyl group;

R ₁₅ to R ₂₀ are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, and Substituted or unsubstituted amino groups.

n is the number of repeating units of the tricarbazole unit in the obtained polymer chain, which is a real number between 1-1000; 1≤m≤3000, which is a real number; 0≤p≤3000, which is a real number.

In Formula 2, R ₁ , R ₂ , and R ₃ may be C1-C20 alkyl groups; R ₁₃ and R ₁₄ may be C1-C20 alkyl groups.

More specifically, the compound shown in Formula 2 may preferably be the compound shown in Formula 4 below:

In the formula, 1≤n≤1000, and it is a real number; 1≤m≤3000, and it is a real number.

In Formula 3, R ₁ , R ₂ , and R ₃ may be C1-C20 alkyl groups; R ₁₅ and R ₁₆ may be C1-C20 alkoxy groups; R ₁₇ to R ₂₀ may be hydrogen atoms.

More specifically, the compound shown in Formula 3 may preferably be the compound shown in Formula 5 below:

In the formula, 1≤n≤1000, and it is a real number; 1≤m≤3000, and it is a real number; 0≤p≤1000, and it is a real number.

The method for preparing the tricarbazole hyperbranched polymer represented by formula 2 and formula 3 will be described below.

First, prepare tribrominated tricarbazole compound according to reaction scheme 1

【Reaction route 1】

In the formula, R ₁ , R ₂ and R ₃ are as defined in formula 2 above; X1 is a halogen atom. Compound A is a reaction precursor, which reacts with alkyl halide under reflux under the action of alkali to prepare compound B. Then, Compound B is dehalogenated under the action of Pd/C catalyst to obtain Compound C. Selective bromination of compound C with NBS at low temperature affords the tribrominated product compound D.

Finally, according to the reaction scheme 2, the tribromotricarbazole D is polymerized with the dibromide of fluorene and the diboronic ester compound E to obtain the polymer shown in formula 2:

【Reaction Route 2】

In the formula, R ₁ to R ₃ , R ₁₃ , and R ₁₄ are as defined in the above formula 2; each of X ₁ and X ₂ is a halogen atom.

The tricarbazole hyperbranched polymer can be prepared by the same method as in the above-mentioned preparation process. For example, polymers of formula 3 can be prepared by the method shown in Scheme 3 similar to Scheme 2:

【Reaction route 3】

In the formula, R ₁ to R ₃ , R ₁₅ to R ₂₀ are as defined in the above formula 3; each of X ₁ , X ₃ , and X ₄ is a halogen atom.

In the polymer obtained according to the embodiment of the present invention, the unsubstituted alkyl group can be methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, and octyl Base etc. One or more H atoms on the alkyl group can be substituted by the following groups: halogen atom; -OH; -NO ₂ ; -CN; substituted or unsubstituted amino (such as -NH ₂ , -NH(R), Or -NH(R')(R"), wherein R' and R" are each independently C1-C10 alkyl), amidino, hydrazine, hydrazone, carboxyl, sulfonyl, phosphoryl, C1-C20 alkyl , C1-C20 haloalkyl, C1-C20 alkenyl, C1-C20 alkynyl, C1-C20 heteroalkyl, C6-C20 aryl, C6-C20 aralkyl, C2-C20 heteroaryl group, or C2-C20 heteroarylalkyl group.

The unsubstituted alkoxy group may be methoxy, ethoxy, propoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, hexyloxy, octyloxy and the like. In unsubstituted alkoxy, at least one H atom

Can be substituted as in unsubstituted alkyl.

The unsubstituted aryl group refers to a carbocyclic aromatic system containing one or more rings, and the rings can be connected or fused to each other in the form of side groups. Here, the aryl group may be an aromatic group such as phenyl, naphthyl, tetrahydronaphthyl, etc. In the aryl group, at least one H atom may be substituted as in the above-mentioned unsubstituted alkyl group.

The heteroaryl refers to a cyclic aromatic system in which the number of ring atoms is 5-30. In this case, at least one different ring atom is selected from N, O, P, and S. The heteroaryl rings may be attached or fused as pendant groups. One or more H's on the heteroaryl group may be substituted as described above for unsubstituted alkyl groups.

The aralkyl group refers to an aryl group in which some H atoms are substituted by lower alkyl groups such as methyl, ethyl, propyl and the like. The aralkyl group may be benzyl, phenethyl and the like. In an aralkyl group, at least one H atom may be substituted as described above for the unsubstituted alkyl group.

The heteroarylalkyl group refers to a heteroaryl group in which some H atoms are replaced by lower alkyl groups. The heteroaryl group included in the heteroarylalkyl group is as described above. In a heteroarylalkyl group, at least one H atom may be substituted as described above for the unsubstituted alkyl group.

Examples of the aryloxy group include phenoxy and naphthyloxy. One or more H atoms on the aryloxy group may be substituted by substituents like the above-mentioned unsubstituted alkyl group.

The heteroaryloxy group may be benzyloxy group, phenoxy group, etc. In the heteroaryloxy group, at least one H atom may be substituted by a substituent like the above-mentioned unsubstituted alkyl group.

The unsubstituted cycloalkyl refers to a monovalent monocyclic ring system containing C3-C30 carbon atoms. One or more H atoms on the cycloalkyl group may be substituted with the same substituents as those described for the alkyl group.

The heterocycloalkyl refers specifically to a monovalent monocyclic ring system of 2-30 carbon atoms containing more than one heteroatom whose ring atoms are N, O, P and S. In the heterocycloalkyl group, at least one H atom may be substituted as in the above-mentioned unsubstituted alkyl group.

The amino group may be -NH ₂ , -NH(R), or -N(R')(R"), wherein R' and R" are each independently an alkyl group with 1-10 carbon atoms.

Hereinafter, the present invention will be described in detail in conjunction with more specific examples, but the examples are only for more specific illustrations, and are not intended to limit the scope of the present invention.

The synthesis of polymer shown in Synthetic Example 1 Formula 4

【Reaction Route 4】

(1) Synthesis of 2,3,7,8,12,13-hexabromo-5,10,15-trihexyltricarbazole (B')

Compound A' (2.45g, 3mmol) and KOH (1.4g, 25mmol) were dissolved in THF (100ml), heated to reflux, 1-bromohexane (2.23g, 13.5mmol) was added dropwise to the above solution, and refluxed for 3h . The mixture was cooled to room temperature _, diluted with _CH2Cl2 , then the organic layer was washed successively with 10% HCl solution, saturated NaCl solution, and finally dried over _{anhydrous Na2SO4} . The crude product obtained after removing the organic solvent was chromatographed by n-hexane/dichloromethane (8:1) to obtain a white solid product (2.96 g, 92%).

(2) Synthesis of 5,10,15-trihexyltricarbazole (C')

Compound B' (2.40g, 2.24mmol), triethylamine (2.5ml), formic acid (0.68ml) and 10% Pd/C (712.3mg, 0.672mmol) in THF (20ml) were heated to reflux for 3 hours. The mixture was filtered, the filtrate was diluted with chloroform, washed with 10% aqueous hydrochloric acid, the organic layer was dried over anhydrous _Na2SO4 , and finally the solvent was removed _. The obtained crude product was subjected to n-hexane/dichloromethane (8:1) column chromatography to obtain a white solid powder (1.25 g, 93%).

(3) Synthesis of 3,8,13-tribromo-5,10,15-trihexyltricarbazole (D')

Compound C' (1.0 g, 1.673 mmol) was dissolved in 30 ml THF; a solution of NBS (0.937 g) in DMF (5 ml) was added dropwise at low temperature. The mixture was stirred at room temperature for half an hour. Then the reaction mixture was poured into an appropriate amount of water, and the organic layer was extracted with chloroform and dried over anhydrous Na ₂ SO ₄ . After removing the solvent, the crude product was subjected to column chromatography using n-hexane/dichloromethane (9:1) as eluent to obtain a white solid powder (1.15 g, 82.4%).

(4) Synthesis of tricarbazole hyperbranched polymer shown in formula 4

【Reaction route 5】

The flask was evacuated and replaced with _N2 several times to completely remove the contained moisture. In an inert gas atmosphere, Ni(COD) (880 mg) and bipyridine (500 mg) were added to a moisture-free flask. Then, the flask was evacuated three more times to replace _N2 . Next, dry DMF (10 ml), 1,5-cyclooctadiene (COD) (346 mg) and dry toluene (10 ml) were added under N ₂ stream. The mixture was stirred and reacted at 80°C for half an hour. Under _N2 atmosphere, compound D' (133.5 mg, 0.16 mmol) and compound E' (708.96 mg, 1.44 mmol) were dissolved in toluene (10 ml), and added to the reaction system. Then add 10ml of toluene again, so that the raw material adhering to the vessel wall is flushed in the reaction system. The mixture was stirred at 80 °C for 4 days, then 4-bromobenzene (17.6 mg, 0.112 mmol) was added to the flask and stirred at this temperature for one day. After the reaction, the reaction solution was cooled to room temperature, and then precipitated in a 1:1:2 mixed solvent of HCl, acetone and methanol. Gained precipitation is eluted 24h in Soxhlet extractor with acetone, then with THF the product of soluble part is extracted, dry in vacuum and make the tricarbazole hyperbranched polymer (300mg) shown in formula 4 , 52%). The polymer was analyzed by gel permeation chromatography (GPC), and the results showed that the number average molecular weight (Mn) was 26,500 and the molecular weight distribution (MWD) was 4.2. In Formula 4, the feed ratio n:m=1:9 is taken.

The synthesis of tricarbazole hyperbranched polymer shown in Synthetic Example 2 Formula 5

【Reaction Route 6】

The flask was evacuated and replaced with _N2 several times to completely remove the contained moisture. In an inert gas atmosphere, Ni(COD) (880 mg) and bipyridine (500 mg) were added to a moisture-free flask. Then, the flask was evacuated three more times to replace _N2 . Next, dry DMF (10 ml), 1,5-cyclooctadiene (COD) (346 mg) and dry toluene (10 ml) were added under N ₂ stream. The mixture was stirred and reacted at 80°C for half an hour. Under _N2 atmosphere, compound D' (133.5 mg, 0.16 mmol), compound F' (865.9 mg, 1.28 mmol) and compound G' (75.9 mg, 0.16 mmol) were dissolved in toluene (15 ml) and added to the reaction in the system. Then add 15ml of toluene again, so that the raw material adhering to the vessel wall is rinsed in the reaction system. The mixture was stirred at 80 °C for 4 days, then 4-bromobenzene (17.6 mg, 0.112 mmol) was added to the flask and stirred at this temperature for one day. After the reaction, the reaction solution was cooled to room temperature, and then precipitated in a 1:1:2 mixed solvent of HCl, acetone and methanol. Gained precipitation uses acetone to elute 24h in Soxhlet extractor, then with THF the product of soluble part is extracted, dry in vacuum and make the tricarbazole hyperbranched polymer (360mg) shown in formula 5 , 44%). The polymer was analyzed by gel permeation chromatography (GPC), and the results showed that the number average molecular weight (Mn) was 12,000 and the molecular weight distribution (MWD) was 3.5. In Formula 5, the feed ratio n:m:p=1:8:1 is taken.

Although we have described the invention in detail with reference to exemplary embodiments, it will be understood by those skilled in the art that changes may be made in form and detail without departing from the spirit and scope of the invention as defined by the foregoing claims. various modifications and changes.

Claims (4)

1. one kind three and carbazole hyperbranched polymer is characterized in that this polymkeric substance is based on three and the polymkeric substance of carbazole primitive, and it is by shown in the following formula 1:

Wherein, Ar is selected to replace or the combination of the heteroarylidene of the arylidene of unsubstituted C6-C30 and replacement or unsubstituted C2-C30 a kind of or some kinds;

R ₁～R ₁₂Be selected from hydrogen independently of one another, the alkyl of replacement or unsubstituted C1-C30, the alkoxyl group of replacement or unsubstituted C1-C30, the aryl of replacement or unsubstituted C6-C30, the heteroaryl of replacement or unsubstituted C2-C30, replace or unsubstituted C6-C30 aralkyl, the heteroaralkyl of replacement or unsubstituted C2-C30, replace or unsubstituted C5-C30 aryloxy, replace or unsubstituted C2-C30 heteroaryloxy, the cycloalkyl of replacement or unsubstituted C3-C30, Heterocyclylalkyl with replacement or unsubstituted C2-C30;

N is in the resulting polymers chain three and the number of repeat unit of carbazole primitive, is the real number between the 1-1000; 1≤m≤3000, and be real number.

2. according to claim 1 three and the carbazole hyperbranched polymer, it is characterized in that three and the carbazole polymkeric substance in, described Ar unit is the combination that is selected from a kind of of the group shown in the following formula 1a to 1q or some kinds:

In the formula, R ₁₃To R ₂₀Be hydrogen independently of one another, the alkyl of replacement or unsubstituted C1-C20, the alkoxyl group of replacement or unsubstituted C1-C20, the aryl of replacement or unsubstituted C6-C20, the heteroaryl of replacement or unsubstituted C2-C20, replace or unsubstituted C6-C20 aralkyl, the heteroaralkyl of replacement or unsubstituted C2-C20, replace or unsubstituted C5-C20 aryloxy, replace or unsubstituted C2-C20 heteroaryloxy, the cycloalkyl of replacement or unsubstituted C3-C20, Heterocyclylalkyl with replacement or unsubstituted C2-C20.

3. according to claim 1 and 2 three and the carbazole hyperbranched polymer, it is characterized in that three and the carbazole polymkeric substance be polymkeric substance by the expression of one of following formula 2 or formula 3:

Wherein, R ₁To R ₃Be selected from hydrogen independently of one another, the alkyl of replacement or unsubstituted C1-C20, the alkoxyl group of replacement or unsubstituted C1-C20, the aryl of replacement or unsubstituted C6-C20, the heteroaryl of replacement or unsubstituted C2-C20, replace or unsubstituted C6-C20 aralkyl, the heteroaralkyl of replacement or unsubstituted C2-C20, replace or unsubstituted C5-C20 aryloxy, replace or unsubstituted C2-C20 heteroaryloxy, the cycloalkyl of replacement or unsubstituted C3-C20, Heterocyclylalkyl with replacement or unsubstituted C2-C20;

R ₁₃To R ₂₀Be selected from cycloalkyl, replacement or unsubstituted C1-C20 alkoxyl group and replacement or the unsubstituted amino of hydrogen atom, replacement or unsubstituted C1-C20 alkyl, replacement or unsubstituted C3-C20 independently of one another;

N is in the resulting polymers chain three and the number of repeat unit of carbazole primitive, is the real number between the 1-1000; 1≤m≤3000, and be real number; 0≤p≤3000, and be real number.

4. according to claim 3 three and the carbazole hyperbranched polymer, it is characterized in that three and the carbazole polymkeric substance be the compound shown in one of following formula 4 or formula 5:

In the formula, 1≤n≤1000, and be real number; 1≤m≤3000, and be real number; 0≤p≤1000, and be real number.