KR100581179B1 - A new type of norbornene monomers and polymers for blue light emitting material - Google Patents

Abstract

The present invention relates to a polymer through ring-opening metathesis polymerization using a noborene derivative, a noborene derivative to which a modified form of florene is added, and a florene as a blue light emitting monomer.

According to the present invention, it is possible to provide a noborene monomer having various derivatives in a novel form by appropriately displacing florene widely used in a blue light emitting material with noborene, and using ring-opening metathesis polymerization from the monomer. By using the present invention can be prepared a polymer that can be applied to a variety of molecular weight blue light emitting material. The polymer contains a florene monomer capable of performing another reduction polymerization, and has a polymer unit of noborene, thereby improving the solubility of polyfluorene, which is a problem of the conventional blue light emitting polymer.

Novorene monomer

Description

A new type of norbornene monomers and polymers for blue light emitting material}

 Organic materials used in electroluminescent devices are largely divided into small molecule materials and polymer materials. The organic EL (electroluminescenec) on a single molecule was first discovered in anthracene crystals in 1963, but no further discovery has since been made, and by 1987 Ching Tang and Steven van Slyke of Eastman Kodak For the first time, a double layer OLED (Organic Light Emitting Diode) was made of an organic compound. However, electroluminescence using poly (1,4-phenylenevinylene) polymer light emitting material, which is heat-stable and efficient blue light emitting material compared to low molecular weight, has been applied to polymer light emitting materials since it was first announced at the University of Cambridge, UK in 1990. Interest and development have increased significantly. In particular, the polymer material has an advantage in that it can be easily processed, which is advantageous in manufacturing a device having a large surface area. Macromolecules, 34, pp8610-8618 (2001), describes the synthesis of organic light emitting polymer materials by applying a new type of ring-opening metathesis reaction, although normal organic reactions are used in the synthesis of such organic light emitting polymers. . In order to synthesize an organic light emitting polymer material by applying a ring-opening metathesis reaction, it is possible that noboene is substituted for the monomer. Polymer, Vol. 41, pp2773-2780 (2000) is an example of monomer synthesis in which a luminescent substance is substituted for noborene. Synthesis and metathesis polymerization of noborene substituted with carbazole, which is applicable to organic EL, Is disclosed. Macromolecules, 28, pp1966-1971 (1995), discloses the synthesis of polymers and polymers containing noboene monomers containing 1,4-phenylenevinylene oligomers for making blue light emitting polymers. Macromolecules, 30, pp3553- 3559 (1997) discloses the synthesis of monomers and polymers in which diphenyl anthracene is included in noborene.

However, in the method of synthesizing the noborene-based monomer for producing the blue light emitting polymer, since the blue light emitting material exists only as the monomer in the polymer made through ring-opening metathesis polymerization, the absorption wavelength of the blue light emitting material is predetermined to reduce the wavelength change. It is not suitable for making various derivatives.

Accordingly, the present inventors have attempted to develop a noborene monomer including various derivatives for making a blue light emitting polymer.

Accordingly, it is an object of the present invention to provide a new type of monomer in which nonorene monomers including nonorene derivatives for blue light-emitting materials and florene are appropriately substituted with noborene.

Another object of the present invention is to provide a polymer for a blue light emitting material using the monomer ring-opening metathesis polymerization.

The object of the present invention is to provide a noborene derivative of Formula 1, a noborene derivative to which a modified form of Formula 2 is added, and a ring opening as a blue light-emitting monomer through ring-opening metathesis polymerization. It can be achieved by providing a polymer of Formula 3 and Formula 4. Florene, a monomer in the polymer of Formula 3 or Formula 4, may be used as a light emitting material, and the reduction polymerization may be used to synthesize polyfluorene, which is a more efficient blue light emitting polymer.

 In the above formula,

R ₁ is H, C ₁ -C ₆ alkyl, phenyl or halogen;

R ₂ is H, C ₁ -C ₂₀ alkyl, phenyl or substituted phenyl; And

R ₃ is H, OH, CHO or CO ₂ H.

In the above formula,

R ₁ is H, C ₁ -C ₆ alkyl, phenyl or halogen;

R ₃ is H, OH, CHO or CO ₂ H; And

R ₄ is C ₁ -C ₂₀ alkylene, phenylene or C ₅ -C ₁₀ cycloalkylene.

In the above formula,

R ₁ is H, C ₁ -C ₆ alkyl, phenyl or halogen;

R ₂ is H, C ₁ -C ₂₀ alkyl, phenyl or substituted phenyl;

R ₃ is H, OH, CHO or CO ₂ H; And

n is an integer from 2 to 100,000.

In the above formula,

R ₁ is H, C ₁ -C ₆ alkyl, phenyl or halogen;

R ₃ is H, OH, CHO or CO ₂ H;

R ₄ is C ₁ -C ₂₀ alkylene, phenylene or C ₅ -C ₁₀ cycloalkylene; And

n is an integer from 2 to 100,000.

The present invention will be described in more detail as follows.

A method for synthesizing a noborene monomer containing a luminescent material from a noborene containing various functional groups is performed by directly adding or modifying a functional group of the noborene, as shown in Scheme 1. Then there is a method of substitution.

The addition reaction method (a) is based on normal butyllithium (n-buthyl lithium) in a tetrahydrofuran solvent, or on a fluorine or substituent-containing florene using potassium hydroxide in a hexane / water solvent. After removing hydrogen at position 9, the method is grafted onto noborene aldehyde. Substitution method (b) is to transform hydroxy methyl norbornene hydroxy (OH) into tosyl or halogen, or introduce chloromethyl phenoxy and replace it with florene. .

The monomer prepared by the above method may be prepared by using a metathesis polymerization initiation catalyst such as ruthenium (Ru) or molybdenum (Mo) based polymer of Formula 3 or Formula 4 having a desired molecular weight.

The invention can be more clearly understood by the following examples, which are not intended to limit the invention.

Example 1 Preparation of Novorene Monomer Containing Florene Represented by Formula 1 (R ₁ = H, R ₂ = H, R ₃ = H)

Magnetic bar was put into a 100 ml round flask with argon and then replaced with argon. Then, Florene (1.66 g, 10 mmol) was added thereto, and 50 ml of tetrahydrofuran was added to dissolve and maintained at -78. 5 ml of normal butyllithium (2.0 M) was slowly added thereto, and the temperature was raised to room temperature, followed by stirring for about 1 hour. To this solution, 5-norborene-2-carboxyaldehyde (5-norbornene-2-carboxaldehyde, 1.22 mL, 10 mmol) was dissolved in 5 mL of tetrahydrofuran and slowly added dropwise at room temperature. After dropping, the mixture was stirred at room temperature for 12 hours, and then the solvent was removed under reduced pressure and extracted with ether (30 mL 3) and water. The organic layer was taken and then water was removed with anhydrous magnesium sulfate and filtered. The solvent was removed again under reduced pressure and recrystallized with methanol / hexane to give 2.3 g (yield 86%) of a white solid.

1 H NMR (CDCl3, 400 MHz) 0.99 to 1.08 (m, 1H), 1.51 to 1.55 (m, 1H), 1.56 to 1.60 (m, 1H) 2.29 to 2.41 (m, 1H), 3.01 (s, 1H), 3.17 (s, 1H), 3.78 to 3.91 (m, 1H) 6.13 to 6.63 (m, 2H) 6.35 (s 0.5H), 6.40 (s, 0.5H) 7.21 to 7.40 (m, 4H), 7.58 to 7.61 ( m, 1H), 7.66-77.7 (m, 2H), 7.78-7.99 (m, 1H).

Example 2 Preparation of Novorene Monomers Containing Florene Represented by Formula 1 (R ₁ = H, R ₂ = H, R ₃ = H)

A magnetic bar was placed in a 200 mL round flask and substituted with argon, and 5-norborene-2-carboxyaldehyde (2.44 mL, 20 mmol) was dissolved in 60 mL of toluene. 60 ml of 50% aqueous NaOH solution was added thereto, followed by addition of tetrabutyl ammonium hydrogen sulfate (0.36 g, 1 mmol), followed by stirring, followed by addition of florene (2.82 g, 17 mmol) in 80 hours for 4 hours. Reacted for a while. After the reaction, the reaction solution was maintained at room temperature and extracted with water and toluene (30 mL 3). The toluene layer was taken and then water was removed with anhydrous magnesium sulfate and filtered. The solvent was removed under reduced pressure and separated by column chromatography (hexane / dichloromethane = 2: 8 (v / v)) to give 2.5 g (54% yield) of a white solid.

1 H NMR (CDCl3, 400 MHz) 1.02 to 1.06 (m, 0.5H), 1.46 to 1.65 (m, 2.5H), 1.72 to 1.82 (m, 0.5H) 2.28 to 2.41 (m, 0.5H), 2.90 (s , 0.5H), 3.01 (s, 0.5H), 3.08 ~ 3.17 (m, 1.5H) 3.77 ~ 3.89 (m, 0.5H) 6.12 ~ 6.32 (m, 2H) 6.35 (s 0.25H), 6.40 (s, 0.25H) 6.72 (s, 0.25H), 6.77 (s, 0.25H), 7.21-7.40 (m, 4H), 7.58-7.85 (m, 3.5H), 7.95-7.99 (m, 0.5H).

Example 3 Preparation of Novorene Monomer Containing Florene Represented by Formula 1 (R ₁ = Br, R ₂ = H, R ₃ = H)

The same reaction was carried out in Example 2, except that 2,7-dibromoflourene was used instead of florene.

After replacing the magnetic bar with argon in a 200 mL round flask, 5-norborene-2-carboxyaldehyde (2.44 mL, 20 mmol) was dissolved in 60 mL of toluene. After adding 60 ml of 50% aqueous NaOH solution, tetrabutyl ammonium hydrogen sulfate (0.36 g, 1 mmol) was added and stirred, followed by 2,7-dibromoflorene (2, 7-Dibromopflorene). (5.50 g, 17 mmol) was added and reacted at 80 ° C. for 4 hours. After the reaction, the reaction solution was maintained at room temperature and extracted with water and toluene (30 mL 3). The toluene layer was taken and then water was removed with anhydrous magnesium sulfate and filtered. The solvent was removed under reduced pressure and separated by column chromatography (hexane / dichloromethane = 2: 8 (v / v)) to give 3.4 g (47% yield) of a white solid.

1 H NMR (CDCl3, 400 MHz) 0.88 to 1.06 (m, 0.5H), 1.49 to 1.63 (m, 2.5H), 1.72 to 1.83 (m, 0.5H) 2.29 to 2.42 (m, 0.5H), 2.88 (s , 0.5H), 2.95-3.04 (m, 1.5H), 3.14 (s, 0.5H) 3.66-3.75 (m, 0.5H) 6.13-6.18 (m, 0.5H) 6.23-6.63 (m, 1.5H), 6.71 (s, 0.25H) 6.76 (s, 0.25H), 7.37 ~ 7.56 (m, 2.5H), 7.66,7.67 (d, 0.25H), 7.51,7.76 (d, 0.25H), 7.88 (s, 0.25 H), 8.02 (s, 0.25 H).

Example 4 Preparation of a Polymer Containing Florene Represented by Formula 3 (R ₁ = H, R ₂ = H, R ₃ = H)

Into a 50 mL round flask with a magnetic bar and substituted with argon, the monomer (0.27 g, 1 mmol) obtained in Example 1 was dissolved in 4 mL of dichloromethane. Grubbs' ruthenium (Ru) catalyst (35 mg, 1/25 mmol) was dissolved in 10 ml of dichloromethane, which was added to the reaction by taking 1 ml (1/250 mmol) with a syringe and reacted for 2 hours. 0.2 mL ethylvinyl ether was added to terminate the reaction and precipitated in 500 mL methanol. The white precipitate was obtained, dried, and then checked for molecular weight by GPC.

Molecular weight (Mw): 203,000 Molecular weight distribution: 1.60

Example 5 Preparation of a Polymer Containing Florene Represented by Formula 3 (R ₁ = H, R ₂ = H, R ₃ = H)

The reaction was carried out in the same manner as in Example 4 except that the amount of dichloromethane was increased.

Into a 50 mL round flask with a magnetic bar and substituted with argon, the monomer (0.27 g, 1 mmol) obtained in Example 1 was dissolved in 9 ml of dichloromethane. Grubbs' ruthenium (Ru) catalyst (35 mg, 1/25 mmol) was dissolved in 10 ml of dichloromethane, which was added to the reaction by taking 1 ml (1/250 mmol) with a syringe and reacted for 2 hours. 0.2 mL ethylvinyl ether was added to terminate the reaction, which was precipitated in 500 mL methanol. The white precipitate was obtained and dried, and the molecular weight was confirmed by GPC.

Molecular weight (Mw): 141,000 Molecular weight distribution: 1.58

Example 6 Preparation of a Polymer Containing Florene Represented by Formula 3 (R ₁ = H, R ₂ = H, R ₃ = H)

The reaction was the same as in Example 5 except that the amount of Grubbs' ruthenium (Ru) catalyst was increased.

Into a 50 mL round flask with a magnetic bar and substituted with argon, the monomer (0.27 g, 1 mmol) obtained in Example 1 was dissolved in 4 mL of dichloromethane. Grubbs' ruthenium (Ru) catalyst (66 mg, 1 / 12.5 mmol) was dissolved in 10 ml of dichloromethane, which was added to the reaction by taking 1 ml (1/125 mmol) with a syringe and reacted for 2 hours. 0.2 mL ethylvinyl ether was added to terminate the reaction, which was precipitated in 500 mL methanol. The white precipitate was obtained, dried, and then checked for molecular weight by GPC.

Molecular weight (Mw): 87,000 Molecular weight distribution: 1.24

Example 7 Preparation of a Polymer Containing Florene Represented by Formula 3 (R ₁ = Br, R ₂ = H, R ₃ = H)

The reaction was carried out in the same manner as in Example 6 except that the monomer amount was increased.

Into a 50 mL round flask with a magnetic bar and substituted with argon, the monomer (0.44 g, 1 mmol) obtained in Example 3 was dissolved in 4 mL of dichloromethane. Grubbs' ruthenium (Ru) catalyst (66 mg, 1 / 12.5 mmol) was dissolved in 10 ml of dichloromethane, which was added to the reaction by taking 1 ml (1/125 mmol) with a syringe and reacted for 2 hours. 0.2 mL ethyl vinyl ether was added to terminate the reaction, which was precipitated in 500 mL methanol. The white precipitate was obtained, dried, and then checked for molecular weight by GPC.

Molecular weight (Mw): 98,000 Molecular weight distribution: 2.39

Example 8 Preparation of Polymer Containing Florene Represented by Formula 3 (R ₁ = Br, R ₂ = H, R ₃ = H)

The reaction was the same as in Example 7, except that tetrahydrofuran was used instead of dichloromethane.

Into a 50 mL round flask with a magnetic bar and substituted with argon, the monomer (0.44 g, 1 mmol) obtained in Example 3 was dissolved in 4 ml of tetrahydrofuran. Grubbs' ruthenium (Ru) catalyst (66 mg, 1 / 12.5 mmol) was dissolved in 10 ml of tetrahydrofuran, which was added to the reaction by taking 1 ml (1/125 mmol) with a syringe and reacted for 2 hours. 0.2 ml ethylvinyl ether was added to terminate the reaction, which was precipitated in 500 ml of methanol. The white precipitate was obtained and dried, and the molecular weight was confirmed by GPC.

Molecular weight (Mw): 57,000 Molecular weight distribution: 1.07

Example 9 Preparation of 2-Norborene-5-tosyl methyl

A magnetic bar was put into a 100 ml round flask, 3.3 g of 5-norborene-2-methanol, 3.3 g of tosyl chloride (TsCl), and 40 ml of pyridine were added and stirred at room temperature for 12 hours. The by-product pyridine hydrochloride salt was filtered off, and then the filtered solution was dissolved in 100 ml of water, extracted three times with 30 ml of ether, and washed again with 50 ml of a 1 normal hydrochloride aqueous solution. Magnesium sulfate was added to the ether layer to remove moisture to obtain 7.3 g (98.7%) of a colorless liquid.

1 H NMR (CDCl 3, 400 MHz) 7.80 (d, 2H), 7.28 (d, 2H), 6.10 (m, 1H), 5.63 (m, 1H), 3.53-4.20 (m, 2H), 2.60-2.92 (m , 2H), 2.41 (s, 3H), 2.3-2.4 (m, 1H), 1.70-1.91 (m, 1H), 1.01-1.50 (m, 3H), 0.40 (m, 1H).

Example 10 Preparation of 2-Norborene-5- (4'-formylphenoxy) methyl (2-Norborene-5- (4'-formyl phenoxy)

Into a 50 mL round flask, a magnetic bar was added, 1.1 g of 2-norborene-5-tosylmethyl, 0.51 g of 4-hydroxy-5-benzaldehyde, 0.58 g of potassium carbonate and 20 ml of dimethyl formamide were stirred at 110 for 12 hours. . The reaction mixture was cooled to room temperature, mixed with 100 ml of water, extracted three times with 30 ml of ether, dried with anhydrous magnesium sulfate to remove moisture, and then the solvent was removed under reduced pressure, followed by column chromatography (silicagel, hexane / dichloromethane). = 1: 1 (v / v)) to give 0.8 g (yield 87.7%) of the title compound.

1 H NMR (CDCl 3, 400 MHz) 9.85 (s, 1H), 7.80 (d, 2H), 6.93 (d, 2H), 6.15 (m, 1H), 5.90 (m, 1H), 3.64-4.20 (m, 2H ), 3.05 (s, 1H), 2.96 (s, 1H), 2.62 (m, 1H), 1.91 (m, 1H), 1.21-1.65 (m, 3H), 0.60 (m, 1H).

Example 11: Preparation of 2-Norborene-5- (4'-hydroxymethylphenoxy) methyl (2-Norborene -5- (4'-hydroxymethylphenoxy)

Into a 50 mL round flask, 0.17 g of lithium aluminum hydride (LiAlH ₄ ) was added to 10 mL of ether, and 0.8 g of 2-norborene-5- (4'-formylphenoxy) methyl was slowly added dropwise to the suspension. After stirring at room temperature for 12 hours. The reaction mixture was mixed with 30 ml of water, extracted three times with 20 ml of ether, anhydrous magnesium sulfate was added to the combined ether to remove moisture, and the solvent was removed under reduced pressure again to obtain 0.63 g (yield 76.0%) of the target compound. .

1 H NMR (CDCl 3, 400 MHz) 7.25 (d, 2H), 6.86 (d, 2H), 6.20 (m, 1H), 5.95 (m, 1H), 4.60 (s, 2H), 3.47-4.10 (m, 2H ), 3.06 (s, 1H), 2.82 (s, 1H), 2.55 (m, 1H), 1.91 (m, 1H), 1.67 (s, 2H), 1.21-1.55 (m, 3H), 0.64 (m, 1H).

Example 12 Preparation of 2-Novoren-5- (4'-chloromethylphenoxy) methyl (2-Norborene-5- (4'-chloromethylphenoxy)

10 ml of dichloromethane, 0.32 ml of thionyl chloride (SOCl2) and 0.63 ml of trimethylamine were added to a 50 ml round flask with agitation, followed by stirring. 2-Novoren-5- (4'-hydroxymethyl 0.8 g of phenoxy) methyl (2-Norborene-5- (4'-hydroxymethylphenoxy) was dissolved in 5 ml of dichloromethane and slowly added dropwise at 0, followed by stirring at room temperature for 2 hours.The reaction was mixed with 30 ml of water to give dichloromethane. Extract anhydrous magnesium chloride into dichloromethane which was extracted three times with 10 ml of methane to remove water, and then remove the solvent under reduced pressure, and then purified by column chromatography (silicagel, dichloromethane) to give 0.3 g of the target compound (yield 41.2%). )

1 H NMR (CDCl 3, 400 MHz) 7.30 (m, 2H), 6.84 (m, 2H), 6.20 (m, 1H), 5.90 (m, 1H), 4.55 (s, 2H), 3.32-4.07 (m, 2H ), 3.02 (s, 1H), 2.85 (s, 1H), 2.56 (m, 1H), 1.93 (m, 1H), 1.67 (s, 2H), 1.24-1.53 (m, 3H), 0.61 (m, 1H).

Example 13: Preparation of norbornene monomers include alkylene Florencio represented by the formula _{2 (R 1 = H, R} 3 = H, R 4 = phenylene)

Into a 25 ml eggplant round flask, a magnetic bar was substituted with nitrogen, and 0.25 g of 2-norborene-5- (4'-chloromethylphenoxy) methyl and 10 ml of tetrahydrofuran (THF) were added thereto. It was kept at room temperature. Into another 25 mL round flask with a magnetic bar, replaced with nitrogen, 0.17 g of florene was dissolved in 10 mL of tetrahydrofuran (THF), and the temperature was kept at -78 while stirring, followed by normal butyllithium (2.0). Mole) 0.5 ml was slowly added and stirred for about 1 hour. After raising the temperature to room temperature, this florenyl lithium solution was added dropwise to a 2-novorene-5- (4'-chloromethylphenoxy) methyl solution prepared initially using a needle. After dropping, the mixture was stirred at room temperature for 12 hours, and then the reaction mixture was mixed with 100 ml of water, extracted twice with 20 ml of ether, combined, anhydrous magnesium sulfate was added to remove water, and the solvent was removed under reduced pressure, followed by column chromatography (silicagel). , Hexane / dichloromethane = 3: 1 (v / v)) to give 0.16 g (yield 43.0%) of the title compound.

1 H NMR (CDCl 3, 400 MHz) 7.65 (d, 2H), 7.70-7.41 (m, 8H), 6.80 (d, 2H), 6.20-5.95 (m, 2H), 4.15 (t, 1H), 3.40-4.02 (m, 2H), 3.08 (d, 2H), 2.85 (s, 1H), 2.45 (m, 1H), 1.85 (m, 1H), 1.21-1.57 (m, 3H), 0.60 (m, 1H).

Example 14 Preparation of a Polymer Containing Florene Represented by Formula 4 (R ₁ = H, R ₃ = H, R ₄ = phenylene)

Into a 50 mL round flask with a magnetic bar and substituted with argon, the monomer (0.16 g, 0.43 mmol) obtained in Example 13 was dissolved in 7.5 ml of dichloromethane. Grubbs' ruthenium (Ru) catalyst (14 mg) was dissolved in 11 ml of dichloromethane, which was added to the reaction by taking 1 ml (1/250 mmol) with a syringe and reacted at room temperature for two hours. 0.2 mL ethylvinyl ether was added to terminate the reaction and precipitated in 200 mL methanol. The white precipitate was obtained, dried, and then checked for molecular weight by GPC.

Molecular weight (Mw): 79,000 Molecular weight distribution: 1.56

Example 15 Preparation of a Polymer Containing Florene Represented by Formula 4 (R ₁ = H, R ₃ = H, R ₄ = phenylene)

The reaction was the same as in Example 4 except that the amount of Grubbs' ruthenium (Ru) catalyst was increased.

Into a 50 mL round flask with a magnetic bar and substituted with argon, the monomer (0.16 g, 0.43 mmol) obtained in Example 13 was dissolved in 7.5 mL of dichloromethane. Grubbs' ruthenium (Ru) catalyst (28 mg) was dissolved in 11 ml of dichloromethane, and this was added to the reaction by taking 1 ml with a syringe and reacted at room temperature for two hours. 0.2 mL ethylvinyl ether was added to terminate the reaction and precipitated in 200 mL methanol. The white precipitate was obtained, dried, and then checked for molecular weight by GPC.

Molecular weight (Mw): 101,000 Molecular weight distribution: 1.39

As described above, the present invention can be produced by the appropriate substitution of the novel fluorene widely used in the blue light emitting material with noborene to produce a noborene monomer having a variety of derivatives. In addition, it is possible to prepare a polymer that can be applied to blue light emitting materials having various molecular weights using ring-opening metathesis polymerization from this monomer. The polymer contains a florene monomer capable of performing another reduction polymerization, and has a polymer unit of noborene, thereby improving the solubility of polyfluorene, which is a problem of the conventional blue light emitting polymer.

Claims (4)

Novorene monomer for a blue light emitting material of the formula (1). [Formula 1]

In the above formula, R ₁ is H, C ₁ -C ₆ alkyl, phenyl or halogen; R ₂ is H, C ₁ -C ₂₀ alkyl, phenyl or substituted phenyl; And R ₃ is H, OH, CHO or CO ₂ H. Novorene monomer for a blue light emitting material of the formula (2). [Formula 2]

In the above formula, R ₁ is H, C ₁ -C ₆ alkyl, phenyl or halogen; R ₃ is H, OH, CHO or CO ₂ H; And R ₄ is C ₁ -C ₂₀ alkylene, phenylene or C ₅ -C ₁₀ cycloalkylene. A polymer for a blue light emitting material of Formula 3 below. [Formula 3]

In the above formula, R ₁ is H, C ₁ -C ₆ alkyl, phenyl or halogen; R ₂ is H, C ₁ -C ₂₀ alkyl, phenyl or substituted phenyl; R ₃ is H, OH, CHO or CO ₂ H; And n is an integer from 2 to 100,000. A polymer for a blue light emitting material of the formula (4). [Formula 4]

In the above formula, R ₁ is H, C ₁ -C ₆ alkyl, phenyl or halogen; R ₃ is H, OH, CHO or CO ₂ H; R ₄ is C ₁ -C ₂₀ alkylene, phenylene or C ₅ -C ₁₀ cycloalkylene; And n is an integer from 2 to 100,000.