White-light hyperbranched conjugated polymer, method for preparing the same and it's use

• US 10,276,799 B2
• Filed: 01/23/2015
• Issued: 04/30/2019
• Est. Priority Date: 01/23/2015
• Status: Active Grant

• Current Assignee: Taiyuan University Of Technology (Province of Shanxi)
• Original Assignee: Taiyuan University Of Technology (Province of Shanxi)
• Inventors: Wang, Hua, Sun, Jing, Li, Jie, Wu, Yuling, Yang, Junli, Liu, Xuguang, Jia, Husheng, Xu, Bingshe, Huang, Wei
• Primary Examiner(s): Heincer, Liam J
• Application Number:
  US15/523,514
• Publication Number:
  US 20170309826A1
• Time in Patent Office: 1,558 Days
• CPC Class Codes: C08G 2261/11 Homopolymers
• CPC Class Codes: C08G 2261/12 Copolymers
• CPC Class Codes: C08G 2261/132 branched or hyperbranched
• CPC Class Codes: C08G 2261/1412 Saturated aliphatic units
• CPC Class Codes: C08G 2261/149 Side-chains having heteroaromatic units
• CPC Class Codes: C08G 2261/1624 of Os, Ir, Pt, Ru, Rh or Pd
• CPC Class Codes: C08G 2261/1646 comprising aromatic or heteroaromatic end groups
• CPC Class Codes: C08G 2261/18 conjugated
• CPC Class Codes: C08G 2261/3142 fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
• CPC Class Codes: C08G 2261/374 of Os, Ir, Pt, Ru, Rh, Pd
• CPC Class Codes: C08G 2261/411 Suzuki reactions
• CPC Class Codes: C08G 2261/5222 electrofluorescent
• CPC Class Codes: C08G 2261/5242 electrophosphorescent
• CPC Class Codes: C08G 2261/60 Glass transition temperature
• CPC Class Codes: C08G 2261/95 Use in organic luminescent diodes
• CPC Class Codes: C08G 61/02 Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• CPC Class Codes: C08G 61/10 only aromatic carbon atoms, e.g. polyphenylenes
• CPC Class Codes: C08G 83/005 Hyperbranched macromolecules
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1416 Condensed systems
• CPC Class Codes: C09K 2211/1425 : Non-condensed systems
• CPC Class Codes: C09K 2211/1466 : containing nitrogen as the only heteroatom
• CPC Class Codes: C09K 2211/185 : of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
• CPC Class Codes: H05B 33/14 : characterised by the chemical or physical composition or the arrangement of the electroluminescent material , or by the simultaneous addition of the electroluminescent material in or onto the light source
• CPC Class Codes: H10K 2101/10 : Triplet emission
• CPC Class Codes: H10K 2101/27 : Combination of fluorescent and phosphorescent emission
• CPC Class Codes: H10K 50/11 : characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 85/115 : Polyfluorene; Derivatives thereof
• CPC Class Codes: H10K 85/342 : comprising iridium
• CPC Class Codes: Y02B 20/00 : Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

This application discloses a white-light hyperbranched conjugated polymer, a method for preparing the same and its use. The polymer uses a red phosphorescent Ir(III) complex as a core and polyfluorene derivative blue fluorescent materials as a framework which either contains or does not contain carbazole derivatives, and the white light hyperbranched polymers realize white-light emission by adjusting the content of the red phosphorescent Ir(III) complex connected using the complementation of blue and red color. The electroluminescent spectrum of the conjugated polymer in the present application covers the whole visible light emission area and is close to the pure white light emission, by which the conjugated polymer could be used as a material used in light-emitting layer to prepare the organic electroluminescent devices.

Claims

1. A white-light hyperbranched conjugated polymer, comprising a red phosphorescent Ir(III) complex as a core and two or more blue fluorescent materials as a framework, the white-light hyperbranched conjugated polymer having a structure formula represented by formula (I):

2. The white-light hyperbranched conjugated polymer according to claim 1, characterized in that:

the content of the red phosphorescent Ir(III) complex M in the hyperbranched polymer is in the range of 0.05 to 0.2 mol %.

3. A method for preparing the white-light hyperbranched conjugated polymer according to claim 2, comprising:

conducting a Suzuki reaction using raw materials represented by structure general formulas

     1),

     2) and

     3), thereby obtaining the white-light hyperbranched conjugated polymer;

wherein;

the raw material represented by structure general formula

     1) is (MBr₃), a bromide of the red phosphorescent Ir(III) complex M;

the raw materials represented by the structure general formula

     2) are derivatives of a fluorene reaction monomer represented by formulas (IV) and (V);

4. The white-light hyperbranched conjugated polymer according to claim 1, characterized in that:

the blue fluorescent material F is 9,9-dioctylfluorene.

5. A method for preparing the white-light hyperbranched conjugated polymer according to claim 4, comprising:

conducting a Suzuki reaction using raw materials represented by structure general formulas

     1),

     2) and

     3), thereby obtaining the white-light hyperbranched conjugated polymer;

wherein;

the raw material represented by structure general formula

     1) is MBr₃, a bromide of the red phosphorescent Ir(III) complex M;

the raw materials represented by the;

structure general formula

     2) are derivatives of a fluorene reaction monomer represented by formulas (IV) and (V);

6. The white-light hyperbranched conjugated polymer according to claim 1, characterized in that:

the end-capping group E is phenyl, α

-naphthyl or β

-naphthyl.

7. A method for preparing the white-light hyperbranched conjugated polymer according to claim 6, comprising:

conducting a Suzuki reaction using raw materials represented by structure general formulas

     1),

     2) and

     3), thereby obtaining the white-light hyperbranched conjugated polymer;

wherein;

the raw material represented by structure general formula

     1) is MBr₃, a bromide of the red phosphorescent Ir(III) complex M;

the raw materials represented by the structure general formula

     2) are derivatives of a fluorene reaction monomer represented by formulas (IV) and (V);

8. A method for preparing the white-light hyperbranched conjugated polymer according to claim 1, comprising:

conducting a Suzuki reaction using raw materials represented by structure general formulas

     1),

     2) and

     3), thereby obtaining the white-light hyperbranched conjugated polymer;

wherein;

the raw material represented by structure general formula

     1) is MBr₃, a bromide of the red phosphorescent Ir(III) complex M;

the raw materials represented by the structure general formula

     2) are derivatives of a fluorene reaction monomer represented by formulas (IV) and (V);

9. The preparing method according to claim 8, characterized in that:

the Suzuki reaction is conducted under the protection of inert gas by;

firstly adding four raw materials of the derivatives of fluorene reaction monomer represented by formulas (IV) and (V), the derivative of carbazole reaction monomer represented by formula (VI) and the bromide of the red phosphorescent Ir(III) complex M represented by MBr₃ with different mole ratios into toluene solvent, and stirring to uniformly mix;

afterwards adding tetrakis(triphenylphosphine)palladium catalyst (Pd(PPh₃)₄), methyl trioctyl ammonium chloride as a phase transfer catalyst and K₂CO₃ aqueous solution, stirring, heating to the refluxing temperature, and reacting for 48˜

60 h; and

finally adding end-capping materials with the end-capping group E, and reacting, thereby obtaining a reacting solution comprising the white-light hyperbranched conjugated polymer;

wherein;

with respect to the four raw materials, the mole ratio of the bromide of the red phosphorescent Ir(III) complex M represented by MBr₃ to the other three blue light emitting raw materials is 1;

200˜

2000.

10. The preparing method according to claim 9, characterized by further comprising:

a post-processing method on the reaction solution comprising the white-light hyperbranched conjugated polymer, said post-processing method comprising;

slowly pouring the reaction solution containing the white-light hyperbranched conjugated polymer cooled to room temperature into a methanol solution being rapidly stirred to separate out a solid,

filtering and drying the solid,

treating the filtered and dried solid with acetone by Soxhlet extraction for 48˜

72h, thereby obtaining a crude product, and

treating the crude product by column chromatography with chloroform or tetrahydrofuran as an eluent, thereby obtaining the white-light hyperbranched conjugated polymer in the form of solid powders with different colors according to the content of the red phosphorescent Ir(III) complex M.

11. The preparing method according to claim 8, characterized in that:

the mole percentage of tetrakis(triphenylphosphine)palladium (Pd(PPh₃)₄) to a functional group participating in the Suzuki reaction is in the range of 1 mol % to 3 mol %.

12. The preparing method according to claim 8, characterized in that:

the bromide of the red phosphorescent Ir(III) complex M represented by MBr₃ is synthesized by a method comprising;

firstly placing 1-(4-bromophenyl)-isoquinoline as the main ligand monomer and Iridium(III) trichloride trihydrate with the molar ratio of 2˜

2.5;

1 into a first solvent system, performing reflux and reacting at 100˜

140°

C. under the protection of inert gas, thereby obtaining cyclometalated iridium(III) μ

-chlorobridged dimer of 1-(4-bromophenyl)-isoquinoline; and

afterwards reacting the cyclometalated iridium(III) μ

-chlorobridged dimer of 1-(4-bromophenyl)-isoquinoline and 3-(4-bromophenyl)-5-(2-pyridyl)-1,2,4-triazole according to the mole ratio of 1;

2˜

2.5 at 100˜

200°

C. in a second solvent system under the protection of inert gas in the presence of an anhydrous alkali metal carbonate or silver trifluoroacetate as a catalyst, thereby obtaining the bromide of red phosphorescent Ir(III) complex M (MBr₃).

13. The preparing method according to claim 8, characterized in that:

the reaction of adding the end-capping materials with the end-capping group E is conducted by a method comprising;

firstly adding a boride of the end-capping group E and reacting for 12 h, and

afterwards adding a bromide of the end-capping group E and reacting for another 12 h;

wherein;

the boride of the end-capping group E is phenylboronic acid, α

-naphthylboronic acid or β

-naphthylboronic acid;

the bromide of end capping group E is bromobenzene, α

-bromonaphthalene or β

-bromonaphthalene;

the percentage of the boride of the end-capping group E to the four raw materials is in the range of 1 to 3 wt %; and

the percentage of the bromide of the end-capping group F to the four raw materials is in the range of 10 wt% to 35 wt %.

14. An organic electroluminescent device, comprising the white-light hyperbranched conjugated polymer according to claim 1.

15. The organic electroluminescent device according to claim 14, characterized in that:

the device comprises a light emitting layer, and

the light emitting layer comprises the white-light hyperbranched conjugated polymer.