WO2020052544A1 - 一种以苯并[1,2-b:5,4-b']二苯并呋喃为核心的化合物及其应用 - Google Patents

一种以苯并[1,2-b:5,4-b']二苯并呋喃为核心的化合物及其应用 Download PDF

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WO2020052544A1
WO2020052544A1 PCT/CN2019/105086 CN2019105086W WO2020052544A1 WO 2020052544 A1 WO2020052544 A1 WO 2020052544A1 CN 2019105086 W CN2019105086 W CN 2019105086W WO 2020052544 A1 WO2020052544 A1 WO 2020052544A1
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李崇
唐丹丹
谢丹丹
王芳
徐浩杰
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江苏三月光电科技有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes

Definitions

  • the invention relates to a compound with benzo [1,2-b: 5,4-b '] dibenzofuran as a core and application thereof, and belongs to the field of semiconductor technology.
  • OLED display technology has been applied in smart phones, tablet computers and other fields, and will further expand to large-scale applications such as televisions.
  • the OLED device's luminous efficiency and service life performance Need to be further improved.
  • Current research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the light-emitting efficiency of the device, and increasing the service life of the device.
  • OLED photoelectric functional materials In order to continuously improve the performance of OLED devices, it is necessary not only to innovate the structure and manufacturing process of OLED devices, but also to continuously research and innovate OLED photoelectric functional materials to create higher-performance OLED functional materials.
  • OLED optoelectronic functional materials used in OLED devices can be divided into two major categories from the uses, which are charge injection transport materials and light emitting materials. Further, the charge injection transport material can be divided into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material can also be divided into a host light emitting material and a doped material.
  • organic functional materials are required to have good photoelectric properties.
  • a charge transport material good carrier mobility and high glass transition temperature are required as the main body of the light-emitting layer.
  • the material has good bipolarity, appropriate HOMO / LUMO energy level, etc.
  • the OLED photoelectric functional material film layer constituting the OLED device includes at least two layers of structures, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and electron transport.
  • Layers, electron injection layers, etc. that is to say, the optoelectronic functional materials used in OLED devices include at least hole injection materials, hole transport materials, light emitting materials, electron transport materials, etc.
  • the material types and matching forms are rich And diversity.
  • the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in devices with different structures may also be completely different.
  • An object of the present invention is to provide a compound having benzo [1,2-b: 5,4-b '] dibenzofuran as a core.
  • the compound of the present invention uses benzo [1,2-b: 5,4-b '] dibenzofuran as the core, has a higher glass transition temperature and molecular thermal stability, and has appropriate HOMO and LUMO energy levels.
  • the high triplet energy level T1 and hole mobility can be used as a hole transport layer material and / or an electron blocking layer material of an organic electroluminescent device through device structure optimization, thereby improving the photoelectric performance of an OLED device. And the lifetime of OLED devices.
  • L represents a single bond, a substituted or unsubstituted C 6-30 arylene group, and a substituted 5 to 30 membered heteroarylene group containing one or more heteroatoms;
  • Ar 1 and Ar 2 are each independently represented as -AR;
  • A is represented as a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted pyridylene, substituted or unsubstituted Biphenylene substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl; each occurrence of R being the same or different is represented by substituted or unsubstituted phenyl, substituted or unsubstituted Pyridylene, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthrene, substituted or unsubstituted fluorenyl, substituted or unsubstituted Diphenylamino, one of the structures represented by the general formula (2) or
  • X 1 , X 2 , and X 3 are each independently represented by -O-, -S-, -C (R 1 ) (R 2 )-, -N (R 3 )-or -Si (R 4 ) (R 5 )-; X 2 and X 3 can also be expressed as single bonds;
  • Z is represented identically or differently as CR 6 or N each time it appears;
  • the Z group bonded to the group A in the general formula (2) is represented as a carbon atom
  • the R 1 to R 5 are each independently represented as a C 1-20 alkyl group, a substituted or unsubstituted C 6-30 aryl group, and a 5- to 30-membered heteroaryl group containing one or more heteroatom substitutions or unsubstitutions.
  • One of the groups; R 1 and R 2 , R 4 and R 5 may also be connected to each other to form a ring;
  • the R 6 represents a hydrogen atom, halo, cyano, C 1-20 alkyl, C 1-20 olefin group, a substituted or unsubstituted C 6-30 aryl group containing one or more heteroatoms Or one of unsubstituted 5-30 membered heteroaryl groups; two or more adjacent R 6 may be bonded to each other to form a ring;
  • the substituent is selected from the group consisting of halogen, cyano, C 1-20 alkyl, C 1-20 alkenyl, C 6-30 aryl, and 5-30 membered heteroaryl containing one or more heteroatoms.
  • the heteroatom is selected from an oxygen atom, a sulfur atom, or a nitrogen atom.
  • the present invention can also be improved as follows.
  • R 1 to R 5 are each independently represented by methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, Substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl;
  • the R 6 represents a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group. , Substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl;
  • the substituent is selected from the group consisting of fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl, furyl, carbazole Or thienyl.
  • Another object of the present invention is to provide a method for preparing the above-mentioned organic compound using benzo [1,2-b: 5,4-b '] dibenzofuran as a core.
  • the preparation method of the compound of the invention is simple, and the market prospect is broad, which is suitable for large-scale popularization and application.
  • a method for preparing the above-mentioned organic compound using benzo [1,2-b: 5,4-b '] dibenzofuran as a core including:
  • the specific preparation method is:
  • a third object of the present invention is to provide an organic electroluminescent device.
  • the device structure can be optimized to maintain high film stability, which can effectively improve the photoelectric performance of the OLED device and the life of the OLED device.
  • the compound of the present invention has a good performance in OLED light-emitting devices. Application effect and industrialization prospect.
  • An organic electroluminescent device at least one functional layer containing the above-mentioned benzo [1,2-b: 5,4-b '] dibenzofuran as the core Compound.
  • the present invention can also be improved as follows.
  • the functional layer is a hole transport layer and / or an electron blocking layer.
  • the material of the hole-transporting layer is the aforementioned compound with benzo [1,2-b: 5,4-b '] dibenzofuran as the core;
  • the material of the electron blocking layer is the above compound with benzo [1,2-b: 5,4-b '] dibenzofuran as the core;
  • the materials of the hole-transporting layer and the electron-blocking layer are the above compounds with benzo [1,2-b: 5,4-b '] dibenzofuran as the core;
  • a fourth object of the present invention is to provide a lighting or display element.
  • the organic electroluminescence device of the present invention can be applied to lighting or display elements, which greatly improves the current efficiency of the device; at the same time, it significantly improves the device life, has a good application effect in OLED light-emitting devices, and has a good industry ⁇ ⁇ Prospects.
  • An illumination or display element includes the organic electroluminescence device as described above.
  • the compound of the present invention is a compound in which benzo [1,2-b: 5,4-b '] dibenzofuran is the parent nucleus and is connected to a branch of a diarylamino group.
  • the compound of the present invention has high thermal stability It can also be used as a hole-transporting material with a high hole-transporting ability and a high hole-transporting ability.
  • a high hole-transporting rate can improve the efficiency of an organic electroluminescent device; at a suitable LUMO energy level
  • it plays the role of electron blocking, improves the recombination efficiency of excitons in the light-emitting layer, reduces the efficiency roll-off at high current density, reduces the device voltage, and improves the current efficiency and life of the device.
  • the compound of the present invention is centered on benzo [1,2-b: 5,4-b '] dibenzofuran, and the diarylamino group is branched. After the film is formed, the branches can cross each other. Forming a dense film layer, thereby reducing the leakage current of the material after the application of the OLED device, thereby increasing the device service life.
  • the compound 1 disclosed in the patent JP2012028548A has a lower glass transition temperature and decomposition temperature, and is easy to crystallize after evaporation to form a film, resulting in a shorter device life of the device containing the compound 1.
  • the diarylamino group is connected with benzo [1,2-b: 5,4-b '] dibenzofuran to have a higher hole mobility; its molecular weight is moderate, and it has a higher Glass transition temperature, suitable decomposition temperature, adjustment of the evaporation temperature by adding aryl or heteroaryl groups in the middle of the core and the branch chain, the industrial window is wider; when the OLED device is applied, the compound of the present invention is optimized by the device structure It can maintain high film layer stability, can effectively improve the photoelectric performance of the OLED device and the life of the OLED device.
  • the compound of the present invention has good application effect and industrialization prospect in OLED light-emitting devices.
  • the compound provided by the present invention has higher glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, and higher Eg. By optimizing the device structure, it can effectively improve the photoelectric performance of the OLED device and the life of the OLED device. .
  • FIG. 1 is a schematic structural diagram of a device to which the compound of the present invention is applied, wherein the components represented by each reference number are as follows:
  • Transparent substrate layer 2. ITO anode layer, 3. Hole injection layer, 4. Hole transport layer, 5. Electron blocking layer, 6. Light emitting layer, 7. Hole blocking / electron transport layer, 8. Electron. Injection layer, 9, cathode layer, 10, CPL layer.
  • FIG. 2 is a curve of the current efficiency of an OLED device according to the present invention as a function of temperature.
  • FIG. 3 is a graph of a leakage current test curve for reverse voltage of a device made in device example 7 and device comparative example 1.
  • FIG. 3 is a graph of a leakage current test curve for reverse voltage of a device made in device example 7 and device comparative example 1.
  • Glass transition temperature Tg measured by differential scanning calorimetry (DSC, DSC204F1 Differential Scanning Calorimeter, Germany), and the heating rate was 10 ° C / min.
  • Thermal weight loss temperature Td This is a temperature of 0.5% of weight loss in a nitrogen atmosphere, and was measured on a TGA-50H thermogravimetric analyzer by Shimadzu Corporation, and the nitrogen flow rate was 20 mL / min.
  • the highest occupied molecular orbital HOMO energy level It is tested by the ionization energy test system (IPS3), and the test is the atmospheric environment.
  • IPS3 ionization energy test system
  • Cyclic voltammetry stability identified by cyclic voltammetry to observe the redox characteristics of the material.
  • Test conditions dissolve the test sample in a mixed solvent of dichloromethane and acetonitrile with a volume ratio of 2: 1 at a concentration of 1 mg / mL
  • the electrolyte is an organic solution of 0.1M tetrabutylammonium tetrafluoroborate
  • the reference electrode is an Ag / Ag + electrode
  • the counter electrode is a titanium plate
  • the working electrode is an ITO electrode. The number of cycles is 20 times.
  • Hole mobility The material was made into a single charge device and measured by the SCLC method.
  • the molar ratio of the raw material E to the raw material G was 1: 1.5 to 3.0; the molar ratio of the Pd (PPh 3 ) 4 to the raw material E is 0.006 to 0.02: 1; the molar ratio of the Na 2 CO 3 to the raw material E is 2.0 to 3.0: 1; the toluene-ethanol mixed solvent
  • the dosage is 0.01mol of raw material E. 30-40ml toluene and 15-20ml ethanol are added;
  • intermediate D the molar ratio of intermediate H to p-toluenesulfonic acid is 1: 1 to 1.5; the amount of toluene is 0.01 mol; intermediate H is added with 30-40 ml toluene; the saturated sodium carbonate solution 5-15 ml of saturated sodium carbonate solution was added to 0.01 mol of intermediate H; 30-45 ml of ethyl acetate was added to 0.01 mol of intermediate H;
  • Elemental analysis structure (molecular formula C 18 H 11 BrO 3 ): theoretical value C, 60.87; H, 3.12; Br, 22.50; O, 13.51; test value: C, 60.84; H, 3.13; Br, 22.51; O, 13.52.
  • Elemental analysis structure (Molecular formula C 18 H 9 BrO 2 ): Theoretical value C, 64.12; H, 2.69; Br, 23.70; O, 9.49; Test value: C, 64.11; H, 2.68; Br, 23.71; O, 9.50.
  • the intermediate D is synthesized according to the preparation method of the intermediate D-1.
  • the synthesis of the intermediate D is divided into two steps: the raw material E and the raw material G are converted into the intermediate H through the Suzuki reaction;
  • the structure is shown in Table 2.
  • Elemental analysis structure (Molecular formula C 42 H 27 NO 2 ): Theoretical value: C, 87.33; H, 4.71; N, 2.42; O, 5.54; Test value: C, 87.34; H, 4.72; N, 2.41; O, 5.53 .
  • Elemental analysis structure (Molecular formula C 48 H 31 NO 2 ): Theoretical value: C, 88.18; H, 4.78; N, 2.14; O, 4.89; Test value: C, 88.17; H, 4.76; N, 2.16; O, 4.90 .
  • Elemental analysis structure (molecular formula C 45 H 31 NO 2 ): Theoretical value: C, 87.49; H, 5.06; N, 2.27; O, 5.18; Test value: C, 87.48; H, 5.05; N, 2.28; O, 5.19 .
  • Elemental analysis structure (molecular formula C 45 H 31 NO 2 ): Theoretical value: C, 87.49; H, 5.06; N, 2.27; O, 5.18; Test value: C, 87.48; H, 5.05; N, 2.28; O, 5.19 .
  • Elemental analysis structure (Molecular formula C 49 H 39 NO 2 ): Theoretical value: C, 87.34; H, 5.83; N, 2.08; O, 4.75; Test value: C, 87.33; H, 5.84; N, 2.07; O, 4.76 .
  • Elemental analysis structure (molecular formula C 51 H 35 NO 2 ): Theoretical value: C, 88.28; H, 5.08; N, 2.02; O, 4.61; Test value: C, 88.27; H, 5.07; N, 2.01; O, 4.64 .
  • Elemental analysis structure (Molecular formula C 44 H 30 N 2 O 2 ): Theoretical value: C, 85.41; H, 4.89; N, 4.53; O, 5.17; Test value: C, 85.42; H, 4.88; N, 4.54; O , 5.16.
  • Elemental analysis structure (molecular formula C 51 H 35 NO 2 ): Theoretical value: C, 88.28; H, 5.08; N, 2.02; O, 4.61; Test value: C, 88.26; H, 5.06; N, 2.04; O, 4.64 .
  • Elemental analysis structure (molecular formula C 48 H 29 NO 3 ): Theoretical value: C, 86.34; H, 4.38; N, 2.10; O, 7.19; Test value: C, 86.35; H, 4.37; N, 2.11; O, 7.18 .
  • Elemental analysis structure (Molecular formula C 48 H 29 NO 3 ): Theoretical value: C, 86.34; H, 4.38; N, 2.10; O, 7.19; Test value: C, 86.33; H, 4.39; N, 2.11; O, 7.17 .
  • Elemental analysis structure (Molecular formula C 54 H 33 NO 3 ): Theoretical value: C, 87.19; H, 4.47; N, 1.88; O, 6.45; Test value: C, 87.17; H, 4.48; N, 1.89; O, 6.46 .
  • Elemental analysis structure (Molecular formula C 54 H 36 N 2 O 2 ): Theoretical value: C, 87.07; H, 4.87; N, 3.76; O, 4.30; Test value: C, 87.06; H, 4.86; N, 3.75; O , 4.33.
  • Elemental analysis structure (Molecular formula C 54 H 34 N 2 O 2 ): Theoretical value: C, 87.31; H, 4.61; N, 3.77; O, 4.31; Test value: C, 87.33; H, 4.62; N, 3.75; O , 4.30.
  • Elemental analysis structure (Molecular formula C 54 H 34 N 2 O 2 ): Theoretical value: C, 87.31; H, 4.61; N, 3.77; O, 4.31; Test value: C, 87.30; H, 4.60; N, 3.78; O , 4.32.
  • Elemental analysis structure (molecular formula C 54 H 34 N 2 O 2 ): Theoretical value: C, 87.31; H, 4.61; N, 3.77; O, 4.31; Test value: C, 87.32; H, 4.60; N, 3.76; O , 4.32.
  • Elemental analysis structure (molecular formula C 47 H 29 N 3 O 2 ): Theoretical value: C, 84.54; H, 4.38; N, 6.29; O, 4.79; Test value: C, 84.55; H, 4.37; N, 6.30; O , 4.78.
  • Elemental analysis structure (Molecular formula C 53 H 33 N 3 O 2 ): Theoretical value: C, 85.58; H, 4.47; N, 5.65; O, 4.30; Test value: C, 85.56; H, 4.45; N, 5.67; O , 4.32.
  • Elemental analysis structure (Molecular formula C 53 H 33 N 3 O 2 ): Theoretical value: C, 85.58; H, 4.47; N, 5.65; O, 4.30; Test value: C, 85.57; H, 4.45; N, 5.66; O , 4.32.
  • Elemental analysis structure (Molecular formula C 48 H 31 NO 2 ): Theoretical value: C, 88.18; H, 4.78; N, 2.14; O, 4.89; Test value: C, 88.19; H, 4.79; N, 2.15; O, 4.87 .
  • Elemental analysis structure (Molecular formula C 54 H 35 NO 2 ): Theoretical value: C, 88.86; H, 4.83; N, 1.92; O, 4.38; Test value: C, 88.85; H, 4.84; N, 1.94; O, 4.37 .
  • Elemental analysis structure (molecular formula C 51 H 35 NO 2 ): Theoretical value: C, 88.28; H, 5.08; N, 2.02; O, 4.61; Test value: C, 88.27; H, 5.06; N, 2.04O, 4.63.
  • Elemental analysis structure (molecular formula C 51 H 35 NO 2 ): Theoretical value: C, 88.28; H, 5.08; N, 2.02; O, 4.61; Test value: C, 88.29; H, 5.09; N, 2.01O, 4.60.
  • Elemental analysis structure (molecular formula C 54 H 33 NO 3 ): Theoretical value: C, 87.19; H, 4.47; N, 1.88; O, 6.45; Test value: C, 87.18; H, 4.48; N, 1.87; O, 6.47 .
  • Elemental analysis structure (Molecular formula C 54 H 33 NO 3 ): Theoretical value: C, 87.19; H, 4.47; N, 1.88; O, 6.45; Test value: C, 87.20; H, 4.46; N, 1.89; O, 6.45 .
  • Elemental analysis structure (molecular formula C 54 H 33 NO 3 ): Theoretical value: C, 87.19; H, 4.47; N, 1.88; O, 6.45; Test value: C, 87.17; H, 4.49; N, 1.86; O, 6.48 .
  • Elemental analysis structure (Molecular formula C 54 H 33 NO 3 ): Theoretical value: C, 87.19; H, 4.47; N, 1.88; O, 6.45; Test value: C, 87.18; H, 4.48; N, 1.88; O, 6.46 .
  • Elemental analysis structure (molecular formula C 54 H 34 N 2 O 2 ): Theoretical value: C, 87.31; H, 4.61; N, 3.77; O, 4.31; Test value: C, 87.32; H, 4.62; N, 3.75; O , 4.31.
  • Elemental analysis structure (Molecular formula C 54 H 34 N 2 O 2 ): Theoretical value: C, 87.31; H, 4.61; N, 3.77; O, 4.31; Test value: C, 87.33; H, 4.63; N, 3.74; O , 4.30.
  • Elemental analysis structure (Molecular formula C 53 H 33 N 3 O 2 ): Theoretical value: C, 85.58; H, 4.47; N, 5.65; O, 4.30; Test value: C, 85.57; H, 4.48; N, 5.64; O , 4.31.
  • the organic compound of the present invention is used in a light emitting device, and can be used as a material for a hole transport layer or as a material for an electron blocking layer.
  • the compounds of the present invention were tested for thermal performance, HOMO energy level, hole mobility, and cyclic voltammetry stability. The test results are shown in Table 3.
  • the organic compounds of the present invention have different HOMO energy levels and good hole mobility, and can be applied to different functional layers.
  • the present invention uses benzo [1,2-b: 5,4-b ']
  • the organic compound with dibenzofuran as the core has higher triplet energy level and higher thermal stability, so that the efficiency and lifetime of the OLED device containing the organic compound of the present invention are improved.
  • device examples 1-35 and device comparative example 1 are used to describe in detail the application effects of the compound synthesized by the present invention as a hole transport layer material or an electron blocking layer material in a device.
  • Device Example 2-35 and Device Comparative Example 1 Compared with Device Example 1, the manufacturing process of the device is exactly the same, and the same substrate material and electrode material are used, and the film thickness of the electrode material remains the same. The difference is that the material of the hole transport layer or the electron blocking layer is changed.
  • the structural composition of the devices obtained in each example is shown in Table 4.
  • the test results of the obtained devices are shown in Table 5.
  • Transparent substrate layer / ITO anode layer / hole injection layer (HAT-CN, thickness 10nm) / hole transport layer (HT-1, thickness 60nm) / electron blocking layer (compound 3, thickness 20nm) / light emitting layer (GH1, GH2 and GD-1 are mixed at a weight ratio of 45:45:10, thickness 40nm) / hole blocking / electron transport layer (ET-1 and Liq, are mixed at a weight ratio of 1: 1, thickness 40nm) / electron Injection layer (LiF, thickness 1 nm) / cathode layer (Mg and Ag, mixed at a weight ratio of 9: 1, thickness 15 nm) / CPL layer (compound CP-1, thickness 70 nm).
  • the transparent substrate layer 1 is a transparent substrate, such as a transparent PI film, glass, or the like.
  • the ITO anode layer 2 (with a film thickness of 150 nm) is washed, that is, alkali washing, pure water washing, drying are performed in that order, and then UV-ozone washing is performed to remove organic residues on the surface of the transparent ITO.
  • a HAT-CN having a film thickness of 10 nm was used as the hole injection layer 3 using a vacuum evaporation device.
  • HT-1 was evaporated to a thickness of 60 nm as a hole transport layer.
  • Compound 3 was subsequently evaporated to a thickness of 20 nm as an electron blocking layer.
  • the light-emitting layer 6 of the OLED light-emitting device is manufactured. Its structure includes GH1, GH2 as the host material, GD-1 as the doping material, and the doping ratio of the doping material is: 10% by weight, the thickness of the light-emitting layer was 40 nm.
  • the materials of the electron transport layer for vacuum evaporation are ET-1 and Liq.
  • the thickness of the vacuum-evaporated film of the material is 40 nm, and this layer is a hole blocking / electron transporting layer 7.
  • a lithium fluoride (LiF) layer having a film thickness of 1 nm was produced by a vacuum evaporation device, and this layer was an electron injection layer 8.
  • a Mg: Ag electrode layer having a film thickness of 15 nm was produced by a vacuum evaporation device, and this layer was used as the cathode layer 9.
  • CP-1 at 70 nm was vacuum-deposited as a CPL layer 10.
  • LT97 refers to the time it takes for the brightness of the device to decay to 97% at a current density of 20mA / cm 2 ;
  • Life test system is Korea Pulse Science M6000 OLED device life tester.
  • the compound of the present invention has a good application effect as a hole transport layer material in an OLED light emitting device, and has a good industrialization prospect. Further, the efficiency of the OLED device prepared by the materials of the present invention is relatively stable at low and high temperatures. Device Examples 7, 24, and 35 and Device Comparative Example 1 were tested for efficiency in the range of -10 to 80 ° C. The obtained results are shown in the table. 6 and Figure 2.
  • device examples 7, 24, and 35 are device structures of the materials of the present invention and known materials. Compared with device comparative example 1, not only the low-temperature efficiency is high, but also the temperature rise process The efficiency has increased steadily.

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Abstract

以苯并[1,2-b:5,4-b']二苯并呋喃为核心和二芳基胺基为支链的通式(1)所示化合物、有机电致发光器件以及照明或显示元件。

Description

一种以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物及其应用 技术领域
本发明涉及一种以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物及其应用，属于半导体技术领域。
背景技术
当前，OLED显示技术已经在智能手机，平板电脑等领域获得应用，进一步还将向电视等大尺寸应用领域扩展，但是，和实际的产品应用要求相比，OLED器件的发光效率和使用寿命等性能还需要进一步提升。目前对OLED发光器件提高性能的研究包括：降低器件的驱动电压、提高器件的发光效率、提高器件的使用寿命等。为了实现OLED器件的性能的不断提升，不但需要从OLED器件结构和制作工艺的创新，更需要OLED光电功能材料不断研究和创新，创制出更高性能的OLED功能材料。
应用于OLED器件的OLED光电功能材料从用途上可划分为两大类，分别为电荷注入传输材料和发光材料。进一步，还可将电荷注入传输材料分为电子注入传输材料、电子阻挡材料、空穴注入传输材料和空穴阻挡材料，还可以将发光材料分为主体发光材料和掺杂材料。
为了制作高性能的OLED发光器件，要求各种有机功能材料具备良好的光电性能，譬如，作为电荷传输材料，要求具有良好的载流子迁移率，高玻璃化转化温度等，作为发光层的主体材料具有良好双极性，适当的HOMO/LUMO能阶等。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件结构则包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层等多种膜层，也就是说应用于OLED器件的光电功能材料至少包括空穴注入材料、空穴传输材料、发光材料、电子传输材料等，材料类型和搭配形式具有丰富性和多样性的特点。另外，对于不同结构的OLED器件搭配而言，所使用的光电功能材料具有较强的选择性，相同的材料在不同结构器件中的性能表现也可能完全迥异。
因此，针对当前OLED器件的产业应用要求以及OLED器件的不同功能膜层，器件的光电特性需求，必须选择更适合、性能更高的OLED功能材料或材料组合，才能实现器件的高效率、长寿命和低电压的综合特性。就当前的OLED显示照明产业的实际需求而言，目前OLED材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
本发明的目的之一，是提供一种以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物。本发明的化合物以苯并[1,2-b:5,4-b’]二苯并呋喃为核心，具有较高的玻璃化温度和分子热稳定性，合适的HOMO和LUMO能级，较高的三线态能级T1及空穴迁移率，通过器件结构优化，可用作有机电致发光器件的空穴传输层材料和/或电子阻挡层材料，从而提升可有效提升OLED器件的光电性能以及OLED器件的寿命。
本发明解决上述技术问题的技术方案如下：一种以苯并[1,2-b:5,4-b']二苯并呋喃为核心的化合物，所述该化合物的结构如通式(1)所示：
Figure PCTCN2019105086-appb-000001
通式(1)中，L表示为单键、取代或未取代的C 6-30亚芳基、含有一个或多个杂原子取代或未取代的5～30元亚杂芳基；
Ar 1、Ar 2各自独立的表示为-A-R；A表示为单键、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的亚吡啶基、取代或未取代的亚联苯基取代或未取代的亚苯并呋喃基、取代或未取代的亚苯并噻吩基；R每次出现相同或不同的表示为取代或未取代的苯基、取代或未取代的亚吡啶基、取代或未取代的联苯基、取代或未取代的萘基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的芘基、取代或未取代的二苯基胺基、通式(2)或通式(3)所示结构中的一种；当A表示为单键时，Ar 1、Ar 2不同时表示为苯基或9,9-二甲基芴基；当R表示为通式(3)所示结构式时，A不表示为单键；
Figure PCTCN2019105086-appb-000002
通式(2)、通式(3)中，X 1、X 2、X 3分别独立地表示为-O-、-S-、-C(R 1)(R 2)-、-N(R 3)-或-Si(R 4)(R 5)-；X 2、X 3还可以表示为单键；
Z每次出现时相同或不同地表示为C-R 6或N；
通式(2)中所述基团A键合的Z基团表示为碳原子；
所述R 1～R 5分别独立地表示为C 1-20的烷基、取代或未取代的C 6-30芳基、含有一个或多个杂原子取代或未取代的5～30元杂芳基中的一种；R 1与R 2、R 4与R 5还可相互连接成环；
所述R 6表示为氢原子、卤素、氰基、C 1-20的烷基、C 1-20的烯烃基、取代或未取代的C 6-30芳基、含有一个或多个杂原子取代或未取代的5～30元杂芳基中的一种；相邻两个或多个R 6还可相互键结成环；
所述取代基选自卤素、氰基、C 1-20的烷基、C 1-20的烯烃基、C 6-30芳基、含有一个或多个杂原子的5～30元杂芳基中的一种或多种；
所述杂原子选自氧原子、硫原子或氮原子。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述通式(1)的结构如通式(4)-(7)中的任一种所示：
Figure PCTCN2019105086-appb-000003
Figure PCTCN2019105086-appb-000004
进一步，所述R 1～R 5分别独立地表示为甲基、乙基、丙基、异丙基、叔丁基、戊基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的联苯基、取代或未取代的吡啶基；
所述R 6表示为氢原子、氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、戊基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的联苯基、取代或未取代的吡啶基；
所述取代基选自氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、戊基、苯基、萘基、联苯基、吡啶基、呋喃基、咔唑基或噻吩基中的一种或多种。
更进一步，所述通式(1)的具体化合物为：
Figure PCTCN2019105086-appb-000005
Figure PCTCN2019105086-appb-000006
Figure PCTCN2019105086-appb-000007
Figure PCTCN2019105086-appb-000008
Figure PCTCN2019105086-appb-000009
本发明的目的之二，是提供上述以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的有机化合物的制备方法。本发明的化合物的制备方法简单，市场前景广阔，适合规模化推广应用。
本发明解决上述技术问题的技术方案如下：一种上述以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的有机化合物的制备方法，包括：
Figure PCTCN2019105086-appb-000010
具体制备方法为：
在氮气保护下，依次称取中间体D、原料F、叔丁醇钠、Pd 2(dba) 3、三叔丁基膦，加入甲苯搅拌混合，加热至100～120℃，回流反应12～24小时，取样点板，显示无中间体D剩余，反应完全； 自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到目标产物；所述中间体D与原料F的摩尔比为1:1～2；所述Pd 2(dba) 3与中间体D的摩尔比为0.006～0.02:1，所述三叔丁基膦与中间体D的摩尔比为0.006～0.02:1；所述叔丁醇钠与中间体D的摩尔比为2.0～3.0:1；所述甲苯用量为0.01mol中间体加入150ml甲苯。
本发明的目的之三，是提供一种有机电致发光器件。本发明的化合物在OLED器件应用时，通过器件结构优化，可保持高的膜层稳定性，可有效提升OLED器件的光电性能以及OLED器件的寿命，本发明所述化合物在OLED发光器件中具有良好的应用效果和产业化前景。
本发明解决上述技术问题的技术方案如下：一种有机电致发光器件，至少一层功能层含有上述以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述功能层为空穴传输层和/或电子阻挡层。
更进一步，所述空穴传输层材料为上述以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物；
更进一步，所述电子阻挡层材料为上述以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物；
更进一步，所述空穴传输层和电子阻挡层材料均为上述以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物；
本发明的目的之四，是提供一种照明或显示元件。本发明的有机电致发光器件可以应用在照明或显示原件，使器件的电流效率得到很大改善；同时，对于器件寿命提升非常明显，在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
本发明解决上述技术问题的技术方案如下：一种照明或显示元件，包括如上所述的有机电致发光器件。
本发明的有益效果是：
1.本发明化合物为苯并[1,2-b:5,4-b’]二苯并呋喃为母核，连接二芳基胺基支链的化合物，本发明化合物具有较高的热稳定性，同时具有很强的空穴传输能力，较高的空穴迁移率，可作为空穴传输材料使用，高的空穴传输速率能够提高有机电致发光器件的效率；在合适的LUMO能级下，又起到了电子阻挡的作用，提升激子在发光层中的复合效率，降低高电流密度下的效率滚降，降低器件电压，提高器件的电流效率和寿命。
2.本发明的化合物以苯并[1,2-b:5,4-b’]二苯并呋喃为中心，二芳基胺基为支链，材料成膜后，各支链可相互交叉形成致密性高的膜层，从而降低材料在OLED器件应用后的漏电流，因此提高器件使用寿命。
3.专利JP2012028548A公开的化合物1具有较低的玻璃化转变温度和分解温度，蒸镀成膜后容易结晶，导致含化合物1的器件寿命较短；本发明化合物与专利JP2012028548A公开的化合物1相比，本发明化合物中，二芳基胺基与苯并[1,2-b:5,4-b’]二苯并呋喃连接具有更高的空穴迁移率；其分子量适中，具有更高的玻璃化转变温度，适宜的分解温度，通过母核和支链中间加入芳基或杂芳基进行蒸镀温度的调控，工业窗口更宽；本发明的化合物在OLED器件应用时，通过器件结构优化，可保持高的膜层稳定性，可有效提升OLED器件的光电性能以及OLED器件的寿命，本发明所述化合物在OLED发光器件中具有良好的应用效果和产业化前景。
4.本发明提供的化合物具有较高的玻璃化温度和分子热稳定性，合适的HOMO和LUMO能级，较高Eg，通过器件结构优化，可有效提升OLED器件的光电性能以及OLED器件的寿命。
附图说明
图1为本发明化合物应用的器件结构示意图，其中，各标号所代表的部件如下：
1、透明基板层，2、ITO阳极层，3、空穴注入层，4、空穴传输层，5、电子阻挡层，6、发光层，7、空穴阻挡/电子传输层，8、电子注入层，9、阴极层，10、CPL层。
图2为本发明OLED器件的电流效率随温度的变化曲线。
图3为本发明器件实施例7与器件对比例1所制作的器件进行反向电压的漏电流测试曲线图。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
本文中所涉及的材料的结构式如下：
Figure PCTCN2019105086-appb-000011
本文中所使用的检测方法如下：
玻璃化转变温度Tg：通过示差扫描量热法(DSC，德国耐驰公司DSC204F1示差扫描量热仪)测定，升温速率10℃/min。
热失重温度Td：其为在氮气气氛中失重0.5％的温度，在日本岛津公司的TGA-50H热重分析仪上进行测定，氮气流量为20mL/min。
最高占据分子轨道HOMO能级：是由电离能量测试系统(IPS3)测试，测试为大气环境。
循环伏安稳定性：通过循环伏安法观测材料的氧化还原特性来鉴定，测试条件：将测试样品溶于体积比为2:1的二氯甲烷和乙腈混合溶剂中，浓度为1mg/mL，电解液是0.1M的四氟硼酸四丁基铵的有机溶液，参比电极是Ag/Ag +电极，对电极为钛板，工作电极为ITO电极，循环次数为20次。
空穴迁移率：将材料制作成单电荷器件，用SCLC方法测定。
中间体D的合成
Figure PCTCN2019105086-appb-000012
(1)称取原料E和原料G，用体积比为1.5～3.0:1的甲苯乙醇混合溶剂溶解；再加入Na 2CO 3水溶液、Pd(PPh 3) 4；在惰性气氛下，将上述混合溶液于90～110℃下，搅拌反应10～24小时，然后冷却至室温、过滤反应溶液，滤液旋蒸，过硅胶柱，得到中间体H；所述原料E与原料G的摩尔比为1:1.5～3.0；所述Pd(PPh 3) 4与原料E的摩尔比为0.006～0.02:1；所述Na 2CO 3与原料E的摩尔比为2.0～3.0:1；所述甲苯乙醇混合溶剂的用量为0.01mol原料E中加入30-40ml甲苯和15-20ml乙醇；
(2)在氮气保护下，称取中间体H和对甲苯磺酸，用甲苯溶解，加热至90～110℃，反应10～24小时；取样点板，显示无中间体H剩余，反应完全；反应结束后，向反应体系中加入饱和碳酸钠溶液淬灭，用乙酸乙酯萃取，分液，有机相用无水硫酸钠干燥后减压旋蒸至无馏分，所得粗产物过中性硅胶柱，得到中间体D；所述中间体H与对甲苯磺酸的摩尔比为1:1～1.5；所述甲苯的用量为0.01mol中间体H中加入30-40ml甲苯；所述饱和碳酸钠溶液的用量为0.01mol中间体H中加入5-15ml饱和碳酸钠溶液；所述乙酸乙酯的用量为0.01mol中间体H中加入30-45ml乙酸乙酯，分三次加入；
此类以中间体D-1的合成为例：
Figure PCTCN2019105086-appb-000013
(1)500mL的三口瓶，在氮气保护下，加入0.05mol原料E，0.1mol原料G-1，用混合溶剂溶解(180ml甲苯，90ml乙醇)，然后加入0.15molNa 2CO 3水溶液(2M)，通氮气搅拌1小时，然后加入0.0005molPd(PPh 3) 4，加热至15小时，取样点板，反应完全。自然冷却，过滤，滤液旋蒸，过硅胶柱，得到中间体H-1，HPLC纯度99.3％，收率61.5％。
元素分析结构(分子式C 18H 11BrO 3)：理论值C,60.87；H,3.12；Br,22.50；O,13.51；测试值：C,60.84；H,3.13；Br,22.51；O,13.52。ESI-MS(m/z)(M +)：理论值为353.99，实测值为354.18。
(3)250mL的三口瓶，在氮气保护下，加入0.03mol中间体H-1和0.036mol对甲苯磺酸，用100ml甲苯溶解，加热至100℃，反应15小时；取样点板，显示无中间体H-1剩余，反应完全；反应结束后，向反应体系中加入30ml的饱和碳酸钠溶液淬灭，用(30ml*3)乙酸乙酯萃取，分液， 有机相用无水硫酸钠干燥后减压旋蒸至无馏分，所得粗产物过中性硅胶柱，得到中间体D-1，HPLC纯度99.2％，收率55.4％。
元素分析结构(分子式C 18H 9BrO 2)：理论值C,64.12；H,2.69；Br,23.70；O,9.49；测试值：C,64.11；H,2.68；Br,23.71；O,9.50。ESI-MS(m/z)(M +)：理论值为335.98，实测值为336.20。
按中间体D-1的制备方法合成中间体D，中间体D的合成分为两步：原料E和原料G通过铃木反应生成中间体H；中间体H缩水成环反应生成中间体D，具体结构如表2所示。
表2
Figure PCTCN2019105086-appb-000014
实施例1：制备化合物3
Figure PCTCN2019105086-appb-000015
在氮气气氛下，向500ml三口烧瓶中加入0.01mol中间体D-1、0.015mol原料F-1、0.03mol叔丁醇钠、5×10 -5molPd 2(dba) 3和5×10 -5mol三叔丁基磷，然后加入150ml甲苯将其溶解，加热至100℃，回流24小时，利用TLC观察反应，直至反应完全。自然冷却至室温，过滤，将滤液旋蒸至无馏分。所得物质通过硅胶柱(石油醚作为洗脱剂)纯化，得到目标产物，纯度99.8％，收率78.8％。
元素分析结构(分子式C 42H 27NO 2)：理论值：C,87.33；H,4.71；N,2.42；O,5.54；测试值：C,87.34；H,4.72；N,2.41；O,5.53。ESI-MS(m/z)(M +)：理论值为577.20，实测值为577.25。
实施例2：制备化合物37
Figure PCTCN2019105086-appb-000016
按化合物3的合成方法制备，不同在于用中间体D-2代替中间体D-1，用原料F-2代替原料F-1，所得目标产物的纯度为99.6％，收率为73.5％。
元素分析结构(分子式C 48H 31NO 2)：理论值：C,88.18；H,4.78；N,2.14；O,4.89；测试值：C,88.17；H,4.76；N,2.16；O,4.90。ESI-MS(m/z)(M +)：理论值为653.24，实测值为653.48。
实施例3：制备化合物79
Figure PCTCN2019105086-appb-000017
按化合物3的合成方法制备，不同在于用原料F-3代替原料F-1，所得目标产物的纯度为99.8％，收率为77.7％。
元素分析结构(分子式C 45H 31NO 2)：理论值：C,87.49；H,5.06；N,2.27；O,5.18；测试值：C,87.48；H,5.05；N,2.28；O,5.19。ESI-MS(m/z)(M +)：理论值为617.24，实测值为617.55。
实施例4：制备化合物87
Figure PCTCN2019105086-appb-000018
按化合物3的合成方法制备，不同在于用原料F-4代替原料F-1，所得目标产物的纯度为99.9％，收率为79.2％。
元素分析结构(分子式C 45H 31NO 2)：理论值：C,87.49；H,5.06；N,2.27；O,5.18；测试值：C,87.48；H,5.05；N,2.28；O,5.19。ESI-MS(m/z)(M +)：理论值为617.24，实测值为617.49。
实施例5：制备化合物109
Figure PCTCN2019105086-appb-000019
按化合物3的合成方法制备，不同在于用中间体D-3代替中间体D-1，用原料F-5代替原料F-1，所得目标产物的纯度为99.9％，收率为76.9％。
元素分析结构(分子式C 49H 39NO 2)：理论值：C,87.34；H,5.83；N,2.08；O,4.75；测试值：C,87.33；H,5.84；N,2.07；O,4.76。ESI-MS(m/z)(M +)：理论值为673.30，实测值为673.62。
实施例6：制备化合物126
Figure PCTCN2019105086-appb-000020
按化合物3的合成方法制备，不同在于用中间体D-2代替中间体D-1，用原料F-6代替原料F-1，所得目标产物的纯度为99.6％，收率为77.3％。
元素分析结构(分子式C 51H 35NO 2)：理论值：C,88.28；H,5.08；N,2.02；O,4.61；测试值：C,88.27；H,5.07；N,2.01；O,4.64。ESI-MS(m/z)(M +)：理论值为693.27，实测值为693.54。
实施例7：制备化合物157
Figure PCTCN2019105086-appb-000021
按化合物3的合成方法制备，不同在于用原料F-7代替原料F-1，所得目标产物的纯度为99.8％，收率为75.6％。
元素分析结构(分子式C 44H 30N 2O 2)：理论值：C,85.41；H,4.89；N,4.53；O,5.17；测试值：C,85.42；H,4.88；N,4.54；O,5.16。ESI-MS(m/z)(M +)：理论值为618.23，实测值为618.47。
实施例8：制备化合物176
Figure PCTCN2019105086-appb-000022
按化合物3的合成方法制备，不同在于用中间体D-4代替中间体D-1，用原料F-8代替原料F-1，所得目标产物的纯度为99.7％，收率为74.5％。
元素分析结构(分子式C 51H 35NO 2)：理论值：C,88.28；H,5.08；N,2.02；O,4.61；测试值：C,88.26；H,5.06；N,2.04；O,4.64。ESI-MS(m/z)(M +)：理论值为693.27，实测值为693.61。
实施例9：制备化合物217
Figure PCTCN2019105086-appb-000023
按化合物3的合成方法制备，不同在于用中间体D-3代替中间体D-1，用原料F-9代替原料F-1，所得目标产物的纯度为99.5％，收率为76.4％。
元素分析结构(分子式C 48H 29NO 3)：理论值：C,86.34；H,4.38；N,2.10；O,7.19；测试值：C,86.35；H,4.37；N,2.11；O,7.18。ESI-MS(m/z)(M +)：理论值为667.21，实测值为667.44。
实施例10：制备化合物243
Figure PCTCN2019105086-appb-000024
按化合物3的合成方法制备，不同在于用原料F-10代替原料F-1，所得目标产物的纯度为99.8％，收率为78.1％。
元素分析结构(分子式C 48H 29NO 3)：理论值：C,86.34；H,4.38；N,2.10；O,7.19；测试值：C,86.33；H,4.39；N,2.11；O,7.17。ESI-MS(m/z)(M +)：理论值为667.21，实测值为667.49。
实施例11：制备化合物259
Figure PCTCN2019105086-appb-000025
按化合物3的合成方法制备，不同在于用原料F-11代替原料F-1，所得目标产物的纯度为99.9％，收率为74.7％。
元素分析结构(分子式C 54H 33NO 3)：理论值：C,87.19；H,4.47；N,1.88；O,6.45；测试值：C,87.17；H,4.48；N,1.89；O,6.46。ESI-MS(m/z)(M +)：理论值为743.25，实测值为743.52。
实施例12：制备化合物275
Figure PCTCN2019105086-appb-000026
按化合物3的合成方法制备，不同在于用原料F-12代替原料F-1，所得目标产物的纯度为99.7％，收率为73.8％。
元素分析结构(分子式C 54H 36N 2O 2)：理论值：C,87.07；H,4.87；N,3.76；O,4.30；测试值：C,87.06；H,4.86；N,3.75；O,4.33。ESI-MS(m/z)(M +)：理论值为744.28，实测值为744.55。
实施例13：制备化合物295
Figure PCTCN2019105086-appb-000027
按化合物3的合成方法制备，不同在于用原料F-13代替原料F-1，所得目标产物的纯度为99.9％，收率为77.9％。
元素分析结构(分子式C 54H 34N 2O 2)：理论值：C,87.31；H,4.61；N,3.77；O,4.31；测试值：C,87.33；H,4.62；N,3.75；O,4.30。ESI-MS(m/z)(M +)：理论值为742.26，实测值为742.57。
实施例14：制备化合物319
Figure PCTCN2019105086-appb-000028
按化合物3的合成方法制备，不同在于用原料F-14代替原料F-1，所得目标产物的纯度为99.8％，收率为75.7％。
元素分析结构(分子式C 54H 34N 2O 2)：理论值：C,87.31；H,4.61；N,3.77；O,4.31；测试值：C,87.30；H,4.60；N,3.78；O,4.32。ESI-MS(m/z)(M +)：理论值为742.26，实测值为742.60。
实施例15：制备化合物335
Figure PCTCN2019105086-appb-000029
按化合物3的合成方法制备，不同在于用原料F-15代替原料F-1，所得目标产物的纯度为99.6％，收率为76.6％。
元素分析结构(分子式C 54H 34N 2O 2)：理论值：C,87.31；H,4.61；N,3.77；O,4.31；测试值：C,87.32；H,4.60；N,3.76；O,4.32。ESI-MS(m/z)(M +)：理论值为742.26，实测值为742.59。
实施例16：制备化合物355
Figure PCTCN2019105086-appb-000030
按化合物3的合成方法制备，不同在于用原料F-16代替原料F-1，所得目标产物的纯度为99.5％，收率为74.8％。
元素分析结构(分子式C 47H 29N 3O 2)：理论值：C,84.54；H,4.38；N,6.29；O,4.79；测试值：C,84.55；H,4.37；N,6.30；O,4.78。ESI-MS(m/z)(M +)：理论值为667.23，实测值为667.42。
实施例17：制备化合物395
Figure PCTCN2019105086-appb-000031
按化合物3的合成方法制备，不同在于用原料F-17代替原料F-1，所得目标产物的纯度为99.8％，收率为75.7％。
元素分析结构(分子式C 53H 33N 3O 2)：理论值：C,85.58；H,4.47；N,5.65；O,4.30；测试值：C,85.56；H,4.45；N,5.67；O,4.32。ESI-MS(m/z)(M +)：理论值为743.26，实测值为743.52。
实施例18：制备化合物415
Figure PCTCN2019105086-appb-000032
按化合物3的合成方法制备，不同在于用原料F-18代替原料F-1，所得目标产物的纯度为99.6％，收率为72.5％。
元素分析结构(分子式C 53H 33N 3O 2)：理论值：C,85.58；H,4.47；N,5.65；O,4.30；测试值：C,85.57；H,4.45；N,5.66；O,4.32。ESI-MS(m/z)(M +)：理论值为743.26，实测值为743.54。
实施例19：制备化合物437
Figure PCTCN2019105086-appb-000033
按化合物3的合成方法制备，不同在于用中间体D-5代替中间体D-1，所得目标产物的纯度为99.9％，收率为78.1％。
元素分析结构(分子式C 48H 31NO 2)：理论值：C,88.18；H,4.78；N,2.14；O,4.89；测试值：C,88.19；H,4.79；N,2.15；O,4.87。ESI-MS(m/z)(M +)：理论值为653.24，实测值为653.44。
实施例20：制备化合物480
Figure PCTCN2019105086-appb-000034
按化合物3的合成方法制备，不同在于用中间体D-6代替中间体D-1，用原料F-19代替原料F-1，所得目标产物的纯度为99.7％，收率为77.9％。
元素分析结构(分子式C 54H 35NO 2)：理论值：C,88.86；H,4.83；N,1.92；O,4.38；测试值：C,88.85；H,4.84；N,1.94；O,4.37。ESI-MS(m/z)(M +)：理论值为729.27，实测值为729.55。
实施例21：制备化合物525
Figure PCTCN2019105086-appb-000035
按化合物3的合成方法制备，不同在于用中间体D-5代替中间体D-1，用原料F-3代替原料F-1，所得目标产物的纯度为99.6％，收率为76.1％。
元素分析结构(分子式C 51H 35NO 2)：理论值：C,88.28；H,5.08；N,2.02；O,4.61；测试值：C,88.27；H,5.06；N,2.04O,4.63。ESI-MS(m/z)(M +)：理论值为693.27，实测值为693.56。
实施例22：制备化合物533
Figure PCTCN2019105086-appb-000036
按化合物3的合成方法制备，不同在于用中间体D-5代替中间体D-1，用原料F-4代替原料F-1，所得目标产物的纯度为99.8％，收率为75.3％。
元素分析结构(分子式C 51H 35NO 2)：理论值：C,88.28；H,5.08；N,2.02；O,4.61；测试值：C,88.29；H,5.09；N,2.01O,4.60。ESI-MS(m/z)(M +)：理论值为693.27，实测值为693.56。
实施例23：制备化合物585
Figure PCTCN2019105086-appb-000037
按化合物3的合成方法制备，不同在于用中间体D-7代替中间体D-1，用原料F-20代替原料F-1，所得目标产物的纯度为99.5％，收率为74.4％。
元素分析结构(分子式C 54H 33NO 3)：理论值：C,87.19；H,4.47；N,1.88；O,6.45；测试值：C,87.18；H,4.48；N,1.87；O,6.47。ESI-MS(m/z)(M +)：理论值为743.25，实测值为743.51。
实施例24：制备化合物591
Figure PCTCN2019105086-appb-000038
按化合物3的合成方法制备，不同在于用中间体D-6代替中间体D-1，用原料F-20代替原料F-1，所得目标产物的纯度为99.9％，收率为78.8％。
元素分析结构(分子式C 54H 33NO 3)：理论值：C,87.19；H,4.47；N,1.88；O,6.45；测试值：C,87.20；H,4.46；N,1.89；O,6.45。ESI-MS(m/z)(M +)：理论值为743.25，实测值为743.49。
实施例25：制备化合物621
Figure PCTCN2019105086-appb-000039
按化合物3的合成方法制备，不同在于用中间体D-7代替中间体D-1，用原料F-10代替原料F-1，所得目标产物的纯度为99.6％，收率为73.3％。
元素分析结构(分子式C 54H 33NO 3)：理论值：C,87.19；H,4.47；N,1.88；O,6.45；测试值：C,87.17；H,4.49；N,1.86；O,6.48。ESI-MS(m/z)(M +)：理论值为743.25，实测值为743.54。
实施例26：制备化合物627
Figure PCTCN2019105086-appb-000040
按化合物3的合成方法制备，不同在于用中间体D-6代替中间体D-1，用原料F-10代替原料F-1，所得目标产物的纯度为99.6％，收率为73.3％。
元素分析结构(分子式C 54H 33NO 3)：理论值：C,87.19；H,4.47；N,1.88；O,6.45；测试值：C,87.18；H,4.48；N,1.88；O,6.46。ESI-MS(m/z)(M +)：理论值为743.25，实测值为743.56。
实施例27：制备化合物653
Figure PCTCN2019105086-appb-000041
按化合物3的合成方法制备，不同在于用中间体D-7代替中间体D-1，用原料F-21代替原料F-1，所得目标产物的纯度为99.9％，收率为79.2％。
元素分析结构(分子式C 54H 34N 2O 2)：理论值：C,87.31；H,4.61；N,3.77；O,4.31；测试值：C,87.32；H,4.62；N,3.75；O,4.31。ESI-MS(m/z)(M +)：理论值为742.26，实测值为742.59。
实施例28：制备化合物663
Figure PCTCN2019105086-appb-000042
按化合物3的合成方法制备，不同在于用中间体D-5代替中间体D-1，用原料F-22代替原料F-1，所得目标产物的纯度为99.6％，收率为75.4％。
元素分析结构(分子式C 54H 34N 2O 2)：理论值：C,87.31；H,4.61；N,3.77；O,4.31；测试值：C,87.33；H,4.63；N,3.74；O,4.30。ESI-MS(m/z)(M +)：理论值为742.26，实测值为742.61。
实施例29：制备化合物725
Figure PCTCN2019105086-appb-000043
按化合物3的合成方法制备，不同在于用中间体D-5代替中间体D-1，用原料F-23代替原料F-1，所得目标产物的纯度为99.7％，收率为78.0％。
元素分析结构(分子式C 53H 33N 3O 2)：理论值：C,85.58；H,4.47；N,5.65；O,4.30；测试值：C,85.57；H,4.48；N,5.64；O,4.31。ESI-MS(m/z)(M +)：理论值为743.26，实测值为743.63。
本发明的有机化合物在发光器件中使用，可以作为空穴传输层材料，也可以作为电子阻挡层材 料使用。对本发明化合物分别进行热性能、HOMO能级、空穴迁移率、循环伏安稳定性的测试，检测结果如表3所示。
表3
Figure PCTCN2019105086-appb-000044
由上表数据可知，本发明的有机化合物具有不同的HOMO能级及良好的空穴迁移率，可应用于 不同的功能层，本发明以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的有机化合物具有较高的三线态能级及较高的热稳定性，使得所制作的含有本发明有机化合物的OLED器件效率和寿命均得到提升。
制备本发明的有机电致发光器件
以下通过器件实施例1-35和器件对比例1详细说明本发明合成的化合物在器件中作为空穴传输层材料或电子阻挡层材料的应用效果。器件实施例2-35、器件对比例1与器件实施例1相比，所述器件的制作工艺完全相同，并且所采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致。所不同的是对空穴传输层材料或电子阻挡层材料做了变换。各实施例所得器件的结构组成如表4所示。所得器件的测试结果见表5所示。
器件实施例1
透明基板层/ITO阳极层/空穴注入层(HAT-CN，厚度10nm)/空穴传输层(HT-1，厚度60nm)/电子阻挡层(化合物3，厚度20nm)/发光层(GH1、GH2和GD-1按照45:45:10的重量比混掺，厚度40nm)/空穴阻挡/电子传输层(ET-1和Liq，按照1:1的重量比混掺，厚度40nm)/电子注入层(LiF，厚度1nm)/阴极层(Mg和Ag，按照9:1的重量比混掺，厚度15nm)/CPL层(化合物CP-1，厚度70nm)。
具体制备过程如下：
如图1所示，透明基板层1为透明基材，如透明PI膜、玻璃等。对ITO阳极层2(膜厚为150nm)进行洗涤，即依次进行碱洗涤、纯水洗涤、干燥，再进行紫外线-臭氧洗涤以清除透明ITO表面的有机残留物。在进行了上述洗涤之后的ITO阳极层2上，利用真空蒸镀装置，蒸镀膜厚为10nm的HAT-CN作为空穴注入层3使用。接着蒸镀60nm厚度的HT-1作为空穴传输层。随后蒸镀20nm厚度的化合物3作为电子阻挡层。上述空穴传输材料蒸镀结束后，制作OLED发光器件的发光层6，其结构包括OLED发光层6所使用GH1、GH2作为主体材料，GD-1作为掺杂材料，掺杂材料掺杂比例为10％重量比，发光层膜厚为40nm。在上述发光层6之后，继续真空蒸镀电子传输层材料为ET-1和Liq。该材料的真空蒸镀膜厚为40nm，此层为空穴阻挡/电子传输层7。在空穴阻挡/电子传输层7上，通过真空蒸镀装置，制作膜厚为1nm的氟化锂(LiF)层，此层为电子注入层8。在电子注入层8上，通过真空蒸镀装置，制作膜厚为15nm的Mg：Ag电极层，此层为阴极层9使用。在阴极层9上，真空蒸镀70nm的CP-1，作为CPL层10。如上所述地完成OLED发光器件后，用公知的驱动电路将阳极和阴极连接起来，测量器件的电流效率以及器件的寿命。
表4
Figure PCTCN2019105086-appb-000045
Figure PCTCN2019105086-appb-000046
Figure PCTCN2019105086-appb-000047
注：*代表器件对比例
表5
Figure PCTCN2019105086-appb-000048
Figure PCTCN2019105086-appb-000049
注：*代表对比例
LT97指的是在电流密度为20mA/cm 2情况下，器件亮度衰减到97％所用时间；
寿命测试系统为韩国脉科学M6000型OLED器件寿命测试仪。
由表5的结果可以看出本发明所述化合物可应用于OLED发光器件制作，并且与对比例1相比，无论是效率还是寿命均获得较大改观，特别是器件的驱动寿命获得较大的提升。
从实施例所提供的测试数据来看，本发明化合物作为空穴传输层材料在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。进一步的本发明材料制备的OLED器件在低温及高温下工作时效率也比较稳定，将器件实施例7、24、35和器件对比例1在-10～80℃区间进行效率测试，所得结果如表6和图2所示。
表6
Figure PCTCN2019105086-appb-000050
从表6和图2的数据可知，器件实施例7、24、35为本发明材料和已知材料搭配的器件结构，和器件对比例1相比，不仅低温效率高，而且在温度升高过程中，效率平稳升高。
为进一步测试本发明化合物所产生的有益效果，将本发明器件实施例7和器件对比例1所制作器件进行反向电压的漏电流测试，测试数据如图3所示。从图3中可得知，应用本发明化合物的器件实施例7和器件对比例1所制作器件相比，漏电流很小，且电流曲线稳定，因此，本发明材料应用于器件制作后，具有较长使用寿命。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

  1. 一种以苯并[1,2-b:5,4-b']二苯并呋喃为核心的化合物，其特征在于，该化合物的结构如通式(1)所示：
    Figure PCTCN2019105086-appb-100001
    通式(1)中，L表示为单键、取代或未取代的C 6-30亚芳基、含有一个或多个杂原子取代或未取代的5～30元亚杂芳基；
    Ar 1、Ar 2各自独立的表示为-A-R；A表示为单键、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的亚吡啶基、取代或未取代的亚联苯基、取代或未取代的亚苯并呋喃基、取代或未取代的亚苯并噻吩基；R每次出现相同或不同的表示为取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的联苯基、取代或未取代的萘基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的芘基、取代或未取代的二苯基胺基、通式(2)或通式(3)所示结构中的一种；当A表示为单键时，Ar 1、Ar 2不同时表示为苯基或9,9-二甲基芴基；当R表示为通式(3)所示结构式时，A不表示为单键；
    Figure PCTCN2019105086-appb-100002
    通式(2)、通式(3)中，X 1、X 2、X 3分别独立地表示为-O-、-S-、-C(R 1)(R 2)-、-N(R 3)-或-Si(R 4)(R 5)-；X 2、X 3还可以表示为单键；
    Z每次出现时相同或不同地表示为C-R 6或N；
    通式(2)中与基团A键合的Z表示为碳原子；
    所述R 1～R 5分别独立地表示为C 1-20的烷基、取代或未取代的C 6-30芳基、含有一个或多个杂原子的取代或未取代的5～30元杂芳基中的一种；R 1与R 2、R 4与R 5还可相互连接成环；
    所述R 6表示为氢原子、卤素、氰基、C 1-20的烷基、C 1-20的烯烃基、取代或未取代的C 6-30芳基、含有一个或多个杂原子的取代或未取代的5～30元杂芳基中的一种；相邻两个或多个R 6还可相互键结成环；
    取代上述可被取代基团的取代基选自卤素、氰基、C 1-20的烷基、C 1-20的烯烃基、C 6-30芳基、含有一个或多个杂原子的5～30元杂芳基中的一种或多种；
    所述杂原子选自氧原子、硫原子或氮原子。
  2. 根据权利要求1所述的化合物，其特征在于，所述化合物的结构如通式(4)～(7)中的任一种所示：
    Figure PCTCN2019105086-appb-100003
    Figure PCTCN2019105086-appb-100004
  3. 根据权利要求1所述的一种以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物，其特征在于，所述R 1～R 5分别独立地表示为甲基、乙基、丙基、异丙基、叔丁基、戊基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的联苯基、取代或未取代的吡啶基；
    所述R 6表示为氢原子、氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、戊基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的联苯基、取代或未取代的吡啶基；
    所述取代基选自氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、戊基、苯基、萘基、联苯基、吡啶基、呋喃基、咔唑基或噻吩基中的一种或多种。
  4. 根据权利要求1所述的一种以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物，其特征在于，所述通式(1)的具体化合物为：
    Figure PCTCN2019105086-appb-100005
    Figure PCTCN2019105086-appb-100006
    Figure PCTCN2019105086-appb-100007
    Figure PCTCN2019105086-appb-100008
    Figure PCTCN2019105086-appb-100009
    中的任意一种。
  5. 一种有机电致发光器件，其特征在于，至少一层功能层含有权利要求1-6任一项所述的以苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物。
  6. 根据权利要求8所述的一种有机电致发光器件，包括空穴传输层和/或电子阻挡层，其特征在于，所述空穴传输层材料和/或电子阻挡层材料为所述苯并[1,2-b:5,4-b’]二苯并呋喃为核心的化合物。
  7. 一种照明或显示元件，其特征在于，包括如权利要求8-9所述的有机电致发光器件。
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