WO2022078434A1 - 有机化合物及其在光电领域的应用 - Google Patents

有机化合物及其在光电领域的应用 Download PDF

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WO2022078434A1
WO2022078434A1 PCT/CN2021/123763 CN2021123763W WO2022078434A1 WO 2022078434 A1 WO2022078434 A1 WO 2022078434A1 CN 2021123763 W CN2021123763 W CN 2021123763W WO 2022078434 A1 WO2022078434 A1 WO 2022078434A1
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group
groups
compound
atoms
organic
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PCT/CN2021/123763
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English (en)
French (fr)
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潘君友
陈翔
黄宏
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浙江光昊光电科技有限公司
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Priority to CN202180069478.8A priority Critical patent/CN116391007A/zh
Publication of WO2022078434A1 publication Critical patent/WO2022078434A1/zh
Priority to US18/300,811 priority patent/US20230255112A1/en

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    • 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
    • H10K85/658—Organoboranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • the present invention relates to the field of organic optoelectronic materials and technologies, in particular to an organic compound, a composition, and its application in the optoelectronic field.
  • the display device made of the red, green and blue three primary colors of light with narrow half-peak width has a large color gamut, a real picture and good picture quality.
  • the display device actively emits light of three primary colors of red, green and blue, typically such as RGB-OLED display; the current mature technology is to use a fine metal mask It is difficult to achieve high-resolution display of more than 600ppi by vacuum evaporation to produce three-color light-emitting devices.
  • the second is to use a color converter to convert a single color light emitted by a light-emitting device into multiple color lights to achieve full-color display, such as Samsung's blue OLED plus red and green quantum dot (QD) films as color converters.
  • QD quantum dot
  • the light-emitting device in this method has a simple process and high yield, and the color converter can be realized by different technologies such as evaporation, inkjet printing, transfer printing, photolithography, etc., and can be applied to display products with different resolution requirements.
  • the resolution can reach more than 3000ppi.
  • inorganic nanocrystals commonly known as quantum dots
  • quantum dots are a class of inorganic semiconductor materials (InP, CdSe, CdS, ZnSe, etc.) with a diameter of 2-8 nm.
  • InP, CdSe, CdS, ZnSe, etc. with a diameter of 2-8 nm.
  • nanoparticles due to the size effect, such materials exhibit quantum confinement effect, they will emit light of a specific frequency, and the frequency of the emitted light will change with the size, so by adjusting their size, You can control the color of the light it emits.
  • the half-peak width of the luminescence peak of Cd-containing quantum dots is currently 25-40nm, the color purity can meet the display requirements of NTSC, and the half-peak width of Cd-free quantum dots is between 35-75nm .
  • Cd pollutes the environment and has serious toxic effects on human health most countries prohibit the use of Cd-containing quantum dots to make electronic products.
  • the extinction coefficient of inorganic quantum dots is generally low, requiring a thicker film, typically a film of more than 10 microns to achieve complete absorption of blue light. The plan is a big challenge.
  • the second is organic dyes, including a variety of organic conjugated small molecules with chromophores.
  • the extinction coefficient of such organic dyes is generally high, but due to the thermal relaxation in the molecule, and the vibrational energy in the organic molecule is relatively high. Large, the luminescence peak of such materials is wider, and the half-peak width is generally more than 60 nm; in addition, color converters or thin films are generally prepared by solution processing, and the currently commonly used organic conjugated systems are relatively rigid, and their solubility in organic solvents Limited and therefore poor processability, difficult to use in the preparation of blue light plus color converter displays.
  • organic materials can be further improved, a class of organic materials with narrow emission half-peak widths, high solubility and good processing performance can be provided as color conversion films, which can solve the problem of current blue OLED plus red and green quantum dots.
  • the technical difficulty is to achieve a display with a high color gamut.
  • the object of the present invention is to provide an organic compound and its application in optoelectronic devices.
  • the present invention provides a compound comprising the structural unit represented by (1) or (2),
  • Ar 1 to Ar 3 are selected from aromatic or heteroaromatic having 5-24 ring atoms;
  • Ar 4 to Ar 5 are selected from empty or aromatic or heteroaromatic with 5-24 ring atoms;
  • X 1 , X 2 are empty or a bridging group
  • R 1 to R 10 may be the same or different selected substituents independently selected from H, D, -F, -Cl, Br, I, -CN, -NO 2 , -CF 3 , and have 1 to 20 C atoms straight-chain alkyl, haloalkyl, alkoxy, thioalkoxy groups, or branched or cyclic alkyl, haloalkyl, alkoxy, thioalkane groups having 3 to 20 C atoms
  • the compound contains at least one alcohol-soluble or water-soluble group.
  • the present invention also provides a composition comprising at least one of said organic compounds, at least one organic solvent, and/or one organic resin.
  • the present invention also provides an organic functional material thin film, which is prepared by using the above-mentioned organic compound.
  • the present invention also provides an optoelectronic device comprising the above compound or organic functional material thin film.
  • Beneficial effects according to an organic compound of the present invention, it has a large solubility in a solvent, especially an alcohol solvent, which is convenient for preparing ink for printing or coating process, and is environmentally friendly; The peak width and large extinction coefficient facilitate the preparation of thin color converters for realizing displays with high color gamut.
  • host material In the present invention, host material, matrix material, Host material and Matrix material have the same meaning and can be interchanged.
  • metal organic complexes metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and can be interchanged.
  • composition printing ink, ink, and ink have the same meaning and are interchangeable.
  • the present invention provides a compound comprising a structural unit represented by chemical formula (1) or (2),
  • Ar 1 to Ar 3 are selected from aromatic or heteroaromatic having 5-24 ring atoms;
  • Ar 4 to Ar 5 are selected from empty or aromatic or heteroaromatic with 5-24 ring atoms;
  • X 1 , X 2 are empty or a bridging group
  • R 1 to R 10 may be the same or different selected substituents independently selected from H, D, -F, -Cl, Br, I, -CN, -NO 2 , -CF 3 , and have 1 to 20 C atoms straight-chain alkyl, haloalkyl, alkoxy, thioalkoxy groups, or branched or cyclic alkyl, haloalkyl, alkoxy, thioalkane groups having 3 to 20 C atoms
  • the compound contains at least one alcohol-soluble or water-soluble group.
  • the compound contains at least two alcohol-soluble or water-soluble groups.
  • the compound contains at least three alcohol-soluble or water-soluble groups.
  • At least one of the bridging groups X 1 and X 2 is empty; it is particularly preferred that both of them are empty, in which case the compound is selected from the group consisting of the following chemical formula (1b) or ( 2b) or the structural unit shown:
  • At least one of X 1 and X 2 is a single bond; it is particularly preferred that both are single bonds, and the compound is selected from the compounds shown in the following chemical formula 1c) or (2c) The structural unit of:
  • X 1 and X 2 when X 1 and X 2 appear, the same or different are two-bridged groups, and the preferred two-bridged groups are:
  • R 3 , R 4 and R 5 are defined as R 1 as described above, and the dashed bond shown in the above group represents a bond bonded to an adjacent structural unit.
  • an aromatic ring system includes in the ring system carbon atoms, the heteroaromatic ring system contains in the ring system carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 4.
  • the heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S.
  • aromatic or heteroaromatic ring systems include not only systems of aryl or heteroaryl groups, but also systems in which multiple aryl or heteroaryl groups can also be interrupted by short non-aromatic units ( ⁇ 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Therefore, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diarylether, etc., are also considered to be aromatic ring systems for the purpose of this invention.
  • R 1 is as described above, preferably, (1) C1-C10 alkyl group, especially preferred Refers to the following groups: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl base, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2- Trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopenten
  • aromatic and heteroaromatic ring systems are taken to mean in particular biphenylene, terphenylene, fluorene, spirobifluorene, dihydrogen, in addition to the aryl and heteroaryl groups mentioned above. phenanthrene, tetrahydropyrene and cis- or trans-indenofluorene.
  • the compound according to formula (1)-(1e) or (2)-(2e), wherein Ar 1 to Ar 5 which are the same or different in each occurrence can be selected from having 5 to 20 Aromatic and heteroaromatic having 1 ring atoms; preferably selected from aromatic and heteroaromatic having 5 to 18 ring atoms; more preferably selected from aromatic and heteroaromatic having 5 to 15 ring atoms; most preferred is selected from aromatic and heteroaromatic having 5 to 10 ring atoms; they may be unsubstituted or substituted with one or two R 1 groups.
  • Preferred aryl or heteroaryl groups are benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene or thiophene.
  • Ar 1 to Ar 5 are selected from the following structural formulas:
  • X 3 is CR 6 or N
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 can be independently selected from one of the following chemical structural formulas or a combination thereof, which can be further optionally substituted:
  • Ar 1 to Ar 5 are phenyl groups.
  • the compounds according to the invention comprise structural units of formula (1a) or (2a) below:
  • X 1 and X 2 are preferably selected from O, S, particularly preferably from O.
  • the compounds according to the invention comprise structural units of formula (1d) or (2d) or (1e) or (2e):
  • X a in formulas (1d) and (1e) are the same or different and are independently selected from N(R 9 ), C(R 9 R 10 ), Si(R 9 R 10 ), O, S.
  • n 1 or 2 or 3 or 4.
  • the compound has the structure shown below:
  • R 21 -R 24 may be H, D, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 20 C atoms, or a branched or thioalkoxy group with 3 to 20 C atoms
  • triplet energy level (T1) and singlet energy level (S1), HOMO, LUMO play a key role.
  • S1 triplet energy level
  • S1 singlet energy level
  • HOMO HOMO
  • LUMO LUMO
  • HOMO and LUMO energy levels can be measured by the photoelectric effect, such as XPS (X-ray Photoelectron Spectroscopy) and UPS (Ultraviolet Photoelectron Spectroscopy) or by Cyclic Voltammetry (hereafter CV).
  • XPS X-ray Photoelectron Spectroscopy
  • UPS Ultraviolet Photoelectron Spectroscopy
  • CV Cyclic Voltammetry
  • the triplet energy level T1 of organic materials can be measured by low-temperature time-resolved luminescence spectroscopy, or obtained by quantum simulation calculations (such as by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian Inc.).
  • the singlet energy level S1 of organic materials can be determined by absorption spectroscopy or emission spectroscopy, or obtained by quantum simulation calculations (such as Time-dependent DFT).
  • the absolute values of HOMO, LUMO, T1 and S1 depend on the measurement method or calculation method used, and even for the same method, different evaluation methods, such as onset and peak point on the CV curve, can give different HOMO /LUMO value. Therefore, reasonably meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, T1 and S1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
  • compounds according to the invention have (S1-T1) ⁇ 0.30 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.20 eV, more preferably ⁇ 0.15 eV, most preferably ⁇ 0.10eV.
  • the alcohol-soluble or water-soluble group is selected from: alcohols, aldehydes, acids, crown ethers, polyethers, primary amines, etc. group.
  • the alcohol-soluble or water-soluble group is selected from the structure shown below:
  • R 31 -R 37 may be straight-chain alkyl, alkoxy or thioalkoxy groups having 1 to 20 C atoms, or branched or cyclic alkyl groups having 3 to 20 C atoms
  • the dashed line represents the bonded bond, and t is an integer greater than zero.
  • the individual H atoms or CH 2 groups in the present invention may be substituted by the above-mentioned groups or groups R, where R is selected from alkyl groups having 1 to 40 C atoms, preferably selected from the following groups Group: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, methylbutyl, n-pentyl, sec Pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, ethylhexyl, trifluoromethyl, pentafluoroethyl, trifluoroethyl, vinyl , propenyl, butenyl, pentenyl,
  • compounds according to the present invention wherein the total amount of SP3 -hybridized groups does not exceed 50% of the total molecular weight, more preferably not more than 30%, most preferably not more than 20%.
  • the existence of fewer SP 3 hybrid groups can effectively ensure the thermal stability of the compound, thereby ensuring the stability of the device.
  • the total amount of SP 3 hybridized groups exceeds 20% of the total molecular weight, preferably more than 30% , better than 40%, preferably more than 50%.
  • the photoluminescence spectral line of the compound has a full width at half maximum (FWHM) ⁇ 50 nm, preferably ⁇ 45 nm, more preferably ⁇ 40 nm, especially good ⁇ 35 nm, most preferably ⁇ 30nm.
  • FWHM full width at half maximum
  • the present invention also relates to a method for synthesizing a compound according to formula (1) or (2), wherein the reaction is carried out using a starting material containing a reactive group.
  • These reactive materials contain at least one leaving group, for example, bromine, iodine, boronic acid or boronic acid ester.
  • Suitable reactions to form C-C linkages are well known to those skilled in the art and are described in the literature, particularly suitable and preferred coupling reactions are the SUZUKI, STILLE, Hartwig and HECK coupling reactions.
  • the present invention also provides a mixture comprising at least one compound as described above and another organic functional material, wherein the other organic functional material can be used for hole (also called hole) injection or transport Materials (HIM/HTM), Hole Blocking Materials (HBM), Electron Injection or Transport Materials (EIM/ETM), Electron Blocking Materials (EBM), Organic Host Materials (Host), Singlet Emitters (Fluorescent Emitters) , triplet emitters (phosphorescence emitters), thermally excited delayed fluorescent materials (TADF materials) and organic dyes.
  • hole also called hole injection or transport Materials
  • HBM Hole Blocking Materials
  • EIM/ETM Electron Injection or Transport Materials
  • EBM Electron Blocking Materials
  • Organic Host Materials Host
  • Singlet Emitters Fluorescent Emitters
  • triplet emitters phosphorescence emitters
  • TADF materials thermally excited delayed fluorescent materials
  • the mixture comprises an organic compound according to the invention, and a fluorescent host material (or singlet host material).
  • the organic compound according to the present invention can be used as a guest or an emitter, and its weight percentage is ⁇ 15wt%, preferably ⁇ 12wt%, more preferably ⁇ 9wt%, more preferably ⁇ 8wt%, most preferably ⁇ 7wt% .
  • the mixture comprises an organic compound according to the invention, another fluorescent emitter (or singlet emitter) and a fluorescent host material.
  • the organic compound according to the invention can be used as a co-luminescent material in a weight ratio of from 1:20 to 20:1 to another fluorescent emitter.
  • the fluorescent host material and fluorescent emitter are described in detail below.
  • Examples of the singlet host material are not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of an emitter, particularly a singlet emitter or a fluorescent emitter.
  • organic compound used as the singlet host material can be selected from the group consisting of ring-containing aromatic hydrocarbon compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, chrysene, perylene, Azulene; aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolecarbazole, pyridine Indole, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine,
  • the singlet host material can be selected from compounds comprising at least one of the following groups:
  • R 1 can be independently selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar 1 is aryl Or heteroaryl, which has the same meaning as Ar 1 defined in the above-mentioned HTM;
  • n is an integer from 0 to 20;
  • X 1 -X 8 are selected from CH or N;
  • X 9 and X 10 are selected from CR 1 R 2 or NR 1 .
  • anthracene-based singlet host materials are listed in the table below:
  • the singlet emitter may be selected from the group consisting of monostyrylamines, di-styrylamines, tristyrylamines, tetrastyrylamines, styryl phosphines, styryl ethers and aromatic amines.
  • a monostyrylamine means a compound containing an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound containing two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a tristyrylamine refers to a compound containing three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound containing four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • Arylamine or aromatic amine refers to a compound containing three unsubstituted or substituted aromatic or heterocyclic ring systems directly attached to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic drolidines and aromatic dridodiamines.
  • aromatic anthraceneamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably in the 9 position.
  • aromatic anthracene diamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably in the 9,10 positions.
  • Aromatic pyreneamines, aromatic pyrene diamines, aryl pyrene amines, and aryl pyrene diamines are similarly defined, with the divalent arylamine group preferably attached to the 1 or 1,6 position of the pyrene.
  • Further preferred singlet emitters can be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindenofluorene-amines and benzoindenofluorene-diamines , as disclosed in WO 2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.
  • polycyclic aromatic hydrocarbon compounds especially derivatives of the following compounds: anthracene such as 9,10-bis(2-naphthanthracene), naphthalene, tetraphenyl, xanthene, phenanthrene , Pyrene (such as 2,5,8,11-tetra-t-butylperylene), indenopyrene, phenylene such as (4,4'-bis(9-ethyl-3-carbazole vinyl)-1 ,1'-biphenyl), bisindenopyrene, decacycloene, hexabenzone, fluorene, spirobifluorene, arylpyrene (such as US20060222886), arylene vinylene (such as US5121029, US5130603), cyclopentadiene Alkenes such as tetraphenylcyclopentadiene, rubrene, coumarin,
  • anthracene such as 9,10
  • the present invention also provides a composition comprising at least one compound of the present invention, at least one organic solvent, and/or one organic resin.
  • the composition comprises one organic resin; in other embodiments, two or more organic resins; in other embodiments, three or more organic resins.
  • the organic resin refers to a resin prepolymer or a resin formed after crosslinking or curing thereof.
  • Organic resins suitable for the present invention include but are not limited to: polystyrene, polyacrylate, polymethacrylate, polycarbonate, polyurethane, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polybutene, Polyethylene glycol, polysiloxane, polyacrylate, epoxy resin, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride (PVDC), polystyrene-acrylonitrile (SAN), polyterephthalic acid Butylene Glycol (PBT), Polyethylene Terephthalate (PET), Polyvinyl Butyrate (PVB), Polyvinyl Chloride (PVC), Polyamide, Polyoxymethylene, Polyimide, Polyether imide or mixtures thereof.
  • organic resins suitable for the present invention include, but are not limited to, the following monomers (resin prepolymers) formed by homopolymerization or copolymerization: styrene derivatives, acrylate derivatives, acrylonitrile derivatives, acrylamide derivatives, Vinyl ester derivatives, vinyl ether derivatives, maleimide derivatives, conjugated diene derivatives.
  • styrene derivatives are: alkylstyrenes such as ⁇ -methylstyrene, o-, m-, p-methylstyrene, p-butylstyrene, especially p-tert-butylstyrene, alkane Oxystyrene such as p-methoxystyrene, p-butoxystyrene, p-tert-butoxystyrene.
  • alkylstyrenes such as ⁇ -methylstyrene, o-, m-, p-methylstyrene, p-butylstyrene, especially p-tert-butylstyrene, alkane Oxystyrene such as p-methoxystyrene, p-butoxystyrene, p-tert-butoxystyrene.
  • acrylate derivatives are: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate ester, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate -Hydroxybutyl, 2-hydroxybutyl methacrylate, 3-hydroxyprop
  • acrylonitrile derivatives are: acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile and vinylidene cyano;
  • acrylamide derivatives are: acrylamide, methacrylamide, alpha-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethylmethacrylamide;
  • vinyl ester derivatives are: vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;
  • vinyl ether derivatives are: vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;
  • maleimide derivatives are: maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide;
  • conjugated diene derivatives are: 1,3-butadiene, isoprene and chloroprene;
  • Said homopolymers or copolymers can be prepared, for example, by free radical polymerization, cationic polymerization, anionic polymerization or organometallic catalyzed polymerization (eg Ziegler-Natta catalysis).
  • the polymerization process can be suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization.
  • Said organic resin generally has an average molar mass Mn (determined by GPC) of 10 000-1 000 000 g/mol, preferably 20 000-750 000 g/mol, more preferably 30 000-500 000 g/mol.
  • the organic resin is a thermosetting resin or an ultraviolet (UV) curable resin. In some embodiments, the organic resin is cured in a method that will facilitate roll-to-roll processing.
  • UV ultraviolet
  • thermosetting resin is epoxy resin, phenolic resin, vinyl resin, melamine resin, urea-formaldehyde resin, unsaturated polyester resin, polyurethane resin, allyl resin, acrylic resin, polyamide resin, polyamide - imide resins, phenolamine polycondensation resins, urea melamine polycondensation resins or combinations thereof.
  • the thermoset resin is an epoxy resin. Epoxies cure easily and do not emit volatiles or by-products from a wide range of chemicals. Epoxies are also compatible with most substrates and tend to wet surfaces easily. See Boyle, M.A. et al., "Epoxy Resins", Composites, Vol. 21, ASM Handbook, pages 78-89 (2001).
  • the organic resin is a silicone thermoset resin.
  • the silicone thermoset resin is OE6630A or OE6630B (Dow Corning Corporation (Auburn, MI)).
  • the composition comprises one solvent; in other embodiments, two or more solvents; in other embodiments, three or more solvents.
  • the composition according to the present invention is a solution.
  • composition according to the invention is a suspension.
  • composition in the embodiments of the present invention may include 0.01 to 20 wt % of organic compounds, preferably 0.1 to 20 wt %, more preferably 0.2 to 20 wt %, and most preferably 1 to 15 wt % of organic compounds.
  • the color conversion layer can be formed by methods such as inkjet printing, transfer printing, photolithography, etc.
  • the color conversion material of the present invention needs to be dissolved in an organic solvent alone or together with other materials to form ink.
  • the mass concentration of the color conversion material of the present invention in the ink is not less than 0.1% wt.
  • the color conversion capability of the color conversion layer can be improved by adjusting the concentration of the color conversion material in the ink and the thickness of the color conversion layer. In general, the higher the concentration or thickness of the color conversion material, the higher the color conversion rate of the color conversion layer.
  • materials that can be added to the ink include but are not limited to the following materials: polyethylene, polypropylene, polystyrene, polycarbonate, polyacrylate, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyethylene glycol, Polysiloxane, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polyvinyl butyrate, polyamide, polyoxymethylene , polyimide, polyetheretherketone, polysulfone, polyarylene ether, polyaramid, cellulose, modified cellulose, cellulose acetate, cellulose nitrate or a mixture of the above materials.
  • the solvent is selected from the group consisting of esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, or inorganic ester compounds such as boronic esters or phosphate esters, or two and two A mixture of more than one solvent.
  • suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, glycols or polyols.
  • alcohols represent the appropriate class of solvents.
  • Preferred alcohols include alkylcyclohexanols, especially methylated aliphatic alcohols, naphthols, and the like.
  • Suitable alcoholic solvents are: dodecanol, phenyltridecanol, benzyl alcohol, ethylene glycol, ethylene glycol methyl ether, glycerol, propylene glycol, propylene glycol ethyl ether, and the like.
  • Said solvent can be used alone or as a mixture of two or more organic solvents.
  • the composition according to the present invention comprises one organic functional compound as described above and at least one organic solvent, and may further comprise another organic solvent.
  • the other organic solvent include (but not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-dichlorobenzene Toluene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-Tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, de
  • a composition according to the present invention wherein said further organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic aliphatic ether, alicyclic or olefin compounds, or inorganic ester compounds such as borate ester or phosphoric acid ester, or a mixture of two or more solvents.
  • said further organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic aliphatic ether, alicyclic or olefin compounds, or inorganic ester compounds such as borate ester or phosphoric acid ester, or a mixture of two or more solvents.
  • aromatic or heteroaromatic based solvents are, but are not limited to: 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropyl Benzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-cymene, dipentylbenzene, o-diethylbenzene, m- Diethylbenzene, p-diethylbenzene, 1,2,3,4-tetratoluene, 1,2,3,5-tetratoluene, 1,2,4,5-tetratoluene, butylbenzene, dodecylbenzene , 1-methylnaphthalene, 1,2,4-trichloro
  • another suitable and preferred organic solvent is aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers.
  • Said other organic solvent may be a naphthenic hydrocarbon such as decalin.
  • a composition according to the present invention comprises at least 50wt% alcohol solvent; preferably at least 80wt% alcohol solvent; particularly preferably at least 90wt% alcohol solvent.
  • solvents particularly suitable for the present invention are those having a Hansen solubility parameter in the following range:
  • ⁇ d (dispersion force) is in the range of 17.0 ⁇ 23.2MPa 1/2 , especially in the range of 18.5 ⁇ 21.0MPa 1/2 ;
  • ⁇ p (polar force) is in the range of 0.2 to 12.5MPa 1/2 , especially in the range of 2.0 to 6.0MPa 1/2 ;
  • ⁇ h (hydrogen bonding force) is in the range of 0.9 to 14.2 MPa 1/2 , especially in the range of 2.0 to 6.0 MPa 1/2 .
  • the boiling point parameter of the organic solvent should be taken into consideration when selecting the organic solvent.
  • the boiling point of the organic solvent is ⁇ 150°C; preferably ⁇ 180°C; more preferably ⁇ 200°C; more preferably ⁇ 250°C; most preferably ⁇ 275°C or ⁇ 300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging of ink jet print heads.
  • the organic solvent can be evaporated from the solvent system to form a thin film containing functional materials.
  • composition according to the present invention is characterized by
  • the organic solvent is selected taking into account its surface tension parameter.
  • Appropriate ink surface tension parameters are suitable for specific substrates and specific printing methods.
  • the surface tension of the organic solvent at 25°C is in the range of about 19 dyne/cm to 50 dyne/cm; more preferably in the range of 22 dyne/cm to 35 dyne/cm; The optimum is in the range of 25 dyne/cm to 33 dyne/cm.
  • the surface tension of the ink according to the present invention at 25°C is about 19 dyne/cm to 50 dyne/cm; more preferably 22 dyne/cm to 35 dyne/cm; most preferably 25 dyne/cm cm to 33dyne/cm range.
  • the organic solvent is selected in consideration of the viscosity parameter of its ink.
  • the viscosity can be adjusted by different methods, such as through the selection of suitable organic solvents and the concentration of functional materials in the ink.
  • the viscosity of the organic solvent is less than 100 cps; more preferably, less than 50 cps; and most preferably, 1.5 to 20 cps.
  • the viscosity here refers to the viscosity at the ambient temperature during printing, which is generally 15-30°C, preferably 18-28°C, more preferably 20-25°C, and most preferably 23-25°C. Compositions so formulated would be particularly suitable for ink jet printing.
  • the composition according to the present invention has a viscosity at 25°C in the range of about 1 cps to 100 cps; more preferably in the range of 1 cps to 50 cps; most preferably in the range of 1.5 cps to 20 cps.
  • the ink obtained from the organic solvent satisfying the above-mentioned boiling point and surface tension parameters and viscosity parameters can form a functional material film with uniform thickness and composition properties.
  • Salt compounds are not easy to purify, easily bring impurities, and affect the photoelectric performance.
  • the above-described compositions or mixtures do not contain any salt compounds, and preferably do not contain any organic acid salts formed from organic acids and metals.
  • the present invention preferentially excludes organic acid salts containing transition metals and lanthanides.
  • the present invention further provides an organic functional material thin film, comprising an organic compound or mixture as described above.
  • the organic functional material thin film is prepared by using a composition as described above.
  • the present invention also provides a method for preparing the organic functional material film, comprising the following steps:
  • the method of printing or coating is selected from ink jet printing, jet printing (Nozzle Printing), letterpress printing, silk screen Printing, dip coating, spin coating, blade coating, roll printing, twist roll printing, offset printing, flexographic printing, rotary printing, spray coating, brush coating or pad printing, slot extrusion coating;
  • the thickness of the organic functional material film is generally 50 nm-200 ⁇ m, preferably 100 nm-150 ⁇ m, more preferably 500 nm-100 ⁇ m, more preferably 1 ⁇ m-50 ⁇ m, and most preferably 1 ⁇ m-20 ⁇ m.
  • the thickness of the organic functional material film is between 20nm-20 ⁇ m, preferably less than 15 ⁇ m, more preferably less than 10 ⁇ m, more preferably less than 8 ⁇ m, particularly preferably less than 6 ⁇ m, Preferably it is less than 4 ⁇ m, most preferably less than 2 ⁇ m.
  • Another object of the present invention is to provide the application of the above organic compounds and mixtures thereof in optoelectronic devices.
  • the optoelectronic device may be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emission diodes (Organic Plasmon Emitting Diode).
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OFET organic field effect transistor
  • OFET organic light emitting field effect transistor
  • organic Lasers organic spintronic devices
  • organic sensors and organic plasmon emission diodes Organic Plasmon Emitting Diode
  • the present invention provides an optoelectronic device comprising one of the above-mentioned organic compounds or mixtures.
  • the optoelectronic device may be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emission diodes (Organic Plasmon Emitting Diode).
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OFET organic field effect transistor
  • OFET organic light emitting field effect transistor
  • organic Lasers organic spintronic devices
  • organic sensors and organic plasmon emission diodes Organic Plasmon Emitting Diode
  • the optoelectronic device is an electroluminescent device, such as an organic light emitting diode (OLED), an organic light emitting cell (OLEEC), an organic light emitting field effect transistor, a perovskite light emitting diode (PeLED), and a quantum dot light emitting diode ( QD-LED), wherein a functional layer contains one of the above-mentioned organic compounds or mixtures.
  • the functional layer can be selected from a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a light emitting layer, and a cathode passivation layer (CPL).
  • the optoelectronic device is an electroluminescent device, comprising two electrodes, and the functional layer is located on the same side of the two electrodes.
  • the optoelectronic device comprises a light-emitting unit and a color conversion layer, wherein the color conversion layer comprises one of the above-mentioned organic compounds or mixtures.
  • the light-emitting unit is selected from solid state light-emitting devices.
  • the solid state light-emitting device is preferably selected from LED, organic light-emitting diode (OLED), organic light-emitting cell (OLEEC), organic light-emitting field effect transistor, perovskite light-emitting diode (PeLED), and quantum dot light-emitting diode (QD-LED) .
  • the light-emitting unit emits blue light, which is converted into green light or red light by the color conversion layer.
  • the present invention further relates to a display, which includes at least three kinds of pixels of red, green and blue, the blue light pixel is enclosed with a blue light emitting unit, and the red and green light pixel includes a blue light emitting unit and a corresponding red and green color conversion layer.
  • Synthesis of compound 1 It was synthesized by classical SUZUKI reaction, and the specific synthesis steps were as follows: under nitrogen protection environment, 10.00 mmol of intermediate 1-1, 20.08 mmol of intermediate 1-2 and 20.00 mmol of potassium carbonate were added to 500 ml of the middle three in turn. Pour 200 ml of toluene into the flask, add 0.3 mol of catalyst Pd(PPh 3 ) 4 under stirring conditions, heat under reflux for the reaction, and follow the reaction by TLC.
  • the preparation method of the color conversion layer is as follows:
  • the present invention has also found that the compounds according to the present invention, i.e. compounds having one, especially two or more alcohol-soluble or water-soluble groups, have a solubility ( Especially in alcoholic solvents) and film-forming properties are good, so that higher quality films can be produced.

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Abstract

公开了一种包含至少一种化学式(1)或(2)结构单元的化合物，此化合物包含有一个醇溶性或水溶性基团；此化合物的光致发光光谱具有较窄的半峰宽，用其制作的颜色转换层可以吸收半峰宽较宽的入射光，然后发射出半峰宽较窄的出射光；所述的醇溶性或水溶性基团使得所述的化合物便于在绿色环保的溶剂中溶解，形成印刷墨水；而且该化合物的光致发光光谱的波峰位置可以通过修饰其分子结构来调节，用不同化学结构的化合物可以制备出不同类型的颜色转换层，能够分别发射不同颜色的光谱。这些不同颜色的窄半峰宽发光器件可以制造具有高色域的显示器件。

Description

有机化合物及其在光电领域的应用 技术领域
本发明涉及有机光电材料及技术领域，特别是涉及一种有机化合物，及组合物，及其在光电领域的应用。
背景技术
根据色度学原理，射入人眼的光的半峰宽越窄，色纯度越高，颜色越鲜艳。用这种半峰宽窄的红绿蓝三原色光制作的显示装置，显示的色域大，画面真实，画质好。
当前主流的全彩显示实现的方法不外乎两种，第一种，显示器件主动发射红、绿、蓝三原色的光，典型的如RGB-OLED显示；目前成熟的技术是利用精细金属掩膜的真空蒸镀制作三种颜色的发光器件，工艺复杂，成本高，难以实现超过600ppi的高分辨率显示。第二种是采用色转换器将发光器件发射的单一色光转换成多种色光，从而实现全彩显示，如三星公司的蓝光OLED加红绿量子点(QD)薄膜作为颜色转换器。这种方法中的发光器件工艺简单，良率高，而且颜色转换器可以通过蒸镀、喷墨打印、转印、光刻等不同技术实现，可以应用在不同分辨率要求的显示产品上，低如大尺寸电视，只有50ppi,高如硅基微型显示，分辨率可达3000ppi以上。
目前主流的颜色转换器中使用的颜色转换材料主要有两种，一种是无机纳米晶，俗称量子点，是一类直径介于2-8nm的无机半导体材料(InP,CdSe,CdS,ZnSe等)的纳米颗粒，由于尺寸效应，这类材料表现出量子限域效应，它们便会发出特定频率的光，而且发出的光的频率会随着尺寸的改变而变化，因而通过调节他们的尺寸就可以控制其发出的光的颜色。限于当前的量子点合成和分离技术，目前含Cd的量子点发光峰的半峰宽在25-40nm，色纯度可以满足NTSC的显示要求，无Cd量子点的半峰宽在35-75nm之间。然而，由于Cd对环境有污染，对人类健康有严重毒害作用，绝大多数国家禁止使用含Cd量子点制作电子产品。另外无机量子点的消光系数普遍较低，需要较厚的膜，典型10微米以上的膜才能实现蓝光的完全吸收，这对量产工艺，特别是三星公司的蓝光OLED加红绿量子点的技术方案是个很大的挑战。第二种是有机染料，包括各种具有生色团的有机共轭小分子，此类有机染料的消光系数普遍较高，但由于存在分子内的热弛豫，且有机分子中的振动能较大，这类材料的发光峰较宽，一般半峰宽在60nm以上；另颜色转换器或薄膜一般用溶液加工的方法制备，目前常用的有机共轭系统相对比较刚性，在有机溶剂中的溶解度有限，因此加工性不佳，难用于蓝光加颜色转换器的显示器的制备中。
因此，若能进一步改进有机材料，提供一类具有较窄发光半峰宽同时有具有较高溶解度和较好加工性能的有机材料，作为颜色转换膜，可以解决当前蓝光OLED加红绿量子点的技术难点，实现高色域的显示器。
发明内容
基于此，本发明的目的是提供一种有机化合物及其在光电器件中的应用。
具体技术方案如下：
本发明提供一种包含有(1)或(2)所示的结构单元的化合物，
Figure PCTCN2021123763-appb-000001
其中使用的符号与标记具有以下含义：
Ar 1～Ar 3相同或不同的选自具有5-24个环原子的芳香族或杂芳香族；
Ar 4～Ar 5相同或不同的选自空或具有5-24个环原子的芳香族或杂芳香族；
当Ar 4～Ar 5不为空时，X a，X b选自N、C(R 9)、Si(R 9)；Y a，Y b选自B、P＝O、C(R 9)、Si(R 9)；
当Ar 4～Ar 5为空时，相应的X a或Y b选自N(R 9)、C(R 9R 10)、Si(R 9R 10)、C＝O、O、C＝N(R 9)、C＝C(R 9R 10)、P(R 9)、P(＝O)R 9、S、S＝O或SO 2；
X 1、X 2是空或一个桥接基团；
R 1～R 10可相同或不同的选自取代基分别独立选自H、D、-F,-Cl,Br,I,-CN,-NO 2,-CF 3,具有1至20个C原子的直链的烷基、卤代烷基、烷氧基、硫代烷氧基基团，或者具有3至20个C原子的支链或环状的烷基、卤代烷基、烷氧基、硫代烷氧基基团或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或具有5至40个环原子的芳胺基或杂芳胺基基团，以上取代基任意位置的二取代单元或这些体系的组合，其中一个或多个取代基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
其特征在于：所述的化合物包含至少一个醇溶性或水溶性基团。
本发明还提供一种组合物，包含至少一种所述的有机化合物，至少一种有机溶剂，和/或一种有机树脂。
本发明还提供一种有机功能材料薄膜，利用如上所述的有机化合物制备而成。
本发明还提供一种光电器件，包含一种如上所述的化合物或有机功能材料薄膜。有益效果：按照本发明的一种有机化合物，在溶剂中，特别是醇类溶剂中具有较大的溶解度，便于制备用于印刷或涂布工艺的油墨，绿色环保；且具有较窄的发光半峰宽和较大的消光系数，便于制备厚度较薄的颜色转换器，用于实现具有高色域的显示器。
具体实施方式
本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多 个相关的所列项目的任意的和所有的组合。
在本发明中，主体材料、基质材料、Host材料和Matrix材料具有相同的含义，可以互换。
在本发明中，金属有机络合物，金属有机配合物，有机金属配合物具有相同的含义，可以互换。
在本发明中，组合物、印刷油墨、油墨、和墨水具有相同的含义，可以互换。
本发明提供一种包含有化学式(1)或(2)所示的结构单元的化合物，
Figure PCTCN2021123763-appb-000002
其中使用的符号与标记具有以下含义：
Ar 1～Ar 3相同或不同的选自具有5-24个环原子的芳香族或杂芳香族；
Ar 4～Ar 5相同或不同的选自空或具有5-24个环原子的芳香族或杂芳香族；
当Ar 4～Ar 5不为空时，X a，X b选自N、C(R 9)、Si(R 9)；Y a，Y b选自B、P＝O、C(R 9)、Si(R 9)；
当Ar 4～Ar 5为空时，相应的X a或Y b选自N(R 9)、C(R 9R 10)、Si(R 9R 10)、C＝O、O、C＝N(R 9)、C＝C(R 9R 10)、P(R 9)、P(＝O)R 9、S、S＝O或SO 2；
X 1、X 2是空或一个桥接基团；
R 1～R 10可相同或不同的选自取代基分别独立选自H、D、-F,-Cl,Br,I,-CN,-NO 2,-CF 3,具有1至20个C原子的直链的烷基、卤代烷基、烷氧基、硫代烷氧基基团，或者具有3至20个C原子的支链或环状的烷基、卤代烷基、烷氧基、硫代烷氧基基团或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或具有5至40个环原子的芳胺基或杂芳胺基基团，以上取代基任意位置的二取代单元或这些体系的组合，其中一个或多个取代基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
其特征在于：所述的化合物包含至少一个醇溶性或水溶性基团。
优选地，R 1～R 10可相同或不同的选自取代基分别独立选自H、D，具有1至10个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有3至10个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，或具有1至10个C原子的取代的酮基基团，或具有2至10个C原子的烷氧基羰基基团，或具有7至10个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联 的基团或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团R 2可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一些较为优选的实施例中，所述的化合物包含至少两个醇溶性或水溶性基团。
在另一些较为优选的实施例中，所述的化合物包含至少三个醇溶性或水溶性基团。
在某些优选的实施例中，桥连基团X 1、X 2至少有一个是空；特别优选的是两个都为空，这时所述的化合物选自包含如下化学式(1b)或(2b)或所示的结构单元：
Figure PCTCN2021123763-appb-000003
在一些较为优选的实施例中，X 1、X 2至少有一个是单键；特别优先的是，两个都为单键，所述的化合物选自包含如下化学式1c)或(2c)所示的结构单元：
Figure PCTCN2021123763-appb-000004
在某些实施例中，X 1、X 2在每一次出现时，相同或不同的是二桥联基，优选的二桥联基有：
Figure PCTCN2021123763-appb-000005
Figure PCTCN2021123763-appb-000006
其中符号R 3、R 4与R 5定义同如上所述的R 1，而上述基团所示虚线键表示与相邻的结构单元键合的键。
对于本发明的目的，芳香环系在环系中包含
Figure PCTCN2021123763-appb-000007
个碳原子，杂芳香环系在环系中包含
Figure PCTCN2021123763-appb-000008
个碳原子和至少一个杂原子，条件是碳原子和杂原子的总数至少为4。杂原子优选选自Si、N、P、O、S和/或Ge，特别优选选自Si、N、P、O和/或S。对于本发明的目的，芳香族或杂芳香族环系不仅包括芳香基或杂芳香基的体系，而且，其中多个芳基或杂芳基也可以被短的非芳族单元间断(<10％的非H原子，优选小于5％的非H原子,比如C、N或O原子)。因此，比如9,9′-螺二芴，9,9-二芳基芴，三芳胺，二芳基醚等体系，对于该发明目的同样认为是芳香族环系。
对于本发明的目的，其中NH上的H原子或桥联基CH 2基团可以被R 1基团取代，R 1的定义如上所述，优选于，(1)C1～C10烷基，特别优选是指如下的基团：甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、2-甲基丁基、正戊基、正己基、环己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、三氟甲基、五氟甲基、2,2,2-三氟乙基、乙烯基、丙烯基、丁烯基、戊烯基、环戊烯基、己烯基、环己烯基、庚烯基、环庚烯基、辛烯基、环辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基和辛炔基；(2)
Figure PCTCN2021123763-appb-000009
烷氧基，特别优选的是指甲氧基，乙氧基，正丙氧基，异丙氧基，正丁氧基，异丁氧基，仲丁氧基，叔丁氧基或者2-甲基丁氧基；(3)C2到C10 芳基或杂芳基，取决于用途其可以是一价或二价的，在每一情况下也可以被上述提及的基团R 1取代并可以通过任何希望的位置与芳香族或杂芳香环连接，特别优选的是指以下的基团：苯、萘、蒽、嵌二萘、二氢芘、屈、茈、萤蒽、丁省、戊省、苯并芘、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、硫芴、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、吩噻嗪、吩恶嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、恶唑、苯并恶唑、萘并恶唑、蒽并恶唑、菲并恶唑、异恶唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、吡嗪、二氮蒽、1,5-二氮杂萘、氮咔唑、苯并咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-恶二唑、1,2,4-恶二唑、1,2,5-恶二唑、1,3,4-恶二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑。1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、中氮茚和苯并噻二唑。用于本发明的目的，芳香和杂芳族环系认为特别是除上述提及的芳基和杂芳基之外，还指亚联苯基、亚三联苯、芴、螺二芴、二氢菲、四氢芘和顺式或者反式茚并芴。
在一个优选的实施例中，按照化学式(1)-(1e)或(2)-(2e)的化合物，其中Ar 1～Ar 5相同或不同的在每一次出现中可选自具有5到20个环原子的芳香、杂芳族；较好的选自具有5到18个环原子的芳香、杂芳族；更好的选自具有5到15个环原子的芳香、杂芳族；最好的选自具有5到10个环原子的芳香、杂芳族；它们可以未被取代或者被一个或二个R 1基团取代。优选的芳基或者杂芳基有苯、萘、蒽、菲、吡啶、嵌二萘或噻吩。
在另一个优先的实施例中，Ar 1～Ar 5选自如下结构式：
Figure PCTCN2021123763-appb-000010
X 3是CR 6或N；
Y 7选自CR 7R 8，SiR 9R 10，NR 6或，C(＝O)，S，或O；R 6，R 7，R 8，R 9，R 10的定义如上所述
进一步，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5可独立选自如下化学结构式之一或其组合，其可进一步被任意取代：
Figure PCTCN2021123763-appb-000011
Figure PCTCN2021123763-appb-000012
对于本发明的目的，按化学式(1)或(2)的结构单元，在一个特别优选的实施例中，Ar 1～Ar 5为苯基。
在一个特别优先的实施例中，按照本发明的化合物包含如下化学式(1a)或(2a)所示的结构单元：
Figure PCTCN2021123763-appb-000013
其中，X 1和X 2优先选自O，S，特别优先选自O。
在另一个特别优先的实施例中，按照本发明的化合物包含如下化学式(1d)或(2d)或(1e)或(2e)所示的结构单元：
Figure PCTCN2021123763-appb-000014
优先的，化学式(2d)和(2e)中的Y b相同或不同的彼此独立的选自C＝O、O、P(＝O)R 9、S＝O或SO 2；特别优先的选自C＝O。
优先的，化学式(1d)和(1e)中的X a相同或不同的彼此独立的选自N(R 9)、C(R 9R 10)、Si(R 9R 10)、O、S。
在某些优选的实施例中，按照化学所(1)，(2)，(1a)-(1e),(2a)-(2e)的结构单元中，其中R 4～R 8在多次出现时，可相同或不同地包含以下结构单元或它们中的组合:
Figure PCTCN2021123763-appb-000015
Figure PCTCN2021123763-appb-000016
其中n是1或2或3或4。
在一个特别优选的实施方案中，所述的化合物具有以下所示的结构：
Figure PCTCN2021123763-appb-000017
其中，R 21-R 24可以是H、D，具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；且，R 21-R 24中至少一个包含一个醇溶性或水溶性基团。
m、n为0-4的整数；o、q为0-5的整数；p为0-3的整数。
优选地，R 21-R 24可以是H、D，具有1至10个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有3至10个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，或具有1至10个C原子的取代的酮基基团，或具有2至10个C原子的烷氧基羰基基团，或具有7至10个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联的基团或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团R 2可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在本发明实施例中，对于有机材料的能级结构，三线态能级(T1)及单线态能级(S1)、HOMO、LUMO、起着关键的作用。以下对这些能级的确定作一介绍。
HOMO和LUMO能级可以通过光电效应进行测量，例如XPS(X射线光电子光谱法)和UPS(紫外光电子能谱)或通过循环伏安法(以下简称CV)。最近，量子化学方法，例如密度泛函理论(以下简称DFT)，也成为行之有效的计算分子轨道能级的方法。
有机材料的三线态能级T1可通过低温时间分辨发光光谱来测量，或通过量子模拟计算(如通过Time-dependent DFT)得到，如通过商业软件Gaussian 03W(Gaussian Inc.)。
有机材料的单线态能级S1，可通过吸收光谱，或发射光谱来确定，也可通过量子模拟计算(如Time-dependent DFT)得到。
应该注意，HOMO、LUMO、T1及S1的绝对值取决于所用的测量方法或计算方法，甚至对于相同的方法，不同评价的方法，例如在CV曲线上起始点和峰点可给出不同的HOMO/LUMO值。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法进行。本发明实施例的描述中，HOMO、LUMO、T1及S1的值是基于Time-dependent DFT的模拟，但不影响其他测量或计算方法的应用。
在某些优先的实施例中，按照本发明的化合物，其(S1-T1)≤0.30eV，较好是≤0.25eV，更好是≤0.20eV，更更好是≤0.15eV，最好是≤0.10eV。
在一个优选的实施例中，按照本发明的化合物，其中所述的醇溶性或水溶性基团选于：醇类，醛类，酸类，冠醚类，聚醚类，伯胺类等基团。
较为优选的，所述的醇溶性或水溶性基团选于如下所示结构：
Figure PCTCN2021123763-appb-000018
R 31-R 37可以是具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
虚线表示键合的键，t是大于0的整数。
此外，本发明中单独的H原子或CH 2基团可被上述提到的基团或基团R取代，R选自具有1～40个C原子的烷基基团，优先选自以下的基团：甲基，乙基，正丙基，异丙基，环丙基，正丁基，异丁基，仲丁基，叔丁基，环丁基，甲基丁基，正戊基，仲戊基，环戊基，正己基，环己基，正庚基，环庚基，正辛基，环辛基，乙基己基，三氟甲基，五氟乙基，三氟乙基，乙烯基，丙烯基，丁烯基，戊烯基，环戊烯基，己烯基，环己烯基，庚烯基，环庚烯基，辛烯基，环辛烯基，乙炔基，丙炔基，丁炔基，戊炔基，己炔基和辛炔基；具有1～40个C原子的烷氧基基团，如甲氧基，三氟甲氧基，乙氧基，正丙氧基，异丙氧基，正丁氧基，异丁氧基，仲丁氧基，叔丁氧基或甲基丁氧基。
在某些实施例中，按照本发明的化合物，其中SP 3杂化的基团的总量不超过总分子量的50％，更好是不超过30％，最好是不超过20％。较少的SP 3杂化基团的存在能够有 效保证化合物的热稳定性，进而保证器件的稳定性。
在另一些优选的实施例中，为了提高溶解性和/或提高成膜性能，按照本发明的化合物，其中SP 3杂化的基团的总量超过总分子量的20％，较好超过30％，更好超过40％，最好是超过50％。
在一些优先的实施例中，所述的化合物，其光致发光谱线的半高宽(FWHM)≤50nm，较好是≤45nm，更好是≤40nm，特别好市≤35nm，最好是≤30nm。
下面给出合适的按照本发明的化合物的例子，但不限于：
Figure PCTCN2021123763-appb-000019
Figure PCTCN2021123763-appb-000020
Figure PCTCN2021123763-appb-000021
Figure PCTCN2021123763-appb-000022
Figure PCTCN2021123763-appb-000023
本发明还涉及一种按照化学式(1)或(2)的化合物的合成方法，其中使用含有活性基团的原料进行反应。这些活性原料包含至少一种离去基团，例如，溴，碘，硼酸或硼酸酯。形成C-C连接的适当的反应是本领域技术人员熟知的并描述于文献中，特别适当和优选的偶联反应是SUZUKI，STILLE，Hartwig和HECK偶联反应。
本发明还提供一种混合物，包含有至少一种如上任所述的化合物和另一种有机功能材料，所述另一种的有机功能材料可选于空穴(也称电洞)注入或传输材料(HIM/HTM)，空穴阻挡材料(HBM)，电子注入或传输材料(EIM/ETM)，电子阻挡材料(EBM)，有机基质材料(Host)，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)、热激发延迟荧光材料(TADF材料)及有机染料。例如在WO2010135519A1,US20090134784A1和WO2011110277A1中对各种有机功能材料有详细的描述，特此将此3专利文件中的全部内容并入本文作为参考。
在一个优先优选的实施例中，所述的混合物包含一种按照本发明的有机化合物，和一种荧光主体材料(或单重态基质材料)。这里按照本发明的有机化合物可以作为客体或发光体，其重量百分比≤15wt％,较好是≤12wt％,更好是≤9wt％，,更更好是≤8wt％，最好是≤7wt％。
在一个较为优先优选的实施例中，所述的混合物包含一种按照本发明的有机化合物，另一种荧光发光体(或单重态发光体)和一种荧光主体材料。在这种实施例中，按照本发明的有机化合物可以作为共同发光材料，其与另一种荧光发光体的重量比为从1:20到20:1。
以下对荧光主体材料和荧光发光体做详细的描述。
1.单重态基质材料(Singlet Host)：
单重态主体材料的例子并不受特别的限制，任何有机化合物都可能被用作为主体,只要其单重态能量比发光体,特别是单重态发光体或荧光发光体更高。
作为单重态主体材料使用的有机化合物的例子可选自含有环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、萉、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起，如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。
在一个优先的实施方案中，单重态主体材料可选于包含至少一个以下基团的化合物：
Figure PCTCN2021123763-appb-000024
Figure PCTCN2021123763-appb-000025
其中，R 1可相互独立地选于如下的基团：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基；Ar 1是芳基或杂芳基，它与上述的HTM中定义的Ar 1意义相同；n是一个从0到20的整数；X 1-X 8选于CH或N；X 9和X 10选于CR 1R 2或NR 1。
在下面的表中列出一些蒽基单重态主体材料的例子：
Figure PCTCN2021123763-appb-000026
2.单重态发光体(Singlet Emitter)
单重态发光体往往有较长的共轭π电子系统。迄今,已有许多例子，例如在JP2913116B和WO2001021729A1中公开的苯乙烯胺及其衍生物，和在WO2008/006449和WO2007/140847中公开的茚并芴及其衍生物。
在一个优先的实施方案中,单重态发光体可选自一元苯乙烯胺，二元苯乙烯胺，三元苯乙烯胺，四元苯乙烯胺，苯乙烯膦，苯乙烯醚和芳胺。
一个一元苯乙烯胺是指一化合物,它包含一个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个二元苯乙烯胺是指一化合物,它包含二个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个三元苯乙烯胺是指一化合物,它包含三个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个四元苯乙烯胺是指一化合物,它包含四个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个优选的苯乙烯是二苯乙烯,其可能会进一步被取代。相应的膦类和醚类的定义与胺类相似。芳基胺或芳香胺是指一种化合物，包含三个直接联接氮的无取代或取代的芳香环或杂环系统。这些芳香族或杂环的环系统中至少有一个优先选于稠环系统，并最好有至少14个芳香环原子。其中优选的例子有芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺。一个芳香蒽胺是指一化合物，其中一个二元芳基胺基团直接联到蒽上,最好是在9的位置上。一个芳香蒽二胺是指一化合物，其中二个二元芳基胺基团直接联到蒽上,最好是在9,10的位置上。芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺的定义类似,其中二元芳基胺基团最好联到芘的1或1,6位置上.
基于乙烯胺及芳胺的单重态发光体的例子,也是优选的例子,可在下述专利文件中找到:WO 2006/000388,WO 2006/058737,WO 2006/000389,WO 2007/065549,WO 2007/115610,US 7250532 B2,DE 102005058557 A1,CN 1583691 A,JP 08053397 A,US 6251531 B1,US 2006/210830 A,EP 1957606 A1和US 2008/0113101 A1特此上述列出的专利文件中的全部内容并入本文作为参考。
基于均二苯乙烯极其衍生物的单重态发光体的例子有US 5121029。
进一步的优选的单重态发光体可选于茚并芴-胺和茚并芴-二胺，如WO 2006/122630所公开的，苯并茚并芴-胺和苯并茚并芴-二胺，如WO 2008/006449所公开的，二苯并茚并芴-胺和二苯并茚并芴-二胺，如WO2007/140847所公开的。
其他可用作单重态发光体的材料有多环芳烃化合物，特别是如下化合物的衍生物:蒽如9,10-二(2-萘并蒽)，萘,四苯，氧杂蒽，菲,芘(如2,5,8,11-四-t-丁基苝)，茚并芘，苯撑如(4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯)，二茚并芘,十环烯,六苯并苯,芴，螺二芴,芳基芘(如US20060222886)，亚芳香基乙烯(如US5121029，US5130603),环戊二烯如四苯基环戊二烯,红荧烯，香豆素，若丹明，喹吖啶酮，吡喃如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃(DCM),噻喃,双(吖嗪基)亚胺硼化合物(US 2007/0092753 A1),双(吖嗪基)亚甲基化合物,carbostyryl化合物,噁嗪酮,苯并恶唑,苯并噻唑,苯并咪唑及吡咯并吡咯二酮。一些单重态发光体的材料可在下述专利文件中找到:US 20070252517 A1,US 4769292,US 6020078,US 2007/0252517 A1,US 2007/0252517 A1。特此将上述列出的专利文件中的全部内容并入本文作为参考。
在下面的表中列出一些合适的单重态发光体的例子:
Figure PCTCN2021123763-appb-000027
以上出现的有机功能材料出版物为公开的目的以参考方式并入本申请。
本发明还提供一种组合物，包含有至少一种本发明所述的化合物，及至少一种有机溶剂，和/或一种有机树脂。
在一个优选的实施方案中，所述的组合物包含一种有机树脂；在另一些实施方案中，包含两种及以上有机树脂；在另一些实施方案中，包含三种及以上有机树脂。
出于本发明的目的，所述有机树脂是指树脂预聚体或其交联或固化后形成的树脂。
适合本发明的有机树脂，包括但不限制于：聚苯乙烯、聚丙烯酸酯、聚甲基丙烯酸酯、聚碳酸酯、聚胺酯、聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚氯乙烯、聚丁烯、聚乙二醇、聚硅氧烷、聚丙烯酸酯、环氧树脂、聚乙烯醇、聚丙烯腈、聚偏二氯乙烯(PVDC)、聚苯乙烯-丙烯腈(SAN)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚丁酸乙烯酯(PVB)、聚氯乙烯(PVC)、聚酰胺、聚甲醛、聚酰亚胺、聚醚酰亚胺或其混合物。
进一步，适合本发明的有机树脂，包含但不限制于由以下单体(树脂预聚体)均聚或共聚形成：苯乙烯衍生物、丙烯酸酯衍生物、丙烯腈衍生物、丙烯酰胺衍生物、乙烯酯衍生物、乙烯醚衍生物、马来酰亚胺衍生物、共轭二烯烃衍生物。
苯乙烯衍生物的例子有：烷基苯乙烯，如α-甲基苯乙烯，邻-、间-、对-甲基苯乙烯，对丁基苯乙烯，尤其是对叔丁基苯乙烯，烷氧基苯乙烯如对甲氧基苯乙烯、对丁氧基苯乙烯、对叔丁氧基苯乙烯。
丙烯酸酯衍生物的例子有：丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸仲丁酯、甲 基丙烯酸仲丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、丙烯酸2-羟基丙酯、甲基丙烯酸2-羟基丙酯、丙烯酸3-羟基丙酯、甲基丙烯酸3-羟基丙酯、丙烯酸2-羟基丁酯、甲基丙烯酸2-羟基丁酯、丙烯酸3-羟基丁酯、甲基丙烯酸3-羟基丁酯、丙烯酸4-羟基丁酯、甲基丙烯酸4-羟基丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸环己酯、甲基丙烯酸环己酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸2-甲氧基乙酯、甲基丙烯酸2-甲氧基乙酯、丙烯酸2-苯氧基乙酯、甲基丙烯酸2-苯氧基乙酯、甲氧基二甘醇丙烯酸酯、甲氧基二甘醇甲基丙烯酸酯、甲氧基三甘醇丙烯酸酯、甲氧基三甘醇甲基丙烯酸酯、甲氧基丙二醇丙烯酸酯、甲氧基丙二醇甲基丙烯酸酯、甲氧基二丙二醇丙烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸双环戊二烯酯、甲基丙烯酸双环戊二烯酯、(甲基)丙烯酸金刚烷酯、(甲基)丙烯酸降冰片酯、丙烯酸2-羟基-3-苯氧基丙酯、甲基丙烯酸2-羟基-3-苯氧基丙酯、单丙烯酸甘油酯和单甲基丙烯酸甘油酯；丙烯酸2-氨基乙酯、甲基丙烯酸2-氨基乙酯、丙烯酸2-二甲基氨基乙酯、甲基丙烯酸2-二甲基氨基乙酯、N,N-二甲基氨基乙基(甲基)丙烯酸、N,N-二乙基氨基乙基(甲基)丙烯酸酯、丙烯酸2-氨基丙酯、甲基丙烯酸2-氨基丙酯、丙烯酸2-二甲基氨基丙酯、甲基丙烯酸2-二甲基氨基丙酯、丙烯酸3-氨基丙酯、甲基丙烯酸3-氨基丙酯、N,N-二甲基-1,3-丙二胺(甲基)丙烯酸苄酯、丙烯酸3-二甲基氨基丙酯和甲基丙烯酸3-二甲基氨基丙酯；丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯；
丙烯腈衍生物的例子有：丙烯腈、甲基丙烯腈、α-氯丙烯腈和偏二氰基乙烯；
丙烯酰胺衍生物的例子有：丙烯酰胺、甲基丙烯酰胺、α-氯丙烯酰胺、N-2-羟乙基丙烯酰胺和N-2-羟乙基甲基丙烯酰胺；
乙烯酯衍生物的例子有：乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯和苯甲酸乙烯酯；
乙烯醚衍生物的例子有：乙烯基甲基醚、乙烯基乙基醚和烯丙基缩水甘油基醚；
马来酰亚胺衍生物的例子有：马来酰亚胺、苄基马来酰亚胺、N-苯基马来酰亚胺和N-环己基马来酰亚胺；
共轭二烯烃衍生物的例子有：1,3-丁二烯、异戊二烯和氯丁二烯；
所述的均聚物或共聚物可以通过例如自由基聚合、阳离子聚合、阴离子聚合或有机金属催化聚合(例如Ziegler-Natta催化)进行制备。聚合的工艺可以是悬浮聚合、乳液聚合、溶液聚合或本体聚合。
所述的有机树脂通常具有10 000-1 000 000g/mol，优选20 000-750000g/mol，更优选30 000-500 000g/mol的平均摩尔质量Mn(由GPC测定)。
在一些优先的实施方案中，有机树脂为热固性树脂或紫外(UV)可固化树脂。在一些实施方案中，用将促进卷对卷加工的方法固化有机树脂。
热固性树脂需要固化，在固化中它们会经历不可逆的分子交联过程，这使得树脂不可熔化。在一些实施方案中，热固性树脂为环氧树脂、酚醛树脂、乙烯基树脂、三聚氰胺树脂、脲醛树脂、不饱和聚酯树脂、聚氨酯树脂、烯丙基树脂、丙烯酸类树脂、聚酰胺树脂、聚酰胺-酰亚胺树脂、酚胺缩聚树脂、脲三聚氰胺缩聚树脂或其组合。
在一些实施方案中，热固性树脂为环氧树脂。环氧树脂易于固化，不会放出挥发物或因广泛的化学品而生成副产物。环氧树脂也可与大多数基板相容并往往易于润湿表面。参见Boyle,M.A.等人，“Epoxy Resins”,Composites,Vol.21,ASM Handbook,pages 78-89(2001)。
在一些实施方案中，有机树脂为有机硅热固性树脂。在一些实施方案中，有机硅热固性树脂为0E6630A或0E6630B(Dow Corning Corporation(密歇根州奥本市))。
在一个优选的实施方案中，所述的组合物包含一种溶剂；在另一些实施方案中，包含两种及以上溶剂；在另一些实施方案中，包含三种及以上溶剂。
在一个优选的实施方案中，按照本发明的组合物是一溶液。
在另一个优选的实施方案中，按照本发明的组合物是一悬浮液。
本发明实施例中的组合物中可以包括0.01至20wt％的有机化合物，较好的是0.1至20wt％，更好的是0.2至20wt％，最好的是1至15wt％的有机化合物。
按照本发明的组合物，可以使用喷墨打印、转印、光刻等方法来形成颜色转换层，此时，需将本发明的颜色转换材料单独或与其他材料一起溶解在有机溶剂中，形成油墨。本发明所述的颜色转换材料在油墨中的质量浓度不低于0.1％wt。可以通过调节油墨中颜色转换材料的浓度和颜色转换层的厚度来改善颜色转换层的颜色转换能力。一般而言，颜色转换材料的浓度越高或厚度越厚，颜色转换层的颜色转换率越高。
可添加在油墨中的其他材料包括不限于以下材料：聚乙烯、聚丙烯、聚苯乙烯、聚碳酸酯、聚丙烯酸酯、聚乙烯吡咯烷酮、聚乙烯醇、聚乙酸乙烯酯、聚乙二醇、聚硅氧烷、聚丙烯腈、聚氯乙烯、聚偏二氯乙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚丁酸乙烯酯、聚酰胺、聚甲醛、聚酰亚胺、聚醚醚酮、聚砜、聚芳醚、聚芳酰胺、纤维素、改性纤维素、醋酸纤维、硝酸纤维或以上材料的混合物。
在一些优先的实施方案中，所述的溶剂选自酯、芳族酮或芳族醚、脂肪族酮或脂肪族醚、或硼酸酯或磷酸酯等无机酯类化合物，或两种及两种以上溶剂的混合物。
在另一些实施例中，适当的和优选的溶剂是脂肪族、脂环族或芳烃族，胺，硫醇，酰胺，腈，酯，醚，聚醚，醇，二醇或多元醇。
在另一些实施例中，醇代表适当类别的溶剂。优选的醇包括烷基环己醇，特别是甲基化的脂肪族醇，萘酚等。
另外适当的醇类溶剂的例子有：十二醇，苯基十三醇，苯甲醇，乙二醇，乙二醇甲醚，丙三醇，丙二醇，丙二醇乙醚等。
所述的溶剂可以是单独使用，也可以是作为两种或多种有机溶剂的混合物使用。
在某些实施例中，按照本发明的组合物，包含有一种如上所述的有机功能化合物及至少一种有机溶剂，还可进一步包含另一种有机溶剂，另一种有机溶剂的例子，包括(但不限于)：甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷、茚和/或它们的混合物。
在一些优先的实施方案中，按照本发明的一种组合物，其中所述的另一种有机溶剂选自芳族或杂芳族、酯、芳族酮或芳族醚、脂肪族酮或脂肪族醚、脂环族或烯烃类化合物，或硼酸酯或磷酸酯等无机酯类化合物，或两种及两种以上溶剂的混合物。
按照本发明的基于芳族或杂芳族溶剂的例子有，但不限于：1-四氢萘酮、3-苯氧基甲苯、苯乙酮、1-甲氧基萘、对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、1-甲基萘、1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、二苯醚、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2-苯基吡啶、3-苯基吡啶、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、N-甲基二苯胺、4-异丙基联苯、α,α-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘、二苄醚等。
在另一些实施例中，适当的和优选的另一种有机溶剂是脂肪族、脂环族或芳烃族，胺，硫醇，酰胺，腈，酯，醚，聚醚。
所述的另一种有机溶剂可以是环烷烃，例如十氢化萘。
在另一些优先的实施方案中，按照本发明的一种组合物，其中包含至少50wt％的醇类溶剂；优选至少80wt％的醇类溶剂；特别优选至少90wt％的醇类溶剂。
一些优选的实施例中，特别适合本发明的溶剂是汉森(Hansen)溶解度参数在以下范围内的溶剂：
δ d(色散力)在17.0～23.2MPa 1/2的范围，尤其是在18.5～21.0MPa 1/2的范围；
δ p(极性力)在0.2～12.5MPa 1/2的范围，尤其是在2.0～6.0MPa 1/2的范围；
δ h(氢键力)在0.9～14.2MPa 1/2的范围，尤其是在2.0～6.0MPa 1/2的范围。
按照本发明的组合物，其中有机溶剂在选取时需考虑其沸点参数。本发明中，所述的有机溶剂的沸点≥150℃；优选为≥180℃；较优选为≥200℃；更优为≥250℃；最优为≥275℃或≥300℃。这些范围内的沸点对防止喷墨印刷头的喷嘴堵塞是有益的。所述的有机溶剂可从溶剂体系中蒸发，以形成包含功能材料薄膜。
在一些优先的实施方案中，按照本发明的一种组合物，其特征在于
1)其粘度@25℃，在1cPs到100cPs范围，和/或
2)其表面张力@25℃，在19dyne/cm到50dyne/cm范围。
按照本发明的组合物，其中有机溶剂在选取时需考虑其表面张力参数。合适的油墨表面张力参数适合于特定的基板和特定的印刷方法。例如对喷墨印刷，在一个优选的实施例中，所述的有机溶剂在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；更优为在22dyne/cm到35dyne/cm范围；最优为在25dyne/cm到33dyne/cm范围。
在一个优选的实施例中，按照本发明的油墨在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；更好是在22dyne/cm到35dyne/cm范围；最好是在25dyne/cm到33dyne/cm范围。
按照本发明的组合物，其中有机溶剂在选取时需考虑其油墨的粘度参数。粘度可以通过不同的方法调节，如通过合适的有机溶剂的选取和油墨中功能材料的浓度。在一个优选的实施例中，所述的有机溶剂的粘度低于100cps；更优为低于50cps；最优为为1.5到20cps。这里的粘度是指在印刷时的环境温度下的粘度，一般在15-30℃，较好的是18-28℃，更好是20-25℃，最好是23-25℃。如此配制的组合物将特别适合于喷墨印刷。
在一个优选的实施例中，按照本发明的组合物，在25℃下的粘度约在1cps到100cps范围；更好是在1cps到50cps范围；最好是在1.5cps到20cps范围。
满足上述沸点及表面张力参数及粘度参数的有机溶剂获得的油墨能够形成具有均匀厚度及组成性质的功能材料薄膜。
盐类化合物不易于提纯，容易带来杂质，影响光电性能。处于本发明的目的，在某些优先的实施例中，上述的组合物或混合物不包含任何盐类化合物，优先的不包含任何由有机酸和金属形成的有机酸盐。处于成本的考虑，本发明优先排除含有过渡金属和镧系元素的有机酸盐。
本发明进一步一种有机功能材料薄膜，包含一种如上所述的有机化合物或混合物。优先的，所述的有机功能材料薄膜利用一种如上所述的组合物制备而成。
本发明还提供一种所述的有机功能材料薄膜的制备方法，包含如下步骤：
1)制备一种按照本发明的组合物；
2)用印刷或涂布的方法将所述的组合物涂布于一基板上形成一薄膜，其中印刷或 涂布的方法选于喷墨打印，喷印(Nozzle Printing)，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂或移印，狭缝型挤压式涂布；
3)将所得的薄膜在至少50摄氏度加热，可选择性的加上紫外光照，使之发生交联反应，固化薄膜。
所述的有机功能材料薄膜厚度一般为50nm-200μm，较好为100nm-150μm，更好为500nm-100μm，更更好为1μm-50μm，最好为1μm-20μm。
在另一个优选的实施例中，所述的有机功能材料薄膜，其厚度介于20nm-20μm，较好是小于15μm，更好是小于10μm，更更好是小于8μm，特别好是小于6μm，最好是小于4μm，最最好是小于2μm。
本发明的另一目的是提供上述有机化合物及其混合物在光电器件中的应用。
在某些实施例中，所述光电器件可选于有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
更进一步，本发明提供一种光电器件，包含一种上述的有机化合物或混合物。
在某些实施例中，所述光电器件可选于有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
优先的，所述的光电器件是电致发光器件，如有机发光二极管(OLED)、有机发光电池(OLEEC)、有机发光场效应管、钙钛矿发光二极管(PeLED)、及量子点发光二极管(QD-LED)，其中一功能层中包含一种上述的有机化合物或混合物。所述的功能层可以选自空穴注入层，空穴传输层，电子注入层，电子传输层，发光层，及阴极钝化层(CPL)。
在一个优先的实施例中，所述的光电器件是电致发光器件，包含两个电极，所述的功能层位于所述的两个电极的同一侧。
在另一个优先的实施例中，所述的光电器件包含一发光单元和一颜色转换层，其中所述的颜色转换层包含一种上述的有机化合物或混合物。
在某些优先的实施例中，所述的发光单元选自固体发光器件。所述的固体发光器件优先选自LED、机发光二极管(OLED)、有机发光电池(OLEEC)、有机发光场效应管、钙钛矿发光二极管(PeLED)、及量子点发光二极管(QD-LED)。
在一个优先的实施例中，所述的发光单元发射蓝光，通过颜色转换层转换成绿光或红光。
本发明进一步涉及一种显示器，包含至少红绿蓝三种像素，蓝光像素包好一个蓝光发光单元，红绿光像素包含一蓝光发光单元和相应的红绿颜色转换层。
下面将结合优选实施例对本发明进行了说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的范围在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例所进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。
实施例1：化合物1的合成
Figure PCTCN2021123763-appb-000028
化合物1的合成：采用经典的SUZUKI反应合成，具体合成步骤如下：氮气保护环境下，将10.00mmol中间体1-1，20.08mmol中间体1-2以及20.00mmol的碳酸钾依次加入500ml的中三口烧瓶中，倒入200ml甲苯，搅拌条件下加入0.3mol催化剂Pd(PPh 3) 4，加热回流反应，TLC跟踪反应，待反应完全后，反应液冷却至室温，加水及二氯甲烷洗涤各三次，合并有机相，加入无水Na 2SO 4燥，过滤，旋干溶剂得粗品，用快速色谱柱纯化得产品7.88mmol，干燥备用，产率：78.8％，MS(ASAP)＝604.2。
实施例2:化合物2的合成
Figure PCTCN2021123763-appb-000029
化合物2的合成：合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：82.4％。真空干燥。MS(ASAP)＝716.4。
实施例3:化合物3的合成
Figure PCTCN2021123763-appb-000030
化合物3的合成：合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：75.3％。真空干燥。MS(ASAP)＝601.2。
实施例4:化合物4的合成
Figure PCTCN2021123763-appb-000031
化合物4的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：78.4％。真空干燥。MS(ASAP)＝888.3。
实施例5:化合物5的合成
Figure PCTCN2021123763-appb-000032
化合物5的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：81.3％。真空干燥。MS(ASAP)＝833.3。
实施例6:化合物6的合成
Figure PCTCN2021123763-appb-000033
化合物6的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：80.4％。真空干燥。MS(ASAP)＝884.5。
实施例7:化合物7的合成
Figure PCTCN2021123763-appb-000034
化合物7的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：79.3％。真空干燥。MS(ASAP)＝599.3。
实施例8:化合物8的合成
Figure PCTCN2021123763-appb-000035
化合物8的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：85.2％。真空干燥。MS(ASAP)＝717.3。
实施例9:化合物9的合成
Figure PCTCN2021123763-appb-000036
化合物9的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：89.3％。真空干燥。MS(ASAP)＝720.3。
实施例10:化合物10的合成
Figure PCTCN2021123763-appb-000037
化合物10的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：79.8％。真空干燥。MS(ASAP)＝774.3。
实施例11:化合物11的合成
Figure PCTCN2021123763-appb-000038
化合物11的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：80.8％。真空干燥。MS(ASAP)＝779.3。
实施例12:化合物12的合成
Figure PCTCN2021123763-appb-000039
化合物12的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：50.4％。真空干燥。MS(ASAP)＝1438.6。
实施例13:化合物13的合成
Figure PCTCN2021123763-appb-000040
化合物13的合成：
合成方法与化合物1的合成方法相似，采用经典的SUZUKI反应，产率：48.9％。真空干燥。MS(ASAP)＝1432.6。
颜色转换层的制备方法如下：
1)将蓝色颜色转换材料、绿色颜色转换材料、红色颜色转换材料分别按照50mg/ml,50mg/ml，50mg/ml溶解于苯基十二醇：甲苯＝3：2的混合溶剂中，同时向该溶液中添加15mg/ml的聚苯乙烯，5mg/ml的二氧化硅纳米球，二氧化硅纳米球的直径为3-5微米。通过狭缝涂布的方式，使其在导光板表面形成厚度约100微米的薄膜，作为红绿蓝三色的颜色转换层。以上所得的颜色转换层，其OD(opticaldensity)都大于4。结合蓝光或近紫外发光光源，可以将其完全转换成绿光或红光。
2)将蓝色颜色转换材料、绿色颜色转换材料、红色颜色转换材料分别按照50mg/ml,50mg/ml，50mg/ml溶解苯基十二醇：甲苯＝3：2的混合溶剂中得到溶液。用刮刀或旋涂的方法成膜，在100C的热板上烘烤10分钟，可以得到100-500nm的颜色转换薄膜。此类颜色转换薄膜可以用来制备RGB显示器件。
另外，本发明也发现，对比没有醇溶性或水溶性基团的相应的化合物，按照本发明的化合物，即具有一个，特别是两个或以上醇溶性或水溶性基团的化合物，溶解性(特别是在醇类溶剂中)和成膜性都较好，从而可以制得较高质量的膜。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种包含有化学式(1)或(2)所示的结构单元的化合物，
    Figure PCTCN2021123763-appb-100001
    其中使用的符号与标记具有以下含义：
    Ar 1～Ar 3相同或不同的选自具有5-24个环原子的芳香族或杂芳香族；
    Ar 4～Ar 5相同或不同的选自空或具有5-24个环原子的芳香族或杂芳香族；
    当Ar 4～Ar 5不为空时，X a，X b选自N、C(R 9)、Si(R 9)；Y a，Y b选自B、P＝O、C(R 9)、Si(R 9)；
    当Ar 4～Ar 5为空时，相应的X a或Y b选自N(R 9)、C(R 9R 10)、Si(R 9R 10)、C＝O、O、C＝N(R 9)、C＝C(R 9R 10)、P(R 9)、P(＝O)R 9、S、S＝O或SO 2；
    X 1、X 2是空或一个桥接基团；
    R 1～R 10可相同或不同的选自取代基分别独立选自H、D、-F,-Cl,Br,I,-CN,-NO 2,-CF 3,具有1至20个C原子的直链的烷基、卤代烷基、烷氧基、硫代烷氧基基团，或者具有3至20个C原子的支链或环状的烷基、卤代烷基、烷氧基、硫代烷氧基基团或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或具有5至40个环原子的芳胺基或杂芳胺基基团，以上取代基任意位置的二取代单元或这些体系的组合，其中一个或多个取代基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    其特征在于：所述的化合物包含至少一个醇溶性或水溶性基团。
  2. 根据权利要求1所述的化合物，包含化学式(1a)或(2a)所示的结构单元：
    Figure PCTCN2021123763-appb-100002
    所述的符号含义同权利要求1。
  3. 根据权利要求1所述的化合物，包含如下化学式(1b)-(1e)或(2b)-(2e) 之一所示的结构单元：
    Figure PCTCN2021123763-appb-100003
    所述的符号含义同权利要求1。
  4. 根据权利要求1所述的化合物，其中所述的醇溶性或水溶性基团选于：醇类，醛类，酸类，冠醚类，聚醚类，伯胺类等基团。
  5. 根据权利要求1所述的化合物，其中所述的醇溶性或水溶性基团选于：
    Figure PCTCN2021123763-appb-100004
    R 31-R 37可以是具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    虚线表示键合的键，t是大于0的整数。
  6. 根据权利要求1所述的一种化合物，其特征在于，化学式(1)或(2)中的Ar 1、Ar 2、Ar 3、Ar 4、Ar 5独立选自如下化学结构式之一或其组合：
    Figure PCTCN2021123763-appb-100005
  7. 一种组合物，包含至少一种如权利要求1-6任一项所述的有机化合物，至少一种有机溶剂，和/或一种有机树脂。
  8. 根据权利要求7所述的一种组合物，其特征在于，所述的溶剂选自水，醇，酯、芳族酮或芳族醚、脂肪族酮或脂肪族醚、或硼酸酯或磷酸酯等无机酯类化合物，或两种及两种以上溶剂的混合物。
  9. 一种有机功能材料薄膜，包含一种如权利要求1所述的有机化合物，或利用一种按照权利要求7的组合物制备而成的薄膜。
  10. 一种光电器件，包含一种如权利要求1所述的有机化合物或一种如权利要求9所述的有机功能材料薄膜。
PCT/CN2021/123763 2020-10-14 2021-10-14 有机化合物及其在光电领域的应用 WO2022078434A1 (zh)

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