Polymer and preparation method thereof, ink, film, photoelectric device and display device

Abstract

The invention discloses a polymer and a preparation method thereof, ink, a film, a photoelectric device and a display device, and relates to the technical field of display. The structural formula of the polymer is as shown in formula (I): # imgabs0 #, wherein Ar1 and Ar2 are respectively and independently selected from substituted or unsubstituted aryl with the carbon atom number of 6-60, substituted or unsubstituted heteroaryl with the ring atom number of 5-60, or a combination of the substituted or unsubstituted aryl with the carbon atom number of 6-60 and the substituted or unsubstituted heteroaryl with the ring atom number of 5-60; n is any integer from 50 to 100, and heteroatoms in heteroaryl include one or more of O, P, N and S. The polymer provided by the invention can effectively resist solvent erosion and is high in stability, and a thin film prepared from the polymer is compact and uniform and can be used for transmitting holes and blocking electrons.

Description

Technical Field

[0001] The present application relates to the field of display technology, and in particular to a polymer and a preparation method thereof, ink, a film, an optoelectronic device, and a display device. Background Art

[0002] At present, display technologies are mainly divided into LCD (Liquid Crystal Display) and OLED (Organic Light-Emitting Diode). Compared with LCD, OLED has wide viewing angle, wide color gamut, high brightness, high contrast, fast response time and low power consumption, which makes it have a huge market share in small and medium sizes; however, in the field of large size, it is difficult to develop commercially due to the bottleneck of OLED evaporation technology, and LCD is still the mainstream display screen; therefore, it is extremely urgent and important to break through OLED large-size display technology.

[0003] In order to overcome the limitations of evaporation technology in the production of large-size OLED displays, the solution method for preparing large-size OLED displays came into being. It configures various organic materials into ink compositions, and forms various functional layers through inkjet printing technology, which are stacked to form a complete OLED device. However, most of the commercially available OLED organic materials on the market are evaporation-type small molecule materials, which are printed into films through the solution method, which can easily cause solution erosion between adjacent organic layers, affecting the display quality. Summary of the invention

[0004] In view of this, the present application provides a polymer and a preparation method thereof, ink, film, optoelectronic device, and display device.

[0005] The embodiment of the present application is implemented as follows: a polymer, the structural formula of the polymer is shown in formula (I):

[0006]

[0007] Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

[0008] Accordingly, the present invention also provides a method for preparing a polymer, comprising:

[0009] Compound a and a first aryl halide are provided, wherein the chemical formula of the first aryl halide is Ar1-X1, and the structural formula of compound a is shown as follows:

[0010]

[0011] The compound a and the first aryl halide are mixed and reacted to obtain a compound b, the structural formula of the compound b is shown below:

[0012]

[0013] Providing a second aryl halide, wherein the chemical formula of the second aryl halide is X2-Ar2-X3; mixing the second aryl halide with the compound b, reacting, and obtaining a polymer, wherein the structural formula of the polymer is shown in formula (I):

[0014]

[0015] Wherein, X1, X2 and X3 are each independently selected from a halogen group; Ar1 ​​and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

[0016] Accordingly, an embodiment of the present application further provides an ink, wherein the ink comprises a polymer, and the structural formula of the polymer is shown in formula (I):

[0017]

[0018] Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

[0019] Accordingly, an embodiment of the present application further provides a film, wherein the material of the film includes a polymer, and the structural formula of the polymer is shown in formula (I):

[0020]

[0021] Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

[0022] Accordingly, an embodiment of the present application further provides a photoelectric device, comprising an anode, a functional layer and a cathode stacked in sequence; wherein the material of the functional layer comprises a polymer, and the structural formula of the polymer is shown in formula (I):

[0023]

[0024] Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

[0025] Correspondingly, an embodiment of the present application further provides a display device, which includes the above-mentioned optoelectronic device.

[0026] The polymer provided in the present application can effectively resist solvent erosion and has high stability. The film prepared using the polymer is dense and uniform and can be used to transport holes and block electrons. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0028] Figure 1 is a flow chart of a method for preparing a polymer provided in an embodiment of the present application;

[0029] Figure 2 is a schematic diagram of the structure of the optoelectronic device provided in an embodiment of the present application;

[0030] Figure 3 This is the morphology of the hole transport layer of Example 1 of the present application

[0031] Figure 4 is a morphology diagram of the hole transport layer after anti-solvent testing of Examples 1 to 10 of the present application;

[0032] Figure 5 It is the morphology picture of the hole transport layer after the anti-solvent test of Comparative Examples 1 to 3 of the present application.

[0033] Reference numerals:

[0034] Anode 10; hole functional layer 20; electron blocking layer 30; light emitting layer 40; electron functional layer 50; cathode 60. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0036] In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

[0037] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0038] In the present application, "at least one" means one or more, and "plurality" means two or more. "One or several", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0039] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0040] In the present application, "aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For a polycyclic ring, at least one is an aromatic ring system. For example, "substituted or unsubstituted aromatic group having 6 to 40 ring atoms" refers to an aromatic group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aromatic group having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted aromatic group having 6 to 14 ring atoms, and the aromatic group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, dinaphthylenyl, acenaphthene and its derivatives. It is understood that multiple aromatic groups may also be interrupted by short non-aromatic units (e.g. <10% non-H atoms, such as C, N or O atoms), such as acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether system should also be included in the definition of aromatic groups. The heteroatom in the heterocyclic ring is one or more of oxygen atom, sulfur atom, nitrogen atom and phosphorus atom.

[0041] It should be noted that, in the present application, "---" in each chemical formula indicates that the atom or group connected to the formula can be connected to the chemical formula through the bonding position. For example, "---" in the formula of Ar1 indicates that the N atom can be connected to Ar1 through the bonding position.

[0042] The technical solution of this application is as follows:

[0043] In a first aspect, an embodiment of the present application provides a polymer, the structural formula of the polymer is shown in formula (I):

[0044]

[0045] Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

[0046] The polymer provided in the present application has a moderate molecular weight, can effectively overcome solvent erosion, and improve the stability of the polymer; and the polymer has a high hole transport performance, and is suitable for transporting holes and blocking electrons. Through the combination of Ar1 and Ar2, when preparing the polymer, it is beneficial to control the degree of polymerization of the polymer to be in a suitable range of 50 to 100, thereby being more conducive to improving the anti-solvent erosion performance of the polymer.

[0047] In some embodiments, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 10 to 50 ring atoms, a substituted or unsubstituted heteroaryl group having 10 to 50 ring atoms, or a combination thereof.

[0048] In some embodiments, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 20 to 40 ring atoms, a substituted or unsubstituted heteroaryl group having 20 to 40 ring atoms, or a combination thereof.

[0049] In some embodiments, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 30 to 35 ring atoms, a substituted or unsubstituted heteroaryl group having 30 to 35 ring atoms, or a combination thereof.

[0050] In some embodiments, the substituted substituents independently include one or more of D, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C6-C15 aryl, C1-C10 alkoxy, halogen, -OH, -NO2, -ONHNH2, -NHNH2, -NH2, -SH, -CN, -CHO, -SO3H.

[0051] Furthermore, the C1-C10 alkyl group may further be a C1-C8 alkyl group, a C1-C6 alkyl group, or a C1-C4 alkyl group. More specifically, the C1-C10 alkyl group includes one or more of a methyl group, an ethyl group, a propyl group, and a butyl group.

[0052] The C2-C10 alkenyl group may further be a C2-C8 alkenyl group, a C2-C6 alkenyl group, or a C2-C4 alkenyl group. More specifically, the C2-C10 alkenyl group includes one or more of vinyl, propenyl, and butenyl.

[0053] The C2-C10 alkynyl group may further be a C3-C9 alkynyl group, a C4-C7 alkynyl group, or a C5-C6 alkynyl group. More specifically, the C2-C10 alkynyl group includes one or more of an ethynyl group, a propynyl group, and a butynyl group.

[0054] The C6-C15 aryl group may further be a C6-C14 aryl group, a C7-C13 aryl group, or a C8-C12 aryl group. More specifically, the C2-C10 aryl group includes one or more of a phenyl group and a naphthyl group.

[0055] The C1-C10 alkoxy group may further be a C3-C8 alkoxy group, a C4-C7 alkoxy group, or a C5-C6 alkoxy group. More specifically, the C2-C10 alkoxy group includes one or more of a methoxy group, an ethoxy group, and a propoxy group.

[0056] The halogen includes one or more of -F, -Cl, -Br, and -I. It is understood that n represents the degree of polymerization of the polymer. Within the range of the degree of polymerization of 50 to 100 provided in the present application, when the polymer is applied to form a thin film, it is conducive to forming a dense and uniform film layer, reducing the difficulty in dissolving into a solution due to a large molecular weight, or the erosion of the film due to a small molecular weight, or the formation of more film defects due to uneven molecular weight.

[0057] Exemplarily, in some embodiments, n is any integer from 60 to 100.

[0058] In some embodiments, n is any integer from 60 to 90.

[0059] In some embodiments, n is any integer from 65 to 85.

[0060] In some embodiments, n is any integer from 70 to 80.

[0061] In some embodiments, Ar1 is selected from any one of the structures shown in the following Formulae 1-1 to 1-26:

[0062]

[0063]

[0064] In some embodiments, Ar2 is selected from any one of the structures shown in the following Formula 2-1 to Formula 2-22:

[0065]

[0066]

[0067] In some embodiments, the polymer is selected from any one of the structures shown in the following formula M1 to formula M155:

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] Wherein, n is any integer between 50 and 100.

[0079] Second, see Figure 1 The present application also provides a method for preparing a polymer, comprising:

[0080] S11, providing compound a and a first aryl halide, wherein the chemical formula of the first aryl halide is Ar1-X1, and the structural formula of compound a is shown as follows:

[0081]

[0082] S12, mixing the compound a and the first aryl halide, reacting to obtain a compound b, the structural formula of the compound b is shown below:

[0083]

[0084] S13, providing a second aryl halide, wherein the chemical formula of the second aryl halide is X2-Ar2-X3; mixing the second aryl halide with the compound b, reacting to obtain a polymer, wherein the structural formula of the polymer is shown in formula (I):

[0085]

[0086] Wherein, X1, X2 and X3 are each independently selected from a halogen group; Ar1 ​​and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

[0087] In some embodiments, X1, X2 and X3 are each independently selected from one of -F, -Cl, -Br, and -I.

[0088] In S12:

[0089] In some embodiments, the molar ratio of the compound a to the first aryl halide is 1:(1.2-2.5), for example, 1:1.2, 1:2.5, 1:1.3, 1:1.4, etc. Within the molar ratio range, the compound a and the first aryl halide can be fully reacted to connect Ar1 to N.

[0090] In some embodiments, the mixing of the compound a and the first aryl halide further comprises adding a first catalyst for reaction. The first catalyst can effectively improve the reaction efficiency of the compound a and the first aryl halide.

[0091] Furthermore, the first catalyst includes one or more of tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), and bis(methyldiphenylphosphine)palladium dichloride.

[0092] The molar ratio of the compound a to the first catalyst is 1:(0.05-0.1), for example, 1:0.05, 1:0.06, 1:0.08, 1:0.1, etc.

[0093] In some embodiments, the mixing of the compound a and the first aryl halide further comprises adding a first base for reaction. The first base can promote the first catalyst to exert a beneficial effect.

[0094] Furthermore, the first base includes one or more of sodium tert-butoxide and potassium tert-butoxide.

[0095] The molar ratio of the compound a to the first base is 1:(5-10), for example, 1:5, 1:6, 1:8, etc.

[0096] In some embodiments, the mixing of the compound a and the first aryl halide further comprises adding a ligand for reaction. The ligand can increase the activity of the first catalyst and promote the reaction.

[0097] Furthermore, the ligand includes one or more of tert-butylphosphine and triphenylphosphine.

[0098] The molar ratio of the compound a to the ligand is 1:(5-10), for example, 1:5, 1:6, 1:8, etc.

[0099] In some embodiments, the reaction of the compound a and the first aryl halide is performed in an inert atmosphere.

[0100] In some embodiments, the reaction temperature of the compound a and the first aryl halide is 85° C. to 110° C., for example, 90° C., 95° C., 100° C., 105° C., etc., and the reaction time is 12 h to 24 h, for example, 15 h, 18 h, 20 h, 22 h, etc. Under the reaction conditions, the yield of the reaction of the compound a and the first aryl halide is high.

[0101] In some embodiments, the chemical formula of the reaction of the compound a and the first aryl halide is shown below:

[0102]

[0103] In S13:

[0104] In some embodiments, the molar ratio of the compound b to the second aryl halide is 1:(1.05-1.15), for example, 1:1.05, 1:1.12, 1:1.1, etc. Within the molar ratio range, the compound b and the second aryl halide can be fully reacted.

[0105] In some embodiments, the mixing of the compound b and the second aryl halide further comprises adding a second catalyst for reaction. The second catalyst can effectively improve the reaction efficiency of the compound b and the second aryl halide.

[0106] Furthermore, the second catalyst includes one or more of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), diphenylphosphine, ferrocene, and palladium dichloride.

[0107] The molar ratio of the compound b to the second catalyst is 1:(3-8), for example 1:4, 1:6, 1:7, etc.

[0108] In some embodiments, the mixing of the compound b and the second aryl halide further comprises adding a second base for reaction. The second base is conducive to the second catalyst exerting a beneficial effect.

[0109] Furthermore, the second alkali includes one or more of potassium phosphate, sodium carbonate, potassium carbonate, and potassium acetate.

[0110] The molar ratio of the compound b to the second base is 1:(0.05-0.1), for example, 1:0.06, 1:0.07, 1:0.08, etc.

[0111] In some embodiments, the reaction of the compound b and the second aryl halide is performed under an inert atmosphere.

[0112] In some embodiments, the reaction temperature of the compound b and the second aryl halide is 75° C. to 90° C., for example, 80° C., 82° C., 85° C., 88° C., etc., and the reaction time is 12 h to 24 h, for example, 15 h, 18 h, 20 h, 22 h, etc. Under the reaction conditions, the yield of the reaction of the compound b and the second aryl halide is high.

[0113] In some embodiments, the chemical formula of the reaction of the compound b and the second aryl halide is as shown below:

[0114]

[0115] In a third aspect, an embodiment of the present application further provides an ink comprising the above-mentioned polymer.

[0116] It can be understood that the ink includes the above-mentioned polymer, which can meet the requirements of inkjet printing film formation and overcome the solvent erosion between adjacent functional layers.

[0117] In a fourth aspect, embodiments of the present application also provide a film, wherein the material of the film includes the above-mentioned polymer.

[0118] The film can be prepared from the ink by conventional techniques in the art. Preferably, the film is prepared from the ink by inkjet printing.

[0119] Fifth, please refer to Figure 2 The embodiment of the present application further provides a photoelectric device, comprising an anode 10, a functional layer and a cathode 60 which are stacked in sequence, wherein the material of the functional layer comprises the above-mentioned polymer.

[0120] The optoelectronic device provided in the present application uses the above-mentioned polymer as the material of the hole functional layer 20 and / or the electron blocking layer 30, which can effectively prevent solvent corrosion between adjacent functional layers, thereby improving the photoelectric efficiency and stability of the optoelectronic device.

[0121] In some embodiments, the functional layer includes a hole functional layer 20, an electron blocking layer 30, a light-emitting layer 40 and an electron functional layer 50 arranged in sequence away from the anode 10, and the material of the hole functional layer 20 and / or the electron blocking layer 30 includes the above-mentioned polymer.

[0122] The hole functional layer 20 includes one or more of a hole injection layer and a hole transport layer.

[0123] The electronic functional layer 50 includes one or more of an electron injection layer and an electron transport layer.

[0124] It can be understood that using the above-mentioned polymer as the material of the hole functional layer 20 and / or the electron blocking layer 30 can improve the migration efficiency of holes, block electrons from crossing the light-emitting layer 40 and entering the hole functional layer 20, and can also effectively prevent electrons and triplet excitons in the light-emitting layer 40 from diffusing toward the anode 10, thereby improving the photoelectric efficiency and stability of the photoelectric device.

[0125] In some embodiments, the material of the light-emitting layer 40 includes a light-emitting host material and a light-emitting guest material.

[0126] Furthermore, the luminescent host material is selected from one or more of the following structural formulas:

[0127]

[0128]

[0129]

[0130] The luminescent guest material is selected from one or more of the following structural formulas:

[0131]

[0132]

[0133] In some embodiments, the material of the electronic functional layer 50 includes one or more of inorganic electronic functional materials and organic electronic materials.

[0134] Furthermore, the inorganic electronic functional material includes one or more of doped metal oxide particles, undoped metal oxide particles, IIB-VIA semiconductor materials, IIIA-VA semiconductor materials and IB-IIIA-VIA semiconductor materials. The material of the undoped metal oxide particles includes one or more of ZnO, TiO2, SnO2, ZrO2, and Ta2O5. The metal oxide in the doped metal oxide particles includes one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, and Al2O3. The doping elements in the doped metal oxide particles include one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, and Ga. The IIB-VIA semiconductor material includes one or more of ZnS, ZnSe, and CdS. The IIIA-VA semiconductor material includes one or more of InP and GaP. The IB-IIIA-VIA semiconductor material includes one or more of CuInS and CuGaS.

[0135] The organic electronic functional material is selected from one or more of the following structural formulas:

[0136]

[0137]

[0138] In some embodiments, the anode 10 and the cathode 60 each independently include one or more of a metal, a carbon material and a metal oxide; the metal includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Yb and Mg; the carbon material includes one or more of graphite, carbon nanotubes, graphene and carbon fiber; the metal oxide includes a metal oxide electrode or a composite electrode in which a metal is arranged between doped or undoped transparent metal oxides, and the material of the metal oxide electrode includes one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, MoO3 and AMO, and the composite electrode includes one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2 and TiO2 / Al / TiO2. Here, “ / ” represents a stacked structure. For example, AZO / Ag / AZO represents a composite electrode including an AZO layer, an Ag layer and an AZO layer stacked in sequence.

[0139] In a sixth aspect, an embodiment of the present application further provides a display device, which includes the above-mentioned optoelectronic device.

[0140] The display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, laptops, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, car displays, televisions or e-book readers, among which smart wearable devices can be, for example, smart bracelets, smart watches, virtual reality (VR) helmets, etc.

[0141] The present application is described in detail below through specific embodiments. The following embodiments are only partial embodiments of the present application and are not limitations of the present application.

[0142] Example 1

[0143] This embodiment provides a polymer M1, and the preparation method thereof is as follows:

[0144] Compound a (CAS: 1344121-06-7) (2.5 mmol, 1.05 g), the first aryl halide 2-(3-bromophenyl)naphthalene (CAS: 667940-23-0) (3 mmol, 848 mg), Pd2(dba)3 (228 mg, 0.25 mmol), sodium tert-butoxide (1200 mg, 12.5 mmol) and tri-tert-butylphosphine (2.5 g, 12.5 mmol) were added to a 250 mL two-necked bottle, and 200 mL of ultra-dry toluene was added. The mixture was stirred and heated to 110 ° C under N2 atmosphere. The reaction was continued for 24 h, extracted with dichloromethane, dried, and filtered to obtain intermediate b1 (1.28 g, yield 82%). Mass spectrum: m / z = 628.33 [M+H] + ;

[0145] Compound b1 (2.5 mmol, 1567 mg), the second aryl halide 3,6-dibromo-9,9-dimethylfluorene (CAS: 865702-19-8) (2.75 mmol, 968 mg), Pd(PPh3)4 (0.125 mmol, 144 mg) and potassium phosphate (12.5 mmol, 1060 mg) were added to a 50 mL two-necked bottle, and then 30 mL of redistilled tetrahydrofuran was added, nitrogen was introduced, and a vacuum pump was used to evacuate the air for 20 min. The reaction solution was stirred and heated to 85 °C for reaction. After 24 hours, the reaction was stopped and cooled to room temperature. A chromatography column plugged with an appropriate amount of cotton was used as a filtering device. The filtrate was collected and added to 150 ml of methanol solution to precipitate the precipitate. The precipitate was allowed to stand, and the solid-liquid mixture was centrifuged at a speed of 100,000 rpm for 5 minutes. The supernatant was then sucked out and repeatedly washed with methanol three times, and then washed with ether three times. Finally, the obtained solid was dried at room temperature until the weight was constant. The yield was 80%. GPC was used for testing. The mobile phase was THF, the standard was polystyrene, and the weight average molecular weight (M w ) is 45000.

[0146] Embodiments 2 to 10

[0147] Examples 2 to 10 are substantially the same as Example 1, except that the compounds b in Examples 2 to 10 are b2 to b 10 The polymers are M3, M7, M8, M10, M88, M125, M139, M151 and M155 respectively.

[0148] Specifically, synthesize b1 to b 10 The first aryl halide used, b1 to b 10 The structural formula, yield and mass spectrum mass-to-charge ratio m / z are shown in Table 1:

[0149] Table 1

[0150]

[0151]

[0152]

[0153]

[0154] Specifically, the second aryl halide used in the synthesis of M1, M3, M7, M8, M10, M88, M125, M139, M151, and M155, the structural formula, yield, and weight average molecular weight M of M1, M3, M7, M8, M10, M88, M125, M139, M151, and M155 w As shown in Table 2:

[0155] Table 2

[0156]

[0157]

[0158]

[0159] Device Example 1

[0160] This embodiment provides a photoelectric device, and the preparation method is as follows:

[0161] Pretreatment of indium zinc oxide (IZO) coated glass (specifications: thickness 75nm, surface 30×30mm): Use a cleaning machine to perform program cleaning in sequence, with each step lasting 120s, for a total of six steps, then place the cleaned substrate on a 230℃ hot stage for baking for 30min, then place the dried substrate in UV exposure and O2 plasma treatment for 15min; use the pretreated glass substrate as the anode;

[0162] The samples were transferred to a nitrogen glove box, and PEDOT:PPS was poured into an inkjet printer cartridge. 9 pL of ink was injected into each pixel, and VD was performed for 5 min (vacuum degree was 1×10 -4 mPa), annealed at 230°C for 30 min to form a 40 nm thick hole injection layer;

[0163] The polymer M1 (concentration of 30 mg / mL) dissolved in a mixed solution of xylene and cyclohexylbenzene was filtered and poured into an inkjet printer cartridge. 12 picoliters of ink was injected into each pixel and subjected to VD5min (vacuum degree of 1×10 - 4 mPa), annealed at 230 ° C for 30 min to form a 35 nm thick hole transport layer;

[0164] The dissolved luminescent layer materials BH01 and BD01 (concentration 20 mg / ml, solvent methyl benzoate: cyclohexylbenzene = 4:1) were prepared into ink and poured into the inkjet printer cartridge. 10 picoliters were injected into each pixel of the hole transport layer and VD was performed for 5 min (vacuum degree 1×10 -4 mPa), annealed at 140°C for 20 min to form a light-emitting layer with a thickness of 35 nm;

[0165] Then transfer it to the vacuum evaporation chamber (vacuum degree is 5×10 -7 Pa), vacuum evaporation was performed to vacuum deposit ET01 and LiQ (in a ratio of 2:8) onto the surface of the light-emitting layer to form a 30 nm electron transport layer;

[0166] 1 nm Yb was evaporated onto the surface of the electron transport layer, and then 18 nm thick Ag was evaporated onto the Yb to form a cathode;

[0167] Then, CPL (60 nm) was evaporated onto the cathode to form a refractive layer. Finally, the device was packaged by UV curing and heated for 20 minutes to obtain a photoelectric device.

[0168] Device Examples 2 to 10

[0169] Device Examples 2 to 10 are substantially the same as Device Example 1, except that in Device Examples 2 to 10, polymer M1 is replaced by M3, M7, M8, M10, M88, M125, M139, M151 and M155, respectively.

[0170] Device Example 11

[0171] This device embodiment is basically the same as device embodiment 1, with the only difference being that, after forming the hole transport layer, this embodiment further includes: injecting polymer M151 (concentration of 15 mg / ml) dissolved in butyl benzoate and 1, 4-diisopropylbiphenyl (ratio of 8:2) into an inkjet printer cartridge, injecting 6 picoliters into each pixel light-emitting point to form a 20 nm thick electron blocking layer; forming a light-emitting layer on the electron blocking layer; the materials of the hole transport layer and the electron blocking layer are M1 / M151, respectively.

[0172] Device Examples 12 to 19

[0173] Device Examples 12 to 19 are basically the same as Device Example 11, with the only difference being that the materials of the hole transport layer and the electron blocking layer in Device Examples 12 to 19 are M1 / M155, M3 / M139, M3 / M151, M3 / M155, M7 / M88, M8 / M125, M10 / M88, and M10 / M139, respectively.

[0174] Device Comparison Examples 1 to 3

[0175] Device Comparative Examples 1 to 3 are substantially the same as Device Example 1, except that the polymer M1 of the hole transport layer is replaced by BH-1, BH-2 and BH-3 in Device Comparative Examples 1 to 3, respectively; wherein the structural formulas of BH-1, BH-2 and BH-3 are as follows:

[0176]

[0177] The anti-solvent properties of the hole transport layers of device embodiments 1 to 10 and device comparative examples 1 to 3 were tested respectively.

[0178] The test method of solvent resistance includes: after the hole transport layer is prepared, the solvent used for EML is dripped on its surface, 100ul (methyl benzoate: cyclohexylbenzene = 4:1) solution is dripped on the surface of the film material using a pipette gun, and spin-coated at 2000rmp / 60s, and then heated on a hot plate at 230°C for 30min, and finally observed and photographed under a microscope under ultraviolet light to obtain the result. Figure 3 , Figure 4 and Figure 5 shown.

[0179] Depend on Figure 3 to Figure 5 It can be obtained that compared with the comparative examples, the polymers provided in the present application have uniform surface film formation and no solvent erosion when the luminescent layer solvent is dropped on the surfaces of M1, M3, M7, M8, M10, M88, M125, M139, M151, and M155, the same as M1 without the luminescent layer solvent being added; while the surfaces of the hole transport layers of comparative examples 1 to 3 all have light and dark alternating patterns or holes to varying degrees, indicating that the luminescent layer solvent is dropped on the surfaces of comparative examples 1 to 3, which will cause varying degrees of erosion on the hole transport layers of comparative examples 1 to 3; this indicates that the polymers provided in the present application have good anti-erosion properties to solvents.

[0180] The turn-on voltage V of device embodiments 1 to 19 and device comparison examples 1 to 3 was measured. on , luminescence wavelength λ max , maximum brightness L max The relative values, external quantum efficiency EQE relative values ​​and lifetime LT95 relative values ​​are shown in Table 3.

[0181] Among them, the corresponding turn-on voltage and maximum brightness were measured by the efficiency test system built by Keithley 2400 and Keithley 6485;

[0182] The test method for external quantum efficiency EQE is: the ratio of the number of electron-hole pairs injected into quantum dots to the number of emitted photons, the unit is %, which is an important parameter to measure the quality of electroluminescent devices and can be obtained by measuring with EQE optical test instruments. The specific calculation formula is as follows:

[0183]

[0184] Among them, η e is the light output coupling efficiency, η r is the ratio of the number of recombined carriers to the number of injected carriers, χ is the ratio of the number of photon-generating excitons to the total number of excitons, K R is the radiation process rate, K NR is the rate of the non-radiative process.

[0185] Test conditions: carried out at room temperature, air humidity is 30-60%.

[0186] The test method for life span T95 is: the time required for the device to reduce its brightness to a certain proportion of the maximum brightness under constant current or voltage drive. The time when the brightness drops to 95% of the maximum brightness is defined as T95, and this life span is the measured life span. In order to shorten the test cycle, the device life span test is usually carried out at high brightness by accelerating device aging, and the life span at high brightness is obtained by fitting the extended exponential decay brightness attenuation fitting formula. For example, the life span at 1000nit is calculated as T95@1000nit. The specific calculation formula is as follows:

[0187]

[0188] Among them, T95 L For lifespan at low brightness, T95 H is the measured lifetime under high brightness, L H To accelerate the device to the highest brightness, L L is 1000nit, A is the acceleration factor, and this experiment measured the lifespan of several groups of green OLED devices at rated brightness and obtained an A value of 1.7.

[0189] Table 3

[0190]

[0191]

[0192] From Table 3, we can see that:

[0193] It can be seen from device embodiments 1 to 10 and device comparative examples 1 to 3 that the use of the polymer provided in the present application as a material for the hole transport layer can effectively improve the solvent corrosion resistance of the hole transport layer and improve the compactness of the hole transport layer, thereby reducing the turn-on voltage of the optoelectronic device and improving the maximum brightness, external quantum efficiency and service life of the optoelectronic device;

[0194] It can be seen from device embodiments 11 to 19 and device comparison example 1 that adding an electron blocking layer in the optoelectronic device can effectively prevent electrons in the light-emitting layer from entering the hole transport layer. Both the hole transport layer and the electron blocking layer use the polymer provided in the present application, which can further improve the solvent corrosion resistance of the hole transport layer and the electron blocking layer, thereby reducing the turn-on voltage of the optoelectronic device and improving the maximum brightness, external quantum efficiency and service life of the optoelectronic device.

[0195] The polymers and preparation methods thereof, inks, films, optoelectronic devices, and display devices provided in the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the methods and core ideas of the present application. At the same time, for technicians in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A polymer, characterized in that The structural formula of the polymer is shown in formula (I): Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

2. The polymer according to claim 1, characterized in that n is any integer from 60 to 90; and / or Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 20 to 40 ring atoms, a substituted or unsubstituted heteroaryl group having 20 to 40 ring atoms, or a combination thereof; and / or The substituted substituents each independently include one or more of D, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C6-C15 aryl, C1-C10 alkoxy, halogen, -OH, -NO2, -ONHNH2, -NHNH2, -NH2, -SH, -CN, -CHO, -SO3H; Optionally, the C1-C10 alkyl group includes one or more of methyl, ethyl, propyl, and butyl; Optionally, the C2-C10 alkenyl group includes one or more of vinyl, propenyl, and butenyl; Optionally, the C2-C10 alkynyl group includes one or more of ethynyl, propynyl, and butynyl; Optionally, the C6-C15 aryl group includes one or more of phenyl and naphthyl; Optionally, the C1-C10 alkoxy group includes one or more of methoxy, ethoxy, and propoxy; Optionally, the halogen includes one or more of -F, -Cl, -Br, and -I.

3. The polymer according to claim 1, characterized in that Ar1 is selected from any one of the structures shown in the following formula 1-1 to formula 1-26: and / or Ar2 is selected from any one of the structures shown in the following formula 2-1 to formula 2-22:

4. The polymer according to claim 1, characterized in that The polymer is selected from any one of the structures shown in the following formulas M1 to M155: Wherein, n is any integer between 50 and 100.

5. A method for preparing a polymer, characterized in that: include: Compound a and a first aryl halide are provided, wherein the chemical formula of the first aryl halide is Ar1-X1, and the structural formula of compound a is shown as follows: The compound a and the first aryl halide are mixed and reacted to obtain a compound b, the structural formula of the compound b is shown below: Providing a second aryl halide, wherein the chemical formula of the second aryl halide is X2-Ar2-X3; mixing the second aryl halide with the compound b, reacting, and obtaining a polymer, wherein the structural formula of the polymer is shown in formula (I): Wherein, X1, X2 and X3 are each independently selected from a halogen group; Ar1 ​​and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

6. The preparation method according to claim 5, characterized in that: X1, X2 and X3 are each independently selected from one of -F, -Cl, -Br, -I; and / or n is any integer from 60 to 90; and / or Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 20 to 40 ring atoms, a substituted or unsubstituted heteroaryl group having 20 to 40 ring atoms, or a combination thereof; and / or The substituted substituents each independently include one or more of D, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C6-C15 aryl, C1-C10 alkoxy, halogen, -OH, -NO2, -ONHNH2, -NHNH2, -NH2, -SH, -CN, -CHO, -SO3H; Optionally, the C1-C10 alkyl group includes one or more of methyl, ethyl, propyl, and butyl; Optionally, the C2-C10 alkenyl group includes one or more of vinyl, propenyl, and butenyl; Optionally, the C2-C10 alkynyl group includes one or more of ethynyl, propynyl, and butynyl; Optionally, the C6-C15 aryl group includes one or more of phenyl and naphthyl; Optionally, the C1-C10 alkoxy group includes one or more of methoxy, ethoxy, and propoxy; Optionally, the halogen includes one or more of -F, -Cl, -Br, and -I.

7. The preparation method according to claim 5, characterized in that: The molar ratio of the compound a to the first aryl halide is 1:(1.2-2.5); and / or The molar ratio of the compound b to the second aryl halide is 1:(1.05-1.15); and / or The reaction temperature of the compound a and the first aryl halide is 85° C. to 110° C. and the reaction time is 12 h to 24 h; and / or The reaction temperature of the compound b and the second aryl halide is 75° C. to 90° C. and the reaction time is 12 h to 24 h; and / or The reaction of the compound a and the first aryl halide, and the reaction of the compound b and the second aryl halide are respectively carried out in an inert atmosphere; and / or The mixing of the compound a and the first aryl halide further comprises adding one or more of a first catalyst, a first base, and a ligand; and / or The mixing of the compound b and the second aryl halide further comprises adding one or more of a second catalyst and a second base.

8. The preparation method according to claim 7, characterized in that: The first catalyst comprises one or more of tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and bis(methyldiphenylphosphine)palladium dichloride; and / or The first base comprises one or more of sodium tert-butoxide and potassium tert-butoxide; and / or The ligand includes one or more of tert-butylphosphine and triphenylphosphine; and / or The second catalyst comprises one or more of tetrakis(triphenylphosphine)palladium, diphenylphosphine, ferrocene, and palladium dichloride; and / or The second base comprises one or more of potassium phosphate, sodium carbonate, potassium carbonate, and potassium acetate; and / or The molar ratio of the compound a to the first catalyst is 1:(0.05-0.1); and / or The molar ratio of the compound a to the first base is 1:(5-10); and / or The molar ratio of the compound a to the ligand is 1:(5-10); and / or The molar ratio of the compound b to the second catalyst is 1:(3-8); and / or The molar ratio of the compound b to the second base is 1:(0.05-0.1).

9. An ink, characterized in that: The ink includes a polymer, and the structural formula of the polymer is shown in formula (I): Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

10. A film, characterized in that: The material of the film includes a polymer, and the structural formula of the polymer is shown in formula (I): Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

11. A photoelectric device, characterized in that: The invention comprises an anode, a functional layer and a cathode which are stacked in sequence; wherein the material of the functional layer comprises a polymer, and the structural formula of the polymer is shown in formula (I): Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

12. The optoelectronic device according to claim 11, characterized in that The functional layer includes a hole functional layer and an electron blocking layer; the material of the hole functional layer and / or the electron blocking layer includes a polymer, and the structural formula of the polymer is shown in formula (I): Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination thereof; n is any integer from 50 to 100, and the heteroatoms in the heteroaryl group include one or more of O, P, N, and S.

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