High-molecular polymers and organic electroluminescent components

Abstract

This invention relates to a polymer and an organic electroluminescent device. The polymer of this invention contains at least one of the following three repeating units and is end-capped by Ar1 and Ar2, wherein Ar1 and Ar2 represent R1 or R12 substituted or unsubstituted C6-C36 aryl groups, or R1 or R12 substituted or unsubstituted C5-C36 heteroaryl groups; m, n, and p represent the number of each repeating unit, m0, n0, and p0, and m and n are not simultaneously zero; at least one of R1-R12 is a crosslinking group. The polymer of this application, when used as a charge injection layer material or charge transport layer material in an organic electroluminescent device, exhibits good device efficiency and a low start-up voltage.

Description

High molecular polymer and organic electroluminescent element The present invention relates to the field of OLED technology and relates to a polymer that can be used to form an organic electroluminescent device (OLED), particularly as a charge injection / transport material. Furthermore, the present invention particularly relates to an organic electroluminescent device having a charge injection / transport layer formed using the polymer by a wet film formation method. Organic light-emitting diodes (OLEDs) are gaining increasing attention in display and lighting applications due to their inherent self-luminescence, high contrast, wide color gamut, wide viewing angle, and fast response time. However, OLEDs struggle to meet market demand due to their high cost and difficulty in mass production. This is primarily due to the need for further technical refinement and improvement of their production processes. There are two main OLED display process technologies: the more mature vapor deposition process and inkjet printing. These two processes differ significantly in terms of equipment, materials, and processes. Vapor deposition uses vacuum deposition to deposit small molecule OLED luminescent materials, but this is time-consuming and labor-intensive, with low material utilization and high costs. Inkjet printing uses a solvent to dissolve the OLED material into a uniform solution, which is then sprayed directly onto the substrate surface to form the RGB organic light-emitting layer. This method boasts high material utilization and low costs. Due to its unique technical characteristics and manufacturing advantages, inkjet printing is gradually becoming the mainstream production process for OLED panels and will revolutionize the production model of the entire display industry. Compared to elements formed by vacuum evaporation, wet film forming methods are difficult to stack and have poor driving stability. Therefore, in order to perform stacking using the wet film forming method, charge transport polymers with cross-linking groups have been developed. WO2009123269A1 and WO2013191088A1 disclose organic electroluminescent elements obtained by stacking polymers containing specific repeating units by wet film forming methods. US8974917B2 describes that in polymers having triarylamine repeating units, it is preferred that a fluorene ring be included in the main chain. In addition, it is described that the triplet energy of the polymer is increased by causing distortion by including a phenylene group having a substituent in the main chain of the polymer. TW201204687A discloses a compound in which a phenylene group having a substituent is connected between the nitrogen atoms of the main chain amine of an aromatic amine polymer or oligomer. WO2011099531A1 and CN102791768B disclose polymers having aromatic amine structures with carbazole structures on their side chains. CN1882632B discloses a polymer comprising fluorene repeating units substituted with crosslinkable groups, including double bonds, triple bonds, precursors capable of forming double bonds in situ, or heterocyclic addition-polymerizable groups. Benzocyclobutane (BCB) is disclosed as an exemplary crosslinkable group. WO2010013723A1 discloses polymers comprising double bond groups and BCB groups. WO2012003485A2 and WO2012003482A2 disclose hole transport layers formed by reacting hole transport compounds substituted with benzocyclobutane. CN101981086 A and WO2013191088A1 proposed benzocyclobutene and styrene crosslinking groups as crosslinking groups for polymers. However, the benzocyclobutene crosslinking group hinders charge transfer due to side reactions during crosslinking. However, light-emitting elements manufactured using polymers have a problem of high driving voltage. The object of the present application is to provide a high molecular weight polymer useful for producing a light-emitting element having a low driving voltage. The present application also aims to provide a light-emitting element containing the high molecular weight polymer. From the perspective of lowering the voltage and increasing the efficiency of an organic electroluminescent element, in some embodiments, the high molecular weight polymer for an organic electroluminescent element of the present application contains an electron-accepting group. From the perspective of lowering the voltage of an organic electroluminescent element, in some embodiments, the high molecular weight polymer for an organic electroluminescent element of the present application further contains a fluorene, an aromatic amine, or a carbazole compound. A polymer containing at least one of the following three repeating units and consisting of Ar 1. Ar 2 end-capping, ; Among them, Ar 1. Ar 2 independent representations are R 1 or R 12 Substituted or unsubstituted C6-C36 aryl, or R 1 or R 12 Substituted or unsubstituted C5-C36 heteroaryl; R 1-R 12 Each independently represents hydrogen, a substituted or unsubstituted C6-C36 aryl group, a substituted or unsubstituted C5-C36 heteroaryl group, a substituted or unsubstituted C1-C24 alkyl group, a substituted or unsubstituted C2-C24 alkenyl group, a substituted or unsubstituted C3-C24 cycloalkenyl group, a substituted or unsubstituted C6-C36 aryloxy group, a substituted or unsubstituted C5-C36 heteroaryloxy group, a substituted or unsubstituted C2-C24 alkoxycarbonyl group, a substituted or unsubstituted di-C1-C24 alkylamino group, a substituted or unsubstituted di-C6-C36 arylamino group, a substituted or unsubstituted C6-C36 aryl-C1-C24 alkylamino group, a substituted or unsubstituted C2-C24 alkanoyl group, a substituted or unsubstituted C8-C36 arylcycloalkyl group, or a substituted or unsubstituted C3-C24 epoxy group; wherein R 1-R 12 At least one of them is a cross-linking group; wherein R 1-R 12 The substitution is substituted by halogen, C1-C8 alkyl, C3-C8 epoxy, C1-C8 alkoxy, C2-C8 alkenyl, C6-C10 aryl or C4-C10 cycloalkenylalkyl; wherein m, n, p represent the number of repeating units, m≥0, n≥0, p≥0, and m and n are not zero at the same time, the weight average molecular weight Mw=10000-1000000, and the dispersion degree PDI=1.0-3.0. In some embodiments, the structure: has the structure of the following formula (I), (I) In some embodiments: R 1-R 12Each independently represents hydrogen, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C5-C24 heteroaryl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkenyl, substituted or unsubstituted C6-C24 aryloxy, substituted or unsubstituted C5-C24 heteroaryloxy, substituted or unsubstituted C2-C12 alkoxycarbonyl, substituted or unsubstituted di-C1-C12 alkylamino, substituted or unsubstituted di-C6-C24 arylamino, substituted or unsubstituted C6-C24 aryl-C1-C12 alkylamino, substituted or unsubstituted C2-C12 alkylyl, substituted or unsubstituted C8-C24 arylcycloalkyl, substituted or unsubstituted C3-C12 epoxy, wherein R 1-R 12 The substitution is substituted by halogen, C1-C6 alkyl, C3-C6 epoxy, C1-C6 alkoxy, C2-C6 alkenyl, C6-C10 aryl or C4-C10 cycloalkenylalkyl; m is greater than 0, n≥0, p≥0; and the weight average molecular weight Mw=20,000-800,000. In some embodiments: R 1. R 4. R 7. R 10 -R 12 Each independently represents hydrogen, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C3-C6 cycloalkenyl, substituted or unsubstituted C6-C12 aryloxy, substituted or unsubstituted C5-C12 heteroaryloxy, substituted or unsubstituted C2-C6 alkoxycarbonyl, substituted or unsubstituted di-C1-C6 alkylamino, substituted or unsubstituted di-C6-C12 arylamino, substituted or unsubstituted C6-C12 aryl-C1-C6 alkylamino, substituted or unsubstituted C2-C6 alkylyl, substituted or unsubstituted C8-C12 arylcycloalkyl, substituted or unsubstituted C3-C6 epoxy, and R 1. R 4. R 7. R 10 -R 12 At least one of them is a cross-linking group, R 2-R 3. R 5-R 6. R 8-R 9 each independently represents a substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted C5-C12 heteroaryl group, or a substituted or unsubstituted C1-C6 alkyl group; Mw = 50,000-500,000, and PDI = 1.5-2.5. The crosslinking group is R-substituted C8-C12 aryl and cycloalkyl, R-substituted C3-C6 epoxy, R-substituted C2-C6 alkenyl, C4-C10 cycloalkenyl substituted C8-C12 aryl, R-substituted vinyl phenylene, wherein R is hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl. In some embodiments: , wherein R is hydrogen, C1-C6 alkyl, or C6-C10 aryl. Ar 1. Ar 2 independent representations are R 1 or R 12 a substituted or unsubstituted C6-C10 aryl group. In some embodiments: (II) R 1. R 4. R 7. R 10 -R 12 Each independently represents hydrogen, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C3-C6 cycloalkenyl, substituted or unsubstituted C8-C12 arylcycloalkyl, substituted or unsubstituted C3-C6 epoxy; R 2 and R 3Same, R 5 and R 6 same, R 8 and R 9; Mw = 100000-300000, PDI = 1.7-2.3. The R 1. R 12 The definitions of m, n, and p are the same as above. In some embodiments: n=0-1000, m=1, p=0-1000. In some further embodiments: n=1-1000, m=1-1000, p=0-1000. Further in some embodiments: n=1-1000, m=1-1000, p=1-1000. R 2 and R 3Same, R 5 and R 6 same, R 8 and R 9 are the same, and R 4. R 7. R 10 -R 11 At least one of them is a cross-linking group. Application of the above-mentioned polymers in OLEDs. The OLED comprises at least one of a light-emitting layer, a charge injection layer, and a charge transport layer, and the high molecular polymer is used as a material in the light-emitting layer, the charge injection layer, and / or the charge transport layer. An organic electroluminescent element comprises at least one of a light-emitting layer, a charge injection layer and a charge transport layer, wherein the high molecular polymer is located in the light-emitting layer, the charge injection layer and / or the charge transport layer. The high molecular polymer is fixed in the organic electroluminescent element through a wet film forming method. Substituent R 1-R 12 , the following structures can be cited, but are not limited to the following structures. For example, a linear, branched, or cyclic alkyl group having generally 1 or more, in some embodiments 4 or more and generally 24 or less, in some embodiments 12 or less, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, and a dodecyl group; For example, an alkenyl group such as a vinyl group usually has 2 or more and usually has 24 or less carbon atoms, and in some embodiments, has 12 or less carbon atoms; an alkynyl group such as an ethynyl group usually has 2 or more and usually has 24 or less carbon atoms, and in some embodiments, has 12 or less carbon atoms; For example, alkoxy groups such as methoxy and ethoxy groups generally have 1 or more carbon atoms and usually 24 or less, and in some embodiments, 12 or less carbon atoms; For example, aryloxy or heteroaryloxy groups such as phenoxy, naphthyloxy, and pyridyloxy groups generally have 4 or more carbon atoms, in some embodiments 5 or more and generally 36 or less, and in some embodiments 24 carbon atoms; For example, alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl generally have 2 or more carbon atoms and usually 24 or less, and in some embodiments, 12 or less carbon atoms; For example, dialkylamino groups such as dimethylamino and diethylamino groups generally have 2 or more carbon atoms and usually 24 or less, and in some embodiments, 12 or less carbon atoms; For example, diarylamino groups such as diphenylamino, ditolylamino, and N-carbazolyl groups generally have 10 or more carbon atoms, in some embodiments 12 or more, and generally 36 or less, in some embodiments 24 or less carbon atoms; For example, an arylalkylamino group having generally 7 or more carbon atoms and generally 36 or less, and in some embodiments, 24 or less carbon atoms, such as a phenylmethylamino group; For example, acyl groups such as acetyl and benzyl groups generally have 2 or more carbon atoms and generally 24 or less, and in some embodiments, 12 or less carbon atoms; For example, aryl groups such as phenyl and naphthyl generally have 6 or more carbon atoms and usually 36 or less, and in some embodiments, 24 or less carbon atoms; For example, heteroaryl groups such as thienyl and pyridyl usually have 3 or more carbon atoms, in some embodiments, 4 or more carbon atoms, and usually have 36 or less carbon atoms, in some embodiments, 24 or less carbon atoms. In some embodiments, it is the above-mentioned alkyl group, alkoxy group, aryl group, or heteroaryl group. In some embodiments, it has no substituent, that is, is hydrogen, from the viewpoint of charge transport properties. Examples of aryl and heteroaryl groups include, but are not limited to, the following structures. For example, groups such as phenyl, naphthyl, phenanthryl, thienyl, pyridyl, furyl, benzofuranyl, benzothienyl, pyrrolyl, pyrazolyl, imidazolyl, oxadiazolyl, indolyl, carbazolyl, pyrroloimidazolyl, pyrrolopyrrolyl, pyrrolopyrazolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuryl, thienofuranyl, benzisoxazolyl, benzisothienyl, benzimidazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, shinorine, quinoxalinyl, phenanthridinyl, benzimidazolyl, perylidenephenyl, quinazolinyl, quinazolinonyl, and azulenyl groups, In addition, the above-mentioned substituents may be further substituted, for example, by the same groups as the above-mentioned substituents (substituents) or by crosslinking groups described below. In some embodiments, they are not further substituted, or are substituted by an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a phenyl group, or a crosslinking group described below. From the viewpoint of charge transport properties, in some embodiments, no further substitution is performed. The polymer of the present application must have a crosslinking group. By having a crosslinking group, a large difference in solubility in a solvent can be generated before and after the reaction (insolubilization reaction) initiated by heat and / or irradiation with active energy rays. The crosslinkable group refers to a group that reacts with the same or different group of another nearby molecule by heat and / or irradiation with active energy rays to form a new chemical bond. The polymer of the present application has three repeated polymerization units, and there is no distinction between the order of the three repeating polymerization units. Formula (I) and formula (II) only represent the structure of the polymerization units. The polymer of the present application, when used as a charge injection layer or transport layer material in an OLED device, has the characteristics of low starting voltage and high device efficiency. The present application is further described in detail below with reference to the embodiments. All raw materials used are commercially available. Method for producing a polymer body The polymer body can be used Rev., 109, 897-1091, 2009, etc., and can be produced by a known polymerization method, for example, a polymerization method using a coupling reaction with a transition metal catalyst such as Suzuki reaction, Yamamoto reaction, Buchwald reaction, Stille reaction, Negishi reaction, and Kumada reaction. Example 1 (Polymer Compound 1) Take a 250 mL double-necked round-bottom flask, accurately weigh compound 1 (1.0 g, 1.431 mmol) and compound 2 (610 mg, 1.431 mmol), then add toluene (50 mL) and the prepared 2M K 2CO 3 (10 mL), replace N 2 three times, then N 2. Bubble with balloon for 20 min. Then, add the weighed catalyst Pd 2(dba) 365.5 mg (0.072 mmol) and ligand x-phos 68.2 mg (0.143 mmol), add one drop of Aliquat 336, and continue N 2. Bubble for 20 min. Remove the balloon, seal the device, heat to 96 °C, and react for 26 h. Dissolve 0.1 g of bromobenzene in 1 mL of toluene, add to the reaction solution and stir for 1 h to cap the end. Dissolve 0.1 g of phenylboronic acid in 1 mL of toluene, add to the reaction solution and stir for 1 h to cap the end. After completion, add 10 mL of saturated sodium diethyldithiocarbamate and continue stirring for 14 h. Cool the reaction to room temperature and 80 oC Most of the toluene and water were removed by spin drying. Then, approximately 20 mL of toluene was added to dissolve the crude product. The product was then precipitated in 800 mL of methanol at room temperature, washed with water, and dried. The product was then concentrated and precipitated again after column chromatography with dichloromethane to yield a white, yellowish solid. Drying at 70°C for 24 h yielded 0.48 g, a 47.1% yield. The product had an Mn of 68,800, an Mw of 133,472, and a PDI (Mw / Mn) of 1.94. The n value was 187 (133,472 / 712). The NMR spectrum is shown in Figure 1. Example 2 (Polymer Compound 2) Take a 250 mL double-necked round-bottom flask, first accurately weigh compound 1 (1.0 g, 1.431 mmol), compound 2 (244 mg, 0.572 mmol), compound 3 (412 mg, 0.859 mmol), then add toluene (50 mL) and the prepared 2M K 2CO 3 (10 mL), replace N 2 three times, then N 2. Bubble with balloon for 20 min. Then, add the weighed catalyst Pd 2(dba) 365.5 mg (0.072 mmol) and ligand x-phos 68.2 mg (0.143 mmol), add a drop of Aliquat 336, and continue N 2 Bubble for 20 min. Remove the balloon, seal the device, heat to 96 °C, and react for 26 h. Dissolve 0.1 g of bromobenzene in 1 mL of toluene, add to the reaction solution and stir for 1 h to cap the end. Dissolve 0.1 g of 4-vinylphenylboronic acid in 1 mL of toluene, add to the reaction solution and stir for 1 h to cap the end. After completion, add 10 mL of saturated sodium diethyldithiocarbamate and continue stirring for 14 h. Cool the reaction to room temperature and 80 oC Most of the toluene and water were removed by spin drying. Then, approximately 20 mL of toluene was added to dissolve the crude product. The product was then precipitated in 800 mL of methanol at room temperature, washed with water, and dried. The product was then concentrated and precipitated again after column chromatography with dichloromethane to yield a white to yellowish solid. This solid was then dried at 70°C for 24 h to yield 0.53 g of product, with a yield of 45.8%. The product had a number-average molecular weight (Mn) of 115,100, a weight-average molecular weight (Mw) of 231,351, and a PDI (Mw / Mn) of 2.01. The NMR spectrum is shown in Figure 2. Example 3 (Polymer Compound 3) Take a 250 mL double-necked round-bottom flask, first accurately weigh compound 1 (1.0 g, 1.431 mmol), compound 2 (244 mg, 0.572 mmol), compound 3 (412 mg, 0.572 mmol), compound 4 (134 mg, 0.287 mmol), then add toluene (50 mL) and the prepared 2M K 2CO 3 (10 mL), replace N 2 three times, then N 2. Bubble with balloon for 20 min. Then, add the weighed catalyst Pd 2(dba) 365.5 mg (0.072 mmol) and ligand x-phos 68.2 mg (0.143 mmol), add a drop of Aliquat 336, and continue N 2. Bubble for 20 min. Remove the balloon, seal the device, heat to 96 °C, and react for 26 h. Dissolve 0.1 g of bromobenzene in 1 mL of toluene, add to the reaction solution and stir for 1 h to cap the end. Dissolve 0.1 g of 4-vinylphenylboronic acid in 1 mL of toluene, add to the reaction solution and stir for 1 h to cap the end. After completion, add 10 mL of saturated sodium diethyldithiocarbamate and continue stirring for 14 h. Cool the reaction to room temperature and 80 oCMost of the toluene and water were removed by spin drying. Then, approximately 20 mL of toluene was added to dissolve the crude product. The product was then precipitated in 800 mL of methanol at room temperature, washed with water, and dried. The product was then filtered through a column using dichloromethane. The resulting product was concentrated and precipitated again to yield a white to yellowish solid. Drying at 70°C for 24 h yielded 0.58 g of the product, with a yield of 46.4%. Mn = 105,200, Mw = 207,244, and PDI = 1.97. The NMR spectrum is shown in Figure 3. Example 4- (Polymer Compound 4) Take a 250 mL double-necked round-bottom flask, first accurately weigh compound 1 (1.0 g, 1.431 mmol), compound 3 (245 mg, 0.572 mmol,), and compound 5 (412 mg, 0.859 mmol), then add toluene (50 mL) and the prepared 2M K 2CO 3 (10 mL), replace N 2 three times, then N 2. Bubble with balloon for 20 min. Then, add the weighed catalyst Pd 2(dba) 365.5 mg (0.072 mmol) of methyl paraben and 68.2 mg (0.143 mmol) of the ligand x-phos were added with a drop of Aliquat 336, and N2 bubbling was continued for 20 minutes. The balloon was removed, the apparatus sealed, and the reaction was heated to 96°C for 26 hours. A small amount of the reaction solution was added dropwise to methanol (1.5 mL) and n-hexane (1.5 mL). The precipitate was filamentous and the reaction solution did not become rubbery. 0.1 g of bromobenzene was dissolved in 1 mL of toluene and added to the reaction solution with stirring for 1 hour to cap the end. 0.1 g of phenylboric acid was dissolved in 1 mL of toluene and added to the reaction solution with stirring for 1 hour to cap the end. After completion, 10 mL of saturated sodium diethyldithiocarbamate was added and stirring continued for 14 hours. The reaction mixture was cooled to room temperature and most of the toluene and water were evaporated at 80°C. Approximately 20 mL of toluene was then added to dissolve the crude product. The product was then precipitated in 800 mL of methanol at room temperature, washed with water, and then dried. The product was then concentrated and precipitated again using dichloromethane to obtain a white to yellowish solid. The product was then dried at 70°C for 24 h to yield 0.48 g of the product, with a yield of 41.9%. Mn = 110100, Mw = 199281, and PDI = 1.81. The NMR spectrum is shown in Figure 4. Example 5 (Polymer Compound 5) Take a 250 mL double-necked round-bottom flask, first accurately weigh compound 1 (1.0 g, 1.431 mmol), compound 3 (0.685 g, 1.431 mmol), then add toluene (50 mL) and the prepared 2M K 2CO 3 (10 mL), replace N 2 three times, then N 2. Bubble with balloon for 20 min. Then, add the weighed catalyst Pd 2(dba) 365.5 mg (0.072 mmol) and ligand x-phos 68.2 mg (0.143 mmol), add a drop of Aliquat 336, and continue N 2 Bubble for 20 min. Remove the balloon, seal the device, heat to 96 °C, and react for 26 h. Take 0.07 g of compound 3 and dissolve it in 1 mL of toluene. Add it to the reaction solution and stir for 1 h. Then take 0.1 g of 4-vinylphenylboronic acid and dissolve it in 1 mL of toluene. Add it to the reaction solution and stir for 1 h to cap the end. After completion, add 10 mL of saturated sodium diethyldithiocarbamate (metal chelator) and continue stirring for 14 h. Cool the reaction to room temperature and 80 oC Most of the toluene and water were removed by spin drying. Then, approximately 20 mL of toluene was added to dissolve the crude product. The product was then precipitated in 800 mL of methanol at room temperature, washed with water, and dried. The product was then filtered through a column using dichloromethane. The resulting product was concentrated and precipitated again to yield a white to yellowish solid. Drying at 70°C for 24 h yielded 0.45 g, a yield of 41.1%. The product had an Mn of 62,220, an Mw of 120,710, and a PDI (Mw / Mn) of 1.94. The NMR spectrum is shown in Figure 5. Example 6 (Polymer Compound 6) Take a 250 mL double-necked round-bottom flask, first accurately weigh compound 1 (1.0 g, 1.431 mmol) and compound 4 (0.668 g, 1.431 mmol), then add toluene (50 mL) and the prepared 2M K 2CO 3 (10 mL), replace N 2 three times, then N 2. Bubble with balloon for 20 min. Then, add the weighed catalyst Pd 2(dba) 365.5 mg (0.072 mmol) and ligand x-phos 68.2 mg (0.143 mmol), add a drop of Aliquat 336, and continue N 2. Bubble for 20 min. Remove the balloon, seal the device, heat to 96 °C, and react for 26 h. Dissolve 0.1 g of compound 4 in 1 mL of toluene, add the reaction solution and stir for 1 h. Dissolve 0.1 g of 4-vinylphenylboronic acid in 1 mL of toluene, add the reaction solution and stir for 1 h to cap the end. After completion, add 10 mL of saturated sodium diethyldithiocarbamate (metal chelator) and continue stirring for 14 h. Cool the reaction to room temperature and 80 oC Most of the toluene and water were removed by spin drying. Then, approximately 20 mL of toluene was added to dissolve the crude product. The product was then precipitated in 800 mL of methanol at room temperature, washed with water, and dried. The product was then filtered through a column using dichloromethane. The resulting product was concentrated and precipitated again to yield a white to yellowish solid. Drying at 70°C for 24 h yielded 0.47 g, a 43.3% yield. The product had an Mn of 57,700, an Mw of 109,640, and a PDI (Mw / Mn) of 1.90. The NMR spectrum is shown in Figure 6. Example 7-Comparative Example 1 (Polymer Compound 7) Take a 250 mL double-necked round-bottom flask, accurately weigh compound 1 (1.0 g, 1.431 mmol) and compound 6 (0.785 mg, 1.431 mmol), then add toluene (50 mL) and the prepared 2M K 2CO 3 (10 mL), replace N 2 three times, then N 2. Bubble with balloon for 20 min. Then, add the weighed catalyst Pd 2(dba) 365.5 mg (0.072 mmol) and ligand x-phos 68.2 mg (0.143 mmol), add a drop of Aliquat 336, and continue N 2 Bubble for 20 min. Remove the balloon, seal the device, heat to 96 °C, and react for 26 h. Take 0.1 g of 4-bromostyrene and dissolve it in 1 mL of toluene. Add it to the reaction solution and stir for 1 h to cap the end. Take 0.1 g of 4-vinylphenylboronic acid and dissolve it in 1 mL of toluene. Add it to the reaction solution and stir for 1 h to cap the end. After completion, add 10 mL of saturated sodium diethyldithiocarbamate (metal chelator) and continue stirring for 14 h. Cool the reaction to room temperature and 80 oC Most of the toluene and water were removed by spin drying. Then, approximately 20 mL of toluene was added to dissolve the crude product. The product was then precipitated in 800 mL of methanol at room temperature, washed with water, and dried. The product was then filtered through a column using dichloromethane. The resulting product was concentrated and precipitated again to yield a white to yellowish solid. Drying at 70°C for 24 h yielded 0.67 g, a yield of 56.3%. The product had an Mn = 77,900, an Mw = 148,100, and a PDI (Mw / Mn) = 1.90. The NMR spectrum is shown in Figure 7. Example 8 Fabrication of Devices OLEDs 1 to 7 OLED devices with an ITO / hole injection layer / hole transport layer / EML / ETL / cathode structure (OLEDs 1 to 7) were fabricated according to the following steps: 1) A 50 nm layer of PEDOT (Clevios™ P VP AI 4083) was applied as a hole injection layer onto an ITO (indium tin oxide) glass substrate by spin coating in a clean room and dried by heating at 230°C in air for 15 minutes. 2) A 20 nm layer of hole transport layer was applied by spin coating a 0.5 wt% methyl benzoate solution of polymers 1-7 in a glove box. 3) The hole transport layer was dried by heating at 230°C for 30 minutes in a glove box. 4) A 40 nm layer of EML / 35 nm layer of ETL / 1 nm layer of Yb / 100 nm layer of Ag were vapor deposited. 5) The device was encapsulated. (TWI774078B) (CPD13 CN 111377969 A) The device results of OLED1 to OLED8 are as follows The results show that OLEDs 1-5 have better device efficiency and lower operating voltage than devices 6 and 7. OLEDs 2-3, in particular, exhibit excellent performance across all performance indicators. This suggests that the choice of repeating unit has a direct impact on device performance. From the device data of OLED 4-7, it can be seen that the device of the present application has a relatively high efficiency and a relatively low starting voltage by adding olefin groups as cross-linking groups, which indicates that the addition of cross-linking groups improves the performance of the polymer of the present application. Figure 1 is the NMR spectrum of polymer compound 1; Figure 2 is the NMR spectrum of polymer compound 2; Figure 3 is the NMR spectrum of polymer compound 3; Figure 4 is the NMR spectrum of polymer compound 4; Figure 5 is the NMR spectrum of polymer compound 5; Figure 6 is the NMR spectrum of polymer compound 6; and Figure 7 is the NMR spectrum of polymer compound 7.

Claims

1. A polymer having the structure of formula (I) below, (I) wherein Ar1 and Ar2 are independently represented as R1 or R12 substituted or unsubstituted C6-C36 aryl, or R1 or R12 substituted or unsubstituted C5-C36 heteroaryl; wherein R1-R12 are each independently represented as hydrogen, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C5-C24 heteroaryl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkenyl, substituted or unsubstituted C6-C24 aryloxy, substituted or unsubstituted C5-C24 heteroaryloxy, substituted or unsubstituted C2-C12 alkoxycarbonyl, substituted or unsubstituted di-C1-C12 alkylamino, substituted or unsubstituted di- C6-C24 arylamino, substituted or unsubstituted C6-C24 aryl-C1-C12 alkylamino, substituted or unsubstituted C2-C12 alkoxy, substituted or unsubstituted C8-C24 arylcycloalkyl, or substituted or unsubstituted C3-C12 epoxy, wherein the substitution in R1-R12 is by halogen, C1-C6 alkyl, C3-C6 epoxy, C1-C6 alkoxy, C2-C6 alkenyl, C6-C10 aryl, or C4-C10 cycloalkenyl. At least one of R1-R12 is a crosslinking group; the crosslinking group is an R-substituted C8-C12 aryl-cycloalkyl group, an R-substituted C3-C6 epoxy group, an R-substituted C2-C6 alkenyl group, a C4-C10 cycloalkenyl-substituted C8-C12 aryl group, or an R-substituted vinylphenyl group, wherein R is hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, or C6-C10 aryl; where m, n, and p represent the number of repeating units, wherein: m=1~1000, n=1~1000, p=0~1000; Mw is 20000-800000, and the dispersion PDI is 1.0-3.

0.

2. The polymer as claimed in claim 1, wherein, R1, R4, R7, and R10-R12 are each independently represented as hydrogen, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C3-C6 cycloalkenyl, substituted or unsubstituted C6-C12 aryloxy, substituted or unsubstituted C5-C12 heteroaryloxy, substituted or unsubstituted C2-C6 alkoxycarbonyl, substituted or unsubstituted di-C1-C6 alkylamino, substituted or unsubstituted di-C6-C12 arylamino, substituted or unsubstituted C6-C12 aryl- C1-C6 alkylamino, substituted or unsubstituted C2-C6 alkyl, substituted or unsubstituted C8-C12 arylcycloalkyl, or substituted or unsubstituted C3-C6 epoxy; at least one of R1, R4, R7, R10-R12 is a crosslinking group; R2-R3, R5-R6, R8-R9 each independently represent substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl, or substituted or unsubstituted C1-C6 alkyl; Mw is 50000-500000, and PDI is 1.5-2.

5.

3. The polymer as claimed in claim 1, wherein, The crosslinking group is one of the following structures, wherein R is hydrogen, C1-C6 alkyl or C6-C10 aryl.

4. The polymer as claimed in any one of claims 1 to 3, wherein, Ar1 and Ar2 are independently represented as aryl groups of C6-C10 with or without R1 or R12 substitution.

5. The polymer as claimed in claim 4, having a structure as shown in formula (II), wherein (II) R1, R4, R7, R10-R12 each independently represent hydrogen, a substituted or unsubstituted C6-C12 aryl, a substituted or unsubstituted C5-C12 heteroaryl, a substituted or unsubstituted C1-C6 alkyl, a substituted or unsubstituted C2-C6 alkenyl, a substituted or unsubstituted C3-C6 cycloalkenyl, a substituted or unsubstituted C8-C12 arylcycloalkyl, or a substituted or unsubstituted C3-C6 epoxy group; R2-R3, R5-R6, R8-R9 each independently represent a substituted or unsubstituted C6-C12 aryl, a substituted or unsubstituted C5-C12 heteroaryl, or a substituted or unsubstituted C1-C6 alkyl; R2 is the same as R3, R5 is the same as R6, and R8 is the same as R9; Mw is 100,000-300,000, and the dispersion PDI is 1.7-2.3; the definitions of m, n, and p are the same as those in request item 1.

6. The polymer as claimed in claim 5, wherein, R1 and R12 are the same and are both cross-linking groups.

7. The polymer as claimed in claim 1, wherein: m=1~1000, n=1~1000, p=1~1000.

8. The polymer as claimed in claim 7, wherein, R2 is the same as R3, R5 is the same as R6, R8 is the same as R9, and at least one of R4, R7, and R10-R11 is a cross-linking group.

9. An organic electroluminescent element comprising a polymer as described in any one of claims 1 to 8.

10. The organic electroluminescent element as claimed in claim 9, wherein, It includes at least one of a light-emitting layer, a charge-injection layer, and a charge-transport layer, wherein the polymer is located in the light-emitting layer, the charge-injection layer, and / or the charge-transport layer.

11. The organic electroluminescent element as claimed in claim 9, wherein, The polymer is immobilized in the organic electroluminescent element using a wet film-forming method.

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