Boron-containing hetero-fused ring polymer and its preparation method and application

Abstract

The present invention provides a boron-containing hetero-fused ring polymer, a preparation method, and an application thereof, wherein the general chemical structure formula of the boron-containing hetero-fused ring polymer is: #imgabs0# The present invention introduces boron, a main group element with excellent photoelectric properties, into a fused ring compound, and by introducing different electron-donating functional groups, the photophysical properties of the resulting fluorescent compound can be regulated over a large range; the boron-containing hetero-fused ring polymer is used as a light-emitting layer material to prepare a semiconductor device, and the resulting semiconductor device exhibits excellent photophysical properties and photochemical stability, and can obtain luminescence with high color purity.

Description

Technical Field

[0001] The present invention relates to the technical field of organic materials, and in particular to a boron-containing hetero-fused ring polymer and a preparation method and application thereof. Technical Background

[0002] According to quantum spin statistics, the electroluminescence process produces 25% singlet excitons and 75% triplet excitons. Due to spin prohibition, these excitons cannot transition between each other in common organic materials. Only singlet excitons can be used for fluorescence, while triplet excitons are typically dissipated as heat. To utilize triplet excitons, noble metal complexes are introduced. Spin-orbit coupling between the heavy metal and its ligand can convert singlet excitons to triplet states, resulting in phosphorescence. However, phosphorescent devices suffer from difficult-to-solve drawbacks such as short lifespan, high cost, and heavy metal toxicity.

[0003] Thermally activated delayed fluorescence (TADF) materials can achieve 100% internal quantum efficiency without the use of heavy metals, thus attracting widespread attention from both academia and industry. In 2011, the first purely organic small molecule TADF luminescent material, PIC-TRZ, was reported [Appl. Phys. Lett., 2011, 98, 1]. Its device achieved a maximum external quantum efficiency (EQE) of 5.3% at low current density. After nearly a decade of development, TADF materials have achieved emission colors covering the entire visible light spectrum, with EQE exceeding 37% [Nat. Photon., 2018, 12, 235].

[0004] However, when small molecule compounds are used in light-emitting devices, they often need to be made by evaporation. The preparation process is complicated, which increases the production cost of the product and makes it difficult to obtain large-area devices. On the other hand, since small molecules are prone to crystallization and agglomeration, it will affect the quality of the film and reduce the efficiency and long-term stability of OLEDs devices. In terms of device performance, there is a certain gap between polymer materials with TADF properties and small molecules. However, the solution method for obtaining OLEDs devices based on polymer TADF materials can not only obtain large-area devices at a low cost, but also because polymers are not easy to crystallize and agglomerate, they also have unique advantages in terms of stability.

[0005] Therefore, the existing technology still needs to be improved and developed. Summary of the Invention

[0006] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a boron-containing heterocyclic polymer and its preparation method and application, aiming to solve the problems of poor stability, sensitivity to water and oxygen, and poor solubility of existing organic light-emitting polymer materials when used in light-emitting devices.

[0007] The technical solutions of the present invention are as follows:

[0008] The present invention provides a boron-containing hetero-fused ring polymer, wherein the general chemical structure formula of the boron-containing hetero-fused ring polymer is:

[0009] Wherein, X and Y are nitrogen group element atoms or oxygen group element atoms, and when X and Y are oxygen group element atoms, there is no substituent;

[0010] The bridging unit in the general chemical structure formula represents the connection mode between the γ ring and the N atom, which is a chemical bond; or the bridging unit in the general chemical structure formula is a conjugated aromatic ring group having 5-50 ring atoms, a non-conjugated aromatic ring group having 5-50 ring atoms, an aromatic heterocyclic group having 5-30 ring atoms, a linear alkyl chain having 1-100 carbon atoms, a branched alkyl chain having 1-100 carbon atoms, or a fluorinated alkyl chain having 1-100 carbon atoms;

[0011] R1, R2, R3, …, R 25 , R 26 , R 27 are independently a hydrogen atom, an aromatic ring group having 5 to 50 ring atoms, an aromatic heterocyclic group having 5 to 30 ring atoms, a linear alkyl chain having 1 to 100 carbon atoms, a branched alkyl chain having 1 to 100 carbon atoms, or a fluorinated alkyl chain having 1 to 100 carbon atoms;

[0012] x1, x2, and n are positive integers.

[0013] The present invention also provides a method for preparing a boron-containing hetero-fused ring polymer, which comprises the steps of:

[0014] Add the following into a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser: The three monomers and dichloromethane are mixed to obtain a 1M concentration of the monomer containing a carbonyl group. After ice bath treatment, trifluoromethanesulfonic acid is added. After the dichloromethane no longer refluxes, the ice bath is removed to obtain a reaction product.

[0015] The reaction product is subjected to solvent treatment, sedimentation treatment, centrifugation treatment, and then dried to obtain a light yellow solid, that is, the boron-containing hetero-condensed ring polymer.

[0016] The present invention also provides an application of the boron-containing hetero-condensed ring polymer, wherein the boron-containing hetero-condensed ring polymer is used as a light-emitting layer material of a semiconductor device.

[0017] Beneficial effect: The present invention provides a chemical structure of Boron-containing hetero-fused ring polymers. The inherent electron deficiency (Lewis acidity) of boron atoms makes boron-containing organic conjugated molecules ideal electron acceptor materials, thus having very broad application prospects in organic optoelectronics. By introducing different electron-donating functional groups, the photophysical properties of the resulting fluorescent compounds can be regulated over a wide range, thereby generating a rich variety of optical behaviors, thereby achieving outstanding optoelectronic applications. The present invention introduces boron, a main-group element with excellent optoelectronic properties, into fused ring compounds to simply and efficiently prepare a series of boron-containing hetero-fused ring polymers. Based on this, semiconductor devices are prepared. The resulting semiconductor devices exhibit excellent photophysical properties and photochemical stability, and can obtain high-color purity luminescence. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 These are the UV-visible absorption spectrum, fluorescence emission spectrum and phosphorescence emission spectrum of polymer P1.

[0019] Figure 2 These are the UV-visible absorption spectrum, fluorescence emission spectrum and phosphorescence emission spectrum of polymer P13.

[0020] Figure 3 These are the UV-visible absorption spectrum, fluorescence emission spectrum and phosphorescence emission spectrum of polymer P17.

[0021] Figure 4 The UV-visible absorption spectrum, fluorescence emission spectrum and phosphorescence emission spectrum of polymer P21 are shown.

[0022] Figure 5 The current-voltage curves and brightness-voltage curves of light-emitting devices based on polymers P1, P13, P17 and P21 are shown.

[0023] Figure 6 This is a graph showing the external quantum efficiency-brightness curves of light-emitting devices based on polymers P1, P13, P17, and P21. DETAILED DESCRIPTION

[0024] The present invention provides a boron-containing hetero-fused ring polymer and its preparation method and application. To make the objectives, technical solutions, and effects of the present invention more clear and explicit, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention.

[0025] The present invention provides a boron-containing hetero-fused ring polymer, wherein the general chemical structure formula of the boron-containing hetero-fused ring polymer is:

[0026] Wherein, X and Y are nitrogen group element atoms or oxygen group element atoms, and when X and Y are oxygen group element atoms, there is no substituent;

[0027] The bridging unit in the general chemical structure formula represents the connection mode between the γ ring and the N atom, which is a chemical bond; or the bridging unit in the general chemical structure formula is a conjugated aromatic ring group having 5-50 ring atoms, a non-conjugated aromatic ring group having 5-50 ring atoms, an aromatic heterocyclic group having 5-30 ring atoms, a linear alkyl chain having 1-100 carbon atoms, a branched alkyl chain having 1-100 carbon atoms, or a fluorinated alkyl chain having 1-100 carbon atoms;

[0028] R1, R2, R3, …, R 25 , R 26 , R 27 are independently a hydrogen atom, an aromatic ring group having 5 to 50 ring atoms, an aromatic heterocyclic group having 5 to 30 ring atoms, a linear alkyl chain having 1 to 100 carbon atoms, a branched alkyl chain having 1 to 100 carbon atoms, or a fluorinated alkyl chain having 1 to 100 carbon atoms;

[0029] x1, x2, and n are positive integers.

[0030] In this embodiment, due to the inherent electron deficiency (Lewis acidity) of boron atoms, boron-containing organic conjugated molecules can become ideal electron acceptor materials, thus having very broad application prospects in organic photoelectricity. This embodiment introduces the main group element boron with excellent photoelectric properties into fused ring compounds, and through the introduction of different electron-donating functional groups, the photophysical properties of the resulting fluorescent compounds can be regulated on a large scale, thereby producing rich optical behaviors, thereby simply and efficiently preparing a series of outstanding boron-containing heterofused ring polymers. The boron-containing heterofused ring polymer is used as a light-emitting layer material to prepare semiconductor devices. The resulting semiconductor devices exhibit excellent photophysical properties and photochemical stability, and can obtain luminescence with high color purity.

[0031] In some embodiments, in the boron-containing hetero-fused ring polymer, R1 and R2 can be linked to each other by covalent bonds to form a ring; the α ring and the β ring, the δ ring and the ε ring, and the ζ ring and the η ring can be linked to each other by covalent bonds to form a ring; R 19 and R 20 It can be independently connected to the α ring, β ring and γ ring by covalent bonds to form a ring.

[0032] In some embodiments, the bridging unit in the general chemical structure is one of the following chemical structures:

[0033] Wherein, R is selected from hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfone, halogen, cyano, alkyl, alkoxy, substituted or unsubstituted C6-C60 aromatic ring group, substituted or unsubstituted C3-C60 aromatic heterocyclic group.

[0034] In some embodiments, the R1 is selected from one of the following chemical formulas:

[0035] Wherein, R is selected from hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfone, halogen, cyano, alkyl, alkoxy, substituted or unsubstituted C6-C60 aromatic ring group, substituted or unsubstituted C3-C60 aromatic heterocyclic group.

[0036] In some embodiments, the R2 is selected from one of the following chemical formulas:

[0037]

[0038] In some embodiments, the R3, R4, R5, R6, R7, R8, R9 and R 10 Independently selected from one of the following chemical structures:

[0039]

[0040] The R 11 、R 12 、R 13 、R 14 、R 15 , R 16 , R 17 and R 18 Independently selected from one of the following chemical structures:

[0041] Wherein, Y1 and Y2 are selected from hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfone, halogen, cyano, alkyl, alkoxy, substituted or unsubstituted C6-C60 aromatic ring group, substituted or unsubstituted C3-C60 aromatic heterocyclic group;

[0042] The R 19 and R 20 Independently selected from one of the following chemical structures:

[0043] Wherein, R is selected from hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfone, halogen, cyano, alkyl, alkoxy, substituted or unsubstituted C6-C60 aromatic ring group, substituted or unsubstituted C3-C60 aromatic heterocyclic group;

[0044] The R 21 、R 22 、R 23 、R 24 、R 25 , R 26 、R 27 、R 28 、R 29 and R 30 Independently selected from one of the following chemical structures:

[0045]

[0046] In some embodiments, the boron-containing hetero-fused ring polymer is one of the following chemical formulas:

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] In some embodiments, a method for preparing a boron-containing hetero-fused ring polymer is also provided, comprising the steps of:

[0080] Add the following into a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser: The three monomers and dichloromethane were stirred in an ice bath for 30 minutes to a concentration of 1 M for the carbonyl-containing monomer. Then, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol to precipitate a large amount of solid. After centrifugation, the supernatant was removed and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times. Drying afforded a pale yellow solid, thus producing the boron-containing hetero-fused ring polymer.

[0081] In some embodiments, a boron-containing hetero-fused ring polymer is used as a light-emitting layer material of a semiconductor device. For example, the semiconductor device is an organic light-emitting diode, but is not limited thereto.

[0082] The present invention will be further explained below by means of specific embodiments:

[0083] Example 1: Synthesis of polymer P1

[0084] The preparation process is shown below:

[0085]

[0086] The specific steps are:

[0087] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 1 (81 mg, 0.1 mmol), 9-(2-ethylhexyl)carbazole (Cz-EH, 2762 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane ceased to reflux, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to yield 3.7 g of a pale yellow solid, polymer P1, in an 85% yield. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 11630 and the molecular weight distribution index PDI was 1.7.

[0088] Example 2: Synthesis of polymer P2

[0089] The preparation process is shown below:

[0090]

[0091] The specific steps are:

[0092] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 2 (89 mg, 0.1 mmol), 9-(2-ethylhexyl)carbazole (Cz-EH, 2762 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring for 30 minutes in an ice bath, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 4.0 g of a pale yellow solid, yielding 91%, polymer P2. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 9921 and the molecular weight distribution index PDI was 1.3.

[0093] Example 3: Synthesis of polymer P3

[0094] The preparation process is shown below:

[0095]

[0096] The specific steps are:

[0097] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 3 (84 mg, 0.1 mmol), 9-(2-ethylhexyl)carbazole (Cz-EH, 2762 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring for 30 minutes in an ice bath, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 3.6 g of a pale yellow solid, yielding 82%, polymer P3. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 10771 and the molecular weight distribution index PDI was 1.4.

[0098] Example 4: Synthesis of polymer P4

[0099] The preparation process is shown below:

[0100]

[0101] The specific steps are:

[0102] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 1 (81 mg, 0.1 mmol), N-(2-ethylhexyl)diphenylamine (DPA-EH, 2786 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane ceased to reflux, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 4.1 g of a pale yellow solid, yielding 92%, polymer P4. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 15638 and the molecular weight distribution index PDI was 1.5.

[0103] Example 5: Synthesis of polymer P5

[0104] The preparation process is shown below:

[0105]

[0106] The specific steps are:

[0107] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 2 (89 mg, 0.1 mmol), N-(2-ethylhexyl)diphenylamine (DPA-EH, 2786 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane ceased to reflux, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 3.9 g of a pale yellow solid, yielding 87%, polymer P5. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 13347 and the molecular weight distribution index PDI was 1.8.

[0108] Example 6: Synthesis of polymer P6

[0109] The preparation process is shown below:

[0110]

[0111] The specific steps are:

[0112] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 3 (84 mg, 0.1 mmol), N-(2-ethylhexyl)diphenylamine (DPA-EH, 2786 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring for 30 minutes in an ice bath, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 3.5 g of a pale yellow solid, yielding 79%, polymer P6. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 8892 and the molecular weight distribution index PDI was 1.3.

[0113] Example 7: Synthesis of polymer P7

[0114] The preparation process is shown below:

[0115]

[0116] The specific steps are:

[0117] To a two-necked round-bottom flask equipped with a magnetic stirrer and reflux condenser, monomer 1 (81 mg, 0.1 mmol), 9,9-dimethyl-10-(2-ethylhexyl)-9,10-dihydroacridine (DMAC-EH, 3183 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL) were added. After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. The ice bath was removed after the dichloromethane ceased to reflux. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the reaction solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 4.2 g of a light yellow solid (polymer P7) with a yield of 88%. The resulting polymer was tested by GPC, and the number average molecular weight (Mn) was 10,720, with a molecular weight distribution index (PDI) of 1.4.

[0118] Example 8: Synthesis of polymer P8

[0119] The preparation process is shown below:

[0120]

[0121] The specific steps are:

[0122] To a two-necked round-bottom flask equipped with a magnetic stirrer and reflux condenser, monomer 2 (89 mg, 0.1 mmol), 9,9-dimethyl-10-(2-ethylhexyl)-9,10-dihydroacridine (DMAC-EH, 3183 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL) were added. After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. The ice bath was removed after the dichloromethane ceased to reflux. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the reaction solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 4.1 g of a light yellow solid in an 85% yield, namely polymer P8. The resulting polymer was tested by GPC, and the number average molecular weight Mn was 9972, with a molecular weight distribution index (PDI) of 1.5.

[0123] Example 9: Synthesis of polymer P9

[0124] The preparation process is shown below:

[0125]

[0126] The specific steps are:

[0127] To a two-necked round-bottom flask equipped with a magnetic stirrer and reflux condenser, monomer 3 (84 mg, 0.1 mmol), 9,9-dimethyl-10-(2-ethylhexyl)-9,10-dihydroacridine (DMAC-EH, 3183 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL) were added. After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. The ice bath was removed after the dichloromethane ceased to reflux. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the reaction solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 3.9 g of a pale yellow solid (polymer P9) with an 80% yield. GPC analysis of the resulting polymer revealed a number average molecular weight (Mn) of 9162 and a molecular weight distribution index (PDI) of 1.4.

[0128] Example 10: Synthesis of polymer P10

[0129] The preparation process is shown below:

[0130]

[0131] The specific steps are:

[0132] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 1 (81 mg, 0.1 mmol), 10-(2-ethylhexyl)-9,10-phenothiazine (PXZ-EH, 2924 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane ceased to reflux, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 3.8 g of a pale yellow solid, polymer P10, in an 83% yield. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 8990 and the molecular weight distribution index PDI was 1.4.

[0133] Example 11: Synthesis of polymer P11

[0134] The preparation process is shown below:

[0135]

[0136] The specific steps are:

[0137] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 1 (89 mg, 0.1 mmol), 10-(2-ethylhexyl)-9,10-phenothiazine (PXZ-EH, 2924 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane ceased to reflux, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to yield 3.8 g of a pale yellow solid, polymer P11, in an 83% yield. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 10028 and the molecular weight distribution index PDI was 1.7.

[0138] Example 12: Synthesis of polymer P12

[0139] The preparation process is shown below:

[0140]

[0141] The specific steps are:

[0142] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 3 (84 mg, 0.1 mmol), 10-(2-ethylhexyl)-9,10-phenothiazine (PXZ-EH, 2924 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. Once the dichloromethane ceased to reflux, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to yield 3.1 g of a pale yellow solid, polymer P12, in a 68% yield. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 7962 and the molecular weight distribution index PDI was 1.3.

[0143] Example 13: Synthesis of polymer P13

[0144] The preparation process is shown below:

[0145]

[0146] The specific steps are:

[0147] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 4 (81 mg, 0.1 mmol), 9-(2-ethylhexyl)carbazole (Cz-EH, 2762 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. Once the dichloromethane ceased to reflux, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to yield 3.7 g of a pale yellow solid, polymer P13, in an 85% yield. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 9654 and the molecular weight distribution index PDI was 1.5.

[0148] Example 14: Synthesis of polymer P14

[0149] The preparation process is shown below:

[0150]

[0151] The specific steps are:

[0152] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 4 (81 mg, 0.1 mmol), N-(2-ethylhexyl)diphenylamine (DPA-EH, 2786 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. Once the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to yield 3.5 g of a pale yellow solid, polymer P14, in a 79% yield. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 11268 and the molecular weight distribution index PDI was 1.7.

[0153] Example 15: Synthesis of polymer P15

[0154] The preparation process is shown below:

[0155]

[0156] The specific steps are:

[0157] To a two-necked round-bottom flask equipped with a magnetic stirrer and reflux condenser, monomer 4 (81 mg, 0.1 mmol), 9,9-dimethyl-10-(2-ethylhexyl)-9,10-dihydroacridine (DMAC-EH, 3183 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL) were added. After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. The ice bath was removed after the dichloromethane ceased to reflux. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the reaction solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 4.2 g of a pale yellow solid in an 88% yield, namely polymer P15. The resulting polymer was tested by GPC, and the number average molecular weight (Mn) was 10,354, with a molecular weight distribution index (PDI) of 1.8.

[0158] Example 16: Synthesis of polymer P16

[0159] The preparation process is shown below:

[0160]

[0161] The specific steps are:

[0162] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 4 (81 mg, 0.1 mmol), 10-(2-ethylhexyl)-9,10-phenothiazine (PXZ-EH, 2924 mg, 9.9 mmol), trifluoroacetophenone (1741 mg, 10 mmol), and dichloromethane (10 mL). After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. Once the dichloromethane ceased to reflux, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to yield 3.7 g of a pale yellow solid, polymer P16, in an 82% yield. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 13724 and the molecular weight distribution index PDI was 2.0.

[0163] Example 17: Synthesis of polymer P17

[0164] The preparation process is shown below:

[0165]

[0166] The specific steps are:

[0167] To a two-mouthful round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 5 (88 mg, 0.1 mmol), 9-(2-ethylhexyl)carbazole (Cz-EH, 2762 mg, 9.9 mmol), 1-methylisatin (1612 mg, 10 mmol), and dichloromethane (10 mL). After stirring for 30 minutes under an ice bath, 10 mL of trifluoromethanesulfonic acid was added in one go. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was dropwise added into a large amount of vigorously stirred methanol to separate out a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasound, the reaction solution was again dropwise added into a large amount of vigorously stirred methanol. The mixture was subjected to three cycles of dissolution-sedimentation-centrifugation and oven-dried to obtain 3.9 g of a light yellow solid, yielding 92%, polymer P17. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 11779 and the molecular weight distribution index PDI was 1.1.

[0168] Example 18: Synthesis of polymer P18

[0169] The preparation process is shown below:

[0170]

[0171] The specific steps are:

[0172] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 5 (88 mg, 0.1 mmol), N-(2-ethylhexyl)diphenylamine (DPA-EH, 2786 mg, 9.9 mmol), 1-methylisatin (1612 mg, 10 mmol), and dichloromethane (10 mL). After stirring for 30 minutes under an ice bath, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in a large amount of solid precipitation. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 3.9 g of a pale yellow solid, yielding 93%, polymer P18. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 13681 and the molecular weight distribution index PDI was 1.2.

[0173] Example 19: Synthesis of polymer P19

[0174] The preparation process is shown below:

[0175]

[0176] The specific steps are:

[0177] To a two-necked round-bottom flask equipped with a magnetic stirrer and reflux condenser, monomer 5 (88 mg, 0.1 mmol), 9,9-dimethyl-10-(2-ethylhexyl)-9,10-dihydroacridine (DMAC-EH, 3183 mg, 9.9 mmol), 1-methylisatin (1612 mg, 10 mmol), and dichloromethane (10 mL) were added. After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. The ice bath was removed after the dichloromethane ceased to reflux. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, causing a large amount of solid to precipitate. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 3.7 g of a pale yellow solid, polymer P19, in an 88% yield. GPC analysis of the resulting polymer revealed a number average molecular weight (Mn) of 11,179 and a molecular weight distribution index (PDI) of 1.2.

[0178] Example 20: Synthesis of polymer P20

[0179] The preparation process is shown below:

[0180]

[0181] The specific steps are:

[0182] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 5 (88 mg, 0.1 mmol), 10-(2-ethylhexyl)-9,10-phenothiazine (PXZ-EH, 2924 mg, 9.9 mmol), 1-methylisatin (1612 mg, 10 mmol), and dichloromethane (10 mL). After stirring for 30 minutes in an ice bath, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 3.5 g of a pale yellow solid, polymer P20, in an 85% yield. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 10849 and the molecular weight distribution index PDI was 1.1.

[0183] Example 21: Synthesis of polymer P21

[0184] The preparation process is shown below:

[0185]

[0186] The specific steps are:

[0187] To a two-mouthful round-bottom flask equipped with a magnetic stirrer and a reflux condenser, monomer 6 (86 mg of monomer 5, 0.1 mmol), 9-(2-ethylhexyl)carbazole (Cz-EH, 2762 mg, 9.9 mmol), 1-methylisatin (1612 mg, 10 mmol), and dichloromethane (10 mL) were added. After stirring for 30 minutes under an ice bath, 10 mL of trifluoromethanesulfonic acid was added in one go. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was dropwise added into a large amount of vigorously stirred methanol to separate out a large amount of solid. After centrifugation, the supernatant was removed and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasound, the reaction solution was again dropwise added into a large amount of vigorously stirred methanol. The solution was subjected to three cycles of dissolution-sedimentation-centrifugation and oven-dried to obtain 3.9 g of a light yellow solid with a yield of 92%, which was polymer P21. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 12151 and the molecular weight distribution index PDI was 1.1.

[0188] Example 22: Synthesis of polymer P22

[0189] The preparation process is shown below:

[0190]

[0191] The specific steps are:

[0192] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 6 (86 mg of monomer 5, 0.1 mmol), N-(2-ethylhexyl)diphenylamine (DPA-EH, 2786 mg, 9.9 mmol), 1-methylisatin (1612 mg, 10 mmol), and dichloromethane (10 mL). The mixture was stirred under an ice bath for 30 minutes, and then 10 mL of trifluoromethanesulfonic acid was added at once. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol to separate out a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasound, the mixture was again added dropwise to a large amount of vigorously stirred methanol. The mixture was subjected to three cycles of dissolution-sedimentation-centrifugation and oven-dried to obtain 4.4 g of a light yellow solid in a yield of 96%, which was polymer P22. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 12584 and the molecular weight distribution index PDI was 1.1.

[0193] Example 23: Synthesis of polymer P23

[0194] The preparation process is shown below:

[0195]

[0196] The specific steps are:

[0197] To a two-necked round-bottom flask equipped with a magnetic stirrer and reflux condenser, monomer 6 (86 mg, 0.1 mmol), 9,9-dimethyl-10-(2-ethylhexyl)-9,10-dihydroacridine (DMAC-EH, 3183 mg, 9.9 mmol), 1-methylisatin (1612 mg, 10 mmol), and dichloromethane (10 mL) were added. After stirring in an ice bath for 30 minutes, 10 mL of trifluoromethanesulfonic acid was added all at once. The ice bath was removed after the dichloromethane ceased to reflux. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of sonication, the mixture was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 4.4 g of a pale yellow solid in a 93% yield, namely polymer P23. GPC analysis of the resulting polymer revealed a number average molecular weight (Mn) of 12,954 and a molecular weight distribution index (PDI) of 1.1.

[0198] Example 24: Synthesis of polymer P24

[0199] The preparation process is shown below:

[0200]

[0201] The specific steps are:

[0202] To a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser were added monomer 6 (86 mg, 0.1 mmol), 10-(2-ethylhexyl)-9,10-phenothiazine (PXZ-EH, 2924 mg, 9.9 mmol), 1-methylisatin (1612 mg, 10 mmol), and dichloromethane (10 mL). After stirring for 30 minutes under an ice bath, 10 mL of trifluoromethanesulfonic acid was added all at once. After the dichloromethane no longer refluxed, the ice bath was removed. After stirring at room temperature for 24 hours, the reaction solution was added dropwise to a large amount of vigorously stirred methanol, resulting in the precipitation of a large amount of solid. After centrifugation, the supernatant was removed, and an appropriate amount of dichloromethane was added to completely dissolve the solid. After 5 minutes of ultrasonication, the solution was again added dropwise to a large amount of vigorously stirred methanol. This dissolution-sedimentation-centrifugation cycle was repeated three times, followed by drying to obtain 4.2 g of a pale yellow solid, yielding 95%, polymer P24. The obtained polymer was tested, and GPC measurement showed that the number average molecular weight Mn was 13698 and the molecular weight distribution index PDI was 1.1.

[0203] Example 25

[0204] The photophysical properties of the polymers P1, P13, P17 and P21 prepared in the above examples were tested, and the results are shown in Table 1 and Figures 1-4 As shown:

[0205] polymer <![CDATA[S1 / eV]]> <![CDATA[T1 / eV]]> <![CDATA[ΔE ST / eV]]> <![CDATA[φ f ]]> P1 2.68 2.50 0.18 0.81 P13 2.69 2.51 0.18 0.75 P17 2.67 2.49 0.18 0.79 P21 2.68 2.49 0.19 0.82

[0206] In Table 1, the S1 energy level is obtained from the room temperature fluorescence spectrum of the polymer toluene solution, the T1 energy level is obtained from the 77K phosphorescence spectrum of the polymer toluene solution, and the absolute fluorescence quantum efficiency φ f The polymer film state at room temperature is excited by light with a wavelength of 330nm and measured using an integrating sphere. Figure 1 The UV-visible absorption spectrum, fluorescence emission spectrum and phosphorescence emission spectrum of polymer P1; Figure 2 The UV-visible absorption spectrum, fluorescence emission spectrum and phosphorescence emission spectrum of polymer P13 are shown; Figure 3 The UV-visible absorption spectrum, fluorescence emission spectrum and phosphorescence emission spectrum of polymer P17; Figure 4 The UV-visible absorption spectrum, fluorescence emission spectrum and phosphorescence emission spectrum of polymer P21 are shown.

[0207] Under the same conditions, the polymers obtained in Examples 1, 13, 17 and 21 of the present invention were used as the light-emitting layer to fabricate electroluminescent devices and characterize their electroluminescent properties. The device structure is ITO / PEDOT:PSS (40 nm) / EML (35 nm) / TmPyPB (60 nm) / LiF (1 nm) / Al (150 nm). The device assembly process is as follows: a conductive polymer polythiophene derivative: polystyrene sulfonate (PEDOT:PSS) solution is spin-coated on the pre-cleaned ITO conductive glass surface to obtain a 40 nm thick film at a speed of 3000 rpm, which is then placed in an oven and heated at 120°C for 30 minutes and then cooled naturally. The polymer having the structure of formula i described in the present invention is dissolved in chlorobenzene to form a 5 mg / mL solution, which is spin-coated on PEDOT:PSS at a speed of 1200 rpm as the light-emitting layer (EML). The film thickness is measured by a step profiler to be 35 nm. After annealing, a 60nm thick layer of 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (TmPyPB) was evaporated on the light-emitting layer as an electron transport layer. Then, a lithium fluoride (1nm) / aluminum (150nm) electrode was evaporated on the electron transport layer. The thickness and deposition rate of the evaporation were monitored and detected by a quartz crystal oscillator. After the electrode evaporation was completed, the device was cooled for 30 minutes and then removed for electroluminescent device performance testing. The test results are shown in Table 2. Figure 5 and Figure 6 shown.

[0208] Table 2 Performance of polymer electroluminescent devices

[0209]

[0210] In Table 2, EQE is the external quantum efficiency of the electroluminescent device, PE is the power efficiency of the electroluminescent device, and CE is the current efficiency of the electroluminescent device. Figure 5 The current-voltage curve and brightness-voltage curve of the light-emitting devices based on polymers P1, P13, P17 and P21 are shown; Figure 6 This is the external quantum efficiency-brightness curve of the light-emitting device based on polymers P1, P13, P17 and P21. Figure 5 and Figure 6 From the curves and parameter changes, it can be seen that at high brightness, the efficiency roll-off is very small, so it has practical value.

[0211] It should be understood that the application of the present invention is not limited to the above examples. For those skilled in the art, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A boron-containing hetero-fused ring polymer, characterized in that: The general chemical structure formula of the boron-containing hetero-fused ring polymer is: Wherein, X and Y are nitrogen group element atoms or oxygen group element atoms, and when X and Y are oxygen group element atoms, there is no substituent; The bridging unit in the general chemical structure formula represents the connection mode between the γ ring and the N atom, which is a chemical bond; or the bridging unit in the general chemical structure formula is a conjugated aromatic ring group having 5-50 ring atoms, a non-conjugated aromatic ring group having 5-50 ring atoms, an aromatic heterocyclic group having 5-30 ring atoms, a linear alkyl chain having 1-100 carbon atoms, a branched alkyl chain having 1-100 carbon atoms, or a fluorinated alkyl chain having 1-100 carbon atoms; R1, R2, R3, …, R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 are independently a hydrogen atom, an aromatic ring group having 5 to 50 ring atoms, an aromatic heterocyclic group having 5 to 30 ring atoms, a linear alkyl chain having 1 to 100 carbon atoms, a branched alkyl chain having 1 to 100 carbon atoms, or a fluorinated alkyl chain having 1 to 100 carbon atoms; x1, x2 and n are positive integers; In the boron-containing hetero-fused ring polymer, R1 and R2 can be linked to each other by covalent bonds to form a ring; the α ring and the β ring, the δ ring and the ε ring, and the ζ ring and the η ring can be linked to each other by covalent bonds to form a ring; R 19 and R 20 It can be independently connected to the α ring, β ring and γ ring by covalent bonds to form a ring.

2. The boron-containing hetero-fused ring polymer according to claim 1, characterized in that The bridging unit in the general chemical structure is one of the following chemical structures: Wherein, R is selected from hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfone, halogen, cyano, alkyl, alkoxy, substituted or unsubstituted C6-C60 aromatic ring group, substituted or unsubstituted C3-C60 aromatic heterocyclic group.

3. The boron-containing hetero-fused ring polymer according to claim 1, characterized in that The R1 is selected from one of the following chemical structural formulas: Wherein, R is selected from hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfone, halogen, cyano, alkyl, alkoxy, substituted or unsubstituted C6-C60 aromatic ring group, substituted or unsubstituted C3-C60 aromatic heterocyclic group.

4. The boron-containing hetero-fused ring polymer according to claim 1, characterized in that The R2 is selected from one of the following chemical structural formulas:

5. The boron-containing hetero-fused ring polymer according to claim 1, characterized in that: R3, R4, R5, R6, R7, R8, R9 and R 10 Independently selected from one of the following chemical structures: and / or, the R 11 、R 12 、R 13 、R 14 、R 15 , R 16 , R 17 and R 18 Independently selected from one of the following chemical structures: Wherein, Y1 and Y2 are selected from hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfone, halogen, cyano, alkyl, alkoxy, substituted or unsubstituted C6-C60 aromatic ring group, substituted or unsubstituted C3-C60 aromatic heterocyclic group; and / or, the R 19 and R 20 Independently selected from one of the following chemical structures: Wherein, R is selected from hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfone, halogen, cyano, alkyl, alkoxy, substituted or unsubstituted C6-C60 aromatic ring group, substituted or unsubstituted C3-C60 aromatic heterocyclic group; and / or, the R 21 、R 22 、R 23 、R 24 、R 25 , R 26 、R 27 、R 28 、R 29 and R 30 Independently selected from one of the following chemical structures:

6. The boron-containing hetero-fused ring polymer according to claim 1, characterized in that: The boron-containing hetero-fused ring polymer is one of the following chemical structural formulas:

7. A method for preparing a boron-containing hetero-fused ring polymer according to any one of claims 1 to 6, characterized in that: Including steps: Add the following into a two-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser: and These three monomers and dichloromethane make The monomer concentration is 1M, and trifluoromethanesulfonic acid is added after ice bath treatment. After dichloromethane no longer refluxes, the ice bath is removed to obtain a reaction product; The reaction product is subjected to solvent treatment, sedimentation, and centrifugation, and then dried to obtain a light yellow solid, thereby obtaining the boron-containing hetero-condensed ring polymer; Among them, R1, R2, R3, ..., R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 As defined in claim 1.

8. Use of the boron-containing hetero-fused ring polymer according to any one of claims 1 to 6, characterized in that: The boron-containing hetero-fused ring polymer is used as a light-emitting layer material of a semiconductor device.

9. The use of the boron-containing hetero-fused ring polymer according to claim 8, characterized in that: The semiconductor device is an organic light emitting diode.

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