Benzene-containing polymer and preparation method thereof, and photoelectric device

Abstract

The present invention provides a benzene-containing polymer, the structure of which is shown in the general formula (1), wherein: * represents a chiral center; each monomer is an optical isomer unit, and the optical isomer unit forms an isotactic form in the chain of the benzene-containing polymer; x is an integer greater than 5; Ar appears each time and is independently selected from: substituted or unsubstituted triphenylamine groups, substituted or unsubstituted carbazole groups. The main chain of the benzene-containing polymer of the present invention has an isotactic structure, which limits the spatial orientation of the triphenylamine group or carbazole group of the polymer side chain, can improve the hole mobility, and thus improve the efficiency of the photoelectric device.

Description

Technical Field

[0001] The invention relates to the field of organic electroluminescence, and in particular to a benzene-containing polymer and a preparation method thereof, and a photoelectric device. Background Art

[0002] Organic electroluminescent device (OLED) display screens have become the mainstream of mid-to-high-end display screens. They have the characteristics of high contrast, low energy consumption, and bendability, and are increasingly widely used in the display and lighting fields. The preparation method of OLED devices mainly adopts vacuum evaporation. On a substrate with an anode attached, the required organic functional layer thin films are deposited in sequence, including a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, etc. Finally, the cathode is prepared by evaporation or sputtering to form a complete device. Vacuum evaporation preparation technology is relatively mature and is currently the main method for producing commercial OLED products. However, due to its principle limitations, the cost of vacuum evaporation preparation is relatively high, making the manufacturing cost of OLED screens higher than that of LCD screens, which is not conducive to the large-scale popularization of OLED screens. Therefore, it is necessary to find a lower-cost manufacturing method, such as the solution method. The cost advantage of preparing OLED devices by the solution method has gradually become a new research direction and development trend.

[0003] In the process of preparing OLED devices by solution method, it is necessary to ensure that the organic functional layer film is not damaged by the solvent of the upper material ink. Therefore, unlike the small molecule functional layer materials used in evaporation method devices, the solution method of preparing OLED devices requires the use of polymer materials with better solvent resistance. However, the hole mobility of traditional polymers is low when used as hole transport layer materials, which limits the efficiency of organic devices. Summary of the invention

[0004] Based on this, the present invention provides a benzene-containing polymer, whose main chain has an isotactic structure, which limits the spatial orientation of the side chain triphenylamine group or carbazole group, can improve the hole mobility, and thus improve the efficiency of the organic electroluminescent device.

[0005] The present invention is achieved through the following technical solutions.

[0006] A benzene-containing polymer, the structure of which is shown in general formula (1):

[0007]

[0008] in:

[0009] * represents a chiral center; each monomer is an optically active isomer unit, and the optically active isomer unit forms an isotactic form in the chain of the benzene-containing polymer;

[0010] x is an integer greater than 5;

[0011] Ar, at each occurrence, is independently selected from: a substituted or unsubstituted triphenylamine group, a substituted or unsubstituted carbazole group.

[0012] In one embodiment, Ar is selected from the following groups:

[0013]

[0014] in:

[0015] X1 is selected from CR1; X2 is selected from CR2;

[0016] Each occurrence of R1, R2, and R3 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a straight-chain alkenyl group having 1 to 20 C atoms, a branched or cyclic alkenyl group having 3 to 20 C atoms, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups; adjacent R1s may be cyclic or non-cyclic, and adjacent R2s may be cyclic or non-cyclic;

[0017] n is selected from any integer from 1 to 4.

[0018] In one embodiment, each occurrence of R1 is independently selected from: -H, -D, a straight chain alkyl group having 1 to 20 C atoms, or a straight chain alkenyl group having 1 to 20 C atoms.

[0019] In one embodiment, each occurrence of R2 is independently selected from: -H, -D, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms.

[0020] In one embodiment, each occurrence of R3 is independently selected from: -H, -D, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms.

[0021] In one embodiment, Ar is selected from any of the following groups:

[0022]

[0023] In one embodiment, adjacent R1 do not form a ring, adjacent R2 do not form a ring, and each occurrence of R1, R2, and R3 is independently selected from -H, -D or any one of the following groups:

[0024]

[0025] In one embodiment, Ar is selected from any of the following groups:

[0026]

[0027] In one embodiment, Ar is selected from any of the following Ar1 to Ar5:

[0028]

[0029] In one embodiment, adjacent R1 forms a ring and / or adjacent R2 forms a ring, and are independently selected from any one of the following groups:

[0030]

[0031] in:

[0032] * indicates the fusion site.

[0033] In one embodiment, Ar is selected from any of the following Ar6 to Ar8:

[0034]

[0035] In one embodiment, the molecular weight of the benzene-containing polymer is 5,000 to 200,000.

[0036] In one embodiment, the benzene-containing polymer is a hole transport material.

[0037] The present invention also provides a method for preparing a benzene-containing polymer, comprising the following steps:

[0038] Compound With compound Perform Suzuki reaction to prepare monomers

[0039] The monomers are polymerized to prepare a benzene-containing polymer represented by the general formula (1);

[0040]

[0041] Wherein, x is an integer greater than 5;

[0042] Ar, at each occurrence, is independently selected from: a substituted or unsubstituted triphenylamine group, a substituted or unsubstituted carbazole group.

[0043] In one embodiment, Ar is selected from any of the following groups:

[0044]

[0045] in:

[0046] X1 is selected from CR1; X2 is selected from CR2;

[0047] Each occurrence of R1, R2, and R3 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a straight-chain alkenyl group having 1 to 20 C atoms, a branched or cyclic alkenyl group having 3 to 20 C atoms, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups; adjacent R1s may be cyclic or non-cyclic, and adjacent R2s may be cyclic or non-cyclic;

[0048] n is selected from any integer from 1 to 4.

[0049] In one embodiment, Ar is selected from any of the following groups:

[0050]

[0051] In one embodiment, the catalyst used in the polymerization reaction is a metallocene catalyst.

[0052] In one embodiment, the metallocene catalyst is selected from at least one of a titanium complex, methylaluminoxane and trimethoxy(pentamethylcyclopentadienyl)titanium.

[0053] The present invention also provides a photoelectric device, which comprises a hole transport layer, wherein the raw material of the hole transport layer comprises the benzene-containing polymer as described above or the benzene-containing polymer prepared by the preparation method as described above.

[0054] Compared with the prior art, the benzene-containing polymer of the present invention has the following beneficial effects:

[0055] In the benzene-containing polymer of the present invention, each monomer is equivalent to an optical isomer unit, and the stereo configuration of the optical isomer unit forms an isotactic or syndiotactic (collectively referred to as isotactic) form in the polymer chain, wherein all optical isomer units in the isotactic polymer have the same stereo configuration, and two stereo configurations in the syndiotactic polymer appear in an alternating arrangement, that is, adjacent optical isomer units have opposite stereo configurations. The triphenylamine group or the carbazole group Ar is located in the polymer side chain, and the above-mentioned isotactic stereostructure of its main chain limits the spatial orientation of the side chain aromatic group to a certain extent, thereby being conducive to achieving orderly arrangement. The benzene-containing polymer of the present invention can be used as a hole transport material to achieve a higher hole mobility and improve the efficiency of the organic electroluminescent device. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1A schematic diagram of the structure of a photoelectric device provided for one embodiment of the present invention; in the figure, 101 is a cathode, 102 is an electron injection layer, 103 is an electron transport layer, 104 is a light-emitting layer, 105 is a hole transport layer, 106 is a hole injection layer, and 107 is an anode. DETAILED DESCRIPTION

[0057] For ease of understanding of the present invention, the present invention will be described more fully below with reference to relevant embodiments. Preferred embodiments of the present invention are provided in the embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0058] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0059] In the present invention, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

[0060] In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The same is true for the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.

[0061] Aromatic groups refer to hydrocarbon groups containing at least one aromatic ring. Heteroaromatic groups refer to aromatic hydrocarbon groups containing at least one heteroatom. The heteroatom is preferably selected from Si, N, P, O, S and / or Ge, and is particularly preferably selected from Si, N, P, O and / or S. A condensed ring aromatic group refers to a ring of an aromatic group that can have two or more rings, in which two carbon atoms are shared by two adjacent rings, i.e., a condensed ring. A condensed heterocyclic aromatic group refers to a condensed ring aromatic hydrocarbon group containing at least one heteroatom. For the purposes of the present invention, aromatic groups or heteroaromatic groups include not only systems of aromatic rings, but also non-aromatic ring systems. Therefore, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, etc. are also considered to be aromatic groups or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused aromatic or fused heteroaromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which multiple aromatic or heteroaromatic groups may be interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc. are also considered fused aromatic ring systems for the purposes of this invention.

[0062] In the present invention, "alkyl" may refer to a linear, branched and / or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10 or 1 to 6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyl decyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and the like.

[0063] In the present invention, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example In which R is connected to any substitutable position of the benzene ring; express Can be used with The benzene ring can be fused at any position.

[0064] The present invention provides a benzene-containing polymer, the structure of which is shown in general formula (1):

[0065]

[0066]

[0067] in:

[0068] * indicates chiral center; each monomer is an optical isomer unit, and the optical isomer unit forms an isotactic form in the chain of the benzene-containing polymer;

[0069] x is an integer greater than 5;

[0070] Ar, at each occurrence, is independently selected from: a substituted or unsubstituted triphenylamine group, a substituted or unsubstituted carbazole group.

[0071] Preferably, Ar, at each occurrence, is independently selected from: a substituted or unsubstituted triphenylamine group, a substituted carbazole group.

[0072] The inventors have found that the substitution site of Ar will affect the technical effect: if the Ar substituent is in the meta position, since the single bond between the benzene ring and the polymer main chain is rotatable, the spatial orientation of the substituent is not fixed, and the spatial stereochemical state of the polymer main chain cannot effectively affect the arrangement and stacking of the substituent group, that is, it is difficult to achieve the advantageous effect of the Ar substituent in the para position.

[0073] More specifically, the stereo configuration of the optically active isomer units forms isotactic or syndiotactic (collectively referred to as isotactic) forms in the polymer chain. Among them, all optically active isomer units in the isotactic polymer have the same stereo configuration, and its structure is shown in polymer A; in the syndiotactic polymer, the two stereo configurations appear alternately, that is, adjacent optically active isomer units have opposite stereo configurations, and its structure is shown in polymer B (the wavy line indicates that the chemical bond is not fully presented).

[0074]

[0075] Preferably, the optically active units are formed in isotactic form in the chain of the benzene-containing polymer.

[0076] In a specific example, Ar is selected from the following groups:

[0077]

[0078] in:

[0079] X1 is selected from CR1; X2 is selected from CR2;

[0080] Each occurrence of R1, R2, and R3 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a straight-chain alkenyl group having 1 to 20 C atoms, a branched or cyclic alkenyl group having 3 to 20 C atoms, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups; adjacent R1 may be cyclic or acyclic, and R2 may be cyclic or acyclic;

[0081] n is selected from any integer from 1 to 4.

[0082] In a specific example, each occurrence of R1 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, or a straight-chain alkenyl group having 1 to 20 C atoms.

[0083] More specifically, each occurrence of R1 is independently selected from: -H, -D or a straight-chain alkyl group having 1 to 10 C atoms or a straight-chain alkenyl group having 1 to 10 C atoms.

[0084] In a specific example, each occurrence of R2 is independently selected from: -H, -D, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms.

[0085] More specifically, each occurrence of R2 is independently selected from: -H, -D, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms.

[0086] In a specific example, each occurrence of R3 is independently selected from: -H, -D, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms.

[0087] More specifically, each occurrence of R3 is independently selected from: -H, -D, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms.

[0088] In a specific example, Ar is selected from the following groups:

[0089]

[0090] In a specific example, adjacent R1s do not form a ring, adjacent R2s do not form a ring, and each occurrence of R1, R2, and R3 is independently selected from -H, -D, or any one of the following groups:

[0091]

[0092] In a specific example, Ar is selected from any of the following groups:

[0093]

[0094] In a specific example, Ar is selected from any of the following Ar1 to Ar5:

[0095]

[0096] In a specific example, adjacent R1s form a ring and / or adjacent R2s form a ring, and are independently selected from any one of the following groups:

[0097]

[0098] in:

[0099] * indicates the fusion site.

[0100] In a specific example, Ar is selected from any of the following Ar6 to Ar8 groups:

[0101]

[0102] Preferably, Ar is selected from Ar1, Ar3, Ar7. More preferably, Ar is selected from Ar1.

[0103] In a specific example, the molecular weight of the benzene-containing polymer is 5000 to 200000. Preferably, the molecular weight of the benzene-containing polymer is 5000 to 20000.

[0104] In one specific example, the benzene-containing polymer is a hole transport material.

[0105] The present invention also provides a method for preparing a benzene-containing polymer, comprising the following steps:

[0106] Compound With compound Perform Suzuki reaction to prepare monomers

[0107] The monomers are polymerized to prepare a benzene-containing polymer represented by the general formula (1);

[0108]

[0109] Wherein, x is an integer greater than 5;

[0110] Ar, at each occurrence, is independently selected from: a substituted or unsubstituted triphenylamine group, a substituted or unsubstituted carbazole group.

[0111] In a specific example, Ar is selected from any of the following groups:

[0112]

[0113] in:

[0114] X1 is selected from CR1; X2 is selected from CR2;

[0115] Each occurrence of R1, R2, and R3 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a straight-chain alkenyl group having 1 to 20 C atoms, a branched or cyclic alkenyl group having 3 to 20 C atoms, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups; adjacent R1s may be cyclic or non-cyclic, and adjacent R2s may be cyclic or non-cyclic;

[0116] n is selected from any integer from 1 to 4.

[0117] In a specific example, each occurrence of R1 is independently selected from: -H, -D or a straight chain alkyl group having 1 to 20 C atoms.

[0118] In a specific example, each occurrence of R2 is independently selected from: -H, -D, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms.

[0119] In a specific example, each occurrence of R3 is independently selected from: -H, -D, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms.

[0120] In a specific example, Ar is selected from the following groups:

[0121]

[0122] In a specific example, adjacent R1s do not form a ring, adjacent R2s do not form a ring, and each occurrence of R1, R2, and R3 is independently selected from -H, -D, or any one of the following groups:

[0123]

[0124] In a specific example, Ar is selected from any of the following groups:

[0125]

[0126] In a specific example, Ar is selected from any of the following Ar1 to Ar5:

[0127]

[0128] In a specific example, adjacent R1s form a ring and / or adjacent R2s form a ring, and are independently selected from any one of the following groups:

[0129]

[0130] in:

[0131] * indicates the fusion site.

[0132] In a specific example, Ar is selected from any of the following Ar6 to Ar8 groups:

[0133]

[0134] In a specific example, the catalyst used in the polymerization reaction is a metallocene catalyst. It can be understood that in the present invention, the metallocene catalyst refers to a catalytic system composed of a complex of a Group IVB transition metal (such as Ti, Zr, Hf) element as a main catalyst and an alkylaluminoxane (such as MAO) or an organic boron compound (such as B(C6F5)3) as a co-catalyst.

[0135] In a specific example, the metallocene catalyst is selected from at least one of a titanium complex, methylaluminoxane and trimethoxy(pentamethylcyclopentadienyl)titanium.

[0136] Preferably, the catalyst used for synthesizing the isotactic polymer is a mixture of a titanium complex and methylaluminoxane.

[0137] Preferably, the catalyst used for synthesizing the syndiotactic polymer is a mixture of trimethoxy(pentamethylcyclopentadienyl)titanium and methylaluminoxane.

[0138] In a more specific example, a method for preparing a benzene-containing polymer comprises the following steps:

[0139]

[0140] Specifically, in the first step, the styrene derivative monomer is synthesized using the Suzuki reaction, and the universal reaction conditions are: reflux overnight in a mixture of toluene and water in a volume ratio of 10:1 under a nitrogen environment, under the co-catalysis of 0.1 times the molar ratio of tetrakistriphenylphosphine palladium and 2 times the molar ratio of potassium carbonate.

[0141] Specifically, in the second step, different metallocene catalysts are used in the polymerization reaction stage to obtain isotactic or syndiotactic polymers. Preferably, the catalyst used to synthesize isotactic polymers is a mixture of titanium complex M0 and methylaluminoxane MAO, and the catalyst used to synthesize syndiotactic polymers is a mixture of trimethoxy(pentamethylcyclopentadiene)titanium Cp*Ti(OMe)3 and methylaluminoxane MAO. The structural formulas of titanium complex M0 and Cp*Ti(OMe)3 are as follows:

[0142]

[0143] The present invention also provides a photoelectric device, which comprises a hole transport layer, wherein the raw material of the hole transport layer comprises the above-mentioned benzene-containing polymer or the benzene-containing polymer prepared by the above-mentioned preparation method.

[0144] The benzene-containing polymer and the preparation method thereof of the present invention are further described in detail below in conjunction with specific examples. The raw materials used in the following examples are all commercially available products unless otherwise specified.

[0145] Example 1 Polymer P1 and its preparation method

[0146] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0147]

[0148] Using double-row tube technology, 100 mg of methylaluminoxane was added to a 100 mL reaction bottle under argon protection, and 15 mL of toluene and 1 g of monomer M1 (about 2.9 mM) were added, and stirred at 20 ° C. 2 mL of toluene solution (0.05 mM) of titanium complex M0 was injected into the reaction bottle to initiate the reaction, and ethanol was added after 10 minutes to terminate the reaction. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P1. Elemental analysis results C89.87, H 6.12, N 4.00.

[0149] Example 2 Polymer P2 and its preparation method

[0150] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0151]

[0152] Using double-row tube technology, 1g of monomer M1 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 100mg of methylaluminoxane was added under stirring. 1mL of Cp*Ti(OMe)3 toluene solution (0.01mM) was injected into the reaction bottle to initiate the reaction, and ethanol was added after stirring at 50°C for 3h to terminate the reaction. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P2. Elemental analysis results C 89.85, H 6.10, N 4.05.

[0153] Example 3 Polymer P3 and its preparation method

[0154] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0155]

[0156] Using double-row tube technology, 2g of monomer M2 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 100mg of methylaluminoxane was added under stirring. 1mL of Cp*Ti(OMe)3 toluene solution (0.01mM) was injected into the reaction bottle to initiate the reaction, and ethanol was added after stirring at 50°C for 3h to terminate the reaction. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P3. Elemental analysis results C 89.23, H 6.60, N 4.16.

[0157] Example 4 Polymer P4 and its preparation method

[0158] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0159]

[0160] Using double-row tube technology, 1.5g of monomer M3 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 100mg of methylaluminoxane was added under stirring. 1mL of Cp*Ti(OMe)3 toluene solution (0.01mM) was injected into the reaction bottle to initiate the reaction, and ethanol was added to terminate the reaction after stirring at 50°C for 3h. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P4. Elemental analysis results C 88.67, H 5.89, N 5.42.

[0161] Example 5 Polymer P5 and its preparation method

[0162] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0163]

[0164] Using double-row tube technology, 1.8g of monomer M4 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 100mg of methylaluminoxane was added under stirring. 1mL of Cp*Ti(OMe)3 toluene solution (0.01mM) was injected into the reaction bottle to initiate the reaction, and ethanol was added to terminate the reaction after stirring at 50°C for 3h. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P5. Elemental analysis results C 89.88, H 6.60, N 4.54.

[0165] Example 6 Polymer P6 and its preparation method

[0166] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0167]

[0168] Using double-row tube technology, 1.7g of monomer M5 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 100mg of methylaluminoxane was added under stirring. 1mL of Cp*Ti(OMe)3 toluene solution (0.01mM) was injected into the reaction bottle to initiate the reaction, and ethanol was added after stirring at 50°C for 3h to terminate the reaction. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P6. Elemental analysis results C 89.45, H 6.82, N 4.72.

[0169] Example 7 Polymer P7 and its preparation method

[0170] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0171]

[0172] Using double-row tube technology, 2g of monomer M6 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 100mg of methylaluminoxane was added under stirring. 1mL of Cp*Ti(OMe)3 toluene solution (0.01mM) was injected into the reaction bottle to initiate the reaction, and ethanol was added after stirring at 50°C for 3h to terminate the reaction. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P7. Elemental analysis results: C 89.45, H 6.82, N 4.72.

[0173] Example 8 Polymer P8 and its preparation method

[0174] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0175]

[0176] Using double-row tube technology, 2.2g of monomer M7 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 100mg of methylaluminoxane was added under stirring. 1mL of Cp*Ti(OMe)3 toluene solution (0.01mM) was injected into the reaction bottle to initiate the reaction, and ethanol was added to terminate the reaction after stirring at 50°C for 3h. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P8. Elemental analysis results C 90.90, H 5.36, N 3.72.

[0177] Example 9 Polymer P9 and its preparation method

[0178] This embodiment provides a benzene-containing polymer, and the preparation steps thereof are as follows:

[0179]

[0180] Using double-row tube technology, 1.6g of monomer M8 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 100mg of methylaluminoxane was added under stirring. 1mL of Cp*Ti(OMe)3 toluene solution (0.01mM) was injected into the reaction bottle to initiate the reaction, and ethanol was added after stirring at 50°C for 3h to terminate the reaction. The reaction mixture was poured into a large amount of acidic ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P9. Elemental analysis results: C 89.00, H 5.86, N 5.10.

[0181] Comparative Example 1 Polymer P10 and preparation method thereof

[0182] This comparative example provides an atactic polymer containing benzene, and the preparation steps thereof are as follows:

[0183]

[0184] Among them, Ar1 represents

[0185] Using double-row tube technology, 1.0g of monomer M1 (about 2.9mM) and 15mL of toluene were added to a 100mL reaction bottle under argon protection, and 4.8mg of 2,2'-azobisisobutyronitrile (AIBN) initiator was added under stirring. The polymerization reaction was started by heating to 65°C, and ethanol was added to room temperature after 24 hours to terminate the reaction. The reaction mixture was poured into a large amount of ethanol solution for precipitation, and the precipitate was collected and washed with ethanol several times, and finally vacuum dried to obtain polymer P10. Elemental analysis results: C 89.92, H6.10, N 4.01.

[0186] Preparation and characterization of OLED devices

[0187] An organic light emitting diode component, comprising: a first electrode, a hole injection layer formed on the first electrode, a hole transport layer formed on the hole injection layer, a light emitting layer formed on the hole transport layer, an electron transport layer formed on the light emitting layer, an electron injection layer formed on the electron transport layer, and a second electrode covering the electron injection layer;

[0188] Among them, the hole transport layer is composed of the polymer hole transport material provided by the present invention alone, or is composed of a mixture of the polymer hole transport material and a p-type dopant; the hole injection layer, the hole transport layer and the light-emitting layer are prepared by a solution method (including spin coating, inkjet printing, etc.), and the electron transport layer, the electron injection layer and the second electrode are prepared by a vapor deposition method.

[0189] Examples of the above organic light emitting diode devices can be found in Figure 1 , its specific structure is:

[0190] ITO(50nm) / PEDOT:PSS(30nm) / HTL(40nm) / 26DCzPPy:Ir(mppy)3(95:550nm) / TPBi(30nm) / LiF(1nm) / Al(100nm).

[0191] Among them, PEDOT:PSS is used as a hole injection layer (HIL), one of the above polymer materials is used as a hole transport layer (HTL), 26DCzPPy is used as a main material of the light-emitting layer, Ir(mppy)3 is used as a guest material of the light-emitting layer, TPBi is used as an electron transport layer material (ETL), LiF is used as an electron injection layer material (EIL), and Al is used as a cathode. The organic material structures involved are as follows:

[0192]

[0193] Referring to the method of this embodiment, polymers P1 to P8 are used as hole transport materials to prepare Figure 1 The devices of the examples are respectively recorded as “P1 device”, “P2 device”, …, “P10 device”. The maximum external quantum efficiencies of the P1 device to the P10 device are tested, and the device performance results are shown in Table 1.

[0194] Table 1

[0195]

[0196]

[0197] As shown in Table 1, the efficiencies of devices P1 to P9 are better than those of devices P10, indicating that the device effect of the isotactic benzene-containing polymer provided by the present invention is better than that of the atactic benzene-containing polymer, and due to the influence of the mobility and energy level of the substituent group itself, the performance of devices P1 to P2 and P4 to P7 is better.

[0198] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0199] The above-described embodiments only express several implementation methods of the present invention, which are convenient for understanding the technical solutions of the present invention in detail, but they cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the protection scope of the claims attached to the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the contents of the attached claims, and the description and drawings can be used to interpret the contents of the claims.

Claims

1. A benzene-containing polymer, characterized in that Its structure is shown in the general formula (1): in: * represents a chiral center; each monomer is an optically active isomer unit, and the optically active isomer unit forms an isotactic form in the chain of the benzene-containing polymer; x is an integer greater than 5; Each occurrence of Ar is independently selected from one of M1 to M8:

2. The benzene-containing polymer according to claim 1, characterized in that The molecular weight of the benzene-containing polymer is 5,000 to 200,000.

3. The benzene-containing polymer according to claim 1, characterized in that The benzene-containing polymer is a hole transport material.

4. A method for preparing a benzene-containing polymer, characterized in that: The steps include: Compound With compound Perform Suzuki reaction to prepare monomers The monomers are polymerized to prepare a benzene-containing polymer represented by the general formula (1); * represents a chiral center; each monomer is an optically active isomer unit, and the optically active isomer unit forms an isotactic form in the chain of the benzene-containing polymer; Wherein, x is an integer greater than 5; Each occurrence of Ar is independently selected from one of M1 to M8:

5. The method for preparing a benzene-containing polymer according to claim 4, characterized in that: The catalyst used in the polymerization reaction is a metallocene catalyst.

6. The method for preparing a benzene-containing polymer according to claim 5, characterized in that: The metallocene catalyst is selected from titanium complexes.

7. The method for preparing a benzene-containing polymer according to claim 6, characterized in that: The titanium complex is selected from trimethoxy(pentamethylcyclopentadienyl)titanium.

8. The method for preparing a benzene-containing polymer according to claim 5, characterized in that: The metallocene catalyst also includes methylaluminoxane.

9. A photoelectric device, characterized in that: The photoelectric device comprises a hole transport layer, and the raw material of the hole transport layer comprises the benzene-containing polymer according to any one of claims 1 to 3 or the benzene-containing polymer prepared by the preparation method according to any one of claims 4 to 8.

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