CN110818726B - Hole transport material, preparation method thereof and electroluminescent device - Google Patents

Hole transport material, preparation method thereof and electroluminescent device Download PDF

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CN110818726B
CN110818726B CN201911023542.XA CN201911023542A CN110818726B CN 110818726 B CN110818726 B CN 110818726B CN 201911023542 A CN201911023542 A CN 201911023542A CN 110818726 B CN110818726 B CN 110818726B
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罗佳佳
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Abstract

A hole transport material, a preparation method thereof and an electroluminescent device, wherein the structural formula of the hole transport material is shown in the specification
Figure DDA0002247970240000011
The designed and synthesized hole transport material has proper energy level and higher hole mobility, and can obtain higher luminous efficiency and prolong the service life of the device when being applied to an electroluminescent device.

Description

Hole transport material, preparation method thereof and electroluminescent device
Technical Field
The invention relates to the technical field of display, in particular to a hole transport material, a preparation method thereof and an electroluminescent device.
Background
Organic Light-emitting Diodes (OLEDs) attract the attention of many researchers due to their advantages of autonomous Light emission, large viewing angle, fast response speed, high Light-emitting efficiency, wide temperature application range, relatively simple production and processing technology, low driving voltage, low energy consumption, sexual display, and the like, and huge application prospects. In the OLED, a light emitting guest material playing a leading role is crucial, the light emitting guest material used in the early OLED is a fluorescent material, and since the exciton ratio of singlet state and triplet state in the OLED is 1:3, the theoretical Internal Quantum Efficiency (IQE) of the OLED based on the fluorescent material can only reach 25%, which greatly limits the application of the fluorescent electroluminescent device. The heavy metal complex phosphorescent material can simultaneously utilize singlet excitons and triplet excitons to realize 100% of theoretical internal quantum efficiency due to the spin-orbit coupling effect of heavy atoms. However, the commonly used heavy metals are precious metals such as Ir and Pt, and the heavy metal complex phosphorescent materials have yet to be broken through in the aspect of blue light materials.
In the currently used top-emitting OLED device, the hole transport material is used as the thickest layer, and the energy level and the hole mobility of the hole transport material always have a contradictory relation, so that the development of the hole transport material with matched energy level and high mobility has important application value.
Disclosure of Invention
The invention provides a hole transport material, a preparation method thereof and an electroluminescent device, and aims to solve the technical problem that the energy level of the hole transport material is not matched with the hole mobility in the conventional OLED device, so that the luminous efficiency of the OLED device is influenced.
In order to solve the above problems, the technical scheme provided by the invention is as follows:
the invention provides a hole transport material, which has a structural formula shown as the following formula:
Figure GDA0002938889460000021
wherein the R group is one of the following structures:
Figure GDA0002938889460000022
the X group is one of the following structural formulas: o, S,
Figure GDA0002938889460000023
The invention also provides a preparation method of the hole transport material, which comprises the following steps:
s10, mixing a first reactant, a second reactant, a catalyst and a solvent to obtain a mixed solution, wherein the structural formula of the first reactant is shown in the specification
Figure GDA0002938889460000024
The X group is one of the following structural formulas: o, S,
Figure GDA0002938889460000025
S20, reacting the mixed solution at 120 ℃ for 24 hours to obtain a reaction solution;
s30, cooling, extracting, separating and purifying the reaction liquidObtaining the hole transport material, wherein the structural formula of the hole transport material is shown in the specification
Figure GDA0002938889460000031
The R group is one of the following structures:
Figure GDA0002938889460000032
in at least one embodiment of the present invention, the second reactant is one of carbazole, diphenylamine, 9' -dimethylacridine.
In at least one embodiment of the present invention, the molar ratio of the first reactant to the second reactant is 1: 1.
In at least one embodiment of the present invention, the method of preparing the first reactant comprises:
reacting a first raw material with 1,3, 5-trimethylbromobenzene to obtain an intermediate, wherein the structural formula of the first raw material is shown in the specification
Figure GDA0002938889460000033
The structural formula of the intermediate is
Figure GDA0002938889460000034
The Y group is one of the following structural formulas: o, S,
Figure GDA0002938889460000041
Reacting the intermediate with 9-phenyl-2, 7-dibromocarbazole to obtain a compound with a structural formula
Figure GDA0002938889460000042
The first reactant of (a).
In at least one embodiment of the present invention, the molar ratio of the first starting material to 1,3, 5-trimethylbromobenzene participating in the reaction is 1:1, and the molar ratio of the intermediate participating in the reaction to 9-phenyl-2, 7-dibromocarbazole is 1: 1.
In at least one embodiment of the invention, the catalyst is palladium acetate, tri-tert-butylphosphine tetrafluoroborate and sodium tert-butyl alkoxide, and the solvent is toluene.
In at least one embodiment of the present invention, the S10 includes:
s101, adding a first reactant, a second reactant, palladium acetate and tri-tert-butylphosphine tetrafluoroborate into a two-mouth bottle;
s102, adding sodium tert-butoxide into the two-mouth bottle in a glove box;
and S103, adding toluene without water and oxygen into the two-mouth bottle under an inert gas atmosphere to obtain the mixed solution.
In at least one embodiment of the present invention, the S30 includes:
s301, cooling the reaction solution to room temperature, adding the reaction solution into 200ml of ice water, extracting the mixture for several times by using dichloromethane, combining organic phases, and spinning the organic phases into silica gel;
and S302, separating and purifying the silica gel by using a column chromatography method to obtain the hole transport material.
The invention also provides an electroluminescent device which comprises a hole transport layer, wherein the hole transport layer is prepared from the hole transport material.
The invention has the beneficial effects that: the hole transport material designed and synthesized by the invention has proper energy level and higher hole mobility, and can obtain higher luminous efficiency and prolong the service life of the device when being applied to an electroluminescent device.
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In order to illustrate the embodiments or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the invention, and it is obvious for a person skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart illustrating steps of a method for preparing a hole transport material according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an electroluminescent device according to an embodiment of the present invention.
Detailed Description
The following description of the various embodiments refers to the accompanying drawings that illustrate specific embodiments in which the invention may be practiced. The directional terms mentioned in the present invention, such as [ upper ], [ lower ], [ front ], [ rear ], [ left ], [ right ], [ inner ], [ outer ], [ side ], are only referring to the directions of the attached drawings. Accordingly, the directional terms used are used for explanation and understanding of the present invention, and are not used for limiting the present invention. In the drawings, elements having similar structures are denoted by the same reference numerals.
Aiming at the technical problem that the energy level of a hole transport material is not matched with the hole mobility so as to influence the luminous efficiency of an OLED device in the conventional OLED device, the embodiment of the invention can solve the defect.
The embodiment of the invention provides a hole transport material, the structural formula of which is
Figure GDA0002938889460000061
Wherein the R group is one of the following structures:
Figure GDA0002938889460000062
the X group is one of the following structural formulas: o, S,
Figure GDA0002938889460000063
As shown in fig. 1, the method for preparing the hole transport material includes:
s10, mixing a first reactant, a second reactant, a catalyst and a solvent to obtain a mixed solution, wherein the structural formula of the first reactant is shown in the specification
Figure GDA0002938889460000064
The X group is one of O, S and,
Figure GDA0002938889460000065
S20, reacting the mixed solution at 120 ℃ for 24 hours to obtain a reaction solution;
and S30, cooling, extracting, separating and purifying the reaction liquid to obtain the hole transport material.
The second reactant is an organic compound corresponding to any one of the above R groups, and for example, the second reactant may be one of carbazole, diphenylamine, and 9, 9' -dimethylacridine.
The molar ratio of the first reactant and the second reactant added during the reaction is 1:1, so that the reactants are fully reacted to the maximum extent.
The catalyst can be palladium acetate, tri-tert-butylphosphine tetrafluoroborate and sodium tert-butyl alkoxide, and the solvent can be toluene. The preparation of the mixed solution specifically comprises the following steps: firstly, adding the first reactant, the second reactant, palladium acetate and tri-tert-butylphosphine tetrafluoroborate into a two-mouth bottle, and then adding sodium tert-butoxide into the two-mouth bottle in a glove box; and finally, adding toluene without water and oxygen into the two-mouth bottle in an inert gas atmosphere to obtain the mixed solution, wherein the inert gas can be one of helium, neon, argon and the like.
The treatment of the reaction solution comprises: cooling the reaction solution to room temperature, adding the reaction solution into 200ml of ice water, extracting the mixture for several times by using dichloromethane, combining organic phases, and spinning the organic phases into silica gel; and then, separating and purifying the silica gel by using a column chromatography method to obtain the hole transport material.
As shown in fig. 2, based on the application of the hole transport material, an embodiment of the invention further provides an electroluminescent device 100, which includes a reflective anode 10, a hole injection layer 20, a hole transport layer 30, an electron blocking layer 40, a light emitting layer 50, a hole blocking layer 60, an electron transport layer 70, an electron injection layer 80, and a semitransparent cathode 90, which are sequentially stacked, and may further include an optical coupling light-emitting layer. The electroluminescent device 100 is a top emission device, and the hole transport layer 20 is made of the hole transport material.
The hole transport material can also be applied to display devices and electronic equipment based on the electroluminescent device.
The present invention will be described in detail with reference to specific examples.
Example one
The first reactant in this example has the formula
Figure GDA0002938889460000081
The second reactant is carbazole with the structural formula
Figure GDA0002938889460000082
The process of synthesizing the target compound 1 by the first reactant and the second reactant is shown as the following formula:
Figure GDA0002938889460000083
specifically, the first reactant (5.44g, 10mmol), carbazole (1.67g, 10mmol), palladium acetate (90mg, 0.4mmol), and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were added to a 250mL two-necked flask, then sodium tert-butoxide NaOt-Bu (1.16g, 12mmol) was added to the two-necked flask in the glove box, adding 100mL of toluene which is dehydrated and deoxidized in advance under the argon atmosphere, reacting at 120 ℃ for 24 hours, cooling to room temperature, pouring the reaction solution into 200mL of ice water, extracting with dichloromethane for three times, mixing organic phases, spinning into silica gel, separating and purifying by column chromatography (the volume ratio of dichloromethane to n-hexane is 1:5) to obtain 3.6g of target compound 1, the yield of the objective compound 1 was 57% as a white powder, and the theoretical relative molecular mass of the objective compound 1 was 631.26, ms (ei) m/z: [ M ].]+：631.06。
The raw materials of the first reactant comprise a first raw material, a second raw material and a third raw material, wherein the first raw material is anthranilate, the second raw material is 1,3, 5-trimethylbromobenzene, the third raw material is 9-phenyl-2, 7-dibromocarbazole, and the first raw material and the second raw material are obtained by reactionTo an intermediate, the molar ratio of the first raw material to the second raw material is 1:1, and the structural formula of the intermediate is shown in the specification
Figure GDA0002938889460000091
The intermediate reacts with the third raw material to obtain the first reactant, the molar ratio of the intermediate to the third raw material is 1:1, and the synthesis process of the first reactant is shown as the following formula:
Figure GDA0002938889460000092
specifically, 1,3, 5-trimethylbromobenzene (1.98g, 10mmol), anthranilic ether (1.23g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) are added into a 250mL two-neck flask, NaOt-Bu (1.16g, 12mmol) is added into a glove box, 100mL of toluene which is previously deaerated is added under an argon atmosphere, the mixture is reacted at 120 ℃ for 24 hours and then cooled to room temperature, the reaction liquid is poured into 200mL of ice water, extraction is carried out three times by using dichloromethane, organic phases are combined, silica gel is formed by spinning, and column chromatography (dichloromethane: n-hexane, v: v, 1:5) is carried out for separation and purification, so as to obtain 1.9g of the intermediate which is white powder with a yield of 79%, and theoretical relative molecular mass of the intermediate is 241.15, MS (EI) M/z: [ M]+：241.10。
Then adding the intermediate (2.41g, 10mmol), 9-phenyl-2, 7-dibromocarbazole (4.00g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) into a 250mL two-neck flask, then adding NaOt-Bu (1.16g, 12mmol) into a glove box, adding 100mL of toluene with water and oxygen removed in advance under an argon atmosphere, reacting at 120 ℃ for 24 hours, cooling to room temperature, adding 0.4g of NaH, reacting at 120 ℃ for 24 hours, cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting three times by using dichloromethane, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (the volume ratio of the n-hexane to the n-hexane is 1:5) to obtain 4.3g of the first reactant which is white powder, wherein the yield is 79% theoretical relative molecular mass of 544.12, MS (EI) M/z: [ M]+：544.01。
Example two
The first reactant in this example has the formula
Figure GDA0002938889460000101
The second reactant is diphenylamine, the structural formula of which is
Figure GDA0002938889460000102
The process of synthesizing the target compound 1 by the first reactant and the second reactant is shown as the following formula:
Figure GDA0002938889460000103
specifically, a 250mL two-necked flask was charged with the first reactant (5.44g, 10mmol), diphenylamine (1.69g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then NaOt-Bu (1.16g, 12mmol) was added into a glove box, 100mL of toluene previously deoxygenated by water was added under an argon atmosphere, reacted at 120 ℃ for 24 hours, cooled to room temperature, the reaction solution was poured into 200mL of ice water, dichloromethane was extracted three times, the organic phase was combined, silica gel was spun, column chromatography (dichloromethane: n-hexane, v: v, 1:5) was performed to separate and purify to obtain 4.0g of the target compound 2, which was a white powder, the yield was 63%, the theoretical relative molecular mass was 633.28, MS (EI) M/z: [ M ], (EI)]+：633.16。
EXAMPLE III
The first reactant in this example has the formula
Figure GDA0002938889460000111
The second reactant is 9, 9' -dimethylacridine with the structural formula
Figure GDA0002938889460000112
Of the target compound 3 synthesized from the first reactant and the second reactantThe process is shown as the following formula:
Figure GDA0002938889460000113
specifically, a 250mL two-necked flask was charged with the first reactant (5.44g, 10mmol), 9, 9' -dimethylacridine (2.09g, 6mmol), palladium acetate (90mg, 0.4mmol) and tri-t-butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then NaOt-Bu (1.16g, 12mmol) was added into a glove box, 100mL of toluene which had been previously dehydrated and deoxygenated were added under an argon atmosphere, reacted at 120 ℃ for 24 hours, cooled to room temperature, the reaction solution was poured into 200mL of ice water, dichloromethane was extracted three times, the organic phase was combined, silica gel was spun, and column chromatography (dichloromethane: n-hexane, v: v, 1:5) was performed to obtain 4.3g of the target compound 3, which was a white powder with a yield of 64%, a theoretical relative molecular mass of 673.31, and MS (EI) M/z: [ M (M is M: [ M ] M]+：673.20。
Example four
The first reactant in this example has the formula
Figure GDA0002938889460000121
The second reactant is carbazole, and the process of synthesizing the target compound 4 by the first reactant and the second reactant is shown as the following formula:
Figure GDA0002938889460000122
specifically, the first reactant (5.60g, 10mmol), carbazole (1.67g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were added to a 250mL two-necked flask, and then NaOt-Bu (1.16g, 12mmol) was added to the glove box, 100mL toluene with water removed beforehand was added under an argon atmosphere, and the reaction was carried out at 120 ℃ for 24 hours. Cooling to room temperature, pouring the reaction solution into 200mL of ice water, extracting with dichloromethane for three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 1:5) to obtain 3.7g of targeted compoundCompound 4, the object 4 was a white powder, the yield was 57%, the relative molecular mass was 647.24, MS (EI) M/z: [ M]+：647.10。
In this embodiment, the raw materials of the first reactant include anthranilic acid sulfide, 1,3, 5-trimethylbromobenzene, 9-phenyl-2, 7-dibromocarbazole, and the structural formula of the intermediate is shown in the specification, wherein the intermediate is obtained by reacting anthranilic acid sulfide with 1,3, 5-trimethylbromobenzene
Figure GDA0002938889460000123
And reacting the intermediate with 9-phenyl-2, 7-dibromocarbazole to obtain the first reactant, wherein the synthesis process of the first reactant is shown as the following formula:
Figure GDA0002938889460000131
specifically, 1,3, 5-trimethylbromobenzene (1.98g, 10mmol), anthranilic acid sulfide (1.39g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were first charged into a 250mL two-necked flask, then NaOt-Bu (1.16g, 12mmol) was added into a glove box, 100mL of toluene previously deoxygenated and dehydrated was charged under an argon atmosphere, and reacted at 120 ℃ for 24 hours. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane for three times, combining organic phases, spinning into silica gel, separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 1:5) to obtain 1.8g of the intermediate, wherein the intermediate is white powder, the yield is 70%, the theoretical relative molecular mass is 257.12, and MS (EI) M/z: [ M (Electron exchange interference)/Z ])]+：257.00。
Then adding the intermediate (2.57g, 10mmol), 9-phenyl-2, 7-dibromocarbazole (4.00g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) into a 250mL two-neck flask, then adding NaOt-Bu (1.16g, 12mmol) into a glove box, adding 100mL of toluene which is dehydrated and deoxidized in advance under argon atmosphere, reacting at 120 ℃ for 24 hours, cooling to room temperature, adding 0.4g of NaH, reacting at 120 ℃ for further 24 hours, cooling to room temperature, pouring the reaction solution into 200mL of iceExtracting with dichloromethane in water for three times, combining organic phases, spinning into silica gel, separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 1:5) to obtain 3.8g of the first reactant, wherein the first reactant is white powder with the yield of 68 percent and the theoretical relative molecular mass of 560.09, and MS (EI) M/z: [ M (EI)]+：560.01。
EXAMPLE five
The first reactant in this example has the formula
Figure GDA0002938889460000141
The second reactant is carbazole with the structural formula
Figure GDA0002938889460000142
The process of synthesizing the target compound 5 by the first reactant and the second reactant is shown as the following formula:
Figure GDA0002938889460000143
specifically, a 250mL two-necked flask was charged with the first reactant (5.70g, 10mmol), carbazole (1.67g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-t-butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then NaOt-Bu (1.16g, 12mmol) was added into a glove box, 100mL of toluene previously deaerated was added under an argon atmosphere, reacted at 120 ℃ for 24 hours, cooled to room temperature, the reaction solution was poured into 200mL of ice water, dichloromethane was extracted three times, the organic phase was combined, silica gel was spun, and column chromatography (dichloromethane: n-hexane, v: v, 1:5) was performed to separate and purify to obtain 3.9g of the target compound 5 as a white powder at a yield of 59% and a theoretical relative molecular mass of 657.31, MS (EI) M/z [ M: [ M ] M]+：657.24。
Wherein the raw materials of the first reactant comprise o-tert-butyl aniline, 1,3, 5-trimethylbromobenzene and 9-phenyl-2, 7-dibromocarbazole, the o-tert-butyl aniline and 1,3, 5-trimethylbromobenzene react to obtain an intermediate, and the structural formula of the intermediate is shown in the specification
Figure GDA0002938889460000144
And reacting the intermediate with 9-phenyl-2, 7-dibromocarbazole to obtain the first reactant, wherein the synthesis process of the first reactant is shown as the following formula:
Figure GDA0002938889460000151
specifically, 1,3, 5-trimethylbromobenzene (1.98g, 10mmol), o-tert-butylaniline (1.49g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were added to a 250mL two-necked flask, and then NaOt-Bu (1.16g, 12mmol) was added to the flask, 100mL of toluene previously deoxygenated and dehydrated under an argon atmosphere was added, and the mixture was reacted at 120 ℃ for 24 hours. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane for three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 1:5) to obtain 1.8g of the intermediate, wherein the intermediate is white powder, the yield is 67%, the theoretical relative molecular mass is 267.20, and MS (EI) M/z: [ M (Electron exchange interference)]+：267.12。
The intermediate (2.67g, 10mmol), 9-phenyl-2, 7-dibromocarbazole (4.00g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were then added to a 250mL two-necked flask, followed by NaOt-Bu (1.16g, 12mmol) in a glove box, 100mL of toluene which is dehydrated and deoxidized in advance is added under the argon atmosphere, the reaction is carried out for 24 hours at 120 ℃, the reaction product is cooled to the room temperature, 0.4g of NaH is added, the reaction was continued at 120 ℃ for 24 hours, cooled to room temperature, poured into 200mL of ice water, extraction with dichloromethane three times, combining the organic phases, spinning to silica gel, column chromatography (dichloromethane: n-hexane, v: v, 1:5) separation and purification to obtain 3.9g of the first reactant, the first reactant was a white powder with a yield of 68%, MS (EI) m/z: [ M ].]+：570.12。
EXAMPLE six
The first reactant in this example has the formula
Figure GDA0002938889460000161
The second reactant is carbazole with the structural formula
Figure GDA0002938889460000162
The process of synthesizing the target compound 6 by the first reactant and the second reactant is shown as the following formula:
Figure GDA0002938889460000163
specifically, the first reactant (5.57g, 10mmol), carbazole (1.67g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were added to a 250mL two-neck flask, NaOt-Bu (1.16g, 12mmol) was added to the flask, 100mL toluene with water removed beforehand was added under argon atmosphere, reaction was carried out at 120 ℃ for 24 hours, the reaction solution was poured into 200mL ice water after cooling to room temperature, dichloromethane was extracted three times, the organic phase was combined, silica gel was spun, column chromatography (dichloromethane: n-hexane, v: v, 1:5) was carried out for separation and purification to obtain 3.9g of the target compound 6, the target compound 6 was a white powder with a yield of 61%, MS (EI) M/z: [ M]+：644.12。
Wherein the raw materials of the first reactant comprise anthranilamine, 1,3, 5-trimethylbromobenzene and 9-phenyl-2, 7-dibromocarbazole, and the structural formula of the intermediate is shown in the specification, wherein the anthranilamine reacts with the 1,3, 5-trimethylbromobenzene to obtain an intermediate
Figure GDA0002938889460000171
And reacting the intermediate with 9-phenyl-2, 7-dibromocarbazole to obtain the first reactant, wherein the synthesis process of the first reactant is shown as the following formula:
Figure GDA0002938889460000172
to this, 1,3, 5-trimethylbromobenzene (1.98g, 10mmol), anthranilamine (1.22g, 10mmol), palladium acetate (90mg,0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol), adding NaOt-Bu (1.16g, 12mmol) into a glove box, adding 100mL of toluene which is dehydrated and deoxidized in advance under the argon atmosphere, reacting at 120 ℃ for 24 hours, cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v, 1:5) to obtain 1.8g of the intermediate, which is white powder, has the yield of 75%, and the theoretical relative molecular mass of 240.16, MS (EI) M/z: [ M (M is an amount of the total molecular mass of the]+：240.12。
Then the intermediate (2.40g, 10mmol), 9-phenyl-2, 7-dibromocarbazole (4.00g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) are added into a 250mL two-neck flask, NaOt-Bu (1.16g, 12mmol) is added into a glove box, 100mL of toluene which is dehydrated and deoxidized in advance is added under argon atmosphere, the mixture is reacted at 120 ℃ for 24 hours, the temperature is cooled to room temperature, 0.4g of NaH is added, the reaction is continued at 120 ℃ for 24 hours, the mixture is cooled to room temperature, the reaction solution is poured into 200mL of ice water, dichloromethane is extracted for three times, organic phases are combined, silica gel is formed, column chromatography (dichloromethane: n-hexane, v: v, 1:5) is separated and purified, 3.9g of the first reactant is obtained, the first reactant is white powder, the yield is 70%, and the theoretical relative molecular mass is 557.15, MS (EI) M/z [ M]+：557.08。
According to the embodiment of the invention, through the collocation of different functional groups, the target compound synthesized according to a reasonable route design has a proper electrochemical energy level and a high migration rate, and through theoretical simulation calculation of target molecules, the electrochemical energy level of the synthesized target compound is shown in the following table 1:
TABLE 1
Target compound HOMO(eV) LUMO(eV)
Object Compound 1 -5.58 -2.45
Target Compound 2 -5.61 -2.46
Target Compound 3 -5.66 -2.46
Target Compound 4 -5.58 -2.55
Target Compound 5 -5.58 -2.53
Target Compound 6 -5.58 -2.67
Each of the synthesized target compounds was applied to an electroluminescent device, and performance data of the electroluminescent device are shown in table 2 below.
TABLE 2
Figure GDA0002938889460000181
Has the advantages that: the hole transport material designed and synthesized by the invention has proper energy level and higher hole mobility, and can obtain higher luminous efficiency and prolong the service life of the device when being applied to an electroluminescent device.
In summary, although the present invention has been described with reference to the preferred embodiments, the above-described preferred embodiments are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore, the scope of the present invention shall be determined by the appended claims.

Claims (10)

1. A hole transport material having a structural formula as shown in the following formula:
Figure FDA0002911060870000011
wherein,
the R group is one of the following structures:
Figure FDA0002911060870000012
the X group is one of the following structural formulas: o, S,
Figure FDA0002911060870000013
2. An electroluminescent device comprising a hole transport layer prepared using the hole transport material of claim 1.
3. A method for preparing a hole transport material, comprising the steps of:
s10, mixing a first reactant, a second reactant, a catalyst and a solvent to obtain a mixed solution, wherein the first reactant isHas the structural formula
Figure FDA0002911060870000021
The X group is one of the following structural formulas: o, S,
Figure FDA0002911060870000022
S20, reacting the mixed solution at 120 ℃ for 24 hours to obtain a reaction solution;
s30, cooling, extracting, separating and purifying the reaction liquid to obtain the hole transport material, wherein the structural formula of the hole transport material is shown in the specification
Figure FDA0002911060870000023
The R group is one of the following structures:
Figure FDA0002911060870000024
4. the method of claim 3, wherein the second reactant is one of carbazole, diphenylamine, and 9, 9' -dimethylacridine.
5. The method of claim 3, wherein the molar ratio of the first reactant to the second reactant is 1: 1.
6. The method of claim 3, wherein the first reactant comprises:
reacting a first raw material with 1,3, 5-trimethylbromobenzene to obtain an intermediate, wherein the structural formula of the first raw material is shown in the specification
Figure FDA0002911060870000031
The structural formula of the intermediate is
Figure FDA0002911060870000032
The Y group is one of the following structural formulas: o, S,
Figure FDA0002911060870000033
Reacting the intermediate with 9-phenyl-2, 7-dibromocarbazole to obtain a compound with a structural formula
Figure FDA0002911060870000034
The first reactant of (a).
7. The preparation method according to claim 6, wherein the molar ratio of the first raw material to 1,3, 5-trimethylbromobenzene participating in the reaction is 1:1, and the molar ratio of the intermediate participating in the reaction to 9-phenyl-2, 7-dibromocarbazole is 1: 1.
8. The method according to claim 3, wherein the catalyst is palladium acetate, tri-tert-butylphosphine tetrafluoroborate, or sodium tert-butyl alkoxide, and the solvent is toluene.
9. The method according to claim 8, wherein the S10 includes:
s101, adding a first reactant, a second reactant, palladium acetate and tri-tert-butylphosphine tetrafluoroborate into a two-mouth bottle;
s102, adding sodium tert-butoxide into the two-mouth bottle in a glove box;
and S103, adding toluene without water and oxygen into the two-mouth bottle under an inert gas atmosphere to obtain the mixed solution.
10. The method according to claim 9, wherein the S30 includes:
s301, cooling the reaction solution to room temperature, adding the reaction solution into 200ml of ice water, extracting the mixture for several times by using dichloromethane, combining organic phases, and spinning the organic phases into silica gel;
and S302, separating and purifying the silica gel by using a column chromatography method to obtain the hole transport material.
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