CN110317141A - A kind of electroluminescent organic material and its synthetic method and application - Google Patents

A kind of electroluminescent organic material and its synthetic method and application Download PDF

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CN110317141A
CN110317141A CN201910584152.3A CN201910584152A CN110317141A CN 110317141 A CN110317141 A CN 110317141A CN 201910584152 A CN201910584152 A CN 201910584152A CN 110317141 A CN110317141 A CN 110317141A
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substituted
unsubstituted
raw material
carbon atom
compound
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王亚龙
李红燕
薛震
王金平
陈志伟
李林刚
闫山
王卫军
任增刚
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Priority to CN201910584152.3A priority Critical patent/CN110317141A/en
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Priority to CN202010616426.5A priority patent/CN112174835B/en
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Abstract

The invention discloses a kind of electroluminescent organic material and its synthetic method and applications, provide the camphor derivative compound for having the excellent characteristics such as high-fire resistance, high chemical stability, high charge mobility, and its as organic matter layer organic electroluminescence device application, there is excellent hole mobility using the organic electroluminescence device of material of the present invention, it is low driving voltage is obtained, photoelectric properties are good, high efficiency, low-cost luminescent device.

Description

A kind of electroluminescent organic material and its synthetic method and application
Technical field
The invention belongs to organic photoelectrical material technical fields, and in particular to a kind of electroluminescent organic material and its synthesis side Method and application.
Background technique
The quality of organic electroluminescence device performance depends on the selection of material.Consider from the structure of device, organic electroluminescence Luminescent material generally comprises three parts: electrode material, carrier transmission material and luminescent material.
It is known that the derivative of aromatic amine as hole mobile material, electron transport material and shines in OLED device Material, hole mobile material should have lower ionization energy with anodic interface, higher hole mobility be provided simultaneously with, thus shape At pin-free film and thermostabilization it is good.Common hole mobile material have aromatic diamines class, tri-arylamine group, carbazoles, etc. Electron rich compound；Electron transport material has biggish conjugated system, they are most of all with preferable reception electronics energy Power, while electronics can be effectively transmitted under certain forward bias.The electron mobility of electron transport material is higher, have compared with High electron affinity has certain barrier effect to hole.Common electron transport material has furodiazole derivative, pyrimidine Analog derivative, quinoxaline derivant etc..Luminescent material is the core material of organic electroluminescence device, it has following characteristics: (1) under solid (film) state, fluorescence quantum efficiency with higher, fluorescence spectrum is mainly distributed on the visible of 400-700nm In light region；(2) there is good characteristic of semiconductor, there is certain carrier transport；(3) there is good film forming, It is easy to be made under vacuum with a thickness of tens nanometers, uniform, fine and close, pin-free film.
Organic electroluminescent has that all solid state, spectral width, brightness height, visual angle money, thickness be thin, usable flexible base board, work Make the advantages that temperature range is wide.Currently, display screen, small size based on OLED have realized commercialization, nevertheless, OLED technology It is real practical and universal there are also very long roads, how to design the better material of new performance and be adjusted, be always ability Field technique personnel's urgent problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of electroluminescent organic material and its synthetic method and applications, above-mentioned to overcome Defect of the existing technology, electroluminescent organic material stability provided by the invention is high, filming performance is good, by the chemical combination The organic electroluminescence device of object preparation, shows high efficiency, low driving voltage and is not easy the characteristics of crystallizing.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of electroluminescent organic material, the electroluminescent organic material have formula (I) structure:
Wherein, A is by the substituted or unsubstituted camphor group of formula (II)；
B is the group indicated by formula (III)；
Wherein, A is by the substituted or unsubstituted camphor group of formula (II), a, b, and c is the integer of 0-1, and 3≤a+b+c≤ 1；
L is the miscellaneous Asia of singly-bound, the arlydene of substituted or unsubstituted carbon number 6-30, substituted or unsubstituted carbon number 6-30 Aryl, the alkylidene of substituted or unsubstituted carbon number 2-11, substituted or unsubstituted carbon number 2-11 ring alkylidene, replace or The alkenylene of unsubstituted carbon number 2-11, the ring alkenylene of substituted or unsubstituted carbon number 2-11, substituted or unsubstituted carbon number The heterocycloalkenylene of 2-11, the alkynylene of substituted or unsubstituted carbon number 2-11, the ring of substituted or unsubstituted carbon number 2-11 are sub- The miscellaneous sub- cycloalkynyl radical of alkynyl, substituted or unsubstituted carbon number 2-11；
Ar1 and Ar2 are each independently selected from: replace perhaps unsubstituted ring carbon atom number be 6-30 aryl replace or Unsubstituted ring carbon atom number is the heteroaryl of 5-30, and combinations thereof；
Adjacent ortho position is connected by C-C key, C-S-C or C-O-C between Ar1 and Ar2 two-by-two aryl.
Further, A is specifically indicated by formula (IV):
Wherein, R1 is indicated monosubstituted, multiple substituted or unsubstituted；When R1 represents multiple substitution, adjacent substitution can Connection forms ring；
R1 be selected from following group: hydrogen, deuterium, halogen, the substituted or unsubstituted alkyl with 1-20 carbon atom, substitution or The unsubstituted naphthenic base with 3-20 ring carbon atom, takes the substituted or unsubstituted miscellaneous alkyl with 1-20 carbon atom Generation or the unsubstituted aralkyl with 7-30 carbon atom, the substituted or unsubstituted alkoxy with 1-20 carbon atom, The substituted or unsubstituted aryloxy group with 6-30 carbon atom, the substituted or unsubstituted alkenyl with 2-20 carbon atom, The substituted or unsubstituted aryl with 6-30 carbon atom, the substituted or unsubstituted heteroaryl with 3-30 carbon atom, The substituted or unsubstituted alkane silicon substrate with 3-20 carbon atom, the substituted or unsubstituted aryl silicon with 6-20 carbon atom Alkyl, the substituted or unsubstituted amido with 0-20 carbon atom, acyl group, carbonyl, carboxylic acid group, ester group, nitrile, isonitrile, sulfenyl, Sulfinyl, sulfonyl or phosphino-.
Further, the substituent group of described R1, L, Ar1 and Ar2 are identical or different, and the substituent group is C1-C30 alkane Base, C1-C30 alkoxy, C1-C30 alkylthio group, cyano, halogen or amino；In Ar1 and Ar2, the aryl is phenyl, thick Polycyclic aromatic group, heterocyclic aromatic base or multiring aromatic.
A kind of preparation method of electroluminescent organic material, comprising the following steps:
(1) raw material Ia, raw material Ib and hydrochloric acid are sequentially added into reaction unit, is stirring evenly and then adding into the concentrated sulfuric acid, are heated After being warming up to 120~140 DEG C, insulation reaction 4-8h, when being down to 60~80 DEG C after reaction, filtering, filter cake washing drying, Intermediate compound I is obtained, reaction equation is as follows:
(2) under nitrogen protection, successively intermediate compound I, raw material Ic and sodium tert-butoxide are dissolved in toluene, stirring while adds Heat is warming up to 150~160 DEG C, and flow back 2-4h, is then cooled to 30~40 DEG C, and Pd2 (dba) 3 and X-phos is added, continues to heat up To after 150~160 DEG C, insulation reaction 4-6h is down to room temperature after reaction, is poured into water liquid separation under stirring, by water phase first After benzene extraction, organic phase is merged, then dry using anhydrous sodium sulfate, gained filtrate is distilled in vacuum to give the organic of concentration Phase pours into the organic phase of concentration in petroleum ether, and solid is precipitated, obtains compound I through filtering drying, compound I is Organic Electricity Electroluminescent material, reaction equation are as follows:
Further, in step (1), raw material Ia: raw material Ib: hydrochloric acid: the concentrated sulfuric acid=0.1mol:(0.10-0.15) mol: (0.10-0.15) mol:(0.04-0.08) mol.
Further, in step (2), intermediate compound I: raw material Ic: sodium tert-butoxide: Pd2 (dba) 3:X-phos=0.1mol: (0.10-0.15) mol:(0.10-0.15) mol:(0.0001-0.0005) mol:(0.0001-0.0005) mol.
A kind of application of electroluminescent organic material on organic electroluminescence device, the organic electroluminescence device packet Anode, a series of organic layers of cathode and deposition between the anode and cathode are included, wherein at least one organic layer includes organic Electroluminescent material.
Further, the organic layer includes hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electronics Transfer layer and electron injecting layer.
It further, include the electroluminescent organic material in the hole transmission layer.
Compared with prior art, the invention has the following beneficial technical effects:
Material of the invention is characterized in that thering is camphor and trisubstituted amine structure in entire compound structure, the present invention The triarylamine compounds of camphor be that each functional molecular of the characteristics such as hole injection, cavity conveying has been subjected to camphor derivatization Compound, have that the preferable low-crystalline of the material as organic electroluminescent device, glass transition temperature be high and high heat resistance Property.The structure feature of camphor is, compared with cycloalkane or heteroaryl structure, in single molecular structure, molecule composition is non-flat Face.In general, the structure of non-flattening is based on the rotary motion of molecule, vibration motion etc. such as the alkyl group with long-chain The loss of bring motility generation energy.On the contrary, although the characteristic that camphor has crystallinity low, forms to its structural upright Therefore mutually firm condensed ring can drop low molecular motility, thus have high-fire resistance, can also reduce movement and bring Energy loss.In addition, if the heteroaryl structure of phenyl structure is due to its delocalization structure, energy rank is influenced, but camphor Structure will not affect energy rank caused by delocalization, and carbon number is more than phenyl, improve molecular mass, vitrifying temperature Degree is high, and the stability of film can be improved.
Material of the invention can be successfully applied to the hole transmission layer of organic electroluminescence device, and driving voltage is obviously low In common hole mobile material NPB, and efficiency all with higher and brightness under low driving voltage.In coloration, glass Changing temperature and half-life period etc. has excellent performance, and thermostabilization is good.
Detailed description of the invention
Fig. 1 is 1 products therefrom hydrogen spectrogram of the embodiment of the present invention；
Fig. 2 is 2 products therefrom hydrogen spectrogram of the embodiment of the present invention.
Specific embodiment
Embodiments of the present invention are described in further detail below:
A kind of electroluminescent organic material has formula (I) structure:
Wherein A is substitution by formula II, unsubstituted camphor group:
B is the group indicated by formula III:
Wherein, A is substitution by formula II, unsubstituted camphor group, and a, b, c are the integers of 0-1, and 3≤a+b+c≤ 1；
L be singly-bound, the arlydene for taking substituted or unsubstituted carbon number 6-30, substituted or unsubstituted carbon number 6-30 it is miscellaneous Arlydene, the alkylidene of substituted or unsubstituted carbon number 2-11, the ring alkylidene of substituted or unsubstituted carbon number 2-11, substitution Or the alkenylene of unsubstituted carbon number 2-11, the ring alkenylene of substituted or unsubstituted carbon number 2-11, substituted or unsubstituted carbon Count the ring of the heterocycloalkenylene of 2-11, the alkynylene of substituted or unsubstituted carbon number 2-11, substituted or unsubstituted carbon number 2-11 The miscellaneous sub- cycloalkynyl radical of alkynylene, substituted or unsubstituted carbon number 2-11；
Ar1 and Ar2 is respectively alone by selected from the group being made up of: replacing or unsubstituted ring carbon atom number is 6-30 Aryl, substitution or unsubstituted ring carbon atom number be 5-30 heteroaryl and combinations thereof.
Adjacent ortho position can be connected by C-C key, C-S-C or C-O-C between Ar1 and Ar2 two-by-two aryl.
Structure A is specifically indicated by formula IV:
Wherein, R1 is indicated monosubstituted, multiple substituted or unsubstituted；When R1 represents multiple substitution, adjacent substitution can be with Connection forms ring；
R1 be selected from following group: hydrogen, deuterium, halogen, the substituted or unsubstituted alkyl with 1-20 carbon atom, substitution or The unsubstituted naphthenic base with 3-20 ring carbon atom, the substituted or unsubstituted miscellaneous alkyl with 1-20 carbon atom, takes Generation or the unsubstituted aralkyl with 7-30 carbon atom, the substituted or unsubstituted alkoxy with 1-20 carbon atom, The substituted or unsubstituted aryloxy group with 6-30 carbon atom, the substituted or unsubstituted alkenyl with 2-20 carbon atom, The substituted or unsubstituted aryl with 6-30 carbon atom, the substituted or unsubstituted heteroaryl with 3-30 carbon atom, The substituted or unsubstituted alkane silicon substrate with 3-20 carbon atom, the substituted or unsubstituted aryl silicon with 6-20 carbon atom Alkyl, the substituted or unsubstituted amido with 0-20 carbon atom, acyl group, carbonyl, carboxylic acid group, ester group, nitrile, isonitrile, sulfenyl, Sulfinyl, sulfonyl, phosphino-.
A kind of synthetic method of electroluminescent organic material, comprising the following steps:
(1) sequentially add raw material Ia, raw material Ib and hydrochloric acid into three mouthfuls of reaction flasks, open stirring, after 20min, slowly to The concentrated sulfuric acid is added in system, opens heating, is warming up to 120~140 DEG C, starts insulation reaction 4-8h, is down to after reaction to about At 60~80 DEG C, filtering, filter cake washing is put into convection oven baking material (50~55 DEG C, 12h), obtains intermediate compound I；Wherein, raw material Ia: raw material Ib: hydrochloric acid: the concentrated sulfuric acid=0.1mol:(0.10-0.15) mol:(0.10-0.15) mol:(0.04-0.08) mol, instead Answer equation as follows:
(2) under nitrogen protection, successively intermediate compound I, raw material Ic, sodium tert-butoxide are dissolved in toluene into three mouthfuls of reaction flasks, Stirring is opened, nitrogen is led to, is warming up to 150~160 DEG C, flow back 2-4h.30~40 DEG C are cooled to, Pd2 (dba) 3, X- is added Phos, heat release are not too obviously, to be continuously heating to 150~160 DEG C or so, and insulation reaction 4-6h is down to room temperature after reaction, It is poured into water under stirring, liquid separation, water phase again with toluene extraction, organic phase merges, and anhydrous sodium sulfate is dry, and filter vacuum distills Concentrate pours into the organic phase of concentration in petroleum ether, there is solid precipitation, and filtering drying obtains compound I, and compound I is to have Electroluminescent material；Wherein, intermediate compound I: raw material Ic: sodium tert-butoxide: Pd2 (dba) 3:X-phos=0.1mol:(0.10- 0.15) mol:(0.10-0.15) mol:(0.0001-0.0005) mol:(0.0001-0.0005) mol, reaction equation is such as Under:
A kind of organic electroluminescence device comprising anode, cathode are deposited on a series of between the anode and cathode Organic layer, organic layer described in wherein at least one include the compound with Formulas I, and the organic matter layer is selected from hole injection Layer, hole transmission layer, luminescent layer, hole blocking layer, electron supplying layer and electron injecting layer, wherein the hole transmission layer packet Containing the compound with Formulas I.
Below with reference to embodiment, the present invention will be further described:
Embodiment 1: compound 1 and its synthetic method include the following steps:
(1) it is opened into three mouthfuls of reaction flasks successively by 0.10mol raw material 1a, 0.1mol raw material 1b, 0.1mol hydrochloric acid It stirs, after 20min, the 0.04mol concentrated sulfuric acid slowly is added to system, opens heating, is warming up to 120 DEG C, starts insulation reaction 4h, When be down to after reaction to about 60 DEG C, filtering, filter cake is eluted with 80ml water, is put into convection oven baking material (50 DEG C, 12h), is obtained Intermediate 1, yield 90%；Reaction equation is as follows:
(2) into four mouthfuls of reaction flasks successively by 0.10mol intermediate 1a, 0.1mol raw material 1c, 0.10mol sodium tert-butoxide It is dissolved in toluene, opens stirring, lead to nitrogen, be warming up to 155 DEG C, flow back 3h.40 DEG C are cooled to, 0.0005mol Pd2 is added (dba) 3,0.0005mol X-phos, heat release are not too obviously, to be continuously heating to 155 DEG C or so, insulation reaction 4h, reaction knot It to be down to room temperature after beam, is poured under stirring in 60ml water, liquid separation, water phase uses toluene 60ml to extract every time, twice, merge organic phase, It is dry that 6g anhydrous sodium sulfate is added, filter vacuum distills to obtain intermediate 1, yield 85%；Reaction equation is as follows:
The calculated value C of 1 constituent content of compound49H43N:C:91.12；H:6.71；N:2.17；Measured value: C49H43N:C: 89.67；H:6.84；N:2.07.Specific hydrogen spectrogram is shown in Fig. 1.Wherein, raw material 1a, raw material 1b, raw material 1c are purchase.
Embodiment 2: compound 2 and its synthetic method include the following steps:
(1) it is opened into three mouthfuls of reaction flasks successively by 0.10mol raw material 2a, 0.11mol raw material 2b, 0.12mol hydrochloric acid It opens stirring, after 20min, the 0.05mol concentrated sulfuric acid slowly is added to system, opens heating, is warming up to 125 DEG C, starts insulation reaction 6h, when be down to after reaction to about 65 DEG C, filtering, filter cake is eluted with 80ml water, is put into convection oven baking material (55 DEG C, 12h), Obtain intermediate 2, yield 90%；Reaction equation is as follows:
(2) into four mouthfuls of reaction flasks successively by 0.10mol intermediate 2,0.12mol raw material 2c, 0.15mol sodium tert-butoxide It is dissolved in toluene, opens stirring, lead to nitrogen, be warming up to 150 DEG C, flow back 4h.30 DEG C are cooled to, 0.0001mol Pd2 is added (dba) 3,0.0001mol X-phos, heat release are not too obviously, to be continuously heating to 150 DEG C or so, insulation reaction 5h, reaction knot It to be down to room temperature after beam, is poured under stirring in 60ml water, liquid separation, water phase uses toluene 60ml to extract every time, twice, merge organic phase, It is dry that 6g anhydrous sodium sulfate is added, filter vacuum distills to obtain intermediate 2, yield 73%；Reaction equation is as follows:
The calculated value C of 2 constituent content of compound38H35N2: C:85.53；H:6.83；N:4.87；O:2.78；Measured value: C38H35N2: C:85.67；H:6.84；N:4.07；O:2.49.Specific hydrogen spectrogram is shown in Fig. 2.Wherein, raw material 2a, raw material 2b, raw material 2c For purchase.
Embodiment 3: compound 3 and its synthetic method include the following steps:
(1) it is opened into three mouthfuls of reaction flasks successively by 0.10mol raw material 3a, 0.15mol raw material 3b, 0.15mol hydrochloric acid It opens stirring, after 20min, the 0.08mol concentrated sulfuric acid slowly is added to system, opens heating, is warming up to 140 DEG C, starts insulation reaction 6h, when be down to after reaction to about 80 DEG C, filtering, filter cake is eluted with 80ml water, is put into convection oven baking material (53 DEG C, 12h), Obtain intermediate 3, yield 86%；Reaction equation is as follows:
(2) into four mouthfuls of reaction flasks successively by 0.10mol intermediate 3,0.13mol raw material 3c, 0.13mol sodium tert-butoxide It is dissolved in toluene, opens stirring, lead to nitrogen, be warming up to 160 DEG C, flow back 2h.35 DEG C are cooled to, 0.0003mol Pd2 is added (dba) 3,0.0003mol X-phos, heat release are not too obviously, to be continuously heating to 155 DEG C or so, insulation reaction 6h, reaction knot It to be down to room temperature after beam, is poured under stirring in 60ml water, liquid separation, water phase uses toluene 60ml to extract every time, twice, merge organic phase, It is dry that 6g anhydrous sodium sulfate is added, filter vacuum distills to obtain intermediate 3, yield 75%；Reaction equation is as follows:
Embodiment 4: compound 4 and its synthetic method include the following steps:
(1) raw material 1a in embodiment 1 is substituted for raw material 4a by the synthetic method of above compound 4, and middle raw material 1b is substituted for Remaining operation of raw material 4b is same as Example 1, obtains intermediate 4, yield 70.88%.Its chemical equation is as follows:
(2) intermediate 1 in embodiment 1 is substituted for intermediate 4, middle raw material 1c by the synthetic method of above compound 4 It is same as Example 1 to be substituted for raw material 4c remaining operation, obtains compound 4, yield 45.88%.The following institute of its chemical equation Show；Reaction equation is as follows:
Embodiment 5: compound 5 and its synthetic method include the following steps:
(1) raw material 1a in embodiment 1 is substituted for raw material 5a by the synthetic method of above compound 5, and middle raw material 1b is substituted for Remaining operation of raw material 5b is same as Example 1, obtains intermediate 5, yield 65.21%.Its chemical equation is as follows:
(2) intermediate 1 in embodiment 1 is substituted for intermediate 5, middle raw material 1c be substituted for remaining operation of raw material 5c with Embodiment 1 is identical, obtains compound 5, yield 43.55%.Its:
Embodiment 6
Raw material 1a in embodiment 1 is substituted for raw material 6a by the synthetic method of compound 6, and raw material 1b is substituted for raw material 6b, former Material 1c is substituted for raw material 6c, remaining operation is same as Example 1, obtains compound 6, yield 67.09%.
Embodiment 7
Raw material 1a in embodiment 1 is substituted for raw material 7a by the synthetic method of compound 7, and raw material 1b is substituted for raw material 7b, former Material 1c is substituted for raw material 7c, remaining operation is same as Example 1, obtains compound 7, yield 58.68%.
Embodiment 8
Raw material 1a in embodiment 1 is substituted for raw material 8a by the synthetic method of compound 8, and raw material 1b is substituted for raw material 8b, former Material 1c is substituted for raw material 8c, remaining operation is same as Example 1, obtains compound 8, yield 44.78%.
Embodiment 9
Raw material 1a in embodiment 1 is substituted for raw material 9a by the synthetic method of compound 9, and raw material 1b is substituted for raw material 9b, former Material 1c is substituted for raw material 9c, remaining operation is same as Example 1, obtains compound 9, yield 55.38%.
Embodiment 10
Raw material 1a in embodiment 1 is substituted for raw material 10a by the synthetic method of compound 10, and raw material 1b is substituted for raw material 10b, raw material 1c are substituted for raw material 8c, remaining operation is same as Example 1, obtain compound 10, yield 45.67%.
Embodiment 11
Raw material 1a in embodiment 1 is substituted for raw material 11a by the synthetic method of compound 11, and raw material 1b is substituted for raw material 11b, raw material 1c are substituted for raw material 11c, remaining operation is same as Example 1, obtain compound 11, yield 53.89%.
Embodiment 12
Raw material 1a in embodiment 1 is substituted for raw material 12a by the synthetic method of compound 12, and raw material 1b is substituted for raw material 12b, raw material 1c are substituted for raw material 12c, remaining operation is same as Example 1, obtain compound 12, yield 39.56%.
Embodiment 13
Raw material 1a in embodiment 1 is substituted for raw material 13a by the synthetic method of compound 13, and raw material 1b is substituted for raw material 8b, raw material 1c are substituted for raw material 13c, remaining operation is same as Example 1, obtain compound 13, yield 46.75%.
Embodiment 14
Raw material 1a in embodiment 1 is substituted for raw material 14a by the synthetic method of compound 14, and raw material 1b is substituted for raw material 14b, raw material 1c are substituted for raw material 14c, remaining operation is same as Example 1, obtain compound 14, yield 49.78%.
Embodiment 15
Raw material 1a in embodiment 1 is substituted for raw material 15a by the synthetic method of compound 15, and raw material 1b is substituted for raw material 15b, raw material 1c are substituted for raw material 15c, remaining operation is same as Example 1, obtain compound 15, yield 48.36%.
Embodiment 16
Raw material 1a in embodiment 1 is substituted for raw material 16a by the synthetic method of compound 16, and raw material 1b is substituted for raw material 16b, raw material 1c are substituted for raw material 16c, remaining operation is same as Example 1, obtain compound 16, yield 54.74%.
Embodiment 17
Raw material 1a in embodiment 1 is substituted for raw material 17a by the synthetic method of compound 17, and raw material 1b is substituted for raw material 17b, raw material 1c are substituted for raw material 17c, remaining operation is same as Example 1, obtain compound 17, yield 55.68%.
Embodiment 18
Raw material 1a in embodiment 1 is substituted for raw material 18a by the synthetic method of compound 18, and raw material 1b is substituted for raw material 18b, raw material 1c are substituted for raw material 18c, remaining operation is same as Example 1, obtain compound 18, yield 50.18%.
Embodiment 19
Raw material 1a in embodiment 1 is substituted for raw material 19a by the synthetic method of compound 8, and raw material 1b is substituted for raw material 19b, raw material 1c are substituted for raw material 19c, remaining operation is same as Example 1, obtain compound 19, yield 56.68%.
Embodiment 20
Raw material 1a in embodiment 1 is substituted for raw material 20a by the synthetic method of compound 20, and raw material 1b is substituted for raw material 20b, raw material 1c are substituted for raw material 20c, remaining operation is same as Example 1, obtain compound 20, yield 48.88%.
Embodiment 21
Raw material 1a in embodiment 1 is substituted for raw material 21a by the synthetic method of compound 21, and raw material 1b is substituted for raw material 21b, raw material 1c are substituted for raw material 21c, remaining operation is same as Example 1, obtain compound 21, yield 39.88%.
Embodiment 22
Raw material 1a in embodiment 1 is substituted for raw material 22a by the synthetic method of compound 22, and raw material 1b is substituted for raw material 22b, raw material 1c are substituted for raw material 22c, remaining operation is same as Example 1, obtain compound 22, yield 47.38%.
Embodiment 23
Raw material 1a in embodiment 1 is substituted for raw material 23a by the synthetic method of compound 23, and raw material 1b is substituted for raw material 23b, raw material 1c are substituted for raw material 23c, remaining operation is same as Example 1, obtain compound 23, yield 59.67%.
Embodiment 24
Raw material 1a in embodiment 1 is substituted for raw material 24a by the synthetic method of compound 24, and raw material 1b is substituted for raw material 24b, raw material 1c are substituted for raw material 24c, remaining operation is same as Example 1, obtain compound 24, yield 69.68%.
Embodiment 25-62
Raw material 1a in embodiment 1 is substituted for raw material (25-62) by the synthetic method of hole mobile material compound 25-62 A, raw material 1b are substituted for raw material (25-62) b, and raw material 1c is substituted for raw material (25-62) c, remaining operation is same as Example 1, obtain To compound 25-62, yield 45%-77%.
Wherein raw material and compound structure and spectrogram see the table below 1 in compound 6-62:
Application examples 1
Compound is used as application of the hole mobile material in the hole transmission layer of organic electroluminescence device, organic light emission The manufacturing method of device, includes the following steps:
(1) successively first there is tin indium oxide (ITO) electrode (first electrode, anode) with distilled water, methanol ultrasonic cleaning Glass film plates, it is dry；
(2) it is cleaned 5 minutes with oxygen plasma again, the anode bottom plate cleaned up is then loaded into vacuum deposition device In；
(3) HIL of about 50nm thickness will be formed in hole injection layer compound 2-TNATA vacuum deposition to ITO electrode, The HTL of about 20nm thickness will be formed in obtained 4 vacuum evaporation to hole injection layer of compound of the embodiment of the present invention 4 again, so Afterwards by main body luminescent materialIt is coprecipitated with the mass ratio of 96:4 with B Alq3 dopant The luminescent layer EML of about 30nm thickness is formed in product to hole transporting zone；
(4) the hole blocking layer DPVBi of about 20nm thickness, the electron transfer layer Alq of about 30nm thickness are finally sequentially depositing3 And the aluminium of cathode LiF and about the 50nm thickness of about 5nm thickness, thus complete the manufacture of organic luminescent device.
Application examples 2- application examples 8
In application examples 2- application examples 7, the compound 4 by application examples 1 as hole transmission layer replaces with compound 5, chemical combination Object 6, compound 7, compound 8, compound 9, compound 10, remaining manufactures organic electroluminescence using method identical with application examples 1 Luminescent device.
Comparative example
In comparative example, the compound 4 by application examples 1 as hole transmission layer replaces with compound N PB, remaining uses and answers The identical method of use-case 1 manufactures organic electroluminescence device.
Wherein NPB is existing common hole mobile material, and structural formula is as follows:
To organic electroluminescence device prepared above, in 15mA/cm2Under conditions of analyze the performance of element, knot Fruit such as table 1:
The electron luminescence characteristic list of 1 organic luminescent device of table
Thus table 1 is as can be seen that the compound of the present invention 4,5,6,7,8,9,10 can succeed as hole mobile material Hole transmission layer applied to organic electroluminescence device.Driving voltage is significantly lower than common hole mobile material NPB, brightness (Cd/m2) and external quantum efficiency (EQE) maximum improves 78% and 48% respectively.Compared with comparative example, it is shown that preferably special Property, the characteristic with low power efficient rate.
The present invention provides the camphors for having the excellent characteristics such as high-fire resistance, high chemical stability, high charge mobility to spread out Raw compounds, and its sent out in the application of organic electroluminescence device using the organic electroluminescence of material of the present invention as organic matter layer Optical device has excellent hole mobility, and it is low to have obtained driving voltage, and photoelectric properties are good, high efficiency, low-cost hair Optical device.

Claims (10)

1. a kind of electroluminescent organic material, which is characterized in that the electroluminescent organic material has formula (I) structure:
Wherein, A is by the substituted or unsubstituted camphor group of formula (II)；
B is the group indicated by formula (III)；
Wherein, A is by the substituted or unsubstituted camphor group of formula (II), a, b, and c is the integer of 0-1, and 3≤a+b+c≤1；
L be singly-bound, the arlydene of substituted or unsubstituted carbon number 6-30, substituted or unsubstituted carbon number 6-30 heteroarylidene, The ring alkylidene, substituted or unsubstituted of the alkylidene of substituted or unsubstituted carbon number 2-11, substituted or unsubstituted carbon number 2-11 The alkenylene of carbon number 2-11, the ring alkenylene of substituted or unsubstituted carbon number 2-11, substituted or unsubstituted carbon number 2-11 Heterocycloalkenylene, the alkynylene of substituted or unsubstituted carbon number 2-11, substituted or unsubstituted carbon number 2-11 ring alkynylene, take The miscellaneous sub- cycloalkynyl radical of generation or unsubstituted carbon number 2-11；
Ar1 and Ar2 are each independently selected from: the aryl that perhaps unsubstituted ring carbon atom number is 6-30 being replaced to replace or do not take The ring carbon atom number in generation is the heteroaryl of 5-30, and combinations thereof；
Adjacent ortho position is connected by C-C key, C-S-C or C-O-C between Ar1 and Ar2 two-by-two aryl.
2. a kind of electroluminescent organic material according to claim 1, which is characterized in that A is specifically indicated by formula (IV):
Wherein, R1 is indicated monosubstituted, multiple substituted or unsubstituted；When R1 represents multiple substitution, adjacent substitution can be connected Form ring；
R1 is selected from following group: hydrogen, halogen, the substituted or unsubstituted alkyl with 1-20 carbon atom, replaces or does not take deuterium The naphthenic base with 3-20 ring carbon atom in generation, the substituted or unsubstituted miscellaneous alkyl with 1-20 carbon atom, replace or The unsubstituted aralkyl with 7-30 carbon atom, replaces the substituted or unsubstituted alkoxy with 1-20 carbon atom Or the unsubstituted aryloxy group with 6-30 carbon atom, the substituted or unsubstituted alkenyl with 2-20 carbon atom, substitution Or the unsubstituted aryl with 6-30 carbon atom, the substituted or unsubstituted heteroaryl with 3-30 carbon atom, substitution Or the unsubstituted alkane silicon substrate with 3-20 carbon atom, the substituted or unsubstituted aryl-silane with 6-20 carbon atom Base, the substituted or unsubstituted amido with 0-20 carbon atom, acyl group, carbonyl, carboxylic acid group, ester group, nitrile, isonitrile, sulfenyl, Asia Sulfonyl, sulfonyl or phosphino-.
3. a kind of electroluminescent organic material according to claim 2, which is characterized in that described R1, L, Ar1 and Ar2's Substituent group is identical or different, and the substituent group is C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio group, cyano, halogen Or amino；In Ar1 and Ar2, the aryl is phenyl, polycyclic aromatic base, heterocyclic aromatic base or multiring aromatic.
4. a kind of electroluminescent organic material according to claim 1, which is characterized in that the electroluminescent organic material In following compound:
5. a kind of preparation method of the described in any item electroluminescent organic materials of claim 1-4, which is characterized in that including with Lower step:
(1) raw material Ia, raw material Ib and hydrochloric acid are sequentially added into reaction unit, are stirring evenly and then adding into the concentrated sulfuric acid, heat temperature raising To after 120~140 DEG C, insulation reaction 4-8h, when being down to 60~80 DEG C after reaction, filtering, filter cake washing drying is obtained intermediate Body I, reaction equation are as follows:
(2) under nitrogen protection, successively intermediate compound I, raw material Ic and sodium tert-butoxide are dissolved in toluene, heating rises while stirring To 150~160 DEG C, flow back temperature 2-4h, is then cooled to 30~40 DEG C, and Pd2 (dba) 3 and X-phos is added, is continuously heating to After 150~160 DEG C, insulation reaction 4-6h is down to room temperature after reaction, is poured into water liquid separation under stirring, by water phase toluene After extraction, organic phase is merged, it is then dry using anhydrous sodium sulfate, gained filtrate through being distilled in vacuum to give the organic phase of concentration, The organic phase of concentration is poured into petroleum ether, solid is precipitated, obtains compound I through filtering drying, compound I is organic electroluminescence hair Luminescent material, reaction equation are as follows:
6. a kind of preparation method of electroluminescent organic material according to claim 5, which is characterized in that in step (1), Raw material Ia: raw material Ib: hydrochloric acid: the concentrated sulfuric acid=0.1mol:(0.10-0.15) mol:(0.10-0.15) mol:(0.04-0.08) mol。
7. a kind of preparation method of electroluminescent organic material according to claim 5, which is characterized in that in step (2), Intermediate compound I: raw material Ic: sodium tert-butoxide: Pd2 (dba) 3:X-phos=0.1mol:(0.10-0.15) mol:(0.10-0.15) Mol:(0.0001-0.0005) mol:(0.0001-0.0005) mol.
8. a kind of application of described in any item electroluminescent organic materials of claim 1-4 on organic electroluminescence device, It is characterized in that, the organic electroluminescence device includes anode, cathode and a series of deposition between the anode and cathode Organic layer, wherein at least one organic layer include electroluminescent organic material.
9. application of the electroluminescent organic material according to claim 8 on organic electroluminescence device, feature exist In the organic layer includes hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron supplying layer and electronics Implanted layer.
10. application of the electroluminescent organic material according to claim 9 on organic electroluminescence device, feature exist In comprising the electroluminescent organic material in the hole transmission layer.
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