CN109942799A - A kind of conjugated polymer of siliceous spiro fluorene acridine unit and preparation method thereof, organic electroluminescence device - Google Patents

Abstract

The present invention provides a kind of conjugated polymer, the conjugated polymer has formula (I) structure.Conjugated polymer provided by the invention with formula (I) structure is the conjugated polymer of a kind of siliceous spiro fluorene acridine unit.The present invention has been specifically incorporated the acridine unit with electron donation, so that polymer HOMO energy level with higher, to show good hole injection and transmittability, thus opens bright voltage and higher power efficiency with lower；It is more copolymerized by introducing suitable, the electron-transport unit with low lumo energy in main polymer chain, can make the polymer that there is thermotropic delayed fluorescence effect living, so as to realize the utilization of triplet excitons, to improve device external quantum efficiency.

Description

A kind of conjugated polymer of siliceous spiro fluorene acridine unit and preparation method thereof, Organic Electricity Electroluminescence device

Technical field

The present invention relates to luminous organic material field, it is related to a kind of conjugated polymer and preparation method thereof, organic electroluminescence hair Optical device more particularly to a kind of conjugated polymer of siliceous spiro fluorene acridine unit and preparation method thereof, organic electroluminescence device.

Background technique

Organic luminescent device (OLEDs) is usually the organic matter layer structure by being inserted between cathode, anode and cathode and anode At, i.e. the composition of device be by transparent ITO anode, hole injection layer (TIL), hole transmission layer (HTL), luminescent layer (EL), Hole blocking layer (HBL), electron transfer layer (ETL), electron injecting layer (EIL) and cathode are formed, and can omit 1~2 as needed has Machine layer.Its mechanism of action is to form voltage between two electrodes to inject from cathode electronics on one side, and hole is injected from anode in another side, Electrons and holes return to stable ground state in conjunction with excitation state, excitation state is formed in luminescent layer, and device shines.Since color is rich Rich, quick response and the features such as can prepare flexible device, organic electroluminescence device is considered most promising Next-generation FPD and solid state lighting technology.

As the display technology of new generation competitively developed in the world, compared with liquid crystal display (LCD), OLEDs is in display matter Amount aspect has the characteristics that self-luminous, high contrast, ultra-thin, with being easily achieved large screen and Flexible Displays etc. in terms of processing Advantage.Different according to the type of luminescent material, OLEDs can be divided into small organic molecule device and organic polymer device two is big Class.Wherein, organic polymer device can prepare low cost, large area using the mode of solution processing (such as ink-jet, spin coating etc.) Preparation equipment, thus there is broad prospect of application in display and lighting area.But for electroluminescent organic material, quotient at present The OLED display screen of industry is mostly or using the small organic molecule luminescent material based on vacuum evaporation process, the device of this kind of material Part efficiency is higher, but there are utilization rates drawbacks such as low, higher cost.In contrast, solution processable (such as inkjet printing and volume pair Roll up printing technology) electroluminescent organic material, have can reduce production cost and energy consumption, easily prepared large scale display screen etc. Advantage.

Polyfluorene and its derivative are a kind of representative polymer luminescent materials, with high film state fluorescence quantum yield Feature still under the action of high temperature or electric field, is easy to generate Fluorenone defect, affects the transmitting of spectrum, lead to spectrum-stable Property is poor.In view of this, researcher develops polysilico fluorene class conjugated polymer, wherein silicon atom is susceptible to oxidation reaction, tool The problem of having the characteristics of not generating Fluorenone defect, can solve spectrum unstability existing for polyfluorene.But polysilico fluorene class high score It is relatively low (about -5.80 eV, J.Am Chem, Soc.2005,127,7662-7663) that sub- luminescent material still has HOMO energy level, The excessive problem of hole injection barrier, causes device drive voltage higher, efficiency is lower.On the other hand, polysilico fluorene class macromolecule Luminescent material is traditional fluorescence polymer luminescent material, can not utilize triplet excitons, cause device external quantum efficiency low.

Therefore, suitable material layout strategy how is found, the molecular structure of above-mentioned polysilico fluorene class high molecular material is solved With defect existing for device performance aspect, it has also become one of urgent problem to be solved in field.

Summary of the invention

In view of this, the technical problem to be solved in the present invention is that providing a kind of conjugated polymer and preparation method thereof, having Organic electroluminescence devices, especially a kind of conjugated polymer of siliceous spiro fluorene acridine unit and preparation method thereof, organic electroluminescence hair Optical device, which has the acridine unit of electron donation, so that polymer HOMO energy level with higher, to show Good hole injection and transmittability out, thus bright voltage and higher power efficiency are opened with lower.

The present invention provides a kind of conjugated polymers, which is characterized in that and the conjugated polymer has formula (I) structure,

Wherein, it is integer between 2~9999 that x, which is 0.001~0.999, n,；

R₁Selected from substituted or non-substituted C₁~C₂₀Alkyl, substituted or non-substituted C₃~C₂₀Naphthenic base, replace or Non-substituted C₆~C₂₀Aromatic rings and substituted or non-substituted C₂~C₂₀One of aromatic heterocycle or a variety of；

R₂、R₃、R₄And R₅It is independently selected from substituted or non-substituted C₁~C₂₀Alkyl；

Ar is selected from substituted or non-substituted C₆~C₂₀Aromatic rings and/or substituted or non-substituted C₂~C₂₀Fragrance it is miscellaneous Ring；

Ar is further selected between the aromatic rings and the aromatic rings, is between the aromatic heterocycle and aromatic heterocycle and described Between aromatic rings and aromatic heterocycle, pass through the combination formed after Z key company；

The Z include singly-bound ,-C-C- ,-C=C- ,-C=N- ,-C=P- ,-C ≡ C-, One of or it is a variety of.

Preferably, in the conjugated polymer, R₁、R₂、R₃、R₄And R₅Respectively at each occurrence, can it is identical can also be with It is different；

The alkyl includes straight chained alkyl and/or branched alkyl；

The substitution of the alkyl includes that one or more non-conterminous carbon atoms can be by a kind of in O, S, Si and-CO-O- Or a variety of substitutions, and/or, one or more hydrogen atoms can be replaced by F；

The Ar is copolymerization units；

The hetero atom of aromatic heterocycle representated by the Ar is independently selected from Si, Ge, N, P, O, S or Se, and carbon is former Sub and heteroatomic sum >=5.

Preferably, the Ar is as copolymerization units, when showing as intrinsic property, is selected from shown in formula (1)~formula (10) and appoints Meaning one:

Wherein, B₁And B₂It is independently selected from substituted or non-substituted C₁~C₂₂Alkyl.

Preferably, the Ar is as copolymerization units, when having hole transporting properties, shown in formula (A)~formula (K) Any one:

Wherein, D₁、D₂And D₃It is independently selected from substituted or non-substituted C₁~C₂₂Alkyl.

5, conjugated polymer according to claim 1, which is characterized in that the Ar has electricity as copolymerization units When sub- transmission characteristic, it is selected from any one shown in formula (a)~formula (k):

Wherein, E₁And E₂It is independently selected from substituted or non-substituted C₁~C₂₂Alkyl.

Preferably, in the Ar, when containing B₁And B₂When, B₁And B₂It respectively at each occurrence, can be identical or not Together；

In the Ar, when containing D₁、D₂And D₃When, D₁、D₂And D₃It respectively at each occurrence, can be identical or not Together；

In the Ar, when containing E₁And E₂When, E₁And E₂Respectively at each occurrence, it can be the same or different；

The C₁~C₂₂Alkyl include straight chained alkyl and/or branched alkyl；

The C₁~C₂₂The substitution of alkyl include that one or more non-conterminous carbon atoms can be by O, S, Si and-CO- One or more substitutions in O-, and/or, one or more hydrogen atoms can be replaced by F.

Preferably, the conjugated polymer has structure shown in any one of formula (I-1)~(I-22):

The present invention provides a kind of preparation methods of conjugated polymer as described in above-mentioned technical proposal any one, special Sign is, comprising the following steps:

1) under protective atmosphere, after bromo compound X-1 is carried out the first butyl lithium reaction, intermediate X -2 is obtained；

Under protective atmosphere, after iodo compound X-3 is carried out the second butyl lithium reaction, then it is anti-with silicon tetrachloride progress Ying Hou obtains intermediate X -4；

2) under protective atmosphere, after the intermediate X -2 and intermediate X -4 that above-mentioned steps are obtained carry out ring closure reaction, Obtain intermediate II；

3) under protective atmosphere, intermediate II that above-mentioned steps are obtained, monomer III, palladium compound, organic phosphine chemical combination Object, alkali compounds, water, organic solvent and phase transfer catalyst mixing carry out Suzuki-Miyauraa polymerization reaction, to tool There is the conjugated polymer of formula (I) structure；

Wherein, M is selected from one of trifluoromethane sulfonic acid base ,-Cl ,-Br ,-I, boronate, boron ester group and boryl or more Kind.

Preferably, the temperature of the first butyl lithium reaction is -78~0 DEG C；

The time of the first butyl lithium reaction is 0.5~4h；

The temperature of the second butyl lithium reaction is -120~-78 DEG C；

The time of the second butyl lithium reaction is 0.5~4h；

The temperature of the reaction is -120~-78 DEG C；

The time of the reaction is 0.5~4h；

The temperature of the ring closure reaction is -78~50 DEG C；

The time of the ring closure reaction is 0.5~12h；

The temperature of the Suzuki-Miyauraa polymerization reaction is 40~100 DEG C；

The time of the Suzuki-Miyauraa polymerization reaction is 0.5~30h；

The palladium compound include one of palladium acetate, tetrakis triphenylphosphine palladium and tris(dibenzylideneacetone) dipalladium or It is a variety of；

The organic phosphine compound includes triphenylphosphine, tricyclohexyl phosphine, tri-tert-butylphosphine, 2- dicyclohexyl phosphorus -2,4, One of 6- tri isopropyl biphenyl, three (2- methoxyphenyl) phosphines and 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl or It is a variety of；

The alkali compounds includes one of sodium carbonate, potassium carbonate, cesium carbonate and potassium phosphate or a variety of；

The phase transfer catalyst includes tri-n-octyl methyl ammonium chloride；

The organic solvent includes one of tetrahydrofuran, toluene and dimethylbenzene or a variety of.

The present invention also provides a kind of organic electroluminescence devices, including luminescent material；The luminescent material includes right It is required that the preparation of preparation method described in conjugated polymer described in 1~7 any one or claim 8~9 any one is total to Conjugated polymer.

The present invention provides a kind of conjugated polymer, the conjugated polymer has formula (I) structure.With prior art phase Than, the present invention is about -5.80eV for the HOMO energy level of existing polysilico fluorene class high molecular material, and hole injection barrier is bigger, Device is caused to open bright voltage height, the low problem of power efficiency.More be directed to this kind of polysilico fluorene class high molecular material, due to HOMO and Lumo energy overlapping degree is higher, and singlet triplet poor (Δ EST) is larger (> 0.5eV), so prolonging without thermal activation Slow fluorescence efficiency can not utilize triplet excitons, the defect for causing luminous efficiency to reduce in electroluminescent device.

The invention provides the conjugated polymer with formula (I) structure, is a kind of siliceous spiro fluorene acridine unit Conjugated polymer.The present invention has been specifically incorporated the acridine unit with electron donation, so that polymer is with higher HOMO energy level to show good hole injection and transmittability, thus opens bright voltage and higher function with lower Rate efficiency；Be based more on the study found that existing polysilico fluorene class high-molecular luminous material HOMO and lumo energy overlapping degree compared with Height, poor (the Δ E of singlet triplet_ST) larger (> 0.5eV), so do not have thermal activation delayed fluorescence efficiency, thus in electricity Triplet excitons can not be utilized in electroluminescence device, and luminous efficiency is caused to reduce.The present invention in main polymer chain also by introducing Suitably, the electron-transport unit with low lumo energy is copolymerized, and the polymer can be made to have thermotropic delay living glimmering Luminous effect, so as to realize the utilization of triplet excitons, to improve device external quantum efficiency.

The experimental results showed that based on the organic of siliceous spiro fluorene acridine unit conjugated polymer material preparation provided by the invention The bright voltage that opens of luminescent device is 4.1V, and maximum current efficiency is 5.37cd/A, and maximum external quantum efficiency is 2.7%, most light Degree is 3808cd/m²。

Detailed description of the invention

Fig. 1 is the cyclic curve of fluorescent material PNSiF-SSPh prepared by the embodiment of the present invention 6；

Fig. 2 is the cyclic curve of fluorescent material PNSiF-BPh prepared by the embodiment of the present invention 5；

Fig. 3 is the cyclic curve of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7；

Fig. 4 is the fluorescence spectrum (room temperature) of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7；

Fig. 5 is the phosphorescence spectrum (77K) of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7；

Fig. 6 is the fluorescence lifetime attenuation curve of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7；

Fig. 7 is the V-I-B curve of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7；

Fig. 8 is current efficiency-current density plot of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7；

Fig. 9 is the EQE- current density plot of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7；

Figure 10 is the electroluminescent light spectral curve of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7.

Specific embodiment

For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention Limitation.

All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art The preparation of conventional method known to member.

All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or organic electroluminescence hair The purity of luminescent material field routine.

In the present invention, those skilled in the art being capable of culvert representated by two kinds of form of presentation of correct understanding formula (*) and formula * Justice is equivalent, and whether there is or not brackets to have no effect on its practical significance.

In the description of the present invention, in substituent groupIndicate connecting key, "-substituent group " indicates substituent group in structural formula It can be in any position of place group.

All compounds of the present invention, structure representation and abbreviation belong to the expression of this field conventional structure and abbreviation, each Structure representation and referred to as in the field of its associated uses be it is explicit, those skilled in the art according to structure representation and Referred to as, it can understand and accurately uniquely be understood.

The present invention provides a kind of conjugated polymer, the conjugated polymer has formula (I) structure,

Wherein, it is integer between 2~9999 that x, which is 0.001~0.999, n,；

R₁Selected from substituted or non-substituted C₁~C₂₀Alkyl, substituted or non-substituted C₃~C₂₀Naphthenic base, replace or Non-substituted C₆~C₂₀Aromatic rings and substituted or non-substituted C₂~C₂₀One of aromatic heterocycle or a variety of；

R₂、R₃、R₄And R₅It is independently selected from substituted or non-substituted C₁~C₂₀Alkyl；

Ar is selected from substituted or non-substituted C₆~C₂₀Aromatic rings or selected from substituted or non-substituted C₂~C₂₀Fragrance it is miscellaneous Ring；

Ar is further selected between the aromatic rings and the aromatic rings, is between the aromatic heterocycle and aromatic heterocycle and described Between aromatic rings and aromatic heterocycle, pass through the combination formed after Z key company；

The Z include singly-bound ,-C-C- ,-C=C- ,-C=N- ,-C=P- ,-C ≡ C-, One of or it is a variety of.

Non-conjugated fluorescence polymer compound of the present invention is preferably a kind of siliceous spiro fluorene acridine unit conjugated polymer, With formula (I) structure.Wherein, the x is 0.001~0.999, more preferably 0.01~0.99, more preferably 0.1~0.9, more Preferably 0.3~0.8, more preferably 0.5~0.6.N be 2~9999 between integer, more preferably 2~9999, more preferably 10~1000, more preferably 50~500, more preferably 100~300.

Wherein, R₁Selected from substituted or non-substituted C₁~C₂₀Alkyl, substituted or non-substituted C₃~C₂₀Naphthenic base, take Generation or non-substituted C₆~C₂₀Aromatic rings and substituted or non-substituted C₂~C₂₀One of aromatic heterocycle or a variety of, it is more excellent It is selected as substituted or non-substituted C₃~C₂₀Alkyl, substituted or non-substituted C₅~C₂₀Naphthenic base, substituted or non-substituted C₈ ~C₂₀Aromatic rings and substituted or non-substituted C₅~C₂₀One of aromatic heterocycle or a variety of, more preferably replace or non-take The C in generation₅~C₂₀Alkyl, substituted or non-substituted C₈~C₂₀Naphthenic base, substituted or non-substituted C₁₀~C₂₀Aromatic rings With substituted or non-substituted C₈~C₂₀One of aromatic heterocycle or a variety of, more preferably substituted or non-substituted C₈~C₂₀'s Alkyl, substituted or non-substituted C₁₀~C₂₀Naphthenic base, substituted or non-substituted C₁₂~C₂₀Aromatic rings and substituted or non-substituted C₁₀~C₂₀One of aromatic heterocycle or a variety of, more preferably substituted or non-substituted C₁₀~C₁₈Alkyl, substitution or non- Substituted C₁₃~C₁₈Naphthenic base, substituted or non-substituted C₁₅~C₁₈Aromatic rings and substituted or non-substituted C₁₂~C₁₈Virtue One of fragrant heterocycle is a variety of.

R₂、R₃、R₄And R₅It is independently selected from substituted or non-substituted C₁~C₂₀Alkyl, more preferably replace or it is non- Substituted C₃~C₂₀Alkyl, more preferably substituted or non-substituted C₅~C₂₀Alkyl, it is more preferably substituted or non-substituted C₈~C₂₀Alkyl, more preferably substituted or non-substituted C₁₀~C₁₈Alkyl, more preferably substituted or non-substituted C₁₂~C₁₆ Alkyl.

In conjugated polymer of the present invention, R₁、R₂、R₃、R₄And R₅Respectively at each occurrence, can it is identical can also With difference.That is, when in n unit of the structural formula in conjugated polymer, the R in each unit₁It can be the same or different. Likewise, R₂、R₃、R₄Or R₅It is also in this way, and R₁、R₂、 R₃、R₄And R₅Between have no effect on mutually.

In the present invention, the alkyl is not particularly limited in principle, those skilled in the art can be according to practical feelings Condition, performance requirement and product requirement are selected and are adjusted, and the present invention is preferably to guarantee the performance of conjugated polymer, it is complete and Refinement technology scheme, the alkyl preferably include straight chained alkyl and/or branched alkyl, more preferably straight chained alkyl or branched alkane Base.

In the present invention, the substituent group on the substituted alkyl is not particularly limited in principle, those skilled in the art Member can according to the actual situation, performance requirement and product requirement selected and adjusted, the present invention is preferably to guarantee that conjugation is poly- The performance of object is closed, complete and refinement technology scheme, the substitution of the alkyl preferably include, one or more non-conterminous carbon atoms Can by one or more substitutions in O, S, Si and-CO-O-, and/or, one or more hydrogen atoms can be replaced by F.That is, the alkane The substitution of base preferably includes, and one or more non-conterminous carbon atoms can be by one or more substitutions in O, S, Si and-CO-O-. The substitution of the alkyl preferably includes, and one or more hydrogen atoms can be replaced by F.

In the present invention, Ar is selected from substituted or non-substituted C₆~C₂₀Aromatic rings and/or substituted or non-substituted C₂~ C₂₀Aromatic heterocycle, more preferably substituted or non-substituted C₈~C₂₀Aromatic rings and/or substituted or non-substituted C₅~C₂₀'s Aromatic heterocycle, more preferably substituted or non-substituted C₁₀~C₂₀Aromatic rings and/or substituted or non-substituted C₈~C₂₀Fragrance Heterocycle, more preferably substituted or non-substituted C₁₂~C₂₀Aromatic rings and/or substituted or non-substituted C₁₀~C₂₀Fragrance it is miscellaneous Ring, more preferably substituted or non-substituted C₁₅~C₁₈Aromatic rings and/or substituted or non-substituted C₁₂~C₁₈Aromatic heterocycle.

Moreover, Ar is further selected between the aromatic rings and the aromatic rings, between the aromatic heterocycle and aromatic heterocycle with And between the aromatic rings and aromatic heterocycle, pass through the combination formed after Z key company.

Z of the present invention include singly-bound ,-C-C- ,-C=C- ,-C=N- ,-C=P- ,-C ≡ C-, One of or it is a variety of, more preferably singly-bound ,- C-C- ,-C=C- ,-C=N- ,-C=P- ,-C ≡ C-, One of or two or more keys even after the group that is formed.

In the present invention, the hetero atom of aromatic heterocycle representated by the Ar is not particularly limited in principle, this field Technical staff can according to the actual situation, performance requirement and product requirement select and adjust, the present invention is preferably to guarantee The hetero atom of the performance of conjugated polymer, complete and refinement technology scheme, aromatic heterocycle representated by the Ar is independent Selected from Si, Ge, N, P, O, S or Se, and carbon atom and heteroatomic sum are preferably >=5.

Ar of the present invention is preferably copolymerization units.In the present invention, when the Ar is as copolymerization units, specificization Formula structure is as described above, and the present invention is specifically chosen mode to it in principle and is not particularly limited, and those skilled in the art can With according to the actual situation, performance requirement and product requirement selected and adjusted, the present invention is preferably to guarantee conjugated polymer Performance, complete and refinement technology scheme, the Ar needs to show or when its intrinsic property of protrusion, is preferably selected from formula (1)~formula (10) any one shown in:

In the present invention, B₁And B₂It is independent to be preferably selected from substituted or non-substituted C₁~C₂₂Alkyl, more preferably Substituted or non-substituted C₃~C₂₂Alkyl, more preferably substituted or non-substituted C₅~C₂₂Alkyl, more preferably replace or Non-substituted C₈~C₂₂Alkyl, more preferably substituted or non-substituted C₁₀~C₂₀Alkyl, it is more preferably substituted or non-substituted C₁₂~C₁₈Alkyl, more preferably substituted or non-substituted C₁₄~C₁₆Alkyl.

The B in Ar of the present invention₁And B₂Respectively at each occurrence, it can be the same or different.That is, when conjugation is poly- In n unit for closing the structural formula in object, the B in each unit Ar₁It can be the same or different.Likewise, B₂It is also such as This, and B₁And B₂Between have no effect on mutually.

In the present invention, in principle to the B₁And B₂In alkyl be not particularly limited, those skilled in the art can root It is selected and is adjusted according to actual conditions, performance requirement and product requirement, the present invention is preferably to guarantee the property of conjugated polymer Can, complete and refinement technology scheme, the alkyl preferably include straight chained alkyl and/or branched alkyl, more preferably straight chained alkyl Or branched alkyl.In principle to the B₁And B₂Middle substituted C₁~C₂₂Substitution on alkyl is not particularly limited, art technology Personnel can according to the actual situation, performance requirement and product requirement select and adjust, the present invention is preferably to guarantee conjugation The performance of polymer, complete and refinement technology scheme, the substitution of the alkyl preferably include, and one or more non-conterminous carbon are former Son can by one or more substitutions in O, S, Si and-CO-O-, and/or, one or more hydrogen atoms can be replaced by F.That is, described B₁And B₂Middle substituted C₁~C₂₂Substitution on alkyl preferably includes, one or more non-conterminous carbon atoms can by O, S, Si and- One or more substitutions in CO-O-.The B₁And B₂Middle substituted C₁~C₂₂Substitution on alkyl preferably includes, one or more Hydrogen atom can be replaced by F.

When the Ar needs to show or protrudes its hole transporting properties, it is preferably selected from any one shown in formula (A)~formula (K) :

In the present invention, D₁、D₂And D₃It is independent to be preferably selected from substituted or non-substituted C₁~C₂₂Alkyl, it is more excellent It is selected as substituted or non-substituted C₃~C₂₂Alkyl, more preferably substituted or non-substituted C₅~C₂₂Alkyl, more preferably take Generation or non-substituted C₈~C₂₂Alkyl, more preferably substituted or non-substituted C₁₀~C₂₀Alkyl, more preferably replace or Non-substituted C₁₂~C₁₈Alkyl, more preferably substituted or non-substituted C₁₄~C₁₆Alkyl.

The D in Ar of the present invention₁、D₂And D₃Respectively at each occurrence, it can be the same or different.That is, when conjugation D in n unit of the structural formula in polymer, in each unit Ar₁It can be the same or different.Likewise, D₂And D₃? It is in this way, and D₁、D₂And D₃Between have no effect on mutually.

In the present invention, in principle to the D₁、D₂And D₃In alkyl be not particularly limited, those skilled in the art can With according to the actual situation, performance requirement and product requirement selected and adjusted, the present invention is preferably to guarantee conjugated polymer Performance, complete and refinement technology scheme, the alkyl preferably include straight chained alkyl and/or branched alkyl, more preferably straight chain Alkyl or branched alkyl.In principle to the D₁、D₂And D₃Middle substituted C₁~C₂₂Substitution on alkyl is not particularly limited, this Field technical staff can according to the actual situation, performance requirement and product requirement select and adjust, the present invention is better Guarantee the performance of conjugated polymer, complete and refinement technology scheme, the substitution of the alkyl preferably include, one or more not phases Adjacent carbon atom can by one or more substitutions in O, S, Si and-CO-O-, and/or, one or more hydrogen atoms can be replaced by F. That is, the D₁、D₂And D₃Middle substituted C₁~C₂₂Substitution on alkyl preferably includes, and one or more non-conterminous carbon atoms can By one or more substitutions in O, S, Si and-CO-O-.The D₁、D₂And D₃Middle substituted C₁~C₂₂Substitution on alkyl is preferably wrapped It includes, one or more hydrogen atoms can be replaced by F.

When the Ar needs to show or protrudes its electron transport property, it is preferably selected from any one shown in formula (a)~formula (k) :

In the present invention, E₁And E₂It is independent to be preferably selected from substituted or non-substituted C₁~C₂₂Alkyl, more preferably Substituted or non-substituted C₃~C₂₂Alkyl, more preferably substituted or non-substituted C₅~C₂₂Alkyl, more preferably replace or Non-substituted C₈~C₂₂Alkyl, more preferably substituted or non-substituted C₁₀~C₂₀Alkyl, it is more preferably substituted or non-substituted C₁₂~C₁₈Alkyl, more preferably substituted or non-substituted C₁₄~C₁₆Alkyl.

The E in Ar of the present invention₁And E₂Respectively at each occurrence, it can be the same or different.That is, when conjugation is poly- In n unit for closing the structural formula in object, the E in each unit Ar₁It can be the same or different.Likewise, E₂It is also such as This, and E₁And E₂Between have no effect on mutually.

In the present invention, in principle to the E₁And E₂In alkyl be not particularly limited, those skilled in the art can root It is selected and is adjusted according to actual conditions, performance requirement and product requirement, the present invention is preferably to guarantee the property of conjugated polymer Can, complete and refinement technology scheme, the alkyl preferably include straight chained alkyl and/or branched alkyl, more preferably straight chained alkyl Or branched alkyl.In principle to the E₁And E₂Middle substituted C₁~C₂₂Substitution on alkyl is not particularly limited, art technology Personnel can according to the actual situation, performance requirement and product requirement select and adjust, the present invention is preferably to guarantee conjugation The performance of polymer, complete and refinement technology scheme, the substitution of the alkyl preferably include, and one or more non-conterminous carbon are former Son can by one or more substitutions in O, S, Si and-CO-O-, and/or, one or more hydrogen atoms can be replaced by F.That is, described E₁And E₂Middle substituted C₁~C₂₂Substitution on alkyl preferably includes, one or more non-conterminous carbon atoms can by O, S, Si and- One or more substitutions in CO-O-.The E₁And E₂Middle substituted C₁~C₂₂Substitution on alkyl preferably includes, one or more Hydrogen atom can be replaced by F.

To further clarify and complete technical solution, conjugated polymer of the present invention preferably have formula (I-1)~(I- Any one of 22) structure shown in.Above-mentioned formula (I-1)~(I-22) is as previously mentioned, this is no longer going to repeat them.

Above-mentioned steps of the present invention provide a kind of conjugated polymer based on siliceous spiro fluorene acridine unit, and are free of acridine list The polysilico fluorene class conjugated polymer of member is compared, such conjugated polymer has higher HOMO energy due to the introducing of acridine unit Hole injection and transmittability can be improved in grade, exists to solve polysilico fluorene class macromolecule because hole injection and transmittability are poor Caused by open the problem that bright voltage is high, power efficiency is low.On the other hand, by the selection of copolymerization units, it can be achieved that HOMO energy Grade is separated with lumo energy, reduces singlet exciton and triplet excitons energy level difference, thus realize thermotropic delayed fluorescence effect living, The utilization to triplet excitons may be implemented in turn, to solve polysilico fluorene class macromolecule due to can not utilize triplet excitons The technical problem for causing device external quantum efficiency relatively low.

The present invention also provides a kind of preparation method of conjugated polymer as described in above-mentioned technical proposal any one, packets Include following steps:

1) under protective atmosphere, after bromo compound X-1 is carried out the first butyl lithium reaction, intermediate X -2 is obtained；

Under protective atmosphere, after iodo compound X-3 is carried out the second butyl lithium reaction, then it is anti-with silicon tetrachloride progress Ying Hou obtains intermediate X -4；

2) under protective atmosphere, after the intermediate X -2 and intermediate X -4 that above-mentioned steps are obtained carry out ring closure reaction, Obtain intermediate II；

3) under protective atmosphere, intermediate II that above-mentioned steps are obtained, monomer III, palladium compound, organic phosphine chemical combination Object, alkali compounds, water, organic solvent and phase transfer catalyst mixing carry out Suzuki-Miyauraa polymerization reaction, to tool There is the conjugated polymer of formula (I) structure；

Wherein, M is selected from one of trifluoromethane sulfonic acid base ,-Cl ,-Br ,-I, boronate, boron ester group and boryl or more Kind.

M of the present invention is more preferably trifluoromethane sulfonic acid base ,-Cl ,-Br ,-I, boronate, boron ester group or boryl.Its In, the boronate, boron ester group, boryl can for containing boric acid compound (boric acid compound) formed substituent group, The substituent group that compound (boron ester type compound) containing boron ester is formed, compound (boranes compound) formation containing borine Substituent group.

The present invention is and preceding to the structure and material and corresponding optimum principle of conjugated polymer in above-mentioned preparation method The material and structure of conjugated polymer are stated, and corresponding optimum principle can be corresponded to, this is no longer going to repeat them.

The present invention after bromo compound X-1 is carried out the first butyl lithium reaction, obtains centre first under protective atmosphere Body X-2；

Under protective atmosphere, after iodo compound X-3 is carried out the second butyl lithium reaction, then it is anti-with silicon tetrachloride progress Ying Hou obtains intermediate X -4.

The protective atmosphere is not particularly limited in the present invention, with conventional protecting gas well known to those skilled in the art Atmosphere, those skilled in the art can select and adjust according to the condition of production, quality requirement and product requirement, the present invention The protective atmosphere is preferably inert gas, more preferably argon gas.

The present invention is in principle not particularly limited the definition and response parameter of first butyl lithium reaction, with this field Butyl lithium known to technical staff reaction definition and response parameter, those skilled in the art can according to the condition of production, Quality requirement and product requirement are selected and are adjusted, and the present invention is preferably to guarantee the purity and receipts of intermediate product and final product Rate, butyl lithium reaction with butyl lithium that is, reacted, more preferably n-BuLi.The butyl lithium reaction is more preferably The condition of the low-temp reaction is not particularly limited in low-temp reaction, the present invention, with dry ice second well known to those skilled in the art Ether bath, those skilled in the art can select and adjust according to the condition of production, quality requirement and product requirement.This hair The temperature of the bright first butyl lithium reaction is preferably -78~0 DEG C, more preferably -68~-10 DEG C, more preferably -58~-20 DEG C, more preferably -48~-30 DEG C.The time of the first butyl lithium reaction is preferably 0.5~4h, more preferably 1~3.5h, More preferably 1.5~3h, more preferably 2~2.5h.

Other raw materials or reagent that the present invention reacts first butyl lithium are not particularly limited, with those skilled in the art The conventional auxiliary material or reagent of such reaction known to member, those skilled in the art can be according to the condition of production, quality It is required that being selected and being adjusted with product requirement.

The present invention is in principle not particularly limited the definition and response parameter of second butyl lithium reaction, with this field Butyl lithium known to technical staff reaction definition and response parameter, those skilled in the art can according to the condition of production, Quality requirement and product requirement are selected and are adjusted, and the present invention is preferably to guarantee the purity and receipts of intermediate product and final product Rate, butyl lithium reaction with butyl lithium that is, reacted, more preferably n-BuLi.The butyl lithium reaction is more preferably The condition of the low-temp reaction is not particularly limited in low-temp reaction, the present invention, with dry ice second well known to those skilled in the art Ether bath, those skilled in the art can select and adjust according to the condition of production, quality requirement and product requirement.This hair The temperature of the bright second butyl lithium reaction is preferably -120~-78 DEG C, more preferably -110~-88 DEG C, more preferably -100 ~-98 DEG C.The time of the second butyl lithium reaction is preferably 0.5~4h, more preferably 1~3.5h, more preferably 1.5~ 3h, more preferably 2~2.5h.

Other raw materials or reagent that the present invention reacts second butyl lithium are not particularly limited, with those skilled in the art The conventional auxiliary material or reagent of such reaction known to member, those skilled in the art can be according to the condition of production, quality It is required that being selected and being adjusted with product requirement.

Silicon tetrachloride of the present invention is preferably excessive silicon tetrachloride.The iodo compound X-3 and silicon tetrachloride Preferred 1:(8~20 of molar ratio), more preferably 1:(10~18), more preferably 1:(12~16).The temperature of reaction of the present invention Preferably -120~-78 DEG C of degree, more preferably -110~-88 DEG C, more preferably -100~-98 DEG C.The time of the reaction is excellent It is selected as 0.5~4h, more preferably 1~3.5h, more preferably 1.5~3h, more preferably 2~2.5h.

Then under protective atmosphere, intermediate X -2 and intermediate X -4 that above-mentioned steps obtain are closed by the present invention After ring reaction, intermediate II is obtained.

The present invention is in principle not particularly limited the definition and response parameter of the ring closure reaction, with those skilled in the art The definition and response parameter of ring closure reaction known to member, those skilled in the art can be according to the condition of production, quality requirement It is selected and is adjusted with product requirement, the present invention is preferably to guarantee the purity and yield of intermediate product and final product, described The temperature of ring closure reaction is preferably -78~50 DEG C, more preferably -58~30 DEG C, more preferably -38~10 DEG C, more preferably -18 ~-10 DEG C.The time of the ring closure reaction is preferably 0.5~12h, more preferably 2.5~10h, more preferably 4.5~8h.

Other raw materials or reagent of the ring closure reaction are not particularly limited in the present invention, known to those skilled in the art Such reaction conventional auxiliary material or reagent, those skilled in the art can according to the condition of production, quality requirement and Product requirement is selected and is adjusted.

The present invention by intermediate II that above-mentioned steps obtain, monomer III, palladium compound, has finally under protective atmosphere It is anti-that machine phosphine compound, alkali compounds, water, organic solvent and phase transfer catalyst mixing carry out Suzuki-Miyauraa polymerization It answers, to the conjugated polymer with formula (I) structure.

The present invention in principle urges the palladium compound, organic phosphine compound, alkali compounds, organic solvent and phase transfer The specific choice of agent is not particularly limited, and those skilled in the art can be according to the condition of production, quality requirement and product requirement It is selected and is adjusted, the present invention is preferably to guarantee the purity and yield of intermediate product and final product, and the palladium compound is excellent Choosing includes one of palladium acetate, tetrakis triphenylphosphine palladium and tris(dibenzylideneacetone) dipalladium or a variety of, more preferably acetic acid Palladium, tetrakis triphenylphosphine palladium or tris(dibenzylideneacetone) dipalladium.Organic phosphine compound of the present invention preferably includes triphenyl Phosphine, tricyclohexyl phosphine, tri-tert-butylphosphine, 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl, three (2- methoxyphenyl) phosphines With one of 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl or a variety of, more preferably triphenylphosphine, tricyclohexyl phosphine, Tri-tert-butylphosphine, 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl, three (2- methoxyphenyl) phosphines or 2- dicyclohexyl phosphine - 2', 6'- dimethoxy-biphenyl.Alkali compounds of the present invention preferably includes in sodium carbonate, potassium carbonate, cesium carbonate and potassium phosphate One or more, more preferably sodium carbonate, potassium carbonate, cesium carbonate or potassium phosphate.Phase transfer catalyst of the present invention is preferred Including tri-n-octyl methyl ammonium chloride.Organic solvent of the present invention preferably includes one of tetrahydrofuran, toluene and dimethylbenzene Or a variety of, more preferably tetrahydrofuran, toluene or dimethylbenzene.

The present invention in principle to the intermediate II, monomer III, palladium compound, organic phosphine compound, alkali compounds, Specific ratio between organic solvent and phase transfer catalyst is not particularly limited, and those skilled in the art can be according to production feelings Condition, quality requirement and product requirement are selected and are adjusted, preferably to guarantee the purity and yield of intermediate product and final product For preferred embodiment.

The definition to the Suzuki-Miyauraa polymerization reaction and response parameter do not limit especially the present invention in principle System, with the definition and response parameter of Suzuki-Miyauraa polymerization reaction well known to those skilled in the art, this field skill Art personnel can select and adjust according to the condition of production, quality requirement and product requirement, and the present invention is in preferably guaranteeing Between product and final product purity and yield, the temperature of the Suzuki-Miyauraa polymerization reaction is preferably 40~100 DEG C, More preferably 50~90 DEG C, more preferably 60~80 DEG C.The time of the Suzuki-Miyauraa polymerization reaction is preferably 0.5 ~30h, more preferably 5.5~25h, more preferably 10.5~20h.

Other raw materials or reagent of the Suzuki-Miyauraa polymerization reaction are not particularly limited in the present invention, with this The conventional auxiliary material or reagent of such reaction known to the technical staff of field, those skilled in the art can be according to production Situation, quality requirement and product requirement are selected and are adjusted.

The present invention is to further clarify and complete technical solution, is easy to understand, the above-mentioned specific reaction route of preparation step It is preferred that formula 1 is the reaction route of the preparation method of conjugated polymer provided by the invention referring to reaction equation 1.The preparation step With as described below.

1) under protective atmosphere and cryogenic conditions, intermediate X-is obtained after bromo compound X-1 is reacted with butyl lithium 2；

After iodo compound X-3 is reacted with butyl lithium, is reacted again with excessive silicon tetrachloride, obtain intermediate X -4；

Under protective atmosphere, by intermediate X -2 and -4 cyclization of intermediate X, intermediate II is obtained.

2) under protective atmosphere, will double halogen monomers of the structure as shown in formula (II), the second repetitive unit III (in it is double Halogen monomer or boric acid class monomer), palladium compound, organic phosphine compound, alkali compounds, water, organic solvent, phase transfer catalyst Mixing carries out Suzuki-Miyauraa polymerization reaction, obtains the conjugated polymer with formula (I) structure.

The present invention also provides a kind of organic electroluminescence devices, including electroluminescent material；The electroluminescent material Including preparation method described in conjugated polymer described in above-mentioned technical proposal any one or above-mentioned technical proposal any one The conjugated polymer of preparation.

The present invention is and corresponding preferred former to the structure and material of conjugated polymer in above-mentioned organic electroluminescence device Then, it can be corresponded to the material and structure of aforementioned conjugated polymer, and corresponding optimum principle, no longer be gone to live in the household of one's in-laws on getting married one by one herein It states.

In the present invention the conjugated polymer in organic electroluminescence device preferably as luminescent material, more preferably Electroluminescent material.

Under above-mentioned optimum condition, the structure of organic electroluminescence device are as follows:

Substrate；

The anode being set on the substrate；

The organic layer being set on the anode, number >=1 of organic layer, and at least one layer in organic layer are Organic Electricity Electroluminescent layer；The organic electro luminescent layer includes one or more fluorescent materials disclosed by the invention；

The cathode being set on the organic layer.

The present invention does not have particular/special requirement, preferably glass or plastics to the substrate, and the thickness of the substrate is preferably 0.3 ~0.7mm.

According to the present invention, the anode is the material for being easy to hole injection, preferably conductive metal or conductive metal oxide Object, more preferably indium tin oxide.

The organic layer can be 1 layer or multilayer, and at least one layer in organic layer is organic electro luminescent layer；It is described to have It include one or more fluorescent materials disclosed by the invention in organic electroluminescent layer.It is preferred in the present invention, the fluorescent material Organic electro luminescent layer is directly constituted as luminescent material.

The preferred metal of cathode, including but not limited to calcium, magnesium, barium, aluminium and silver, preferably aluminium.

In order to improve the performance and efficiency of device, the organic layer between the anode and organic electro luminescent layer is preferably also wrapped Include hole injection layer, hole transmission layer and electronic barrier layer；Organic layer between the organic electro luminescent layer and cathode is preferred It further include hole blocking layer and electron injection/transport layer.The present invention is to the hole injection layer, hole transmission layer, electronic blocking Layer, hole blocking layer and electron injection/transport layer material and thickness are not particularly limited, can be according to those skilled in the art Well known material and thickness are selected.

The present invention is not particularly limited the preparation method of the organic electroluminescence device, can in accordance with the following methods into Row:

Anode is formed over the substrate；

One or more layers organic layer is formed on the anode, wherein including one layer of organic electro luminescent layer；

Cathode is formed on the organic layer；

The organic electro luminescent layer includes one or more fluorescent materials of the present invention.

During preparing the organic electroluminescence device, anode is formed on the substrate first, the present invention is to the sun The generation type of pole is not particularly limited, according to method well known to those skilled in the art.The present invention does not have the substrate There are particular/special requirement, preferably glass or plastics, the thickness of the substrate is preferably 0.3~0.7mm.According to the present invention, the sun Extremely it is easy to the material of hole injection, preferably conductive metal or conductive metal oxide, more preferably indium tin oxide.

After obtaining anode, organic layer is formed on the anode.Organic electro luminescent layer in the organic layer includes one Kind or a variety of fluorescent materials of the present invention.The present invention is to the organic electro luminescent layer and luminescent layer organic layer below Generation type is not particularly limited, can be by solution spin coating, ink jet printing, hectographic printing or stereosopic printing in the anode shape At.After the organic luminous layer is formed, also hole blocking layer can be formed by way of vacuum evaporation or spin coating on the surface thereof With electron injection/transport layer.

After prepared by the organic layer, cathode is prepared on the surface thereof, and the present invention does not have special limit to cathode generation type System, method preferably well known to those skilled in the art, including but not limited to vacuum deposition.The cathode is preferably metal, packet Include but be not limited to calcium, magnesium, barium, aluminium and silver, preferably aluminium.

Above-mentioned steps of the present invention provide a kind of conjugated polymer and preparation method thereof, using (specially organic electroluminescence is sent out Optical device), it is a kind of conjugated polymer based on siliceous spiro fluorene acridine unit, the present invention passes through the introducing of acridine unit, can have Effect mentions high molecular HOMO energy level, reduces hole injection barrier, to show good hole injection and transmittability, has Conducive to the driving voltage for reducing device, thus has and lower open bright voltage and higher power efficiency；On the other hand, by altogether HOMO energy level and lumo energy separation can be achieved in the selection of poly- unit, be conducive to triplet excitons to singlet exciton anti-system Between pass through, to use triplet excitons, this is very favorable to the raising of device performance.

Above-mentioned steps of the present invention provide the conjugated polymer of a kind of siliceous spiro fluorene acridine unit, this quasi polymer solves The problem of HOMO energy level present in polysilico fluorene class Polymer Systems is low and leads to Gao Qiliang voltage, low device efficiency；Meanwhile containing Silicon spiral shell acridine contained by the conjugated polymer of silicon spiro fluorene acridine unit as electron donor unit, by be copolymerized suitable electronics by Body unit realizes the polymer with thermotropic delayed fluorescence living, has thermal activation delayed fluorescence effect, swashs using triplet state Son improves device maximum external quantum efficiency.And the conjugated polymer preparation side of siliceous spiro fluorene acridine unit provided by the invention Method is carried out by double halogen monomers of siliceous spiro fluorene acridine unit and double halogen monomers of second comonomer or double boron derivative monomers Suzuki-Miyaura is copolymerized to obtain required polymer.This contains the electroluminescent device of the polymer of silicon spiro fluorene unit, Using the quasi polymer as electroluminescence layer, ideal efficiency can be obtained, meets the requirement that solution processing prepares luminescent device.

The experimental results showed that based on the organic of siliceous spiro fluorene acridine unit conjugated polymer material preparation provided by the invention The bright voltage that opens of luminescent device is 4.1V, and maximum current efficiency is 5.37cd/A, and maximum external quantum efficiency is 2.7%, most light Degree is 3808cd/m²。

In order to further illustrate the present invention, with reference to embodiments to a kind of conjugated polymer provided by the invention and its system Preparation Method, organic electroluminescence device are described in detail, but it is to be understood that these embodiments are with the technology of the present invention side Implemented under premised on case, the detailed implementation method and specific operation process are given, only to further illustrate this hair Bright feature and advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following realities Apply example.

Embodiment 1

The synthesis of PNSiF-PFO:

Under the atmosphere of argon gas, intermediate X -3 (0.79g, 1.41mmol), THF (80mL) are added to sufficiently drying In round-bottomed flask, temperature is reduced to -100 DEG C, in 20min, slowly by n-BuLi (2.26 mL, 5.64mmol n-hexane Solution) it is added in reaction system, it reacts and continues 2h.Silicon tetrachloride (1.60 mL, 14.1mmol) is disposably added directly into In reaction system, low temperature 4h, spontaneous recovery to room temperature are maintained；Vacuum distillation, removes unreacted silicon tetrachloride and THF, obtains Intermediate X -4.

Under argon atmosphere, compound X-1 (0.8g, 1.41mmol) and 60mL ether are added to sufficiently dry round bottom In flask, temperature is reduced to -78 DEG C, and n-BuLi (1.12mL, 2.82mmol hexane solution) is added dropwise to reactant In system, reacts and continue 4h, spontaneous recovery to room temperature.- 78 DEG C are again decreased to, intermediate X -4 is dissolved in the tetrahydrofuran of 70mL In, it is added dropwise in system.Reaction system spontaneous recovery is to room temperature, aqueous ammonium chloride solution quenching reaction；Diethyl ether solution is added, Extraction 3 times, saturated common salt water washing 3 times, dry, solvent evaporated.Using petroleum ether as mobile phase, post separation, ethyl alcohol/second Monomer X-II (0.49g, yield 48%) is recrystallized to give in ether.

MALDI-TOF MS:m/z 741.2.Anal.Calcd.for C₄₁H₄₉Br₂NSi:C,66.21；H,6.64； N, 1.88；Found:C,66.85；H,6.32；N,1.80.

It weighs monomer X-II (0.1116g, 0.15mmol), monomer X-5 (0.0963g, 0.15mmol) and catalyst Pd (PPh₃)₄, (1.0mg) is added in reaction flask, is added phase transfer catalyst Aliq uat336 (20 mg)；In the atmosphere of argon gas Under, into reaction system, 5mL toluene and 2mL potassium carbonate (2M) aqueous solution is added；Temperature is increased to 95 DEG C, and reaction continues 90min；Toluene (1.5mL) solution of phenyl boric acid (15mg) is added into system using syringe, reacts and continues 4h；To reactant Bromobenzene (1.0mL) is added in system, reacts and continues 4h；Temperature is reduced to 80 DEG C.It is cooled to room temperature, methylene chloride 5mL is added, satisfy It is sufficiently washed 3 times with saline solution, dry, sedimentation in methyl alcohol, for 24 hours using acetone extraction, is deposited in methanol solution again, obtains To target compound PNSiF-PFO (78mg, yield: 56%).

It is 887000Da through its number-average molecular weight (Mn) of size exclusion chromatography, polydispersity coefficient (PDI) is 2.10. Anal.Calcd.for C₇₀H₉₁NSi:C,86.27；H,9.41；N,1.44；Found:C,86.40； H,9.49；N,1.54.

Embodiment 2

The synthesis of PNSiF-PSF:

It weighs monomer X-II (0.1116g, 0.15mmol), monomer X-6 (0.0987g, 0.15mmol) and catalyst Pd (PPh₃)₄, (1.0mg) is added in reaction flask, is added phase transfer catalyst Aliq uat336 (20 mg)；In the atmosphere of argon gas Under, into reaction system, 5mL toluene and 2mL potassium carbonate (2M) aqueous solution is added；Temperature is increased to 95 DEG C, and reaction continues 70min；Toluene (1.5mL) solution of phenyl boric acid (15mg) is added into system using syringe, reacts and continues 4h；To reaction Bromobenzene (1.0mL) is added in system, reacts and continues 4h；Temperature is reduced to 80 DEG C.It is cooled to room temperature, methylene chloride 5mL is added, Saturated salt solution sufficiently washs 3 times, dry, and sedimentation in methyl alcohol, for 24 hours using acetone extraction, is deposited in methanol solution again, Obtain target compound PNSiF-PSF (84mg, yield: 59%).

It is 457000Da through its number-average molecular weight (Mn) of size exclusion chromatography, polydispersity coefficient (PDI) is 2.05. Anal.Calcd.for C₆₉H₉₁NSi₂C,83.66；H,9.26；N,1.41；Found:C,83.86；H, 9.30；N,1.52.

Embodiment 3

The synthesis of PNSiF-TPN:

It weighs monomer X-II (0.1116g, 0.15mmol), monomer X-7 (0.0745g, 0.15mmol) and catalyst Pd (PPh₃)₄, (1.0mg) is added in reaction flask, is added phase transfer catalyst Aliq uat336 (20 mg)；In the atmosphere of argon gas Under, into reaction system, 5mL toluene and 2mL potassium carbonate (2M) aqueous solution is added；Temperature is increased to 95 DEG C, and reaction continues 90min；Toluene (1.5mL) solution of phenyl boric acid (15mg) is added into system using syringe, reacts and continues 4h；To reaction Bromobenzene (1.0mL) is added in system, reacts and continues 4h；Temperature is reduced to 80 DEG C.It is cooled to room temperature, methylene chloride 5mL is added, Saturated salt solution sufficiently washs 3 times, dry, and sedimentation in methyl alcohol, for 24 hours using acetone extraction, is deposited in methanol solution again, Obtain target compound PNSiF-TPN (68mg, yield: 60%).

It is 628000 Da through its number-average molecular weight (Mn) of size exclusion chromatography, polydispersity coefficient (PDI) is 2.40. Anal.Calcd.for C₅₉H₆₄N₂Si C,85.46；H,7.78；N,3.38；Found:C,85.56；H, 7.72；N,3.42.

Embodiment 4

The synthesis of PNSiF-Cz:

It weighs monomer X-II (0.1116g, 0.15mmol), monomer X-8 (0.0745g, 0.15mmol) and catalyst Pd (PPh₃)₄, (1.0mg) is added in reaction flask, is added phase transfer catalyst Aliq uat336 (20 mg)；In the atmosphere of argon gas Under, into reaction system, 5mL toluene and 2mL potassium carbonate (2M) aqueous solution is added；Temperature is increased to 95 DEG C, and reaction continues 90min；Toluene (1.5mL) solution of phenyl boric acid (15mg) is added into system using syringe, reacts and continues 4h；To reaction Bromobenzene (1.0mL) is added in system, reacts and continues 4h；Temperature is reduced to 80 DEG C.It is cooled to room temperature, methylene chloride 5mL is added, Saturated salt solution sufficiently washs 3 times, dry, and sedimentation in methyl alcohol, for 24 hours using acetone extraction, is deposited in methanol solution again, Obtain target compound PNSiF-Cz (72mg, yield: 63%).

It is 428000 Da through its number-average molecular weight (Mn) of size exclusion chromatography, polydispersity coefficient (PDI) is 2.26. Anal.Calcd.for C₅₉H₆₂N₂Si C,85.66；H,7.55；N,3.39；；Found:C,85.57；H, 7.62；N,3.42.

Embodiment 5

The synthesis of PNSiF-BPh:

Precise monomer X-II (0.1116g, 0.15mmol), monomer X-9 (0.0651g, 0.15mmol) and catalyst Pd(PPh₃)₄, (1.0mg) is added in reaction flask, and Aliq uant336 mono- is added and drips；Under the atmosphere of argon gas, syringe is used Into reaction flask, 5mL toluene and 2mL potassium carbonate (2M) aqueous solution is added；

Temperature is increased to 95 DEG C, reacts and continues 90min；The first of phenyl boric acid (15 mg) is added into system using syringe Benzene (1.5mL) solution reacts and continues 4h；Bromobenzene (1.0mL) is added into reaction system, reacts and continues 4h；Temperature is reduced to 80 DEG C, it weighs three water sodium diethyldithiocarbamate 1g of chelating agent and is dissolved in water, be added in system, reaction continues for 24 hours. It is cooled to room temperature, methylene chloride 5mL is added, saturated salt solution sufficiently washs 3 times, and dry, sedimentation in methyl alcohol, is done using acetone Dissolution extracting for 24 hours, is deposited in methanol solution again, obtains target compound PNSiF-BPh (68mg, yield: 60%).

It is 667000 Da through its number-average molecular weight (Mn) of size exclusion chromatography, polydispersity coefficient (PDI) is 2.30. Anal.Calcd.for C₅₄H₅₉NOSi C,84.66；H,7.76；N,1.83；；Found:C,84.76； H,7.80；N,1.85.

Embodiment 6

The synthesis of PNSiF-SSPh:

Precise monomer X-II (0.1116g, 0.15mmol), monomer X-9 (0.0948g, 0.15mmol) and catalyst Pd(PPh₃)₄, (1.0mg) is added in reaction flask, and Aliq uant336 mono- is added and drips；Under the atmosphere of argon gas, syringe is used Into reaction flask, 5mL toluene and 2mL potassium carbonate (2M) aqueous solution is added；

Temperature is increased to 95 DEG C, reacts and continues 80min；The first of phenyl boric acid (15 mg) is added into system using syringe Benzene (1.5mL) solution reacts and continues 4h；Bromobenzene (1.0mL) is added into reaction system, reacts and continues 4h；Temperature is reduced to 80 DEG C, it weighs three water sodium diethyldithiocarbamate 1g of chelating agent and is dissolved in water, be added in system, reaction continues for 24 hours. It is cooled to room temperature, methylene chloride 5mL is added, saturated salt solution sufficiently washs 3 times, and dry, sedimentation in methyl alcohol, is done using acetone Dissolution extracting for 24 hours, is deposited in methanol solution again, obtains target compound PNSiF-SSPh (74mg, yield: 65%).

It is 767000 Da through its number-average molecular weight (Mn) of size exclusion chromatography, polydispersity coefficient (PDI) is 2.15. Anal.Calcd.for C₆₆H₆₅NO₂SSi C,82.20；H,6.79；N,1.45；Found:C,82.28； H,6.82；N,1.56.

Embodiment 7

The synthesis of PNSiF-SO-CO:

Precise monomer X-II (0.1116g, 0.15mmol), monomer X-II (0.0744g, 0.15mmol)) and catalysis Agent Pd (PPh₃)₄, (1.0mg) is added in reaction flask, is added phase transfer catalyst Aliq uat336 (20mg)；In argon gas Under atmosphere, into reaction system, 5mL toluene and 2mL potassium carbonate (2 M) aqueous solution is added；Temperature is increased to 95 DEG C, and reaction continues 90min；Toluene (1.5mL) solution of phenyl boric acid (15mg) is added into system using syringe, reacts and continues 4h；To reactant Bromobenzene (1.0mL) is added in system, reacts and continues 4h；Temperature is reduced to 80 DEG C.It is cooled to room temperature, methylene chloride 5mL is added, satisfy It is sufficiently washed 3 times with saline solution, dry, sedimentation in methyl alcohol, for 24 hours using acetone extraction, is deposited in methanol solution again, obtains To target compound PNSiF-SO-CO (89mg, yield: 72%).

It is 662000 Da through its number-average molecular weight (Mn) of size exclusion chromatography, polydispersity coefficient (PDI) is 2.28. Anal.Calcd.for C₅₄H₅₇NO₃SSi C,78.31；H,6.94；N,1.69；Found:C,78.37； H,6.87；N,1.62.

Embodiment 8

To the embodiment of the present invention preparation fluorescent material PNSiF-PFO, PNSiF-Cz, PNSiF-BPh, PNSiF-SSPh, PNSiF-SO-CO carry out performance detection, select alkyl polysilico fluorene (PSF) reported in the literature as reference material (J.Am Chem, Soc.2005,127,7662-7663), structural formula is as follows:

Referring to table 1, table 1 is the conjugated polymer PNSiF-PFO, PNSiF-Cz, PNSiF- of preparation of the embodiment of the present invention BPh, PNSiF-SSPh, PNSiF-SO-CO, alkyl polysilico fluorene (PSF) photophysical property.

Table 1

As shown in table 1, siliceous spiro fluorene unit conjugated polymer provided by the invention, compared to alkyl silicon fluorene PSF, HOMO energy level improves 0.15eV, reduces hole injection barrier, this is very favorable to the raising of device performance.Another party Face, by with the siliceous spiro fluorene unit conjugated polymer (PNSiF-SO-CO) that suitable copolymerization units are copolymerized show compared with Small singlet-triplet is poor (0.05 eV), thus shows significant thermal activation delayed fluorescence effect, postpones glimmering The service life of light component is 2.28 μ s, which is applied to may be implemented in organic electroluminescence device to triplet excitons It utilizes, thus there is high luminous efficiency.

Performance detection is carried out to the fluorescent material of preparation of the embodiment of the present invention.

It is the cyclic curve of fluorescent material PNSiF-SSPh prepared by the embodiment of the present invention 6 referring to Fig. 1, Fig. 1.

Referring to fig. 2, Fig. 2 is the cyclic curve of fluorescent material PNSiF-BPh prepared by the embodiment of the present invention 5.

It is the cyclic curve of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7 referring to Fig. 3, Fig. 3.

Referring to fig. 4, Fig. 4 is the fluorescence spectrum (room temperature) of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7.

It is the phosphorescence spectrum (77K) of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7 referring to Fig. 5, Fig. 5.

Decay referring to the fluorescence lifetime that Fig. 6, Fig. 6 are fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7 bent Line.

Embodiment 9

Device example 1: spin coating poly- (3,4- Ethylenedioxy Thiophene)-is poly- on the tin indium oxide for be carried on substrate of glass (styrene sulfonic acid) (PEDOT/PSS), 120 DEG C of annealing 30min, then high molecular toluene (6mg/ is invented in 1500rpm spin coating ML) solution 1min, and in 80 DEG C of annealing 30min, the luminescent layer of 40nm is formed on PEDOT/PSS, then 4 × 10^-4Pa's It is sequentially depositing TPBI and LiF/Al cathode under vacuum degree, obtains organic electroluminescence device, wherein 3,3'- [5'- [3- (3- pyrroles Piperidinyl) phenyl] [1,1':3', 1 "-terphenyl] -3,3 "-diyl] two pyridines (Tm) electron transfer layer.Specifically device architecture is PEDOT:PSS(40 nm)/EML(40nm)/Tm/(50nm)/LiF(1nm)/Al(100nm)。

Using PNSi-SO-CO as embodiment 1, resulting electroluminescent device is tested.The alkyl of bibliography report Polysilico fluorene (PSF) device performance.

It is to implement that table 2, which is respectively with alkyl polysilico fluorene (PSF) reported in the literature and above-mentioned fluorescent material PNSi-SO-CO, Example carries out test comparison to gained electroluminescent device.

Table 2

As can be seen from the above-described embodiment, the bright voltage that opens compared to PSF is 8.6V, and the bright voltage of PNSi-SO-CO is aobvious Work is reduced to 4.1V, illustrates that the promotion of HOMO energy level effectively reduces hole injection barrier；Meanwhile maximum external quantum efficiency from 0.5% is increased to 2.70%, promotes nearly 5 times, this aspect is caused by reducing due to its hole injection barrier；On the other hand be by In it with thermotropic delayed fluorescence characteristic living, so as to utilize triplet, therefore device efficiency correlation can be improved.It can See that the conjugated polymer provided by the invention based on siliceous spiro fluorene acridine unit solves previous polysilico fluorene class high molecular material and deposits Open that bright voltage is higher, the relatively low problem of device efficiency.

It is the V-I-B curve of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7 referring to Fig. 7, Fig. 7.

Referring to Fig. 8, Fig. 8 is that current efficiency-electric current of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7 is close It writes music line.

The EQE- current density for being fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7 referring to Fig. 9, Fig. 9 is bent Line.

Referring to Figure 10, Figure 10 is that the electroluminescent light of fluorescent material PNSiF-SO-CO prepared by the embodiment of the present invention 7 is set a song to music Line.

Above to a kind of conjugated polymer of siliceous spiro fluorene acridine unit provided by the invention and preparation method thereof, Organic Electricity Electroluminescence device is described in detail, and specific case used herein carries out the principle of the present invention and embodiment It illustrates, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas, including best mode, and And but also any person skilled in the art can practice the present invention, including any device or system of manufacture and use, and Implement the method for any combination.It should be pointed out that for those skilled in the art, not departing from original of the invention , can be with several improvements and modifications are made to the present invention under the premise of reason, these improvement and modification also fall into right of the present invention and want In the protection scope asked.The range of the invention patent protection is defined by the claims, and may include those skilled in the art It is conceivable that other embodiments.If there is these other embodiments the structure for being not different from claim character express to want Element, or if they include the equivalent structural elements with the character express of claim without essence difference, these other Embodiment should also be included in the scope of the claims.

Claims (10)

1. a kind of conjugated polymer, which is characterized in that the conjugated polymer has formula (I) structure,

Wherein, it is integer between 2~9999 that x, which is 0.001~0.999, n,；

R₁Selected from substituted or non-substituted C₁~C₂₀Alkyl, substituted or non-substituted C₃~C₂₀Naphthenic base, substituted or non-substituted C₆~C₂₀Aromatic rings and substituted or non-substituted C₂~C₂₀One of aromatic heterocycle or a variety of；

R₂、R₃、R₄And R₅It is independently selected from substituted or non-substituted C₁~C₂₀Alkyl；

Ar is selected from substituted or non-substituted C₆~C₂₀Aromatic rings and/or substituted or non-substituted C₂~C₂₀Aromatic heterocycle；

Ar is further selected between the aromatic rings and the aromatic rings, between the aromatic heterocycle and aromatic heterocycle and the fragrance Between ring and aromatic heterocycle, pass through the combination formed after Z key company；

The Z include singly-bound ,-C-C- ,-C=C- ,-C=N- ,-C=P- ,-C ≡ C-, One of or it is a variety of.

2. conjugated polymer according to claim 1, which is characterized in that in the conjugated polymer, R₁、R₂、R₃、R₄And R₅ Respectively at each occurrence, it can be the same or different；

The alkyl includes straight chained alkyl and/or branched alkyl；

The substitution of the alkyl includes that one or more non-conterminous carbon atoms can be by one or more in O, S, Si and-CO-O- Replace, and/or, one or more hydrogen atoms can be replaced by F；

The Ar is copolymerization units；

The hetero atom of aromatic heterocycle representated by the Ar is independently selected from Si, Ge, N, P, O, S or Se, and carbon atom and Heteroatomic sum >=5.

3. conjugated polymer according to claim 1, which is characterized in that the Ar is shown as intrinsic as copolymerization units When characteristic, it is selected from any one shown in formula (1)~formula (10):

Wherein, B₁And B₂It is independently selected from substituted or non-substituted C₁~C₂₂Alkyl.

4. conjugated polymer according to claim 1, which is characterized in that the Ar as copolymerization units there is hole to pass When defeated characteristic, it is selected from any one shown in formula (A)~formula (K):

Wherein, D₁、D₂And D₃It is independently selected from substituted or non-substituted C₁~C₂₂Alkyl.

5. conjugated polymer according to claim 1, which is characterized in that the Ar as copolymerization units there is electronics to pass When defeated characteristic, it is selected from any one shown in formula (a)~formula (k):

Wherein, E₁And E₂It is independently selected from substituted or non-substituted C₁~C₂₂Alkyl.

6. according to conjugated polymer described in claim 3~5 any one, which is characterized in that in the Ar, when containing B₁With B₂When, B₁And B₂Respectively at each occurrence, it can be the same or different；

In the Ar, when containing D₁、D₂And D₃When, D₁、D₂And D₃Respectively at each occurrence, it can be the same or different；

In the Ar, when containing E₁And E₂When, E₁And E₂Respectively at each occurrence, it can be the same or different；

The C₁~C₂₂Alkyl include straight chained alkyl and/or branched alkyl；

The C₁~C₂₂The substitution of alkyl include that one or more non-conterminous carbon atoms can be by O, S, Si and-CO-O- one Kind or a variety of substitutions, and/or, one or more hydrogen atoms can be replaced by F.

7. conjugated polymer according to claim 1, which is characterized in that the conjugated polymer has formula (I-1)~(I- Any one of 22) structure shown in:

8. a kind of preparation method of the conjugated polymer as described in 1~7 any one of the claims, which is characterized in that packet Include following steps:

1) under protective atmosphere, after bromo compound X-1 is carried out the first butyl lithium reaction, intermediate X -2 is obtained；

Under protective atmosphere, reacted after iodo compound X-3 the second butyl lithium reaction of progress, then with silicon tetrachloride Afterwards, intermediate X -4 is obtained；

2) it under protective atmosphere, after the intermediate X -2 and intermediate X -4 that above-mentioned steps are obtained carry out ring closure reaction, obtains Intermediate II；

3) under protective atmosphere, intermediate II that above-mentioned steps are obtained, monomer III, palladium compound, organic phosphine compound, Alkali compounds, water, organic solvent and phase transfer catalyst mixing carry out Suzuki-Miyauraa polymerization reaction, to formula (I) conjugated polymer of structure；

Wherein, M is selected from one of trifluoromethane sulfonic acid base ,-Cl ,-Br ,-I, boronate, boron ester group and boryl or a variety of.

9. preparation method according to claim 8, which is characterized in that the temperature of the first butyl lithium reaction is -78~0 ℃；

The time of the first butyl lithium reaction is 0.5~4h；

The temperature of the second butyl lithium reaction is -120~-78 DEG C；

The time of the second butyl lithium reaction is 0.5~4h；

The temperature of the reaction is -120~-78 DEG C；

The time of the reaction is 0.5~4h；

The temperature of the ring closure reaction is -78~50 DEG C；

The time of the ring closure reaction is 0.5~12h；

The temperature of the Suzuki-Miyauraa polymerization reaction is 40~100 DEG C；

The time of the Suzuki-Miyauraa polymerization reaction is 0.5~30h；

The palladium compound includes one of palladium acetate, tetrakis triphenylphosphine palladium and tris(dibenzylideneacetone) dipalladium or more Kind；

The organic phosphine compound includes triphenylphosphine, tricyclohexyl phosphine, tri-tert-butylphosphine, 2- dicyclohexyl phosphorus -2,4,6- three One of isopropyl biphenyl, three (2- methoxyphenyl) phosphines and 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl are a variety of；

The alkali compounds includes one of sodium carbonate, potassium carbonate, cesium carbonate and potassium phosphate or a variety of；

The phase transfer catalyst includes tri-n-octyl methyl ammonium chloride；

The organic solvent includes one of tetrahydrofuran, toluene and dimethylbenzene or a variety of.

10. a kind of organic electroluminescence device, which is characterized in that including luminescent material；The luminescent material includes claim 1 The conjugated polymers of the preparation of preparation method described in conjugated polymer described in~7 any one or claim 8~9 any one Object.