CN106928435A - A kind of co-polymer luminescent material containing fluoro side base and preparation method and application - Google Patents

A kind of co-polymer luminescent material containing fluoro side base and preparation method and application Download PDF

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CN106928435A
CN106928435A CN201710176431.7A CN201710176431A CN106928435A CN 106928435 A CN106928435 A CN 106928435A CN 201710176431 A CN201710176431 A CN 201710176431A CN 106928435 A CN106928435 A CN 106928435A
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side base
luminescent material
structures
material containing
containing fluoro
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CN106928435B (en
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应磊
王小君
郭婷
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses a kind of co-polymer luminescent material containing fluoro side base and preparation method and application.This contains fluoro side base co-polymer luminescent material, and due to there is larger conjugate length, preferable flatness, good is interface characteristics, so there is fluorescence quantum yield higher, is conducive to improving the device efficiency of material；Meanwhile, the synthetic method that this contains fluoro side base co-polymer luminescent material is simple, and with preferable dissolubility, film forming and film morphology stability, the luminescent layer based on the material is when organic luminescent device is prepared without annealing so that preparation technology is simpler.

Description

A kind of co-polymer luminescent material containing fluoro side base and preparation method and application
Technical field
The invention belongs to organic photoelectrical material technical field, and in particular to a kind of co-polymer luminescent material containing fluoro side base And preparation method and application.
Background technology
Organic Light Emitting Diode (O/PLED) arises at the historic moment as the flat panel display of a new generation, compared to traditional the moon Extreme ray diode, with light weight, High Efficiency Luminescence, energy-conserving and environment-protective, Flexible Displays and the low advantage of processing cost, answers with extensive Use prospect.Although organic/high score light emitting diode is all achieved in terms of organic FPD and white-light illuminating and breakthrough entered Exhibition, but the degree of its industrialization well below people's it is anticipated that still there is many key issues urgently to solve in the area research Certainly.The mainly optimization of luminescent material, colorization technology, paper membrane technology, high-resolution Display Technique, active matrix driving technology, encapsulation It is unclear that the aspects such as technology still suffer from great underlying issue so that it extensively should as restriction for overall performance and manufacturing cost etc. " bottleneck " problem.With the depth that countries in the world academic institution and major company are studied polymer electroluminescence material and device Enter, it is believed that these problems can gradually be solved, application of the organic/polymer LED in terms of display and illumination also can There are wide market prospects.Wherein, the material for developing new and effective stabilization turns into key.
The polymer that the present invention relates to, because having preferable solubility property, it is adaptable to which solution is processed, and preferably Fluorescence quantum yield, its luminescent device not only efficient stable, and be more blue saturation blue light can meet full-color display It is required that.So having huge development potentiality and prospect in organic electronic display field.
The content of the invention
It is an object of the invention to be directed to current polymer LED (PLED) problems faced, there is provided a kind of fluorine-containing For the co-polymer luminescent material of side unit.The co-polymer luminescent material has preferable dissolubility, and good interface performance is fitted Together in solution processing and inkjet printing, with good development prospect.
Take side unit containing fluoro as the excited state molecule of copolymer in the co-polymer luminescent material, by with narrow band gap Dipole-dipole effect between ground state molecule, makes excited state molecule that radiation transistion is directly passed into ground state molecule, makes ground state point Son is excited and lighted, and realizes light emitting polymer carrier transport balance in itself, improves the luminous efficiency of device, has polymer There is fluorescence quantum yield higher.
The object of the invention also resides in a kind of offer preparation method of the co-polymer luminescent material containing fluoro side base.
The object of the invention also resides in a kind of offer co-polymer luminescent material containing fluoro side base in light emitting diode Application in luminescent layer.
The present invention is achieved through the following technical solutions.
A kind of co-polymer luminescent material containing fluoro side base, with following chemical structural formula：
In formula, x, y is molar fraction, 0 ＜ x≤0.4,0 ＜ y≤0.4, x+y≤0.5；N is the degree of polymerization, 20<n<500； Ar1 and Ar2 are functional groups；R is H, the straight chain or branched alkyl of carbon number 1~20, or is carbon number 1~20 Alkoxy.
Further, functional groups Ar1 is any one in following structural formula：
Wherein, R1It is H, the straight chain or branched alkyl of carbon number 1~20, or is the alkoxy of carbon number 1~20.
Further, functional groups Ar2 is any one in following structural formula：
Wherein, R2It is fluorine-containing or fluorobenzene the straight or branched alkyl of carbon number 1~20.
The preparation method of described a kind of conjugated polymer luminescent material containing fluoro side base, mainly including fluorine-containing side base list Unit preparation, and the conjugated polymer of side base containing fluoro synthesis.
A kind of preparation method of described co-polymer luminescent material containing fluoro side base, comprises the following steps：
(1) by the bromide of Ar1 structures, the bromide of Ar2 structures, the bromo- S of 3,7- bis-, S- dibenzothiophene dioxides, three Cyclohexyl phosphine and palladium are added in there-necked flask, substitute gas；
(2) under argon gas protection, add benzotrifluoride and organic alkali solution to be dissolved, be heated to reflux；Sequentially add Phenyl boric acid and bromobenzene carry out end capping reaction；
(3) after end capping reaction terminates, room temperature is cooled to, reaction solution is poured into methyl alcohol and is precipitated, filtering, then with toluene to wash De- agent alumina column chromatography；
(4) after chromatography terminates, the washing lotion of concentration is poured into methyl alcohol and is precipitated, filtering is dried, and obtains described side containing fluoro The co-polymer luminescent material of base.
Further, in step (1), the bromide of the Ar1 structures, the bromide of Ar2 structures and the bromo- S of 3,7- bis-, The mol ratio of S- dibenzothiophene dioxides is 0.5:0.45~0.1:0.05~0.4.
Further, in step (1), the mol ratio of the bromide of the Ar1 structures and three cyclohexyl phosphines is 0.5： 0.02。
Further, in step (1), the bromide of the Ar1 structures and the mol ratio of palladium are 0.5：0.02.
Further, in step (2), the organic base is tetraethyl ammonium hydroxide, and the concentration of organic alkali solution is 1.5M, Organic alkali solution addition is 1 with the volume ratio of benzotrifluoride addition:5.
Further, in step (2), the temperature being heated to reflux is 80~100 DEG C, and the time is 24~48h.
Further, in step (2), the temperature that adding phenyl boric acid and bromobenzene carries out end capping reaction is 80~100 DEG C, when Between be 6~12h.
Further, in step (2), the addition of the phenyl boric acid is 0.1 with the mol ratio of the bromide of Ar1 structures： 0.5。
Further, in step (2), the bromobenzene is 0.2 with the mol ratio of the bromide of Ar1 structures:0.5.
Further, the bromide of the Ar1 structures is substituted using the boron ester of Ar1 structures；The bromide of the Ar2 structures Substituted using the boron ester of Ar2 structures.
A kind of described co-polymer luminescent material containing fluoro side base is applied to the luminescent layer of light emitting diode, contains described Fluoro side base co-polymer luminescent material organic solvent dissolves, then by spin coating, inkjet printing or printing process film forming, obtains institute The luminescent layer of light emitting diode is stated, the light emitting diode based on the luminescent layer is applied in the preparation of organic electro-optic device, including Flat-panel monitor.
Further, the organic solvent includes dimethylbenzene, chlorobenzene, chloroform etc..
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) co-polymer luminescent material of side base containing fluoro of the invention, due to having larger conjugate length, preferable plane Property, good is interface characteristics, so there is fluorescence quantum yield higher, is conducive to improving the device efficiency of material；
(2) synthetic method of the co-polymer luminescent material of side base containing fluoro of the invention is simple, with preferable dissolubility, into Film and film morphology stability, the luminescent layer based on the material is when organic luminescent device is prepared without annealing so that Preparation technology is simpler.
Brief description of the drawings
Fig. 1 is compound M1's1H NMR spectras；
Fig. 2 is compound M1's13C NMR spectras；
Fig. 3 is compound M1's18F NMR spectras；
Fig. 4 is polymer P FSO1, PFSO2 in Current density-voltage-brightness curve figure；
Fig. 5 is the luminous efficiency-current density spectrogram of the electroluminescent device based on polymer P FSO1, PFSO2；
Fig. 6 is the electroluminescent light spectrogram of polymer P FSO1, PFSO2 under filminess；
Specific implementation method
Content for a better understanding of the present invention, below by specific example, the invention will be further described, but Implementation of the invention and protection domain not limited to this.
Embodiment 1
The preparation of PFSO1：
(1) under nitrogen atmosphere, by 2,7- bis- bromo- (9,9- hexichol hydroxyl) fluorenes (2g, 3.94mol), C8H8F9I (3.96g, 9.84mmol), K2CO3(2.18g, 15.74mmol) and 100ml N ' N- dimethylacetylamides are added in 250ml two-mouth bottles, plus After heat reacts 12h to 80 DEG C, recover room temperature, be extracted with ethyl acetate, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate is dried. After vacuum distillation, the purification of crude product purified by silica gel post, for dichloromethane and petroleum ether mixed solvent, (volume ratio is 1 to leacheate:5), Ethyl alcohol recrystallization, finally obtains white solid for compound M1, yield 80%.1H NMR、13CNMR、18F NMR spectras are respectively such as Shown in Fig. 1, Fig. 2 and Fig. 3, analysis knows to be target product.Chemical equation is as follows：
(2) under argon atmosphere, by M1 (49.32mg, 46.69 μm of ol), M2 (27.94mg, 46.69 μm of ol) M3 (76.82mg, 140.06 μm of ol) and M4 (150.00mg, 233.44 μm of ol) are added in 50ml two-mouth bottles, add 8ml fluoroforms Benzene is completely dissolved, and substitutes gas three times, then rapidly joins palladium (2.10mg, 9.34 μm of ol) and tricyclohexyl phosphine (5.24mg, 18.68 μm of ol), substitute gas three times, are subsequently adding 2ml tetraethyl ammonium hydroxides, are warming up to 80 DEG C, and reaction 24 is small When.It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then is blocked with 0.3ml bromobenzenes, continues to react 12 hours； Product is added dropwise and is precipitated out in methyl alcohol, stirred, filtering, then crude product is dissolved in the toluene of 20mL, with 200~300 mesh Silica gel is fixing phase, is that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, is separated out in methyl alcohol again Come, stirring, filtering obtains polymer solids after vacuum drying.Finally respectively extract 24 with methyl alcohol, acetone, tetrahydrofuran successively again Hour, remove small molecule.By precipitating in the tetrahydrofuran solution instillation methyl alcohol after concentration, what is obtained after vacuum drying is cotton-shaped solid Body.Yield 82%.1H NMR、13CNMR、18F NMR analyses are target product.Chemical equation is as follows：
Embodiment 2
The preparation of PFSO2：
Under argon atmosphere, by M1 (49.32mg, 46.69 μm of ol), M5 (17.46mg, 46.69 μm of ol) M3 (76.82mg, 140.06 μm of ol) and M4 (150.00mg, 233.44 μm of ol) add 50ml two-mouth bottles in, adding 8ml benzotrifluorides has been carried out CL, substitutes gas three times, then rapidly joins palladium (2.10mg, 9.34 μm of ol) and tricyclohexyl phosphine (5.24mg, 18.68 μ Mol), substitute gas three times, be subsequently adding 2ml tetraethyl ammonium hydroxides, be warming up to 80 DEG C, react 24 hours.It is subsequently adding 30mg Phenyl boric acid is blocked, and after 12 hours, then is blocked with 0.3ml bromobenzenes, continues to react 12 hours；Product is added dropwise in methyl alcohol In be precipitated out, stir, then be dissolved in crude product in the toluene of 30mL by filtering, is fixing phase with 200~300 mesh silica gel, uses first Benzene carries out column chromatography for eluant, eluent, then after solvent under reduced pressure is concentrated, separates out to come in methyl alcohol again, stirring, filtering, vacuum Polymer solids are obtained after drying.Finally respectively extracted 24 hours with methyl alcohol, acetone, tetrahydrofuran successively again, remove small molecule.Will Tetrahydrofuran solution after concentration instills precipitating, the fluffy solid obtained after vacuum drying in methyl alcohol.Yield 75%.1H NMR、13CNMR、18F NMR analyses are target product.Chemical equation is as follows：
Embodiment 3
The preparation of PFSO3：
(1) under nitrogen atmosphere, by 2,7- dibromos fluorenes (2.00g, 6.17mmol), C8H8F9I (6.2g, 15.43mmol), hydrogen Sodium oxide molybdena (24g, 1.04mol), TBAB (200mg, 0.62mmol) and 100ml toluene are added to 250ml two-mouth bottles In, after being heated to 180 DEG C of reaction 12h, recover room temperature, it is extracted with ethyl acetate, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate Dry.After vacuum distillation, crude product purified by silica gel post purification, leacheate is that (volume ratio is for dichloromethane and petroleum ether mixed solvent 1:5), recrystallizing methanol, finally obtains white solid for compound M6, yield 67%.1H NMR、13CNMR、18F NMR are analyzed Target product.Chemical equation is as follows：
(2) under argon atmosphere, by M6 (40.73mg, 46.69 μm of ol), M5 (17.46mg, 46.69 μm of ol) M3 (76.82mg, 140.06 μm of ol) and M4 (150.00mg, 233.44 μm of ol) are added in 50ml two-mouth bottles, add 8ml fluoroforms Benzene is completely dissolved, and substitutes gas three times, then rapidly joins palladium (2.10mg, 9.34 μm of ol) and tricyclohexyl phosphine (5.24mg, 18.68 μm of ol), substitute gas three times, are subsequently adding 2ml tetraethyl ammonium hydroxides, are warming up to 80 DEG C, and reaction 24 is small When.It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then is blocked with 0.3ml bromobenzenes, continues to react 12 hours； Product is added dropwise and is precipitated out in methyl alcohol, stirred, filtering, then crude product is dissolved in the toluene of 20mL, with 200~300 mesh Silica gel is fixing phase, is that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, is separated out in methyl alcohol again Come, stirring, filtering obtains polymer solids after vacuum drying.Finally respectively extract 24 with methyl alcohol, acetone, tetrahydrofuran successively again Hour, remove small molecule.By precipitating in the tetrahydrofuran solution instillation methyl alcohol after concentration, what is obtained after vacuum drying is cotton-shaped solid Body.Yield 75%.1H NMR、13CNMR、18F NMR analyses are target product.Chemical equation is as follows：
Embodiment 4
The preparation of PFSO4：
(1) in 250mL there-necked flasks, fluorenes (1g, 6.02mmol) and anhydrous tetrahydro furan 40mL are added, is cooled to -78 DEG C Afterwards, n-BuLi (1.54g, 24.06mmol) is added dropwise, reacts 30 minutes；Recover to room temperature, react 1 hour, be again cooled to- 78 DEG C, then C will be dissolved with10H4F17The anhydrous tetrahydro furan of I (17.27g, 30.08mol) is added drop-wise in reaction solution, stirs 10 points Zhong Hou, reacts 4 hours under normal temperature.By reaction solution hang it is dry obtain crude product, be extracted with ethyl acetate, organic layer is complete with saline solution After washing, plus anhydrous magnesium sulfate is dried, and (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, obtains white solid A, yield 43%.1H NMR、13CNMR、18F NMR analyses are target product.Chemical equation is as follows：
(2) in 250mL there-necked flasks, compound A (2g, 1.89mmol), iron powder (11mg, 0.196mmol) and three are added Chloromethanes 50mL, ice-water bath cooling；Bromine (634.14m g, 3.97mol)/chloroform mixed solution 5mL is added dropwise, bottle during dropwise addition Interior temperature is no more than 5 DEG C.Reaction is finished, filtering, Gossypol recrystallized from chloroform, obtains white solid M7, yield 83%.1H NMR、13CNMR、18F NMR analyses are target product.Chemical equation is as follows：
(3) under argon atmosphere, by M7 (100.00mg, 82.22 μm of ol), M5 (20.50mg, 54.81 μm of ol) M8 (130.89mg, 137.04 μm of ol) are added in 50ml two-mouth bottles, are added 8ml benzotrifluorides and are completely dissolved, and substitute gas three It is secondary, then palladium (1.23mg, 5.48 μm of ol) and tricyclohexyl phosphine (3.07mg, 10.96 μm of ol) are rapidly joined, substitute gas three It is secondary, 2ml tetraethyl ammonium hydroxides are subsequently adding, 80 DEG C are warming up to, react 24 hours.30mg phenyl boric acids are subsequently adding to be sealed End, after 12 hours, then is blocked with 0.3ml bromobenzenes, continues to react 12 hours；Product is added dropwise and is precipitated out in methyl alcohol, Stirring, filtering, then crude product is dissolved in the toluene of 30mL, it is fixing phase with 200~300 mesh silica gel, it is eluant, eluent with toluene Carry out column chromatography, then after solvent under reduced pressure is concentrated, separate out to come in methyl alcohol again, stirring, filtering is obtained after vacuum drying Polymer solids.Finally respectively extracted 24 hours with methyl alcohol, acetone, tetrahydrofuran successively again, remove small molecule.After by concentration four Hydrogen tetrahydrofuran solution instills precipitating, the fluffy solid obtained after vacuum drying in methyl alcohol.Yield 60%.1H NMR、13CNMR、18F NMR analyses are target product.Chemical equation is as follows：
Embodiment 5
The preparation of PFSO5：
Under argon atmosphere, by M9 (72.78mg, 46.69 μm of ol), M2 (27.94mg, 46.69 μm of ol), M3 (76.82mg, 140.06 μm of ol) and M4 (150.00mg, 233.44 μm of ol) are added in 50ml two-mouth bottles, add 8ml fluoroforms Benzene is completely dissolved, and substitutes gas three times, then rapidly joins palladium (1.23mg, 5.48 μm of ol) and tricyclohexyl phosphine (3.07mg, 10.96 μm of ol), substitute gas three times, are subsequently adding 2ml tetraethyl ammonium hydroxides, are warming up to 80 DEG C, and reaction 24 is small When.It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then is blocked with 0.3ml bromobenzenes, continues to react 12 hours； Product is added dropwise and is precipitated out in methyl alcohol, stirred, filtering, then crude product is dissolved in the toluene of 30mL, with 200~300 mesh Silica gel is fixing phase, is that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, is separated out in methyl alcohol again Come, stirring, filtering obtains polymer solids after vacuum drying.Finally respectively extract 24 with methyl alcohol, acetone, tetrahydrofuran successively again Hour, remove small molecule.By precipitating in the tetrahydrofuran solution instillation methyl alcohol after concentration, what is obtained after vacuum drying is cotton-shaped solid Body.Yield 74%.1H NMR、13CNMR、18F NMR analyses are target product.Chemical equation is as follows：
Embodiment 6
The preparation of electroluminescent device：
On tin indium oxide (ITO) glass of well in advance, its square resistance is 10-20 Ω/, and acetone is first used successively, Detergent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes.Spin coating is mixed on ITO polystyrene sulphur Polyethoxy thiophene (the mass ratio PEDOT of acid:PSS=1:1) film, thickness is 150nm, PEDOT:PSS films are in vacuum drying oven Dried 8 hours at 80 DEG C.The xylene solution (1wt%) of the copolymer containing fluoro side base is then spin-coated on PEDOT:PSS films Surface, thickness is 80nm, used as luminescent layer；It is last to be deposited with a thin layer CsF (1.5nm) and 120nm thickness successively on luminescent layer Metal Al layer.
Fig. 4 is the Current density-voltage-brightness curve figure of polymer P FSO1, PFSO2 for preparing, as shown in Figure 4, The brightness of PFSO2 and current density are higher with respect to PFSO1.
Fig. 5 is the spectrogram of the luminous efficiency-current density of the electroluminescent device based on polymer P FSO1, PFSO2, by Fig. 5 understands that PFSO1 reaches 1.83mA/cm in current density2When, luminous efficiency reaches maximum 1.9cd/A, and PFSO2 is in electric current Density reaches 0.29mA/cm2When, luminous efficiency reaches maximum 2.8cd/A, PFSO2 has preferable efficiency with respect to PFSO1.
Fig. 6 is electroluminescent light spectrograms of polymer P FSO1, the PFSO2 for preparing under filminess, the maximum of PFSO1 Emission peak is 425nm, and the maximum emission peak of PFSO2 is 447nm.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment Limitation, other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification all should It is equivalent substitute mode, is included within protection scope of the present invention.

Claims (10)

1. a kind of co-polymer luminescent material containing fluoro side base, it is characterised in that with following chemical structural formula：
In formula, x, y is molar fraction, 0 ＜ x≤0.4,0 ＜ y≤0.4, x+y≤0.5；N is the degree of polymerization, 20<n<500；Ar1 Functional groups are with Ar2；R is H, the straight or branched alkyl of carbon number 1~20, or is the alkane of carbon number 1~20 Epoxide.
2. a kind of co-polymer luminescent material containing fluoro side base according to claim 1, it is characterised in that functional groups Ar1 is any one in following structural formula：
Wherein, R1It is H, the straight or branched alkyl of carbon number 1~20, or is the alkoxy of carbon number 1~20.
3. a kind of co-polymer luminescent material containing fluoro side base according to claim 1, it is characterised in that functional groups Ar2 is any one in following structural formula：
Wherein, R2It is fluorine-containing or fluorobenzene the straight or branched alkyl of carbon number 1~20.
4. a kind of preparation method of the co-polymer luminescent material containing fluoro side base described in any one of claims 1 to 3, its feature It is to comprise the following steps：
(1) by the bromide of Ar1 structures, the bromide of Ar2 structures, the bromo- S of 3,7- bis-, S- dibenzothiophene dioxides, three rings are Base phosphine and palladium are added in there-necked flask, substitute gas；
(2) under argon gas protection, add benzotrifluoride and organic alkali solution to be dissolved, be heated to reflux；Sequentially add benzene boron Acid and bromobenzene carry out end capping reaction；
(3) after end capping reaction terminates, room temperature is cooled to, reaction solution is poured into methyl alcohol and is precipitated, filtering, then with toluene as eluant, eluent Use alumina column chromatography；
(4) after chromatography terminates, the washing lotion of concentration is poured into methyl alcohol and is precipitated, filtering is dried, obtain described containing fluoro side base Co-polymer luminescent material.
5. the preparation method of a kind of co-polymer luminescent material containing fluoro side base according to claim 4, it is characterised in that In step (1), the bromide of the Ar1 structures, the bromide of Ar2 structures and 3,7- bis- bromo- S, S- titanium dioxide dibenzo thiophene The mol ratio of fen is 0.5:0.45~0.1:0.05~0.4.
6. the preparation method of a kind of co-polymer luminescent material containing fluoro side base according to claim 4, it is characterised in that In step (1), the mol ratio of the bromide of the Ar1 structures and three cyclohexyl phosphines is 0.5：0.02；The bromination of the Ar1 structures The mol ratio of thing and palladium is 0.5：0.02.
7. the preparation method of a kind of co-polymer luminescent material containing fluoro side base according to claim 4, it is characterised in that In step (2), the organic base is tetraethyl ammonium hydroxide, and the concentration of organic alkali solution is 1.5M, organic alkali solution addition It is 1 with the volume ratio of benzotrifluoride addition:5；The addition of the phenyl boric acid is with the mol ratio of the bromide of Ar1 structures 0.1：0.5；The bromobenzene is 0.2 with the mol ratio of the bromide of Ar1 structures:0.5.
8. the preparation method of a kind of co-polymer luminescent material containing fluoro side base according to claim 4, it is characterised in that In step (2), the temperature being heated to reflux is 80~100 DEG C, and the time is 24~48h；Phenyl boric acid and bromobenzene is added to be sealed The temperature of reaction is held to be 80~100 DEG C, the time is 6~12h.
9. the preparation method of a kind of co-polymer luminescent material containing fluoro side base according to claim 4, it is characterised in that The bromide of the Ar1 structures is substituted using the boron ester of Ar1 structures；The bromide of the Ar2 structures uses the boron ester of Ar2 structures Substitute.
10. a kind of co-polymer luminescent material containing fluoro side base described in any one of claims 1 to 3 is applied to light emitting diode Luminescent layer, it is characterised in that will the co-polymer luminescent material of side base containing fluoro organic solvent dissolving, then by spin coating, Inkjet printing or printing process film forming, obtain the luminescent layer of the light emitting diode；The organic solvent includes dimethylbenzene, chlorobenzene Or chloroform.
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