CN108503800A - One kind contains S, the polymer and preparation method of S- dioxo-dibenzothiophene macrocyclic units and application - Google Patents
One kind contains S, the polymer and preparation method of S- dioxo-dibenzothiophene macrocyclic units and application Download PDFInfo
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Abstract
The invention belongs to organic photoelectric fields, disclose a kind of containing S, the polymer and preparation method of S dioxydibenze bithiophene macrocyclic units and application.The chemical structural formula of Inventive polymers meets one of following general formula：In formula：m1And m2For the molar fraction of each unit component, 0≤m1<1,0<m2≤ 1, m1+m2=1；N is number of repeat unit, n=10~1000；X is C (R1)2‑、‑NR1‑、‑Si(R1)2‑、‑O‑、‑S‑、‑SO2Or CO2‑；R1For the alkyl of C1~30, the naphthenic base of C3~30, the aromatic hydrocarbyls of C6~60 or the aromatic heterocycle of C3~60；Ar is the aromatic hydrocarbyl of C6~60 or the aromatic heterocycle of C3~60.Inventive polymers have injection and transmission, the carrier mobility of the fluorescence quantum yield, electronics that significantly improve, can be applied in organic photoelectric field.
Description
Technical field
The invention belongs to organic photoelectric fields, more particularly to a kind of to contain S, S- dioxo-dibenzothiophene macrocyclic units gather
Close object and preparation method and application.
Background technology
There is Organic Light Emitting Diode light, active to shine, visual angle is wide, low cost, low energy consumption, flexible and big ruler easy to manufacture
The advantages such as very little panel have broad application prospects in organic FPD and white-light illuminating field.Organic Light Emitting Diode
It is made of anode, hole injection and the multilayered structure of transport layer, luminescent layer, electron injection and transport layer, anode, wherein shine
Layer can be prepared as core by small molecule emitter material and polymer luminescent material.
The usual dissolubility of small molecule emitter material is poor, need to prepare film by vacuum vapour deposition, stock utilization is low, energy
Consumption is high so that device manufacturing cost is higher.Polymer luminescent material have preferable dissolubility, can by spin coating, printing, beat
The solwution methods such as print prepare uniform film, have apparent advantage especially in the preparation of large area film, in summary, gather
It closes object luminescent material and prepares that device process in which materials utilization rate is high, low energy consumption, there is the advantage of low cost, the processing of wet method large area
Prepare the trend that Organic Light Emitting Diode is development in the future.
Main problem existing for polymer luminescent material is that luminous efficiency is high not enough at present, mainly since polymer is sent out
Luminescent material is more difficult while meeting the carrier mobility of high fluorescence quantum yield, suitable energy level, height and balance, therefore, opens
Send out that meet the high efficiency polymer luminescent material of these conditions be a current research emphasis.
Most common polymer luminescent material includes polyfluorene, polycarbazole etc., the carrier mobilities of these polymer is relatively low,
Hole mobility is significantly stronger than electron mobility, while lumo energy is shallower, is unfavorable for the injection of electronics.It introduces and inhales electrical unit
(such as unit containing sulfuryl, imidazole unit) can reduce the lumo energy of polymer, improve electron injection and transmission performance so that
Carrier transport more balances, and then improves electroluminescent efficiency.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of containing S, S- bis-
The polymer of oxygen-dibenzothiophenes macrocyclic units.Containing S, S- dioxo-dibenzothiophene macrocyclic units contain the strong sulfuryl of electronegativity
Group can improve the electron injection ability of this kind of polymer, this kind of to contain S, the polymerization of S- dioxo-dibenzothiophene macrocyclic units
Object has higher fluorescence quantum yield, has larger potential as light emitting polymer, can also pass through polymerized unit content
Adjusting realize different colours transmitting polymer.This kind of polymer has good dissolubility, can be beaten by spin coating, ink-jet
The Solution processing techniques such as print, printing prepare large area film.
Another object of the present invention be to provide it is a kind of it is above-mentioned contain S, the polymer of S- dioxo-dibenzothiophene macrocyclic units
Preparation method.
Still a further object of the present invention be to provide it is above-mentioned contain S, the polymer of S- dioxo-dibenzothiophene macrocyclic units is organic
The application of photoelectric field.
The purpose of the present invention is realized by following proposal：
One kind contains S, the polymer of S- dioxo-dibenzothiophene macrocyclic units, and chemical structural formula meets one of following general formula：
In formula：m1And m2For the molar fraction of each unit component, 0≤m1<1,0<m2≤ 1, m1+m2=1；N is repetitive unit
Number, n=10~1000；
X is-C (R1)2-、-NR1-、-Si(R1)2-、-O-、-S-、-SO2Or-CO2-；
R1For the alkyl of C1~30, the naphthenic base of C3~30, the aromatic hydrocarbyls of C6~60 or the aromatic heterocycle of C3~60；
Ar is the aromatic hydrocarbyl of C6~60 or the aromatic heterocycle of C3~60.
Further, the Ar is preferably more than one of following chemical constitution or following structural derivative：
Wherein, R2For the alkyl of C1~30, the naphthenic base of C3~30, the aromatic hydrocarbyls of C6~60 or the aromatic series of C3~60
Heterocycle；R3、R4、R5Independently it is expressed as H, D, F, CN, alkenyl, alkynyl, amido, nitro, acyl group, alkoxy, carbonyl, sulfone
Base, the alkyl (alkoxy) of C1~30, the naphthenic base of C3~30, the aromatic hydrocarbyls of C6~60 or the heteroaromatic of C3~60
Base.
The present invention provides a kind of above-mentioned containing S, the preparation method of the polymer of S- dioxo-dibenzothiophene macrocyclic units, packet
Include following steps：
(1) boronic acid containing or the S of borate functional group, S- dioxo-dibenzothiophene units spread out with the benzene of bromo or iodo
Biological unit carries out Suzuki couplings, obtains intermediate, and ring closure reaction obtains containing S, S- dioxo-dibenzothiophene macrocyclic units
Monomer；
(2) S will be contained, the monomer of S- dioxo-dibenzothiophene macrocyclic units and the monomer of Ar units are polymerize by Suzuki
After reaction, phenyl boric acid, bromobenzene progress end capping reaction are sequentially added, is obtained described containing S, the big ring list of S- dioxo-dibenzothiophenes
The polymer of member.
Further, step (2) specifically may include following steps in above-mentioned preparation method：
(1) under inert gas protection, S, the monomer of S- dioxo-dibenzothiophene macrocyclic units, the list of Ar units will be contained
Body dissolves in a solvent, and catalyst is then added, and is heated to 60~100 DEG C of generation Suzuki polymerisations, reaction time 12
~36 hours；
(2) phenyl boric acid is added, the reaction was continued 6~12 hours for heat preservation；It adds bromobenzene and continues insulation reaction 6~12 hours,
Gained reaction solution is purified up to target product after reaction.
Solvent described in step (1) can be at least one of toluene, tetrahydrofuran, dimethylbenzene；
The catalyst of Suzuki polymerisations described in step (1) is palladium and tricyclohexyl phosphine, four (triphenylphosphines)
At least one of palladium；The Suzuki polymerisations carry out under alkaline condition, and the alkali is that tetraethyl ammonium hydroxide is water-soluble
At least one of liquid, tetrabutylammonium hydroxide aqueous solution, potassium carbonate.
Described in step (1) contain S, the monomer of S- dioxo-dibenzothiophene macrocyclic units, the monomer of Ar units dosage
Meet the monomer integral molar quantity containing double borates and/or double boric acid functional groups and the monomer containing double bromines and/or Shuan Dian functional groups is total
Mole is equal；The dosage of the catalyst is 2 ‰~the 3% of reaction monomers moles total number；Benzene boron described in step (2)
The dosage of acid is the 10~40% of reaction monomers moles total number；The dosage of the bromobenzene is 5~20 times of phenyl boric acid mole.
Purifying described in step (2) refers to being cooled to room temperature gained reaction solution, is added dropwise in the methanol in stirring and sinks
It forms sediment, filtering is dry that crude product, crude product successively use methanol, acetone extraction, again with toluene dissolving, column chromatography for separation, after concentration
Precipitating filters in methanol solution again, dry, obtains target product.
The present invention's contains S, and the polymer of S- dioxo-dibenzothiophene macrocyclic units has good dissolubility, dissolves in
Common organic solvent.
The present invention will contain S, and S- dioxo-dibenzothiophene macrocyclic units monomers are introduced into the main chain of polymer by copolymerization,
Containing S, S- dioxo-dibenzothiophenes macrocyclic units can improve the electronic transmission performance of polymer, at the same make polymer keep compared with
High fluorescence quantum yield.By adjusting copolymerization units ratio, the luminescent spectrum of polymer can be adjusted, different colours light is obtained
The polymer of transmitting.The present invention's contains S, and the polymer of S- dioxo-dibenzothiophene macrocyclic units can be applied to prepare polymer
In the luminescent layer of light emitting diode, as luminescent material, polymer LED is prepared by the method that solution is processed.
It specifically may include following steps, the present invention contained into S, the polymer of S- dioxo-dibenzothiophene macrocyclic units is dissolved in
Organic solvent, then by spin coating, inkjet printing or printing film forming to get to the luminescent layer of the polymer LED.
The organic solvent is dimethylbenzene, tetrahydrofuran or chlorobenzene.
The present invention compared with the existing technology, has the following advantages and advantageous effect：
(1) of the invention to contain S, S- dioxo-dibenzothiophene macrocyclic units have electrophilic sulfuryl, are introduced into polymer
In can improve the injection and transmission of electronics.
(2) of the invention to contain S, S- dioxo-dibenzothiophene macrocyclic units are big conjugated structure, can improve polymer
Carrier mobility.
(3) one kind of the invention contains S, and the polymer of S- dioxo-dibenzothiophene macrocyclic units has higher fluorescence volume
Sub- yield.
Description of the drawings
Fig. 1 is current efficiency-current density plot of polymer P 1.
Fig. 2 is photoluminescence spectra figure of the polymer P 4 in toluene solution.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Material involved in the following example can be obtained from commercial channel.
Embodiment 1
The preparation of compound M1
(1) preparation of compound 1
Under nitrogen protection, dibenzothiophenes (1.84g, 10mmol) and 50mL acetic acid are added into the two-mouth bottle of 150mL, adds
Heat continues heating stirring and reacts 8 hours to aqueous hydrogen peroxide solution (5mL, 50mmol) is slowly added dropwise after 110 DEG C.Reaction finishes,
White crystal 1.99g, yield 92% is obtained by filtration in cooling and standings.1H NMR、13CNMR, MS and elemental analysis are the result shows that gained
The compound arrived is target product.
(2) preparation of compound 2
Under nitrogen atmosphere, compound 1 (2.16g, 10mmol) and the 100mL concentrated sulfuric acids are added into the two-mouth bottle of 300mL, keeps away
N- bromo-succinimides (4.45g, 25mmol) are added in reaction bulb in three batches under the conditions of light, stirring at normal temperature 12 hours.
Reaction finishes, and reaction solution is poured slowly into 1000mL ice water, and filtering, filter residue is rinsed three times with ethyl alcohol, then tied again with chlorobenzene
Obtain white crystal 2.47g, yield 66% brilliant 2 times.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained chemical combination
Object is target product.
(3) preparation of compound 3
Under nitrogen atmosphere, compound 2 (3.74g, 10mmol) and the anhydrous tetrahydrochysene furans of 60mL are added into the two-mouth bottle of 100mL
It mutters, is slowly added to lithium aluminium hydride reduction (1.14g, 30mmol) and stirs 8 hours.Reaction finishes, and is slowly gone out, is added with 10mL water quenchings
10mL sodium hydrate aqueous solutions and 30mL water quenchings are gone out.Product is extracted with dichloromethane, saturated sodium-chloride water solution is washed three times, removed
After removing organic phase solvent, crude product petroleum ether makees the purification of eluent column chromatography, obtains white solid 2.74g, yield 80%.1H
NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(4) preparation of compound 4
Under nitrogen protection, compound 3 (3.42g, 10mmol), connection boric acid pinacol ester are added into the two-mouth bottle of 300mL
(6.35g, 25mmol), [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.49g, 0.5mmol), potassium acetate
(3.92g, 40mmol) and 150mL dioxane is heated to 80 DEG C and reacts 12 hours.Reaction is finished removes two by being evaporated under reduced pressure
Six ring of oxygen extracts product with dichloromethane, and saturated sodium-chloride water solution washs three times, after vacuum distillation removes dichloromethane, slightly
Product petroleum ether：Dichloromethane=4：The mixed solvent of 1 (v/v) makees the purification of eluent column chromatography, obtains white solid 3.05g,
Yield 70%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(5) preparation of compound 5
Under nitrogen atmosphere, compound 4 (4.36g, 10mmol), the bromo- 2- iodo-benzoic acids of 5- are added into the two-mouth bottle of 150mL
Methyl esters
(10.23g, 30mmol), potassium carbonate (3.45g, 25mmol), tetrakis triphenylphosphine palladium (0.58g, 0.5mmol),
12mL deionized waters and 80mL toluene are heated to 80 DEG C and react 12 hours.Reaction finishes, and product, saturation are extracted with dichloromethane
Sodium-chloride water solution washs three times, and after removing organic phase solvent, crude product petroleum ether makees the purification of eluent column chromatography, uses oil
Ether/re-crystallizing in ethyl acetate obtains light yellow solid 3.84g, yield 63%.1H NMR、13CNMR, MS and elemental analysis result table
Bright obtained compound is target product.
(6) preparation of compound 6
Under nitrogen protection, compound 5 (6.10g, 10mmol) and the anhydrous tetrahydrochysenes of 100mL are added into the two-mouth bottle of 300mL
Furans is cooled to -78 DEG C, is added dropwise to the tetrahydrofuran solution (50mL, 50mmol) of n-octyl magnesium bromide, it is anti-to be slowly increased to room temperature
It answers 12 hours.Reaction finishes, and a small amount of water quenching is added and goes out reaction, removes tetrahydrofuran by vacuum distillation, is extracted with dichloromethane
Product, saturated sodium-chloride water solution wash three times, after vacuum distillation removes dichloromethane, crude product petroleum ether：Ethyl acetate
=4：The mixed solvent of 1 (v/v) makees the purification of eluent column chromatography, obtains yellow solid 7.52g, yield 75%.1H NMR、13C
NMR, MS and elemental analysis are the result shows that obtained compound is target product.
(7) preparation of compound 7
Under nitrogen protection, compound 6 (10.03g, 10mmol) and 150mL acetic acid are added into the two-mouth bottle of 300mL, adds
5mL concentrated hydrochloric acids are added to after 100 DEG C in heat, continue heating reaction 8 hours.Reaction finishes, and 500mL is poured into after reaction solution cooling
Ice water in, filtering, filter residue with 50mL ethyl alcohol rinse twice, crude product petroleum ether：Dichloromethane=8：The mixing of 1 (v/v)
Solvent makees the purification of eluent column chromatography, obtains white solid 7.06g, yield 73%.1H NMR、13CNMR, MS and elemental analysis result
Show that obtained compound is target product.
(8) preparation of compound M1
Under nitrogen protection, compound 7 (9.67g, 10mmol) and 120mL tetrahydrofurans are added into the two-mouth bottle of 300mL
With the mixed solvent (1 of acetic acid：1, v：V), aqueous hydrogen peroxide solution (5mL, 50mmol) is slowly added dropwise after being heated to 70 DEG C, continues
Heating stirring is reacted 8 hours.Reaction finishes, and extracts product with dichloromethane, saturated sodium-chloride water solution is washed 3 times, has been spin-dried for
After machine phase solvent, by silica gel chromatographic column purified product, eluent is petroleum ether：Dichloromethane (6：1, v：V), with petroleum ether weight
Crystallization, obtains white solid 8.59g, yield 86%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained chemical combination
Object is target product.
The chemical equation for synthesizing compound 1~7 and compound M1 is as follows：
Embodiment 2
The preparation of compound M2
(1) preparation of compound 8
Under nitrogen atmosphere, compound 4 (4.36g, 10mmol), o-bromonitrobenzene are added into the two-mouth bottle of 150mL
(6.06g, 30mmol), potassium carbonate (3.45g, 25mmol), tetrakis triphenylphosphine palladium (0.58g, 0.5mmol), 12mL deionizations
Water and 50mL toluene are heated to 80 DEG C and react 12 hours.Reaction finishes, and extracts product with dichloromethane, saturated sodium-chloride is water-soluble
Liquid washs three times, after removing organic phase solvent, crude product petroleum ether：Dichloromethane (v：V=4：1) mixed solvent elutes
Agent column chromatography purifies, and obtains yellow solid 3.20g, yield 75%.1H NMR、13CNMR, MS and elemental analysis are the result shows that acquired
Compound be target product.
(2) preparation of compound 9
Under nitrogen protection, compound 8 (4.26g, 10mmol) and 50mL phosphorous triethylenetetraminehexaacetic acids are added into the two-mouth bottle of 150mL
Ester is heated to 120 DEG C and reacts 12 hours.Reaction finishes, and removes triethyl phosphite by vacuum distillation, is extracted with dichloromethane
Product, saturated sodium-chloride water solution wash three times, after removing organic phase solvent, crude product petroleum ether：Dichloromethane=3：1
(v：V) make the purification of eluent column chromatography, white solid 1.99g, yield 55% are recrystallized to obtain with ethyl alcohol/tetrahydrofuran.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(3) preparation of compound 10
Under nitrogen protection, into the two-mouth bottle of 300mL be added compound 9 (3.62g, 10mmol), 1- bromooctanes (5.8g,
30mmol), potassium carbonate (8.28g, 60mmol) and 120mL n,N-Dimethylformamide are heated to 100 DEG C and react 12 hours.Instead
It should finish, product is extracted with dichloromethane, saturated sodium-chloride water solution washs five times, and after removing organic phase solvent, crude product is used
Petroleum ether makees the purification of eluent column chromatography, obtains white solid 4.99g, yield 85%.1H NMR、13CNMR, MS and elemental analysis result
Show that obtained compound is target product.
(4) preparation of compound 11
Under nitrogen protection, compound 10 (5.87g, 10mmol) and 150mL chloroforms are added into the two-mouth bottle of 300mL, keeps away
Under the conditions of light, 22mL is added dropwise to dissolved with the chloroformic solution of bromine (3.52g, 22mmol) in reaction, stirring at normal temperature reaction 24 is small
When.Unreacted bromine is quenched with a small amount of sodium hydrogensulfite, product, saturated sodium-chloride water solution washing 3 are extracted with dichloromethane
Time, after being spin-dried for organic phase solvent, by silica gel chromatographic column purified product, eluent is petroleum ether：Dichloromethane (6：1, v：V),
With petroleum ether/tetrahydrofuran mixed solvent recrystallization, white solid 5.51g, yield 74% are obtained.1H NMR、13CNMR, MS and
Elemental analysis is the result shows that obtained compound is target product.
(5) preparation of compound M2
Under nitrogen protection, compound 11 (7.45g, 10mmol) and 120mL tetrahydrofurans are added into the two-mouth bottle of 300mL
With the mixed solvent (1 of acetic acid：1, v：V), aqueous hydrogen peroxide solution (10mL, 100mmol) is slowly added dropwise after being heated to 70 DEG C, after
Continuous heating stirring is reacted 12 hours.Reaction finishes, and extracts product with dichloromethane, saturated sodium-chloride water solution is washed 3 times, is spin-dried for
After organic phase solvent, by silica gel chromatographic column purified product, eluent is petroleum ether：Dichloromethane (4：1, v：V), petroleum ether is used
Recrystallization, obtains white solid 6.76g, yield 87%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtainedization
Conjunction object is target product.
The chemical equation for synthesizing compound 8~11 and compound M2 is as follows：
Embodiment 3
The preparation of compound M3
(1) preparation of compound 12
Under nitrogen atmosphere, by dibenzothiophenes -2,8- hypoboric acid (2.72g, 10mmol) and the bromo- 2- iodo-benzoic acids methyl esters of 5-
(10.23g, 30mmol), potassium carbonate (3.45g, 25mmol), tetrakis triphenylphosphine palladium (0.58g, 0.5mmol), 12mL deionizations
Water and 50mL toluene are heated to 80 DEG C and react 12 hours.Reaction finishes, and extracts product with dichloromethane, saturated sodium-chloride is water-soluble
Liquid washs three times, and after removing organic phase solvent, crude product petroleum ether makees the purification of eluent column chromatography, with petroleum ether/acetic acid second
Ester recrystallizes, and obtains light yellow solid 4.39g, yield 72%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained
Compound is target product.
(2) preparation of compound 13
Under nitrogen protection, compound 12 (6.10g, 10mmol) and the anhydrous tetrahydrochysenes of 100mL are added into the two-mouth bottle of 300mL
Furans is cooled to -78 DEG C, is added dropwise to the tetrahydrofuran solution (60mL, 60mmol) of n-octyl magnesium bromide, it is anti-to be slowly increased to room temperature
It answers 12 hours.Reaction finishes, and a small amount of water quenching is added and goes out reaction, removes tetrahydrofuran by vacuum distillation, is extracted with dichloromethane
Product, saturated sodium-chloride water solution wash three times, after vacuum distillation removes dichloromethane, crude product petroleum ether：Ethyl acetate
=4：The mixed solvent of 1 (v/v) makees the purification of eluent column chromatography, obtains yellow solid 7.22g, yield 72%.1H NMR、13C
NMR, MS and elemental analysis are the result shows that obtained compound is target product.
(3) preparation of compound 14
Under nitrogen protection, compound 13 (10.03g, 10mmol) and 150mL acetic acid are added into the two-mouth bottle of 300mL, adds
5mL concentrated hydrochloric acids are added to after 100 DEG C in heat, continue heating reaction 8 hours.Reaction finishes, and 500mL is poured into after reaction solution cooling
Ice water in, filtering, filter residue with 50mL ethyl alcohol rinse twice, crude product petroleum ether：Dichloromethane=6：The mixing of 1 (v/v)
Solvent makees the purification of eluent column chromatography, obtains white solid 7.35g, yield 76%.1H NMR、13CNMR, MS and elemental analysis result
Show that obtained compound is target product.
(4) preparation of compound M3
Under nitrogen protection, compound 14 (9.67g, 10mmol) and 150mL tetrahydrofurans are added into the two-mouth bottle of 300mL
With the mixed solvent (1 of acetic acid：1, v：V), aqueous hydrogen peroxide solution (10mL, 100mmol) is slowly added dropwise after being heated to 70 DEG C, after
Continuous heating stirring is reacted 8 hours.Reaction finishes, and extracts product with dichloromethane, saturated sodium-chloride water solution is washed 3 times, is spin-dried for
After organic phase solvent, by silica gel chromatographic column purified product, eluent is petroleum ether：Dichloromethane (6：1, v：V), petroleum ether is used
Recrystallization, obtains white solid 9.19g, yield 92%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtainedization
Conjunction object is target product.
The chemical equation for synthesizing compound 12~14 and compound M3 is as follows：
Embodiment 4
The preparation of polymer P 1
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes
Bis- bromo- 9,9- di-n-octyls fluorenes (131.6mg, 0.24mmol) of (192.6mg, 0.3mmol), 2,7- and compound M1 (59.9mg,
It 0.06mmol) is dissolved in 10mL toluene, adds tetraethyl aqueous hydroxylamine solution (1mL, wt%=20%), palladium (1mg)
With tricyclohexyl phosphine (2mg)；Be heated to 80 DEG C reaction 24 hours after, be added phenyl boric acid (20mg) block 6 hours, add bromobenzene
(0.2mL) is blocked 6 hours；Reaction stops, and after cooling, by organic phase precipitating in methanol (300mL), filtering is thick to produce after dry
Object successively with methanol, acetone, n-hexane extracting, is carried out using toluene as eluent with neutral alumina with toluene dissolving polymer
Column chromatography purifies；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains chartreuse fibre
Tie up shaped polymer.Pass through1H NMR spectras and elemental analysis confirm to obtain subject polymer.Gel permeation chromatography：Mn=87KDa,
PDI=2.22.Fluorescence quantum yield：0.80.Fig. 1 is current efficiency-current density plot of polymer P 1.As shown in Figure 1, gather
It is 4.02cdA to close object P1 to have higher electroluminescent properties, maximum current efficiency-1, and the efficiency roll-off of polymer P 1 is very
It is small, in 300mAcm-2Current density under current efficiency still have 3.48cdA-1.Chemical equation is as follows：
Embodiment 5
The preparation of polymer P 2
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes
Bis- bromo- 9,9- di-n-octyls fluorenes (131.6mg, 0.24mmol) of (192.6mg, 0.3mmol), 2,7- and compound M2 (46.6mg,
It 0.06mmol) is dissolved in 10mL toluene, adds tetraethyl aqueous hydroxylamine solution (1mL, wt%=20%), palladium (1mg)
With tricyclohexyl phosphine (2mg)；Be heated to 80 DEG C reaction 24 hours after, be added phenyl boric acid (20mg) block 6 hours, add bromobenzene
(0.2mL) is blocked 6 hours；Reaction stops, and after cooling, by organic phase precipitating in methanol (300mL), filtering is thick to produce after dry
Object successively with methanol, acetone, n-hexane extracting, is carried out using toluene as eluent with neutral alumina with toluene dissolving polymer
Column chromatography purifies；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains chartreuse fibre
Tie up shaped polymer.Pass through1H NMR spectras and elemental analysis confirm to obtain subject polymer.Gel permeation chromatography：Mn=65KDa,
PDI=2.07.Fluorescence quantum yield：0.77.Chemical equation is as follows：
Embodiment 6
The preparation of polymer P 3
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl clicks
Azoles (197.3mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyls carbazoles (152.1mg, 0.18mmol) and compound M1
(119.9mg, 0.12mmol) is dissolved in 12mL toluene, adds tetraethyl aqueous hydroxylamine solution (1mL, wt%=20%), vinegar
Sour palladium (1mg) and tricyclohexyl phosphine (2mg)；Be heated to 80 DEG C reaction 24 hours after, be added phenyl boric acid (20mg) block 6 hours,
Bromobenzene (0.2mL) is added to block 6 hours；Reaction stops, after cooling, by organic phase precipitating in methanol (300mL), and filtering,
After drying, crude product successively with methanol, acetone, n-hexane extracting, dissolves polymer, using toluene as eluent, in toluene
Property aluminium oxide carry out column chromatography purification；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains
To chartreuse fibrous polymer.Pass through1H NMR spectras and elemental analysis confirm to obtain subject polymer.Gel infiltration color
Spectrum：Mn=99KDa, PDI=2.45.Fluorescence quantum yield：0.70.Chemical equation is as follows：
Embodiment 7
The preparation of polymer P 4
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes
Bis- bromo- 9,9- di-n-octyls fluorenes (88.9mg, 0.162mmol) of (192.6mg, 0.3mmol), 2,7-, 4,6- dibromo benzos thiophene two
Azoles (5.3mg, 0.018mmol) and compound M3 (119.9mg, 0.12mmol) are dissolved in 10mL toluene, add tetraethyl
Aqueous hydroxylamine solution (1mL, wt%=20%), palladium (1mg) and tricyclohexyl phosphine (2mg)；80 DEG C are heated to react 24 hours
Afterwards, phenyl boric acid (20mg) is added to block 6 hours, adds bromobenzene (0.2mL) and blocks 6 hours；Reaction stops, and after cooling, will have
Machine phase precipitating is in methanol (300mL), filtering, and after dry, crude product is molten with toluene successively with methanol, acetone, n-hexane extracting
Depolymerize object, and using toluene as eluent, column chromatography purification is carried out with neutral alumina；The toluene solution of concentrated polymer, again
Precipitating filters in methanol solution, dry, obtains chartreuse fibrous polymer.Pass through1H NMR spectras and elemental analysis
Confirmation obtains subject polymer.Gel permeation chromatography：Mn=76KDa, PDI=2.42.Fluorescence quantum yield：0.87.Fig. 2 is poly-
Photoluminescence spectra figures of the object P4 in toluene solution is closed, as seen from the figure, it is 520nm that polymer P 4, which shows as maximum emission wavelength,
Green emission.
Chemical equation is as follows：
Embodiment 8
The preparation of polymer P 5
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes
Bis- bromo- 9,9- di-n-octyls fluorenes (121.8mg, 0.222mmol) of (192.6mg, 0.3mmol), 2,7-, 4,7- it is bis- (5- bromines (and 4- oneself
Base thiophene) -2- bases) -2,1,3- diazosulfide (11.3mg, 0.018mmol) and compound M3 (59.9mg, 0.06mmol) are molten
Solution adds tetraethyl aqueous hydroxylamine solution (1mL, wt%=20%), palladium (1mg) and tricyclohexyl phosphine in 12mL toluene
(2mg)；Be heated to 80 DEG C reaction 24 hours after, be added phenyl boric acid (20mg) block 6 hours, add bromobenzene (0.2mL) sealing end 6
Hour；Reaction stops, after cooling, by organic phase precipitating in methanol (300mL), and filtering, after dry, crude product priority first
Alcohol, acetone, n-hexane extracting are carried out column chromatography with neutral alumina and carried with toluene dissolving polymer using toluene as eluent
It is pure；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains the polymerization of chartreuse threadiness
Object.Pass through1H NMR spectras and elemental analysis confirm to obtain subject polymer.Gel permeation chromatography：Mn=85KDa, PDI=
2.59.Fluorescence quantum yield：0.71.Chemical equation is as follows：
Embodiment 9
The preparation of polymer LED
Take well in advance square resistance be 20 Ω tin indium oxide (ITO) glass, successively use acetone, detergent, go from
Sub- water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes.The polyethoxy for having polystyrolsulfon acid is mixed in spin coating on ITO
Thiophene (PEDOT:PSS) film, thickness 40nm.PEDOT:PSS films are 8 hours dry at 80 DEG C in vacuum drying oven.To then it gather
The xylene solution (1wt.%) for closing object P1~P5 is spin-coated on PEDOT:The surface of PSS films, thickness 80nm.Finally in luminescent layer
On be deposited successively one layer of 1.5nm thickness CsF and 120nm thickness metal Al layer, device architecture ITO/PEDOT:PSS/ polymer/
CsF/Al.Its performance is characterized, the results are shown in Table 1.
1 polymer device performance of table
Device architecture：ITO/PEDOT:PSS/ polymer/CsF/Al
It is can be found that from the performance of 1 polymer device of table：Light emitting polymer P1~P5 of the present invention has the device of very little
Open bright voltage (<4V), polymer P 1, P2 and P3 are blue emission, and the device of polymer P 4 is green emission, and polymer P 5 is red
Light emitting, all these polymer have higher electroluminescent efficiency.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. one kind contains S, the polymer of S- dioxo-dibenzothiophene macrocyclic units, it is characterised in that chemical structural formula meets following
One of general formula：
In formula：m1And m2For the molar fraction of each unit component, 0≤m1<1,0<m2≤ 1, m1+m2=1；N is number of repeat unit, n
=10~1000；
X is-C (R1)2-、-NR1-、-Si(R1)2-、-O-、-S-、-SO2Or-CO2-；
R1For the alkyl of C1~30, the naphthenic base of C3~30, the aromatic hydrocarbyls of C6~60 or the aromatic heterocycle of C3~60；
Ar is the aromatic hydrocarbyl of C6~60 or the aromatic heterocycle of C3~60.
2. according to claim 1 contain S, the polymer of S- dioxo-dibenzothiophene macrocyclic units, it is characterised in that：Institute
The Ar stated is more than one of following chemical constitution or following structural derivative：
Wherein, R2For the alkyl of C1~30, the naphthenic base of C3~30, the aromatic hydrocarbyls of C6~60 or the heteroaromatic of C3~60
Base；R3、R4、R5Independently it is expressed as H, D, F, CN, alkenyl, alkynyl, amido, nitro, acyl group, alkoxy, carbonyl, sulfuryl, C1
~30 alkyl, the alkoxy of C1~30, the naphthenic base of C3~30, the aromatic hydrocarbyls of C6~60 or the heteroaromatic of C3~60
Base.
3. a kind of claim 1~2 any one of them contains S, the preparation of the polymer of S- dioxo-dibenzothiophene macrocyclic units
Method, it is characterised in that include the following steps：
(1) boronic acid containing or the S of borate functional group, S- dioxo-dibenzothiophene units and bromo or the benzene derivate of iodo
Unit carries out Suzuki couplings, obtains intermediate, and ring closure reaction obtains containing S, the list of S- dioxo-dibenzothiophene macrocyclic units
Body；
(2) S will be contained, the monomer of S- dioxo-dibenzothiophene macrocyclic units and the monomer of Ar units pass through Suzuki polymerisations
Afterwards, sequentially add phenyl boric acid, bromobenzene carries out end capping reaction, obtain it is described contain S, S- dioxo-dibenzothiophene macrocyclic units
Polymer.
4. according to claim 3 contain S, the preparation method of the polymer of S- dioxo-dibenzothiophene macrocyclic units is special
Sign is that step (2) specifically includes following steps：
(1) under inert gas protection, S will be contained, monomer, the monomer of Ar units of S- dioxo-dibenzothiophene macrocyclic units are molten
In a solvent, catalyst is then added in solution, is heated to 60~100 DEG C of generation Suzuki polymerisations, and the reaction time is 12~36
Hour；
(2) phenyl boric acid is added, the reaction was continued 6~12 hours for heat preservation；It adds bromobenzene and continues insulation reaction 6~12 hours, reaction
After gained reaction solution is purified up to target product.
5. according to claim 4 contain S, the preparation method of the polymer of S- dioxo-dibenzothiophene macrocyclic units is special
Sign is：The catalyst of Suzuki polymerisations described in step (1) is palladium and tricyclohexyl phosphine, tetrakis triphenylphosphine palladium
At least one of；The Suzuki polymerisations carry out under alkaline condition, and alkali is tetraethyl ammonium hydroxide aqueous solution, four fourths
At least one of base ammonium hydroxide aqueous solution, potassium carbonate.
6. according to claim 4 contain S, the preparation method of the polymer of S- dioxo-dibenzothiophene macrocyclic units is special
Sign is：Described in step (1) contain S, the monomer of S- dioxo-dibenzothiophene macrocyclic units, the monomer of Ar units dosage
Meet the monomer integral molar quantity containing double borates and/or double boric acid functional groups and the monomer containing double bromines and/or Shuan Dian functional groups is total
Mole is equal.
7. according to claim 4 contain S, the preparation method of the polymer of S- dioxo-dibenzothiophene macrocyclic units is special
Sign is：The dosage of catalyst described in step (1) is 2 ‰~the 3% of reaction monomers moles total number.
8. according to claim 4 contain S, the preparation method of the polymer of S- dioxo-dibenzothiophene macrocyclic units is special
Sign is：The dosage of phenyl boric acid described in step (2) is the 10~40% of reaction monomers moles total number；The use of the bromobenzene
Amount is 5~20 times of phenyl boric acid mole.
9. claim 1~2 any one of them contains S, the polymer of S- dioxo-dibenzothiophene macrocyclic units is in organic photoelectric
The application in field.
10. according to claim 9 contain S, the polymer of S- dioxo-dibenzothiophene macrocyclic units is in organic photoelectric field
Application, it is characterised in that specifically include following steps, by claim 1~2 any one of them contain S, S- dioxies-dibenzo
The polymer of thiophene macrocyclic unit is dissolved in organic solvent, is then gathered to get to described by spin coating, inkjet printing or printing film forming
The luminescent layer of polymer LEDs.
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