CN107987255B - Containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer and its preparation method and application - Google Patents
Containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to organic photoelectric technical fields, disclose a kind of containing 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer and its preparation method and application.9,9,10,10- tetra- oxygen-thianthrene, five yuan of condensed ring units are a kind of strong units for inhaling electrical property, and the electronic transmission performance of polymer can be improved.By adjusting copolymerization units ratio, the luminescent spectrum and band gap of polymer can also be adjusted well, obtains the polymer of different purposes.Five yuan and ring structure further increase the carrier mobility and thermal stability of polymer.Of the invention can be used as luminous organic material or polymer solar cells material containing 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer, prepare polymer LED and polymer solar cells by the method that solution is processed.
Description
Technical field
The invention belongs to organic photoelectric technical fields, in particular to a kind of to contain 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring
Unit polymer and its preparation method and application.
Background technique
Organic/polymer LED (O/PLED) is one kind based on small organic molecule and polymer material
Light emitting diode, have it is light, actively shine, visual angle is wide, low cost, low energy consumption, flexible and large size panel easy to manufacture etc. are excellent
Gesture has broad application prospects in organic FPD and white-light illuminating field.Organic solar battery material is started in
The nineties in last century is a kind of novel sustainable regenerated inexpensive green energy resource material, and easily prepares large area flexible electricity
There is huge application potential in pond.
Realize efficient polymer LED, luminescent material needs to have high-fluorescence quantum yield, balance
The characteristics such as carrier transport.Currently used polymer luminescent material usually only has single carrier transport feature, especially uses
In the polyfluorene analog derivative of blue light frequency-doubling, polyfluorene analog derivative is that hole transport accounts for a leading quasi polymer, lumo energy
Shallower, electron injection barrier is larger, limits its electron injection and transmission performance, using equal polyfluorene as the polymer light-emitting of luminescent layer
The electroluminescent efficiency of device is lower [Progress in Polymer Science, 2012,37,1192-1264].It prepares
Efficient organic photovoltaic cell device, it is important to have high carrier transport performance, high visible suction rate it is living to receptor
Property layer material.
Suction electric unit electron affinity with higher containing sulfuryl, polymer can be reduced by being introduced into main polymer chain
Lumo energy and improve polymer electronic transmission performance, be conducive to improve polymer electroluminescent properties.In addition, containing sulfone
When the suction electric unit of base and strong electron-donating unit are copolymerized, the band gap of polymer can be reduced, improves polymer in visible-range
Interior absorption, and then improve the photoelectric conversion efficiency of this kind of polymer solar cells material.That reports at present is more containing sulfuryl
Unit include S, S- dioxo-dibenzothiophene unit, diphenyl sulphone (DPS), S, S- dioxy thioxanthene etc., the polymerization synthesized with these units
Object can be used as luminescent material and battery-active layer material [Chem.Mater.2008,20,4499-4506；Macromolecules,
2014,47,2907-2914；Journal of Polymer Science Part A:Polymer Chemistry,2017,
55,2332–2341.].However, current report is also not directed to gather containing 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit
Object is closed, 9,9,10,10- tetra- oxygen-thianthrene, five yuan of condensed ring units contain at least two sulfuryls, with the phase of unit containing sulfuryl enumerated before
Than electrically, being introduced into polymer with stronger suction, lumo energy can be further decreased, five yuan simultaneously ring structure can be into one
Step improves 9,9,10,10- tetra- oxygen-five yuan of condensed ring units of thianthrene electron mobility, improves the luminescent properties and photoelectricity of polymer
Transfer efficiency.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing one kind contains 9,9,
Tetra- oxygen of 10,10--thianthrene, five yuan of condensed ring unit polymer.Five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene make this birds of the same feather flock together
Closing object has good electron injection and transmission characteristic, can adjust polymer material well by the adjustment of unit content
Band gap has relatively narrow band gap, this quasi polymer as battery material as luminescent material fluorescence quantum yield with higher
Large area film can be prepared by Solution processing techniques such as spin coating, inkjet printing, printings.
Another object of the present invention is to provide the system of above-mentioned five yuan of condensed ring unit polymer containing tetra- oxygen of 9,9,10,10--thianthrene
Preparation Method.
Still a further object of the present invention is that providing above-mentioned five yuan of condensed ring unit polymer containing tetra- oxygen of 9,9,10,10--thianthrene is making
Application in standby organic electro-optic device.
The purpose of the present invention is realized by following proposal:
One kind containing 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer, and chemical structure is structure as shown below
One of:
In formula, x1、x2For the molar fraction of unit component, meet: 0≤x1< 1,0 < x2≤ 1, x1+x2=1；N is to repeat list
Member, n=10~1000；
Y is C (R1)2、NR1、Si(R1)2、O、S、SO2Or CO2；Wherein R1Alkyl, carbon atom number 3 for carbon atom number 1~30
~30 naphthenic base, the aromatic heterocycle that carbon atom number is 6~60 aromatic hydrocarbyls or carbon atom number is 3~60；
Ar be the aromatic hydrocarbyl of carbon atom number 6~60, carbon atom number 3~60 aromatic heterocycle in it is a kind of or more
Kind, when Ar represents multiple groups, the sum of molar fraction of multiple groups is equal to x1.
Preferably, in the derivative of the Ar is as follows chemical structure or chemical structure as follows
It is one or more:
Wherein, R2It is 6~60 virtues for the alkyl of carbon atom number 1~30, the naphthenic base of carbon atom number 3~30, carbon atom number
The aromatic heterocycle that fragrant race's alkyl or carbon atom number are 3~60；R3、R4、R5Independently it is expressed as H, D, F, CN, alkenyl, alkynes
Base, amido, nitro, acyl group, alkoxy, carbonyl, sulfuryl, the alkyl of carbon atom number 1~30 or alkoxy, carbon atom number 3~30
Naphthenic base, the aromatic heterocycle that carbon atom number is 6~60 aromatic hydrocarbyls or carbon atom number is 3~60.
A kind of above-mentioned preparation method containing 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene comprising with
Lower step:
Tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring units will be contained Monomer and the unit containing Ar monomer polymerize by Suzuki it is anti-
Ying Hou sequentially adds phenyl boric acid, bromobenzene carries out end capping reaction to get thick containing 9,9,10,10- tetra- oxygen-five yuan of thianthrene described in
Ring element polymer；Wherein Y is defined as described above.
The above-mentioned preparation method containing 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene, specifically includes following
Step:
(1) under inert gas protection, will contain 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit monomer and containing Ar it is mono-
The monomer dissolution of member in a solvent, is then added catalyst and alkali, is heated to 60~100 DEG C of generation Suzuki polymerization reactions, instead
It is 12~36h between seasonable；
(2) phenyl boric acid, heat preservation the reaction was continued 6~12h is added；It adds bromobenzene and continues 6~12h of insulation reaction, reaction knot
Gained reaction solution is purified up to target product after beam.
Solvent described in step (1) is at least one of toluene, tetrahydrofuran, dimethylbenzene；The catalyst is
At least one of palladium acetate, tricyclohexyl phosphine and tetrakis triphenylphosphine palladium；The alkali is basic matterial or basic matterial
At least one of aqueous solution, such as tetraethyl ammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution, potassium carbonate, preferably
For the tetraethyl ammonium hydroxide aqueous solution of 20wt%.
It is double that the monomer of five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene described in step (1), which is preferably end group,
Bromine, double iodine, double boric acid or double borates monomer；The monomer of the unit containing Ar is preferably that end group is double borate, double boron
The monomer of sour, double bromines or double iodine.
It is furthermore preferred that the monomer finger tip base containing 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit described in step (1)
For double bromines or the monomer of double iodine.
The monomer of five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene described in step (1) and the list of the unit containing Ar
The dosage of body meets the monomer integral molar quantity containing double borates and/or double boric acid functional groups and contains double bromines and/or Shuan Dian functional group
Monomer integral molar quantity it is equal；The dosage of the catalyst is 2 ‰~the 3% of all reaction monomers moles total numbers；Described
The dosage of alkali is that the mole of the basic matterial in alkali is 2~5 times of monomer integral molar quantity；
The dosage of phenyl boric acid described in step (2) is the 10~40% of all reaction monomers moles total numbers；The bromine
The dosage of benzene is 5~20 times of phenyl boric acid mole.
Purifying described in step (2), which refers to, is cooled to room temperature gained reaction solution, is added to precipitating in methanol, filtering,
It is dry that crude product, crude product successively use methanol, acetone, n-hexane extracting, again with toluene dissolution, column chromatography for separation, after concentration
Precipitating filters in methanol solution again, dry, obtains target product.
Alternatively,
A kind of above-mentioned preparation method containing 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene comprising with
Lower step:
Tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring units will be contained Monomer and the unit containing Ar monomer polymerize by Stille it is anti-
It answers, sequentially adds tributyl tin thiophene, bromo thiophene progress end capping reaction, obtain described containing 9,9,10,10- tetra- oxygen-thianthrene
Five yuan of condensed ring unit polymer.Wherein Y is defined as described above.
Preferably, the above-mentioned preparation method containing 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene is specific to wrap
Include following steps:
(1) under inert gas protection, will contain 9,9,10,10- tetra- oxygen-five yuan of condensed ring units of thianthrene monomer, containing Ar it is mono-
The monomer dissolution of member in a solvent, is then added catalyst, is heated to 80~150 DEG C of generation Stille polymerization reactions, when reaction
Between be 12~36h；
(2) tributyl tin thiophene, heat preservation the reaction was continued 6~12h is added；Add bromo thiophene continue insulation reaction 6~
12h after reaction purifies gained reaction solution up to target product.
Solvent described in step (1) is dry toluene, tetrahydrofuran, dimethylbenzene, chlorobenzene, at least one in dichloro-benzenes
Kind；The Stille polymerization catalyst is tetrakis triphenylphosphine palladium, bis- (dibenzyl subunit acetone) palladiums and three (o-methyl-phenyls)
At least one of phosphorus.
It is double that the monomer of five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene described in step (1), which is preferably end group,
The monomer of bromine or double iodine；The monomer of the unit containing Ar is preferably the monomer that end group is double methyl tin or double butyl tins.
The monomer of five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene described in step (1) and the list of the unit containing Ar
The dosage of body meets the monomer integral molar quantity containing double methyl tin and/or double butyl tin functional groups and contains double bromines and/or double iodine functions
The monomer integral molar quantity of group is equal；The dosage of the catalyst is 2 ‰~the 3% of reaction monomers moles total number；
The dosage of tributyl tin thiophene described in step (2) is the 10~40% of reaction monomers moles total number；Described
The dosage of bromobenzene is 5~20 times of phenyl boric acid mole.
Tributyl tin thiophene described in step (2) is preferably 2- (tributyl tin) thiophene；
Purifying described in step (2), which refers to, is cooled to room temperature gained reaction solution, is added in methanol and precipitates, filtering,
Dry crude product, crude product successively uses methanol, acetone extraction, then is dissolved with chlorobenzene, column chromatography for separation, precipitating again after concentration
Into methanol, filter, it is dry, obtain target product.
Described has good dissolubility containing 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer, dissolves in
Common organic solvent.
Described five yuan of condensed ring unit polymer containing tetra- oxygen of 9,9,10,10--thianthrene are preparing polymer LED
Application in the active layer of luminescent layer and polymer solar cells.
The luminescent layer for preparing polymer LED is the following steps are included: contain 9,9,10,10- tetra- for described
Five yuan of condensed ring unit polymer of oxygen-thianthrene are dissolved in organic solvent, then by spin coating, inkjet printing or printing film forming to get arriving
The luminescent layer of the polymer LED；The organic solvent is preferably dimethylbenzene, chlorobenzene or tetrahydrofuran.
Described is applied to polymer LED containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer
Luminescent layer, be conducive to improve polymer LED electroluminescent properties；Meanwhile containing 9,9,10,10- tetra- based on described
The polymer LED of five yuan of condensed ring unit polymer of oxygen-thianthrene can be used for the display of flat-panel monitor.
The active layer for preparing polymer solar cells will be the following steps are included: will contain tetra- oxygen of 9,9,10,10--thianthrene
Five yuan of condensed ring unit polymer mix at least one solar cell donor or/and acceptor material and are dissolved in organic solvent, then lead to
Spin coating, inkjet printing or printing film forming are crossed to get the active layer for arriving the polymer solar cells.The organic solvent is preferred
For chlorobenzene or dichloro-benzenes.
It is applied to polymer solar cells containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer for described
Active layer is conducive to the photoelectric conversion efficiency for improving polymer solar cells；Meanwhile containing 9,9,10,10- tetra- oxygen-based on described
The polymer solar cells of five yuan of condensed ring unit polymer of thianthrene can be used for solar cell panel energy storage.
Mechanism of the invention are as follows:
The present invention provides one kind and contains 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer, which contains
There are tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring units.Tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring units are a kind of strong suction electricity
Property unit, the electronic transmission performance of polymer can be improved, can also adjust the band gap of polymer well, five yuan and ring knot
Structure further increases the carrier mobility and thermal stability of polymer.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) of the invention 9,9,10,10- tetra- oxygen-thianthrene, five yuan of condensed ring units are five yuan and ring structure, have biggish point
Sub- rigidity, can be improved containing 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene thermal stability；
(2) of the invention to inhale electrical group containing strong containing 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer, it can be with
It reduces the lumo energy of polymer and improves electron mobility, improve electron injection, transmission and the performance of extraction of polymer；
(3) present invention provides the simplicity of five yuan of condensed ring unit polymer containing tetra- oxygen of 9,9,10,10--thianthrene, the side of efficiently synthesizing
Method, the series polymer that available high molecular weight is connected with different loci.
(4) present invention, which provides, contains 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer, can pass through copolymerization units
Adjusting, realize the light emitting polymer of redgreenblue transmitting, and the battery material of different band gap.
Detailed description of the invention
Fig. 1 is the thermogravimetric curve of polymer P 1；
Fig. 2 is uv-visible absorption spectra of the polymer P 4 under filminess；
Fig. 3 is photoluminescence spectra of the polymer P 2 under filminess.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
The sum of the molar fraction of each unit is defaulted as 1 in obtained polymer architecture in the present embodiment, therefore is not required to
The molar fraction of all unit components is marked out, does not mark the molar fraction default of the structural unit of molar fraction
=1- has marked the sum of molar fraction of structural unit of molar fraction.In P1Molar fraction be 1-
In 0.1=0.9, i.e. P1Subscript it is practical be 0.9；As x1=x2, can not both mark.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Embodiment 1
The preparation of compound 4 and 5
(1) preparation of compound 1
Under nitrogen protection, iodo- 9, the 9- dimethyl fluorene (3.99g, 10mmol) of the bromo- 7- of 2-, 4- are added into 300mL two-mouth bottle
Bromo- 1,2- dimercaptobenzene (2.21g, 10mmol), sodium tert-butoxide (4.81g, 50mmol), tris(dibenzylideneacetone) dipalladium
(458mg, 0.5mmol), bis- (2- diphenylphosphine phenyl) ethers (269mg, 0.5mmol) and 120mL toluene are heated to 50 DEG C of stirrings
Reaction 6 hours.Product is extracted with dichloromethane in end of reaction, washs organic phase with saturated sodium-chloride water solution, decompression boils off molten
Agent, crude product petroleum ether: the mixed solvent of methylene chloride=6:1 (v/v) makees eluant, eluent column Chromatographic purification, obtains white solid
3.11g, yield 63%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(2) preparation of compound 2
Under nitrogen protection, into 300mL two-mouth bottle be added compound 1 (4.92g, 10mmol), bromoethane (2.18g,
20mmol), sodium hydroxide (4.00g, 50mmol) and 150mL n,N-Dimethylformamide, stirring at normal temperature are reacted 12 hours.Instead
It should finish, product is extracted with dichloromethane, wash organic phase 5 times with saturated sodium-chloride water solution and clarified to water layer, is removed under reduced pressure
Solvent, crude product petroleum ether: the mixed solvent of methylene chloride=7:1 (v/v) makees eluant, eluent column Chromatographic purification, obtains white solid
4.00g, yield 77%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(3) preparation of compound 3
Compound 2 (5.20g, 10mmol) and 150mL tetrahydrofuran and acetic acid mixed solvent are added into 300mL two-mouth bottle
(v:v=1:1), aqueous hydrogen peroxide solution (1mL, 10mmol) is slowly added dropwise, is stirred to react 12 hours.End of reaction uses dichloro
Methane extracts product, is washed with saturated sodium-chloride water solution, solvent is removed under reduced pressure, crude product petroleum ether: methylene chloride=5:1
(v/v) mixed solvent makees eluant, eluent column Chromatographic purification, obtains white solid 3.87g, yield 72%.1H NMR、13CNMR, MS and
Elemental analysis is the result shows that obtained compound is target product.
(4) preparation of compound 4 and 5
Under nitrogen protection, compound 3 (5.36g, 10mmol), phosphorus pentoxide (2.84g, 20mmol) and 50mL fluoroform
Base sulfonic acid is added 300mL two-mouth bottle and has reacted and reaction solution is poured slowly into 200mL ice water at stirring at normal temperature 24 hours, filters
Filter residue is rinsed with deionized water afterwards.Filter residue no longer purifies, and is transferred in the 300mL two-mouth bottle of 50mL pyridine, back flow reaction 12
After hour, reaction solution is poured into ice water and is quenched, appropriate hydrochloric acid is added.Product is extracted with dichloromethane, uses saturated sodium chloride water
Solution washing, solvent is removed under reduced pressure, crude product petroleum ether: the mixed solvent of methylene chloride=8:1 (v/v) makees eluant, eluent column layer
Analysis purification, obtaining compound 4 is white solid 1.77g, and yield 36%, obtaining compound 5 is white solid 1.33g, yield 27%.1H
NMR、13C NMR, MS and elemental analysis are the result shows that obtained compound is target product.
The chemical equation for synthesizing compound 1~5 is as follows:
Embodiment 2
The preparation of compound M1
Compound 4 (4.90g, 10mmol) and 150mL tetrahydrofuran and acetic acid mixed solvent are added into 300mL two-mouth bottle
(v:v=1:1), aqueous hydrogen peroxide solution (10mL, 100mmol) is added dropwise, is stirred to react 12 hours.End of reaction uses dichloromethane
Alkane extracts product, is washed with saturated sodium-chloride water solution, solvent is removed under reduced pressure, crude product petroleum ether: methylene chloride=3:1
(v/v) mixed solvent makees eluant, eluent column Chromatographic purification, obtains white solid 4.44g, yield 80%.1H NMR、13C NMR, MS and
The result shows that obtained compound is target product, chemical equation is as follows for elemental analysis:
Embodiment 3
The preparation of compound M2
Compound 5 (4.90g, 10mmol) and 150mL tetrahydrofuran and acetic acid mixed solvent are added into 300mL two-mouth bottle
(v:v=1:1), aqueous hydrogen peroxide solution (10mL, 100mmol) is slowly added dropwise, is stirred to react 12 hours.End of reaction, with two
Chloromethanes extracts product, is washed with saturated sodium-chloride water solution, solvent is removed under reduced pressure, crude product petroleum ether: methylene chloride=
The mixed solvent of 3:1 (v/v) makees eluant, eluent column Chromatographic purification, obtains white solid 4.72g, yield 85%.1H NMR、13C NMR、
The result shows that obtained compound is target product, chemical equation is as follows for MS and elemental analysis:
Embodiment 4
The preparation of compound 9 and 10
(1) preparation of compound 6
Under nitrogen protection, the iodo- dibenzothiophenes of 2- (3.10g, 10mmol), 4- bromo- 1,2- are added into 300mL two-mouth bottle
Dimercaptobenzene (2.21g, 10mmol), sodium tert-butoxide (4.81g, 50mmol), tris(dibenzylideneacetone) dipalladium (458mg,
0.5mmol), bis- (2- diphenylphosphine phenyl) ethers (269mg, 0.5mmol) and 150mL toluene, being heated to 50 DEG C, to be stirred to react 8 small
When.Product is extracted with dichloromethane in end of reaction, washs organic phase with saturated sodium-chloride water solution, decompression boils off solvent, thick to produce
Object petroleum ether: the mixed solvent of methylene chloride=7:1 (v/v) makees eluant, eluent column Chromatographic purification, obtains white solid 2.43g, produces
Rate 60%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(2) preparation of compound 7
Under nitrogen protection, into 300mL two-mouth bottle be added compound 6 (4.03g, 10mmol), bromoethane (2.18g,
20mmol), sodium hydroxide (4.00g, 50mmol) and 180mL n,N-Dimethylformamide, stirring at normal temperature are reacted 12 hours.Instead
It should finish, product is extracted with dichloromethane, wash organic phase 5 times with saturated sodium-chloride water solution and clarified to water layer, is removed under reduced pressure
Solvent, crude product petroleum ether: the mixed solvent of methylene chloride=8:1 (v/v) makees eluant, eluent column Chromatographic purification, obtains white solid
2.32g, yield 54%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
(3) preparation of compound 8
Compound 7 (4.31g, 10mmol) and 150mL tetrahydrofuran and acetic acid mixed solvent are added into 300mL two-mouth bottle
(v:v=1:1), aqueous hydrogen peroxide solution (1mL, 10mmol) is added dropwise, is stirred to react 12 hours.End of reaction uses methylene chloride
Product is extracted, is washed with saturated sodium-chloride water solution, solvent is removed under reduced pressure, crude product petroleum ether: methylene chloride=6:1 (v/
V) mixed solvent makees eluant, eluent column Chromatographic purification, obtains white solid 3.03g, yield 68%.1H NMR、13CNMR, MS and element
Analysis is the result shows that obtained compound is target product.
(4) preparation of compound 9 and 10
Under nitrogen protection, compound 8 (4.47g, 10mmol), phosphorus pentoxide (2.84g, 20mmol) and 50mL fluoroform
Base sulfonic acid is added 300mL two-mouth bottle and has reacted and reaction solution is poured slowly into 200mL ice water at stirring at normal temperature 24 hours, filters
Filter residue is rinsed with deionized water afterwards.Filter residue no longer purifies, and is transferred in the 300mL two-mouth bottle of 50mL pyridine, back flow reaction 12
After hour, reaction solution is poured into ice water and is quenched, appropriate hydrochloric acid is added.Product is extracted with dichloromethane, uses saturated sodium chloride water
Solution washing, solvent is removed under reduced pressure, crude product petroleum ether: the mixed solvent of methylene chloride=8:1 (v/v) makees eluant, eluent column layer
Analysis purification, obtaining compound 9 is white solid 1.09g, and yield 27%, obtaining compound 10 is white solid 1.20g, yield 30%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
The chemical equation for synthesizing compound 6~10 is as follows:
Embodiment 5
The preparation of compound M3
(1) preparation of compound 11
Compound 9 (4.01g, 10mmol) and 150mL tetrahydrofuran and acetic acid mixed solvent are added into 300mL two-mouth bottle
(v:v=1:1), aqueous hydrogen peroxide solution (10mL, 100mmol) is slowly added dropwise, is stirred to react 12 hours.End of reaction, with two
Chloromethanes extracts product, is washed with saturated sodium-chloride water solution, solvent is removed under reduced pressure, crude product petroleum ether: methylene chloride=
The mixed solvent of 6:1 (v/v) makees eluant, eluent column Chromatographic purification, obtains white solid 4.38g, yield 88%.1H NMR、13C NMR、
MS and elemental analysis are the result shows that obtained compound is target product.
(2) preparation of compound M3
Under nitrogen protection, compound 11 (4.97g, 10mmol) is dissolved in the 120mL concentrated sulfuric acid, is protected from light N- bromine under state
Reaction flask is added in three times for succimide (1.87g, 10.5mmol), is stirred 12 hours under room temperature.End of reaction will react
Liquid is poured slowly into ice water, and filtering, filter residue is recrystallized three times with chlorobenzene, obtains white solid 3.29g, yield 57%.1H NMR
、13C NMR, MS and elemental analysis are the result shows that obtained compound is target product.
The chemical equation for synthesizing compound 11 and M3 is as follows:
Embodiment 6
The preparation of compound M4
(1) preparation of compound 12
Compound 9 (4.01g, 10mmol) and 150mL tetrahydrofuran and acetic acid mixed solvent are added into 300mL two-mouth bottle
(v:v=1:1), aqueous hydrogen peroxide solution (10mL, 100mmol) is slowly added dropwise, is stirred to react 12 hours.End of reaction, with two
Chloromethanes extracts product, is washed with saturated sodium-chloride water solution, solvent is removed under reduced pressure, crude product petroleum ether: methylene chloride=
The mixed solvent of 6:1 (v/v) makees eluant, eluent column Chromatographic purification, obtains white solid 4.07g, yield 82%.1H NMR、13C NMR、
MS and elemental analysis are the result shows that obtained compound is target product.
(2) preparation of compound M4
Under nitrogen protection, compound 12 (4.97g, 10mmol) is dissolved in the 100mL concentrated sulfuric acid, is protected from light N- bromine under state
Reaction flask is added in three times for succimide (1.87g, 10.5mmol), is stirred 12 hours under room temperature.End of reaction will react
Liquid is poured slowly into ice water, and filtering, filter residue is recrystallized three times with chlorobenzene, obtains white solid 3.17g, yield 55%.1H NMR
、13C NMR, MS and elemental analysis are the result shows that obtained compound is target product.
The chemical equation for synthesizing compound 12 and M4 is as follows:
Embodiment 7
The preparation of polymer P 1
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryl) -9,9- di-n-octyl fluorenes
Bromo- 9, the 9- di-n-octyl fluorenes (115.0mg, 0.24mmol) of (192.6mg, 0.3mmol), 2,7- bis- and compound M1 (33.3mg,
It 0.06mmol) is dissolved in 12mL toluene, adds tetraethyl aqueous hydroxylamine solution (1mL, wt%=20%), palladium acetate (1mg)
With tricyclohexyl phosphine (2mg)；After being heated to 80 DEG C of reactions 24 hours, phenyl boric acid (20mg) is added and blocks 6 hours, adds 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 uses methanol, acetone, n-hexane extracting, is carried out using toluene as eluent with neutral alumina with toluene dissolution polymer
Column Chromatographic purification；The toluene solution of concentrated polymer, precipitating filters in methanol solution again, dry, obtains chartreuse fibre
Tie up shaped polymer.Pass through1H NMR spectra and elemental analysis confirm to obtain subject polymer.Gel permeation chromatography: Mn=
101KDa, PDI=2.27.Fluorescence quantum yield: 0.63.Chemical equation is as follows:
Attached drawing 1 is the thermogravimetric curve of polymer P 1, and test condition is 30 DEG C and is to slowly warm up to 850 DEG C, and heating rate is
20 DEG C/min.The thermal weight loss temperature of 1 mass loss 5% of polymer P is 433 DEG C as seen from the figure, and it is fine to illustrate that polymer P 1 has
Thermal stability.
Embodiment 8
The preparation of polymer P 2
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryl) -9,9- di-n-octyl fluorenes
Bromo- 9, the 9- di-n-octyl fluorenes (115.0mg, 0.24mmol) of (192.6mg, 0.3mmol), 2,7- bis-, 4,6- dibromo benzo thiophene two
Azoles (8.8mg, 0.03mmol) and compound M2 (16.6mg, 0.03mmol) are dissolved in 12mL toluene, add tetraethyl hydroxyl
Amine aqueous solution (1mL, wt%=20%), palladium acetate (1mg) and tricyclohexyl phosphine (2mg)；After being heated to 80 DEG C of reactions 24 hours,
Phenyl boric acid (20mg) is added to block 6 hours, adds bromobenzene (0.2mL) and blocks 6 hours；Reaction stops, after cooling, by organic phase
Precipitating is in methanol (300mL), filtering, and after dry, crude product successively uses methanol, acetone, n-hexane extracting, is dissolved with toluene poly-
It closes object and carries out column Chromatographic purification with neutral alumina using toluene as eluent；The toluene solution of concentrated polymer, again precipitating
In methanol solution, filter, it is dry, obtain chartreuse fibrous polymer.Pass through1H NMR spectra and elemental analysis confirmation
Obtain subject polymer.Gel permeation chromatography: Mn=87KDa, PDI=2.11.Fluorescence quantum yield: 0.80.Chemical reaction side
Formula is as follows:
Attached drawing 2 is the photoluminescence spectra under filminess of polymer P 2, as seen from the figure the maximum hair of polymer P 2
The a length of 538nm of ejected wave is green emission.
Embodiment 9
The preparation of polymer P 3
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryl) -9,9- di-n-octyl fluorenes
Bromo- 9, the 9- di-n-octyl fluorenes (115.0mg, 0.24mmol) of (192.6mg, 0.3mmol), 2,7- bis-, 4,7- it is bis- (5- bromine (and 4- oneself
Base thiophene) -2- base) -2,1,3- diazosulfide (18.8mg, 0.03mmol) and compound M4 (17.3mg, 0.03mmol) are molten
Solution adds tetraethyl aqueous hydroxylamine solution (1mL, wt%=20%), palladium acetate (1mg) and tricyclohexyl phosphine in 12mL toluene
(2mg)；After being heated to 80 DEG C of reactions 24 hours, phenyl boric acid (20mg) is added and blocks 6 hours, adds bromobenzene (0.2mL) sealing end 6
Hour；Reaction stops, and after cooling, by organic phase precipitating in methanol (300mL), filtering, after dry, crude product successively uses first
Alcohol, acetone, n-hexane extracting, dissolve polymer with toluene, using toluene as eluent, carry out column chromatography with neutral alumina and mention
It is pure；The toluene solution of concentrated polymer, precipitating filters in methanol solution again, dry, obtains the polymerization of chartreuse threadiness
Object.Pass through1H NMR spectra and elemental analysis confirm to obtain subject polymer.Gel permeation chromatography: Mn=76KDa, PDI=
2.01.Fluorescence quantum yield: 0.72.Chemical equation is as follows:
Embodiment 10
The preparation of polymer P 4
Under nitrogen protection, by 2,7- bis- (tin trimethyl) -4,9- dihydro -4,4,9,9- tetra- (4- hexyl phenyl)-benzos two
Indeno [1,2-b:5,6-b ']-Dithiophene (369.9mg, 0.3mmol) and 2,7- bis- bromo- 5,5 ', 10,10 '-four oxygen thianthrenes
(131.4mg, 0.3mmol) is dissolved in 12mL dry toluene, adds tris(dibenzylideneacetone) dipalladium (4mg) and three (2-
Tolyl) phosphine (8mg).It is reacted 24 hours at 100 DEG C, carries out first time sealing end, reaction 6 with 2- (tributyl tin) thiophene (20mg)
After hour, second is carried out with 2- bromothiophene (30mg) and is blocked, the reaction was continued 6 hours.Reaction was completed, drops to room temperature wait react
Afterwards, in methyl alcohol by reaction solution precipitating, the polymer being obtained by filtration successively carries out soxhlet type with methanol, acetone, is with chloroform
Eluant, eluent carries out column chromatography, dry, obtains red fiber shaped polymer.Pass through1H NMR spectra and elemental analysis confirm to obtain mesh
Mark polymer.Gel permeation chromatography: Mn=43KDa, PDI=1.83.Chemical equation is as follows:
Attached drawing 3 is the ultraviolet-visible absorption spectroscopy under filminess of polymer P 4, and polymer P 4 is 300 as seen from the figure
~650nm wave-length coverage has preferable absorption, is 2.01eV according to the band gap that ABSORPTION EDGE is calculated.
Embodiment 11
Take well in advance square resistance be 20 Ω tin indium oxide (ITO) glass, successively use acetone, detergent, go from
Sub- water and isopropanol ultrasonic cleaning, plasma treatment 10 minutes.The polyethoxy for having polystyrolsulfon acid is mixed in spin coating on ITO
Thiophene (PEDOT:PSS) film, with a thickness of 40nm.PEDOT:PSS film is 8 hours dry at 80 DEG C in vacuum drying oven.To then it gather
The xylene solution (1wt.%) for closing object is spin-coated on the surface of PEDOT:PSS film, with a thickness of 80nm.Finally on the light-emitting layer successively
The metal Al layer of CsF and the 120nm thickness of one layer of 1.5nm thickness is deposited, device architecture is ITO/PEDOT:PSS/ polymer/CsF/
Al.To compare, polymeric light-emitting devices are also prepared for homopolymerization n-octyl fluorenes (PFO) luminescent layer.
1 polymer electroluminescent device performance of table
Device architecture: ITO/PEDOT:PSS/ polymer/CsF/Al
It is obtained as it can be seen from table 1 introducing 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit M1 in polyfluorene main chain
The device efficiency (including current efficiency, brightness, open bright voltage) in single layer device of polymer P 1 is obviously improved, and blue light light
Spectrum is held essentially constant.Device based on polymer P 2 and P3 has respectively obtained efficient green light and red emission, corresponding
Chromaticity coordinates is respectively (0.31,0.60) and (0.65,0.37).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. one kind contains 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer, it is characterised in that chemical structure is following institute
Show one of structure:
In formula, x1、x2For the molar fraction of unit component, meet: 0≤x1< 1,0 < x2≤ 1, x1+x2=1；N is repetitive unit, n
=10~1000；
Y is C (R1)2、NR1、Si(R1)2、O、S、SO2Or CO2；Wherein R1Alkyl, carbon atom number 3~30 for carbon atom number 1~30
Naphthenic base, the aromatic heterocycle that carbon atom number is 6~60 aromatic hydrocarbyls or carbon atom number is 3~60；
Ar be the aromatic hydrocarbyl of carbon atom number 6~60, carbon atom number 3~60 aromatic heterocycle in it is one or more, when
When Ar represents multiple groups, the sum of molar fraction of multiple groups is equal to x1。
2. according to claim 1 contain 9,9,10,10- tetra- oxygen-five yuan of thianthrene condensed ring unit polymer, it is characterised in that:
One of chemical structure that the Ar is as follows or the derivative of chemical structure as follows are a variety of:
Wherein, R2It is 6~60 aromatic hydrocarbons for the alkyl of carbon atom number 1~30, the naphthenic base of carbon atom number 3~30, carbon atom number
The aromatic heterocycle that base or carbon atom number are 3~60；R3、R4、R5Independently it is expressed as H, D, F, CN, alkenyl, alkynyl, amine
Base, nitro, acyl group, alkoxy, carbonyl, sulfuryl, the alkyl of carbon atom number 1~30, the naphthenic base of carbon atom number 3~30, carbon are former
The aromatic heterocycle that subnumber is 6~60 aromatic hydrocarbyls or carbon atom number is 3~60.
3. a kind of preparation of five yuan of condensed ring unit polymer according to claim 1 or 2 containing tetra- oxygen of 9,9,10,10--thianthrene
Method, it is characterised in that the following steps are included:
The monomer of monomer containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring units and the unit containing Ar is polymerize by Suzuki
After reaction, phenyl boric acid is sequentially added, bromobenzene carries out end capping reaction and contains 9,9,10,10- tetra- oxygen-five yuan of thianthrene to get to described
Condensed ring unit polymer；
Alternatively,
The monomer of monomer containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring units and the unit containing Ar is polymerize by Stille
Reaction sequentially adds tributyl tin thiophene, bromo thiophene progress end capping reaction, obtains described containing 9,9,10,10- tetra- oxygen-thiophene
Five yuan of condensed ring unit polymer of anthracene.
4. according to claim 3 contain 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene preparation method,
It is characterized in that:
The preparation side of five yuan of condensed ring unit polymer containing tetra- oxygen of 9,9,10,10--thianthrene is obtained by Suzuki polymerization reaction
Method specifically includes the following steps:
(1) under inert gas protection, 9,9,10,10- tetra- oxygen-five yuan of condensed ring units of thianthrene monomers, the unit containing Ar will be contained
Monomer dissolves in a solvent, and catalyst and alkali is then added, and is heated to 60~100 DEG C of generation Suzuki polymerization reactions, when reaction
Between be 12~36h；
(2) phenyl boric acid, heat preservation the reaction was continued 6~12h is added；It adds bromobenzene and continues 6~12h of insulation reaction, after reaction
Gained reaction solution is purified up to target product.
5. according to claim 4 contain 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene preparation method,
It is characterized in that:
Solvent described in step (1) is at least one of toluene, tetrahydrofuran, dimethylbenzene；The catalyst is acetic acid
At least one of palladium, tricyclohexyl phosphine and tetrakis triphenylphosphine palladium；The alkali is the water-soluble of basic matterial or basic matterial
At least one of liquid；
The monomer finger tip base of five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene described in step (1) be double bromines, double iodine,
The monomer of double boric acid or double borates；The monomer finger tip base of the unit containing Ar is double borates, double boric acid, double bromines or double iodine
Monomer；
The monomer of the monomer and unit containing Ar of five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene described in step (1)
Dosage meets the monomer integral molar quantity containing double borates and/or double boric acid functional groups and the list containing double bromines and/or Shuan Dian functional group
Body integral molar quantity is equal；The dosage of the catalyst is 2 ‰~the 3% of all reaction monomers moles total numbers；The alkali
Dosage refers to that the mole of basic matterial is 2~5 times of monomer integral molar quantity；The dosage of phenyl boric acid described in step (2) is institute
There are 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), which refers to, is cooled to room temperature gained reaction solution, is added to precipitating in methanol, filters, dry
Crude product is obtained, crude product successively uses methanol, acetone, n-hexane extracting, and again with toluene dissolves, column chromatography for separation, after concentration again
Precipitating filters in methanol solution, dry, obtains target product.
6. according to claim 3 contain 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene preparation method,
It is characterized in that:
The preparation side of five yuan of condensed ring unit polymer containing tetra- oxygen of 9,9,10,10--thianthrene is obtained by Stille polymerization reaction
Method specifically includes the following steps:
(1) under inert gas protection, 9,9,10,10- tetra- oxygen-five yuan of condensed ring units of thianthrene monomers, the unit containing Ar will be contained
Monomer dissolves in a solvent, and catalyst is then added, is heated to 80~150 DEG C of generation Stille polymerization reactions, and the reaction time is
12~36h；
(2) tributyl tin thiophene, heat preservation the reaction was continued 6~12h is added；It adds bromo thiophene and continues 6~12h of insulation reaction,
Gained reaction solution is purified up to target product after reaction.
7. according to claim 6 contain 9,9,10,10- tetra- oxygen-five yuan of condensed ring unit polymer of thianthrene preparation method,
It is characterized in that:
Solvent described in step (1) is at least one of dry toluene, tetrahydrofuran, dimethylbenzene, chlorobenzene, dichloro-benzenes；Institute
The Stille polymerization catalyst stated is in tetrakis triphenylphosphine palladium, bis- (dibenzyl subunit acetone) palladiums and three (o-methyl-phenyl) phosphorus
It is at least one；
The monomer finger tip base of five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene described in step (1) is double bromines or double iodine
Monomer；The monomer finger tip base of the unit containing Ar is the monomer of double methyl tin or double butyl tins；
The monomer of the monomer and unit containing Ar of five yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene described in step (1)
Dosage meet monomer integral molar quantity containing double methyl tin and/or double butyl tin functional groups with containing double bromines and/or Shuan Dian functional group
Monomer integral molar quantity is equal；The dosage of the catalyst is 2 ‰~the 3% of reaction monomers moles total number；Described in step (2)
Tributyl tin thiophene dosage be reaction monomers moles total number 10~40%；The dosage of the bromo thiophene is tributyl
5~40 times of tin thiophene mole；
Purifying described in step (2), which refers to, is cooled to room temperature gained reaction solution, is added to stir in methanol and precipitate, and filters, and does
Dry to obtain crude product, crude product successively uses methanol, acetone extraction, then is dissolved with chlorobenzene, and column chromatography for separation, precipitating arrives again after concentration
In methanol, filter, it is dry, obtain target product.
8. according to claim 1 or 2 polymerize containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer in preparation
Application in the luminescent layer of object light emitting diode and the active layer of polymer solar cells.
9. five yuan of condensed ring unit polymer according to claim 8 containing tetra- oxygen of 9,9,10,10--thianthrene are preparing polymer
Application in the luminescent layer of light emitting diode and the active layer of polymer solar cells, it is characterised in that:
The luminescent layer for preparing polymer LED is the following steps are included: contain tetra- oxygen of 9,9,10,10--for described
Five yuan of condensed ring unit polymer of thianthrene are dissolved in organic solvent, then by spin coating, inkjet printing or printing film forming to get described in
The luminescent layer of polymer LED；
The active layer for preparing polymer solar cells will be the following steps are included: will contain five yuan of tetra- oxygen of 9,9,10,10--thianthrene
Condensed ring unit polymer mixes at least one solar cell donor or/and acceptor material and is dissolved in organic solvent, then passes through rotation
It applies, inkjet printing or printing film forming are to get the active layer for arriving the polymer solar cells.
10. five yuan of condensed ring unit polymer according to claim 9 containing tetra- oxygen of 9,9,10,10--thianthrene are preparing polymer
Application in the luminescent layer of light emitting diode and the active layer of polymer solar cells, it is characterised in that:
Preparing organic solvent described in the luminescent layer of polymer LED is dimethylbenzene, chlorobenzene or tetrahydrofuran；
Preparing organic solvent described in the active layer of polymer solar cells is chlorobenzene or dichloro-benzenes.
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| CN112047958B (en) * | 2020-09-14 | 2023-01-31 | 广东技术师范大学 | Organic conjugated micromolecule material containing thianthrene terminal group and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061463A (en) * | 2015-08-15 | 2015-11-18 | 华南理工大学 | Nine-membered fused ring derivatives as well as synthesis method and application thereof |
| CN106565960A (en) * | 2016-11-11 | 2017-04-19 | 华南理工大学 | Block copolymer luminescent material containing dibenzothiophene-S,S-dioxide, preparation method and application thereof |
| CN106832229A (en) * | 2016-12-09 | 2017-06-13 | 华南理工大学 | Polymer and its application containing the hexa-atomic sulfuryl condensed ring unit of dibenzo |
-
2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061463A (en) * | 2015-08-15 | 2015-11-18 | 华南理工大学 | Nine-membered fused ring derivatives as well as synthesis method and application thereof |
| CN106565960A (en) * | 2016-11-11 | 2017-04-19 | 华南理工大学 | Block copolymer luminescent material containing dibenzothiophene-S,S-dioxide, preparation method and application thereof |
| CN106832229A (en) * | 2016-12-09 | 2017-06-13 | 华南理工大学 | Polymer and its application containing the hexa-atomic sulfuryl condensed ring unit of dibenzo |
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