CN108586712A - A kind of electroluminescent monomer, electroluminescent polymer and its preparation method and application - Google Patents
A kind of electroluminescent monomer, electroluminescent polymer and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to organic photoelectric field, a kind of electroluminescent monomer, electroluminescent polymer and its preparation method and application are disclosed.The structural formula of the electroluminescent polymer of the present invention is as described below, it is 10,12 indanes [2,1 b] it is fluorene structured on the basis of introduce naphthalene nucleus, both remaining 10,12 indanes [2,1 b] fluorenes can effectively inhibit exciplex generation and conjugate length to become smaller, cause emission wavelength hypsochromic shift dynamic, the advantages of being conducive to emit purer blue light；The dissymmetrical structure of its structure itself advantageously forms unformed film again, inhibits fluorescent quenching.Electroluminescent polymer of the present invention has preferable solubility property, it is processed suitable for solution, device manufacturing cost can be reduced, and large area flexible OLED device can be prepared, and when preparing electroluminescent device without annealing, preparation process is simpler, has huge development potentiality and foreground in organic electronic display field.
Description
Technical field
The invention belongs to organic photoelectric field, more particularly to a kind of electroluminescent monomer, electroluminescent polymer and its system
Preparation Method and application.
Background technology
Using organic material as luminescent material in Organic Light Emitting Diode (OLED) display, material structure is easy modification
And improve, range of choice is wide；Driving voltage is low, only needs the DC voltage of 3~12V；Can self-luminous, do not need backlight；Extensively regard
Angle is close to 180 °；Fast response time, up to 1 μ s magnitudes；In addition, also light weight, it is ultra-thin, large scale, flexible face can be made
The advantages that plate, easy processing and forming.Due to the numerous advantage of OLED display, the extensive pass of scientific circles and industrial quarters has been obtained
Note, since Kodak in 1987 develops OLED device, so far, existing more mechanisms input resources arrive OLED technology
Exploitation.By the fast development of decades, OLED flat panel displays are tending to ripe, and are occupied in flat display field
One seat, but still need to continue to improve in service life, stability, cost etc..
OLED device is prepared at present using vacuum evaporation process, and instrument and equipment is expensive.Stock utilization it is low (~
20%) so that OLED product prices are high.Solution processing technology can make up the deficiency of vacuum evaporation, gradually attract scientific research
The concern of mechanism and manufacturer of company.Polymer can form the film of high quality, be not easy to crystallize；Chemical constitution, example can also be changed
Such as, by the regulation and control to conjugate length, the transformation of substituent group, the main, adjustment of side chain type structure and the change of rate of charge etc. come real
Now shining such as the different colours of red, green, blue；Also there is solution processing, such as spin coating, inkjet printing to print simultaneously, it is roll-to-roll
Etc. modes form a film, can large scale molding the advantages of.
6,12- indanes [1,2-b] fluorenes (abbreviation indenofluorene) is a kind of common fluorenes class formation, indenofluorene (a) and its same
The chemical structural formula of enantiomers (b) is as follows：
Wherein, (b) be indenofluorene isomer, i.e. 10,12- indanes [2,1-b] fluorenes, effective conjugation of configuration
Length is reduced.The rigidity and flatness of indenofluorene improve, and optics, chemistry and electrical property all increase, but are based on
The fluorescent molecular of indenofluorene easily occurs to assemble or formed excimer, leads to shining at long wave, to reduce device
Excitation purity and efficiency.
European organic chemistry (European Journal of Organic Chemitry, 2012,14:2748-2755)
The compound (c) containing indenofluorene and its isomer and (d) are reported, structural formula is as follows：
By experiment test, it is found that control compounds (c), the absorption spectrum of compound (d) have larger blue shift, emission spectrum
But red shift illustrates that the performance of its excitation state has large change, can inhibit the formation of excimer.
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 electroluminescent
Monomer.
Another object of the present invention is to provide the preparation methods of above-mentioned electroluminescent monomer.
Another object of the present invention is to provide the electroluminescent polymer that above-mentioned electroluminescent polymerized monomer polymerize.
Another object of the present invention is to provide the preparation method of above-mentioned electroluminescent polymer.
Still a further object of the present invention is to provide the application of above-mentioned electroluminescent polymer.
The purpose of the present invention is realized by following proposal：
A kind of electroluminescent monomer M1, structural formula are as follows：
Wherein, R be straight chain with 1~20 carbon atom, branched or cricoid alkyl, there is 1~20 carbon atom
Straight chain, branched either cricoid alkoxy there is the straight chain of 2~20 carbon atoms, branched or cricoid alkenyl, have 2
The straight chain of~20 carbon atoms, branched either cricoid alkynyl have the straight chain, branched or cricoid of 2~20 carbon atoms
Alkyl carbonyl, the heteroatomic aryl or heteroaryl for being selected from O, N, S with 4~20, the miscellaneous original for being selected from O, N, S with 4~20
The aralkyl or heteroaryl alkyl of son, the heteroatomic aryloxy group or heteroaryloxy for being selected from O, N, S with 4~20 have 4
~20 heteroatomic alkoxy aryls or heteroarylalkoxy for being selected from O, N, S；
A kind of preparation method of above-mentioned electroluminescent monomer M1, mainly includes the following steps that：
(1) with ethyl alcohol esterification occurs under concentrated sulfuric acid existence condition for o-bromobenzoic acid, and it is (adjacent that dehydration obtains compound 1
Bromobenzoic acid ethyl ester), then compound 1 (o-bromo-benzoic acid ethyl ester) is dissolved completely in anhydrous tetrahydro furan, in indifferent gas
Under body environment, after -78 DEG C are added n-BuLi stirring 1 hour, 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- bis- is added
Oxa- borine warms naturally to room temperature reaction 12 hours, obtains compound 2 (ethyl 2- (4,4,5,5- tetramethyls -1,3,2- bis-
Oxa- borine -2- bases) ethyl benzoate)；
(2) compound 2, Isosorbide-5-Nitrae-dibromine naphthalene, four butyl bromation amine and catalyst are added in toluene under an inert atmosphere,
Then K is added2CO3Aqueous solution reacts 12h at 80~90 DEG C, obtains (ethyl 2- (4- bromonaphthalene base -1- bases) the benzoic acid second of compound 3
Ester)；
(3) compound 3 is dissolved in anhydrous methylene chloride under an inert atmosphere, aluminium chloride is added under the conditions of 0 DEG C, then
16h is reacted at room temperature, obtains compound 4 (bromo- 7H- benzos [c] fluorenyl -7- ketone of 5-)；
(4) compound 4, hydrazine hydrate and potassium hydroxide are dissolved in diethylene glycol (DEG), compound 5 is obtained after heating reflux reaction 12h
(bromo- 7H- benzos [c] fluorenes of 5-)；
(5) under inert gas environment, compound 5 is dissolved in toluene, the sodium hydrate aqueous solution of 50wt% is added, is heated
To 80 DEG C of stirring 1h, RBr is added, isothermal reaction obtains compound 6 after 12 hours；
(6) under inert gas environment, compound 6 and compound 2 are coupled by suzuki, obtain compound 7；
(7) compound 7 is dissolved completely in anhydrous tetrahydro furan, at ambient temperature, grignard reagent RMgBr is added,
80 DEG C of back flow reaction 16h are heated to, compound 8 is obtained；
(8) compound 8 is dissolved in anhydrous methylene chloride, boron trifluoride ether solution is added, react at room temperature 2h, then will
Gained reaction solution purifies to obtain compound 9；
(9) compound 9 is dissolved in anhydrous chloroform, under -20~0 DEG C of cryogenic conditions, in ferric trichloride catalytic
Under effect, bromine is added and carries out bromination reaction, gained reaction solution is obtained into M1 after purification after reaction；
The synthetic route of electroluminescent monomer M1 is described in detail below：
The definition of the R in the grignard reagent (RMgBr) described in RBr, step (7) described in step (5) with it is above-mentioned
The definition of R in the structure of electroluminescent monomer M1 is consistent, preferably-C6H13。
Compound 1 used in step (1), n-BuLi and 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxies
The molar ratio of miscellaneous borine is 1:1~1.2：2~3, preferably 1:1.1:3；
Compound 2,1,4- dibromine naphthalenes, four butyl bromation amine described in step (2) and K2CO3Molar ratio be 1：0.91：
0.045：4.54；Wherein the amount of catalyst is catalytic amount；
The molar ratio of compound 3 and aluminium chloride described in step (3) is 1：2；
The molar ratio of compound 4, hydrazine hydrate and potassium hydroxide described in step (4) is 1:31.8:5；
The molar ratio of compound 5 and RBr described in step (5) is 1:2.1；
Suzuki couplings described in step (6) refer to reacting 8~16h in 70~100 DEG C under alkali and catalyst action；
The molar ratio of compound 6 and compound 2 described in step (6) is 1:1.1；
The molar ratio of compound 7 and grignard reagent RMgBr described in step (7) is 1:5；
The molar ratio of compound 8 and boron trifluoride described in step (8) is 1:1~5；Trifluoro described in step (8)
The concentration for changing borate ether solution is preferably 2mol/L；
Bromination reaction described in step (9) refer at -5~0 DEG C reaction 12~for 24 hours；The compound 9 and bromine
Molar ratio is 1:2~3；
A kind of electroluminescent polymer obtained by above-mentioned electroluminescent monomer polymerization, structure are as follows：
Wherein, polymerization degree n is 1~1000；X represents molar fraction, 0≤x≤1；
Ar is one or more in following conjugation or non-conjugated structure unit：
Wherein, R1For H, aryl, triphenylamine base, the straight chain of carbon atom number 1-20 or branched alkyl or carbon atom number 1-
20 alkoxy；Z1、Z2It is former to be independently expressed as H, D, F, alkenyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxy, carbon
Naphthenic base that alkyl that subnumber is 1~30, carbon atom number are 3~30, carbon atom number are 6~60 aromatic hydrocarbyls or carbon atom number
For 3~60 aromatic heterocycle.
The sum of the molar fraction of each unit is defaulted as 1 in polymer architecture in the present invention, therefore need not will be all
The molar fraction of unit component, which marks out, to be come, and the molar fraction acquiescence=1- for not marking the structural unit of molar fraction has been marked
The sum of molar fraction of structural unit of molar fraction.When Ar represents multiple groups, the sum of molar fraction of multiple groups etc.
In 1-x.
A kind of preparation method of above-mentioned electroluminescent polymer, mainly includes the following steps that：
(1) under inert gas protection, the list of the polymeric monomeric unit M1 and the structure containing Ar are completely dissolved with solvent
Body is heated to 60~100 DEG C and Suzuki polymerizations occurs instead under catalyst action and the effect of tetraethyl ammonium hydroxide aqueous solution
It answers, the reaction time is 12~36h；
(2) step (1) is added phenyl boric acid after reaction, constant temperature the reaction was continued 6~12h；It adds bromobenzene and continues constant temperature
React 6~12h；Reaction purifies gained reaction solution up to target product after stopping.
In step (1), the organic solvent is toluene, tetrahydrofuran, dimethylbenzene, dioxane, N, N- dimethyl methyls
At least one of amide；
Catalyst described in step (1) is the mixture of palladium and thricyclohexyl phosphorus, three (dibenzalacetones) two
At least one of the mixture of palladium and thricyclohexyl phosphorus, tetra-triphenylphosphine palladium or triphenylphosphine palladium；
The monomer of the structure containing Ar described in step (1) is preferably that end group is double borates, double boric acid, double bromines or double iodine
At least one of monomer, and must include the monomer that end group is double borates or double boric acid；Polymerization list described in step (1)
Body M1, the structure containing Ar monomer dosage meet monomer integral molar quantity containing double borate (boric acid) functional groups with containing double bromines (iodine)
The monomer integral molar quantity of functional group is equal；The dosage of the catalyst is the 3%~5% of reaction monomers moles total number；It is described
The volume ratio of tetraethyl aqueous ammonium hydroxide (20%) and solvent be 1:4~6；
The dosage of phenyl boric acid described in step (2) is the reaction monomers moles total number (list of polymerized monomer M1+ structures containing Ar
Body) 10~20%；The dosage of the bromobenzene is 15~20 times of phenyl boric acid mole.
Purifying described in step (2) refers to being cooled to room temperature gained reaction solution, pours into methanol and precipitates, and is filtered, and is done
Dry crude product, crude product toluene dissolve then column chromatography for separation, after column chromatography by after solvent concentration again precipitating in first
In alcoholic solution, filter, it is dry, use methanol, acetone, tetrahydrofuran to extract successively obtained solid, by the tetrahydrofuran after extracting
Precipitation in methyl alcohol, is drying to obtain target product to solution by precipitating again.
Illustrate if being not known in the present invention, the room temperature refers both to 5~35 DEG C, preferably 25 DEG C；The stirring refers both to
Mixing speed is 1000~2000r/min.
Above-mentioned electroluminescent polymer is in light emitting diode, organic field effect tube, organic solar batteries, organic
Application in the fields such as laser diode, the application preferably in the luminescent layer for preparing LED device.
Application of the above-mentioned electroluminescent polymer in the luminescent layer for preparing LED device, specifically by following step
It is rapid to realize：The electroluminescent polymer is dissolved with organic solvent, then is formed a film by spin coating, inkjet printing or printing, i.e.,
It can be used as the luminescent layer of LED device.
The organic solvent is at least one of chlorobenzene, dichloro benzene,toluene,xylene, tetrahydrofuran, chloroform.
The thickness of the luminescent layer is 10~1000nm.
The present invention mechanism be：
The present invention changes intermediate phenyl ring into naphthalene nucleus, asymmetrical junction on the basis of isomer (b) structure of indenofluorene
Structure advantageously forms unformed film, inhibits fluorescent quenching.Conjugate length becomes smaller simultaneously, leads to emission wavelength hypsochromic shift
It is dynamic, be conducive to emit purer blue light.
The present invention compared with the existing technology, has the following advantages and advantageous effect：
(1) on the basis of the isomer of indenofluorene, naphthalene nucleus is introduced, synthesis obtains that the present invention relates to electroluminescent
Polymerized monomer, synthetic route is easy, and purification is convenient.
(2) for polymerized monomer M1 of the invention while retaining naphtho- fluorenes isomer advantage, structure is asymmetrical junction
Structure advantageously forms unformed film, inhibits fluorescent quenching.Conjugate length becomes smaller simultaneously, leads to emission wavelength hypsochromic shift
It is dynamic, be conducive to emit purer blue light.
(3) the present invention relates to electroluminescent polymers to have preferable solubility property, is suitable for solution and processes, can reduce
Device manufacturing cost, and large area flexible OLED device can be prepared；And when preparing electroluminescent device without making annealing treatment,
Preparation process is simpler.
Description of the drawings
Fig. 1 is thermal weight loss (TG) curve of polymer P 1.
Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of polymer P 1, P2, P3 under filminess.
Fig. 3 is the fluorescence spectra of polymer P 5 and P6 in toluene solution.
Fig. 4 is the fluorescence spectrum of polymer P 7 and P8 under filminess.
Specific implementation mode
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.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Embodiment 1：The preparation of polymerized monomer M1
The preparation of o-bromo-benzoic acid ethyl ester：In 500mL there-necked flasks, o-bromobenzoic acid (20.1g, 0.1mol) is dissolved in
In 200ml ethyl alcohol, and it is added dropwise into reaction solution the concentrated sulfuric acid of 20ml, after stirring 12 hours at room temperature, stops reaction, use water quenching
Go out reaction, with dichloromethane extract and be dried with anhydrous magnesium sulfate, after solution concentration yellow liquid, pass through silica gel
Column chromatography purifies, and the mixed solvent (4/1, v/v) of petroleum ether/dichloromethane is eluent, yield 87%.1H NMR、13CNMR、
The result shows that obtained compound is target product, preparation process chemical equation is as follows for MS and elemental analysis：
The preparation of ethyl 2- (4,4,5,5- tetramethyl -1,3,2- dioxa boron -2- bases) ethyl benzoate：In argon gas atmosphere
Under, o-bromo-benzoic acid ethyl ester (17.2g, 75.3mmol) is dissolved in 250ml anhydrous tetrahydro furans, is cooled to -78 DEG C, is slowly added dropwise
The hexane solution (34.5ml, 82.8mmol) of the n-BuLi of a concentration of 2.4mol/L, after stirring 1 hour, to reaction system
Middle addition 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- dioxaborinates (41.9g, 0.225mol) then allow reaction bulb
Room temperature reaction 12 hours is warmed naturally to, stops reaction, reaction is quenched with water, is extracted with dichloromethane and uses anhydrous slufuric acid
Magnesium is dried, and obtains khaki liquid after solution concentration, is purified by silica gel column chromatography, the mixing of petroleum ether/dichloromethane is molten
Agent (2/1, v/v) is eluent, obtains white solid, yield 65%.1H NMR、13CNMR, MS and elemental analysis are the result shows that institute
Obtained compound is target product, and preparation process chemical equation is as follows：
The preparation of ethyl 2- (4- bromonaphthalene base -1- bases) ethyl benzoate：Under an argon atmosphere, into 500mL three-necked flasks,
Ethyl 2- (4,4,5,5- tetramethyls -1,3,2- dioxa boron -2- bases) ethyl benzoate (8.4g, 30.4mmol), Isosorbide-5-Nitrae-is added
Dibromine naphthalene (7.89g, 27.6mmol), four butyl bromation amine (0.44g, 1.38mmol), catalyst tetra-triphenylphosphine palladium (1.60g,
1.38mmol) and K is added when temperature is stablized at 85 DEG C in 200mL toluene, agitating and heating2CO3(19.0g, 0.138mol) is water-soluble
Liquid 19mL reacts 12h.It after reaction solution is concentrated, is purified by silica gel column chromatography, petroleum ether and dichloromethane mixed solvent (3/
1, v/v) it is eluent, obtains faint yellow solid, yield 60%.1H NMR、13CNMR, MS and elemental analysis are the result shows that gained
The compound arrived is target product, and preparation process chemical equation is as follows：
The preparation of bromo- 7H- benzos [c] fluorenyl -7- ketone of 5-：Under an argon atmosphere, by ethyl 2- (4- bromonaphthalene base -1- bases) benzene
Ethyl formate (4.97g, 14mmol) is dissolved in the refined anhydrous methylene chlorides of 80ml, be added under the conditions of 0 DEG C aluminium chloride (17g,
28mmol), 16h is reacted at room temperature.When stopping reaction, reaction mixture is poured into water, is extracted with ethyl acetate, organic layer food
After brine washing completely, dried with anhydrous magnesium sulfate.After solution concentration, purified by silica gel column chromatography, petroleum ether and dichloromethane
Alkane mixed solvent (2/1, v/v) is eluent, obtains white solid, yield 80%.1H-NMR、13C-NMR, MS and elemental analysis
The result shows that obtained compound is target product, preparation process chemical equation is as follows：
The preparation of bromo- 7H- benzos [c] fluorenes of 5-：By bromo- 7H- benzos [c] fluorenyl -7- ketone (6.6mmol) of 5-, hydrazine hydrate
(10.0ml, 0.21mol), potassium hydroxide (1.85g, 33mmol) are dissolved in 80ml diethylene glycol (DEG)s, are heated to flowing back, and react 12h.Stop
After only reacting, reaction solution is poured into water, is extracted with ethyl acetate, organic layer is washed with sodium-chloride water solution, anhydrous magnesium sulfate
Dry, concentration is purified, petroleum ether is eluent, obtains white solid by silica gel column chromatography.Yield 83%.1H-NMR、13C-
NMR, MS and elemental analysis the result shows that obtained compound be target product, the following institute of preparation process chemical equation
Show：
The preparation of bromo- 7,7- dihexyls -7H- benzos [c] fluorenes of 5-：In 500mL there-necked flasks, bromo- 7H- benzos [c] fluorenes of 5-
(14.8g, 0.05mol) is dissolved in 200ml toluene, be added the sodium hydroxide of 50wt% aqueous solution (20g/20ml deionized waters,
0.5mol), be heated to 80 DEG C stirring 1 hour after, be added bromohexane (17.3g, 0.105mol), isothermal reaction 12 hours, stop
After reaction, organic phase is detached, yellow liquid is obtained after solution concentration, is purified by silica gel column chromatography, petroleum ether/dichloromethane mixes
Bonding solvent (5/1, v/v) is eluent, yield 73%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtainedization
Conjunction object is target product, and preparation process chemical equation is as follows：
The preparation of ethyl 2- (7,7- dihexyl -7H- benzos [c] fluorenes -5- bases) ethyl benzoate：Under an argon atmosphere, to
In 500mL three-necked flasks, ethyl 2- (4,4,5,5- tetramethyls -1,3,2- dioxa boron -2- bases) ethyl benzoate is added
(8.4g, 30.4mmol), bromo- 7,7- dihexyls -7H- benzos [c] fluorenes (12.8g, 27.6mmol) of 5-, four butyl bromation amine
(0.44g, 1.38mmol), catalyst tetra-triphenylphosphine palladium (1.60g, 1.38mmol) and 200mL toluene, agitating and heating wait for temperature
Degree is stablized at 85 DEG C, and K is added2CO3(19.0g, 0.138mol) aqueous solution 19mL reacts 12h.After reaction solution is concentrated, pass through
Silica gel column chromatography purifies, and petroleum ether and dichloromethane mixed solvent (3/1, v/v) are eluent, obtain faint yellow solid, yield
60%.1H NMR、13The result shows that obtained compound is target product, preparation process chemistry is anti-for CNMR, MS and elemental analysis
Answer equation as follows：
The preparation of 7- (2- (7,7- dihexyl -7H- benzos [c] fluorenes -5- bases) phenyl) tridecane -7- alcohol：In argon gas atmosphere
Under, ethyl 2- (7,7- dihexyl -7H- benzos [c] fluorenes -5- bases) ethyl benzoate (8.8g, 16.5mmol) is dissolved in 80ml
In refined anhydrous THF, 1.0mol L are added dropwise dropwise-1Octyl magnesium bromide (82.5ml, 82.5mmol) is warming up to 80 DEG C of heating
16h is reacted in reflux.It is cooled to room temperature, reaction mixture is poured into water, be extracted with ethyl acetate, organic layer saline solution is complete
After full washing, dried with anhydrous magnesium sulfate.After solution concentration, next step reaction is directly carried out.
The preparation of 13,13,14,14- tetra- hexyl -13,14- dihydro-dibenzos [c] indoles [2,1-a] fluorenes：By 7- (2- (7,
7- dihexyl -7H- benzos [c] fluorenes -5- bases) phenyl) tridecane -7- alcohol (5.1g, 7.8mmol) is dissolved in 30ml anhydrous methylene chlorides
In solution, a concentration of 2mol/L boron trifluoride ether solutions (23.4mmol) of 11.7ml are added dropwise, react at room temperature 1h.Solution concentrates
Afterwards, it is purified with silica gel column chromatography method, petroleum ether and dichloromethane mixed solvent (8/1, v/v) are eluent.Crude product ethyl alcohol
Recrystallization, obtains white crystal, yield 80%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is
Target product, preparation process chemical equation are as follows：
The system of bis- bromo- 13,13,14,14- of 2,11-, tetra- hexyl -13,14- dihydro-dibenzos [c] indoles [2,1-a] fluorenes (M1)
It is standby：13,13,14,14- tetra- hexyl -13,14- dihydro-dibenzo [c] indoles [2,1-a] fluorenes (5.9g, 9.2mmol) are dissolved in
In 10ml carbon tetrachloride, ferric trichloride (FeCl is added3) (76mg, 0.46mmol) under condition of ice bath (0 DEG C), bromine is added
(3.24g, 20.24mmol) is quenched reaction with saturation sodium hydrogensulfite after reacting 24 hours, and is extracted with ethyl acetate, anhydrous
It after magnesium sulfate drying, is purified with silica gel column chromatography, petroleum ether and dichloromethane mixed solvent (8/1, v/v) are eluent, are obtained
White solid.Yield：86%.1H NMR、13CNMR, MS and elemental analysis the result shows that obtained compound be target product,
Preparation process chemical equation is as follows：
Embodiment 2：The synthesis of electroluminescent polymer P1
It is under argon atmosphere, 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl) -9,9- bis- is pungent
Base fluorenes (321mg, 0.50mmol), 2,7- bis- bromo- 9,9- dioctyl fluorenes (246.8mg, 0.45mmol) and 2,11- bis- bromo- 13,
50ml is added in 13,14,14- tetra- hexyl -13,14- dihydro-dibenzo [c] indoles [2,1-a] fluorenes (M1) (39.9mg, 0.05mmol)
In two-mouth bottle, 12ml refined toluenes are added, add palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine
(6.98mg, 24.90 μm of ol) are then added 3ml tetraethyl ammonium hydroxide aqueous solutions, are warming up to 80 DEG C, react 24 hours；Then
20mg phenyl boric acids are added to be blocked, after 12 hours, then are blocked with 0.3ml bromobenzenes；After the reaction was continued 12 hours, stop
Reaction, waits for that temperature is down to room temperature, and the precipitating in 300ml methanol is added dropwise in product, is filtered, then crude product is dissolved in the toluene of 20mL
In, it is that eluant, eluent carries out column chromatography with toluene, solvent concentration sinks in methyl alcohol again using 200~300 mesh silica gel as stationary phase
It separates out, stirs, filtering obtains polymer solids after vacuum drying；Finally respectively taken out with methanol, acetone, tetrahydrofuran successively again
It carries 24 hours, removes small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the fiber obtained after vacuum drying
Shape solid electroluminescent polymer P1.1H NMR, GPC and elemental analysis the result shows that obtained compound be target product,
Preparation process chemical equation is as follows：
Thermal weight loss (TG) curve of polymer P 1 is as shown in Figure 1.It can be seen that polymer P 1 is in entire heating process
In, only there is a thermal decomposition process, is the thermal decomposition process of conjugated main chain.When the Mass lost 5% of polymer P 1, institute is right
The temperature answered is 446 DEG C, i.e., the heat decomposition temperature of polymer P 1 is 446 DEG C.It is single that this higher heat decomposition temperature has benefited from polymerization
Body M1 has stronger rigidity, illustrates that polymer P 1 has stronger heat resistance, can meet polymer functionization demand.
Polymer P 1 is dissolved in toluene solvant, a concentration of 15mg/ml is then spin coated onto on the quartz plate of 1 × 4cm,
Film, ultraviolet-visible absorption spectroscopy of the polymer P 1 under filminess such as Fig. 2 institutes is made in rotating speed 1500r/min, film thickness 80nm
Show, as shown in Figure 2, maximum absorption band of the polymer P 1 under filminess is located at 380nm, belongs to 1 conjugated main chain of polymer P
π-π transition.Polymer P 1 is in the maximum ABSORPTION EDGE (λ of filminessmax) it is 412nm, rule of thumb formula has, polymer P 1
Optical band gap Eg=1240/ λmax=1240/412eV=3.010eV.Wider optical band gap illustrates that polymer P 1 is blue light
Polymer material.
Embodiment 3：The synthesis of electroluminescent polymer P2
It is under argon atmosphere, 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl) -9,9- bis- is pungent
Base fluorenes (321mg, 0.50mmol), 2,7- bis- bromo- 9,9- dioctyl fluorenes (219.4mg, 0.40mmol) and 2,11- bis- bromo- 13,
50ml is added in 13,14,14- tetra- hexyl -13,14- dihydro-dibenzo [c] indoles [2,1-a] fluorenes (M1) (79.9mg, 0.10mmol)
In two-mouth bottle, 12ml exquisiteness toluene is added, adds palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine
(6.98mg, 24.90 μm of ol) are then added 3ml tetraethyl ammonium hydroxide aqueous solutions, are warming up to 80 DEG C, react 24 hours；Then
20mg phenyl boric acids are added to be blocked, after 12 hours, then are blocked with 0.3ml bromobenzenes；After the reaction was continued 12 hours, stop
Reaction, waits for that temperature is down to room temperature, and the precipitating in 300ml methanol is added dropwise in product, is filtered, then crude product is dissolved in the toluene of 20mL
In, it is that eluant, eluent carries out column chromatography with toluene, solvent concentration sinks in methyl alcohol again using 200~300 mesh silica gel as stationary phase
It separates out, stirs, filtering obtains polymer solids after vacuum drying；Finally respectively taken out with methanol, acetone, tetrahydrofuran successively again
It carries 24 hours, removes small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the fiber obtained after vacuum drying
Shape solid electroluminescent polymer P2.1H NMR, GPC and elemental analysis the result shows that obtained compound be target product,
Preparation process chemical equation is as follows：
Polymer P 2 is dissolved in toluene solvant, a concentration of 15mg/ml is then spin coated onto on the quartz plate of 1 × 4cm,
Film is made in rotating speed 1500r/min, film thickness 80nm, and fluorescence spectrum of the polymer P 2 under filminess is as shown in Fig. 2, by Fig. 2
It is found that maximum emission peak of the polymer P 2 under filminess is located at 424nm, acromion is located at 447nm.The content of monomer M1 increases
It is added to 10%, polyfluorene main chain and the electric charge transfer effect of monomer M1 enhance, and compared to polymer P 1, the spectrum of polymer P 2 is red
It moves, polymer P 2 is located at blue region in the regions of fluorescence emissions of filminess.
Polymer P 2 is in the maximum ABSORPTION EDGE (λ of filminessmax) it is 413nm, rule of thumb formula has, polymer P 2
Optical band gap Eg=1240/ λmax=1240/413eV=3.002eV.With the increase of monomer M1 contents, the band gap of polymer by
It is in gradually the trend that narrows.And the wider band gap of 3.002eV illustrates that monomer M1 increases to 10%, polymer P 2 is still blue light material.
Embodiment 4：The synthesis of electroluminescent polymer P3
It is under argon atmosphere, 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl) -9,9- bis- is pungent
Base fluorenes (321mg, 0.50mmol), 2,7- bis- bromo- 9,9- dioctyl fluorenes (191.9mg, 0.35mmol) and 2,11- bis- bromo- 13,
13,14,14- tetra- hexyl -13,14- dihydro-dibenzo [c] indoles [2,1-a] fluorenes (M1) (119.8mg, 0.15mmol) are added
In 50ml two-mouth bottles, 12ml exquisiteness toluene is added, adds palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine
(6.98mg, 24.90 μm of ol) are then added 3ml tetraethyl ammonium hydroxide aqueous solutions, are warming up to 80 DEG C, react 24 hours；Then
20mg phenyl boric acids are added to be blocked, after 12 hours, then are blocked with 0.3ml bromobenzenes；After the reaction was continued 12 hours, stop
Reaction, waits for that temperature is down to room temperature, and the precipitating in 300ml methanol is added dropwise in product, is filtered, then crude product is dissolved in the toluene of 20mL
In, it is that eluant, eluent carries out column chromatography with toluene, solvent concentration sinks in methyl alcohol again using 200~300 mesh silica gel as stationary phase
It separates out, stirs, filtering obtains polymer solids after vacuum drying；Finally respectively taken out with methanol, acetone, tetrahydrofuran successively again
It carries 24 hours, removes small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the fiber obtained after vacuum drying
Shape solid electroluminescent polymer P3.1H NMR, GPC and elemental analysis the result shows that obtained compound be target product,
Preparation process chemical equation is as follows：
Polymer P 3 is dissolved in toluene solvant, a concentration of 15mg/ml is then spin coated onto on the quartz plate of 1 × 4cm,
Film is made in rotating speed 1500r/min, film thickness 80nm, and fluorescence spectrum of the polymer P 3 under filminess is as shown in Fig. 2, by Fig. 2
It is found that maximum emission peak of the polymer P 3 under filminess is located at 424nm, acromion is located at 450nm.The content of monomer M1 increases
It is added to 15%, polyfluorene main chain and the electric charge transfer effect of monomer M1 further enhance, compared to polymer P 1, P2, polymer P 3
Spectral red shift, and along with widthization phenomenon.Polymer P 3 is located at blue region in the regions of fluorescence emissions of filminess.
Polymer P 3 is in the maximum ABSORPTION EDGE (λ of filminessmax) it is 414nm, rule of thumb formula has, polymer P 3
Optical band gap Eg=1240/ λmax=1240/414eV=2.995eV.With the increase of monomer M1 contents, the band gap of polymer by
It is in gradually the trend that narrows.And the wider band gap of 2.995eV illustrates that monomer M1 increases to 15%, polymer P 3 is still blue light material.
Comparative polymer P1, P2 and P3 in structural constituent, polymer monomer 2,11- bis- bromo- 13,13,14,14- tetra- oneself
The content of base -13,14- dihydro-dibenzo [c] indoles [2,1-a] fluorenes (M1) increases to 10mol%, 15mol% by 5mol%, most
Big ABSORPTION EDGE is in red shift trend, and optical band gap slightly narrows therewith, this is that the conjugate length of M1 is longer than fluorenes, and the content for introducing M1 increases
It is more, caused by the conjugate length of strand also increases.
Embodiment 5：The synthesis of electroluminescent polymer P4
It is under argon atmosphere, 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl) -9,9- bis- is pungent
Base fluorenes (321mg, 0.50mmol), 2,7- bis- bromo- 9,9- dioctyl fluorenes (274.2mg, 0.50mmol) are added in 50ml two-mouth bottles,
12ml exquisiteness toluene is added, palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine (6.98mg, 24.90 μ are added
Mol), 3ml tetraethyl ammonium hydroxide aqueous solutions are then added, are warming up to 80 DEG C, react 24 hours；Then 20mg phenyl boric acids are added
It is blocked, after 12 hours, then is blocked with 0.3ml bromobenzenes；After the reaction was continued 12 hours, stop reaction, waits for that temperature drops
To room temperature, the precipitating in 300ml methanol, filtering is added dropwise in product, then crude product is dissolved in the toluene of 20mL, with 200~300
Mesh silica gel is stationary phase, is that eluant, eluent carries out column chromatography with toluene, solvent concentration separates out come again in methyl alcohol, stirring, mistake
Filter, polymer solids are obtained after vacuum drying；It is finally respectively extracted 24 hours, is removed small with methanol, acetone, tetrahydrofuran successively again
Molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the fibrous solids electroluminescent obtained after vacuum drying
Polymer P 4.1The result shows that obtained compound is target product, preparation process chemistry is anti-for H NMR, GPC and elemental analysis
Answer equation as follows：
Embodiment 6：The synthesis of electroluminescent polymer P5
The preparation of bis- bromo- 2,1,3- diazosulfides of 4,7-
Under the conditions of being protected from light, 2,1,3- diazosulfide (5.0g, 36.8mmol) and hydrogen are added into the three-necked flask of 250ml
Bromic acid aqueous solution (100ml, 47wt%), is warming up to reflux, hydrobromic acid solution and liquid then is slowly added dropwise with constant pressure funnel
The mixed liquor (V/V=20/1, volume ratio) of bromine solutions (4.8ml, 92mmol).After 6 hours, saturation NaHSO is added3Aqueous solution stirs
It mixes to colourless and removes excessive bromine, then filtered with Buchner funnel, filter cake uses deionized water, ethyl alcohol to wash for several times successively.Solid
With the silicagel column of 100-200 mesh, PE/DCM purifies for 1/1 (volume ratio) as eluent, then further with chloroform soln
Purifying, obtains 11.8g yellow needle-like crystals, yield：80%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained
Compound is target product, and preparation process chemical equation is as follows：
The synthesis of electroluminescent polymer P5：Under argon atmosphere, by 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- bis-
Oxa- borine-diyl) -9,9- dioctyl fluorenes (321mg, 0.50mmol), 2,7- bis- bromo- 9,9- dioctyl fluorenes (274.2mg,
0.43mmol), bis- bromo- 13,13,14,14- of 2,11- tetra- hexyl -13,14- dihydro-dibenzos [c] indoles [2,1-a] fluorenes (M1)
(39.9mg, 0.05mmol) and 4,7- bis- bromo- 2,1,3- diazosulfide (5.8mg, 0.02mmol) are added in 50ml two-mouth bottles,
8ml toluene is added to be completely dissolved, add palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine (6.98mg,
24.90 μm of ol), 2ml tetraethyl ammonium hydroxide aqueous solutions are then added, are warming up to 80 DEG C, react 24 hours；Then 30mg is added
Phenyl boric acid is blocked, and after 12 hours, then is blocked with 0.30ml bromobenzenes；After the reaction was continued 12 hours, stops reaction, wait for
Temperature is down to room temperature, the precipitating in 300ml methanol, filtering is added dropwise in product, then crude product is dissolved in the toluene of 20mL, with
200~300 mesh silica gel are stationary phase, are that eluant, eluent carries out column chromatography with toluene, solvent concentration separates out in methyl alcohol again
Come, stir, filtering obtains polymer solids after vacuum drying；Finally 24 are respectively extracted with methanol, acetone, tetrahydrofuran successively again
Hour, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the threadiness obtained after vacuum drying is solid
Body conjugated polymer P5.1H NMR, GPC and elemental analysis the result shows that obtained compound be target product, preparation process
Chemical equation is as follows：
Fluorescence spectrum of the polymer P 5 in toluene solution is as shown in figure 3, from the figure 3, it may be seen that polymer P 5 is in toluene solution
In maximum emission peak be located at 429nm, belong to poly- (fluorenes-co13,13,14,14- tetra- hexyl -13,14- dihydro-dibenzos [c]
Indoles [2,1-a] fluorenes) transmitting；Acromion is located at 520nm, belongs to the transmitting of 2,1,3- diazosulfide monomer, fluorescent emission
Region is located at green wavelength.Since intramolecular energy is incomplete, Two peak emission is shown.
Embodiment 7：The synthesis of electroluminescent polymer P6
The preparation of 4,7- bis- (4- hexyl thiophene -2- bases) -2,1,3- diazosulfides：Tributyl-(4- hexyl thiophenes -2-
Base) stannane (being purchased from SAGECHEM LIMITIED) (15.0g, 33.1mmol), 4,7- bis- bromo- 2,1,3- diazosulfide
(4.4g, 15.0mmol) is dissolved in 100mL and refines THF solvents at room temperature.In a nitrogen atmosphere, catalyst PdCl is rapidly joined2
(PPh3)2(221mg, 0.15mmol) is heated with stirring to reflux, and reaction is overnight.After stopping reaction, it is spin-dried for solvent, mixture is used
The silicagel column of 100-200 mesh, PE/DCM are that 5/1 (volume ratio) makees eluent, obtain Orange red solid 5.8g, yield 82%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
The preparation of bis- (bromo- (4- the hexyl thiophenes) -2- bases of the 5-) -2,1,3- diazosulfides of 4,7-：It is added into reaction bulb
4,7- bis- (4- hexyl thiophene -2- bases) -2,1,3- diazosulfide (4.68g, 10mmol), then it is complete with 150ml THF solvents
Raw material is dissolved, NBS (N-bromosuccinimide) powder (2.28g, 24mmol) is added in reaction bulb, room temperature is protected from light
24 hours.It is spin-dried for solvent, crude product is by the method separating-purifying of column chromatography, and PE/DCM is that 3/1 (volume ratio) makees eluent, so
It is recrystallized afterwards with n-hexane, obtains 4.86g red needle-like solids.Yield is 78%.1H NMR、13CNMR, MS and elemental analysis knot
Fruit shows that obtained compound is target product.Preparation process chemical equation is as follows：
The synthesis of electroluminescent polymer P6：Under argon atmosphere, by 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- bis-
Oxa- borine-diyl) -9,9- dioctyl fluorenes (321mg, 0.50mmol), 2,7- bis- bromo- 9,9- dioctyl fluorenes (241.3mg,
0.44mmol) and bis- bromo- 13,13,14,14- of 2,11- tetra- hexyl -13,14- dihydro-dibenzos [c] indoles [2,1-a] fluorenes (M1)
(39.9mg, 0.05mmol) and 4,7- bis- (bromo- (4- the hexyl thiophenes) -2- bases of 5-) -2,1,3- diazosulfide (6.3mg,
0.01mmol) be added 50ml two-mouth bottles in, add 8ml toluene and be completely dissolved, add palladium (2.80mg, 12.45
μm ol) and tricyclohexyl phosphine (6.98mg, 24.90 μm of ol), 2ml tetraethyl ammonium hydroxide aqueous solutions are then added, are warming up to 80
DEG C, it reacts 24 hours；Then 30mg phenyl boric acids are added to be blocked, after 12 hours, then are blocked with 0.30ml bromobenzenes；Continue
After reaction 12 hours, stop reaction, wait for that temperature is down to room temperature, the precipitating in 300ml methanol is added dropwise in product, is filtered, then will
Crude product is dissolved in the toluene of 20mL, is that eluant, eluent carries out column chromatography, solvent with toluene using 200~300 mesh silica gel as stationary phase
Concentration separates out come again in methyl alcohol, stirs, and filtering obtains polymer solids after vacuum drying；Finally use first successively again
Alcohol, acetone, tetrahydrofuran respectively extract 24 hours, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol,
The fibrous solids conjugated polymer P6 obtained after vacuum drying.1H NMR, GPC and elemental analysis are the result shows that obtainedization
Conjunction object is target product, and preparation process chemical equation is as follows：
Fluorescence spectrum of the polymer P 6 in toluene solution is as shown in figure 3, from the figure 3, it may be seen that polymer P 6 is in toluene solution
In maximum emission peak be located at 429nm, belong to poly- (fluorenes-co13,13,14,14- tetra- hexyl -13,14- dihydro-dibenzos [c]
Indoles [2,1-a] fluorenes) transmitting；Acromion is located at 606nm, belongs to 4,7- bis- ((4- hexyl thiophenes) -2- bases) -2,1,3- benzo
The transmitting of thiadiazoles monomer, regions of fluorescence emissions are located at red light region.Similar with polymer P 5, intramolecular energy is endless
Entirely, Two peak emission, and comparative polymer P5 and P6 are shown, the content of monomer M1 is all mutually 5mol%, and difference is another component
Difference, identical fluorescence main peak, different fluorescence acromions are shown as on fluorescence spectrum.
Embodiment 8：The synthesis of electroluminescent polymer P7
The preparation of 4- n-octyl triphenylamines：It is dissolved full liquid dissolving 4- octyls bromobenzene (2.69g, 10mmol) with 150ml toluene
With aniline (0.93g, 23mmol), tertiary butyl sodium alkoxide (3.94g, 41mmol) and palladium (96mg, 0.5mmol) are added,
Under argon atmosphere, oil bath is warming up to 85 DEG C, continuously adds the three tertiary fourth of toluene solution (1.0mol/L, 0.5mL) of tri-tert-butylphosphine
The toluene solution of base phosphine；After reaction 12 hours, adds water in reaction solution and reaction is quenched, it is three times with dichloromethane extraction, organic
Dry after being mutually washed with deionized three times, concentration, crude product silica gel column chromatography separating-purifying, pure petroleum ether is as elution
Agent obtains thick liquid.Yield 82%.1H NMR、13C NMR, MS and elemental analysis are the result shows that obtained compound is target
Product, chemical equation are as follows：
The preparation of 4,4 '-two bromo- 4 "-octyl triphenylamines：It is completely dissolved 4- n-octyls with 20ml N,N-dimethylformamides
Triphenylamine (2.50g, 7mmol), under condition of ice bath (0 DEG C), be added dropwise dropwise N- bromo-succinimides (NBS, 2.74g,
N,N-Dimethylformamide solution 15.4mmol) reacts 4 hours under the conditions of being protected from light；After reaction, then by reaction solution it falls
Enter in water, stir, filtering, filter cake silica gel column chromatography separating-purifying, pure petroleum ether obtains white solid as eluent.
Yield 78%.1H NMR、13C NMR, MS and elemental analysis the result shows that obtained compound be target product, chemical reaction side
Formula is as follows：
4,4 '-two (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-phenyl) -4 "-octyl triphenylamine
It prepares：It is completely dissolved 4 with 100ml anhydrous tetrahydro furans (THF) solution, 4 '-two bromo- 4 "-octyl triphenylamines (2.58g,
5mmol), under argon atmosphere, -78 DEG C are cooled to, the hexane solution that the n-BuLi of 5.3ml is added dropwise dropwise is (a concentration of
2.4mol L-1), after reacting 1 hour, it is added at one time 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- ethylenedioxy boric acid
Ester (2.6g, 14mmol) continues stirring 2 hours；Reaction system is gradually increased to room temperature reaction 24 hours；Reaction solution is concentrated, according to
It is secondary to be extracted with ethyl acetate three times, dry after organic phase is washed with deionized three times, concentration, crude product silica gel column chromatography
Separating-purifying, petrol ether/ethyl acetate (5/1, v/v) mixed solvent obtain white solid as eluent.Yield 69%.1H
NMR、13The result shows that obtained compound is target product, chemical equation is as follows for C NMR, MS and elemental analysis：
The synthesis of electroluminescent polymer P7：Under argon atmosphere, by 4,4 '-two (4,4 ', 5,5 '-tetramethyls -1,3,2-
Dioxaborinate-diyl)-phenyl) -4 "-octyl triphenylamine (304.7mg, 0.50mmol), 2,11- bis- bromo- 13,13,14,14-
Four hexyl -13,14- dihydro-dibenzo [c] indoles [2,1-a] fluorenes (M1) (399.4mg, 0.5mmol) are added in 50ml two-mouth bottles,
12ml exquisiteness toluene is added, palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine (6.98mg, 24.90 μ are added
Mol), 3ml tetraethyl ammonium hydroxide aqueous solutions are then added, are warming up to 80 DEG C, react 24 hours；Then 20mg phenyl boric acids are added
It is blocked, after 12 hours, then is blocked with 0.3ml bromobenzenes；After the reaction was continued 12 hours, stop reaction, waits for that temperature drops
To room temperature, the precipitating in 300ml methanol, filtering is added dropwise in product, then crude product is dissolved in the toluene of 20mL, with 200~300
Mesh silica gel is stationary phase, is that eluant, eluent carries out column chromatography with toluene, solvent concentration separates out come again in methyl alcohol, stirring, mistake
Filter, polymer solids are obtained after vacuum drying；It is finally respectively extracted 24 hours, is removed small with methanol, acetone, tetrahydrofuran successively again
Molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the fibrous solids electroluminescent obtained after vacuum drying
Polymer P 7.1The result shows that obtained compound is target product, preparation process chemistry is anti-for H NMR, GPC and elemental analysis
Answer equation as follows：
Fluorescence spectrum of the polymer P 7 under filminess is as shown in figure 4, as shown in Figure 4, polymer P 7 is in filminess
Under maximum emission peak be located at 458nm, belong to the transmitting of polymer conjugated main chain, regions of fluorescence emissions is located at blue region.
Embodiment 9：The synthesis of electroluminescent polymer P8
The synthesis of bis- bromo- N- iso-octyl carbazoles of 3,6-：With 80ml toluene solutions be completely dissolved 3,6- dibromos carbazole (2.28g,
7mmol), tetrabutylammonium bromide (0.11g, 0.35mmol) is added, under argon gas protection, oil bath is warming up to 85 DEG C, after
Continuous sodium hydroxide (2.8g/2.8ml deionized waters, 70mmol) aqueous solution that 50wt% is added rapidly joins after stirring 1 hour
Iso-octyl bromine (2.03g, 10.5mmol)；After reaction 8 hours, adds water in reaction solution and reaction is quenched, extracted with dichloromethane
Three times, dry after organic phase is washed with deionized three times, concentration, crude product silica gel column chromatography separating-purifying, pure petroleum ether
As eluent, white solid is obtained.Yield 94%.1H NMR、13C NMR, MS and elemental analysis are the result shows that obtained chemical combination
Object is target product, and chemical equation is as follows：
The synthesis of 3,6- bis- (4,4 ', 5,5 '-tetramethyl -1,3,2- dioxaborinates-diyl)-N- iso-octyl carbazoles：With
100ml anhydrous tetrahydro furans (THF) solution is completely dissolved 3,6-, bis- bromo- N- iso-octyl carbazoles (2.19g, 5mmol), in argon gas gas
Under body protection, -78 DEG C are cooled to, 2.4mol L are added dropwise dropwise-1N-BuLi hexane solution (5.3ml, 12.5mmol),
After reaction 1 hour, it is added at one time 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- ethylenedioxies borate (2.79g,
15mmol), continue stirring 2 hours.Reaction system is gradually increased to normal-temperature reaction 24 hours；Reaction solution is concentrated, uses acetic acid successively
Ethyl ester extracts three times, dry after organic phase is washed with deionized three times, concentration, crude product silica gel column chromatography separating-purifying,
Petrol ether/ethyl acetate (6/1, v/v) mixed solvent obtains white solid as eluent.Yield 67%.1H NMR、13C
The result shows that obtained compound is target product, chemical equation is as follows for NMR, MS and elemental analysis：
It is under argon atmosphere, 3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl)-N-9 '-is different pungent
Base carbazole (265.2mg, 0.50mmol), 2,11- bis- bromo- 13,13,14,14- tetra- hexyl -13,14- dihydro-dibenzo [c] indoles
[2,1-a] fluorenes (M1) (399.4mg, 0.50mmol) is added in 50ml two-mouth bottles, adds 12ml exquisiteness toluene, adds acetic acid
3ml tetraethyl ammonium hydroxides are then added in palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine (6.98mg, 24.90 μm of ol)
Aqueous solution is warming up to 80 DEG C, reacts 24 hours；Then 20mg phenyl boric acids are added to be blocked, after 12 hours, then with 0.3ml bromines
Benzene is blocked；After the reaction was continued 12 hours, stop reaction, wait for that temperature is down to room temperature, product is added dropwise in 300ml methanol
Precipitating, filtering, then crude product is dissolved in the toluene of 20mL, it is eluant, eluent with toluene using 200~300 mesh silica gel as stationary phase
Column chromatography is carried out, solvent concentration separates out come again in methyl alcohol, stirs, and filtering obtains polymer solids after vacuum drying；
It is finally respectively extracted 24 hours with methanol, acetone, tetrahydrofuran successively again, removes small molecule；By the tetrahydrofuran solution after concentration
Instill precipitating in methanol, the fibrous solids electroluminescent polymer P8 obtained after vacuum drying.1H NMR, GPC and element point
The result shows that obtained compound is target product, preparation process chemical equation is as follows for analysis：
Fluorescence spectrum of the polymer P 8 under filminess is as shown in figure 4, as shown in Figure 4, polymer P 8 is in filminess
Under maximum emission peak be located at 430nm, belong to the transmitting of polymer conjugated main chain, regions of fluorescence emissions is located at blue region.
Compared to polymer P 7, monomer 2,11- bis- bromo- 13,13,14,14- tetra- hexyl -13,14- dihydro-dibenzo [c] Yin
The content of diindyl [2,1-a] fluorenes (M1) is all mutually 50%, but the apparent red shift of fluorescence spectrum of polymer P 7, this is because 3,6 substitutions
The electron donation of carbazole does not have 4- octyls-triphenylamine strong so that electric charge transfer effect is better than poly- in the strand of polymer P 7
Close object P8.
Case study on implementation 10：The preparation of electroluminescent polymer electroluminescent device
1) cleaning of ITO electro-conductive glass：Ito glass substrate is placed on film hanger, is cleaned by ultrasonic using ultrasonic device, is washed
It is acetone, isopropanol, liquid detergent, deionized water and isopropanol that liquid, which is washed, using sequence, and the purpose is to fully remove ito glass substrate
Possible remaining spot such as photoresist in surface etc., and improve interfacial contact.Then it is dried in vacuum drying oven；
2) ITO is placed in oxygen plasma etch instrument, uses oxygen plasma (O2Plasma it) carries out 20 minutes
Bombardment thoroughly removes the possible remaining organic matter of ito glass substrate surface；
3) on ITO spin coating 40nm thickness hole injection layer PEDOT:PSS (Baytron P4083), then at 80 DEG C
It is 12 hours dry in vacuum drying oven；
4) in the glove box of nitrogen atmosphere, in PEDOT:The light emitting polymer film of one layer of 80nm thickness of spin coating in PSS layer
Afterwards, heating anneal 20 minutes at a temperature of 80 DEG C on warm table, to remove residual solvent and improve the pattern for the tunic that shines；
5) less than 3 × 10 in vacuum evaporation storehouse-4One layer of 1.5nm is first deposited under the vacuum degree of Pa on organic thin film
Thick cesium fluoride (CsF), contributes to electron injection.Then the aluminium cathode (Al) of one layer of 110nm thickness, wherein fluorine are deposited on CsF
It is vacuum-deposited by mask plate progress to change caesium and aluminium layer.
The effective area of device is 0.16cm2.The thickness of organic layer is measured with quartz crystal monitoring thickness gauge.It is prepared by device
Epoxy resin and thin layer of glass polarity solidification and encapsulation in ultraviolet light are used afterwards.Single layer device structure is (ITO/PEDOT:PSS/
EMITTER(80nm)/CsF(1.5nm)/Al(110nm))。
Photoelectric properties test is carried out respectively to obtained electroluminescent device, test result is as shown in table 1.
The electroluminescent properties data of 1 polymer P 1-P8 of table
Single layer PLED devices, structure ITO/PEDOT are prepared by luminescent layer of electroluminescent polymer P1~P8:PSS/
EMITTER/CsF/Al。
Comparative polymer P1~P4, in molecular composition, polymer P 4 is obtained by fluorenes homopolymerization；Polymer P 1 be by
What 95mol% and 5mol% polymerized monomers M1 was copolymerized；Polymer P 2 is total to by 90mol% and 10mol% polymerized monomers M1
It is poly- to obtain；Polymer P 3 is copolymerized to obtain by 85mol% and 15mol% polymerized monomers M1；The data from table 1 it is found that with
The increase for M1 contents, the maximum lumen efficiency of the single layer device based on polymer be respectively 0.37cd/A, 1.38cd/A,
3.63cd/A, 2.36cd/A are in increase tendency.When the content of M1 is 10mol%, device performance is best, mono- compared to without M1
The polymer P 4 of member, maximum lumen efficiency improve nearly 9 times, this explanation can significantly carry being introduced into main polymer chain for monomer M1
High device performance.
The maximum lumen efficiency of single layer device based on polymer P 5 is 8.78cd/A, and chromaticity coordinates is (0.38,0.56), real
Green emission is showed.
The maximum lumen efficiency of single layer device based on polymer P 6 is 2.56cd/A, and chromaticity coordinates is (0.63,0.36), with
Standard feux rouges chromaticity coordinates (0.67,0.33) is close, has preferable excitation purity.
The maximum lumen efficiency of single layer device based on polymer P 7 and P8 is respectively 1.78cd/A and 1.59cd/A, and color is sat
Mark is respectively (0.16,0.15) and (0.16,0.10), wherein x+y≤0.3 in the chromaticity coordinates value of the device based on polymer P 8,
For dark blue light emitting；Device based on polymer P 7 is blue emission.
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. a kind of electroluminescent monomer M1, it is characterised in that structural formula is as follows：
Wherein, R be straight chain with 1~20 carbon atom, branched or cricoid alkyl, it is straight with 1~20 carbon atom
Chain, branched either cricoid alkoxy have the straight chain of 2~20 carbon atoms, branched or cricoid alkenyl, have 2~20
The straight chain of a carbon atom, branched either cricoid alkynyl have the straight chain of 2~20 carbon atoms, branched or cricoid alkane carbonyl
Base, the heteroatomic aryl or heteroaryl for being selected from O, N, S with 4~20 are heteroatomic selected from O, N, S with 4~20
Aralkyl or heteroaryl alkyl, the heteroatomic aryloxy group or heteroaryloxy for being selected from O, N, S with 4~20 have 4~20
A heteroatomic alkoxy aryl or heteroarylalkoxy selected from O, N, S.
2. a kind of preparation method of electroluminescent monomer M1 described in claim 1, it is characterised in that specifically include following steps：
(1) with ethyl alcohol esterification occurs under concentrated sulfuric acid existence condition for o-bromobenzoic acid, and dehydration obtains compound 1, then will
Compound 1 is dissolved completely in anhydrous tetrahydro furan, and in an inert atmosphere, -78 DEG C are added n-BuLi and stir 1 hour
Afterwards, 2- isopropoxies -4,4,5,5- tetramethyls -1,3 is added, 2- dioxaborinates warm naturally to room temperature reaction 12 hours, obtain
To compound 2；
(2) compound 2, Isosorbide-5-Nitrae-dibromine naphthalene, four butyl bromation amine and catalyst are added in toluene under an inert atmosphere, then
K is added2CO3Aqueous solution reacts 12h at 80~90 DEG C, obtains compound 3；
(3) compound 3 is dissolved in anhydrous methylene chloride under an inert atmosphere, aluminium chloride is added under the conditions of 0 DEG C, then in room
Temperature is lower to react 16h, obtains compound 4；
(4) compound 4, hydrazine hydrate and potassium hydroxide are dissolved in diethylene glycol (DEG), compound 5 is obtained after heating reflux reaction 12h；
(5) under inert gas environment, compound 5 is dissolved in toluene, the sodium hydrate aqueous solution of 50wt% is added, is heated to 80
After DEG C stirring 1h, RBr is added, isothermal reaction obtains compound 6 after 12 hours；
(6) under inert gas environment, compound 6 and compound 2 are coupled by suzuki, obtain compound 7；
(7) compound 7 is dissolved completely in anhydrous tetrahydro furan, at ambient temperature, grignard reagent RMgBr, heating is added
To 80 DEG C of back flow reaction 16h, compound 8 is obtained；
(8) compound 8 is dissolved in anhydrous methylene chloride, boron trifluoride ether solution is added, 2h is reacted at room temperature, then by gained
Reaction solution purifies to obtain compound 9；
(9) compound 9 is dissolved in anhydrous chloroform, under -20~0 DEG C of cryogenic conditions, is acted in ferric trichloride catalytic
Under, bromine is added and carries out bromination reaction, gained reaction solution is obtained into M1 after purification after reaction；
The definition of the R in the grignard reagent RMgBr described in RBr, step (7) described in step (5) and electroluminescent hair above-mentioned
The definition of R in the structure of light monomer M1 is consistent.
3. according to the preparation method of the electroluminescent monomer M1 described in claim 2, it is characterised in that：
Compound 1 used in step (1), n-BuLi and 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxa boron
The molar ratio of alkane is 1:1~1.2：2~3；
Compound 2,1,4- dibromine naphthalenes, four butyl bromation amine described in step (2) and K2CO3Molar ratio be 1：0.91：
0.045：4.54；Wherein the amount of catalyst is catalytic amount；
The molar ratio of compound 3 and aluminium chloride described in step (3) is 1：2；
The molar ratio of compound 4, hydrazine hydrate and potassium hydroxide described in step (4) is 1:31.8:5；
The molar ratio of compound 5 and RBr described in step (5) is 1:2.1；
Suzuki couplings described in step (6) refer to reacting 8~16h in 70~100 DEG C under alkali and catalyst action；Step
(6) molar ratio of compound 6 and compound 2 described in is 1:1.1；
The molar ratio of compound 7 and grignard reagent RMgBr described in step (7) is 1:5；
The molar ratio of compound 8 and boron trifluoride described in step (8) is 1:1~5；Boron trifluoride described in step (8)
A concentration of 2mol/L of diethyl ether solution；
Bromination reaction described in step (9) refer at -5~0 DEG C reaction 12~for 24 hours；Mole of the compound 9 and bromine
Than being 1:2~3.
4. according to the preparation method of the electroluminescent monomer M1 described in claim 2, it is characterised in that：
In step (1)~(9), the room temperature refer both to temperature be 5~35 DEG C, the stirring refer both to mixing speed be 1000~
2000r/min。
5. a kind of electroluminescent polymer being polymerize by electroluminescent monomer M1 described in claim 1, it is characterised in that
Structure is as follows：
Wherein, polymerization degree n is 1~1000；X represents molar fraction, 0≤x≤1；
Ar is one or more in following conjugation or non-conjugated structure unit：
Wherein, R1For H, the alkane of aryl, triphenylamine base, the straight chain of carbon atom number 1-20 or branched alkyl or carbon atom number 1-20
Oxygroup；Z1、Z2Independently it is expressed as H, D, F, alkenyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxy, carbon atom number 1
Naphthenic base that~30 alkyl, carbon atom number are 3~30, carbon atom number is 6~60 aromatic hydrocarbyls or carbon atom number is 3~60
Aromatic heterocycle.
6. a kind of preparation method of the electroluminescent polymer described in claim 5, it is characterised in that include the following steps：
(1) under inert gas protection, the monomer of polymeric monomeric unit M1 and the structure containing Ar are completely dissolved with solvent, in catalyst
Under effect and the effect of tetraethyl ammonium hydroxide aqueous solution, 60~100 DEG C of generation Suzuki polymerisations are heated to, the reaction time is
12~36h；
(2) step (1) is added phenyl boric acid after reaction, constant temperature the reaction was continued 6~12h；It adds bromobenzene and continues isothermal reaction 6
~12h；Reaction purifies gained reaction solution up to target product after stopping.
7. the preparation method of electroluminescent polymer according to claim 6, it is characterised in that：
In step (1), the organic solvent is toluene, tetrahydrofuran, dimethylbenzene, dioxane, n,N-Dimethylformamide
At least one of；
Catalyst described in step (1) is the mixture of palladium and thricyclohexyl phosphorus, tris(dibenzylideneacetone) dipalladium and
At least one of mixture, tetra-triphenylphosphine palladium or triphenylphosphine palladium of thricyclohexyl phosphorus；
The monomer of the structure containing Ar described in step (1) is in the monomer that end group is double borates, double boric acid, double bromines or double iodine
At least one, and must include the monomer that end group is double borates or double boric acid；Polymerized monomer M1 described in step (1), contain
The dosage of the monomer of Ar structures meets the monomer integral molar quantity containing double borates and/or boric acid functional group and contains double bromines and/or iodine
The monomer integral molar quantity of functional group is equal；The dosage of the catalyst is the 3%~5% of reaction monomers moles total number；It is described
The dosage of tetraethyl aqueous ammonium hydroxide to meet the volume ratio of its 20% aqueous solution and solvent be 1:4~6；
The dosage of phenyl boric acid described in step (2) is the 10~20% of reaction monomers moles total number；The dosage of the bromobenzene
It is 15~20 times of phenyl boric acid mole；
Purifying described in step (2) refers to being cooled to room temperature gained reaction solution, pours into methanol and precipitates, filtering, dry
Crude product, crude product toluene dissolve then column chromatography for separation, and column chromatography is later by precipitating is molten in methanol again after solvent concentration
In liquid, filter, it is dry, use methanol, acetone, tetrahydrofuran to extract successively obtained solid, by the tetrahydrofuran solution after extracting
Precipitation in methyl alcohol, is drying to obtain target product by precipitating again.
8. electroluminescent polymer according to claim 5 is in light emitting diode, organic field effect tube, organic sun
Application in energy battery, organic laser diode field.
9. application of the electroluminescent polymer according to claim 5 in the luminescent layer for preparing LED device.
10. application of the electroluminescent polymer according to claim 9 in the luminescent layer for preparing LED device,
It is specifically realized by following steps：The electroluminescent polymer is dissolved with organic solvent, then passes through spin coating, inkjet printing
Or printing film forming is to get the luminescent layer of LED device.
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| CN111574693A (en) * | 2020-06-15 | 2020-08-25 | 李建辉 | PLED polymer for polar solvent processing and preparation method thereof |
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