CN1193049C - Conjugated polymer containing pyridine on main chain, preparation process and use thereof - Google Patents
Conjugated polymer containing pyridine on main chain, preparation process and use thereof Download PDFInfo
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- CN1193049C CN1193049C CNB031189873A CN03118987A CN1193049C CN 1193049 C CN1193049 C CN 1193049C CN B031189873 A CNB031189873 A CN B031189873A CN 03118987 A CN03118987 A CN 03118987A CN 1193049 C CN1193049 C CN 1193049C
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Abstract
The present invention relates to a conjugated polymer containing pyridine on a main chain; in the structural formula of the conjugated polymer, Ar or Ar' is selected from aromatic heterocycle or aromatic carbocycle or derivates thereof. The present invention also provides a preparing method of the polymer containing pyridine. In the method, pyridine oxide and corresponding aromatic heterocycle or corresponding aromatic carbocycle or corresponding derivates thereof are used as raw materials; halogenated hydrocarbon or nitrobenzene are used as a solvent; the reaction is carried out at-10 DEG C to 40 DEG C under the condition of the existence of Lewis acid to obtain a polymer whose main chain contains the pyridine oxide; then, phosphorus trichloride or titanium trichloride is used for reduction to obtain the required polymer whose main chain contains the pyridine oxide. The conjugated polymer obtained by the preparing method of the polymer containing pyridine can be used as luminescent material and electric charge transferring material of electroluminescence devices. The present invention has the advantages of simple method, high yield, low cost, easy post processing, little pollution and easy commercial production.
Description
Technical field
The present invention relates to contain conjugated polymers of pyridine and its production and use on a kind of main chain.
Background technology
Pyridine is a kind of aromatic nucleus of electron deficiency, and polypyridine is a kind of luminescent material, is again a kind of effective electron transport material, and to oxidation stability.Polypyridine is successfully used to organic luminescent device, and has improved the performance [S.Daily, etal., J.Phys.:Condens.Matter, 10,5171 (1998)] of device.Patent WO9629,747 have reported that Wang Yunzhang etc. has made bipolar el light emitting device with polypyridine.These pyridine polymers are confined to the homopolymer and the polypyridine acetylene of pyridine, these polymkeric substance can only be dissolved in acidic solutions such as formic acid or hydrochloric acid, can not be dissolved in common organic solvent, acid solvent is contaminate environment but also influential to the polymer light-emitting performance not only, causes the emission wavelength red shift.The individual layer luminescent device efficient that this polymkeric substance is made very low [A.P.Monkman et al., SPIE, 1997,3145,208-18].Reason is well transporting holes of polypyridine.
Summary of the invention
Problem to be solved by this invention is to provide on a kind of main chain at above-mentioned the deficiencies in the prior art to contain conjugated polymers of pyridine and its production and use, and the preparation cost of this method material therefor is lower, and method is easy, is easy to suitability for industrialized production.This polymkeric substance has electronics and hole transport performance simultaneously, can be used as the luminescent material and the charge transfer material of electroluminescent device.
Technical scheme provided by the invention is: contain the conjugated polymers of pyridine on a kind of main chain, its structural formula is
Ar and Ar ' are selected from phenyl, substituted-phenyl in the formula; Condensed ring carbocyclic rings such as naphthalene, replacement naphthalene, fluorenes, 9-alkyl substituted fluorene, 9-aryl substituted fluorene or anthracene; Triphenylamine; Thiophene, alkylthrophene, pyridine, alkyl pyridine, carbazole, N-alkyl carbazole, oxine, tonka bean camphor or 7-diethylin-heterocycles such as 4-methylcoumarin; M=8-60, n=15-80, x=0-50.Work as x=0, the m preferred value is 10-60, and the n preferred value is 20-80; For the ternary conjugated polymers, the m preferred value is=8-30 that the n preferred value is=15-50 that the x preferred value is 15-50.
The present invention also provides the preparation method of above-mentioned pyridine polymers: with pyridine oxide and corresponding aroma heterocycle or aromatic carbocyclic and derivative thereof is raw material, halohydrocarbon or oil of mirbane are solvent, in the presence of lewis acid,-10 ℃～40 ℃ of reactions obtain containing on the main chain polymkeric substance of pyridine oxide, obtain the polymkeric substance that needed main chain contains pyridine with phosphorus trichloride or titanous chloride reduction then.
The amount ratio of above-mentioned pyridine oxide and corresponding aroma heterocycle or aromatic carbocyclic is 1: 3 to 3: 1 (mol ratio).
Above-mentioned aromatic heterocycle can be selected from thiophene, alkylthrophene, pyridine, alkyl pyridine, carbazole, N-alkyl carbazole, oxine or tonka bean camphor, is preferably hexyl carbazole, thiophene, oxine, tonka bean camphor; Aromatic carbocyclic can be selected from phenyl, substituted-phenyl, naphthalene, replacement naphthalene, fluorenes, 9-alkyl substituted fluorene, anthracene, phenanthrene, triphenylamine etc.
Above-mentioned lewis acid is FeCl
3, CuCl
2, AlCl
3Deng, be preferably FeCl
3
Above-mentioned solvent is methyl chloride (as trichloromethane or methylene dichloride), monochloroethane or oil of mirbane isopolarity solvent, is preferably chloroform.
Gained conjugated polymers of the present invention can be used as the luminescent material and the charge transfer material of electroluminescent device.
The present invention is pyridine and other aromatic hydrocarbon monomer copolymerization, fluorenes, and triphenylamine, alkyl carbazole, naphthalene, another kind of aromatic ring structure such as thiophene unit is incorporated in the pyridine polymers, and the conjugated polymers that contains pyridine on a series of new main chains is provided.Make product have luminous and charge transmission simultaneously.And the most important thing is to change the luminescent properties of polymkeric substance, can raise the efficiency, improve solvability, change the friendship emission wavelength, can realize panchromatic luminous from the blue light to ruddiness.For example, the multipolymer of pyridine and fluorenes is a kind of electron transport material and luminescent material; With triphenylamine, or the multipolymer of alkyl carbazole, then have electronics and cavity transmission ability concurrently.And, in these multipolymers, introduce the 3rd monomer, that material also can have is luminous, electric transmission and this three specific character of hole transport, and resulting polymers is not only good luminescent material, but also is the excellent electric charge transport material.The present invention can be by pyridine oxide and the monomer copolymerization that contains the solubility group, the polymkeric substance that can obtain having good solubility, energy spin-coating film, processing device.The present invention is introduced directly into the pyridine of electron deficiency on the main polymer chain with oxidative coupling method (be Scholl reaction), and method is easy, and productive rate is higher, and cost is lower, and aftertreatment is easy, pollutes for a short time, is easy to suitability for industrialized production.The present invention uses pyridine oxide to make polymerization single polymerization monomer, and the pyridine oxidation prepares easy than the polymerization single polymerization monomer dihalo pyridine halogenation of existing preparation polypyridine, pollute little.
Embodiment:
In reactor, add pyridine oxide, second monomer, or the 3rd monomer, methyl chloride, monochloroethane, oil of mirbane isopolarity solvent, lewis acid such as FeCl
3, CuCl
2, AlCl
3Deng the friedel-crafts reaction catalyzer, at-10 to 40 ℃, argon gas or nitrogen protection of inert gas were reacted 24 to 72 hours down, in the methyl alcohol or ethanol with four times of the direct impourings of reactant, stirred the back suction filtration, collecting precipitation then.This precipitation is carried out extracting with methyl alcohol or ethanol, reduces with phosphorus trichloride or titanous chloride in chloroform then, promptly obtains material requested.
Three mouthfuls of reaction flasks of embodiment 1:100 milliliter are equipped with water condensing tube, constant pressure funnel, argon gas ingress pipe.Argon gas is derived by the prolong top, and connects through a drying tower and the atmosphere that calcium chloride or sodium hydroxide are housed.Place one in the bottle and stir magneton, reaction flask is put on the magnetic stirring apparatus.Earlier logical argon gas is five minutes before the reaction; under the argon gas stream protection; add N-pyridine oxide 0.38g (4mmol); add chloroform 20ml, make the pyridine oxide dissolving, add FERRIC CHLORIDE ANHYDROUS 3.9g (24mmol) again; adding N-hexyl carbazole 0.5g (2mmol) in the constant pressure funnel is dissolved in the 15ml chloroform; N-hexyl carbazole slowly is added drop-wise in the there-necked flask, magnetic agitation, and 28 ℃ were reacted 40 hours down.In the reaction solution impouring 100ml ethanol, stirred two hours then, suction filtration obtains the conjugated polymers of greyish-green solid oxidation pyridine and N-hexyl carbazole, after drying, in apparatus,Soxhlet's, use the methyl alcohol extracting, oven dry (50 ℃), be weighed as: 0.53g, productive rate 60.2%.Reduction: the 0.4g products therefrom is dissolved in the 30ml tetrahydrofuran (THF), under 0 ℃, slowly drip Titanium Trichloride Solution to the purple in the reaction solution under the induction stirring and no longer take off, then with the neutralization of 50% sodium hydroxide solution, the adularescent precipitation produces, centrifugation removes the solid-liquid phase, the solid phase chloroform extraction, and the extraction liquid of gained and the liquid phase of former centrifugal gained merge, use chloroform extraction again, collect organic phase, use the water pump evaporated under reduced pressure, obtain light yellow solid.Use alcohol flushing, obtain the conjugated polymers 0.36g of final product pyridine and N-hexyl carbazole after drying, productive rate 90%.
Embodiment 2: equipment therefor is with example 1.In there-necked flask, add N-pyridine oxide 0.67g (7mmol), chloroform 25ml, the dissolving back adds FERRIC CHLORIDE ANHYDROUS 6.8g (42mmol).Add triphenylamine 0.86g (3.5mmol), chloroform 15ml in the constant pressure funnel.Slowly drip triphenylamine, 40 ℃ of reactions 36 hours in the impouring 120ml ethanol, were stirred 2 hours, and suction filtration obtains the conjugated polymers of yellow mercury oxide pyridine oxide and triphenylamine, dries back ethanol extracting, dries (50 ℃), is weighed as 0.72g, productive rate 47.1%.Reduction: the 0.31g products therefrom is dissolved in the frappe chloroform of 20ml, add the 0.4ml phosphorus trichloride, 75 ℃ of temperature controls react a hour postcooling, adding 20ml water then stirs, be neutralized to alkalescence with sodium hydroxide, collect organic phase in the reaction flask, add dried over sodium sulfate, be evaporated to 8ml, add the 30ml ethanol sedimentation, suction filtration obtains the conjugated polymers 0.29g of light yellow solid pyridine and triphenylamine, productive rate 95% at last.
Three mouthfuls of reaction flasks of embodiment 3:100 milliliter are equipped with water condensing tube, argon gas ingress pipe.Argon gas is derived by the prolong top, and connects through a drying tower and the atmosphere that calcium chloride is housed.Place one in the bottle and stir magneton, reaction flask is put on the magnetic stirring apparatus.Earlier logical argon gas is five minutes before the reaction; under the argon gas stream protection; add N-pyridine oxide 0.57g (6mmol) from another opening (clogging with grinding port plug before this) of there-necked flask; fluorenes 0.51g (3mmol); chloroform 30ml; make it dissolving, add FERRIC CHLORIDE ANHYDROUS 5.85g (36mmol) then, cryosel is bathed reaction down 48 hours; in the impouring 100ml ethanol; stirred 2 hours, suction filtration obtains the conjugated polymers of yellow solid pyridine oxide and fluorenes; dry back ethanol extracting; oven dry (50 ℃) is weighed as: 0.68g, productive rate 63.0%.Reduce (reactions steps and condition are with example 2) down at 75 ℃ with phosphorus trichloride 0.65g products therefrom is dissolved in the chloroform, finally obtain the conjugated polymers of light yellow solid pyridine and fluorenes, productive rate 86%, molecular weight is: Mn:4735, Mw:8179.
Embodiment 4: reaction unit is with example 1.In there-necked flask, add N-pyridine oxide 0.38g (4mmol), oil of mirbane 10ml, the dissolving back adds FERRIC CHLORIDE ANHYDROUS 3.9g (24mmol), adds 2-naphthol methyl ether 0.32g (2mmol), oil of mirbane 10ml in the constant pressure funnel.Slowly drip the 2-naphthol methyl ether.Under 16 ℃, reacted 50 hours, in the impouring 80ml methyl alcohol, stirred 2 hours, suction filtration obtains the conjugated polymers of black precipitate pyridine oxide and 2-naphthol methyl ether, dries back methyl alcohol extracting, dries (50 ℃), is weighed as 0.31g, productive rate 44.3%.Reduce (reactions steps and condition are with example 2) down at 75 ℃ with phosphorus trichloride 0.3g products therefrom is dissolved in the chloroform, finally obtain the conjugated polymers of 0.25g light yellow solid pyridine and 2-naphthol methyl ether, productive rate 84%.
Embodiment 5: reaction unit is with example 1.In there-necked flask, add N-pyridine oxide 0.38g (4mmol), thiophene 0.25g (3mmol), chloroform 25ml, after treating sample dissolution, add iron trichloride 5.85g (36mmol), add triphenylamine 0.49g (2mmol) in the constant pressure funnel, chloroform 15ml, slowly drip triphenylamine, 6 ℃ were reacted 48 hours down, in the impouring 100ml ethanol, stirred one hour, suction filtration obtains the conjugated polymers of garnet solid oxidation pyridine and thiophene and triphenylamine, after drying, use the ethanol extracting, oven dry (50 ℃) is weighed as 0.72g, productive rate 64.3%.Reduce (reactions steps and condition are with example 2) down at 75 ℃ with phosphorus trichloride 0.7g products therefrom is dissolved in the chloroform, finally obtain the conjugated polymers of 0.62g garnet solid pyridine, thiophene and triphenylamine, productive rate is 88%.
Embodiment 6: reaction unit is with example 3.In there-necked flask, add N-pyridine oxide 0.19g (2mmol), oxine 0.26g (2mmol), chloroform 20ml, after the sample dissolution, add aluminum trichloride (anhydrous) 2.14g (16mmol), 15 ℃ were reacted 60 hours down, in the impouring 80ml ethanol, stirred one hour, and obtained the conjugated polymers of gray solid pyridine oxide and oxine.Water is washed back oven dry (50 ℃) repeatedly, obtains the 0.18g product, productive rate 40.0%.Reduction (with example 2) gets the conjugated polymers of required pyridine and oxine.
Embodiment 7: reaction unit is with example 1.In there-necked flask, add N-pyridine oxide 0.38g (4mmol), fluorenes 0.33g (2mmol), chloroform 25ml, after the sample dissolution, add anhydrous cupric chloride 4.32g (32mmol), add triphenylamine 0.49g (2mmol) in the constant pressure funnel, chloroform 10ml, 5 ℃ were reacted 60 hours down, directly are poured in the 100ml ethanol, stirred 2 hours, obtain the conjugated polymers of yellow solid pyridine oxide and fluorenes and triphenylamine, after drying, use the ethanol extracting, oven dry (50 ℃) obtains 0.78g product, productive rate 65.0%.Reduce (reactions steps and condition are with example 2) down at 75 ℃ with phosphorus trichloride 0.75g products therefrom is dissolved in the chloroform, finally obtain the conjugated polymers of 0.66g yellow solid pyridine and fluorenes and triphenylamine, productive rate 88%, molecular weight is: Mn:10690, Mw:11490.
Embodiment 8: the product purification method: thick product 0.5 gram of conjugated polymers that contains pyridine in 100 milliliters of single port flasks on above-mentioned main chain is dissolved in 30 milliliters of chloroforms, makes it dissolving in ultrasonic 20 minutes.Filter, in 100 milliliters of ethanol of filtrate impouring, stirred 60 minutes, suction filtration, collecting precipitation dry below 50 ℃, obtains containing on the required main chain conjugated polymers straight product of pyridine.
Claims (8)
1. contain the conjugated polymers of pyridine on the main chain, its structural formula is
M=8-60 in the formula, n=15-80, x=0-50, Ar and Ar ' are selected from phenyl, substituted-phenyl, naphthalene, replacement naphthalene, fluorenes, 9-alkyl substituted fluorene, 9-aryl substituted fluorene, anthracene, phenanthrene, triphenylamine, thiophene, alkylthrophene, pyridine, alkyl pyridine, carbazole, N-alkyl carbazole, oxine, tonka bean camphor or 7-diethylin-4-methylcoumarin.
2. conjugated polymers according to claim 1 is characterized in that: m=10-60 in the structural formula, n=20-80, x=0.
3. conjugated polymers according to claim 1 is characterized in that: m=8-30 in the structural formula, n=15-50, x=15-50.
4. the preparation method of the described conjugated polymers of claim 1, it is characterized in that: with pyridine oxide and corresponding aroma heterocycle or aromatic carbocyclic and derivative thereof is raw material, halohydrocarbon or oil of mirbane are solvent, in the presence of lewis acid,-10 ℃～40 ℃ of reactions obtain containing on the main chain polymkeric substance of pyridine oxide, obtain the polymkeric substance that needed main chain contains pyridine with phosphorus trichloride or titanous chloride reduction then; The consumption mol ratio of pyridine oxide and corresponding aroma heterocycle or aromatic carbocyclic is 1 to 3 to 3 to 1.
5. preparation method according to claim 4, it is characterized in that: above-mentioned aromatic heterocycle is selected from thiophene, alkylthrophene, pyridine, alkyl pyridine, carbazole, N-alkyl carbazole, oxine, 7-diethylin-4-methylcoumarin or tonka bean camphor, and aromatic carbocyclic is selected from phenyl, substituted-phenyl, naphthalene, replacement naphthalene, fluorenes, 9-aryl substituted fluorene, 9-alkyl substituted fluorene, anthracene, phenanthrene or triphenylamine.
6. preparation method according to claim 5 is characterized in that: above-mentioned lewis acid is iron trichloride, cupric chloride or aluminum chloride.
7. preparation method according to claim 5 is characterized in that: above-mentioned halogenated hydrocarbon solvent is trichloromethane, methylene dichloride or monochloroethane.
8. the described conjugated polymers of claim 1 is as the luminescent material and the charge transfer material of electroluminescent device.
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| CN100341977C (en) * | 2004-10-20 | 2007-10-10 | 中国科学院化学研究所 | Intramolecular charge transfer type red luminescent material and preparation and application thereof |
| CN101643479B (en) * | 2008-08-07 | 2012-07-18 | 通用电气公司 | Compound containing benzene pyridine unit |
| CN110776621B (en) * | 2018-07-31 | 2022-01-18 | 华南理工大学 | D-pi-A type polymer containing quinoline-based fused ring unit and preparation method and application thereof |
| CN110776619B (en) * | 2018-07-31 | 2022-11-18 | 华南理工大学 | Regular polymer containing quinoline-based fused ring unit and preparation method and application thereof |
| CN114276551B (en) * | 2020-09-28 | 2023-10-10 | Tcl科技集团股份有限公司 | Composite nano material, preparation method thereof and quantum dot light emitting diode |
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