CN103483556A - Hydroxyethyl-containing biradicals conjugated polymer and application thereof - Google Patents

Hydroxyethyl-containing biradicals conjugated polymer and application thereof Download PDF

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CN103483556A
CN103483556A CN201310413985.6A CN201310413985A CN103483556A CN 103483556 A CN103483556 A CN 103483556A CN 201310413985 A CN201310413985 A CN 201310413985A CN 103483556 A CN103483556 A CN 103483556A
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isophthalic
bromine
conjugated polymers
alcohol amido
hydrogen atom
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陈军武
阚媛媛
朱永祥
曹镛
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South China University of Technology SCUT
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Abstract

The invention relates to a hydroxyethyl-containing biradicals conjugated polymer and application of the hydroxyethyl-containing biradicals conjugated polymer. Various conjugated aromatic monomers are selected and the conjugated aromatic monomers and biradicals monomers replaced byhydroxyethyl are copolymerized to acquire the hydroxyethyl-containing biradicals conjugated polymer. The prepared hydroxyethyl-containing biradicals conjugated polymer can be used for manufacturing photoelectrical function devices containing boundary layers used for making contact with negative electrodes in organic light emitting diodes and organic photovoltaic cells.

Description

A kind of isophthalic conjugated polymers and application thereof containing the di-alcohol amido
Technical field
The present invention relates to a kind of new polymers that is applied to photoelectron material and devices field, more specifically relate to a kind of isophthalic Optical Properties of Novel Conjugated containing the di-alcohol amido and preparation method thereof and application.
Background technology
Since Japanese scientist's Hideki Shirakawa in 1977 is found the polyacetylene conduction, this being called as the conductive polymers photoelectric properties outstanding with it of " the 4th generation polymer " material attracted numerous scientists to be studied.Conducting polymer is compared with the inorganic materials with identical or close purposes, has density low, and easily processing, synthesize the advantages such as range of choice is wide.Due to the conjugate property of this class material structure, make its can transmission charge, stimulated luminescence, thus can or potential may being applied on many electronics or opto-electronic device, for example comprise polymer LED, photovoltaic cell, field effect transistor etc.Potential application prospect and wide application field impel scientist competitively to study the conjugation material that this class has photoelectric activity, comprise the small molecules of multiple conjugated structure, and polyacetylene, polypyrrole, Polythiophene, polyaniline, poly-fluorenes, polycarbazole etc.
Since 20 century 70s, the conjugated polymers of many different structures and function emerges in large numbers one after another, wherein contains the performance that differs from common conjugated polymers that the polymer materials of hydrophilic radical possesses and more and more causes people's interest.For the preliminary study of this class material since the eighties in last century, the existence of conjugated main chain makes this base polymer have the essential characteristic of general neutral semi-conducting polymer, and the existence of alkyl chain terminal hydrophilic group group makes this class material possess some distinguished chemistry and physicalies.Existence due to strong hydrophilicity group on side chain, make most polymers can be dissolved in the organic solvent or water of polarity, make this class material can many eco-friendly solvents (such as: alcohol and water), processed, the photoelectric device that their this special solvabilities also prepare multilayer for us provides may.Simultaneously, some special functional group can have with some protein, nucleic acid etc. the metal ion generation complexing action of bioactive material or different volumes, and then the difference response that shows main polymer chain spectrum, this phenomenon makes this class material that application widely arranged aspect chemistry and biosensor.Because absorption mutually occurs the different ions with positive and negative charge, affect piling up between main polymer chain, this base polymer can form the state of aggregation pattern with supramolecular structure; , with the ion of positive and negative charge, under the effect of electric field, can move, the carrier transmission characteristics of conjugated polymer main chain and energy band structure, also make this class material also become the effective subsidiary material of a class in the photoelectric device of multilayer simultaneously.
In recent years, the researchist is making great efforts to seek to improve polymer LED always, photovoltaic cell, and the method for field-effect transistor, chemistry and bioprobe performance, the preparation of material is one of very important key element.So all being devoted to exploitation, many research groups there is high-quantum efficiency, high color purity, the luminescence polymer that contains hydrophilic radical of good stability; And carrier mobility is high, energy band structure is controlled, has special deliquescent interface function material.Realize these targets, need to develop the more novel conjugated molecule that contains hydrophilic radical and polymer materials.
Summary of the invention
The object of the invention is to the deficiency existed for prior art, a kind of isophthalic conjugated polymers containing the di-alcohol amido is provided, there is potential special solvability and energy band structure, can be used for preparation and make the photoelectric functional device.
The present invention also aims to provide the preparation method of the described isophthalic conjugated polymers containing the di-alcohol amido.
The present invention also aims to provide the described application of isophthalic conjugated polymers in Organic Light Emitting Diode and organic photovoltaic battery containing the di-alcohol amido.
Isophthalic conjugated polymers containing the di-alcohol amido of the present invention has structure as follows:
Figure BDA0000380724440000021
Wherein, m is 2～12; Ar is conjugate unit; 0<x≤1,0≤y<1, x+y=1; N=3-1000.
The Ar conjugate unit comprises a kind of or its multiple combination in the aromatic heterocycle that aromatic nucleus that ethene support group, acetylene support group, hydrocarbon atom form, aromatic heterocycle that carbon nitrogen hydrogen atom forms, aromatic heterocycle that carbon nitrogen oxygen hydrogen atom forms, aromatic heterocycle that carbon sulphur hydrogen atom forms, aromatic heterocycle that carbon silicon hydrogen atom forms, aromatic heterocycle that carbon nitrogen sulphur hydrogen atom forms and carbon silicon sulphur hydrogen atom form.
The Ar conjugate unit, can be with substituted radical, and substituted radical comprises one or more combinations in alkyl, fluoro-alkyl, alkoxyl group, ester group, carbonyl.
The preparation method of the described isophthalic conjugated polymers containing the di-alcohol amido will carry out copolymerization containing benzene monomer between the di-alcohol amido and Ar monomer.
The isophthalic monomer structure containing the di-alcohol amido used is as follows:
Figure BDA0000380724440000031
Wherein, R 1for reaction active groups, comprise bromine, iodine, chlorine, trialkyltin, 4,4,5,5-tetramethyl--1,3, a kind of in 2-dioxa pentaborane-2-base, z is 2～12; The carbon number of the alkyl in described trialkyltin is 1～4.
The structure of the Ar monomer used is: R 2-Ar-R 2, R wherein 2for reaction active groups, comprise bromine, iodine, chlorine, trialkyltin, 4,4,5,5-tetramethyl--1,3, a kind of in 2-dioxa pentaborane-2-base; The carbon number of the alkyl in described trialkyltin is 1～4.
The described isophthalic conjugated polymers containing the di-alcohol amido can be applicable to be prepared with OLED.
The described isophthalic conjugated polymers containing the di-alcohol amido can be applicable to prepare organic photovoltaic battery.
Compared with prior art, the present invention has following advantage and technique effect: adopt the isophthalic conjugated polymers that contains the di-alcohol amido as the cathodic modification layer, can successfully prepare Organic Light Emitting Diode and organic photovoltaic battery device with multilayered structure.In organic light emitting diode device, containing the auxiliary electronic injection of having realized cathodic area of the isophthalic conjugated polymers cathodic modification layer of di-alcohol amido.In the organic photovoltaic battery device, containing the auxiliary electron collection that has realized cathodic area of the isophthalic conjugated polymers cathodic modification layer of di-alcohol amido.
Embodiment
Preparation and application below in conjunction with specific embodiment to the isophthalic conjugated polymers containing the di-alcohol amido are further described.But protection domain of the presently claimed invention is not limited to the related scope of embodiment.
Embodiment 1:
The preparation of the bromo-5-of 1,3-bis-(bromine alkoxyl group) benzene, reaction formula is as follows:
Figure BDA0000380724440000041
To prepare the bromo-5-of 1,3-bis-(2-bromine oxethyl) benzene, be that example is explained.Under the protection of inert atmosphere, by 3 of 50 mmoles, the 5-dibromophenol, 60 mmole potassium hydroxide are dissolved in the methyl alcohol of 150 milliliters, and reaction mixture stirs 1 hour.The glycol dibromide of 150 mmoles is dissolved in the acetone of 150 milliliters, joins in reaction flask reflux 12 hours.Question response is cooled to room temperature by mixing solutions after finishing, and uses dichloromethane extraction, with isolating organic phase after distilled water wash.The organic phase anhydrous magnesium sulfate drying, except desolventizing, obtain white solid with the silica gel chromatographic column separating-purifying after filtering.Warp 1h NMR, 13c NMR and ultimate analysis test are indicated as target product 1, the bromo-5-of 3-bis-(2-bromine oxethyl) benzene.
To prepare the bromo-5-of 1,3-bis-(4-bromine butoxy) benzene, be that example is explained again.Under the protection of inert atmosphere, by 3 of 50 mmoles, the 5-dibromophenol, 60 mmole potassium hydroxide are dissolved in the methyl alcohol of 150 milliliters, and reaction mixture stirs 1 hour.Isosorbide-5-Nitrae-the dibromobutane of 150 mmoles is dissolved in the acetone of 150 milliliters, joins in reaction flask reflux 12 hours.Question response is cooled to room temperature by mixing solutions after finishing, and uses dichloromethane extraction, with distilled water wash, repeatedly isolates afterwards organic phase.The organic phase anhydrous magnesium sulfate drying, except desolventizing, obtain white solid with the silica gel chromatographic column separating-purifying after filtering.Warp 1h NMR, 13c NMR and ultimate analysis test are indicated as target product 1, the bromo-5-of 3-bis-(4-bromine butoxy) benzene.
To prepare the bromo-5-of 1,3-bis-(6-bromine hexyloxy) benzene, be that example is explained again.Under the protection of inert atmosphere, by 3 of 50 mmoles, the 5-dibromophenol, 60 mmole potassium hydroxide are dissolved in the methyl alcohol of 150 milliliters, and reaction mixture stirs 1 hour.By 1 of 150 mmoles, the 6-dibromo-hexane is dissolved in the acetone of 150 milliliters, joins in reaction flask reflux 12 hours.Question response is cooled to room temperature by mixing solutions after finishing, and uses dichloromethane extraction, with isolating organic phase after distilled water wash.The organic phase anhydrous magnesium sulfate drying, except desolventizing, obtain white solid with the silica gel chromatographic column separating-purifying after filtering.Warp 1h NMR, 13c NMR and ultimate analysis test are indicated as target product 1, the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene.
To prepare the bromo-5-of 1,3-bis-(8-bromine octyloxy) benzene, be that example is explained again.Under the protection of inert atmosphere, by 3 of 50 mmoles, the 5-dibromophenol, 60 mmole potassium hydroxide are dissolved in the methyl alcohol of 150 milliliters, and reaction mixture stirs 1 hour.By 1 of 150 mmoles, 8-bis-bromooctanes are dissolved in the acetone of 150 milliliters, join in reaction flask reflux 12 hours.Question response is cooled to room temperature by mixing solutions after finishing, and uses dichloromethane extraction, with isolating organic phase after distilled water wash.The organic phase anhydrous magnesium sulfate drying, except desolventizing, obtain white solid with the silica gel chromatographic column separating-purifying after filtering.Warp 1h NMR, 13c NMR and ultimate analysis test are indicated as target product 1, the bromo-5-of 3-bis-(8-bromine octyloxy) benzene.
Alkoxyl group in the bromo-5-of 1,3-bis-(bromine alkoxyl group) benzene also comprises: 10-bromine ten alkoxyl groups and 12-bromo-dodecane oxygen base etc., but be not limited only to this.
Embodiment 2:
The preparation of 1,3-pair-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane)-5-(bromine alkoxyl group)-benzene, reaction formula is as follows:
Figure BDA0000380724440000051
With 1,3-two-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane)-5-(2-bromine oxethyl)-benzene is that example is explained.Under the protection of inert atmosphere, by 3 mmoles 1, the bromo-5-of 3-bis-(2-bromine oxethyl) benzene, 9 mmole connection pinacol boric acid esters, 27 mmole potassium acetates, 0.09 mmole PdCl 2(dppf) be dissolved in 50 milliliters of anhydrous Isosorbide-5-Nitrae-dioxane, be heated to 80 ℃ of reactions and spend the night.Question response is cooled to room temperature by mixing solutions after finishing, and reaction product is poured in distilled water, uses dichloromethane extraction, with distilled water wash, repeatedly isolates afterwards organic phase.The organic phase anhydrous magnesium sulfate drying, except desolventizing, obtain white solid with the silica gel chromatographic column separating-purifying after filtering.Warp 1h NMR, 13c NMR and ultimate analysis test are indicated as target product 1,3-pair-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane)-5-(2-bromine oxethyl)-benzene.
Again with 1,3-two-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane)-5-(4-bromine butoxy)-benzene is that example is explained.Under the protection of inert atmosphere, by 3 mmoles 1, the bromo-5-of 3-bis-(4-bromine butoxy) benzene, 9 mmole connection pinacol boric acid esters, 27 mmole potassium acetates, 0.09 mmole PdCl 2(dppf) be dissolved in 50 milliliters of anhydrous Isosorbide-5-Nitrae-dioxane, be heated to 80 ℃ of reactions and spend the night.Question response is cooled to room temperature by mixing solutions after finishing, and reaction product is poured in distilled water, uses dichloromethane extraction, with distilled water wash, repeatedly isolates afterwards organic phase.The organic phase anhydrous magnesium sulfate drying, except desolventizing, obtain white solid with the silica gel chromatographic column separating-purifying after filtering.Warp 1h NMR, 13cNMR and ultimate analysis test are indicated as target product 1,3-pair-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane)-5-(4-bromine butoxy)-benzene.
Again with 1,3-two-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane)-5-(6-bromine hexyloxy)-benzene is that example is explained.Under the protection of inert atmosphere, by 3 mmoles 1, the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene, 9 mmole connection pinacol boric acid esters, 27 mmole potassium acetates, 0.09 mmole PdCl 2(dppf) be dissolved in 50 milliliters of anhydrous Isosorbide-5-Nitrae-dioxane, be heated to 80 ℃ of reactions and spend the night.Question response is cooled to room temperature by mixing solutions after finishing, and reaction product is poured in distilled water, uses dichloromethane extraction, with distilled water wash, repeatedly isolates afterwards organic phase.The organic phase anhydrous magnesium sulfate drying, except desolventizing, obtain white solid with the silica gel chromatographic column separating-purifying after filtering.Warp 1h NMR, 13cNMR and ultimate analysis test are indicated as target product 1,3-pair-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane)-5-(6-bromine hexyloxy)-benzene.
5-bromine alkoxyl group in 1,3-pair-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane)-5-(bromine alkoxyl group)-benzene also comprises: 8-bromine octyloxy, 10-bromine ten alkoxyl groups, 12-bromo-dodecane oxygen base etc., but be not limited only to this.
Embodiment 3:
The preparation of poly-isophthalic, reaction formula is as follows:
Figure BDA0000380724440000071
Under the protection of inert atmosphere, by 1, the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene and 1, 3-two-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxa pentaborane) each 0.5 mmole of-5-(6-bromine hexyloxy)-benzene, several Aliquat336, with the 2 ml concns wet chemical that is 2 mol/L, be dissolved in 10 milliliters of toluene, heating reflux reaction 48 hours, reaction is poured mixing solutions in 300 ml methanol into after finishing, by the precipitation of collection dissolution filter again, the crude product use washing with acetone obtained 12 hours and dry 24 hours in a vacuum, obtain white polymer.
The number-average molecular weight of this polymkeric substance is 5000, and weight-average molecular weight is 7000.The tetrahydrofuran solution of polymkeric substance the UV absorption peak occurs in 250 nanometers.The fluorescence spectrum of the tetrahydrofuran solution of polymkeric substance glow peak occurs in 350 nanometers.
Embodiment 4:
The preparation of the conjugated polymers of bromine alkoxyl group isophthalic and 1,3-hypoboric acid ester substituted benzene, reaction formula is as follows:
Figure BDA0000380724440000072
Under nitrogen atmosphere, add 1 in reaction flask, 3-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane) benzene and 1, each 0.5 mmole of the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene, several Aliquat336, and the 2 ml concns wet chemical that is 2M, be dissolved in 10 milliliters of toluene, heating reflux reaction 48 hours, reaction is poured mixing solutions in 300 ml methanol into after finishing, by the precipitation of collection dissolution filter again, the crude product use washing with acetone obtained 12 hours and dry 24 hours in a vacuum, obtain white polymer.
The number-average molecular weight of this polymkeric substance is 7000, and weight-average molecular weight is 9800.The tetrahydrofuran solution of polymkeric substance the UV absorption peak occurs in 255 nanometers.The fluorescence spectrum of the tetrahydrofuran solution of polymkeric substance glow peak occurs in 345 nanometers.
Embodiment 5:
The preparation of the conjugated polymers of bromine alkoxyl group isophthalic and fluorenes, reaction formula is as follows:
Figure BDA0000380724440000081
Under the protection of inert atmosphere, by 1, 3-two-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxa pentaborane)-5-(6-bromine hexyloxy)-benzene 0.5 mmole, 1, the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene 0.49 mmole, 9, 9-dibromo hexyl-3, 6-dibromo fluorenes 0.01 mmole, several Aliquat336, with the 2 ml concns wet chemical that is 2 mol/L, be dissolved in 10 milliliters of toluene, heating reflux reaction 48 hours, reaction is poured mixing solutions in 300 ml methanol into after finishing, by the precipitation of collection dissolution filter again, the crude product use washing with acetone obtained 12 hours and dry 24 hours in a vacuum, obtain white polymer.The number-average molecular weight of this polymkeric substance is 5500, and weight-average molecular weight is 8000.
Embodiment 6:
The preparation of the conjugated polymers of bromine alkoxyl group isophthalic and carbazole, reaction formula is as follows:
Figure BDA0000380724440000082
Under the protection of inert atmosphere, by 1, the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene 0.01 mmole, N-bromine hexyl-3, 6-dibromo carbazole 0.49 mmole, N-bromine hexyl-3, 6-bis-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxa pentaborane-2-yl) carbazole 0.5 mmole, several Aliquat336, with the 2 ml concns wet chemical that is 2 mol/L, be dissolved in 10 milliliters of toluene, heating reflux reaction 48 hours, reaction is poured mixing solutions in 300 ml methanol into after finishing, by the precipitation of collection dissolution filter again, the crude product use washing with acetone obtained 12 hours and dry 24 hours in a vacuum, obtain white polymer.The number-average molecular weight of this polymkeric substance is 5500, and weight-average molecular weight is 8000.
Embodiment 7:
The preparation of the conjugated polymers of bromine alkoxyl group isophthalic and thiophene, reaction formula is as follows:
Under the protection of inert atmosphere, by 1, 3-two-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxa pentaborane)-5-(6-bromine hexyloxy)-benzene 0.5 mmole, 1, the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene 0.49 mmole, 2, 5-dibromo thiophene 0.01 mmole, several Aliquat336, with the 2 ml concns wet chemical that is 2 mol/L, be dissolved in 10 milliliters of toluene, heating reflux reaction 48 hours, reaction is poured mixing solutions in 300 ml methanol into after finishing, by the precipitation of collection dissolution filter again, the crude product use washing with acetone obtained 12 hours and dry 24 hours in a vacuum, obtain white polymer.The number-average molecular weight of this polymkeric substance is 4000, and weight-average molecular weight is 6700.
Embodiment 8:
The preparation of the conjugated polymers of bromine alkoxyl group isophthalic and silicon fluorenes, reaction formula is as follows:
Under the protection of inert atmosphere, by 1, 3-two-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxa pentaborane)-5-(6-bromine hexyloxy)-benzene 0.5 mmole, 1, the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene 0.49 mmole, 9, 9-dibromo hexyl-3, 6-dibromo silicon fluorenes 0.01 mmole, several Aliquat336, with the 2 ml concns wet chemical that is 2 mol/L, be dissolved in 10 milliliters of toluene, heating reflux reaction 48 hours, reaction is poured mixing solutions in 300 ml methanol into after finishing, by the precipitation of collection dissolution filter again, the crude product use washing with acetone obtained 12 hours and dry 24 hours in a vacuum, obtain white polymer.The number-average molecular weight of this polymkeric substance is 4000, and weight-average molecular weight is 6400.
Embodiment 9:
The preparation of the conjugated polymers of bromine alkoxyl group isophthalic and diazosulfide, reaction formula is as follows:
Figure BDA0000380724440000101
Method is with embodiment 8.Bromo-2,1 with 4,7-bis-, the 3-diazosulfide replaces 9,9-dibromo hexyl-3,6-dibromo silicon fluorenes.The number-average molecular weight of the faint yellow polymkeric substance of gained is 12000, and weight-average molecular weight is 27000.
Embodiment 10:
The preparation of bromine alkoxyl group isophthalic and 4,7-bithiophene benzthiadiazole's conjugated polymers, reaction formula is as follows:
Method is with embodiment 8.With two (the bromo-2-thiophene of 5-)-2,1 of 4,7-, the 3-diazosulfide replaces 9,9-dibromo hexyl-3,6-dibromo silicon fluorenes.The number-average molecular weight of gained red polymer is 6500, and weight-average molecular weight is 10000.
Embodiment 11:
The preparation of the conjugated polymers of bromine alkoxyl group isophthalic and 5,8-, bis-thiophene-quinoxaline, reaction formula is as follows:
Figure BDA0000380724440000111
Under nitrogen atmosphere, add 1 in reaction flask, 3-(4,4,5,5-tetramethyl--1,3,2-dioxa pentaborane) benzene and 1, each 0.5 mmole of the bromo-5-of 3-bis-(6-bromine hexyloxy) benzene, several Aliquat336, and the 2 ml concns wet chemical that is 2M, be dissolved in 10 milliliters of toluene, heating reflux reaction 48 hours, reaction is poured mixing solutions in 300 ml methanol into after finishing, by the precipitation of collection dissolution filter again, the crude product use washing with acetone obtained 12 hours and dry 24 hours in a vacuum, obtain white polymer.The number-average molecular weight of resulting polymers is 7000, and weight-average molecular weight is 13100.
Embodiment 12:
Poly-bromine alkoxyl group isophthalic changes into the polymkeric substance containing di-alcohol amido isophthalic, and reaction formula is as follows:
Figure BDA0000380724440000112
Under inert atmosphere, by embodiment 3,100 milligrams of prepared poly-bromine hexyloxy isophthalic are dissolved in 10 milliliters of THF and 10 milliliters of DMF, add 0.5 gram diethanolamine, under 60 ℃, stir 48 hours.After reaction finishes, mixing solutions is poured in 300 ml waters, by the white precipitate collected dry 24 hours in a vacuum, obtained white polymer.The number-average molecular weight of this polymkeric substance is 4800, and weight-average molecular weight is 6500.
Embodiment 13:
The alternating copolymer of bromine alkoxyl group isophthalic and isophthalic changes into the alternating copolymer replaced containing the di-alcohol amido, and reaction formula is as follows:
Figure BDA0000380724440000121
Method is with embodiment 12.The isophthalic that prepared bromine alkoxyl group replaces with embodiment 4 and the polymkeric substance of isophthalic replace poly-bromine hexyloxy isophthalic.The number-average molecular weight of gained white polymer is 6500, and weight-average molecular weight is 9300.
Embodiment 14:
The random copolymers of isophthalic and fluorenes changes into the random copolymers replaced containing the di-alcohol amido, and reaction formula is as follows:
Figure BDA0000380724440000122
Method is with embodiment 12.The multipolymer of the fluorenes that prepared bromine alkoxyl group isophthalic and alkyl bromide replace with embodiment 5 replaces poly-bromine hexyloxy isophthalic.The number-average molecular weight of gained red polymer is 5000, and weight-average molecular weight is 7500.
Embodiment 15:
The random copolymers of isophthalic and carbazole changes into the random copolymers replaced containing the di-alcohol amido, and reaction formula is as follows:
Method is with embodiment 12.The multipolymer of the carbazole that prepared bromine alkoxyl group isophthalic and alkyl bromide replace with embodiment 6 replaces poly-bromine hexyloxy isophthalic.The number-average molecular weight of gained red polymer is 5500, and weight-average molecular weight is 8000.
Embodiment 16:
The random copolymers of isophthalic and thiophene changes into the random copolymers containing the di-alcohol amido, and reaction formula is as follows:
Figure BDA0000380724440000131
Method is with embodiment 12.With embodiment 7, the random copolymers of prepared bromine alkoxyl group isophthalic and thiophene replaces poly-bromine hexyloxy isophthalic.The number-average molecular weight of gained white polymer is 4000, and weight-average molecular weight is 6700.
Embodiment 17:
The random copolymers of isophthalic and silicon fluorenes changes into the random copolymers containing the di-alcohol amido, and reaction formula is as follows:
Figure BDA0000380724440000132
Method is with embodiment 12.With embodiment 8, the multipolymer of prepared bromine alkoxyl group isophthalic and silicon fluorenes replaces poly-bromine hexyloxy isophthalic.The number-average molecular weight of gained white polymer is 3900, and weight-average molecular weight is 6000.
Embodiment 18:
The random copolymers of isophthalic and diazosulfide changes into the random copolymers containing the di-alcohol amido, and reaction formula is as follows:
Figure BDA0000380724440000141
Method is with embodiment 12.With embodiment 9, the random copolymers of prepared bromine alkoxyl group isophthalic and diazosulfide replaces poly-bromine hexyloxy isophthalic.The number-average molecular weight of gained white polymer is 9000, and weight-average molecular weight is 10000.
Embodiment 19:
Isophthalic and 4,7-, bis-thiophene-2,1, the random copolymers of 3-diazosulfide changes into the random copolymers containing the di-alcohol amido, and reaction formula is as follows:
Figure BDA0000380724440000142
Method is with embodiment 12.Prepared bromine alkoxyl group isophthalic and 4,7-, bis-thiophene-2,1 with embodiment 10, the multipolymer of 3-diazosulfide replaces poly-bromine hexyloxy isophthalic.The number-average molecular weight of gained white polymer is 5500, and weight-average molecular weight is 8000.
Embodiment 20:
The random copolymers of isophthalic and 5,8-, bis-thiophene-quinoxaline changes into the random copolymers containing the di-alcohol amido, and reaction formula is as follows:
Figure BDA0000380724440000151
Method is with embodiment 12.With embodiment 11, the multipolymer of prepared bromine hexyloxy isophthalic and 5,8-, bis-thiophene-quinoxaline replaces poly-bromine hexyloxy isophthalic.The number-average molecular weight of gained white polymer is 7000, and weight-average molecular weight is 13100.
Embodiment 21:
Preparation and the performance of the organic light emitting diode device that the metallic aluminium of take is negative electrode
The structure of the organic light emitting diode device that the metallic aluminium of take is negative electrode is: the ITO/PEDOT:PSS/P-PPV/ isophthalic conjugated polymers/Al containing the di-alcohol amido.Device fabrication processes is: the ito glass cleaned in advance of take is anode, the water-soluble polymers PEDOT:PSS of spin coating 40 nanometers on ito glass, continue the luminescence polymer P-PPV of spin coating 80 nanometers after dry, follow the methanol solution of the prepared isophthalic conjugated polymers containing the di-alcohol amido of spin coating embodiment 13 after dry, the thickness of controlling this polymkeric substance is 10 nanometers, the Al metallic cathode of last vacuum evaporation 100 nanometers.Apply positive bias between ITO and Al metal electrode, the chromaticity coordinates of luminescent spectrum is (0.43,0.55), current density approximately under 40 milliamperes every square centimeter corresponding brightness be 2250cd/m 2, corresponding efficiency is 5.62cd/A.
Adopt the prepared isophthalic conjugated polymers containing the di-alcohol amido of embodiment 14, prepare organic light emitting diode device by above-mentioned identical process, luminescent properties is: the chromaticity coordinates of luminescent spectrum is (0.43,0.55), current density approximately under 256 milliamperes every square centimeter corresponding brightness be 8327cd/m 2, corresponding efficiency is 3.25cd/A.
Ito glass noted earlier refers to indium tin oxide-coated glass; PEDOT:PSS be English Poly (3,4-ethylendioxy-thiophene): the abbreviation of poly (styrene sulfonic acid); The abbreviation that P-PPV is English Poly (2-(4-(3', 7'-dimethyloctyloxy) phenyl)-Isosorbide-5-Nitrae-phenylene vinylene).
Embodiment 22:
Preparation and the performance of the organic light emitting diode device that the ITO of take is negative electrode
The structure of the organic light emitting diode device that the ITO of take is negative electrode is: the ITO/ isophthalic conjugated polymers/P-PPV/MoO containing the di-alcohol amido 3/ Al.Device fabrication processes is: the ito glass cleaned in advance of take is negative electrode, the prepared methanol solution containing the isophthalic conjugated polymers of di-alcohol amido of spin coating embodiment 13 on ito glass, the thickness of controlling this polymkeric substance is 10 nanometers, continue the luminescence polymer P-PPV of spin coating 80 nanometers, the MoO of 10 nanometers of vacuum evaporation afterwards after dry 3, then the Al metal anode of vacuum evaporation 100 nanometers.Apply negative bias between ITO and Al metal electrode, the chromaticity coordinates of luminescent spectrum is (0.43,0.55), current density approximately under 238 milliamperes every square centimeter corresponding brightness be 21.3cd/m 2, corresponding efficiency is 0.009cd/A.
Adopt the prepared isophthalic conjugated polymers containing the di-alcohol amido of embodiment 14, prepare organic light emitting diode device by above-mentioned identical process, luminescent properties is: the chromaticity coordinates of luminescent spectrum is (0.43,0.55), current density approximately under 265 milliamperes every square centimeter corresponding brightness be 17cd/m 2, corresponding efficiency is 0.0064cd/A.
Embodiment 23:
Preparation and the performance of the organic photovoltaic battery device that the metallic aluminium of take is negative electrode
The structure of the organic photovoltaic battery device that the metallic aluminium of take is negative electrode is ITO/PEDOT:PSS/ (PTB7:PC 70bM=1:1.5)/containing the isophthalic conjugated polymers/Al of di-alcohol amido.Device fabrication processes is: the ito glass cleaned in advance of take is anode, the water-soluble polymers PEDOT:PSS of spin coating 40 nanometers on ito glass, the dry rear photovoltaic active coating (PTB7:PC that continues spin coating 80 nanometers 70bM=1:1.5, weight ratio), the methanol solution of the isophthalic conjugated polymers containing the di-alcohol amido that dry rear then spin coating embodiment 13 is prepared, controlling thickness is 10 nanometers, the Al metallic cathode of last vacuum evaporation 100 nanometers.Apply positive bias between ITO and Al metal electrode, measure its battery behavior under the irradiation of the AM1.5 of every square centimeter of 80 milliwatt simulated solar irradiation, the open circuit voltage of this battery device is 0.73 volt, short-circuit current is 14.88 milliamperes every square centimeter, packing factor 67%, effciency of energy transfer 7.27%.
Adopt the prepared isophthalic conjugated polymers containing the di-alcohol amido of embodiment 14, prepare the organic photovoltaic battery device by above-mentioned identical process, the battery device performance is: open circuit voltage is 0.71 volt, short-circuit current is 13.90 milliamperes every square centimeter, packing factor 69.2%, effciency of energy transfer 6.83%.
Foregoing PC 70bM is English " [6,6]-phenyl C 70-butyric acid methyl ester " abbreviation; Polymer P TB7 is by benzodithiophene and thieno[3,4-b] alternating copolymer that forms of thiophene.
Embodiment 24:
Preparation and the performance of the organic photovoltaic battery device that the ITO of take is negative electrode
The structure of the organic photovoltaic battery device that the ITO of take is negative electrode as: ITO/ containing the isophthalic conjugated polymers of di-alcohol amido/(PTB7:PCBM=1:1.5)/MoO 3/ Al.Device fabrication processes is: the ito glass cleaned in advance of take is negative electrode, the prepared methanol solution containing the isophthalic conjugated polymers of di-alcohol amido of spin coating embodiment 13 on ito glass, the thickness of controlling this polymkeric substance is 10 nanometers, continue the photovoltaic active coating (PTB7:PCBM=1:1.5 of spin coating 80 nanometers after dry, weight ratio), the MoO of 10 nanometers of vacuum evaporation afterwards 3, then the Al metal anode of vacuum evaporation 100 nanometers.Apply negative bias between ITO and Al metal electrode, measure its battery behavior under the irradiation of the AM1.5 of every square centimeter of 80 milliwatt simulated solar irradiation, the open circuit voltage of this battery device is 0.73 volt, short-circuit current is 15.26 milliamperes every square centimeter, packing factor 69.2%, effciency of energy transfer 7.71%.
Adopt the prepared isophthalic conjugated polymers containing the di-alcohol amido of embodiment 14, prepare the organic photovoltaic battery device by above-mentioned identical process, the battery device performance is: open circuit voltage is 0.75 volt, short-circuit current is 15.19 milliamperes every square centimeter, packing factor 63%, effciency of energy transfer 7.18%.

Claims (6)

1. the isophthalic conjugated polymers containing the di-alcohol amido is characterized in that having following structure:
Figure FDA0000380724430000011
Wherein, m is 2～12; 0<x≤1,0≤y<1, x+y=1; N=3-1000; Ar is conjugate unit, comprises one or more combinations in the aromatic heterocycle that aromatic nucleus that ethene support group, acetylene support group, hydrocarbon atom form, aromatic heterocycle that carbon nitrogen hydrogen atom forms, aromatic heterocycle that carbon nitrogen oxygen hydrogen atom forms, aromatic heterocycle that carbon sulphur hydrogen atom forms, aromatic heterocycle that carbon silicon hydrogen atom forms, aromatic heterocycle that carbon nitrogen sulphur hydrogen atom forms and carbon silicon sulphur hydrogen atom form.
2. the isophthalic conjugated polymers containing the di-alcohol amido according to claim 1, is characterized in that described Ar conjugate unit is with substituted radical, and substituted radical comprises one or more combinations in alkyl, fluoro-alkyl, alkoxyl group, ester group, carbonyl.
3. the method for preparing the isophthalic conjugated polymers containing the di-alcohol amido claimed in claim 1, is characterized in that carrying out the copolymerization preparation containing benzene monomer and Ar monomer between the di-alcohol amido; The isophthalic monomer structure containing the di-alcohol amido used is as follows:
Figure FDA0000380724430000012
Wherein, R 1for reaction active groups, comprise bromine, iodine, chlorine, trialkyltin, 4,4,5,5-tetramethyl--1,3, a kind of in 2-dioxa pentaborane-2-base; Z is 2～12; The carbon number of the alkyl in described trialkyltin is 1～4;
The structure of the Ar monomer used is: R 2-Ar-R 2, R wherein 2for reaction active groups, comprise bromine, iodine, chlorine, trialkyltin, 4,4,5,5-tetramethyl--1,3, a kind of in 2-dioxa pentaborane-2-base; The carbon number of the alkyl in described trialkyltin is 1～4.
4. the application of the described isophthalic conjugated polymers containing the di-alcohol amido of claim 1 in making the photoelectric functional device.
5. application according to claim 4, it is characterized in that: described photoelectric functional device is Organic Light Emitting Diode.
6. application according to claim 4, it is characterized in that: described photoelectric functional device is organic photovoltaic battery.
CN201310413985.6A 2013-09-11 2013-09-11 Hydroxyethyl-containing biradicals conjugated polymer and application thereof Pending CN103483556A (en)

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