CN1176976C - High-molecular hole conduction material and its preparing process - Google Patents
High-molecular hole conduction material and its preparing processInfo
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- CN1176976C CN1176976C CNB021160473A CN02116047A CN1176976C CN 1176976 C CN1176976 C CN 1176976C CN B021160473 A CNB021160473 A CN B021160473A CN 02116047 A CN02116047 A CN 02116047A CN 1176976 C CN1176976 C CN 1176976C
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Abstract
The present invention relates to macromolecule hole transmission materials and a preparation method thereof. A terminal amino phenylamine polymer m is prepared by adopting an Ullmann reaction and an oxidative coupling reaction, the terminal amino phenylamine polymer m as a basic raw material reacts with 4-bromophenyl-methyl-sulfoixde in the Ullmann mode through the protection of acetyl, and finally, an acetyl protecting group is removed to synthesize nitrogen sulfur conjugated polymers containing different phenylamino groups. Different side groups are led onto an imino group by using the nitrogen sulfur conjugated polymers as precursors through an alkyl substitution reaction and an Ullmann reaction to further improve the stability, the film-forming property and the hole transmission capability of the materials and construct a series of macromolecule hole transmission materials having high performance. The polymers show favorable oxidation-reduction reversibility between 0.6 and 1.2V; the thermal decomposition temperature of the polymers is between 370 and 430DEG C to show high thermal stability; the polymers which can be dissolved in organic solvents, such as dichloromethane, trichloromethane, tetrahydrofuran and N, N dimethylformamide, frequently used show a favorable film-forming property.
Description
Technical field: the present invention relates to high-molecular hole conduction material and preparation method thereof, belong to photoelectron material and technical field.
Background technology: since C.W.Tang in 1987 utilizes oxine aluminium (Alq
3) be that luminescent layer, arylamine molecule are that hole transmission layer has prepared since the double-deck organic electroluminescence device, cause international competition in the worldwide-organic panel display material and device in Materials science and areas of information technology, and obtained the achievement that attracts people's attention.
Organic molecule, as phthalocyanine ketone, three arylamine etc. have been proved to be the organic hole transport material of excellent property, but because existence is separated, shortcomings such as easy crystallization cause device stability relatively poor.In addition, organic molecule evaporation film-forming technology is complicated, and large size and mass preparation will be subjected to the restriction of evaporation film-forming technology.On the contrary, shortcoming, especially high-molecular hole conduction material that high-molecular hole conduction material then can solve in the application of organic molecule hole mobile material can make the flexible device of big area by spin-coating film, and preparation is simple, and energy consumption is low.At present, with respect to organic molecule, high-molecular hole conduction material research also is not very extensive and gos deep into.For example: Adv.Mater.1994,6,784 disclose the high-molecular hole conduction material that Gr ü ner etc. synthesizes the suspended side chain carbazole; Chem.Mater.1998,10,1668 disclose the high-molecular hole conduction material that Bellman etc. synthesizes suspended side chain three arylamine.There are defectives such as poor heat stability, trigger voltage height, luminous efficiency be low in the device of these materials and gained.Thereby design and synthetic high-molecular hole conduction material with good hole transport ability and thermostability are one of present research emphasis directions.
Summary of the invention: the purpose of this invention is to provide the new and effective high-molecular hole conduction material of a class.
Another purpose of invention provides a kind of preparation method of new and effective high-molecular hole conduction material.
Based on the actual needs of simplifying organic electroluminescence device preparation technology and the new and effective high-molecular hole conduction material of development, the present invention's design synthesizes a series of nitrogen sulphur conjugated polymerss that contain different aniline primitives, and with it is parent, by on nitrogen, introducing stability, film-forming properties and the cavity transmission ability that different side groups further improves material, construct a series of high performance polymer hole mobile materials.These polymkeric substance show good redox reversible between 0.6-1.2V; Its heat decomposition temperature shows high thermostability between 370-430 ℃; Dissolve in organic solvent commonly used such as methylene dichloride, trichloromethane, tetrahydrofuran (THF), N, in the N dimethyl formamide, and demonstrate good film-forming properties.
Novel high polymer hole mobile material provided by the invention has following structure:
Wherein n is the number of polymer repeat unit; M=1-8; R is hydrogen, alkyl or aryl, and alkyl is that the number of carbon is the straight-chain paraffin of 2-16; Aryl has following structure:
Or:
Wherein n=20-100 is the number of polymer repeat unit; M=1-8; X=2-16;
Ar：
The preparation method of novel high polymer hole mobile material provided by the invention mainly comprises the steps: the sulfoxide monomer preparation of (1) different aniline primitive number; (2) the monomeric preparation of functionalized sulfoxide; (3) the sulfoxide monomer is from polycondensation;
1). the monomeric preparation of sulfoxide of different aniline primitive numbers: according to the odevity of aniline primitive; adopt Ullmann reaction and oxidative coupling reaction preparation end amino aniline m aggressiveness respectively; subsequently it is carried out amido protecting; carry out the Ullmann reaction with 4-bromo phenyl-methyl-sulfoxide again; last deacetylate blocking group, acquisition has the sulfoxide monomer of different aniline primitives.
A). after taking by weighing aniline m aggressiveness, the Glacial acetic acid dissolving is under argon shield, slowly drip the diacetyl oxide of m times of molar weight, after 50-100 ℃ of following stirring reaction 2-6 hour, in the reaction product impouring water, dichloromethane extraction, column chromatography separate the product that obtains pure ethanoyl protection;
B). the 4-bromo phenyl-methyl-sulfoxide of products therefrom and equimolar amount is at the Anhydrous potassium carbonate of 1.5-3 times of molar weight, 0.03-0.4 the cuprous iodide of molar weight doubly, 0.01-0.1 doubly 1 of the 18-of molar weight hat-6 and 0.5-2 times of molar weight, 3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone (DMPU) exists down, at 150-200 ℃ of following stirring reaction 10-30 hour, behind dichloromethane extraction, rotary evaporation falls solvent, the potassium hydroxide that adds 2-5 times of molar weight in the products therefrom, in ethanol temperature rising reflux 2-10 hour, dichloromethane extraction, column chromatography is separated the nitrogen sulphur monomer that obtains to contain the aniline primitive;
2) the monomeric preparation of functionalized sulfoxide: by alkyl substitution and Ullmann reaction, the arylamine micromolecular that the imino-on 4-methyl sulfoxide base-benzene end-blocking aniline m aggressiveness is introduced alkyl, aryl or linked to each other with flexible chain is prepared functionalized sulfoxide monomer.
A). alkyl substitution: take by weighing 2-6 doubly to the sodium hydride of aniline primitive molar weight, after 4-methyl sulfoxide base-benzene end-blocking aniline m aggressiveness dissolves in tetrahydrofuran (THF), all be added dropwise in the sodium hydride, under nitrogen protection, stirring at room 0.5-3 hour, to be dissolved in the tetrahydrofuran solution with the alkyl chain of the functionalization of the single-ended bromo of aniline primitive equimolar amount then, all be added dropwise to above-mentioned system, 30-70 ℃ following stirring reaction 10-20 hour; Use the dichloromethane extraction product, the salt washing, the anhydrous sodium sulphate drying, behind the rotary evaporation solvent, silica gel chromatographic column separates, and obtains pure functionalized sulfoxide polymerization single polymerization monomer;
B) .Ullmann reaction: take by weighing 4-methyl sulfoxide base-benzene end-blocking aniline m aggressiveness, add 1.5-3 doubly to the single-ended iodo of aniline primitive molar weight or the functional group of bromo, 1.5-3 doubly to the Anhydrous potassium carbonate of aniline primitive molar weight, 0.03-0.4 doubly to the cuprous iodide of aniline primitive molar weight, 0.01-0.1 doubly to the 18-of aniline primitive molar weight hat-6 and 0.5-2 doubly to 1 of aniline primitive molar weight, 3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone (DMPU), at 150-200 ℃ of following stirring reaction 10-30 hour, dilute hydrochloric acid reacts away remaining salt of wormwood, dichloromethane extraction, salt solution is washed till neutrality, and the anhydrous sodium sulphate drying is after rotary evaporation falls solvent, silica gel chromatographic column separates, and obtains pure functionalized sulfoxide polymerization single polymerization monomer;
3). the preparation of high-molecular hole conduction material:
Adopt sulfoxide from polycondensation method; take by weighing 4-methyl sulfoxide base-benzene end-blocking aniline m aggressiveness or functionalized nitrogen sulphur polymerization single polymerization monomer; the methylsulphonic acid that under nitrogen protection, adds 2-6 times of molar weight then; under room temperature, stirred 1-3 days, and after reaction finishes, the full-bodied liquid that obtains was slowly splashed in 10% the perchloric acid solution of 10-20 times of molar weight; stir after 1-4 hour; filter solid, after the vacuum-drying, dissolve with pyridine; the temperature rising reflux reaction is 8-15 hour under nitrogen protection; after being chilled to room temperature, pour in the distilled water agitation and filtration into; product is repeatedly with distilled water and alcohol flushing; the ethanol sedimentation after the vacuum-drying, obtains product.
The present invention adopts polymerization process as above, the high-molecular hole conduction material that obtains has good solubility, film-forming properties and high thermostability, with them is hole transmission layer, oxine aluminium is that the device that luminescent layer and electron transfer layer make has low trigger voltage 4.4V, high luminosity 4800cd/m
2And high luminous efficiency 2.7cd/A.
Embodiment is as follows:
Embodiment 1: Acetanilide synthetic
After in 250ml round bottom reaction flask, adding the new distillatory aniline of 32.6g (0.35mol), 29.5ml (0.37mol) pyridine and 80ml methylene dichloride; place cryosel to bathe down; after treating that temperature drops to below 0 ℃, under protection of nitrogen gas, slowly drip the mixed solution of 26.2ml (0.37mol) Acetyl Chloride 98Min. and 20ml methylene dichloride by constant pressure funnel.After dripping, stirred 0.5 hour, remove cryosel and bathe, continue under the room temperature to stir 10 hours, solution colour becomes faint yellowly by colourless, and has acid mist to produce.Pour in the 200ml distilled water, with dichloromethane extraction three times, merge organic phase after, it is inferior to give a baby a bath on the third day after its birth with the dilute hydrochloric acid of 1M, the pyridine that flush away is excessive, salt solution are washed till the neutral anhydrous sodium sulfate drying.After rotary evaporation falls methylene dichloride, use the distilled water recrystallization, vacuum-drying gets colourless tabular crystal, productive rate 80% after 48 hours.
Synthesizing of embodiment 2:4-methyl sulfoxide base-pentanoic
Join in the 100ml round bottom reaction flask after taking by weighing 4.38g (20mmol) 4-bromo phenyl-methyl-sulfoxide, 2.38g (24mmol) salt of wormwood, 0.6g cuprous iodide, 0.3g18-hat-6,2.7g (20mmol) Acetanilide; after adding 3mlDMPU again, under argon shield, be warming up to 180 ℃ of reactions 16 hours.After being cooled to room temperature, adding dilute hydrochloric acid and react away salt of wormwood, with dichloromethane extraction three times, merge organic phase after, it is colourless to be washed to water layer with rare amine again, salt solution is washed till neutrality, anhydrous sodium sulfate drying.After rotary evaporation falls methylene dichloride, get the khaki color viscous material.
Above-mentioned product is inserted in the 100ml reaction flask, add 50ml dehydrated alcohol and 6.2g potassium hydroxide, be warming up to alcohol reflux reaction 4 hours under the argon shield.After being cooled to room temperature, pour in the 400ml distilled water yellow flocks, with dichloromethane extraction three times, merge organic phase after, salt solution is washed till neutrality, anhydrous sodium sulfate drying.After rotary evaporation falls methylene dichloride, be that leacheate is crossed silica gel chromatographic column with ethyl acetate/acetone=4/1.After the solvent evaporated, vacuum-drying gets colorless solid, productive rate 75% after 48 hours.
Embodiment 3:N-phenyl-N, N '-diacetyl-1,4-Ursol D synthetic.
In the round bottom reaction flask of 250ml, add 10g (10mmol) 4-amino-pentanoic and 70ml Glacial acetic acid, under argon shield, slowly drip the 11g diacetyl oxide.Be warming up to 70 ℃ of stirring reactions after dropwising 4 hours.Pressure reducing and steaming Glacial acetic acid, product are that leacheate carries out the silica gel chromatographic column separation with the ethyl acetate.After the solvent evaporated, vacuum-drying gets colorless solid, productive rate 75% after 48 hours.
Synthesizing of embodiment 4:N-phenyl-N '-(4-methyl sulfoxide base) phenyl-1,4 Ursol D.
The reaction monomers Acetanilide is replaced by 5.36g (20mmol) N-phenyl-N, N '-diacetyl-1, the 4-Ursol D, other monomeric charge when reaction conditions and treatment step with embodiment 2.Product is a light gray solid, productive rate 70%.
Embodiment 5:4-methyl sulfoxide base-benzene end-blocking aniline is trimerical synthetic.
The reaction monomers Acetanilide is replaced by 5.36g (20mmol) N-phenyl-N; N '-diacetyl-1; the 4-Ursol D; 4-bromo phenyl-methyl-sulfoxide is replaced by 7.2g (20mmol) 4-iodo-4 '-methyl sulfoxide base-pentanoic, other monomeric charge when reaction conditions and treatment step with embodiment 2.Product is a light gray solid, productive rate 70%.
Embodiment 6: aniline is tetrameric synthetic.
The hydrochloric acid mixed solution that 5.5g (30mmol) 4-amino-pentanoic is dissolved in 250ml acetone and 200ml 2M is placed in ice-salt bath, after treating that temperature drops to below 0 ℃, 5.5g (24mmol) ammonium persulphate is dissolved in 50ml distilled water/acetone=1/1 after dropping funnel slowly drops in the above-mentioned solution, after dropwising, continued violent stirring 4-5 hour.After the filtration, the gained precipitation is respectively washed once with dilute hydrochloric acid and acetone, and distilled water is washed till neutrality.40 ℃ of following vacuum-dryings got the purple powder in 24 hours.Gained purple powder is joined 2-3 hour after-filtration of stirring in ethanol/water=1/1 mixed solution that contains excessive phenylhydrazine, continue to wash to filtrate colourless with ethanol/water=1/1 mixed solvent.40 ℃ of following vacuum-dryings got in 48 hours goes back ortho states blue powder, productive rate 90% entirely.
Embodiment 7: the tetrameric acetylize of aniline.
Monomer 4-amino-pentanoic is replaced by 5.8g (16mmol) the aniline tetramer, adds 70ml Glacial acetic acid and 7.3g (70mmol) diacetyl oxide, other monomeric charge when reaction conditions and treatment step with embodiment 3.Product is a light gray solid, productive rate 75%.
Synthesizing of embodiment 8:4-methyl sulfoxide base-benzene ended aniline tetramer.
The reaction monomers Acetanilide is replaced by the aniline tetramer of 5.0g (9.7mmol) ethanoyl protection, other monomeric charge when reaction conditions and treatment step with embodiment 2.Product is a light gray solid, productive rate 70%.
Embodiment 9: aniline eight aggressiveness synthetic.
Monomer 4-amino-pentanoic is replaced by 11g (30ml) the aniline tetramer, other monomeric charge when reaction conditions and treatment step with embodiment 6.Product is a blue solid, productive rate 90%.
The acetylize of embodiment 10 aniline eight aggressiveness.
Monomer 4-amino-pentanoic is replaced by 11.6g (16mmol) aniline eight aggressiveness, adds 70ml Glacial acetic acid and 14.6g (140mmol) diacetyl oxide, other monomeric charge when reaction conditions and treatment step with embodiment 3.Product is a light gray solid, productive rate 70%.
Synthesizing of embodiment 11:4-methyl sulfoxide base-benzene end-blocking eight aggressiveness.
The reaction monomers Acetanilide is replaced by aniline eight aggressiveness of 10g (9.7mmol) ethanoyl protection, other monomeric charge when reaction conditions and treatment step with embodiment 2.Product is a light gray solid, productive rate 70%.
Synthesizing of embodiment 12:4-methyl sulfoxide base-N-ethyl-pentanoic.
At first in 100ml round bottom reaction flask, take by weighing 0.4g (8mmol) sodium hydride, add purified tetrahydrofuran (THF) (20ml) then, under argon shield, drip tetrahydrofuran (THF) (20ml) solution of 0.9g (4mmol) 4-methyl sulfoxide base-pentanoic.After dropwising, at room temperature continue to stir 1 hour.Drip tetrahydrofuran (THF) (10ml) solution of 0.87g (8mmol) 1-monobromethane then, after dropwising, 40 ℃ of following stirring reactions 16 hours.Behind the stopped reaction, system is poured in the 200ml water, and dichloromethane extraction, salt solution are given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying.With the ethyl acetate is that leacheate is crossed the silica gel chromatographic column separated product, gets yellow viscous material, productive rate 96%.
Synthesizing of embodiment 13:4-methyl sulfoxide base-N-normal-butyl-pentanoic.
Reaction monomers 1-monobromethane is replaced by 1.1g (8mmol) 1-bromine normal butane, other monomeric charge when reaction conditions and treatment step with embodiment 12.Product is yellow viscous material, productive rate 94%.
Synthesizing of embodiment 14:4-methyl sulfoxide base-N-n-hexyl-pentanoic.
Reaction monomers 1-monobromethane is replaced by 1.3g (8mmol) 1-bromine normal hexane, other monomeric charge when reaction conditions and treatment step with embodiment 12.Product is yellow viscous material, productive rate 95%.
Synthesizing of embodiment 15:4-methyl sulfoxide base-N-n-octyl-pentanoic.
Reaction monomers 1-monobromethane is replaced by 1.5g (8mmol) 1-bromine octane, other monomeric charge when reaction conditions and treatment step with embodiment 12.Product is yellow viscous material, productive rate 95%.
Synthesizing of embodiment 16:4-methyl sulfoxide base-N-dodecyl-pentanoic.
Reaction monomers 1-monobromethane is replaced by 2.0g (8mmol) 1-bromine n-dodecane, other monomeric charge when reaction conditions and treatment step with embodiment 12.Product is yellow viscous material, productive rate 94%.
Synthesizing of embodiment 17:4-methyl sulfoxide base-N-n-hexadecyl-pentanoic.
Reaction monomers 1-monobromethane is replaced by 2.44g (8mmol) 1-bromine n-hexadecane, other monomeric charge when reaction conditions and treatment step with embodiment 12.Product is yellow viscous material, productive rate 92%.
Embodiment 18:N-phenyl-N, N '-two (ethyl)-N '-(4-methyl sulfoxide base) penylene-1,4-Ursol D synthetic.
At first in 100ml round bottom reaction flask, take by weighing 0.8g (16mmol) sodium hydride; add purified tetrahydrofuran (THF) (20ml) then; under argon shield, drip 1.3g (4mmol) N-phenyl-N '-(4-methyl sulfoxide base) penylene-1, the tetrahydrofuran (THF) of 4-Ursol D (20ml) solution.After dropwising, at room temperature continue to stir 1 hour.Drip tetrahydrofuran (THF) (10ml) solution of 1.7g (16mmol) 1-monobromethane then, after dropwising, 40 ℃ of following stirring reactions 16 hours.Behind the stopped reaction, system is poured in the 200ml water, and dichloromethane extraction, salt solution are given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying.With the ethyl acetate is that leacheate is crossed the silica gel chromatographic column separated product, gets yellow viscous material, productive rate 95%.
Embodiment 19:N-phenyl-N, N '-two (normal-butyl)-N '-(4-methyl sulfoxide base) penylene-1,4-Ursol D synthetic.
Reaction monomers 1-monobromethane is replaced by 2.2g (16mmol) 1-bromine normal butane, other monomeric charge when reaction conditions and treatment step with embodiment 18.Product is yellow viscous material, productive rate 94%.
Embodiment 20:N, N ', N "-triethyl-N-methyl sulfoxide base phenyl-trimerization aniline synthetic.
At first in 100ml round bottom reaction flask, take by weighing 1.2g (24mmol) sodium hydride, add purified tetrahydrofuran (THF) (20ml) then, under argon shield, drip tetrahydrofuran (THF) (20ml) solution of 1.65g (4mmol) 4-methyl sulfoxide base phenyl-trimerization aniline.After dropwising, at room temperature continue to stir 1 hour.Drip tetrahydrofuran (THF) (10ml) solution of 2.6g (24mmol) 1-monobromethane then, after dropwising, 40 ℃ of following stirring reactions 16 hours.Behind the stopped reaction, system is poured in the 200ml water, and dichloromethane extraction, salt solution are given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying.With the ethyl acetate is that leacheate is crossed the silica gel chromatographic column separated product, gets yellow viscous material, productive rate 95%.
Embodiment 21:N, N ', N "-tributyl-N-methyl sulfoxide base phenyl-trimerization aniline synthetic.
Reaction monomers 1-monobromethane is replaced by 3.3g (24mmol) 1-bromine normal butane, other monomeric charge when reaction conditions and treatment step with embodiment 20.Product is yellow viscous material, productive rate 94%.
Embodiment 22:N, N ', N ", N -tetraethyl--N-methyl sulfoxide base phenyl-four polyaniline synthetic.
At first in 100ml round bottom reaction flask, take by weighing 1.6g (32mmol) sodium hydride, add purified tetrahydrofuran (THF) (30ml) then, under argon shield, drip tetrahydrofuran (THF) (20ml) solution of 2.0g (4mmol) 4-methyl sulfoxide base phenyl-four polyaniline.After dropwising, at room temperature continue to stir 1 hour.Drip tetrahydrofuran (THF) (10ml) solution of 3.5g (32mmol) 1-monobromethane then, after dropwising, 40 ℃ of following stirring reactions 16 hours.Behind the stopped reaction, system is poured in the 200ml water, and dichloromethane extraction, salt solution are given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying.With the ethyl acetate is that leacheate is crossed the silica gel chromatographic column separated product, gets yellow viscous material, productive rate 95%.
Embodiment 23:N, N ', N ", N -tetrabutyl-N-methyl sulfoxide base phenyl-four polyaniline synthetic.
Reaction monomers 1-monobromethane is replaced by 4.4g (32mmol) 1-bromine normal butane, other monomeric charge when reaction conditions and treatment step with embodiment 22.Product is yellow viscous material, productive rate 94%.
Synthesizing of the positive hexyloxy-triphenylamine of embodiment 24:4-methyl sulfoxide base-N-.
Add 0.69g (3mmol) 4-methyl sulfoxide base-pentanoic, 1.1g (3.6mmol) 4-iodo-phenyl-n-hexyl ether, 0.6g salt of wormwood, 0.4g cuprous iodide and 1 in the 100ml round bottom reaction flask successively; 3-dimethyl-3; 4; 5; 6-tetrahydrochysene-2-pyrimidone (DMPU) (3ml) rises under argon shield and asks that temperature was to 185 ℃ of stirring reactions 16 hours.Be chilled to room temperature, dilute hydrochloric acid reacts away remaining salt of wormwood, dichloromethane extraction, and it is colourless that weak ammonia is washed till water layer, and salt is washed to neutrality, anhydrous sodium sulfate drying.Silica gel chromatographic column is crossed for leacheate in ethyl acetate/acetone=6/1, gets the sticking shape body of khaki color, productive rate 90%
Synthesizing of embodiment 25:4-methyl sulfoxide base-N-naphthyl-pentanoic.
With reaction monomers 4-iodo-phenyl-n-hexyl ether be replaced by other monomeric charge of 0.75g (3.6mmol) 2-bromonaphthalene when reaction conditions and treatment step with embodiment 24.Product is yellow decorating film, productive rate 80%.
Synthesizing of embodiment 26:4-methyl sulfoxide base-4 '-carbazyl-triphenylamine.
Reaction monomers 4-iodo-phenyl-n-hexyl ether is replaced by 1.26g (3mmol) N-4-iodo phenyl-carbazole, other monomeric charge when reaction conditions and treatment step with embodiment 24.Product is yellow decorating film, productive rate 80%.
Synthesizing of embodiment 27:4-methyl sulfoxide base-4 '-phenyl-triphenylamine.
Reaction monomers 4-iodo-phenyl-n-hexyl ether is replaced by 0.7g (3mmol) 4-bromo-biphenyl, other monomeric charge when reaction conditions and treatment step with embodiment 24.Product is yellow decorating film, productive rate 83%.
Synthesizing of embodiment 28:4-methyl sulfoxide base-4 '-[N, N-two (p-methylphenyl)]-triphenylamine.
Reaction monomers 4-iodo-phenyl-n-hexyl ether is replaced by 1.35g (3mmol) 4-iodo-4 ', 4 "-dimethyl-triphenylamine, other monomeric charge when reaction conditions and treatment step with embodiment 24.Product is yellow decorating film, productive rate 70%.
Embodiment 29:4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group ethyl]-pentanoic synthetic.
At first in 100ml round bottom reaction flask, take by weighing 0.4g (8mmol) sodium hydride, add purified tetrahydrofuran (THF) (20ml) then, under argon shield, drip tetrahydrofuran (THF) (20ml) solution of 1.58g (4mmol) 4-methyl sulfoxide base-pentanoic.After dropwising, continue down to stir 1 hour at 40 ℃.Drip 1.7g (4.4mmol) N-(4-bromine oxethyl)-phenyl-4 ' then, 4 "-tetrahydrofuran (THF) (10ml) solution of dimethyl-pentanoic, after dropwising, be warming up to tetrahydrofuran (THF) and reflux, reacted 16 hours.Behind the stopped reaction, system is poured in the 200ml water, and dichloromethane extraction, salt solution are given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying.With the ethyl acetate is that leacheate is crossed the silica gel chromatographic column separated product, gets yellow viscous material, productive rate 75%.
Embodiment 30:4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group butyl]-pentanoic synthetic.
With reaction monomers N-(4-bromine oxethyl)-phenyl-4 '; 4 "-dimethyl-pentanoic is replaced by 1.86g (4.4mmol) N-(4-bromine butoxy)-phenyl-4 '; 4 "-dimethyl-pentanoic, other monomeric charge when reaction conditions and treatment step with embodiment 29.Product is yellow viscous material, productive rate 76%.
Embodiment 31:4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group hexyl]-pentanoic synthetic.
With reaction monomers N-(4-bromine oxethyl)-phenyl-4 '; 4 "-dimethyl-pentanoic is replaced by 2.0g (4.4mmol) N-(4-bromine hexyloxy)-phenyl-4 '; 4 "-dimethyl-pentanoic, other monomeric charge when reaction conditions and treatment step with embodiment 29.Product is yellow viscous material, productive rate 75%.
Embodiment 32:4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group octyl group]-pentanoic synthetic.
With reaction monomers N-(4-bromine oxethyl)-phenyl-4 '; 4 "-dimethyl-pentanoic is replaced by 2.1g (4.4mmol) N-(4-bromine octyloxy)-phenyl-4 ' 4 "-dimethyl-pentanoic, other monomeric charge when reaction conditions and treatment step with embodiment 29.Product is yellow viscous material, productive rate 75%.
Embodiment 33:4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group hexadecyl]-pentanoic synthetic.
With reaction monomers N-(4-bromine oxethyl)-phenyl-4 '; 4 "-dimethyl-pentanoic is replaced by 2.6g (4.4mmol) N-(4-bromine n-Hexadecane oxygen base)-phenyl-4 ' 4 "-dimethyl-pentanoic, other monomeric charge when reaction conditions and treatment step with embodiment 29.Product is yellow viscous material, productive rate 75%.
Synthesizing of embodiment 34:4-methyl sulfoxide base-N-(6-carbazyl butyl)-pentanoic.
With reaction monomers N-(4-bromine oxethyl)-phenyl-4 ', 4 "-dimethyl-pentanoic is replaced by 1.2g (4mmol) N-brombutyl carbazole, other monomeric charge when reaction conditions and treatment step with embodiment 29.Product is yellow viscous material, productive rate 76%.
Embodiment 35: the synthetic and sign of high-molecular hole conduction material.
Take by weighing 1.3g (5mmol) 4-methyl sulfoxide base-N-ethyl-pentanoic in the 25ml round bottom reaction flask, argon shield adds the 10ml methylsulphonic acid down, and stirring reaction is 24 hours under the room temperature.After reaction finishes, be added dropwise among 10% the perchloric acid solution 200ml, stir 30 minutes after-filtration, distilled water must white solid after being washed till neutral vacuum-drying.White solid is placed the 100ml reaction flask, add the 50ml pyridine, back flow reaction is 10 hours under argon shield.After being chilled to room temperature, pouring into and stir 1 hour after-filtration in the 300ml distilled water, precipitation is with distilled water and alcohol flushing, and after a small amount of then tetrahydrofuran (THF) dissolving, precipitation is three times in dehydrated alcohol, and vacuum-drying gets white floss, productive rate 90%.Product property is as follows: number-average molecular weight is 25637; Second-order transition temperature is 106 ℃; Heat decomposition temperature is 423 ℃; The HOMO value is about-5.18eV.With this polymkeric substance is hole transmission layer, and Alq3 is a luminescent layer, and ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 4.4V; Luminosity is 4800cd/m
2Luminous efficiency is 2.7cd/A.
Embodiment 36: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.4g (5mmol) 4-methyl sulfoxide base-N-normal-butyl-pentanoic, and other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a white solid, productive rate 88%.Product property is as follows: number-average molecular weight is 22875; Second-order transition temperature is 87 ℃; Heat decomposition temperature is 425 ℃; The HOMO value is about-5.13eV.Device performance is that trigger voltage is 6V; Luminosity is 2802cd/m
2Luminous efficiency is 2.30cd/A.
Embodiment 37: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.57g (5mmol) 4-methyl sulfoxide base-N-n-hexyl-pentanoic, and other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a white solid, productive rate 90%.Product property is as follows: number-average molecular weight is 17554; Second-order transition temperature is 58 ℃; Heat decomposition temperature is 423 ℃; The HOMO value is about-5.20eV.Device performance is that trigger voltage is 8V; Luminosity is 430cd/m
2Luminous efficiency is 1.1cd/A.
Embodiment 38: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.7g (5mmol) 4-methyl sulfoxide base-N-n-octyl-pentanoic, and other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a white solid, productive rate 86%.Product property is as follows: number-average molecular weight is 10928; Second-order transition temperature is 50 ℃; Heat decomposition temperature is 430 ℃; The HOMO value is about-5.24eV.Device performance is that trigger voltage is 8V; Luminosity is 647cd/m
2Luminous efficiency is 1.8cd/A.
Embodiment 39: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 2.0g (5mmol) 4-methyl sulfoxide base-N-dodecyl-pentanoic, and other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a white solid, productive rate 84%.Product property is as follows: number-average molecular weight is 25100; Second-order transition temperature is 46 ℃; Heat decomposition temperature is 391 ℃.Device performance is that trigger voltage is 6V; Luminosity is 1140cd/m
2Luminous efficiency is 0.36cd/A.
Embodiment 40: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.37g (3mmol) 4-methyl sulfoxide base-N-n-hexadecyl-pentanoic, and other reaction conditions and treatment step are with embodiment 35.Product is a white solid, productive rate 85%.
Embodiment 41: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.5g (4mmol) N-phenyl-N, N '-two (ethyl)-N '-(4-methyl sulfoxide base) penylene-1, the 4-Ursol D, other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a white solid, productive rate 81%.
Embodiment 42: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.5g (4mmol) N-phenyl-N, N '-two (normal-butyl)-N '-(4-methyl sulfoxide base) penylene-1, the 4-Ursol D, other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a white solid, productive rate 81%.
Embodiment 43: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by the positive hexyloxy-triphenylamine of 1.6g (4mmol) 4-methyl sulfoxide base-N-, and other reaction conditions and treatment step and preparation of devices are with embodiment 34.Product is a light gray solid, productive rate 81%.Product property is as follows: number-average molecular weight is 7300; Second-order transition temperature is 73 ℃; Heat decomposition temperature is 380 ℃.Device performance is that trigger voltage is 4V; Luminosity is 1440cd/m
2Luminous efficiency is 0.34cd/A.
Embodiment 44: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.1g (2mmol) 4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group ethyl]-pentanoic, other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a light gray solid, productive rate 70%.
Embodiment 45: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.15g (2mmol) 4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group butyl]-pentanoic, other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a light gray solid, productive rate 72%.
Embodiment 46: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.2g (2mmol) 4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group hexyl]-pentanoic, other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a light gray solid, productive rate 73%.
Embodiment 47: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.26g (2mmol) 4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group octyl group]-pentanoic, other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a light gray solid, productive rate 70%.
Embodiment 48: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.42g (2mmol) 4-methyl sulfoxide base-N-[4-N, N-two (p-methylphenyl)-phenoxy group hexadecyl]-pentanoic, other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a light gray solid, productive rate 70%.
Embodiment 49: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 0.46g (2mmol) 4-methyl sulfoxide base-pentanoic, and other reaction conditions and treatment step and preparation of devices are with embodiment 35.Product is a light gray solid, productive rate 95%.Product property is as follows: number-average molecular weight is 56600; Second-order transition temperature is 120 ℃; Heat decomposition temperature is 380 ℃.Device performance is that trigger voltage is 8V; Luminosity is 301cd/m
2Luminous efficiency is 0.4cd/A.
Embodiment 50: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 0.64g (2mmol) N-phenyl-N '-(4-methyl sulfoxide base) phenyl-1,4 Ursol D, and other reaction conditions and treatment step are with embodiment 35.Product is a light gray solid, productive rate 90%.
Embodiment 51: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 0.82 (2mmol) 4-methyl sulfoxide base-benzene end-blocking aniline tripolymer, and other reaction conditions and treatment step are with embodiment 35.Product is a light gray solid, productive rate 90%.
Embodiment 52: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.0g (2mmol) 4-methyl sulfoxide base-benzene ended aniline tetramer, and other reaction conditions and treatment step are with embodiment 35.Product is a light gray solid, productive rate 90%.
Embodiment 53: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.7g (2mmol) 4-methyl sulfoxide base-benzene end-blocking aniline eight aggressiveness, and other reaction conditions and treatment step are with embodiment 35.Product is light solid, productive rate 85%.
Embodiment 54: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-aniline is replaced by 0.7g (2mmol) 4-methyl sulfoxide base-N-naphthyl-pentanoic, and other reaction conditions and treatment step are with embodiment 35.Product is a light gray solid, productive rate 85%.
Embodiment 55: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 0.94g (2mmol) 4-methyl sulfoxide base-4 '-carbazyl-triphenylamine, and other reaction conditions and treatment step are with embodiment 35.Product is a light gray solid, productive rate 88%.
Embodiment 56: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 0.77g (2mmol) 4-methyl sulfoxide base-4 '-phenyl-triphenylamine, and other reaction conditions and treatment step are with embodiment 35.Product is a light gray solid, productive rate 88%.
Embodiment 57: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.0g (2mmol) 4-methyl sulfoxide, and base-4 '-[other reaction conditions and treatment step are with embodiment 35 for N, N-two (p-methylphenyl)-triphenylamine.Product is a light gray solid, productive rate 88%.
Embodiment 58: the synthetic and sign of high-molecular hole conduction material.
Reaction monomers 4-methyl sulfoxide base-N-ethyl-pentanoic is replaced by 1.0g (2mmol) 4-methyl sulfoxide base-N-(6-carbazyl butyl)-pentanoic, and other reaction conditions and treatment step are with embodiment 35.Product is a light gray solid, productive rate 85%.
Claims (5)
1. the new and effective high-molecular hole conduction material of a class is characterized in that having following structure:
Wherein n is the number of polymer repeat unit; M=1-8; R is hydrogen, alkyl or aryl, and alkyl is that the number of carbon is the straight-chain paraffin of 2-16; Aryl has following structure:
Or:
Wherein n is the number of polymer repeat unit; M=1-8; X=2-16;
Ar：
2. high-molecular hole conduction material as claimed in claim 1 is characterized in that described alkyl is ethyl, butyl, hexyl, octyl group, dodecyl or hexadecyl.
3. high-molecular hole conduction material as claimed in claim 1 is characterized in that described aryl is 4-hexyloxy phenyl, naphthyl, 4-(N-carbazyl) phenyl, 4-xenyl or 4-(N, N-di-p-tolyl)-phenyl.
4. high-molecular hole conduction material as claimed in claim 1 is characterized in that described Ar is N-carbazyl or 4-(N, N-di-p-tolyl)-phenoxy group.
5. the preparation method of a new and effective high-molecular hole conduction material is characterized in that preparation process is as follows:
1). the monomeric preparation of sulfoxide of different aniline primitive numbers:
A). after taking by weighing aniline m aggressiveness, the Glacial acetic acid dissolving is under argon shield, slowly drip the diacetyl oxide of m times of molar weight, after 50-100 ℃ of following stirring reaction 2-6 hour, in the reaction product impouring water, dichloromethane extraction, column chromatography separate the product that obtains pure ethanoyl protection;
B). the 4-bromo phenyl-methyl-sulfoxide of products therefrom and equimolar amount is at the Anhydrous potassium carbonate of 1.5-3 times of molar weight, 0.03-0.4 the cuprous iodide of molar weight doubly, 0.01-0.1 doubly 1 of the 18-of molar weight hat-6 and 0.5-2 times of molar weight, 3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone exists down, at 150-200 ℃ of following stirring reaction 10-30 hour, behind dichloromethane extraction, rotary evaporation falls solvent, the potassium hydroxide that adds 2-5 times of molar weight in the products therefrom, in ethanol temperature rising reflux 2-10 hour, dichloromethane extraction, column chromatography is separated the nitrogen sulphur monomer that obtains to contain the aniline primitive;
2) the monomeric preparation of functionalized sulfoxide:
A). alkyl substitution: take by weighing 2-6 doubly to the sodium hydride of aniline primitive molar weight, after 4-methyl sulfoxide base-benzene end-blocking aniline m aggressiveness dissolves in tetrahydrofuran (THF), all be added dropwise in the sodium hydride, under nitrogen protection, stirring at room 0.5-3 hour, to be dissolved in the tetrahydrofuran solution with the alkyl chain of the functionalization of the single-ended bromo of aniline primitive equimolar amount then, all be added dropwise to above-mentioned system, 30-70 ℃ following stirring reaction 10-20 hour; Use the dichloromethane extraction product, the salt washing, the anhydrous sodium sulphate drying, behind the rotary evaporation solvent, silica gel chromatographic column separates, and obtains pure functionalized sulfoxide polymerization single polymerization monomer;
B) .Ullmann reaction: take by weighing 4-methyl sulfoxide base-benzene end-blocking aniline m aggressiveness, add 1.5-3 doubly to the single-ended iodo of aniline primitive molar weight or the functional group of bromo, 1.5-3 doubly to the Anhydrous potassium carbonate of aniline primitive molar weight, 0.03-0.4 doubly to the cuprous iodide of aniline primitive molar weight, 0.01-0.1 doubly to the 18-of aniline primitive molar weight hat-6 and 0.5-2 doubly to 1 of aniline primitive molar weight, 3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone, at 150-200 ℃ of following stirring reaction 10-30 hour, dilute hydrochloric acid reacts away remaining salt of wormwood, dichloromethane extraction, salt solution is washed till neutrality, and the anhydrous sodium sulphate drying is after rotary evaporation falls solvent, silica gel chromatographic column separates, and obtains pure functionalized sulfoxide polymerization single polymerization monomer;
3). the preparation of high-molecular hole conduction material:
Adopt sulfoxide from polycondensation method; take by weighing 4-methyl sulfoxide base-benzene end-blocking aniline m aggressiveness or functionalized nitrogen sulphur polymerization single polymerization monomer; the methylsulphonic acid that under nitrogen protection, adds 2-6 times of molar weight then; under room temperature, stirred 1-3 days, and after reaction finishes, the full-bodied liquid that obtains was slowly splashed in 10% the perchloric acid solution of 10-20 times of molar weight; stir after 1-4 hour; filter solid, after the vacuum-drying, dissolve with pyridine; the temperature rising reflux reaction is 8-15 hour under nitrogen protection; after being chilled to room temperature, pour in the distilled water agitation and filtration into; product is repeatedly with distilled water and alcohol flushing; the ethanol sedimentation after the vacuum-drying, obtains product.
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