CN1329419C - Color adjustable poly(p-phenylene vinylene) copolymer electroluminescent materials and preparation method and use thereof - Google Patents
Color adjustable poly(p-phenylene vinylene) copolymer electroluminescent materials and preparation method and use thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 9
- -1 poly(p-phenylene vinylene) copolymer Polymers 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title description 10
- 229920000553 poly(phenylenevinylene) Polymers 0.000 title 1
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 230000003287 optical effect Effects 0.000 claims abstract description 5
- 239000004065 semiconductor Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 3
- WAXIFMGAKWIFDQ-UHFFFAOYSA-N 1-tert-butyl-4-(chloromethyl)benzene Chemical compound CC(C)(C)C1=CC=C(CCl)C=C1 WAXIFMGAKWIFDQ-UHFFFAOYSA-N 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical group [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 claims 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000008859 change Effects 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000005669 field effect Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 7
- 229920000547 conjugated polymer Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OSOLHARQJQEMBZ-UHFFFAOYSA-N 1-chloropentylbenzene Chemical group CCCCC(Cl)C1=CC=CC=C1 OSOLHARQJQEMBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- MDAOJDZYRBCMLY-UHFFFAOYSA-N 1,4-dibutoxy-2,5-bis(chloromethyl)benzene Chemical compound CCCCOC1=CC(CCl)=C(OCCCC)C=C1CCl MDAOJDZYRBCMLY-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000001194 electroluminescence spectrum Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to an MEHPPV-CO-DRPPV copolymer synthesized by utilizing an improved Gilch reaction. The conditions of a polymerization reaction are easy to control, the yield of the polymerization reaction is high, and the occurrence of the precipitation phenomenon and a cross-linking reaction can be avoided. The obtained copolymer has the advantages of good dissolvability and good performance. The adjustment for the light emitting color can be realized by the structure of the copolymer, the structure of a device and the change of voltage. The copolymer has wide application prospects on the aspects of organic semiconductors, photoelectric devices, multi-color display devices, nonlinear optical materials, field effect transistors, optical detectors, lasers, etc.
Description
Technical field
The invention belongs to organic polymer electronic material and preparation thereof and applied technical field.More particularly, the present invention relates to the electroluminescent organic material and preparation method thereof and application, especially p-phenylene vinylene's analog copolymer of a class color tunable and preparation method thereof and application of a class color tunable.
Background technology
Since nineteen ninety univ cambridge uk research group reported p-phenylene vinylene (PPV) photodiode since (Burroughes J.H., Bradbey D.D.C., Brown A.R., people such as Friend R.H., Nature, 1990,347:539～541; Burroughes J.H., Bradbey D.D.C., Fricnd R.H., European Patent EP423283), the various countries scientist has dropped into very big energy and studied conjugated polymers, has formed poly-fluorenes class (PFs), and is poly-to benzene class (PPPs), polythiophene class (PTs), the conjugated polymers of series such as p-phenylene vinylene's class (PPVs).In these conjugated polymerss, PPV class conjugated polymers is owing to good film-forming property, photoluminescence efficiency (η
PL) and electroluminescent efficiency (η
EL) high and aggregate into high purity, high molecular weight polymers easily, thereby become the electroluminescent material that has development prospect most.
The main method of at present synthetic PPV base polymer has two kinds: and prepolymer method and side chain method (HsiehB.R., Yuan.Y, people such as William A.E., Macromolecules, 1997,30:8094).Prepolymer method generally is the prepolymer for preparing solubility earlier, and it is coated with film forming, becomes conjugated polymers by light, thermal transition.Because prepolymer method is to carry out in water or methyl alcohol, the prepolymer meeting defectiveness of generation (as-OH), also can be in conversion process because of trace O
2Existence make film generation oxidation, produce carbonyl, thereby reduce luminous efficiency.The side chain method is improved on the basis of Gilch reaction (Gilch H.G., Wheelwrigh W.L., J Polym Sci:A-1,1966,4:1337～1349), and has become the method that synthetic PPV often uses.General Gilch synthetic route is by having 1 of soluble groups, and the polymerization of 4-xylylene dihalide obtains the PPV derivative of solubility.The side chain method can one the step be conjugated polymers with conversion of monomer, do not need pyrolytic conversion, can directly film, the textural defect of having avoided high temperature to bring, effectively the structure of controlling polymers (Wang Jianying, Li Yinkui, people such as Hu Wenxiang, CN1108328C).Unfortunately, tend to occur gel or microgel phenomenon in actual building-up process, this becomes the very serious problem of PPV in polymer LED is used.PPV produces gel in organic solvent or microgel mainly is that crosslinked in the reaction process also may be one of them reason because of rapid reaction and the quick kinetic chain length that increases.
From early stage document, can produce in the PPV building-up process and be not with substituent quinoid structure, this structure can stable existence at-78 ℃, but when temperature rises, cyclisation can take place in the quinoid intermediate, generates dimer, tripolymer, the tetramer, thereby reduces the output of polymkeric substance.The result of Rehahn has also confirmed to exist in the polyreaction cyclisation recently, and carry out with free radical mechanism, therefore temperature controlling can have influence on output (the Errede L.A. of polymkeric substance in the polymerization process, Gregorian R.S., Hoyt J.M., Journal of American Society, 1960,82:5218～5223).The generation of conjugated structure has very big influence to luminous in the polyreaction, if there is an amount of non-conjugated structure, will reduce luminous efficiency, influences the local current of device, to the performance generation destruction of device.The initiator of free radical reaction is the active intermediate that is generated by the quinoid structure, and it is combined into diradical with tail-tail form.Because existence-CH in the structure
2-CH
2-, also can there be multi-form combination in the reaction, can existence-C ≡ C-in the therefore last polymkeric substance ,-CH
2-CH
2The textural defect of-form.Because ionic reaction speed is slow, the polymkeric substance of generation is almost with head-tail form combination.People such as Andersson are by influence (the Johansson M.D. of research temperature to polymer reaction, Theander M., Ingan s O., people such as Andersson M.R., Macromolecules, 2001,34:3716～3719), the polymer architecture defective of finding low temperature polymerization reaction generation is less, only exists with trace, has been difficult to detect by HNMR, IR etc. with head-capitiform formula bonded structure.Therefore, the low temperature embodiment also is important, for example human ice-water mode such as Hsieh is cooled off (Hsieh B.R., Yuan.Y, people such as William A.F., Macromolecules, 1997,30:8094), yet this mode often makes airborne moisture concentration improve, the productive rate that obtains is low, also can make polymkeric substance produce gel.About this phenomenon, people such as Cao Yong once reported (Mo Y.Q., Huang J., Jiang J.X., Deng X.Y., Niu Y.H., Cao Y., Chinese Journal of Polymer Science, 2002,20 (5): 461～465).
Recently, the Organic Light Emitting Diode of color tunable has caused very big concern.These devices can pass through the adjusting of device parameters such as voltage, electric current, local temperature, realize the adjustable of color.The most general method is that the adjusting by voltage realizes the adjustable of color.At present, being manufactured with of multicolor display device four types (Ohmori Y., Tada N., people such as Jujii A., Thin Solid Films, 1998,331:89～95), but all be to realize by the variation that in device, forms quantum well or recombination region.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in field of organic electroluminescent materials, in the hope of developing a kind of PPV based electroluminescent material that can be used for organic flat pannel display.Found that polymeric reaction condition is easily controlled by the synthetic MEHPPV-CO-DRPPV multipolymer of improved Gilch reaction, polyreaction productive rate height can be avoided the generation of deposited phenomenon and crosslinking reaction, good, the excellent property of the multipolymer solvability that obtains.The variation of structure that can be by multipolymer, device architecture, voltage realizes the adjustable of glow color.The multipolymer that obtains thus causes aspects such as transistor, photo-detector, laser apparatus and is with a wide range of applications in organic semiconductor, photoelectric device, multicolor displaying, nonlinear optical material, field.
Therefore, the objective of the invention is to overcome the shortcoming of prior art, provide that a kind of preparation process is simple, the gel-free by product generates in the building-up process, textural defect is few and the p-phenylene vinylene's multipolymer and the synthetic method thereof of favorable solubility; The present invention also aims to the monomer copolymerization that utilizes energy level different, form quantum well, realize the adjustable of color, the phenomenon of phase separation of having avoided multilayered structure to bring at intramolecule.
One aspect of the present invention provides the p-phenylene vinylene's multipolymer shown in the following general formula of a class (I):
Wherein R is optional straight chain, side chain or the ring-type C that replaces
4～C
12Alkyl, n: m are 99: 1～1: 99.
The present invention provides the method for p-phenylene vinylene's multipolymer shown in a kind of synthetic above-mentioned general formula (I) on the other hand, comprise use to tertiary butyl benzyl chloride as initiator, make monomer earlier in polymerization in the presence of alkali under the temperature below 4 ℃, and then at room temperature carry out polymerization, thereby obtain required multipolymer.
Further aspect of the present invention relates to the application of p-phenylene vinylene's multipolymer shown in the above-mentioned general formula (I).
To become clear after others of the present invention, the explanation of feature and advantage below the reference accompanying drawing reads.
The accompanying drawing summary
Fig. 1 is ultraviolet-visible (UV-Vis) spectrum (a) and photoluminescence (PL) spectrum (b) of the synthetic MEHPPV-CO-DBPPV of embodiment 1-3 institute multipolymer;
Fig. 2 is device ITO/MEHPPV-CO-DBPPV (1: 1)/Alq
3Luminosity-voltage of/LiF/Al (L-V) spectrum a) and electroluminescent (EL) spectrum (b);
Fig. 3 is the EL spectrum of device ITO/MEHPPV-CO-DBPPV (1: 1)/Al;
Fig. 4 is device ITO/MEHPPV-CO-DBPPV (4: 1)/Alq
3The EL spectrum (a) of/LiF/Al and current-voltage-luminosity (I-V-L) curve (b); With
Fig. 5 is I-V-L curve (a) and the EL spectrum (b) of device ITO/MEHPPV-CO-DBPPV (4: 1)/PBD/LiF/Al.
Detailed Description Of The Invention
In the copolymer shown in the general formula of the present invention (I), R is optional straight chain, side chain or the ring-type C that replaces4-C
12Alkyl, preferred C4-C
8Alkyl. Its instantiation is normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-heptyl, n-octyl etc., preferred normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, more preferably normal-butyl.
In the copolymer shown in the general formula of the present invention (I), the ratio of n and m can change, and the change of this ratio can realize the adjustable of color. Particularly, n: m is 99: 1～1: 99, preferred 9: 1～1: 9, and more preferably 4: 1～1: 4.
The present inventor finds after having summed up the various existing method of synthetic PPV analog derivative: no matter be the Gilch reaction, or prepolymer method, all can produce the quinoid intermediate, and the quantity of quinoid intermediate has directly determined the speed of reaction. Therefore, the present inventor believes and can reduce reaction rate by the generation of control intermediate, thereby controls the generation of gel and microgel. The preparation method of the copolymer shown in the general formula of the present invention (I) adopts tert-butyl group benzyl chloride as initator, select the temperature below 4 ℃, preferred 0 ℃～-70 ℃, more preferably-5 ℃～-20 ℃, reduce thus reaction speed, make reaction tend to ionic reaction mechanism. In preparation method of the present invention, used alkali can be tert-butyl alcohol lithium, sodium tert-butoxide, potassium tert-butoxide etc., and the consumption of alkali is 2～10 times of used monomer molar amount. The adding of alkali has a great impact reaction in the polymerization process, and the people such as Hsieh adopt the method that together alkali is added, but the present inventor finds that the addition of alkali is too much, often can cause the fluctuation of temperature, and the productive rate of polymer can be affected. Polymerisation is no more than 16 hours at low temperatures, preferred 4～10 hours, more preferably 6～8 hours, then is in and reacts spend the night (about 12 hours) under the room temperature. Use methyl alcohol carried out the result that purifying can obtain to product after polymerization was finished, and characterized proof polymer architecture defective trace by means such as HNMR, IR, less than the HNMR detection limit.
Preparation method of the present invention carries out in the presence of solvent usually. Operable solvent is such as being the non-proton property polar solvents such as DMSO, THF and Isosorbide-5-Nitrae-dioxane.
In preparation method of the present invention, as initator be 0.05-10% to the consumption of tert-butyl group benzyl chloride based on the gross weight of monomer, preferred 0.08-8%, more preferably 0.10-5%.
The PPV analog copolymer that the color that the present invention synthesizes is adjustable preferably uses a kind of PPV derivatives monomer of low-lying level to carry out copolymerization and obtains. By the variation of two kinds of monomer ratio, can realize that in visible-range color is adjustable. For example, benzene is as low-lying level monomer in the copolymer, and with Isosorbide-5-Nitrae-dichloromethyl-2, the 5-Dibutoxy Benzene is as the high level monomer can to use Isosorbide-5-Nitrae-dichloromethyl-2-methoxyl group-5-(2 '-ethyl hexyl oxy). PPV (MEHPPV) based on Isosorbide-5-Nitrae-dichloromethyl-2-methoxyl group-5-(2 '-ethyl hexyl oxy) benzene is soluble in organic solvent, but can produce gelatin phenomenon in solution, has affected its application. On the contrary, based on Isosorbide-5-Nitrae-dichloromethyl-2, it is bad that the PPV of 5-Dibutoxy Benzene (DBPPV) can dissolubility occur, and the polymerisation of synthetic DBPPV is difficult to control. By adopting two kinds of monomer copolymerizations, the condition ratio is easier to control, has obtained being soluble in the copolymer of organic solvent. By the sign to copolymer structure, proved under polymeric reaction condition of the present invention, can effectively suppress the generation of side reaction.
Copolymer of the present invention has stable spectrum color, although its mechanism it be unclear that, the applicant thinks that the stable mechanism of spectrum color is as follows:
The exciton fast transfer with capture: because the participation of DBPPV, the exciton of generation is captured by potential well, and is difficult to jump out, and has increased luminous probability.
2. because the introducing of DBPPV has reduced the interchain interaction, reduced the formation of excimer, exciplex, thereby improved luminous efficiency.
Cause aspects such as transistor, photo-detector, laser apparatus and be with a wide range of applications in organic semiconductor, photoelectric device, multicolor displaying, nonlinear optical material, field according to multipolymer shown in the general formula of the present invention (I).
Compared with prior art, the invention provides following advantage:
1. utilize improved Gilch reaction synthetic polymer architecture defective few, handle easily.
2. pass through the control of temperature, alkali in the building-up process, controlled chain growth speed effectively, prevented the generation of deposited phenomenon and crosslinking reaction.
3. the change of refrigeration modes in the building-up process has reduced the influence of water in air branch to polyreaction, has improved the productive rate of polymkeric substance, has avoided deposited phenomenon and crosslinking reaction to take place.
4. by the variation of polymer architecture, device architecture, voltage, can realize the adjustable of color, and simple to operate.
5. adopt two kinds of monomers of symmetrical structure and unsymmetric structure to carry out polymerization, can reduce intermolecular effect, improve luminous efficiency.
Embodiment
The present invention will describe in detail by the following example, but these embodiment do not limit the scope of the invention.
2-methoxyl group-5-(2 '-ethyl hexyl oxy)-1,4-phenylacetylene/2,5-dibutoxy-1,4-phenylacetylene [MEHPPV-CO-DBPPV] (4: 1) synthetic
In the four-hole bottle of cleaning, add 0.7992g 1,4-dichloromethyl-2-methoxyl group-5-(2 '-ethyl hexyl oxy) benzene, 0.1914g 2,5-dichloromethyl-1,4-dibutoxy benzene, 0.001ml be to tertiary butyl benzyl chloride and 100ml THF, charges into nitrogen then and stirred 30 minutes.System temperature is reduced to about-20 ℃ with dry ice-propanone.Inject the 2ml potassium tert.-butoxide with syringe then.Low-temp reaction 6 hours returns to room temperature again and reaction is spent the night.In reaction mixture impouring 100ml methyl alcohol, separate out a large amount of sanguine flocculent substances immediately, filter, obtain red product.With this product of 200ml water washing, then with THF 150ml dissolving, obtain the solution of dark orange, 50ml separates out with methyl alcohol.Operation above repeating 2 times, and, obtain the red fibrous solid (productive rate 60%) of 0.62g with the vacuum drying oven oven dry of products therefrom under 40 ℃.
FT-IR：3057cm
-1(C＝C-H，trans)，2955.6cm
-1(-CH
3，v
as)，2927cm
-1(-CH
2，v
as)，2869cm
-1(-CH
2，v
s)，1503cm
-1(C＝C(Ar))，1462.8cm
-1(-CH
3，δ
as，-CH
2-，δ，C＝C(Ar))，1412cm
-1(CH
3，δ
s)，1252.8cm
-1(C-O-C，v
as)，1202cm
-1(Ar-H，β)，1038cm
-1(O-C-C，γ)，967cm
-1(C＝C，trans)，855cm
-1(Ar-H，γ)，534cm
-1(Ar-H，δ)。
1H-NMR：7.56(2H)，7.2(2H)，3.99～4.1(9H)，0.94～1.86(29H)。
2-methoxyl group-5-(2 '-ethyl hexyl oxy)-1,4-phenylacetylene/2,5-dibutoxy-1,4-phenylacetylene [MEHPPV-CO-DBPPV] (1: 1) synthetic
In the four-hole bottle of cleaning, add 0.333g 1,4-dichloromethyl-2-methoxyl group-5-(2 '-ethyl hexyl oxy) benzene, 0.319g 2,5-dichloromethyl-1,4-dibutoxy benzene, 0.001ml be to tertiary butyl benzyl chloride and 100ml THF, charges into nitrogen then and stirred 30 minutes.System temperature is reduced to about-30 ℃ with dry ice-propanone.Then, inject the 2ml potassium tert.-butoxide with syringe.Low-temp reaction 6 hours returns to room temperature again and reaction is spent the night.In reaction mixture impouring 100ml methyl alcohol, separate out a large amount of sanguine flocculent substances immediately, filter, obtain red product.With this product of 200ml water washing, then with THF 150ml dissolving, obtain the solution of dark orange, 50ml separates out with methyl alcohol.Operation above repeating 2 times, and, obtain the red fibrous solid (productive rate 54%) of 0.31g with the vacuum drying oven oven dry of products therefrom under 40 ℃.
The FT-IR of products therefrom,
1H-NMR characterizes similar to the MEHPPV-CO-DBPPV (4: 1) of embodiment 1, and just peak shape slightly changes.
Embodiment 3
2-methoxyl group-5-(2 '-ethyl hexyl oxy)-1,4-phenylacetylene/2,5-dibutoxy-1,4-phenylacetylene [MEHPPV-CO-DBPPV] (1: 4) synthetic
In the four-hole bottle of cleaning, add 0.1998g 1,4-dichloromethyl-2-methoxyl group-5-(2 '-ethyl hexyl oxy) benzene, 0.7656g 2,5-dichloromethyl-1,4-dibutoxy benzene, 0.001ml be to tertiary butyl benzyl chloride and 100ml THF, charges into nitrogen then and stirred 30 minutes.System temperature is reduced to about-10 ℃ with dry ice-propanone.Then, inject the 2ml potassium tert.-butoxide with syringe.Low-temp reaction 6 hours returns to room temperature again and reaction is spent the night.In reaction mixture impouring 100ml methyl alcohol, separate out a large amount of sanguine flocculent substances immediately, filter, obtain red product.With this product of 200ml water washing, then with THF 150ml dissolving, obtain the solution of dark orange, 50ml separates out with methyl alcohol.Operation above repeating 2 times, and, obtain the red powdery solid (productive rate 50%) of 0.40g with the vacuum drying oven oven dry of products therefrom under 40 ℃.
The FT-IR of products therefrom,
1H-NMR characterizes similar to the MEHPPV-CO-DBPPV (4: 1) of embodiment 1, and just peak shape slightly changes.
This embodiment is used for the chemical property of embodiment 1-3 gained multipolymer is characterized.For this reason, at computer-controlled HCI 420 (HC Instruments, Inc., USA) carry out electrochemistry volt-ampere (CV) experiment on, wherein reference electrode is a saturated calomel electrode, and working electrode is 213 type platinum electrodes, and counter electrode is the platinized platinum of area 15nm * 15nm, supporting electrolyte is the tetrabutylammonium perchlorate, and solvent is an anhydrous acetonitrile.Polymkeric substance is coated on the working electrode, in vacuum drying oven, dries, under nitrogen protection, experimentize then.The gained result is as shown in the table.
The electrochemical parameter of the MEHPPV-CO-DBPPV multipolymer of embodiment 1-3
| Multipolymer | E ox(v)vs. SCE | E red(v)vs. SCE | HOMO(ev) | LUMO(ev) | E g(ev) |
| MEHPPV-co- DBPPV(1∶4) | 1.47 | -1.3 | -5.87 | -3.1 | 2.77 |
| MEHPPV-co- DBPPV(1∶1) | 0.81 | -1.81 | -5.21 | -2.59 | 2.62 |
| MEHPPV-co- DBPPV(4∶1) | 0.82 | -1.72 | -5.22 | -2.68 | 2.54 |
As can be seen from the above table, along with the increase of MEHPPV composition in the multipolymer, HOMO raises, and illustrates that the polymkeric substance ratio is easier to lose electronics, oxidation easily, but E
gDiminish.The LUMO of DBPPV-CO-MEHPPV multipolymer is lower than MEHPPV, illustrates that the electronics injectability is more eager to excel in whatever one does than MEHPPV.Along with increasing of MEHPPV component in the multipolymer, energy level (E
g) inferior reducing.
Embodiment 5
This embodiment is used to illustrate the UV-Vis and the PL spectrum of embodiment 1-3 gained multipolymer.
UV-Vis and PL spectrum is at ambient temperature, sample is dissolved in writes down in the methylene dichloride.The gained result as shown in Figure 1.
As seen from Figure 1, along with increasing of MEHPPV component in the multipolymer, UV-Vis and PL spectrum generation red shift, red shift is many more, shows that the conjugated structure of system is big more, the transition of easy more generation π-π * electronics.
This embodiment is used to illustrate the device application of embodiment 1-3 gained multipolymer.
3 * 10
-3Under the Pa, with the chloroformic solution (5mg/g) of embodiment 1-3 gained MEHPPV-CO-DBPPV under rotating speed 2000r/min, get rid of to the ITO transparent conducting glass of using acetone, Virahol, deionized water to handle in advance successively, the about 100nm of the thickness of polymkeric substance, direct then evaporating Al is made single layer device; Perhaps use PBD or Alq
3As electron transfer layer, LiF prepares multilayer device as buffer layer.PBD, Alq
3, Al and LiF evaporation rate be 0.02nm/s, PBD, Alq
3, Al and LiF thickness be respectively 15nm, 15nm, 150nm, 0.2nm.Luminous, electric current, voltage tester all in room temperature, air, carry out at same device by all tests, and light-emitting area is π * 2
2Mm
2The result is shown in Fig. 2-5.
By Fig. 2-5 as can be seen, use Alq
3As electron transfer layer, the injection barrier of electronics is littler than PBD, so Alq
3During as electron transfer layer, starting voltage will be hanged down.When voltage raises, blue shift all can take place in the MEHPPV-CO-DBPPV glow color of various compositions, to this phenomenon comparatively popular explain it is that energy shifts with trap and captures mechanism, when voltage was low, the exciton of formation was captured by the potential well of low-lying level, when voltage is high, exciton is captured by the high potential well of energy level, when therefore voltage changed, glow color also can change, but also the transfer of energy may take place.Wherein, Fig. 2 has shown device ITO/MEHPPV-CO-DBPPV (1: 1)/Alq
3/ LiF/Al voltage is elevated to 10V from 6V, and emission peak is reduced to 580nm from 591nm.Simultaneously, discovery is in the device of the multipolymer of other various compositions, and maximum value can appear in emission peak.For device ITO/MEHPPV-CO-DBPPV (4: 1)/PBD/LiF/Al, at 19V maximum luminousing brightness 2129cd/m appears for example
2, and the voltage rising, emission peak does not almost change (Fig. 5), illustrates that MEHPPV-CO-DBPPV (4: 1) is more stable.
Claims (16)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1213672A (en) * | 1997-10-06 | 1999-04-14 | 中国人民解放军国防科工委后勤部军事医学研究所 | Synthetizing of poly-p-phenylacetylene |
| US6403238B1 (en) * | 1998-07-10 | 2002-06-11 | Hoerhold Hans-Heinrich | Organic light-emitting diodes (OLED) including poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene-1,2-ethenylene-2,5-dimethoxy-1,4-phenylene-1,2-ethenylene] as electroluminescent material |
| RU2186821C2 (en) * | 1999-12-01 | 2002-08-10 | Институт проблем химической физики РАН | Method of synthesis of poly-[2-methoxy-5-(2'-ethyl- -hexyloxy)-1,4-phenylenevinylene], electroluminescent device and method of its embodiment |
| JP2003197371A (en) * | 2001-10-19 | 2003-07-11 | Sony Corp | Manufacturing method for electroluminescent element |
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2003
- 2003-10-08 CN CNB2003101000617A patent/CN1329419C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1213672A (en) * | 1997-10-06 | 1999-04-14 | 中国人民解放军国防科工委后勤部军事医学研究所 | Synthetizing of poly-p-phenylacetylene |
| US6403238B1 (en) * | 1998-07-10 | 2002-06-11 | Hoerhold Hans-Heinrich | Organic light-emitting diodes (OLED) including poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene-1,2-ethenylene-2,5-dimethoxy-1,4-phenylene-1,2-ethenylene] as electroluminescent material |
| RU2186821C2 (en) * | 1999-12-01 | 2002-08-10 | Институт проблем химической физики РАН | Method of synthesis of poly-[2-methoxy-5-(2'-ethyl- -hexyloxy)-1,4-phenylenevinylene], electroluminescent device and method of its embodiment |
| JP2003197371A (en) * | 2001-10-19 | 2003-07-11 | Sony Corp | Manufacturing method for electroluminescent element |
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