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
- Publication number
- CN1329419C CN1329419C CNB2003101000617A CN200310100061A CN1329419C CN 1329419 C CN1329419 C CN 1329419C CN B2003101000617 A CNB2003101000617 A CN B2003101000617A CN 200310100061 A CN200310100061 A CN 200310100061A CN 1329419 C CN1329419 C CN 1329419C
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- butyl
- reaction
- copolymer
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- 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)
1. the p-phenylene vinylene's multipolymer shown in the following general formula (I)
Wherein R is identical and be optional straight chain, side chain or the ring-type C that replaces
4～C
12Alkyl, n: m are 99: 1～1: 99.
2. according to the multipolymer of claim 1, wherein R is C
4-C
8Alkyl.
3. according to the multipolymer of claim 2, wherein R is normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-heptyl or n-octyl.
4. according to the multipolymer of claim 3, wherein R is normal-butyl, sec-butyl, isobutyl-or the tertiary butyl.
5. according to the multipolymer of claim 4, wherein R is a normal-butyl.
6. according to the multipolymer of claim 1, wherein n: m is 9: 1～1: 9.
7. according to the multipolymer of claim 6, wherein n: m is 4: 1～1: 4.
8. preparation is according to the method for the multipolymer of claim 1, comprise use to tertiary butyl benzyl chloride as initiator, make 2-methoxyl group-5-(2 '-ethyl hexyl oxy)-1,4-phenylacetylene and 2,5-two (C
4～C
12Alkoxyl group)-1, the 4-phenylacetylene is first in polymerization in the presence of alkali under the temperature below 4 ℃, and then at room temperature carries out polymerization, thereby obtains required multipolymer.
9. method according to Claim 8, wherein said alkali is trimethyl carbinol lithium, sodium tert-butoxide or potassium tert.-butoxide etc., and its consumption is 2～10 times of used monomer molar amount.
10. method is according to Claim 8 wherein used and is selected from methyl-sulphoxide, tetrahydrofuran (THF) and 1, the non-proton property polar solvent of 4-dioxane.
11. each method according to Claim 8-10, wherein low temperature polymerization is carried out under 0 ℃～-70 ℃.
12. according to the method for claim 11, wherein low temperature polymerization is carried out under-5 ℃～-20 ℃.
13. according to the method for claim 11, wherein the low temperature polymerization time is no more than 16 hours, and polymerized at room temperature carried out 12 hours.
14. according to the method for claim 13, wherein the low temperature polymerization time is 6～8 hours.
15. method according to Claim 8, wherein the consumption to tertiary butyl benzyl chloride as initiator is 0.05-10% based on monomeric gross weight.
16. the multipolymer according to claim 1 causes the application in transistor, photo-detector, the laser apparatus etc. in organic semiconductor, photoelectric device, multicolor displaying, nonlinear optical material, field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101000617A CN1329419C (en) | 2003-10-08 | 2003-10-08 | Color adjustable poly(p-phenylene vinylene) copolymer electroluminescent materials and preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101000617A CN1329419C (en) | 2003-10-08 | 2003-10-08 | Color adjustable poly(p-phenylene vinylene) copolymer electroluminescent materials and preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1605595A CN1605595A (en) | 2005-04-13 |
| CN1329419C true CN1329419C (en) | 2007-08-01 |
Family
ID=34755806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101000617A Expired - Fee Related CN1329419C (en) | 2003-10-08 | 2003-10-08 | Color adjustable poly(p-phenylene vinylene) copolymer electroluminescent materials and preparation method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1329419C (en) |
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 |
-
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1605595A (en) | 2005-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Becker et al. | Soluble PPVs with enhanced performance—a mechanistic approach | |
| Jin et al. | Poly (fluorenevinylene) derivative by Gilch polymerization for light-emitting diode applications | |
| Beaupre et al. | Fluorene‐Based Copolymers for Red‐Light‐Emitting Diodes | |
| JP5274745B2 (en) | Materials that can be structured, methods of manufacturing the same, and uses thereof | |
| Shih et al. | Stable and efficient white electroluminescent devices based on a single emitting layer of polymer blends | |
| EP1257611B1 (en) | Luminescent polymer | |
| Wang et al. | High-efficiency red and green light-emitting polymers based on a novel wide bandgap poly (2, 7-silafluorene) | |
| US20040115473A1 (en) | Monomer for use in preparation of a polymer to be used in optical devices | |
| KR101141465B1 (en) | Conjugated polymers, their preparation and use thereof | |
| JP2008517135A (en) | Monomers for the production of crosslinked polymers | |
| KR20050102101A (en) | Conjugated polymers and blends containing carbazole, representation and use thereof | |
| Liu et al. | Highly efficient green light emitting polyfluorene incorporated with 4-diphenylamino-1, 8-naphthalimide as green dopant | |
| EP2927258A1 (en) | Benzodithiophene based copolymer containing thieno [3,4-b]thiophene units and preparing method and applications thereof | |
| Chuang et al. | Polymers with alkyl main chain pendent biphenyl carbazole or triphenylamine unit as host for polymer light emitting diodes | |
| Liu et al. | Green light-emitting polyfluorenes with improved color purity incorporated with 4, 7-diphenyl-2, 1, 3-benzothiadiazole moieties | |
| KR20060025538A (en) | Polymer | |
| EP2927259B1 (en) | Benzodithiophene based copolymer containing thiophene pyrroledione units and preparing method and applications thereof | |
| Song et al. | Emission color tuning of copolymers containing polyfluorene, benzothiadiazole, porphyrin derivatives | |
| Chen et al. | Germafluorene conjugated copolymer—synthesis and applications in blue-light-emitting diodes and host materials | |
| CN1329419C (en) | Color adjustable poly(p-phenylene vinylene) copolymer electroluminescent materials and preparation method and use thereof | |
| Liu et al. | Electroluminescence performances of 1, 1-bis (4-(N, N-dimethylamino) phenyl)-2, 3, 4, 5-tetraphenylsilole based polymers in three cathode architectures | |
| Liu et al. | Highly efficient red electroluminescent polymers with dopant/host system and molecular dispersion feature: polyfluorene as the host and 2, 1, 3-benzothiadiazole derivatives as the red dopant | |
| Martin et al. | Efficient blue–green light emitting poly (1, 4-phenylene vinylene) copolymers Electronic supplementary information (ESI) available: normal optical absorption, PL and EL spectra (Fig. S1) and cyclic voltammograms (Fig. S2) for BDMOS-DB-PPV. See http://www. rsc. org/suppdata/cc/a9/a909382f | |
| Chen et al. | Red electroluminescent polyfluorenes containing highly efficient 2, 1, 3-benzoselenadiazole-and 2, 1, 3-naphthothiadiazole-based red dopants in the side chain | |
| Hwang et al. | Light-emitting properties of a germyl-substituted PPV derivative synthesized via a soluble precursor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070801 Termination date: 20121008 |