CN105254855A

CN105254855A - White light polymer material, preparation method and applications thereof

Info

Publication number: CN105254855A
Application number: CN201410337798.9A
Authority: CN
Inventors: 黄达; 孙艳雪; 刘静; 赵继健; 谭玉东; 靳灿辉; 孙仲猛; 曹林法
Original assignee: JIANGSU HECHENG NEW MATERIALS Co Ltd
Current assignee: JIANGSU HECHENG NEW MATERIALS Co Ltd
Priority date: 2014-07-15
Filing date: 2014-07-15
Publication date: 2016-01-20

Abstract

The present invention provides a polymer material having a structure represented by a general formula I, wherein x is more than 0 and is less than or equal to 0.995, y is more than or equal to 0.005 and is less than 1, x+y is equal to 1, n is an integer between 1-100, and R and R' are the same or different, and independently represent alkyl having a carbon atom number of 1-10. The polymer material has high stability and high luminous efficiency, and can improve the service life and the stability of the device; and due to the characteristic of the easy exciplex formation from the single polymer, various color group components in the polymer can be regulated to obtain the white light polymer material. The present invention further provides a white light device using the polymer material of the present invention. The formula I is defined in the specification.

Description

A kind of white light polymer materials and its preparation method and application

Technical field

The invention belongs to electroluminescent organic material technical field, relate to a kind of white light electroluminescent organic material, particularly relate to a kind of white light organic electroluminescence polymer materials.

Background technology

Semiconductor lighting is 21 century one of high-tech sector most with prospects, compared with the lighting source that incandescent light, luminescent lamp, high-pressure mercury lamp etc. are traditional, semiconductor illuminating light source has the remarkable advantages such as long lifetime, energy-conservation, environmental protection, and semiconductor lighting is causing a revolution of world wide intraoral illumination light source.

Organic Light Emitting Diode (OLED) is a kind of new photodiode developed in recent years, its simple preparation technology, low operating voltage, abundant material source, high-effect, less energy-consumption, rich color and many excellent specific properties such as flat luminous, ultra-thin, be subject to the common concern of global display and lighting industrial community.

As lighting source, be that the OLED of feature has the advantage more easily realizing white light, ultra-thin light source and arbitrary shape light source with flat luminous, there is the advantages such as efficient, environmental protection, safety simultaneously.Therefore, white light OLED more and more causes the concern of people as a kind of novel solid state light emitter.In lighting field, OLED not only as indoor and outdoor general illumination, backlight and decorative illumination etc., even can prepare the flexible luminescent wallpaper being rich in artistry, can the window of monochromatic or colorful light-emitting, the product that wearable luminous alarm plate etc. are fantasy.

As OLED illumination material, small molecule material (SM-OLED) can be adopted, also can adopt macromolecular material (P-OLED).Polymer OLED can utilize the way efficiency utilization material of spin coating proceeding or spray ink Printing, good film-forming property, and equipment cost is low, is conducive to industrialized mass.

At present, the way of white light is obtained based on single polymer OLED, primarily of following several: 1. physical mixed but not the method for chemical bonding obtain white light, small molecules and polymer mixing (Appl.Phys.Lett., 1994 can be adopted, 64,815) polymer and polymer mixing (Appl.Phys.Lett., 1996 can, also be adopted, 68,147).Although these class methods are simple, all there is the problem be separated, cause device stability poor, the life-span sharply declines.2. chemical bonding polymkeric substance emits white light.By the orange two color base groups (CN1580179A) of blueness or the blue three color base group (CN1632045A of red green, CN1800297B) bonding emits white light, the each component concentration of fine adjustment can be passed through, effectively obtain required white light, shortcoming requires high to the regulation and control of assorted group, is not easy to obtain multiple batches of stable product; Emitted white light by single polymers, there is synthesis difficulty large (CN1126729A), easily form exciplex, cause broad band luminous.

Therefore, be badly in need of a kind of single polymeric material containing multiple chromophoric group and transmitting white, make to improve device spectral stability, reduce driving voltage, increase device work-ing life.

Summary of the invention

The object of the invention is the polymer materials by development with high stability, obtain high luminous efficiency, thus the work-ing life of boost device and stability.

Another object of the present invention is the feature easily forming exciplex according to single polymers, by assorted group component in regulation and control polymkeric substance, obtains white light polymer materials.

Another object of the present invention is to provide the white light parts using polymer materials of the present invention.

In order to solve the problem, the invention provides a kind of white light polymer materials, described white light polymer materials has the structure of formula I:

Wherein,

0<x≤0.995,0.005≤y<1, x+y=1, n are the integer between 1-100;

R and R ' is identical or different, independently represents that carbonatoms is the alkyl of 1-10.

In certain embodiments of the present invention, preferred 0.1≤x≤0.9; 0.1≤y≤0.9; More preferably 0.3≤x≤0.8; 0.2≤y≤0.7.

In certain embodiments of the present invention, R and R ' is identical or different, preferable methyl, hexyl, heptane base, octyl or octane-iso base.

The preparation method of Inventive polymers is as follows:

1), under nitrogen protection, in DMSO (dimethyl sulfoxide (DMSO)), compound 1 is added

Tetrabutyl amonium bromide, aqueous sodium hydroxide solution, drip brominated alkanes, and after stirring, reaction is spent the night, and after reaction terminates, obtains compound 2

2), under low temperature nitrogen protection, in anhydrous THF, add described compound 2, drip n-BuLi, drip boric acid three isobutyl ester after dropwising again, reaction overnight, with ethyl acetate and sherwood oil recrystallization, obtain compound 3

3) described compound 3 is added in flask with tetramethyl ethylene ketone with mol ratio 1:2 ~ 1:2.4 ratio, react under nitrogen protection, obtain compound 4

4) by compound 5

Add in flask with brominated alkanes by 1:2 mol ratio, add KOH and keep alkaline environment, after reaction terminates, obtain compound 6

5) add in flask with paraformaldehyde with 1:2 ~ 3.5 mol ratio by described compound 6, add acetic acid and HBr, back flow reaction obtains compound 7 simultaneously

6) be added in dry toluene solvent with triphenylphosphine with 1:2.4 mol ratio by described compound 7, back flow reaction obtains compound 8

7) containing compound 9

Tetrahydrofuran solution in add magnesium rod and iodine, after adding thermal initiation, drip containing the tetrahydrofuran solution of compound 9, dropwise, at dry ice ethanol system borehole cooling, drip boric acid three isobutyl ester, be obtained by reacting compound 10

8) the described compound 10 of mol ratio 1:1:0.1, compound 11 is added successively

With tetra-triphenylphosphine palladium in flask, and add a certain amount of Na ₂cO ₃solution, stirring reaction, after reaction terminates, obtains compound 12

9) be dissolved in methylene dichloride by described compound 12, drip the dichloromethane solution of bromine after lucifuge process, stirring is spent the night, and is separated by silicagel column, obtains compound 13

10) under anhydrous and oxygen-free condition, add described compound 8, potassium tert.-butoxide and tetrahydrofuran (THF), after stirring, continue the tetrahydrofuran solution of instillation containing described compound 13, stirring reaction, obtains compound 14

11) in toluene, described compound 2, described compound 4 and described compound 14 is added, add sodium carbonate solution, tetra-triphenylphosphine palladium, methyl tricapryl ammonium chloride again, rise to temperature of reaction, there is described in obtaining after having reacted the polymer materials of the structure of formula I

Present invention also offers a kind of electroluminescent device, described electroluminescent device, comprise two electrodes and at least one deck organic electro luminescent layer, this organic electro luminescent layer comprises the polymer materials described in general formula I:

Wherein,

0<x≤0.995,0.005≤y<1, x+y=1, n are the integer between 1-100; Preferably 0.1≤x≤0.9; 0.1≤y≤0.9; More preferably 0.3≤x≤0.8; 0.2≤y≤0.7;

R and R ' is identical or different, independently represents that carbonatoms is the alkyl of 1-10, preferable methyl, hexyl, heptane base, octyl or octane-iso base.

The synthetic method of polyaromatic (Polyarylenes) has a lot, such as oxidation style (Makromol.Chem.1989,190,3105 – 3116), but oxidation style is applicable to thiophene-based self-polymerization, the molecular weight that other aromatic compounds adopt this method to obtain is very low; Such as reduction method (Prog.Polym.Sci., 1992,17,1153-1205), but reduction method needs the nickel catalyzator of stoichiometric ratio, and cost is too high and be not suitable for industrialization; Such as cyclization polymerization (ActaPolym., 1998,49,52-55), but cyclization polymerization is only suitable for specific system, and universality is poor.So what utilization was maximum at present is metal catalysed processes (Metal-CatalysedCrosscouplingReactions, A.DeMeijere, F.Diederich, Eds., Wiley-VCH, Weinheim, Germany, 2004.).Suzuki reaction (the J.Polym.Sci.A:Polym.Chem.2001 of palladium chtalyst, 39,1533 – 1556), having the feature (optimize reacted molecular weight and can be greater than 10000) of reaction high yield and product high molecular, is the reaction of most important metal-catalyzed polymerization.

As the knowledge of this area, the molecular structural formula of polymkeric substance represents with minimum repeated structural unit, and symbol n represents the multiplicity of this repeated structural unit.Because the mixture that polymkeric substance is made up of the macromole homologue that a series of relative molecular weight is different usually, so n is generally a scope, but not a value determined.Common polymericular weight has: number-average molecular weight (Mn), take quantity as statistical weight; Weight-average molecular weight (Mw) take weight as statistical weight; Viscosity-average molecular weight (Mv) take viscosity as statistical weight.

Inventive polymers n is the integer between 1-100, namely represents that the repeated structural unit of Inventive polymers is between 1-100.Due to Suzuki polyreaction, statistically n more has more between present 1-50, and the possibility occurred further is 1-25.

In certain embodiments of the present invention, the polymer materials in described luminescent layer emits white light.

The typical structure of electroluminescent device is: anode/hole injection layer/hole transmission layer/organic luminous layer/electron transfer layer/electron injecting layer/negative electrode.According to the difference of target and application, can simplify or some functional layer complicated.The present invention adopts following structure to carry out device research: anode/hole injection layer/organic luminous layer/electron transfer layer/electron injecting layer/negative electrode.

Anode layer can adopt inorganic materials, is generally the higher metal of work function or metal oxide, preferential oxidation indium tin (hereinafter referred to as ITO) of the present invention; Hole-injecting material generally adopts Polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter referred to as PEDOT:PSS), CuPc (CuPc) and 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), the preferred Polythiophene of the present invention/polyvinylbenzenesulfonic acid sodium (PEDOT:PSS); Hole transmission layer generally adopts tri-arylamine group material, '-two (1-naphthyl)-N, the N'-phenylbenzene-1,1-xenyl-4,4-diamines (NPB) as N, N, 4,4', 4''-tri-(N-carbazole) triphenylamine (TCTA); Organic luminous layer is polymer materials of the present invention; Electron transfer layer is generally a metal-organic complex, as three (oxine) aluminium, also can be benzimidazoles, as 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TBPI) etc.; Electron injection material generally adopts inorganic fluoride, as lithium fluoride (LiF), and cesium fluoride (CsF), preferred fluorinated lithium (LiF) of the present invention; Cathode layer generally adopts metal that the work functions such as lithium, magnesium, calcium, strontium, aluminium or indium are lower or any one and copper, gold or silver-colored alloy in them.

Electroluminescent device preparation method of the present invention is as follows:

(1) anode purge ITO.Divide the cleaning of a few step with the glass substrate of anode by clean-out system, deionized water and organic solution;

(2) hole injection layer is prepared.By spin coating or evaporation coating method, the hole injection layer of fabricate devices;

(3) luminescent layer is prepared.By spin coating or evaporation coating method, the luminescent layer of fabricate devices;

(4) electron transfer layer is prepared.By spin coating or evaporation coating method, the electron transfer layer of fabricate devices;

(5) electron injecting layer is prepared.By spin coating or evaporation coating method, the electron injecting layer of fabricate devices;

(6) negative electrode is prepared.By the method for evaporation or sputtering, prepare metallic cathode.

Accompanying drawing explanation

Fig. 1 is the H-NMR spectrogram of Compound C.

Fig. 2 is the H-NMR spectrogram of compd E.

Fig. 3 is the H-NMR spectrogram of compound P.

Fig. 4 is the H-NMR spectrogram of compound W.

Fig. 5 is the H-NMR spectrogram of polymkeric substance (Poly3).

Fig. 6 is the thermostability DSC figure of polymkeric substance (Poly3).

Fig. 7 is solution and the film PL spectrogram of polymkeric substance (Poly3).

Fig. 8 is the CIE chromaticity coordinates figure of the solution of polymkeric substance (Poly3), film and device 5.

Embodiment

Below by specific embodiment, the present invention is further illustrated, but the present invention is not limited thereto.Any based on modifications or improvements on the basis of spirit of the present invention, all belong to the scope of protection of present invention.

Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.

The measuring method of Polymer optical characteristic is as described below:

1) pass through polymer dissolution in dichloromethane solvent, measure photoluminescence (PL) spectrum of its solution state;

2) pass through polymer dissolution in dichloromethane solvent, solution is spin-coated on quartz substrate, and the certain thickness film of dry formation.Observe formed filminess by polarizing microscope, and measure photoluminescence (PL) spectrum of described film;

3) by polymkeric substance to be made the OLED of a fixed structure with certain thickness, photoluminescence (PL) spectrum of its device is measured.

Luminosity is the light technology amount of the surface bright degree weighing shiner, can measure with various luminance meter.The unit of luminosity is cd/m ², the luminous intensity on representation unit area.High-high brightness (cd/m ²) refer in device measuring process, maximum luminosity.

Open bright voltage (V), referring at device is 1cd/m ²time voltage required for device.Unit is volt (V).

Luminous efficiency (cd/A), refers to the ratio of luminosity and Injection Current.

Electroluminescent device in embodiment can be prepared as follows:

(1) anode purge ITO.Sheet glass supersound process in clean-out system of ITO transparency conducting layer will be coated with, rinse in deionized water, ultrasonic oil removing in acetone and alcohol mixed solvent, be baked under clean environment and remove moisture content completely, 10 minutes are irradiated with ultraviolet rays cleaning machine, and with low energy positively charged ion bundle bombarded surface;

(2) hole injection layer is prepared.By PEDOT:PSS aqueous solution rotary coating under certain rotating speed, then 120 DEG C of annealing 15 minutes, form hole injection layer;

(3) luminescent layer is prepared.By the organic solvent rotary coating under certain rotating speed containing general formula (I) polymkeric substance, anneal 10 minutes for 80 DEG C;

(4) electron transfer layer is prepared.On luminescent layer, the certain thickness TPBI of evaporation is as electron transfer layer, and evaporation rate is 0.1nm/s;

(5) electron injecting layer is prepared.On electron transfer layer, the certain thickness LiF of evaporation is as electron transfer layer, and evaporation rate is 0.1nm/s;

(6) negative electrode is prepared.On electron injecting layer, the certain thickness Al of evaporation is as negative electrode, and evaporation rate is 0.1nm/s.Synthetic example 1

The preparation of 9,9-dioctyl-2,7-dibromo fluorenes (Compound C)

Under nitrogen protection; 2 are added in single port bottle; 7-dibromo fluorenes (compd B) 0.01mol and DMSO (dimethyl sulfoxide (DMSO)); stir and add Tetrabutyl amonium bromide; add 10ml aqueous sodium hydroxide solution in batches; feed in raw material after complete stirring, drip the bromooctane of 0.021mol, reaction is spent the night.

Be cooled to room temperature after reaction terminates, add water 20mL in reaction flask, after flask being placed in ice-water bath 0.5h, has a large amount of solid to separate out, suction filtration in flask, collects filter cake, dry to obtain white solid (Compound C).

The H-NMR spectrogram of Compound C is see Fig. 1.

Synthetic example 2

The preparation of 9,9-dioctyl-2,7-dibromo fluorenes boric acid (Compound D)

After flask being vacuumized displacement nitrogen, add C and 20mlTHF of 0.01mol, after dissolving completely, temperature is adjusted to-78 DEG C, drip the n-BuLi of 0.021mol, time for adding controls to drip off at 0.5h, stirs one hour, drip 0.023mol boric acid three isobutyl ester, time for adding is 0.5h, and drip and be incubated half an hour, reaction is spent the night.

After reaction terminates, reaction solution is poured in dilute hydrochloric acid solution (0.1mol/L), the pH value of mixing solutions is 2, with the washing of 25ml*3 ethyl acetate separatory after stirring, get organic layer drying, be spin-dried for, pull an oar with 20ml sherwood oil, suction filtration, obtains white solid, namely obtains product Compound D with ethyl acetate and sherwood oil (1:1) recrystallization.

Synthetic example 3

The preparation of 9,9-dioctyl-2,7-dibromo fluorenes boric acid ester (compd E)

0.01molD and 0.023mol tetramethyl ethylene ketone is added in flask, at 25 DEG C of reaction 5h under nitrogen protection.Reaction terminates the making beating of rear 50ml ethanol, and suction filtration obtains white solid, i.e. compd E.

The H-NMR spectrogram of compd E is see Fig. 2.

Synthetic example 4

The preparation of Isosorbide-5-Nitrae-two octyloxy benzene (compound O)

M and the 0.021mol bromooctane of 0.01mol is joined in flask, then adds 0.5gKOH and keep alkaline environment, react 36 hours at 110 DEG C of temperature.

After reaction terminates, in reaction solution, add frozen water, suction filtration, namely obtain white solid with recrystallization after the dissolve with ethanol filter cake of 30ml, i.e. compound O.

Synthetic example 5

The preparation of Isosorbide-5-Nitrae-two octyloxy-2,5-xylylene bromide (compound P)

Compound O0.01mol and 0.025mol paraformaldehyde are added in flask, add 12ml acetic acid and 5mlHBr simultaneously, after mixing at 140 DEG C back flow reaction 24h.

After reaction terminates, reaction solution is poured in the frozen water (0 DEG C) of 50ml, suction filtration, get after filter cake adds 20ml petroleum ether dissolution and obtain white solid (compound P) after recrystallization.

The H-NMR spectrogram of compound P is see Fig. 3.

Synthetic example 6

The preparation of Isosorbide-5-Nitrae-two octyloxy-2,5-bis-Xiu Jia Ji Ben phosphonium salt (compound Q)

P and the 0.025mol triphenylphosphine of 0.01mol is joined in reaction flask, adds 30ml dry toluene and dissolve, after stirring at 120 DEG C of temperature, back flow reaction 24h.

After reaction terminates, reaction solution suction filtration is obtained pressed powder, with the washing of 20ml*3 dry toluene, obtain compound Q.

Synthetic example 7

The preparation of 2-bromothiophene boric acid (compound S)

0.05g magnesium rod and 0.02g iodine is added in there-necked flask, and the tetrahydrofuran solution (0.2mol/L) dripped containing R, add the tetrahydrofuran solution (R is 0.01mol) of the follow-up continuous dropping R of thermal initiation, dropwise, stirring reaction 1 hour, is then down to-78 DEG C by reacting liquid temperature, drips 0.023mol boric acid three isobutyl ester, be incubated one hour, react 8 hours after being naturally warmed up to room temperature.

After reaction terminates, poured into by reaction solution in dilute hydrochloric acid (0.1mol/L), regulate mixed solution pH value to be 1, with the washing of 30ml*3 ethyl acetate separatory, be directly spin-dried for, then add the making beating of 30ml sherwood oil, suction filtration, obtains compound S.Synthetic example 8

The preparation of 2-aldehyde radical bithiophene (compound U)

Add 0.010mol compound S, 0.012mol compound T and 0.001mol tetra-(triphenyl) phosphine palladium successively, and add the sodium carbonate solution 20ml of 4mol/L, be warming up to 90 DEG C of reaction 12h.

Reaction terminates rear suction filtration, with the washing of 30ml*3 ethyl acetate separatory, is spin-dried for, and adopt column chromatography for separation method to purify, leacheate is mixed solvent (sherwood oil: ethyl acetate=2:1), is spin-dried for leacheate, and 30ml sherwood oil is pulled an oar, and namely suction filtration obtains compound U.

Synthetic example 9

The preparation of compound V

Putting up exhaust gas processing device passes in aqueous sodium hydroxide solution, and the U adding 0.01mol in single port bottle is dissolved in 10ml methylene dichloride, and drip the dichloromethane solution (bromine 0.022mol) of 2mol/L bromine after lucifuge process, after stirring, reaction is spent the night.

After reaction terminates, with 50ml5% sodium sulfite aqueous solution and the washing of methylene dichloride separatory, organic phase drying is spin-dried for, add the making beating of 30ml sherwood oil, namely suction filtration obtains dark green solid, purified by column chromatography for separation, leacheate is mixed solvent (sherwood oil: ethyl acetate=2:1), obtains compound V.

Synthetic example 10

The preparation of compound W

Under anhydrous and oxygen-free condition, add 0.01mol compound Q, 0.002mol potassium tert.-butoxide and THF20ml, after stirring, instill the THF solution (V0.025mol) of V at 0 DEG C, stirring reaction 12h.

Add 50ml methyl alcohol after reaction terminates, filtering precipitate after leaving standstill, then purified by column chromatography, leacheate is mixed solvent (sherwood oil: methylene dichloride=2:1), obtains red solid powder, i.e. compound W.

The H-NMR spectrogram of compound W is see Fig. 4.

Synthetic example 11

The preparation of white light polymkeric substance (Poly3)

0.02mol compd E, 0.01mol Compound C and 0.01mol compound W are joined in flask, adds the Na of 2mol/L immediately ₂cO ₃solution 20ml, toluene 10ml, catalyzer tetra-triphenylphosphine palladium 0.005mol and methyl tricapryl ammonium chloride 1ml, be warming up to 80 DEG C, and reaction 48h stops.

After reaction terminates, reaction solution is poured in 50ml methyl alcohol, filter the precipitation separated out, 15ml*3 is washed with the HCl of concentration 2mol/L, then with the extraction of 20ml*3 chloroformic solution, collect organic phase, use 20ml*3 deionized water wash, then be placed in apparatus,Soxhlet's, do extraction agent extracting to effluent liquid is colourless with acetone.Drying obtains blackish green powder, is subject polymer poly3, its M _w=9640.

The H-NMR spectrogram of polymkeric substance (Poly3) is see Fig. 5.The thermostability DSC figure of polymkeric substance (Poly3) is see Fig. 6.The solution of polymkeric substance (Poly3) and film PL spectrogram are see Fig. 7.

The value of x, y in white light polymkeric substance can be regulated by the ratio of compd E, C, W in telo merization in synthesis; In building-up process, the selection of halogenated alkane can regulate R and R ' simultaneously; Adopt aforesaid method synthetic table 1 polymkeric substance:

Table 1

Polymkeric substance	x	y	R	R’
					Poly1	0.3	0.7	Octyl	Methyl
Poly2	0.5	0.5	Octane-iso base	Octane-iso base
					Poly3	0.75	0.25	Octyl	Octyl
Poly4	0.7	0.3	Methyl	Methyl
					Poly5	0.6	0.4	Hexyl	Octyl

Device embodiments 1

On cleaned ito glass, with 2000rpm speed spin coating PEDOT:PSS, anneal 15 minutes at 120 DEG C after spin coating 70s, then above with the chloroformic solution (7mg/mL) of 1500rpm speed spin coating Poly3, after spin coating 40s, 80 DEG C of annealing 20 minutes, then evaporation electron transfer layer TBPI (30nm), electron injecting layer LiF (1.2nm) and negative electrode Al (1000nm) successively.Obtain device 1.

Device embodiments 2

Except changing the spin speed of Poly3 solution into 1000rpm, electric transmission layer thickness changes into outside 40nm, and warp and device embodiments 1 same operation, obtain device 2.

Device embodiments 3

Except changing the spin speed of Poly3 solution into 800rpm, electric transmission layer thickness changes into outside 40nm, and warp and device embodiments 1 same operation, obtain device 3.

Device embodiments 4

Except changing the spin speed of PEDOT:PSS solution into 1500rpm, the spin speed of Poly3 solution changes 800rpm into, and electric transmission layer thickness changes into outside 40nm, and warp and device embodiments 1 same operation, obtain device 4.

Device embodiments 5

Except changing the spin speed of PEDOT:PSS solution into 2500rpm, the spin speed of Poly3 solution changes 800rpm into, and electric transmission layer thickness changes into outside 40nm, and warp and device embodiments 1 same operation, obtain device 5.

The CIE chromaticity coordinates figure of the solution of polymkeric substance (Poly3), film and device 5 is see Fig. 8.

Evaluating the OLED of above-mentioned gained, is 10mA/cm in current density ²condition under measure the luminescent properties of device, result is as shown in table 2:

Table 2

Device	Open bright voltage (V)	High-high brightness (cd/m ²)	Luminous efficiency (cd/A)
				Device 1	7.105	913	0.843
Device 2	6.258	1338	1.352
				Device 3	7.354	1789	1.686
Device 4	5.132	1787	1.420
				Device 5	4.837	1914	1.933

Can see, along with the optimization of device, open bright voltage and significantly decline, luminous efficiency obviously promotes, and the space continuing to optimize is very large.Adopt the manufacture craft of device 5 that polymer P oly1-5 is made device, record the chromaticity coordinates data presentation of device, device spectral is white light, and concrete CIE value is as shown in table 3, and the device of 5 polymkeric substance all belongs to white light range.

Table 3

	CIE x	CIE y
			Poly1	0.37	0.40
Poly2	0.36	0.39
			Poly3	0.35	0.43
Poly4	0.31	0.31
			Poly5	0.34	0.41

Industrialized feasibility

Polymer materials of the present invention has good film-forming property, and thermostability is high, and the advantage of easily synthesis, can prepare white light parts of high quality and at a reasonable price, have great commercial viability.

Claims

1. a polymer materials, has the structure of formula I:

Wherein,

0<x≤0.995,0.005≤y<1, x+y=1, n are the integer between 1-100;

2. polymer materials according to claim 1, is characterized in that, 0.1≤x≤0.9; 0.1≤y≤0.9.

3. polymer materials according to claim 2, is characterized in that, 0.3≤x≤0.8; 0.2≤y≤0.7.

4. polymer materials according to claim 1, is characterized in that, n is the integer between 1-50.

5. polymer materials according to claim 4, is characterized in that, n is the integer between 1-25.

6. polymer materials according to claim 1, wherein R and R ' is identical or different, expression methyl independent of each other, hexyl, heptane base, octyl or octane-iso base.

7. compound according to claim 6, is characterized in that, described compound is selected from the group of following compounds composition:

and

8. prepare the method with the polymer materials of the structure of general formula I according to any one of claim 1-7 for one kind:

4) by compound 5

7) containing compound 9

9. an electroluminescent device, comprise two electrodes and at least one deck organic electro luminescent layer, described organic electro luminescent layer comprises the polymer materials with the structure of general formula I as described in any one of claim 1-8.

10. electroluminescent device according to claim 9, the polymer materials described in it is characterized in that with the structure of general formula I emits white light.