CN102786666A - Benzotriazolyl-containing copolymer, preparation method and organic electroluminescent devices thereof - Google Patents
Benzotriazolyl-containing copolymer, preparation method and organic electroluminescent devices thereof Download PDFInfo
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- CN102786666A CN102786666A CN2011101262277A CN201110126227A CN102786666A CN 102786666 A CN102786666 A CN 102786666A CN 2011101262277 A CN2011101262277 A CN 2011101262277A CN 201110126227 A CN201110126227 A CN 201110126227A CN 102786666 A CN102786666 A CN 102786666A
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Abstract
The present invention belongs to the technical field of organic photoelectric materials, and discloses a benzotriazolyl-containing copolymer, a preparation method and an application thereof. The benzotriazolyl-containing copolymer has the following general formula (I), wherein R1 and R2 are respectively C1-C20 alkyl, and n is an integer of 10-100. The benzotriazolyl-containing copolymer of the present invention has the following advantages that: a synthesis process is simple, manufacturing cost is reduced, and mass production of the benzotriazolyl-containing copolymer can be achieved; and electroluminescent devices of the benzotriazolyl-containing copolymer have characteristics of high purity and stable luminescence performance, and can be used as red-light emitting polymers.
Description
Technical field
The present invention relates to the organic photoelectrical material technical field, relate in particular to containing benzotriazole base co-polymer and preparation method thereof and using of a kind of organic semiconductor material.The invention still further relates to and a kind ofly use this to contain the organic electroluminescence device of benzotriazole base co-polymer as luminescent layer.
Background technology
Nineteen ninety, the J.H.Burroughes of univ cambridge uk etc. has released the PPV polymer LED first, has started the beginning of solution method processing and preparing device, has predicted it as the flexible possibility that shows.The feasibility of this technology has been confirmed in the successful development of polymer LED, lets people see the hope of this technology as FPD or large area flexible display screen.As everyone knows, under lower driven, electroluminescent material sends, and three primary colours light high efficiency, high brightness is very important for panchromatic colour developing.Yet the red light-emitting polymkeric substance is slightly inferior the relative green glow in aspects such as brightness, efficient.In general, the ruddiness Organic Light Emitting Diode is through red light-emitting material such as porphyrin, the compound that contains pyrans, europium and complex of iridium etc. are entrained in as in the Alq3 broad-band gap material of main part.But when doping content was higher, these doping red light-emitting materials were easy to accumulate on the solid film, and this can cause fluorescent quenching usually; When doping content is low, energy shift can not be fully from the material of main part to the red illuminating material in, this can cause the device luminance purity not high usually.The result is, optimum doping concentration is lower usually, and effectively the doping content scope is narrower, causes luminous efficiency lower, device preparation difficulty.Therefore, for large-scale production process, non-adulterated red-light-emitting polymer photodiode is preferable.So developing a kind of non-doping red-light-emitting polymer photodiode novel, stable luminescent property is a major challenge in current polymer semiconductor field.
Summary of the invention
The object of the present invention is to provide a kind of non-adulterated benzotriazole base co-polymer that contains of stable luminescent property, it is the multipolymer of following structural formula (I) expression:
In the formula, R
1, R
2Be respectively C
1～C
20Alkyl, n is 10～100 integer; Preferably, R
1Be C
8～C
16Alkyl, R
1Be C
6～C
12Alkyl.
Another object of the present invention is to provide a kind of benzotriazole base co-polymer preparation method that contains, comprise the steps:
Step S1, the compd A and the B that provide following structural formula to represent,
Wherein, R
1Be C
1～C
20Alkyl, R
2Be C
1～C
20Alkyl;
Step S2, under oxygen-free environment, compd A and B are added in the organic solvent that contains catalyzer, under 90～120 ℃, carry out Stille coupling reaction 12～48h, obtain the said benzotriazole base co-polymer that contains of following structural formula (I) expression:
In the formula, n is 10～100 integer.
Among above-mentioned preparing method's the step S2, said catalyzer can be in mixture, tetra-triphenylphosphine palladium or the bi triphenyl phosphorus palladium chloride of three dibenzalacetones, two palladiums and tri-butyl phosphine any; Wherein, when catalyzer was the mixture of three dibenzalacetones, two palladiums and tri-butyl phosphine, the molar weight of three dibenzalacetones, two palladiums was 1/80～1/120 of a compd A, and the molar weight of tri-butyl phosphine is 4 times of three dibenzalacetones, two palladiums.
Among above-mentioned preparing method's the step S2, said organic solvent can be toluene, THF or N, any in the dinethylformamide.
Further purpose of the present invention is to provide a kind of organic electroluminescence device, and this device is a straticulate structure, and this structure is followed successively by: substrate/conductive layer/hole injection-transport layer/luminescent layer/hole barrier-electron transfer layer/cathode layer; Wherein, the material of said luminescent layer is the above-mentioned benzotriazole base co-polymer that contains; Substrate is that glass, conductive layer are ITO, and both lump together and are ito glass; Cathode layer is the Mg:Ag metal level.
The benzotriazole base co-polymer that contains provided by the invention, its synthesis technique is simple, the attenuating manufacturing cost, can produce in enormous quantities, and contain high, the stable luminescent property of electroluminescent device luminance purity of benzotriazole base co-polymer, can be used as red-light-emitting polymer.
Description of drawings
Fig. 1 contains preparation technology's schema of benzotriazole base co-polymer for the present invention;
Fig. 2 is the electroluminescent spectrum figure of the electroluminescent device of luminescent layer for the polymkeric substance among the embodiment 2; Wherein, curve 1 is represented the 4V driving voltage, and curve 2 is represented the 5V driving voltage, and curve 3 is represented the 7V driving voltage;
Fig. 3 is the structural representation of organic electroluminescence device among the embodiment 6.
Embodiment
A kind of benzotriazole base co-polymer that contains provided by the invention, it is the multipolymer of following structural formula (I) expression:
In the formula, R
1, R
2Be respectively C
1～C
20Alkyl, n is 10～100 integer; Preferably, R
1Be C
8～C
16Alkyl, R
2Be C
6～C
12Alkyl.
Another object of the present invention is to provide a kind of benzotriazole base co-polymer preparation method that contains, as shown in Figure 1, comprise the steps:
Step S1, the compd A and the B that provide following structural formula to represent,
Wherein, R
1Be C
1～C
20Alkyl, R
2Be C
1～C
20Alkyl; Preferably, R
1Be C
8～C
16Alkyl, R
2Be C
6～C
12Alkyl;
Step S2, under oxygen-free environment, (constitute) by nitrogen or rare gas element; Compd A and B are added in the organic solvent that contains catalyzer; Under 90～120 ℃, carry out Stille coupling reaction 12～48h, obtain the said benzotriazole base co-polymer that contains of following structural formula (I) expression:
In the formula, n is 10～100 integer.
The above-mentioned benzotriazole base co-polymer that contains that makes also contains a lot of impurity, also need carry out purification process to it, and promptly this preparation method also comprises the steps:
Step S3, with after containing of obtaining among the step S2, the benzotriazole base co-polymer filtered through methyl alcohol precipitating, apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Be solvent extraction then with the chloroform to colourless, collect chloroformic solution and also revolve the dried red solid that obtains, collect back 50 ℃ of dry 24h under vacuum, what promptly obtain purifying contains benzotriazole base co-polymer solid.
Among above-mentioned preparing method's the step S2, said catalyzer can be in mixture, tetra-triphenylphosphine palladium or the bi triphenyl phosphorus palladium chloride of three dibenzalacetones, two palladiums and tri-butyl phosphine any; Wherein, when catalyzer was the mixture of three dibenzalacetones, two palladiums and tri-butyl phosphine, the molar weight of three dibenzalacetones, two palladiums was 1/80～1/120 of a compd A, and the molar weight of tri-butyl phosphine is 4 times of three dibenzalacetones, two palladiums.
Among above-mentioned preparing method's the step S2, said organic solvent can be toluene, THF or N, any in the dinethylformamide.
Further purpose of the present invention is to provide a kind of organic electroluminescence device, and this device is a straticulate structure, and this structure is followed successively by: substrate/conductive layer/hole injection-transport layer/luminescent layer/hole barrier-electron transfer layer/cathode layer; Wherein, substrate is that glass, conductive layer are ITO, and both lump together and are ito glass; Cathode layer is the Mg:Ag metal level; The material of said luminescent layer is the above-mentioned benzotriazole base co-polymer that contains, and its this structural formula (I) is:
In the formula, R
1Be C
1～C
20Alkyl, R
2Be C
1～C
20Alkyl, n is 10～100 integer; Preferably, R
1Be C
8～C
16Alkyl, R
2Be C
6～C
12Alkyl;
The benzotriazole base co-polymer that contains provided by the invention, its synthesis technique is simple, the attenuating manufacturing cost, can produce in enormous quantities, and contain high, the stable luminescent property of electroluminescent device luminance purity of benzotriazole base co-polymer, can be used as red-light-emitting polymer.
In order to understand the content of patent of the present invention better, below through specific embodiment illustrate contain benzotriazole base co-polymer preparation method with and performance.
Among the following embodiment, compd A is directly buied from market, and compd B then gets through reference disclosed method (Chem.Mater., 2008,20,7510) preparation.
Embodiment 1
Present embodiment contain the benzotriazole base co-polymer for gathering { 4,8-two (2-ethyl hexyl oxy)-benzo two thiophene-2-dodecyl benzo triazole }, wherein, R
1Be 2-ethylhexyl, R
2Be dodecyl, n=63; The structural formula of this multipolymer is following:
The preparation process of above-mentioned polymkeric substance is following:
The preparation of step 1,2-dodecyl benzotriazole, reaction formula is as follows:
Detailed process is following: with 1,2, the 3-benzotriazole (5.0g, 42mmol), Pottasium Hydroxide (5.6g, 100mmol) and bromododecane (12.2g 49mmol) is dissolved in the 50mL methyl alcohol reflux 24h; Stop behind the cool to room temperature stirring, rotary evaporation removes and desolvates, and surplus materials is poured in the 200mL trichloromethane, washes 2 times and separates organic phase, uses anhydrous magnesium sulfate drying, and steaming desolventizes, and obtains out product.
Crude product uses sherwood oil to obtain colorless oil as leacheate through the silica gel column chromatography separation and is 2-dodecyl benzo triazole, and productive rate is 31%.
1H?NMR(400MHz，CDCl
3，δ)：7.76(m，2H)，7.26(m，2H)，4.62(t，J＝7.1Hz?2H)，2.12(m，2H)，1.25-1.15(m，18H)，0.78(t，J＝6.0Hz，3H)；
Step 2,4, the preparation of 7-two bromo-2-dodecyl benzotriazoles, reaction formula is as follows:
With compound 2-dodecyl benzotriazole (3.7g, 13.1mmol) (5.8mol/L 15mL) joins in the 100mL there-necked flask with HBr solution; At 100 ℃ of stirring reaction 1h; And then in flask slowly the dropping liquid bromine (5.9g, 36mmol), mixture is at 135 ℃ of following vigorous stirring reaction 12h; Make 4,7-two bromo-2-dodecyl benzotriazole crude product mixed solutions;
Reaction finishes postcooling to room temperature, toward 4, adds sodium hydrogen carbonate solution, chloroform extraction in the 7-two bromo-2-dodecyl benzotriazole crude product mixed solutions; Use the anhydrous magnesium sulfate drying after-filtration then, steaming desolventizes, and residuum adopts silica gel column chromatography to separate, and obtains 4 of glassy yellow oil, 7-two bromo-2-dodecyl benzotriazole products.Productive rate is 75%.
1H?NMR(400MHz，CDCl
3，δ)：7.36(s，2H)，4.60(t，J＝7.0Hz，2H)，2.10(m，2H)，1.38-1.12(m，18H)，0.80(t，J＝6.9Hz，3H).
Step 3, gather the preparation of { 4,8-two (2-ethyl hexyl oxy)-benzo two thiophene-2-dodecyl benzo triazole }, reaction formula is as follows:
Under the nitrogen protection, 2,6-two tin trimethyls-4; 8-two (2-ethyl hexyl oxy)-benzo two thiophene (231.6mg, 0.3mmol), 2-dodecyl-4; 7-two bromo-benzotriazoles (133.5mg, 0.3mmol) and 10mL toluene (Tol) join respectively in the two-mouth bottle of 50mL, behind the fully logical about 20min of nitrogen purge gas; Then the 17mg tetrakis triphenylphosphine palladium is added wherein, behind the fully logical more about 10min of nitrogen purge gas, at 100 ℃ of stirring reaction 24h; Stop polyreaction after the cooling, gathered { 4,8-two (2-ethyl hexyl oxy)-benzo two thiophene-2-dodecyl benzo triazole } crude product mixed solution.
{ 4,8-two (2-ethyl hexyl oxy)-benzo two thiophene-2-dodecyl benzo triazole } the crude product mixed solution adding of gathering in flask 40mL methyl alcohol precipitating is through use methyl alcohol and normal hexane extracting 24h after the apparatus,Soxhlet's filtration successively; Be that solvent extraction is extremely colourless then with the chloroform, collect chloroformic solution and also revolve the dried red solid that obtains, collect back 50 ℃ of dry 24h under vacuum, promptly gathered { 4,8-two (2-ethyl hexyl oxy)-benzo two thiophene-2-dodecyl benzo triazole }.Productive rate is 78%.
GPC：M
n＝46100，PDI＝1.7.
Embodiment 2
Present embodiment contain the benzotriazole base co-polymer for gathering { 4,8-two (dodecyloxy)-benzo two thiophene-2-hexyl benzotriazole }; Wherein, R
1Be dodecyl, R
2Be hexyl, n=65; The structural formula of this multipolymer is following:
The preparation process of above-mentioned polymkeric substance is following:
Step 1, with embodiment 1 in the step 1 difference be: replace bromo-dodecane with bromohexane, other steps are all identical;
Step 2, identical with step 2 among the embodiment 1;
Step 3, gather the preparation of { 4,8-two (dodecyloxy)-benzo two thiophene-2-hexyl benzotriazole }, reaction formula is as follows:
Under the argon shield, 2,6-two tin trimethyls-4,8-two (dodecyloxy)-benzo two thiophene (265.8mg; 0.3mmol), 2-n-hexyl-4,7-two bromo-benzotriazole (107.7mg; 0.3mmol) and 10mL N, dinethylformamide joins respectively in the two-mouth bottle of 50mL, behind the fully logical about 20min of argon gas emptying gas; Then 15mg bi triphenyl phosphorus palladium chloride palladium is added wherein, behind the fully logical more about 10min of argon gas emptying gas, at 120 ℃ of stirring reaction 12h; Stop polyreaction after the cooling, gathered { 4,8-two (n-dodecane oxygen base)-benzo two thiophene-2-hexyl benzotriazole } crude product mixed solution.
In flask, gather { 4,8-two (n-dodecane oxygen base)-benzo two thiophene-2-hexyl benzotriazole } crude product mixed solution and add 40mL methyl alcohol precipitating, use methyl alcohol and normal hexane extracting 24h successively after filtering through apparatus,Soxhlet's; Be that solvent extraction is extremely colourless then with the chloroform, collect chloroformic solution and also revolve the dried red solid that obtains, collect back 50 ℃ of dry 24h under vacuum, promptly gathered { 4,8-two (dodecyloxy)-benzo two thiophene-2-hexyl benzotriazole }.Productive rate is 75%.
GPC：M
n＝49500，PDI＝1.8.
Fig. 2 is the electroluminescent spectrum figure of the electroluminescent device of luminescent layer for the polymkeric substance among the embodiment 2.Can find out, its 643nm place, when under driving voltage 4～7V, emission peak changes little, has showed stable red emission, shows the injection and the compound balance that is able to of current carrier, and exciton is confined in the luminescent layer well.
Embodiment 3
Present embodiment contain the benzotriazole base co-polymer for gathering { 4,8-two (n-Hexadecane oxygen base)-benzo two thiophene-2-octyl group benzotriazole }, wherein, R
1Be n-Hexadecane oxygen base, R
2Be octyl group, n=61; The structural formula of this multipolymer is following:
Below introduce its preparation process in detail.
Step 1, with embodiment 1 in the step 1 difference be: replace bromo-dodecane with bromooctane;
Step 2, identical with step 2 among the embodiment 1;
Step 3, gather the preparation of { 4,8-two (n-Hexadecane oxygen base)-benzo two thiophene-2-octyl group benzotriazole }, reaction formula is as follows:
Under the nitrogen protection, 2,6-two tin trimethyls-4; 8-two (n-Hexadecane oxygen base)-benzo two thiophene (299.4mg, 0.3mmol), 2-octyl group-4; 7-two bromo-benzotriazoles (116.1mg, 0.3mmol) and the 10mL THF join respectively in the two-mouth bottle of 50mL, behind the fully logical about 20min of nitrogen purge gas; Then 13mg three dibenzalacetones, two palladiums and 15g tri-butyl phosphine are added wherein, behind the fully logical more about 10min of nitrogen purge gas, at 90 ℃ of stirring reaction 48h; Stop polyreaction after the cooling, gathered { 4,8-two (n-Hexadecane oxygen base)-benzo two thiophene-2-octyl benzotriazole } crude mixture.
In flask, gather { 4,8-two (n-hexadecane oxygen base)-benzo two thiophene-2-octane base benzotriazole } crude mixture and add 40mL methyl alcohol precipitating, use methyl alcohol and normal hexane extracting 24h successively after filtering through apparatus,Soxhlet's; Be that solvent extraction is extremely colourless then with the chloroform, collect chloroformic solution and also revolve the dried red solid that obtains, collect back 50 ℃ of dry 24h under vacuum, promptly gathered { 4,8-two (n-Hexadecane oxygen base)-benzo two thiophene-2-octyl benzotriazole }.Productive rate is 72%.
GPC：M
n＝55200，PDI＝1.7.
Embodiment 4
Present embodiment contain the benzotriazole base co-polymer for gathering { 4,8-two (methoxyl group)-benzo two thiophene-2-octyl group benzotriazole }, wherein, R
1Be methoxyl group, R
2Be octyl group, n=92; The structural formula of this multipolymer is following:
Below introduce its preparation process in detail.
Step 1, with embodiment 1 in the step 1 difference be: replace positive bromo-dodecane with positive bromo spicy silane;
Step 2, identical with step 2 among the embodiment 1;
Step 3, gather the preparation of { 4,8-two (methoxyl group)-benzo two thiophene-2-octyl group benzotriazole }, reaction formula is as follows:
Under the nitrogen protection, 2,6-two tin trimethyls-4; 8-two (methoxyl group)-benzo two thiophene (173.4mg, 0.3mmol), 2-octyl group-4; 7-two bromo-benzotriazoles (116.1mg, 0.3mmol) and the 10mL THF join respectively in the two-mouth bottle of 50mL, behind the fully logical about 20min of nitrogen purge gas; Then 13mg three dibenzalacetones, two palladiums and 15g tri-butyl phosphine are added wherein, behind the fully logical more about 10min of nitrogen purge gas, at 90 ℃ of stirring reaction 48h; Stop polyreaction after the cooling, gathered { 4,8-two (methoxyl group)-benzo two thiophene-2-octyl benzotriazole } crude mixture.
In flask, gather { 4,8-two (methoxyl group)-benzo two thiophene-2-octyl benzotriazole } crude mixture and add 40mL methyl alcohol precipitating, use methyl alcohol and normal hexane extracting 24h successively after filtering through apparatus,Soxhlet's; Be that solvent extraction is extremely colourless then with the chloroform, collect chloroformic solution and also revolve the dried red solid that obtains, collect back 50 ℃ of dry 24h under vacuum, promptly gathered { 4,8-two (methoxyl group)-benzo two thiophene-2-octyl benzotriazole }.Productive rate is 65%.
GPC：M
n＝44100，PDI＝1.8.
Embodiment 5
Present embodiment contain the benzotriazole base co-polymer for gathering { 4,8-two (dodecyloxy)-benzo two thiophene-2-eicosyl benzotriazole }; Wherein, R
1Be dodecyl, R
2Be eicosyl, n=49; The structural formula of this multipolymer is following:
The preparation process of above-mentioned polymkeric substance is following:
Step 1, be with step 1 difference among the embodiment 1: with bromine eicosyl replacement bromo-dodecane, other steps are all identical;
Step 2, identical with step 2 among the embodiment 1;
Step 3, gather the preparation of { 4,8-two (dodecyloxy)-benzo two thiophene-2-eicosyl benzotriazole }, reaction formula is as follows:
Under the argon shield, 2,6-two tin trimethyls-4,8-two (dodecyloxy)-benzo two thiophene (265.8mg; 0.3mmol), eicosyl-4,7-two bromo-benzotriazole (166mg; 0.3mmol) and 10mL N, dinethylformamide joins respectively in the two-mouth bottle of 50mL, behind the fully logical about 20min of argon gas emptying gas; Then 15mg bi triphenyl phosphorus palladium chloride palladium is added wherein, behind the fully logical more about 10min of argon gas emptying gas, at 120 ℃ of stirring reaction 12h; Stop polyreaction after the cooling, gathered { 4,8-two (dodecyloxy)-benzo two thiophene-2-eicosyl benzotriazole } crude product mixed solution.
In flask, gather { 4,8-two (dodecyloxy)-benzo two thiophene-2-eicosyl benzotriazole } crude product mixed solution crude product mixed solution and add 40mL methyl alcohol precipitating, use methyl alcohol and normal hexane extracting 24h successively after filtering through apparatus,Soxhlet's; Be that solvent extraction is extremely colourless then with the chloroform, collect chloroformic solution and also revolve the dried red solid that obtains, collect back 50 ℃ of dry 24h under vacuum, promptly gathered { 4,8-two (dodecyloxy)-benzo two thiophene-2-eicosyl benzotriazole }.Productive rate is 72%.
GPC：M
n＝47300，PDI＝1.8.
Following embodiment contains the application of benzotriazole base co-polymer in organic photoelectrical material, organic solar batteries device, organic field effect tube device, organic electroluminescence device, organic light storage device or organic laser apparatus.
Illustrate at present and contain the application of benzotriazole base co-polymer in organic electroluminescence device.
Embodiment 6
Present embodiment 6 adopts and gathers the application of { 4,8-two (2-ethyl hexyl oxy)-benzo two thiophene-2-dialkyl group benzo triazole } blue phosphorescent material as the luminescent layer of organic electroluminescence device among the embodiment 1; Wherein, promptly substrate is a glass, and conductive layer is the ITO layer, and both lump together and are ito glass, can buy acquisition.
A kind of organic electroluminescence device, as shown in Figure 2, its structure is arranged in order and is glass/ITO layer/hole injection-transport layer/luminescent layer/hole barrier-electron transfer layer/Mg:Ag metal level; Wherein, the mass percent of Mg and Ag is 10: 1.
The preparation technology of this organic electroluminescence device is:
All material is all carried out the device preparation after purifying;
Ito glass is successively through sanitising agent, deionized water, acetone, and ethanol to clean the back dry in baking oven;
Earlier (promptly 3,4-enedioxy thiophene: poly styrene sulfonate) film is as hole injection-transport layer at the ITO of ito glass surface spin coating PEDOT:PSS;
Spin coating luminescent layer then, luminescent layer is for gathering { 4,8-two (2-ethyl hexyl oxy)-benzo two thiophene-2-dodecyl benzo triazole };
The TPBI that the about 40nm of vapor deposition last layer is thick again (promptly 1; 3; 5-three (N-phenyl-2-benzimidazolyl-2 radicals) benzene) as hole barrier-electron transfer layer; The lithium fluoride that in addition 1nm is thick strengthens electronics and injects, and the vapor deposition speed of lithium fluoride is
At last, with the vapor deposition mode of 3000rpm, on hole barrier-electron transfer layer, prepare the thick Mg:Ag metal level of the about 60nm of one deck; The light-emitting area of the organic electroluminescence device that makes is 2mm
2Wherein, Mg:Ag vapor deposition speed does
Thickness is by near the quartz crystal oscillator sheet monitoring that is positioned at the substrate in the evaporate process, and proofreaies and correct through XP-2 step appearance (Ambios company).
Should be understood that above-mentioned statement to preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. one kind has formula (I) and contains the benzotriazole base co-polymer,
In the formula, R
1, R
2Be respectively C
1～C
20Alkyl, n is 10～100 integer.
2. the benzotriazole base co-polymer that contains according to claim 1 is characterized in that said R
1Be C
8～C
16Alkyl.
3. the benzotriazole base co-polymer that contains according to claim 1 is characterized in that said R
2Be C
6～C
12Alkyl.
4. a preparation method who contains the benzotriazole base co-polymer is characterized in that, this preparation method comprises the steps:
Step S1, following compd A and B are provided:
Wherein, R
1Be C
1～C
20Alkyl, R
2Be C
1～C
20Alkyl;
Step S2, under oxygen-free environment, compd A and B are added in the organic solvent that contains catalyzer, under 90～120 ℃, carry out Stille coupling reaction 12～48h, obtain the said benzotriazole base co-polymer that contains of following structural formula (I) expression:
In the formula, n is 10～100 integer.
5. preparation method according to claim 4 is characterized in that, among the step S1, and said R
1Be C
8～C
16Alkyl.
6. preparation method according to claim 4 is characterized in that, among the step S1, and said R
2Be C
6～C
12Alkyl.
7. preparation method according to claim 4 is characterized in that, among the step S2, said catalyzer is among arbitrary in mixture, tetra-triphenylphosphine palladium or the bi triphenyl phosphorus palladium chloride of three dibenzalacetones, two palladiums and tri-butyl phosphine.
8. preparation method according to claim 7; It is characterized in that; Said catalyzer is in the mixture of three dibenzalacetones, two palladiums and tri-butyl phosphine; The molar weight of said three dibenzalacetones, two palladiums is 1/80～1/120 of a compd A, and the molar weight of tri-butyl phosphine is 4 times of three dibenzalacetones, two palladiums.
9. preparation method according to claim 4 is characterized in that, among the step S2, said organic solvent is toluene, THF or N, any in the dinethylformamide.
10. organic electroluminescence device, this device is a straticulate structure, this structure is followed successively by: substrate/conductive layer/hole injection-transport layer/luminescent layer/hole barrier-electron transfer layer/cathode layer; It is characterized in that the material of said luminescent layer is the arbitrary described benzotriazole base co-polymer that contains of claim 1 to 3.
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| CN103664994A (en) * | 2012-08-31 | 2014-03-26 | 昆山维信诺显示技术有限公司 | Benzodithiophene derivative organic electroluminescent material and application thereof |
| CN103865041A (en) * | 2012-12-12 | 2014-06-18 | 海洋王照明科技股份有限公司 | Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof |
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| CN103865041A (en) * | 2012-12-12 | 2014-06-18 | 海洋王照明科技股份有限公司 | Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof |
| CN103865041B (en) * | 2012-12-12 | 2016-02-10 | 海洋王照明科技股份有限公司 | Containing the conjugated polymers and its preparation method and application of bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene |
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