CN102464794B - Copolymer containing benzotriazol group as well as preparation method and application of copolymer - Google Patents
Copolymer containing benzotriazol group as well as preparation method and application of copolymer Download PDFInfo
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- CN102464794B CN102464794B CN201010545773.XA CN201010545773A CN102464794B CN 102464794 B CN102464794 B CN 102464794B CN 201010545773 A CN201010545773 A CN 201010545773A CN 102464794 B CN102464794 B CN 102464794B
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- polymer
- benzotriazole base
- alkyl
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical group C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229920001577 copolymer Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000012964 benzotriazole Substances 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- -1 monosubstituted phenyl Chemical group 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229960001701 chloroform Drugs 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 238000005401 electroluminescence Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 4
- 230000005669 field effect Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 11
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 239000002585 base Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 0 CC(C)(c1ccc(-c2ccc(-c3ccc(-c4ccc(c5ccc(C(C)(C)c6ccccc6)cc5[n]5*)c5c4)[s]3)c3n[n](*)nc23)[s]1)c1ccccc1 Chemical compound CC(C)(c1ccc(-c2ccc(-c3ccc(-c4ccc(c5ccc(C(C)(C)c6ccccc6)cc5[n]5*)c5c4)[s]3)c3n[n](*)nc23)[s]1)c1ccccc1 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WESNTVKWORZVQQ-UHFFFAOYSA-N 2-octylbenzotriazole Chemical compound C1=CC=CC2=NN(CCCCCCCC)N=C21 WESNTVKWORZVQQ-UHFFFAOYSA-N 0.000 description 3
- YXPUNWKYPJPPFC-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P YXPUNWKYPJPPFC-UHFFFAOYSA-N 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229940093916 potassium phosphate Drugs 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- GZUJVYIVNFYWSU-UHFFFAOYSA-N 2-dodecylbenzotriazole Chemical compound C1=CC=CC2=NN(CCCCCCCCCCCC)N=C21 GZUJVYIVNFYWSU-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OHOVBSAWJQSRDD-UHFFFAOYSA-N thiophen-2-yloxyboronic acid Chemical compound OB(O)OC1=CC=CS1 OHOVBSAWJQSRDD-UHFFFAOYSA-N 0.000 description 2
- LYFJGDKTBBGJJS-UHFFFAOYSA-N 2-octyl-4,7-dithiophen-2-ylbenzotriazole Chemical compound C(CCCCCCC)N1N=C2C(=N1)C(=CC=C2C=1SC=CC=1)C=1SC=CC=1 LYFJGDKTBBGJJS-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- BDDIUTHMWNWMRJ-UHFFFAOYSA-N octane;hydrobromide Chemical compound Br.CCCCCCCC BDDIUTHMWNWMRJ-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
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Abstract
The invention relates to the technical field of organic materials and provides a copolymer containing a benzotriazol group. The copolymer has a structural formula (I) shown as the specification, wherein R is an alkyl group from C1 to C32 or alkoxy-monosubstituted phenyl group from C1 to C38, R' is an alkyl group from C1 to C32, and n is an integer of 10-50. The invention also provides a preparation method and application of the copolymer containing the benzotriazol group. The copolymer containing the benzotriazol group contains benzotriazol and carbazole groups and has favorable photoelectric properties, thermal stability and film forming capability, thereby being a novel red-light-emitting copolymer.
Description
Technical field
The invention belongs to organic materials technical field, be specifically related to a kind of containing benzotriazole base co-polymer, its preparation method and application.
Background technology
Nineteen ninety, the J.H.Burroughes of univ cambridge uk etc. has released PPV polymer LED first, has started the beginning of solution method processing fabricate devices, has predicted it as the flexible possibility showing.The successful development of polymer LED, has determined the feasibility of this technology, allows people see the hope of this technology as flat pannel display or large area flexible display screen.As everyone knows, under lower voltage drives, electroluminescent material sends, and three primary colours light high efficiency, high brightness is very important for panchromatic colour developing.Yet red light-emitting polymkeric substance is slightly inferior the relative green glow in the aspects such as brightness, efficiency.In general, ruddiness Organic Light Emitting Diode be by by red emitting material as porphyrin, be entrained in as in Alq3 broad-band gap material of main part containing compound, europium and the complex of iridium etc. of pyrans.But when doping content is higher, these doping red emitting materials are easy to be gathered on solid film, this can cause fluorescent quenching conventionally; When doping content is lower, energy shift can not be completely from material of main part to red illuminating material in, this can cause device luminance purity not high conventionally.Result is, optimum doping concentration is conventionally lower, and effectively doping content scope is narrower, causes luminous efficiency lower, device preparation difficulty.Therefore,, for large-scale production process, the red-light-emitting polymer photodiode of non-doping 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
It is a kind of containing benzotriazole base co-polymer, its preparation method and application that the object of the embodiment of the present invention is to provide, and is intended to solve the technical problem of organic electro-optic device in prior art.
Embodiments of the invention are achieved in that a kind of containing benzotriazole base co-polymer, and it is the multipolymer that following structural formula (I) represents:
In formula, R is C
1～C
32alkyl or C
1～C
38alkoxyl group monosubstituted phenyl, R ' is C
1～C
32alkyl, the integer that n is 10-50.
Another object of the embodiment of the present invention is to provide that a kind of synthetic route is simple, cost is low containing benzotriazole base co-polymer preparation method, and described preparation method comprises the steps:
The compd A and the B that provide respectively following structural formula to represent,
wherein, R is C
1～C
32alkyl or C
1～C
38alkoxyl group monosubstituted phenyl, R ' is C
1～C
32alkyl;
Under oxygen-free environment, compd A and B are added in the organic solvent that contains catalyzer and alkaline solution, at 80～100 ℃, carry out Suzuki coupling reaction 36～60h, obtain described containing benzotriazole base co-polymer that following structural formula (I) represents:
The integer that n in structural formula (I) is 10-50.
A further object of the present invention be to provide structural formula (I) containing 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, this structural formula (I) is:
In formula, R is C
1～C
32alkyl or C
1～C
38alkoxyl group monosubstituted phenyl, R ' is C
1～C
32alkyl, the integer that n is 10-50.
The embodiment of the present invention containing benzotriazole base co-polymer, 1,2,3-benzotriazole is an important electron acceptor(EA) unit, and it has two strong electrophilic imido grpups, is the heterogeneous ring compound that has strong electrophilic performance, simultaneously, N-H bond energy on 1,2,3-benzotriazole enough easily modifies to regulate solvability and photoelectric properties with functional groups such as other alkyl flexible chains.Thiophene is five-membered ring structure, meets shock youngster rule, has moderate band gap, wider spectral response, preferably thermostability and environmental stability.In addition, 2,7-carbazole and derivative thereof have good hole transport performance, superior chemical stability and the photophysical property of easily modifying.Above-mentioned, containing in the preparation method of benzotriazole base co-polymer, adopt better simply synthetic route, thereby reduce technical process, reduce manufacturing cost.This multipolymer is applicable in organic photoelectrical material, solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties or organic laser apparatus, stable luminescent property not only, and luminance purity is high, and be convenient to large batch of preparation.
Accompanying drawing explanation
Fig. 1 is the structural formula containing benzotriazole base co-polymer of the embodiment of the present invention;
Fig. 2 is the schema containing benzotriazole base co-polymer preparation method of the embodiment of the present invention;
Fig. 3 adopts the structural representation of the organic electroluminescence device containing benzotriazole base co-polymer of the embodiment of the present invention;
Fig. 4 is 2-n-octyl-4 of the embodiment of the present invention, 7-bis-(5,5 '-dibromo thiophene base)-1,2, and 3-benzotriazole is at CDCl
3in
1hNMR figure;
Fig. 5 is the thermogravimetic analysis (TGA) containing benzotriazole base co-polymer of the embodiment of the present invention 1;
Fig. 6 is the differential thermal analysis containing benzotriazole base co-polymer of the embodiment of the present invention 1;
Fig. 7 is the uv-visible absorption spectroscopy figure containing benzotriazole base co-polymer of the embodiment of the present invention 1;
Fig. 8 is the fluorescence spectrum figure containing benzotriazole base co-polymer of the embodiment of the present invention 1;
Fig. 9 is the cyclic voltammetry curve containing benzotriazole base co-polymer of the embodiment of the present invention 1;
Figure 10 is the XRD figure containing benzotriazole base co-polymer of the embodiment of the present invention 1;
Figure 11 is the electroluminescent spectrum containing benzotriazole base co-polymer of the embodiment of the present invention 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Refer to Fig. 1, show the structural formula containing benzotriazole base co-polymer of the embodiment of the present invention, be the multipolymer that following structural formula represents:
In formula, R is C
1～C
32alkyl or C
1～C
38alkoxyl group monosubstituted phenyl, R ' is C
1～C
32alkyl, the integer that n is 10-50.
In the multipolymer representing in said structure formula (I), comprise benzotriazole derivatives, thiophene-structure and carbazole unit.It has good film-forming properties, thermostability, fluorescence display glow preferably, and the carrier mobility of simultaneous electrochemical stable performance, polymkeric substance is high, is the non-doping red-light-emitting polymer of excellent performance.Preferably, R is C
6～C
12alkyl or C
6～C
18alkoxyl group monosubstituted phenyl, preferred, R is C
6～C
18alkoxyl group monosubstituted phenyl because alcoxyl substituted-phenyl can increase the rigidity of polymkeric substance, can significantly improve the thermal stability of polymkeric substance.R ' is C
6～C
12alkyl, abovementioned alkyl can be straight chained alkyl or branched-chain alkyl.Preferably, the integer that n is 20-40.By introducing alkyl chain or alkoxyl group to improve the solubility property of material, be conducive to film forming processing, expand its range of application.
Refer to Fig. 2, the above-mentioned preparation method containing benzotriazole base co-polymer comprises the steps:
S01: the compd A and the B that provide respectively following structural formula to represent,
S02: under oxygen-free environment, compd A and B are added in the organic solvent that contains catalyzer and alkaline solution, carry out Suzuki coupling reaction 36～60h at 80～100 ℃, obtain described containing benzotriazole base co-polymer that following structural formula (I) represents:
The integer that n in structural formula (I) is 10-50.
In step S01, compd A, B can directly buy from the market or prepare by existing synthetic method.Wherein, basic identical with the above-mentioned description containing benzotriazole base co-polymer, R is preferably C
6～C
12alkyl or C
6～C
18alkoxyl group monosubstituted phenyl, R ' is preferably as C
6～C
12alkyl, abovementioned alkyl can be straight chained alkyl or branched-chain alkyl.N is preferably the integer of 20-40.R and R ' adopt above-described structure formation, do not repeat them here.
In the present embodiment, compd A and B prepare respectively and obtain, specific as follows:
1, the preparation of compd A
Take compd A as example, and its syntheti c route is expressed as follows:
The first step, is dissolved in 1,2,3-benzotriazole and bromoalkane in alkaline organic solvent and carries out substitution reaction, obtains compound i.
Second step, is added in compound 1 and HBr solution in reaction vessel, after 100 ℃ of reaction 1h, then drips bromine, and reaction obtains compound ii.
The 3rd step, under protection of inert gas, is dissolved in compound ii and 2-thienyl boric acid in the organic solvent that contains sodium carbonate and palladium catalyst and reacts, and obtains compound iii.
The 4th step, under lucifuge condition, is dissolved in compound 3 in organic solvent and Glacial acetic acid, adds N-bromo-succinimide, and room temperature reaction, obtains compd A.
2, the preparation of compd B
The detailed step of preparing of compd B can reference: < < advanced material > > (Advanced Materials), 2007,19,2295.
In step S02, under protection of inert gas, in organic solvent, add compd A and B, and the catalyzer of compd A molar weight 1/80～1/120, then add basic solution, logical rare gas element deoxygenation, stirring reaction 36-60h at 80-100 ℃.For guarantee to obtain suitable polymeric degree containing benzotriazole based polyalcohol, to it, can carry out end capping.Concrete steps are: bromobenzene is joined in the mixture after Suzuki coupling reaction, after reaction 2-4h, then the phenylo boric acid that is dissolved in organic solvent is added wherein, continue the end capping that spent the night that refluxes.After cooling, stop polyreaction, in flask, add methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, obtains polymkeric substance (I) after collection under vacuum after 50 ℃ of dry 24h.Wherein, catalyzer can for three dibenzalacetone two palladiums and 2-dicyclohexyl phosphine-2 ', the 6 ' mixture of-dimethoxy-biphenyl, tetra-triphenylphosphine palladium, bi triphenyl phosphorus palladium chloride.When catalyzer be three dibenzalacetone two palladiums and 2-dicyclohexyl phosphine-2 ', the mixture of 6 '-dimethoxy-biphenyl, the molar weight of three dibenzalacetone two palladiums is compd A 1/80～1/120,2-dicyclohexyl phosphine-2 ', the molar weight of 6 '-dimethoxy-biphenyl is four times of three dibenzalacetone two palladiums.Basic solution can be the NaOH aqueous solution, Na for alkaline solution
2cO
3the aqueous solution, NaHCO
3the aqueous solution, Na
3pO
4the alkaline aqueous solutions such as the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, the consumption of alkaline solution is 2～20 times of compd B molar weight.Described organic solvent can be toluene, ether, methylene dichloride, tetrahydrofuran (THF), trichloromethane, ethyl acetate or DMF.
In aforesaid method, the synthetic route of compd A and B monomer is fairly simple and ripe, thereby reduces technical process, reduces manufacturing cost.And Suzuki coupling reaction is a kind of very ripe organometallic coupling reaction, productive rate is high, mild condition, be easy to control, and easily by introducing alkyl and/or alkoxyl group, improve solvability and the molecular weight of product, with realize can spin coating polymkeric substance.
The benzotriazole base co-polymer that contains of the present embodiment can be used as organic photoelectrical material, be applied in various photoelectricity or semiconducter device, for example, solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device and organic laser apparatus etc.Wherein, above-mentioned containing benzotriazole base co-polymer, during as organic electroluminescence device, can be used as luminescent layer.The electroluminescent device of take below describes as example.Other is as organic light storage device, and organic non-linear optical properties and organic laser apparatus and similar are below all to using optical memory material, nonlinear material, laserable material or the semiconductor material etc. as it containing benzotriazole base co-polymer of the present embodiment.
Refer to Fig. 3, show and adopt the polymer electroluminescent device that contains benzotriazole base co-polymer in above-described embodiment, it comprises glass-base 41, transparent anode 42, middle supplementary layer 43, luminescent layer 44, the negative electrode 45 being cascading.Transparent anode 42 can adopt tin indium oxide (referred to as ITO).Middle supplementary layer 43 adopts poly-(3, the sub-ethylene dioxythiophene of 4-): polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS), luminescent layer 44 adopts that above-mentioned negative electrode 45 can adopt bimetallic electrodes containing benzotriazole base co-polymer, such as Mg/Ag etc.Concrete steps are, elder generation's spin coating PEDOT:PSS film on ITO conductive glass, it not only can improve hole injectability, and can strengthen the cohesive force of polymkeric substance on ITO conductive glass, then the benzotriazole base co-polymer that contains of the embodiment of the present invention is dissolved with appropriate solvent, by conventional spin coating technique shape, be coated on PEDOT:PSS film, finally, by mode evaporation metal electrode on polymkeric substance of vacuum evaporation, prepare polymer electroluminescent device.
Below by specific embodiment illustrate containing benzotriazole base co-polymer preparation method with and the aspect such as performance.A in embodiment and B can distinguish according to the method described above directly preparation and obtain below, certainly, also can directly buy from the market in other embodiments, are not limited to this.
Embodiment 1:
(PCDTBTz1), its structural formula is as follows for poly-{ 9-(4 '-n-octyloxy phenyl)-2,7-carbazole-co-2-n-octyl-4, the 7-dithienyl benzotriazole } of the present embodiment:
The preparation process of above-mentioned PCDTBTz1 polymkeric substance is as follows:
The preparation of step 1,2-n-octyl benzo triazole, reaction formula is as follows:
Detailed process is as follows: 1,2,3-benzotriazole (5.0g, 42mmol), potassium hydroxide (5.6g, 100mmol) and n-octane bromide (9.5g, 49mmol) are dissolved in 50mL methyl alcohol to reflux 24h.After cool to room temperature, stop stirring, rotary evaporation is except desolventizing, and surplus materials is poured in 200mL trichloromethane, washes 2 times separated organic phase, with anhydrous magnesium sulfate drying, except desolventizing.Crude product sherwood oil is that leacheate obtains colorless oil through silica gel column chromatography separation and is 2-n-octyl benzo triazole, and output is 2.9g, and productive rate is 30%.
Test result is:
1h NMR (400MHz, CDCl
3, ppm): 7.87 (m, 2H), 7.37 (m, 2H), 4.72 (t, 2H), 2.12 (m, 2H), 1.34-1.22 (m, 10H), 0.86 (t, 3H).
Detailed process is as follows: by compound 2-n-octyl benzo triazole (2.9g, 12.6mmol) with HBr solution (5.8mol/L, 14.4mL) join in 100mL there-necked flask, at 100 ℃ of stirring reaction 1h, and then slowly drip bromine (5.5g in flask, 34.6mmol), mixture vigorous stirring reaction 12h at 135 ℃.Be cooled to after completion of the reaction room temperature, add saturated sodium bicarbonate solution, chloroform extraction.Then with filtering after anhydrous magnesium sulfate drying, steaming desolventizes, and residuum adopts silica gel column chromatography separation to obtain glassy yellow oily liquids 2.Output is 3.7g, and productive rate is 75%.
Test result is:
1h NMR (400MHz, CDCl
3, ppm): 7.43 (s, 2H), 4.78 (t, 2H), 2.15 (m, 2H), 1.40-1.25 (m, 10H), 0.87 (t, 3H).
Detailed process is as follows: under nitrogen protection; by compound 4; the bromo-2-n-octyl of 7-bis-benzo triazole (3.5g; 9mmol), 2-thienyl boric acid (3.0g; 23.4mmol) and tetra-triphenylphosphine palladium (208mg; 0.18mmol) be dissolved in the glycol dimethyl ether of 80ml, then add sodium carbonate solution (1.0mol/L, 90mL).Mixture is vigorous stirring reaction 12h at 90 ℃.Cool to room temperature, with dichloromethane extraction three times, merge organic phase, with 1mol/L sodium hydroxide solution, wash again, after anhydrous magnesium sulfate drying, be spin-dried for, crude product adopts sherwood oil: ethyl acetate (10: 1) obtains yellow-green colour crystal 2.9g for leacheate through silica gel column chromatography separation, and productive rate is 82%.
Test result is:
1h NMR (400MHz, CDCl
3, ppm): 8.01 (d, 2H), 7.52 (s, 2H), 7.28 (d, 2H), 7.09 (t, 2H), 4.60 (t, 2H), 2.10 (m, 2H), 1.35-1.17 (m, 10H), 0.80 (t, 3H).
Step 4,2-n-octyl-4,7-bis-(5,5 '-dibromo thiophene base)-1,2, the preparation of 3-benzotriazole, reaction formula is as follows:
Detailed process is as follows: under lucifuge condition, by compound 2-n-octyl-4,7-dithienyl-1,2,3-benzotriazole (2.37g, 6mmol) be dissolved in trichloromethane (60mL) and Glacial acetic acid (60mL) mixed solution, move in ice bath, then by N-bromo-succinimide (NBS) (2.35g, 13.2mmol) add wherein in batches, at room temperature react after 12h, dichloromethane extraction washes with water for three times again, merge organic phase, with revolving after anhydrous magnesium sulfate drying, steam except desolventizing.Crude product obtains yellow needle-like crystal with DMF recrystallization, and output is 2.5g, and productive rate is 75%.
As shown in Figure 4, test result is:
1h NMR (400MHz, CDCl
3, ppm): 7.79 (d, 2H), 7.51 (s, 2H), 7.13 (d, 2H), 4.80 (t, 2H), 2.18 (m, 2H), 1.41-1.27 (m, 10H), 0.87 (t, 3H).
The preparation of step 5, PCDTBTz1, reaction formula is as follows:
Detailed process is as follows: under nitrogen protection, 2, 7-hypoboric acid pinacol ester-9-(4 '-n-octyloxy phenyl)-carbazole (reference literature < < advanced material > > Advanced Materials, 2007, 19, described in 2295, method is synthetic) (187.5mg, 0.3mmol), 2-n-octyl-4, 7-bis-(5, 5 '-dibromo thiophene base)-1, 2, 3-benzotriazole (166mg, 0.3mmol), three dibenzalacetone two palladium (2.75mg, 0.003mmol), 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (5mg), potassiumphosphate (509.4mg, 2.4mmol) be dissolved in the water of 5mL toluene and 1.2mL.After the fully logical about 30min of nitrogen purge gas, at 95 ℃ of stirring reaction 48h.Then bromobenzene (31.5 μ L, 0.23mmol) is joined in mixture, after reaction 3h, then phenylo boric acid (36.6mg, 0.25mmol) and 2mL toluene are added wherein, continue the end capping that spent the night that refluxes.After cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, is polymer PC DTBTz1.Output is 158mg, and productive rate is 70%.
Test result is: Mn (number-average molecular weight)=22.4kDa; Mw (matter average molecular weight)=39.8kDa; PDI (dispersity)=1.77; N=29.
Fig. 5 is the thermogravimetic analysis (TGA) figure of PCDTBTz1, and Fig. 6 is the differential thermal analysis of PCDTBTz1, from Fig. 5 and Fig. 6, has proved that PCDTBTz1 has good thermostability; The uv-visible absorption spectroscopy figure of PCDTBTz1 as shown in Figure 7; Fig. 8 is the fluorescence spectrum figure containing benzotriazole base co-polymer of PCDTBTz1, and its emission peak, at 600nm place, belongs to red emitting material; Fig. 9 is the cyclic voltammetry curve of PCDTBTz1, can find out that PCDTBTz1 has suitable HOMO and lumo energy, based on oxidizing potential, show that this polymer materials has shown satisfactory stability in air, is applicable to doing the luminescent material of polymer LED very much.Figure 10 is the XRD figure of PCDTBTz1, can find out that it has good peak crystallization, the complanation degree of the regularity of polymkeric substance and its molecular chain has very close relationship, all relevant with its degree of crystallinity. the regularity of polymkeric substance is better, the degree of order that main chain is arranged is higher, complanation degree is higher, and conjugated degree is larger; Figure 11 is the electroluminescent spectrum of PCDTBTz1, the luminous intensity under 5V voltage and 8V voltage luminous intensity basic identical, illustrate that the electroluminescent properties of PCDTBTz1 is fine.
Embodiment 2:
Poly-{ 9-(4 '-n-octyloxy phenyl)-2,7-carbazole-co-2-dodecyl-4,7-dithienyl benzotriazole } PCDTBTz 2 of the present embodiment, its structural formula is as follows:
Below introduce in detail its preparation process.
The preparation of step 1,2-dodecyl benzotriazole, reaction formula is as follows:
Detailed process is as follows: 1,2,3-benzotriazole (5.0g, 42mmol), potassium hydroxide (5.6g, 100mmol) and N-dodeeyl bromide (9.5g, 49mmol) are dissolved in 50mL methyl alcohol to reflux 24h.After cool to room temperature, stop stirring, rotary evaporation is except desolventizing, and surplus materials is poured in 200mL trichloromethane, washes 2 times separated organic phase, with anhydrous magnesium sulfate drying, except desolventizing.Crude product sherwood oil is that leacheate obtains colorless oil through silica gel column chromatography separation and is 2-dodecyl benzotriazole.
The preparation of step 5, PCDTBTz 2, reaction formula is as follows:
Detailed process is as follows: under nitrogen protection, 2, 7-hypoboric acid pinacol ester-9-(4 '-n-octyloxy phenyl)-carbazole (reference literature < < advanced material > > Advanced Materials, 2007, 19, described in 2295, method is synthetic) (187.5mg, 0.3mmol), 2-dodecyl-4, 7-bis-(5, 5 '-dibromo thiophene base)-1, 2, 3-benzotriazole (166mg, 0.3mmol), three dibenzalacetone two palladium (2.75mg, 0.003mmol), 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (5mg), potassiumphosphate (509.4mg, 2.4mmol) be dissolved in the water of 5mL toluene and 1.2mL.After the fully logical about 30min of nitrogen purge gas, at 95 ℃ of stirring reaction 48h.Then bromobenzene (31.5 μ L, 0.23mmol) is joined in mixture, after reaction 3h, then phenylo boric acid (36.6mg, 0.25mmol) and 2mL toluene are added wherein, continue the end capping that spent the night that refluxes.After cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, is polymer PC DTBTz2.Productive rate is 65%.
Test result is: Mn (number-average molecular weight)=21.8kDa; Mw (matter average molecular weight)=42.5kDa; PDI (dispersity)=1.95; N=27.
Embodiment 3:
Poly-{ 9-n-octyl-2,7-carbazole-co-2-n-octyl-4,7-dithienyl benzotriazole } PCDTBTz3 of the present embodiment, its structural formula is as follows:
Below introduce in detail its preparation process.
The preparation of step 5, PCDTBTz 3, reaction formula is as follows:
Detailed process is as follows: under nitrogen protection, 2, 7-hypoboric acid pinacol ester-9-(4 '-n-octyl)-carbazole (reference literature < < advanced material > > Advanced Materials, 2007, 19, described in 2295, method is synthetic) (187.5mg, 0.3mmol), 2-n-octyl-4, 7-bis-(5, 5 '-dibromo thiophene base)-1, 2, 3-benzotriazole (166mg, 0.3mmol), three dibenzalacetone two palladium (2.75mg, 0.003mmol), 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (5mg), potassiumphosphate (509.4mg, 2.4mmol) be dissolved in the water of 5mL toluene and 1.2mL.After the fully logical about 30min of nitrogen purge gas, at 95 ℃ of stirring reaction 48h.Then bromobenzene (31.5 μ L, 0.23mmol) is joined in mixture, after reaction 3h, then phenylo boric acid (36.6mg, 0.25mmol) and 2mL toluene are added wherein, continue the end capping that spent the night that refluxes.After cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, is polymer PC DTBTz3.Output is 158mg, and productive rate is 76%.
Test result is: Mn (number-average molecular weight)=25.4kDa; Mw (matter average molecular weight)=45.2kDa; PDI (dispersity)=1.78; N=36.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. containing a benzotriazole base co-polymer, it is the multipolymer that following structural formula (I) represents:
In formula, R is C
1～C
32alkyl or C
1～C
38alkoxyl group monosubstituted phenyl, R' is C
1～C
32alkyl, the integer that n is 10-50.
2. the benzotriazole base co-polymer that contains as claimed in claim 1, is characterized in that, described R is C
6～C
12alkyl or C
6～C
12alkoxyl group monosubstituted phenyl, described R' is C
6～C
12alkyl, the integer that described n is 20-40.
3. the benzotriazole base co-polymer that contains as claimed in claim 1 or 2, is characterized in that, described R is C
6～C
12alkoxyl group monosubstituted phenyl.
4. containing a benzotriazole base co-polymer preparation method, it comprises the steps:
The compd A and the B that provide respectively following structural formula to represent,
Under oxygen-free environment, compd A and B are added in the organic solvent that contains catalyzer and alkaline solution, at 80～100 ℃, carry out Suzuki coupling reaction 36～60h, obtain described containing benzotriazole base co-polymer that following structural formula (I) represents:
The integer that n in structural formula (I) is 10-50; Wherein, described alkaline solution is the NaOH aqueous solution, Na
2cO
3the aqueous solution, NaHCO
3the aqueous solution, Na
3pO
4the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, described organic solvent is at least one in toluene, ether, methylene dichloride, tetrahydrofuran (THF), trichloromethane, ethyl acetate or DMF;
To reaction system, add bromobenzene, carry out substitution reaction, then add phenylo boric acid, the end capping that continues to have refluxed, makes structural formula and is
compound.
5. as claimed in claim 4 containing benzotriazole base co-polymer preparation method, it is characterized in that, after described Suzuki coupling reaction, also need product to carry out aftertreatment, described aftertreatment is: in product, add methyl alcohol precipitating, after filtering, use successively methyl alcohol and normal hexane extracting by apparatus,Soxhlet's; Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, and after collection, under vacuum, 40～60oC obtains the polymkeric substance shown in structural formula (I) after being dried.
6. as claimed in claim 4 containing benzotriazole base co-polymer preparation method, it is characterized in that, described catalyzer is three dibenzalacetone two palladiums and 2-dicyclohexyl phosphine-2', at least one in the mixture of 6'-dimethoxy-biphenyl, tetra-triphenylphosphine palladium or bi triphenyl phosphorus palladium chloride, the molar weight of described catalyzer is 1/80～1/120 of compd A molar weight.
7. the benzotriazole base co-polymer preparation method that contains as claimed in claim 4, is characterized in that, the consumption of described alkaline solution is 2～20 times of compd B molar weight.
As described in claim 1-3 any one containing 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.
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| US9382424B2 (en) | 2011-09-26 | 2016-07-05 | Nitto Denko Corporation | Highly-fluorescent and photo-stable chromophores for enhanced solar harvesting efficiency |
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| US9287419B2 (en) | 2011-01-05 | 2016-03-15 | Nitto Denko Corporation | Wavelength conversion perylene diester chromophores and luminescent films |
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| CN104211917A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Polymer containing benzotriazole unit, preparation method thereof, and solar cell device |
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| CN101171320B (en) * | 2005-05-03 | 2013-04-10 | 默克专利有限公司 | Organic electroluminescent device |
| DE102006031990A1 (en) * | 2006-07-11 | 2008-01-17 | Merck Patent Gmbh | New materials for organic electroluminescent devices |
| IT1393059B1 (en) * | 2008-10-22 | 2012-04-11 | Eni Spa | LOW-GAP PI-CONJUGATED COPOLYMERS CONTAINING BENZOTRIAZOLIC UNITS |
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| US9394479B2 (en) | 2011-10-05 | 2016-07-19 | Nitto Denko Corporation | Wavelength conversion film having pressure sensitive adhesive layer to enhance solar harvesting efficiency |
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