CN100366646C - Polymer charge-conveying materials and preparing method thereof - Google Patents
Polymer charge-conveying materials and preparing method thereof Download PDFInfo
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- CN100366646C CN100366646C CNB2006100271988A CN200610027198A CN100366646C CN 100366646 C CN100366646 C CN 100366646C CN B2006100271988 A CNB2006100271988 A CN B2006100271988A CN 200610027198 A CN200610027198 A CN 200610027198A CN 100366646 C CN100366646 C CN 100366646C
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Abstract
The present invention belongs to the technical field of electroluminescent materials, particularly to electric charge transferring material of macromolecules for organic electroluminescent device and other devices. The present invention uses bithiobenzoate benzoate cumene as a chain transferring agent, azobisisobutyronitrile (AIBN) as initiator and benzene as a solvent; functional macromolecules whose side chain contains a cavity transition group (carbazole group) or an electronic transfer group (1, 3, 4-oxdiazole group) are synthesized by a method of reversible addition-transferring free radical polymerization of breaking chains at 60 to 80DEGC and under the condition of inert atmosphere; the relative molecular weight of obtained polymers is controllable, and the molecular weight distribution is narrow.
Description
Technical field
The invention belongs to the electroluminescent material new technical field, be specifically related to a class and be used for high molecular polymer charge transfer material of OLED and other photoelectric device and preparation method thereof.
Background technology
Contain 1,3, the compound electron affinity and the electronic mobility height of 4-oxadiazole (Oxadiazole) group, the electronics injection efficiency is good, thereby is the good electron transport material of a class, uses very wide at optoelectronic areas
[1-4]In addition, the compound of carbazolyl-containing group is the hole mobile material of a class in field widespread uses such as electroluminescent owing to have quite high cavity transmission ability, thermostability and photochemical stability and good electroluminescent properties
[5,6]
Angle from structure contains 1,3, the polymkeric substance of charge transfer groups such as 4-oxadiazole or carbazole can be divided into two types: a kind of is to contain 1 in the main chain, 3,4-oxadiazole or carbazole group, another kind are that these groups overhang on the main chain of polymkeric substance as side chain.This functional polymer material that contains the charge transfer group has a wide range of applications in the organic electronic devices field.For the system of conjugated radicle cumularsharolith on polymer lateral chain, a lot of functional polymers can be easily radical polymerization by various functional monomers obtain, and can change polymer properties by the copolymerization of modifying monomeric molecular structure or different monomers.Side chain contains the polymkeric substance of functional group, and for example, side chain contains the methyl acrylic ester of carbazole group, Huo person's oxadiazole group, and is synthetic and be applied to OLED by free radical polymerisation process.But because organic polymer institute inherent polymolecularity, their chain length differs, and molecular weight distribution broad, and very difficult purifying can influence the performance of corresponding photoelectric device like this.Therefore need a kind of like this synthetic method, the topological framework of molecular weight that not only can controlling polymers and molecular weight distribution, molecule, and can prepare the polymkeric substance of the functional group of containing the special light electrical property, to satisfy the demand in organic optoelectronic device field.
The development of controlled/active free radical polymerization makes that synthetic molecular weight is controlled, narrow molecular weight distribution, various functional polymer materials that structure is clear and definite become possibility.Reversible addition-fragmentation chain transfer free radical polymerization (RAFT) method is a kind of of controlled/active free radical polymerization system, monomer whose adapts to wide, can be used to control the radical polymerization of acrylamide, vinylformic acid isopolarity monomer or water-soluble monomer, the polymerizing condition gentleness can be undertaken by several different methods such as body, solution, letex polymerizations.The existing a lot of reports of many common monomeric homopolymerizations, random copolymerization, block copolymerization, gradient copolymerization and synthetic predefined complex construction.But the report that the RAFT method is applied to the synthetic functional polymer that contains the charge transfer group is few.
Summary of the invention
The object of the present invention is to provide that a kind of polymericular weight is controlled, the high molecular polymer charge transfer material of narrow molecular weight distribution and preparation method thereof.
The present invention proposes can be used for polymer charge transport material in OLED or other photoelectric devices, adopt reversible addition-fragmentation chain transfer free radical polymerization method to prepare, contain electric transmission group or cavity transmission group on the polymer lateral chain of this material, the molecular weight of polymkeric substance is controlled, generally between 10000-30000, generally between 1.03-1.25, Mw is a weight-average molecular weight to Mw/Mn to number-average molecular weight Mn here, as seen its molecular weight distribution is narrow
It is as follows that the present invention adopts reversible addition one fracture transfer radical polymerization method to prepare the concrete steps of polymer charge transport material: with function monomer, initiator, chain-transfer agent in 60～500: 1: 1～4 ratio constitutes polymerization system under nitrogen atmosphere, the system solvent is a benzene, under 60～80 ℃, carry out solution polymerization, reaction times 18-35 hour.Use the liquid nitrogen quenching, termination reaction; Then negative pressure is taken out reaction solution and be added drop-wise in the methyl alcohol, be settled out polymkeric substance; Filter oven dry.
Among the present invention, described initiator is Diisopropyl azodicarboxylate (AIBN), is used for initiated polymerization; Described chain-transfer agent claims RAFT reagent again, is two thiobenzoic acid isopropyl benzene esters or two thiobenzoic acid benzyl ester; Described function monomer contains the methyl acrylic ester of electric transmission group or cavity transmission group.
The present invention adopts such scheme to synthesize to dangle on the class side chain functional high molecule material of cavity transmission group or electric transmission group, by control to chain-transfer agent and monomer ratio, the dispersion index of the molecular weight of controlled polymerization reaction product, and molecular weight easily is little.Hot analysis revealed, resulting polymers all have good thermostability.The polymer materials of preparation can be widely used in electroluminescent device and other photoelectric device.
Description of drawings
Fig. 1 is the GPC graphic representation of related polymer.Wherein, (a) different [CzEMA]
0/ [CDB]
0The GPC figure solid line of the polymkeric substance poly (CzEMA) that obtains under the mol ratio, [CzEMA]
0/ [CDB]
0=57, M
n=12,600, M
w/ M
n=1.03; Dotted line, [CzEMA]
0/ [CDB]
0=35, M
n=6,500, M
w/ M
n=1.21; Dotted line, [CzEMA]
0/ [CDB]
0=28, M
n=6,300, M
w/ M
n=1.13); (b) GPC of polymkeric substance poly (t-Bu-OxaMA) figure (solid line, M
n=24,300, M
w/ M
n=1.05; Dotted line, M
n=27,100, M
w/ M
n=1.05); (c) GPC of polymkeric substance poly (CzHMA) figure (M
n=13,900, M
w/ M
n=1.18); (d) GPC of polymkeric substance poly (Naph-OxaMA) figure (M
n=10,100, M
w/ M
n=1.21).
Fig. 2 is the nuclear magnetic spectrogram of polymer P oly (t-Bu-OxaMA).(a) nucleus magnetic hydrogen spectrum of Poly (t-Bu-OxaMA), (b) the nuclear-magnetism carbon of Poly (t-Bu-OxaMA) spectrum.
Fig. 3 is the nuclear magnetic spectrogram of polymer P oly (CzEMA).(a) nucleus magnetic hydrogen spectrum of Poly (CzEMA), (b) the nuclear-magnetism carbon of Poly (CzEMA) spectrum.
Fig. 4 is at CHCl by the poly (CzEMA) of RAFT method preparation and the poly (CzEMA) by the preparation of conventional radical polymerization method
3UV-Vis abosrption spectrogram in the solution.The former is M
n=12600, M
w/ M
n=1.03; Latter M
n=47700, M
w/ M
n=2.04.
Fig. 5 is at CH by RAFT process synthetic polymkeric substance
2Cl
2UV-Vis absorption spectrum in the solution and fluorescence emission spectrogram.Wherein, (a) poly (CzEMA), M
n=12600, M
w/ M
n=1.03; (b) poly (CzHMA), M
n=13900, M
w/ M
n=1.18; (c) poly (t-Bu-OxaMA), M
n=27100, M
w/ M
n=1.05; (d) poly (Naph-OxaMA), M
n=10100, M
w/ M
n=1.21.
Fig. 6 is the TGA graphic representation by RAFT process synthetic polymkeric substance.Wherein, (a) poly (CzEMA), M
n=12600, M
w/ M
n=1.03; (b) poly (CzHMA), M
n=13900, M
w/ M
n=1.18; (c) poly (t-Bu-OxaMA), M
n=27100, M
w/ M
n=1.05; (d) poly (Naph-OxaMA), M
n=10100, M
w/ M
n=1.21.
Fig. 7. by the cyclic voltammetry curve figure of RAFT process synthetic polymkeric substance.Wherein, supporting electrolyte is (n-Bu)
4NPF
6Acetonitrile solution (0.1M), polymkeric substance forms film as working electrode on glass-carbon electrode, reference electrode is Ag/AgNO
3Electrode: (a) poly (CzEMA), M
n=12600, M
w/ M
n=1.03; (b) poly (CzHMA), M
n=13900, M
w/ M
n=1.18; (c) poly (t-Bu-OxaMA), M
n=27100, M
w/ M
n=1.05; (d) poly (Naph-OxaMA), M
n=10100, M
w/ M
n=1.21.
Embodiment
In order to understand the content of patent of the present invention better, further specify technical scheme of the present invention below by concrete example and legend.
Example carries out according to the following steps:
Monomer t-Bu-OxaMA (130.0mg, 0.358mmol), chain-transfer agent CDB (1.73mg, 6.36 * 10
-3Mmol), initiator A IBN (0.34mg, 2.10 * 10
-3Mmol), benzene (0.1mL), and magnetic stir bar place the Schlenk reaction tubes, stir to make it dissolving (rediance solution).Seal mouthful the back and adopt a freeze-thaw method deoxygenation, the liquid nitrogen freezing-degassing-fusion-fill nitrogen after 4 times, at room temperature stirs 15min with reaction solution repeatedly, and heated and stirred in being preheating to 70 ℃ oil bath is carried out the about 31h of polyreaction then.Use the liquid nitrogen quenching, termination reaction.Reaction solution slowly is added drop-wise to is settled out polymkeric substance in the methyl alcohol, filter, 40 ℃ of following vacuum dryings obtain pale pink polymer powder poly (t-Bu-OxaMA): 104.0mg, productive rate 78.9%.Monomer conversion calculates by following equation (1):
Conv(％)＝[(W
p-W
CTA)/W
m]×100％(1)
Wherein, W
p, W
CTAAnd W
mBe respectively that resulting polymers, institute add chain-transfer agent and institute adds monomeric quality.
Polymerisate GPC determining molecular weight and molecular weight distribution, molecular weight M
n=27100, molecular weight distribution M
w/ M
n=1.05.FT-IR(KBr)v：2962，1751，1612，1552，1492，1413，1363，1269，1203，1165，1093，1014，962，842，752，733，709cm
-1；
1H NMR(400MHz，CDCl
3，ppm)：δ8.08(s，2H)，7.91(s，2H)，7.44(s，2H)，7.28(s，2H)，2.42(s，2H)，1.59(d，3H)，1.29(s，9H)；
13C NMR(400MHz，CDCl
3，ppm)：δ207.2，175.2，174.6，165.0，163.6，155.4，153.1，128.5，126.9，126.2，122.2，120.9，46.3，35.2，31.3，19.5。
This polymkeric substance can be used as electron transport material and is used to prepare electroluminescent device.
Monomer Naph-OxaMA (123.0mg, 0.345mmol), CDB (0.98mg, 3.59 * 10
-3Mmol), AIBN (0.22mg, 1.36 * 10
-3Mmol), the CHCl that the THF that 0.3mL benzene, 0.2mL newly steamed, 0.05mL heavily steamed
3, dissolving.With the liquid nitrogen freezing-degassing-fusion-fill nitrogen, 4 deoxygenations of freeze thawing, heated and stirred in being preheating to 70 ℃ oil bath is carried out polyreaction 25h, and polymers soln is faint yellow.After stopping polymerization with the liquid nitrogen quenching, removal of solvent under reduced pressure with a small amount of methylene dichloride dissolving, is settled out polymkeric substance then in methyl alcohol.Suction filtration, and then with the methylene dichloride dissolving, precipitate in the methyl alcohol and analyse, to filter and obtain fawn-coloured polymer powder, dried overnight in 45 ℃ of following vacuum drying ovens obtains the 63.0mg polymkeric substance, yield 51.2%.Gpc analysis result: M
n=10100, M
w/ M
n=1.21.
1H NMR(400MHz，CDCl
3，ppm)：δ9.07(s，1H)，8.04(s，4H)，7.68(s，2H)，7.29(s，4H)，2.46(s，2H)，1.60(d，3H)；
13CNMR(400MHz，CDCl
3，ppm)：δ175.6，174.5，164.8，163.2，153.2，133.8，132.7，130.0，128.6，126.7，126.3，125.0，122.3，120.1，46.3，20.9，19.4。This polymkeric substance can be used as electron transport material and prepares electroluminescent device.
The RAFT polymerization of the monomer (CzEMA) of embodiment 3, carbazolyl-containing group: poly (CzEMA)
Monomer CzEMA (0.10g, 0.36mmol), chain-transfer agent CDB (1.72mg, 6.31 * 10
-3Mmol), initiator A IBN (0.47mg, 2.88 * 10
-3Mmol), benzene (0.1mL) and magnetic stir bar place the Schlenk reaction tubes, stir to make it dissolving.Seal mouthful the back and adopt a freeze thawing deoxygenation, the liquid nitrogen freezing-degassing-fusion-fill nitrogen, 4 times repeatedly, heated and stirred in being preheating to 60 ℃ oil bath is carried out polyreaction 32h then.In the polymerization process, the color of reaction mixture changes to rose pink from the characteristic color rediance of CDB solution.Use the liquid nitrogen quenching, termination reaction.Reaction solution slowly is added drop-wise to is settled out polymkeric substance in the methyl alcohol, filter, 40 ℃ of following vacuum dryings obtain pale pink polymer powder poly (CzEMA): 80.0mg, yield 78.86%.Gpc analysis result: M
n=13300, M
w/ M
n=1.03.FT-IR(KBr)v：3047，2943，1732，1628，1597，1485，1456，1351，1325，1259，1215，1153，1075，1020，748，723cm
-1；
1H NMR(400MHz，CDCl
3，ppm)：δ7.92(s，2H)，7.17(d，6H)，4.07(d，4H)，1.26(broad s，2H)，0.15(broad s，3H)；
13C NMR(400MHz，CDCl
3，ppm)：δ175.9，140.4，125.9，123.2，120.7，119.5，108.8，62.6，53.7，44.6，41.1，18.6。
This polymkeric substance can be used as electron transport material and is used to prepare electroluminescent device.
The RAFT polymerization of the monomer (CzHMA) of embodiment 4, carbazolyl-containing group: poly (CzHMA)
Monomer CzHMA (125.6mg, 0.374mmol), chain-transfer agent CDB (1.19mg, 4.36 * 10
-3Mmol), initiator A IBN (0.33mg, 2.02 * 10
-3Mmol), benzene (0.3mL) and magnetic stir bar place the Schlenk reaction tubes, stir to make it dissolving.With the liquid nitrogen freezing-degassing-fusion-fill nitrogen, 4 deoxygenations of freeze thawing, heated and stirred in being preheating to 70 ℃ oil bath then, polyreaction 18h.After stopping polymerization, polymers soln is thickness very, with a small amount of methylene dichloride dilution, is settled out polymkeric substance then in methyl alcohol; Suction filtration, and then with the methylene dichloride dissolving, precipitate in the methyl alcohol, obtaining rose pink polymer powder, 45 ℃ of following vacuum-dryings are spent the night, and obtain the 75.0mg polymkeric substance, yield 55.7%.Gpc analysis result: M
n=13900, M
w/ M
n=1.18.
1HNMR(400MHz，CDCl
3，ppm)：δ8.00(s，2H)，7.35(s，2H)，7.23(s，2H)，7.13(s，2H)，4.03(s，2H)，3.75(s，2H)，1.62-1.91(m，2H)，1.33(s，3H)，1.11(s，2H)，0.84(s，2H)；
13C NMR(400MHz，CDCl
3，ppm)：δ178.6，140.5，125.8，122.9，120.5，119.0，108.8，65.1，42.9，29.0，28.1，26.9，26.0，16.8。
This polymkeric substance can be used as hole mobile material and is used to prepare electroluminescent device.
Table 1. is initiator with AIBN, and the RAFT polymerizing condition of CDB regulation and control and result are for embodiment
| Monomer (concn(M)) | CDB (concn 10 2×M) | [CDB]/ [AIBN] | Time (h) | Yield (％) | M n | PDI (M w/M n) | |
| Theory | GPC | ||||||
| CzEMA(3.59) CzHMA(1.25) t-Bu-OxaMA(3.60) Naph-OxaMA(0.63) | 6.31 1.45 6.16 0.65 | 2.19 2.16 2.81 2.60 | 30 18 41 25 | 78.86 55.70 74.80 51.20 | 12,800 16,400 21,400 17,500 | 12,600 13,900 24,300 10,100 | 1.03 1.18 1.05 1.21 |
The structural formula of compound that the present invention relates to:
Claims (3)
1. polymer charge-conveying materials, it is characterized in that adopting reversible addition-fragmentation chain transfer free radical polymerization method to prepare, this polymer lateral chain contains electric transmission group or cavity transmission group, the molecular weight of polymkeric substance is controlled between 10000-30000, and molecular weight distribution is between 1.03-1.25; Wherein, polymerization single polymerization monomer is the methacrylic ester that contains electric transmission group or cavity transmission group.
2. the preparation method of a polymer charge-conveying materials as claimed in claim 1, adopt the method for reversible addition-fragmentation chain transfer free radical polymerization, it is characterized in that: by function monomer, initiator, chain-transfer agent in 60～500: 1: 1～4 mol ratio ratio constitutes polymerization system under nitrogen atmosphere, under 60～80 ℃, carry out solution polymerization, reaction times 18-35 hour.
3. method according to claim 2, it is characterized in that: described function monomer is the methacrylic ester that contains electric transmission group or cavity transmission group, described initiator is a Diisopropyl azodicarboxylate, and described chain-transfer agent is two thiobenzoic acid isopropyl benzene esters or two thiobenzoic acid benzyl ester.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006126820A (en) * | 2004-09-30 | 2006-05-18 | Dainippon Printing Co Ltd | Composition for alignment layer, method of manufacturing alignment layer, and optical element |
| CN1856741A (en) * | 2003-09-23 | 2006-11-01 | E.I.内穆尔杜邦公司 | Low-polydispersity photoimageable polymers and photoresists and processes for microlithography |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856741A (en) * | 2003-09-23 | 2006-11-01 | E.I.内穆尔杜邦公司 | Low-polydispersity photoimageable polymers and photoresists and processes for microlithography |
| JP2006126820A (en) * | 2004-09-30 | 2006-05-18 | Dainippon Printing Co Ltd | Composition for alignment layer, method of manufacturing alignment layer, and optical element |
Non-Patent Citations (1)
| Title |
|---|
| 新型光电材料-乙烯咔唑共聚物. 邓舜扬.化工技术与开发. 1982 * |
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