CN102137902A - 新型聚合物 - Google Patents
新型聚合物 Download PDFInfo
- Publication number
- CN102137902A CN102137902A CN2009801239587A CN200980123958A CN102137902A CN 102137902 A CN102137902 A CN 102137902A CN 2009801239587 A CN2009801239587 A CN 2009801239587A CN 200980123958 A CN200980123958 A CN 200980123958A CN 102137902 A CN102137902 A CN 102137902A
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- CN
- China
- Prior art keywords
- alkyl
- aryl
- alkoxyl group
- independently
- polymkeric substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- 239000000126 substance Substances 0.000 claims description 91
- 229910052799 carbon Inorganic materials 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000005669 field effect Effects 0.000 claims description 2
- 230000010354 integration Effects 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002800 charge carrier Substances 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 230000037230 mobility Effects 0.000 abstract 1
- -1 isobutyl- Chemical group 0.000 description 89
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000002585 base Substances 0.000 description 44
- 239000010410 layer Substances 0.000 description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 239000010408 film Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 239000004793 Polystyrene Substances 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 13
- 125000004093 cyano group Chemical group *C#N 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 0 C*C1C(*=*C**)=Cc2c(*)c(*)c(C=C(C(C)C=C3C(*)=C4*)NI[Al]*)c3c2C4=C1 Chemical compound C*C1C(*=*C**)=Cc2c(*)c(*)c(C=C(C(C)C=C3C(*)=C4*)NI[Al]*)c3c2C4=C1 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000005525 hole transport Effects 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 229920006254 polymer film Polymers 0.000 description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000001544 thienyl group Chemical group 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 238000000434 field desorption mass spectrometry Methods 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- 238000007341 Heck reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Chemical group C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000001374 small-angle light scattering Methods 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 3
- 150000004646 arylidenes Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000005561 phenanthryl group Chemical group 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical group COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- 229920001621 AMOLED Polymers 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000005787 Castro-Stephens coupling reaction Methods 0.000 description 2
- ZVGCGHVMJAECEG-UHFFFAOYSA-N Chinol Natural products COC1=C(O)C(C)=C(C)C(O)=C1OC ZVGCGHVMJAECEG-UHFFFAOYSA-N 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- GTZOZDOTOWNSJH-UHFFFAOYSA-N [O].CCCCCCC Chemical compound [O].CCCCCCC GTZOZDOTOWNSJH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 210000001072 colon Anatomy 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 150000002815 nickel Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003933 pentacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C12)* 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
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- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
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- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 238000012552 review Methods 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007155 step growth polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000004627 thianthrenyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3SC12)* 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
- C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/687—Unsaturated compounds containing a keto groups being part of a ring containing halogen
- C07C49/697—Unsaturated compounds containing a keto groups being part of a ring containing halogen containing six-membered aromatic rings
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- 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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- 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
- C08G61/123—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 derived from five-membered heterocyclic compounds
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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Abstract
本发明涉及包含式(I)重复单元的聚合物以及它们在电子器件中的用途。本发明聚合物具有在有机溶剂中的优异溶解性和优异的成膜性能。此外,当本发明聚合物在聚合物发光二极管(PLED)中使用时,可观察到高电荷载体迁移率和发射颜色高温稳定性。
Description
本发明涉及包含式I重复单元的新型聚合物以及它们在电子器件中的用途。本发明聚合物具有在有机溶剂中的优异溶解性和优异的成膜性能。此外,当本发明聚合物在聚合物发光二极管(PLED)中使用时,可观察到高电荷载体迁移率和发射颜色高温稳定性。
WO2006043539公开了尤其是发射蓝光并且包含芘的发光聚合物。
EP0964045描述了在固态显示可见荧光的聚合荧光物质,其中聚合荧光物质包含由下式(1)表示的一个或多个重复单元并且这些重复单元的量为基于重复单元总量的0.5摩尔%-100摩尔%:
-Ar1-CR1=CR2-(1),其中Ar1表示可被选自氰基、烷基、具有1-20个碳原子的烷氧基或烷硫基、具有3-60个碳原子的烷基甲硅烷基、具有1-40个碳原子的烷基氨基、具有6-20个碳原子的芳基或芳氧基、具有8-20个碳原子的芳基烯基或芳基炔基、具有7-14个碳原子的芳烷基和具有4-14个碳原子的杂环化合物基团的取代基取代的稠合多环芳基,R1和R2各自独立地表示选自氢原子、具有1-20个碳原子的烷基、具有6-20个碳原子的芳基、具有4-20个碳原子的杂环化合物和氰基的基团。
Ar1的实例尤其为下式基团:
其中,R5-R20相互独立地表示选自氢原子、氰基、烷基、具有1-20个碳原子的烷氧基或烷硫基;具有3-60个碳原子的烷基甲硅烷基;具有1-40个碳原子的烷基氨基;具有6-20个碳原子的芳基或芳氧基;具有8-20个碳原子的芳基烯基或芳基炔基;具有7-14个碳原子的芳烷基;和具有4-14个碳原子的杂环化合物基的基团。
当它们的性能与现有技术相比时,有机EL发光显示器的引入面临许多挑战。获得由专门指导方针(即NTSC)所要求的确切彩色坐标(color coordinate)一直是有问题的。EL器件的运行寿命当与阴极射线管(CRT)和液晶显示器(LCD)的现有无机技术相比使仍然较短。此外,生产具有纯蓝色和长寿命的材料对于本行业是最大问题之一。
因此,本发明的目的为提供新型材料,当引入电子光学器件时,其在色纯度、器件效率和/或运行寿命显示显著优点。
所述目的通过包含式I重复单元的本发明聚合物解决。包含本发明聚合物的有机发光器件(OLED)可在色纯度、器件效率和/或运行寿命中显示显著优点。此外,聚合物可具有良好溶解特性和相对高的玻璃化转变温度,这促进它们制备成为热和机械稳定的而且相对无缺陷的涂层和膜。如果聚合物包含能够交联的端基,则薄膜或涂层形成后这种基团的交联提高其耐溶剂性,这有益于将一层或多层溶剂基材料沉积于其上的应用。
因此,本发明涉及包含下式重复单元的聚合物:
R1、R2、R3、R4、R5和R6相互独立地为氢、F、SiR100R101R102、或有机取代基,或
R1和R2、R3和R4,和/或任意取代基R1、R2、R3、R4、R5和/或R6,其为彼此相邻的,一起形成可任选被取代的芳族或杂芳族环或环体系,m为0、或1或2的整数,
n1和n2为0、或1或2的整数,
R100、R101和R102相互独立地为C1-C18烷基,取代或未取代的C6-C18芳基,且Ar1和Ar2相互独立地为取代或未取代的亚芳基或杂亚芳基。取代或未取代的亚芳基或杂亚芳基的实例为选自取代或未取代的苯基、取代或未取代的萘基、取代或未取代的蒽基、取代或未取代的二苯基蒽基、取代或未取代的菲基、取代或未取代的二氢苊基、取代或未取代的联苯基、取代或未取代的芴基、取代或未取代的咔唑基、取代或未被取代的噻吩基、取代或未取代的三唑基和取代或未取代的噻二唑基的二价基团。
本发明聚合物应该具有高于100℃的玻璃化转变温度,特别是高于150℃的玻璃化转变温度。
R1和R2以及R3和R4可彼此不同,但优选相同。最优选R1、R2、R3和R4具有相同含义。
R1、R2、R3和R4优选选自C1-C18烷基、被E取代C1-C18烷基和/或被插入D的C1-C18;C1-C18烷氧基、被E取代C1-C18烷基和/或被插入D的C1-C18烷氧基;C1-C18全氟烷基且最优选为任选取代的C6-C24芳基、或C2-C20杂芳基。
在本发明优选的实施方案中,至少一个、非常特别是至少两个R1、R2、R3和R4不同于H。最优选所有取代基R1、R2、R3和R4不同于H。在本发明的另一个优选实施方案中,至少一个、优选两个取代基R1、R2、R3和R4为任选取代的C1-C18烷氧基。最优选所有的取代基R1、R2、R3和R4为任选取代的C1-C18烷氧基。
优选地,本发明聚合物包含式I的重复单元,其中R1,R2,R3和R4相互独立地为H、F、C1-C18烷基、被E取代和/或被插入D的C1-C18烷基,C1-C18全氟烷基、C6-C24芳基、被G取代的C6-C24芳基、C2-C20杂芳基、被G取代的C2-C20杂芳基;
在每一情况下,各个基团R5和R6相互独立地为H、卤素,特别是F、C1-C18烷基、被E取代和/或被插入D的C1-C18烷基、C1-C18全氟烷基、C6-C24芳基、被G取代的C6-C24芳基、C2-C20杂芳基、被G取代的C2-C20杂芳基、C2-C18烯基、C2-C18炔基、C1-C18烷氧基、被E取代和/或被插入D的C1-C18烷氧基、C7-C25芳烷基、CN或-CO-R28,
m为0、或1或2的整数,
D为-CO-;-COO-;-S-;-SO-;-SO2-;-O-;-NR25-;-SiR30R31-;-POR32-;-CR23=CR24-;或-C≡C-;且
E为-OR29;-SR29;-NR25R26;-COR28;-COOR27;-CONR25R26;-CN;或卤素,特别是F;
G为E、C1-C18烷基、被插入D的C1-C18烷基、C1-C18全氟烷基、C1-C18烷氧基,或被E取代和/或被插入D的C1-C18烷氧基,
R23、R24、R25和R26相互独立地为H;C6-C18芳基;被C1-C18烷基或C1-C18烷氧基取代的C6-C18芳基;C1-C18烷基;或被插入-O-的C1-C18烷基;
R27为氢;C6-C18芳基;被C1-C18烷基或C1-C18烷氧基取代的C6-C18芳基;特别是C1-C18烷基;或被插入-O-的C1-C18烷基,
R28为氢;C6-C18芳基;被C1-C18烷基或C1-C18烷氧基取代的C6-C18芳基;C1-C18烷基;或被插入-O-的C1-C18烷基,
R29为氢;C6-C18芳基;被C1-C18烷基或C1-C18烷氧基取代的C6-C18芳基;C1-C18烷基;或被插入-O-的C1-C18烷基,
R30和R31相互独立地为C1-C18烷基、C6-C18芳基、或被C1-C18烷基取代的C6-C18芳基,且
R32为C1-C18烷基、C6-C18芳基、或被C1-C18烷基取代的C6-C18芳基。
特别是至少一个,非常特别是至少两个R1、R2、R3和R4不同于H。
在特别优选的实施方案中,聚合物包含下式重复单元:
其中R1、R2、R3和R4相互独立地为C6-C12芳基、或可任选被一个或多个基团G取代的C2-C11杂芳基,其中G如上所定义,或R1、R2、R3和R4相互独立地为C1-C18烷基、被插入-O-、C1-C18烷氧基的C1-C18烷基;或被插入-O-的C1-C18烷氧基。优选地,R1、R2、R3和R4具有相同含义。更优选R3和R4具有相同含义且为C1-C18烷氧基;或被插入-O-的C1-C18烷氧基。
在本发明的另一个优选实施方案中,式Ia的聚合物为优选的,其中R1、R2、R3和R4相互独立地为其中n3为0,或1、2、3、4或5的整数,R11在每一情况下可相同或不同且为C1-C25烷基、或C1-C25烷氧基,或R1、R2、R3和R4相互独立地为C1-C18烷基、被插入-O-、C1-C18烷氧基的C1-C18烷基;或被插入-O-的C1-C18烷氧基;特别是被插入-O-的C1-C18烷基、C1-C18烷氧基;或被插入-O-的C1-C18烷氧基。优选地,R1、R2、R3和R4具有相同含义。
优选地,R5和R6相互独立地为H、C1-C18烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、异戊基、正己基、2-乙基己基、或正庚基;被E取代和/或被插入D的C1-C18烷基,例如-CH2OCH3、-CH2OCH2CH3、-CH2OCH2CH2OCH3、或-CH2OCH2CH2OCH2CH3;C1-C18烷氧基,例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、2-甲基丁氧基、正戊氧基、异戊氧基、正己氧基、2-乙基己氧基、或正庚氧基;C6-C14芳基,例如苯基、萘基、或联苯基、C5-C12环烷基,例如环己基、被G取代的C6-C14芳基,例如-C6H4OCH3、-C6H4OCH2CH3、-C6H3(OCH3)2、或-C6H3(OCH2CH3)2、-C6H4CH3、-C6H3(CH3)2、-C6H2(CH3)3、-C6H4OtBu、或-C6H4tBu。最优选R5和R6为H。
m优选为0。如果多于一个基团R5或R6存在于一个分子内,它们可具有不同含义。
D优选为-CO-、-COO-、-S-、-SO-、-SO2-、-O-、-NR25-,其中R25为C1-C12烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、或仲丁基,或C6-C14芳基,例如苯基、萘基、或联苯基。
E优选为-OR29;-SR29;-NR25R25;-COR28;-COOR27;-CONR25R25;或-CN;其中R25、R27、R28和R29相互独立地为C1-C12烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、己基、辛基、或2-乙基己基、或C6-C14芳基,例如苯基、萘基、或联苯基。
G的优选项与E相同,或为C1-C18烷基,特别是C1-C12烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、己基、辛基、1-(2-己基)癸烷、或2-乙基己基。
特别优选的包含式(Ia)重复单元的聚合物实例为如在权利要求5中描述的化合物A-1至A-34。
用于制备本发明聚合物的单体为新型的并且形成本发明的另一实施方案。因此,本发明还涉及式(XI)的单体:
其中Ar1、Ar2、n1、n2、R1、R2、R3、R4、R5、R6和m如上所定义。X11在每一情况下独立地为卤素原子,特别是I、CI、或Br;-ZnX12、-SnR207R208R209,其中R207、R208和R209相同或不同且为H或C1-C6烷基,其中两个基团任选形成共同的环以及这些基团任选为支化或未支化的且X12为卤素原子,非常特别是I、或Br;或-OS(O)2CF3、-OS(O)2-芳基,特别是-OS(O)2CH3、-B(OH)2、-B(OY11)2、-BF4Na、或-BF4K,其中Y11在每一情况下独立地为C1-C10烷基且Y12在每一情况下独立地为C2-C10亚烷基,例如-CY13Y14-CY15Y16-、或-CY17Y18-CY19Y20-CY21Y22-,其中Y13、Y14、Y15、Y16、Y17、Y18、Y19、Y20、Y21和Y22相互独立地为氢、或C1-C10烷基,特别是-C(CH3)2C(CH3)2-、或-C(CH3)2CH2C(CH3)2-,式(XIV)为新型化合物并且形成本发明的另外的实施方案。因此,本发明还涉及式XIV的化合物,其中X11、Ar1、Ar2、n1、n2、R5、R6和m如上所定义。
可通过使式XV的2,7-二叔丁基芘-4,5,9,10-四酮或式XII的芘-4,5,9,10-四酮分别与Br2/Fe和NBS/H2SO4反应制备式XIVa的2,7-二溴芘-4,5,9,10-四酮(n1=n2=0;X11=Br)。
根据在J.Org.Chem.2005,70,707-708页中描述的方法,通过在二氯甲烷中三氯酸钌的存在下用高氯酸钠或高碘酸钠氧化式XVI的芘可制备式XII的芘-4,5,9,10-四酮。
或者,根据在J.Org.Chem.2005,70,第707-708页中描述的方法,在二氯甲烷中三氯酸钌的存在下,通过用高氯酸钠或高碘酸钠氧化式XVII的芘可制备式XIVa的2,7-二溴芘-4,5,9,10-四酮(n1=n2=0;X11=Br)。2,7-二溴芘的合成例如描述在J.Org.Chem.1986,51,第2847页中。
式XIa单体(n1=n2=0)可通过已知方法或与已知方法类似的方法反应至式XIb单体(n1=n2≠0):
-WO04039786的实施例22a:
-J.Org.Chem.2007,72,2279:
式XIVa的2,7-二溴芘-4,5,9,10-四酮(n1=n2=0;X11=Br)可通过已知方法或与已知方法类似的方法反应至式XI单体(n1=n2=0;X11=Br):
-WO2005/104264(R1=烷基和芳基):
-Org.Lett.10(2008)773:
或者,式XI单体可通过使式XIII化合物与双(三环己基锡)硫化物或B2S3反应得到。参考文献例如为US20070191583和Macromolecules 39(2006)5213-5221页。式XIII化合物的合成可根据或类似于其中描述的方法进行。
在一个实施方案中,本发明聚合物仅由一种或多种式I的重复单元构成。在优选的实施方案中,本发明聚合物由一种式I的重复单元构成(均聚物)。
根据本发明,术语“聚合物”包含聚合物和低聚物,其中聚合物为相对高分子量的分子,其结构基本包含实际上或概念上衍生自相对低分子量分子的单元的重复,而低聚物为中等分子量的分子,其结构基本包含少量多数个实际上或概念上衍生自相对较低分子量的分子的单元。若其性能不随一个或少数几个单元的去除而显著变化则分子视为具有相对高分子量。若其性能随一个或少数几个单元的去除而显著变化则分子视为具有中等分子量。
根据本发明,均聚物为衍生自一种(真实、隐含或假设的)单体的聚合物。许多聚合物通过互补单体的相互反应制备。这些单体容易作为形象化为给出“隐含单体”的反应,隐含单体的均聚将给出可视为均聚物的实际产物。通过其它聚合物的化学改性获得某些聚合物,因此可认为构成所得聚合物的高分子的结构是通过假设单体的均聚形成。
因此,共聚物为衍生自多于一种单体的聚合物,例如二元共聚物、三元共聚物、四元共聚物等。
本发明低聚物的重均分子量为<2,000道尔顿。本发明聚合物的重均分子量优选为2,000道尔顿或更大,特别是2,000-2,000,000道尔顿,更优选10,000-1,000,000,最优选20,000-500,000道尔顿。分子量是根据凝胶渗透色谱法使用聚苯乙烯标准测定的。
本发明基于以下特别优选实施方案更详细进行说明,但不限于所述实施方案。在所述实施方案中,聚合物为下式聚合物:(VII),其中Ar1、n1、Ar2、n2、R1、R2、R3、R4、R5、R6和m如上所述,T和Ar3如在WO06/097419中所定义,其中Ar3可为式的重复单元,特别是 如在WO06/097419中所描述,和/或特别是如在WO08/012250中所描述,其中R1”、R2”和R3”相互独立地为可任选被一个或多个基团G取代的C6-C12芳基、或C2-C11杂芳基,其中G如上所定义且R4”具有R3”的含义,或为C1-C18烷基,特别是C4-C18烷基,
R7’为有机取代基,其中在同一分子中的两个或更多个取代基R7’可具有不同含义,或可一起形成芳族环、或杂芳族环、或环体系,且
x’为0、或1-5的整数。
A为包含一个选自氮、氧和硫的杂原子的5-、6-或7员杂芳族环,其可被取代和/或可为稠合芳族或杂芳族环体系的部分。
R1’和R4’为氢,
R2’、R3’、R5’和R6’相互独立地为H、C1-C18烷基、被插入D的C1-C18烷基、C1-C18全氟烷基、C1-C18烷氧基、被插入D的C1-C18烷氧基、C7-C25芳烷基、或基团-X2-R18’,
R8’和R9’相互独立地为H、C1-C18烷基、被插入D的C1-C18烷基、C1-C18全氟烷基、C1-C18烷氧基、被插入D的C1-C18烷氧基、或基团-X2-R18’,或两个取代基R2’和R3’和/或R5’和R’6,其彼此相邻,一起形成基团或两个取代基R5’和R3’,其彼此相邻,一起形成基团或R8’和R9’一起形成基团其中R205’、R206’、R207’、R208’、R209’和R210’相互独立地为H、C1-C18烷基、被E取代和/或被插入D的C1-C18烷基,C1-C18烷氧基,或被E取代和/或被插入D的C1-C18烷氧基、C1-C18全氟烷基,
R10’为H、可被G取代的C6-C18芳基、可被G取代的C2-C18杂芳基、C1-C18烷基、可被插入D的C1-C18烷基、C1-C18全氟烷基、C1-C18烷氧基,可被E取代和/或被插入D的C1-C18烷氧基,或基团-X2-R18’,其中X2为间隔基团,例如C6-C12芳基、或C6-C12杂芳基,特别是苯基、或萘基,其可被C1-C18烷基取代多于一次,特别是一到两次,被插入D的C1-C18烷基、C1-C18全氟烷基、C1-C18烷氧基,或被E取代和/或被插入D的C1-C18烷氧基,且R18’为H、C1-C18烷基、被插入D的C1-C18烷基、C1-C18金氟烷基、C1-C18烷氧基,被插入D的C1-C18烷氧基、或-NR25’R26’-;
X’为O、S、或NR17’,
R11’和R14’为氢,
R12’、R13’、R15’和R16’为氢,
R17’为C6-C18芳基;被C1-C18烷基取代的C6-C18芳基、C1-C18全氟烷基、或C1-C18烷氧基;C1-C18烷基;或被插入-O-的C1-C18烷基;或
两个取代基R11’和R12’、和/或R14’以及R16’、R12’和R13’,和/或R15’和R16’,其彼此相邻,一起形成基团或两个取代基R15’和R13’,其彼此相邻,一起形成基团其中R105’、R106’、R107’和R108’相互独立地为H、或C1-C8烷基,D、E和G如上所定义;
a为1,
b为0、或1,
c为0.005-1,
d为0、或1,
e为0、或1,其中如果d为0,则e不为1
f为0.995-0,其中c和f的和为1。
Ar3优选选自下式的重复单元:
R44和R41为氢、C1-C18烷基、或C1-C18烷氧基,且
R45为H、C1-C18烷基、或被E取代和/或被插入D的C1-C18烷基,特别是被插入-O-的C1-C18烷基,
R116和R117相互独立地为H、卤素、-CN、C1-C18烷基、被E取代和/或被插入D的C1-C18烷基、C6-C24芳基、被插入G的C6-C24芳基、C2-C20杂芳基、被G取代的C2-C20杂芳基、C2-C18烯基、C2-C18炔基、C1-C18烷氧基、被E取代和/或被插入D的C1-C18烷氧基、C7-C25芳烷基、-C(=O)-R127、-C(=O)OR127、或-C(=O)NR127R126,
R119和R120相互独立地为H、C1-C18烷基、被E取代和/或被插入D的C1-C18烷基、C6-C24芳基、被G取代的C6-C24芳基、C2-C20杂芳基、被G取代的C2-C20杂芳基、C2-C18烯基、C2-C18炔基、C1-C18烷氧基、被E取代和/或被插入D的C1-C18烷氧基、或C7-C25芳烷基,或
R119和R120一起形成式=CR121R122的基团,其中
R121和R122相互独立地为H、C1-C18烷基、被E取代和/或被插入D的C1-C18烷基、C6-C24芳基、被G取代的C6-C24芳基、或C2-C20杂芳基、或被G取代的C2-C20杂芳基、或
R119和R120一起形成五或六元环,其任选可被C1-C18烷基、被E取代和/或被插入D的C1-C18烷基,C6-C24芳基,被G取代的C6-C24芳基、C2-C20杂芳基,被G取代的C2-C20杂芳基、C2-C18烯基、C2-C18炔基、C1-C18烷氧基、被E取代和/或被插入D的C1-C18烷氧基、C7-C25芳烷基、或-C(=O)-R127取代,且
R126和R127相互独立地为H;C6-C18芳基;任选被C1-C18烷基、或C1-C18烷氧基取代的C6-C18芳基;C1-C18烷基;或被插入-O-的C1-C18烷基,其中G、D和E如上所定义。
重复单元T尤其选自以下基团VI:
X1为氢原子、或氰基,
R116和R117如上所定义,
R41在每一情况下可相同或不同且为Cl、F、CN、N(R45)2、C1-C25烷基、C4-C18环烷基、C1-C25烷氧基,其中不彼此相邻的一个或多个碳原子可被-NR45-、-O-、-S-、-C(=O)-O-、或-O-C(=O)-O-替换,和/或其中一个或多个氢原子可被F、C6-C24芳基、或C6-C24芳氧基替换,其中一个或多个碳原子可被O、S、或N替换,和/或其可被一个或多个非芳族基团R41取代,或两个或更多个基团R41形成环体系;
R45为H、C1-C25烷基、C4-C18环烷基,其中不彼此相邻的一个或多个碳原子可被-NR45’-、-O-、-S-、-C(=O)-O-或-O-C(=O)-O-替换,和/或其中一个或多个氢原子可被F、C6-C24芳基、或C6-C24芳氧基替换,其中一个或多个碳原子可被O、S、或N替换,和/或其可被一个或多个非芳族基团R41取代,
R45’为H、C1-C25烷基、或C4-C18环烷基,
n在每一情况下可相同或不同并且为0、1、2、或3,特别是0、1、或2,非常特别是0或1,且u为1、2、3、或4;
A4为C6-C24芳基、C2-C30杂芳基,特别是苯基、萘基、蒽基、联苯基、2-芴基、菲基、或苝基,其可被一个或多个非芳族基团R41取代,其中T优选为式VIa、VIb或VIf的重复单元。
式VII的均聚物,其中a=1、b=0、c=1、d=0、e=0、f=0,例如可通过镍偶合反应,特别是Yamamoto反应得到:
(I),其中Ar1、n1、Ar2、n2、R1、R2、R3、R4、R5、R6和m如上所定义。在所述方面,优选为由式Ia重复单元构成的均聚物。
涉及式I和-Ar3-重复单元的式VII共聚物(a=1、c=0.995-0.005、b=0、d=1、e=0、f=0.005-0.995),可通过镍偶合反应得到:
可使用镍偶合反应进行仅涉及二卤官能反应物的聚合方法。一种此类偶合反应由Colon等人在J.Pol.Sci.,A部分,Polymer Chemistry,第28版(1990)第367页中以及Colon等人在J.Org.Chem.51(1986)第2627页中所描述。该反应通常在极性无质子溶剂(例如二甲基乙酰胺)中以催化量的镍盐、显著量的三苯基膦和大量剩余锌粉进行。这一方法的另一方案由Ioyda在Bull.Chem.Soc.Jpn,63(1990)80中所描述,其中有机可溶性碘化物用作加速剂。
另一种镍偶合反应由Yamamoto公开于Progress in Polymer Science 17(1992)1153中,其中二卤芳族化合物的混合物是在惰性溶剂中以过量的镍(1,5-环辛二烯)配合物处理的。所有镍偶合反应,当应用于两种或更多种芳族二卤化物的反应物混合物时,产生基本上无规的共聚物。这种聚合反应可通过向聚合反应混合物中添加少量将以氢基团替换末端卤素基团的水来终止。或者,单官能芳基卤可在这种反应中用作链终止剂,这将导致末端芳基的生成。
镍偶合聚合基本上产生均聚物或包含式I单元和衍生自其它共聚单体的单元的无规共聚物。
式VII的均聚物,其中a=1、c=1、b=0、d=1、e=0、f=1,例如可通过Suzuki反应得到:
芳族硼酸酯与卤化物,特别是溴化物的缩合反应通常称为“Suzuki反应”,容许各种有机官能团的存在,如由N.Miyaua和A.Suzuki在Chemical Reviews,第95卷,第457-2483页(1995)中报告的。这一反应可应用于制备高分子量聚合物和共聚物。优选的催化剂为2-二环己基膦基-2’,6’-二烷氧基联苯/乙酸钯(II)。特别优选的2-二环己基膦基-2’,6’-二甲氧基联苯(sPhos)/乙酸钯(II)。
为了制备对应于式VIIc的聚合物,使二卤化物,例如二溴化物或二氯化物,特别是对应于式Br-X10-Br的二溴化物,与等摩尔量对应于式的二硼酸或二硼酸酯反应,其中在每一情况下X11独立地为-B(OH)2、-B(OY11)2或其中Y11在每一情况下独立地为C1-C10烷基且Y12在每一情况下独立地为C2-C10亚烷基,例如-CY13Y14-CY15Y16-、或-CY17Y18-CY19Y20-CY21Y22-,其中Y13、Y14、Y15、Y16、Y17、Y18、Y19、Y20、Y21和Y22相互独立地为氢、或C1-C10烷基,特别是-C(CH3)2C(CH3)2-、或-C(CH3)2CH2C(CH3)2-,在Pd和膦配体,特别是三苯膦的催化作用下。反应通常在约70℃-180℃下在芳族烃溶剂如甲苯中进行。其它溶剂如二甲基甲酰胺和四氢呋喃也可单独或以与芳族烃的混合物使用。水性碱,优选碳酸钠、碳酸钾、K3PO4或碳酸氢盐用作HBr清除剂。取决于反应物的反应性,聚合反应可能需要2-100小时。有机碱如氢氧化四烷基铵和相转移催化剂,例如TBAB,能促进硼的活性(例如参见Leadbeater和Marco;Angew.Chem.Int.Ed.Eng.42(2003)1407和本文中引用的参考文献)。反应条件的其它方案由T.I.Wallow和B.M.Novak在J.Org.Chem.59(1994)5034-5037;以及M.Remmers,M.Schulze,和G.Wegner在Macromol.Rapid Commun.17(1996)239-252中给出。
如果期望,单官能芳基卤或芳基硼酸酯在这种反应中可用作链终止剂,这将导致末端芳基的生成。
通过控制在Suzuki反应中单体进料的顺序和组成有可能控制所得共聚物中单体单元的排序。
式VII的均聚物,其中a=1、c=1、b=1、d=0、e=0、f=0,例如可通过Heck反应得到:
聚亚苯基亚乙烯衍生物和聚亚甲基亚乙炔衍生物可通过二乙烯基或二乙炔基化合物与二卤化合物通过Heck反应(R.F.Heck,Palladium Reagents in Organic Synthesis,Academic Press,New York 1985,第179页;L.S.Hegedus,Organometalics in Synthesis,Ed.M.Schlosser,Wiley,Chichester,UK 1994,第383页;Z.Bao,Y.Chen,R.Cai,L.Yu,Macromolecules 26(1993)第5281页;W.-K.Chan,L.Yu,Macromolecules 28(1995)第6410页;A.Hilberer,H.-J.Brouwer,B.-J.van der Scheer,J.Wildeman,G.Hadziioannou,Macromolecules 1995,28,4525)和Sonogaschira反应(Dmitri Gelman和Stephen L.Buchwald,Angew.Chem.Int.Ed.42(2003)5993-5996;Rik R.Tykwinski,Angew.Chem.115(2003)1604-1606;Jason M.Nolan和Daniel L.Comins,J.Org.Chem.68(2003)3736-3738;Jiang Cheng等,J.Org.Chem.69(2004)5428-5432;Zolta′Nova′k等,Tetrahedron 59(2003)7509-7513)聚合得到:
Sonogashira反应在铜(I)催化剂、和/或钯(0),例如四(三苯膦)钯(0)的存在下,任选在溶剂如甲苯、二甲基甲酰胺或二甲基亚砜和任选的碱如氢化钠、碳酸钾、碳酸钠或胺碱如哌啶的溶剂中完成。用特殊的钯催化剂,不需要铜催化剂(Angew.Chem.2007,119,850-888页)。反应时间和温度取决于原料和反应条件。二溴化合物与炔烃通常在50℃-100℃,特别是60-80℃的温度下反应1h-48h小时。这一反应,称为Sonogashira反应(Pd/Cu催化的有机卤化物与端基炔烃的交叉偶合)、Cadiot-Chodkiewicz偶合或Castro-Stephens反应(Castro-Stephens偶合使用化学计量的铜,而Sonogashira方案使用催化量的钯和铜),描述在Sonogashira K.;Tohda,Y.;Hagihara,N.Tetrahedron Lett.1975,4467;Richard Heck(使用钯而未使用铜发现相同转化)J.Organomet.Chem.1975,93,259;McCrindle,R.;Ferguson,G.;Arsenaut,G.J.;McAlees,A.J.;Stephenson,D.K.J.Chem.Res.(S)1984,360;Sakamoto,T.;Nagano,T.;Kondo,Y.;Yamanaka,H.Chem.Pharm.Bull.1988,36,2248;Rossi,R.Carpita,A.;Belina,F.Org.Prep.Proc.Int.1995,27,129;Ernst,A.;Gobbi,L.;Vasella,A.Tetrahedron Lett.1996,37,7959;Campbell,I.B.在Organocopper Reagents;Taylor,R.J.K.Ed.;IRL Press:Oxford,UK,1994,217.(综述);Hundermark,T.;Littke,A.;Buchwald,S.L.;Fu,G.C.Org.Lett.2000,2,1729;Dai,W.-M.;Wu,A.Tetrahedron Lett.2001,42,81;Alami,M.;Crousse,B.;Ferri,F.J.Organomet.Chem.2001,624,114;Bates,R.W.;Boonsombat,J.J.Chem.Soc.,Perkin Trans.1 2001,654;Batey,R.A.;Shen,M.;Lough,A.J.Org.Lett.2002,4,1411;Balova,I.A.;Morozkina,S.N.;Knight,D.W.;Vasilevsky,S.F.Tetrahedron Lett.2003,44,107;Garcia,D.;Cuadro,A.M.;Alvarez-Builla,J.;Vaquero,J.J.Org.Lett.2004,6,4175;Li,P.;Wang,L.;Li,H.Tetrahedron 2005,61,8633,Lemhadri,M.;Doucet,H.;Santelli,M.Tetrahedron 2005,61,9839,Angew.Chem.2007,119,8632-8635,Angew.Chem.2006,118,6335-6339,J.Am.Chem.Soc.2005,127,9332-9333,和Adv.Mater.2007,19,1234-1238中。
式VII的(无规)共聚物,其中a为1、b为1、c为0.005-0.995、d为1、e为1、f为0.995-0.005,其中c和f的和为1,也可由Heck反应得到:
(VIIe),其中a、b、c、d、e、f、X10、Ar3和T如上所定义。
含有式(I)基团的聚合物可由任何合适的方法制备,但是优选由以上所述方法制备。
本发明聚合物可任选包含末端结构部分E1,其中E1为芳基结构部分其可任选被这样的反应性基团取代,即其能够进行链增长或交联,或三(C1-C18)甲硅烷氧基。本文所用的、能够进行链增长或交联的反应性基团是指能够与另一个相同基团或另一种基团反应从而形成制备聚合物的链接的任何基团。优选地,这种反应性基团为羟基、缩水甘油醚、丙烯酸酯、甲基丙烯酸酯、乙烯基、乙炔基、马来酰亚胺、萘二甲酰亚胺(naphthimide)、氧杂环丁烷、三氟乙烯基醚结构部分或稠合到E1的芳族环上的环丁烯结构部分。
本发明的聚合物,其中E1为如上所定义的反应性基团,能够交联而形成耐溶剂的、在100℃或更高,更优选150℃或更高耐热的膜。优选地,这样的交联在350℃或更低,更优选300℃或更低,最优选250℃或更低进行。本发明的交联聚合物在100℃或更高,更优选150℃或更高是稳定的。本文所用的“稳定”是指这种聚合物在所述温度或以下不发生交联或聚合反应。如果可交联材料是期望的,E1优选为乙烯基苯基、乙炔基苯基,或4-(或3-)苯并环丁烯基。在另一个实施方案中,E1选自式-C6H4-O-Y的苯酚衍生物,其中Y为-H、-CN、或如果期望,可交联基团可存在于聚合物链的其它部分。例如,共聚单体T的取代基之一可为可交联基团E1。
将封端剂E1-X12(E1为如上所定义且X12为Cl或Br)在其中所得聚合物基本上由反应性基团E1封端的条件下引入本发明聚合物中。为此可用的反应为如上所述的镍偶合,Heck反应和Suzuki反应。平均聚合度是由单体与封端剂的摩尔比控制的。
本发明聚合物可通过本领域技术人员所熟知的已知方法,例如,像在D.Braun,H.Cherdron,H.Ritter,Praktikum der makromolekularen Stoffe,1st Edn.,Wiley VCH,Weinheim 1999,第68-79页或R.J.Young,P.A.Lovell,Introduction to Polymers,Chapman & Hall,London 1991中所描述的已知方法进行后处理。例如,反应混合物可以过滤、用酸水溶液稀释、抽提,而在干燥和将溶剂分离出来之后得到的粗产物可进一步通过添加沉淀剂而从合适溶剂中再沉淀出来进行提纯。残留钯可以使用活性炭、色谱法等去除。有利地,通过在室温至有机溶剂沸点下用L-半胱氨酸水溶液洗涤包含聚合物的粗有机溶剂层,特别是通过在85-90℃下用L-半胱氨酸水溶液洗涤包含聚合物的甲苯层,任选随后在78-82℃下用L-半胱氨酸和硫代硫酸钠的溶液洗涤,可以使残留钯降低至<3ppm(Mahavir Prashad,Yugang Liu,Oljan Repicoe,Adv.Synth.Catal.2003,345,533-536;Christine E.Garrett,Kapa Prasad,Adv.Synth.Catal.2004,346,889-900)。此外,通过用NaCN水溶液洗涤聚合物可除去Pd,如在US-B-6,956,095中所描述。随后可进行聚合物类似反应,以使聚合物进一步官能化。因此,例如可以通过用如LiAlH4还原来还原去除末端卤素原子(例如参见J.March,Advanced Organic Chemistry,第3版,McGraw-Hill,第510页)。
本发明的另一方面涉及包含1-99%至少一种包含式I单元的聚合物的聚合物共混物。共混物的其余1-99%由一种或多种聚合物材料组成,该聚合物材料选自链增长聚合物如聚苯乙烯、聚丁二烯、聚(甲基丙烯酸甲酯)和聚(氧化乙烯);逐步增长聚合物如苯氧基树脂、聚碳酸酯、聚酰胺、聚酯、聚氨酯和聚酰亚胺;和交联聚合物如交联环氧树脂、交联酚醛树脂、交联丙烯酸酯树脂和交联氨基甲酸酯树脂。这些聚合物的实例可以在Preparative Methods of Polymer Chemistry,W.R.Sorenson and T.W.Campbell,Second Edition,Interscience Publishers(1968)中找到。还可用于共混物中的为共轭聚合物如聚(亚苯基亚乙烯基)、取代的聚(亚苯基亚乙烯基)、取代的聚亚苯基和聚噻吩。这些共轭聚合物的实例由Greenham和Friend在Solid State Physics,第49卷,第1-149页(1995)中给出。
在特别优选的实施方案中,本发明涉及下式聚合物:
其中R1、R2、R3和R4相互独立地为其中n3为0,或1、2或3的整数特别是0,或1;且R11在每一情况下可相同或不同且为H、可任选被插入O的C1-C25烷基,或可任选被插入O的C1-C25烷氧基,且
R1”、R2”和R3”相互独立地为或其中n1’为0、或1、2、3或4的整数,特别是0、1、或2;n2’为0,或1、2或3的整数,特别是0、1或2;n3’为0,或1、2、3、4或5的整数,特别是0、1、2或3;且R10”和R11”相互独立地为C1-C25烷基或C1-C25烷氧基,且R4”具有R3”的含义,或为C1-C18烷基,特别是C4-C18烷基,
R44、R116、R117、R119和R120如上所定义,
R10’为R8’,或其中n2为0、1或2。
下述聚合物为特别优选的:
本发明聚合物可显示高光致发光和/或电致发光。
卤素是氟、氯、溴和碘。
C1-C25烷基(C1-C18烷基)通常为线性或支化的,只要有可能。实例为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、2-戊基、3-戊基、2,2-二甲基丙基、1,1,3,3-四甲基戊基、正己基、1-甲基己基、1,1,3,3,5,5-六甲基己基、正庚基、异庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、1,1,3,3-四甲基丁基和2-乙基己基、正壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、二十烷基、二十一烷基、二十二烷基、二十四烷基或二十五烷基。C1-C8烷基通常为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、2-戊基、3-戊基、2,2-二甲基丙基、正己基、正庚基、正辛基、1,1,3,3-四甲基丁基和2-乙基己基。C1-C4烷基通常为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基。
C1-C25烷氧基(C1-C18烷氧基)为线性或支化的烷氧基,例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、戊氧基、异戊氧基或叔戊基氧基、庚氧基、辛氧基、异辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基、十四烷氧基、十五烷氧基、十六烷氧基、十七烷氧基和十八烷氧基。C1-C8烷氧基的实例为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基、正戊氧基、2-戊氧基、3-戊氧基、2,2-二甲基丙氧基、正己氧基、正庚氧基、正辛氧基、1,1,3,3-四甲基丁氧基和2-乙基己氧基。C1-C4烷氧基的实施例为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基。术语“烷硫基”是指与烷氧基相同的集团,只是醚键的氧原子由硫原子替换。
C2-C25烯基(C2-C18烯基)为直链或支化烯基,例如乙烯基、烯丙基、甲基烯丙基、异丙烯基、2-丁烯基3-丁烯基、异丁烯基、正戊-2,4-二烯基、3-甲基丁-2-烯基、正辛-2-烯基、正十二-2-烯基、异十二烯基、正十二-2-烯基或正十八-4-烯基。
C2-24炔基(C2-18炔基)为直链或支化的且优选为可未被取代或取代的C2-8炔基,例如乙炔基、1-丙炔-3-基、1-丁炔-4-基、1-戊炔-5-基、2-甲基-3-丁炔-2-基、1,4-戊二炔-3-基、1,3-戊二炔-5-基、1-己炔-6-基、顺式3-甲基-2-戊烯-4-炔-1-基(cis 3-methyl-2-penten-4-yn-1-yl)、反式-3-甲基-2-戊烯-4-炔-1-基(trans-3-methyl-2-penten-4-yn-1-yl)、1,3-己二炔-5-基、1-辛炔-8-基、1-壬炔-9-基、1-癸炔-10-基、或1-二十四炔-24-基。
C1-C18全氟烷基,特别是C1-C4全氟烷基是支化或未支化基团,例如CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-(CF2)3CF3、和-C(CF3)3。
术语“卤代烷基、卤代烯基和卤代炔基”是指以上所述烷基、烯基和炔基用卤素部分或完全取代而给出的基团,例如三氟甲基等。“醛基、酮基、酯基、氨基甲酰基和氨基”包括被烷基、环烷基、芳基、芳烷基或杂环基团取代的那些,其中烷基、环烷基、芳基、芳烷基和杂环基团可未被取代或取代。术语“甲硅烷基”是指式-SiR62R63R64,其中R62,R63和R64相互独立地为C1-C8烷基,尤其是C1-C4烷基、C6-C24芳基或C7-C12芳烷基,例如三甲基甲硅烷基。
术语“环烷基”通常为C4-C18环烷基,特别是C5-C12环烷基,例如环戊基、环己基、环庚基、环辛基、环壬基、环癸基;环十一烷基、环十二烷基、优选环戊基、环己基、环庚基或环辛基,这些可为未取代或取代的。术语“环烯基”是指包含一个或多个双键的不饱和脂环烃,例如环戊烯基、环戊二烯基、环己烯基等,这些可为未取代或取代的。环烷基,尤其是环己基可由苯基稠合一或两次,苯基可由C1-C4烷基、卤素和氰基取代一至三次。
芳基通常为可任选取代的C6-C30芳基,优选C6-C24芳基(C6-C18芳基),例如苯基、4-甲基苯基、4-甲氧基苯基、萘基,特别是1-萘基、或2-萘基、联苯基、三联苯基、芘基、2-或9-芴基、菲基、蒽基、并四苯基(teracyl)、并五苯基(pentacyl)、并六苯基(henacyl)或四联苯基(quaderphenylyl),这些可为未取代或取代的。
术语“芳烷基”通常为C7-C25芳烷基,例如苯甲基、2-苯甲基-2-丙基、β-苯基乙基、α,α-二甲基苯甲基、ω-苯基丁基、ω,ω-二甲基-ω-苯基丁基、ω-苯基十二烷基、ω-苯基十八烷基、ω-苯基二十烷基或ω-苯基二十二烷基,优选C7-C18芳烷基如苯甲基、2-苯甲基-2-丙基、β-苯基乙基、α,α-二甲基苯甲基、ω-苯基丁基、ω,ω-二甲基-ω-苯基丁基、ω-苯基十二烷基或ω-苯基十八烷基,特别优选C7-C12芳烷基如苯甲基、2-苯甲基-2-丙基、β-苯基乙基、α,α-二甲基苯甲基、ω-苯基丁基或ω,ω-二甲基-ω-苯基丁基,其中脂族烃基和芳族烃基二者均可为未被取代或取代的。
术语“芳醚基”通常为C6-24芳氧基,即O-C6-24芳基,例如苯氧基或4-甲氧基苯基。术语“芳硫醚基”通常为C6-24芳硫基,即S-C6-24芳基,例如苯硫基或4-甲氧基苯硫基。术语“氨基甲酰基”通常为可未取代或取代的C1-18氨基甲酰基,优选C1-8氨基甲酰基,例如氨基甲酰基、甲基氨基甲酰基、乙基氨基甲酰基、正丁基氨基甲酰基、叔丁基氨基甲酰基、二甲基氨基甲酰基、吗啉代氨基甲酰基或吡咯烷基氨基甲酰基。
在烷基氨基、二烷基氨基、烷芳基氨基、芳基氨基和二芳基氨基中的术语“芳基”和“烷基”通常分别为C1-C25烷基和C6-C24芳基。
烷基芳基是指烷基取代的芳基,特别是C7-C12烷基芳基。实例为甲苯基如3-甲基苯基或4-甲基苯基、或二甲基苯基如3,4-二甲基苯基或3,5-二甲基苯基。
杂芳基通常为C2-C26杂芳基(C2-C20杂芳基),即具有5-7个环原子的环或稠环体系、其中氮、氧或硫为可能的杂原子,且通常为具有5-30个原子、具有至少6个共轭π电子的不饱和杂环基,例如噻吩基、苯并[b]噻吩基、二苯并[b,d]噻吩基、噻蒽基、呋喃基、糠基、2H-吡喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、苯氧噻吩基、吡咯基、咪唑基、吡唑基、吡啶基、联吡啶基、三嗪基、嘧啶基、吡嗪基、哒嗪基、中氮茚基、异吲哚基、吲哚基、吲唑基、嘌呤基、喹嗪基、醌醇基、异醌醇基、2,3-二氮杂萘基、萘啶基、喹喔啉基、喹唑啉基、噌啉基、喋啶基、咔唑基、咔啉基、苯并三唑基、苯并噁唑基、菲啶基、吖啶基、嘧啶基、菲咯啉基、吩嗪基、异噻唑基、吩噻嗪基、异噁唑基、呋咱基或吩噁嗪基,这些可为未取代或取代的。
上述基团的可能取代基为C1-C8烷基、羟基、巯基、C1-C8烷氧基、C1-C8烷硫基、卤素、卤代C1-C8烷基、氰基、醛基、酮基、羧基、酯基、氨基甲酰基、氨基、硝基或甲硅烷基,特别是C1-C8烷基、C1-C8烷氧基,C1-C8烷硫基、卤代C1-C8烷基、或氰基。
如果取代基,例如R6,在基团中出现多于1次,则它在每一情况下可不同。
词“被G取代”是指可存在一个或多个,特别是1-3个取代基G。
如上所述,上述基团可被E取代和/或如果期望被插入D。插入当然只有在包含至少2个由单键彼此连接的碳原子的基团的情况下才有可能;C6-C18芳基不被插入;插入的芳基烷基或烷基芳基在烷基结构部分中包含单元D。被一个或多个E取代和/或被插入一个或多个单元D的C1-C18烷基例如为(CH2CH2O)1-9-Rx,其中Rx为H或C1-C10烷基或C2-C10烷酰基(例如CO-CH(C2H5)C4H9)、CH2-CH(ORy′)-CH2-O-Ry,其中Ry为C1-C18烷基、C5-C12环烷基、苯基、C7-C15苯基烷基,且Ry′包含与Ry相同的含义或为H;
C1-C8亚烷基-COO-Rz,例如CH2COORz、CH(CH3)COORz、C(CH3)2COORz,其中Rz为H、C1-C18烷基,(CH2CH2O)1-9-Rx,且Rx包含以上所述定义;CH2CH2-O-CO-CH=CH2;CH2CH(OH)CH2-O-CO-C(CH3)=CH2。
优选的亚芳基为1,4-亚苯基、2,5-苯亚甲基、1,4-亚萘基、1,9-亚蒽基(1,9-antracylene)、2,7-亚菲基(2,7-phenantrylene)和2,7-二氢亚菲基(2,7-dihydrophenantrylene)。
优选的杂亚芳基为2,5-亚吡嗪基、3,6-亚哒嗪基、2,5-亚吡啶基、2,5-亚嘧啶基、1,3,4-噻二唑-2,5-亚基、1,3-噻唑-2,4-亚基、1,3-噻唑-2,5-亚基、2,4-亚噻吩基、2,5-亚噻吩基、1,3-噁唑-2,4-亚基、1,3-噁唑-2,5-亚基和1,3,4-噁二唑-2,5-亚基、2,5-亚茚基和2,6-亚茚基。
本发明的另一方面为由本发明聚合物形成的膜。这种膜可用于聚合物发光二极管(PLED)中。优选地,这种膜是用作发光层的。这些膜还可用作电子器件保护涂层和作为荧光涂层。涂层或膜的厚度取决于最终用途。一般而言,这种厚度可为0.01-200μm。在涂层用作荧光涂层的实施方案中,涂层或膜厚度为10-200μm。在涂层用作电子保护层的实施方案中,涂层厚度可为5-20μm。在涂层用于聚合物发光二极管的实施方案中,所形成层厚为0.01-0.5μm。本发明聚合物形成良好的无针孔和无缺陷膜。这样的膜可以通过本领域熟知的方式制备,包括旋涂、喷涂、浸涂和辊涂。这样的涂层是通过包括以下步骤的方法制备:将组合物施用至基材上,和使所施用的组合物暴露于形成膜的条件下。形成膜的条件取决于施用技术。优选地,溶液包含0.1-10重量%聚合物。通过期望方法将这种组合物施用至合适基材上,并且让溶剂蒸发。可通过真空和/或热干燥除去残留溶剂。膜优选为基本上厚度均匀且基本上无针孔。在另一个实施方案中,聚合物可为部分固化。这称为B-分段(B-staging)。
因此本发明的另一实施方案涉及电子器件或部件,包含基材和本发明聚合物。
在这种器件中,本发明聚合物用作电致发光材料。为了本发明的目的,术语“电致发光材料”是指这样的材料,其可用作电致发光器件中的活性层或用于电致发光器件中的活性层中。术语“活性层”是指在施加电场时能够发光(发光层)和/或改善正电荷和/或负电荷的注入和/或传输(电荷注入或电荷传输层)。本发明因此还涉及本发明聚合物作为电致发光材料的用途。本发明还涉及包含本发明聚合物的电致发光材料。电致发光器件例如用作自照明显示元件,例如控制灯、字母数字式显示器、信号和用于光电偶合器中。
本发明的器件可根据WO99/48160公开的内容制备,其内容引入本文供参考。本发明聚合物可作为唯一发光聚合物或作为还包含空穴和/或电子传输聚合物的共混物中的组分存在于器件中。或者,器件可包含本发明聚合物、空穴传输聚合物和/或电子传输聚合物的不同的层。
在一个实施方案中,电子器件包含电致发光器件,后者包含
(a)用于注入正电荷载体的电荷注入层,
(b)用于注入负电荷载体的电荷注入层,
(c)位于层(a)和(b)之间、包含本发明聚合物的发光层。
层(a)可以是位于发光层(c)和阳极电极层之间的正电荷载体传输层,或可以是阳极电极层。层(b)可以是位于发光层(c)和阴极层之间的负电荷载体传输层,或可以是阴极层。任选地,有机电荷传输层可位于发光层(c)和电荷载体注入层(a)和(b)之间。
EL器件发射在400nm-780nm之间,优选蓝色的430nm-470nm之间,优选绿色的520nm-560nm之间,优选红色的600nm-650nm之间的可见电磁谱的光。通过在聚合物主链中引入特定重复单元,甚至可以使发射移向近红外(NIR,>780nm)。
应该理解的是,光发射层可由包括一种或多种本发明聚合物和任选其它不同聚合物的材料的共混物或混合物形成。该其它不同聚合物可为所谓的空穴传输聚合物(即改善发光材料的空穴传输效率)或电子传输聚合物(即改善发光材料的电子传输效率)。优选地,共混物或混合物将包含至少0.1重量%本发明聚合物,优选至少0.5重量%,更优选至少1重量%。
有机EL器件通常由夹在阳极和阴极之间的有机膜组成,以便当对器件施加正偏压时,空穴从阳极向该有机膜中注入,且电子从阴极向有机膜中注入。空穴和电子的组合可产生激子,其可以通过释放光子而进行向基态的辐射衰变。实践中,由于其导电性和透明度,阳极通常为锡和铟的混合氧化物。混合氧化物(ITO)沉积在透明基材如玻璃或塑料上,从而可以观察到由有机膜发射的光。有机膜可为若干个各自为不同功能设计的单层的复合物。由于空穴是从阳极注入,因而毗邻阳极的层需要具有空穴传输功能。类似地,毗邻阴极的层需要具有电子传输功能。在许多情况下,空穴-(电子)传输层还充当发光层。在一些情况下,一个层可进行空穴与电子传输和发光的组合功能。有机膜的各个层可以性质上都是聚合物的或者聚合物的膜和通过热蒸发沉积的小分子的膜的组合。有机膜的总厚度为小于1000纳米(nm),特别是小于500nm。优选总厚度为小于300nm,然而更优选活性层的厚度为40-160nm。
用作基材和阳极的ITO-玻璃可以在用通常的洗涤剂、有机溶剂清洗和UV臭氧处理之后用于涂布。它还可首先用导电物质的薄层涂布,以促进空穴注入。这种物质包括酞菁铜、聚苯胺(PANI)和聚(3,4-亚乙基二氧基-噻吩)(PEDOT);(掺杂)导电形式的后两种例如掺杂了FeCl3或Na2S2O8。它们包含聚(苯乙烯磺酸)(PSS)作为反离子以确保水溶性。优选这一层的厚度为200nm或更小;更优选厚度为100nm或更小。
在其中使用空穴传输层的情况下,可以使用在美国专利No.5,728,801中所描述的聚合物芳基胺。还可以使用其它已知的空穴传导聚合物,例如聚乙烯咔唑。这一层对待随后施用的共聚物薄膜的溶液的腐蚀耐受性,对多层器件的成功制造显然至关重要。这一层的厚度可为500nm或更小,优选300nm或更小,最优选150nm或更小。
在其中使用电子传输层的情况下,它可通过低分子量材料的热蒸发或通过聚合物与不会对底层薄膜造成显著损害的溶剂的溶液涂布施用。
低分子量材料的实例包括8-羟基喹啉的金属配合物(如由Burrows等人在Appl.Phys.Lett.64(1994)2718-2720中所描述)、10-羟基苯并喹啉的金属配合物(如由Hamada等人在Chem.Lett.(1993)906-906中所描述)、1,3,4-噁二唑(如由Hamada等人在Optoelectronics-Devices and Technologies 7(1992)83-93中所描述)、1,3,4-三唑(如由Kido等人在Chem.Lett.(1996)47-48中所描述)、和苝的二羧酰亚胺(如由Yoshida等人在Appl.Phys.Lett.69(1996)734-736中所描述)。
聚合物电子传输材料的例子是含1,3,4-噁二唑的聚合物(如由Li等人在J.Chem.Soc.(1995)2211-2212中、由Yang和Pei在J.Appl.Phys.77(1995)4807-4809中所描述)、含1,3,4-三唑的聚合物(如由Strukelj等人在Science 267(1995)1969-1972中所描述)、含喹喔啉的聚合物(如由Yamamoto等人在Jpn.J.Appl.Phys.33(1994)L250-L253,O′Brien等人在Synth.Met.76(1996)105-108中所描述),和氰基-PPV(如由Weaver等人在Thin Solid Films 273(1996)39-47中所描述)。这一层的厚度可为500nm或更小,优选300nm或更小,最优选150nm或更小。
阴极材料可通过热蒸发或溅射沉积。阴极的厚度可为1nm-10,000nm,优选5nm-500nm。
根据本发明制备的OLED可以包括分散在器件的发光层中、能够达到接近100%的内部量子效率的磷光掺杂物。本文中所用的术语“磷光”是指源自有机或金属有机分子的三重激发态(triplet excited state)的发射。使用磷光掺杂物的高效率有机发光器件已经使用若干不同导电主体材料证实(M.A.Baldo等人,Nature,第395卷,151(1998),C.Adachi等人,Appl.Phys.Lett.,第77卷,904(2000))。
在优选的实施方案中、电致发光器件包含至少一种空穴传输聚合物膜和包含本发明的聚合物的发光聚合物膜,本发明的聚合物排列在阳极材料和阴极材料之间,从而使得当为器件施加偏压时,在施加电压下空穴从阳极材料注入空穴传输聚合物膜而电子从阴极材料注入发光聚合物膜,导致由发光层发光。
在另一个优选实施方案中,空穴传输聚合物层这样地排列,以使最靠近阳极的层具有较低的氧化电位,而相邻层具有越来越高的氧化电位。通过这些方法,可以制备每单位电压具有相对较高的光输出的电致发光器件。
本文中所用的术语“空穴传输聚合物膜”是指这样的聚合物的膜的层,其当置于两个施加电场的电极之间而且从阳极注入空穴时,容许空穴充分传输到发光聚合物中的。空穴传输聚合物通常包含三芳基胺结构部分。本文中所用的术语“发光聚合物膜”是指其激发态可通过发射优选对应于可见范围内的波长的光子而松弛(relex)到基态的聚合物膜层。本文中所用的术语“阳极材料”是指功函数(work function)为4.5电子伏特(eV)-5.5eV的半透明或透明的导电膜。实例为金、银、铜、铝、铟、铁、锌、锡、铬、钛、钒、钴、镍、铅、锰、钨等,金属合金如镁/铜、镁/银、镁/铝、铝/铟等,半导体如Si、Ge、GaAs等,金属氧化物如铟-锡氧化物(“ITO”)、ZnO等,金属化合物如CuI等,和导电性聚合物如聚乙炔、聚苯胺、聚噻吩、聚吡咯、聚对亚苯基等。铟和锡的氧化物和混合氧化物以及金为优选的。最优选为ITO,特别是玻璃上或在作为基材的塑性材料上的ITO,塑性材料如聚酯,例如聚对苯二甲酸乙二醇酯(PET)。
本文中所用的术语“阴极材料”是指功函数为2.0eV-4.5eV的导电膜。实例为碱金属、碱土金属、第13族元素、银和铜以及其合金或混合物如钠、锂、钾、钙、氟化锂(LiF)、钠-钾合金、镁、钡、镁-银合金、镁-铜合金、镁-铝合金、镁-铟合金、铝、铝-氧化铝合金、铝-锂合金、铟、钙,和EP-A 499,011中列举的材料,例如导电性聚合物如聚吡咯、聚噻吩、聚苯胺、聚乙炔等。优选使用锂、钡、钙、镁、铟、银、铝或上述的共混物和合金。在使用金属或金属合金作为用于电极的材料的情况下,还可通过真空沉积方法形成电极。在使用金属或金属合金作为材料形成电极的情况下,还可用化学镀方法形成电极(参见例如Handbook of Electrchemistry,第383-387页,Mazuren,1985)。在使用导电性聚合物的情况下,电极可以这样地制备,即将其借助阳极氧化聚合方法在预先提供了导电性涂层的基材上成形为膜。
作为形成所述薄膜的方法,例如存在真空沉积方法,旋涂方法、浇铸方法、Langmuir-Blodgett(“LB”)方法、喷墨打印方法等。在这些方法中,考虑到操作容易和费用,真空沉积方法、,旋涂方法、喷墨打印方法和浇铸方法为特别优选的。
在通过使用旋涂方法、浇铸方法和喷墨打印方法形成层的情况下,涂层可使用溶液进行,该溶液是通过将组合物以0.0001-90重量%的浓度溶解在合适有机溶剂如苯、甲苯、二甲苯、四氢呋喃、甲基四氢呋喃、N,N-二甲基甲酰胺、丙酮、乙腈、苯甲醚、二氯甲烷、二甲亚砜及其混合物中制备。
可使用激光诱导热成像(LITI;Organic Light-Emitting Materials and Devices VII,由Zakya H.Kafafi,Paul A.Lane编辑,Proceedings of SPIE,第5519卷,12-23页)进行活性基质OLED(AMOLED)材料用于大规格、高分辨率显示器的成像。
本发明的有机EL器件被视为壁挂式电视机的平板显示器、平面发光器件如壁纸、复印机或打印机光源、液晶显示器或计数器(counter)的光源、显示信号牌和信号灯的未来替代技术,或许甚至能替代白炽灯和荧光灯。本发明的聚合物和组合物可用于有机EL器件、光电器件、电子照相感光器、光电转换器、太阳能电池、图像传感器等领域。
因此,本发明还涉及包含一种或多种本发明聚合物的PLED、有机集成电路(O-IC)、有机场效应晶体管(OFET)、有机薄膜晶体管(OTFT)、有机太阳能电池(O-SC)、热电器件、或有机激光二极管。
下列实施例仅仅为说明目的而包括的,并不限定权利要求的保护范围。除非另有说明,所有的份数和百分比以重量计。
重均分子量(Mw)和分子量分布(Mw/Mn=PD)是由凝胶渗透色谱法(GPC)测定的[设备:GPCmax+TDA 302,购自Viscotek(休斯敦,TX,美国),从折射率(RI)、低角度光散射(LALS)、直角光散射(RALS)和差示粘度(DP)测定产生响应。色谱条件:柱:PLgel mixed C(300x7.5mm,5μm颗粒),覆盖约1x103-约2.5x106Da的分子量范围,购自Polymer Laboratories(Church Stretton,UK);移动相:包含5g/l三氟乙酸钠的四氢呋喃;流动相流量:0.5或0.7ml/min;溶质浓度:约1-2mg/ml;注入体积:100μl;检测:RI、LALS、RALS、DP。分子量校准程序:相对校准是通过使用从Polymer Laboratories(Church Stretton,UK)获得的一组10个聚苯乙烯校准标准进行的,跨越的分子量范围为1'930'000Da-5'050Da,即PS 1'930'000、PS 1'460'000、PS 1'075'000、PS 560'000、PS 330'000、PS 96'000、PS 52'000、PS 30'300、PS 10'100、PS 5'050Da。绝对校准是根据LALS、RALS和DP的响应进行的。如同在大量研究中经历的,这种组合提供了分子量数据的最佳计算。通常使用PS 96'000作为分子量校准标准,但一般而言,处于待测定分子量范围内的每一个其它PS标准可以选择用于此目的。
以下实施例给出的所有聚合物结构为通过所描述聚合程序得到的聚合物产品的理想化表述。如果多于两种组分互相共聚,则取决于聚合条件在聚合物中的顺序可为交替或无规。
实施例
实施例1
a)将4-氯-2,6-二甲基碘代苯(9.6g,36mmol)溶解在芘(60ml)中。向这一溶液中倒入KMnO4热溶液(28g,0.18mol)并且在115℃下搅拌混合物8小时。在补充加热5小时后,加入1M HCl溶液。滤出沉淀并且用THF洗涤。用THF洗涤所形成的滤液并且在Na2SO4上干燥。蒸发后,获得二羧酸衍生物,为固体。产量9.1g(78%)。FD-MS(8kV):m/z=326.7。1H NMR(250MHz,DMSO-d6)δppm 7.24(s,Ar):13C NMR(62.5MHz,CD3OD-d4):δppm 126.7,128.1,134.5,150.1,174.6。
b)将5-氯-2-碘代间苯二甲酸(实施例1a的产物,3.8g,12mmol)加入SOCl2(30ml,过量)中并且在氮气下使混合物回流2天。在减压下蒸发过量SOCl2,然后将所形成的含5-氯-2-碘代间苯二酰二氯(4.2g,12mmol)溶解在二氯甲烷(50ml)中。在0℃下向这一溶液中加入1-苯基十二烷(10g,47mmol)和AlCl3(4.7g,35mmol)。在0℃-室温下搅拌混合物过夜。用1M HCl溶液淬灭(quench)后,用二氯甲烷将残留物提取。在MgSO4上干燥混合物并且通过柱色谱提纯(硅胶,己烷/乙酸乙酯=80∶1)得到氯碘代二苯甲酰基苯,为无色油。产量2.3g(27%)。FD-MS(8kV):m/z=727.7.1H NMR(250MHz,CDCl3-d)δppm 0.88-0.90(m,6H,CH3),1.26-1.30(m,32H,CH2),2.69(t,J=7.3,4H,CH2),7.27-7.41(m,6H,Ar),7.75(t,J=7.9,4H,Ar);13CNMR(62.5MHz,CD2Cl2-d2):13C NMR(250MHz,CD2Cl2-d2):δppm 14.3,23.1,29.7,29,8,29.9,30.0,31.4,32.3,36.5,128.8,129.4,130.9,132.9,135.3,148.2,151.1,195.4。
c)在氩气下,将二苯甲酰基衍生物(实施例1b的产物,0.57g,0.22mmol)和铜粉(0.11g,1.8mmol)加入DMF(10ml)中。在110℃下搅拌混合物2天。冷却后,过滤残留物并且将乙酸乙酯和盐水加入滤液中。用盐水洗涤有机相三次并且在MgSO4上干燥。通过柱色谱提纯残留物(硅胶,己烷/乙酸乙酯=20∶1)提供联苯衍生物,为无色油。产量0.52g(42%)。FD-MS(8kV):m/z=1202.3.1H NMR(250MHz,CDCl3-d)δppm 0.81(m,12H,CH3),1.10-1.20(m,64H,CH2),2.51(t,J=7.6,8H,CH2),7.02(d,J=7.9,8H,Ar),7.42(s,4H,Ar),7.55(d,J=7.9,8H,Ar);13C NMR(62.5MHz,CD2Cl2-d2):δppm 14.3,21.9,23.1,29.7,29,8,29.9,30.0,31.6,32.3,36.4,128.4,131.2,131.8,131.9,134.9,136.8,140.9,149.2,194.4。
d)在氩下,将联苯生物(实施例1c的产物,0.26g,0.22mmol)和双(三环己基锡)硫化物(0.70g,0.91mmol)溶解在甲苯(50ml)中。向这一溶液中加入在二氯甲烷中的1M BCl3(0.91ml,0.91mmol)。在室温下搅拌混合物10分钟并且在125℃下回流3天。冷却后,蒸发溶剂并且将乙酸乙酯和盐水加入滤液中。用盐水洗涤有机相三次并且在MgSO4上干燥。通过柱色谱提纯残留物(硅胶,己烷)提供新型2,7-二氯芘衍生物,为粉末。产量:80mg(33%)。FD-MS(8kV):m/z=1135.9.1H NMR(250MHz,CD2Cl2-d2)δppm 0.89(t,J=6.6,12H,CH3),1.20-1.30(m,56H,CH2),1.50-1.60(m,8H,CH2),2.62(t,J=7.3,8H,CH2),7.15(m,16H,Ar),7.80(s,4H,Ar);13C NMR(175MHz,CD2Cl2-d2):δppm 14.3,23.1,29.7,29.8,29.9,31.7,32.4,36.0,122.2,125.1,128.2,131.2,132.6,133.3,136.3,138.8,142.2。
实施例2
a)低聚(2,7-亚芘)的合成:
在氩气下,使包含DMF(3.5ml)和干燥甲苯(3.5ml)、(1,5-环辛二烯)镍(0)(64mg,0.23mmol)、2,2’-联吡啶(36mg,0.23mmol)和1,5-环辛二烯(28μL,0.23mmol)的Schlenk管在80℃下加热30分钟。将2,7-二氯-(4,5,9,10-四苯基)芘衍生物(实施例1d的产物,0.11g,97μmol)溶解在干燥甲苯(5ml)中并且在氩气下加入溶液中。使反应混合物在80℃下在黑暗中保持3天。将溴苯(0.1ml)加入反应混合物中。再使混合物反应一天。然后将反应混合物倒入浓盐酸/甲醇 1∶1(300ml)中。将分离的聚合物溶于二氯甲烷中并且在甲醇中再沉淀。用Soxhlet提取器在丙酮中提纯残留物2天洗掉小分子。将残留物溶于THF中并且从甲醇中沉淀以及干燥。产量0.056g(54%)。1H NMR(250MHz,C2D2Cl4-d2)δppm 0.86-0.89(m,CH3),1.20-1.40(m,CH2),1.50-1.60(m,CH2),2.59(t,J=7.3,CH2),7.00-7.15(m,Ar),7.86-7.91(m,Ar),8.10(s,Ar);13C NMR(175MHz,C2D2Cl4-d2):δppm 13.7,22.2,28.6,28.9,29.0,29.2,30.8,31.4,35.1,121.2,124.3,127.1,127.3,130.2,131.7,132.1,132.4,135.0,135.3,138.0,140.3,140.7,140.9。
Mn=2600g/mol;Mw=3100g/mol;PD=1.2(标准PPP)。
b)聚(2,7-亚芘)的合成:
在氩气下,使包含DMF(3ml)和干燥甲苯(2ml)、(1,5-环辛二烯)镍(0)(58mg,0.21mmol)、2,2′-联吡啶(33mg,0.21mmol)和1,5-环辛二烯(26μL,0.21mmol)的微波试样管在80℃下加热30分钟。将2,7-二氯芘衍生物(实施例1d的产物,0.1g,88μmol)溶解在干燥甲苯(3mL)中并且在氩气下加入溶液中。在微波中保持反应混合物在80℃下并反应(80W,60min)。将溴苯(0.2ml)加入反应混合物中并且使混合物在微波中反应(80W,30min)。然后将反应混合物倒入浓盐酸/甲醇 1∶1(300ml)中。过滤沉淀的聚合物并且溶于二氯甲烷中且在甲醇中再沉淀。用Soxhlet提取器在丙酮中提纯残留物2天洗掉小分子。将残留物溶于THF中并且从甲醇中沉淀以及干燥。产量:66mg(66%)。1H NMR(250MHz,C2D2Cl4-d2)δppm 0.86-0.89(m,CH3),1.20-1.40(m,CH2),1.50-1.70(m,CH2),2.80-2.83(m,CH2),6.90-7.25(m,Ar),8.00-8.25(m,Ar);13C NMR(175MHz,C2D2Cl4-d2):δppm 14.4,19.9,21.1,24.6,25.0,25.7,27.2,30.3,32.9,33.3,34.3,35.9,37.2,37.6,125.0,126.5,127.4,127.7,129.1,129.9,131.1,131.8,136.3,136.3,136.4,138.6,140.6,149.8。
Mn=21800g/mol;Mw=39000g/mol PD=1.7(标准PPP)。
在1,2-二氯苯中的最大吸收值在376nm观察到,而最大荧光值产生在429nm。
实施例3-聚[2,7-(4,5,9,10-四烷氧基)亚芘]
在氩气下,使包含DMF(2mL)和干燥甲苯(2ml)、(1,5-环辛二烯)镍(0)(0.13g,0.48mmol)、2,2′-联吡啶(76μg,0.48mmol)和1,5-环辛二烯(60μL,0.48mmol)的微波试样管在80℃下加热30分钟。将2,7-二溴-(4,5,9,10-四烷氧基)芘衍生物(0.2g,0.20mmol)溶解在干燥甲苯(3mL)中并且在氩气下加入溶液中。在微波中保持反应混合物在80℃下并反应(80W,60min)。将溴苯(0.2ml)加入反应混合物中并且使混合物在微波中反应(80W,30min)。然后将反应混合物倒入浓盐酸/甲醇 1∶1(300ml)中。过滤沉淀的聚合物并且溶于二氯甲烷中且在甲醇中再沉淀。用Soxhlet提取器在丙酮中提纯残留物2天洗掉小分子。将残留物溶于THF中并且从甲醇中沉淀以及干燥。产量:0.1g(50%)。
1H NMR(250MHz,C2D2Cl4)δppm 0.75-0.78(24H,CH3),1.05-2.0(m,CH3,CH2),2.19(4H,m,CH),4.59(m,8H,OCH2),9.05(m,4H,Ar)。
GPC分析得到分子量Mn=29700g/mol Mw=58800g/mol和分子量分布PD=2.0(标准PPP)。
在THF溶液和薄膜中测量光学性能,分别在371和375nm显示最大吸收值λmax。对于溶液和薄膜,在蓝光范围内的发射最大值分别为441和451nm。
实施例4
a)2,7-二溴芘-4,5,9,10-四酮
a)根据J.Org.Chem.2005,70,707-708由芘在单步法中获得4,5,9,10-芘四酮。
将3g芘-4,5,9,10-四酮溶于80ml浓H2SO4中。在室温下,缓慢加入过量的2.2当量N-溴代琥珀酰亚胺(NBS)。再搅拌反应混合物1小时并且最后放置于冰水中。沉淀后,过滤产物并且用水洗涤。在甲醇中搅拌粗产物、干燥以及再一次在乙基醚以及最后在二氯甲烷中煮沸。获得2,7-二溴芘-4,5,9,10-四酮,产率为78%。
FD-MS(8KV):m/z 420.1(100%),计算420.0。
1H-NMR(C2D2Cl4,250MHz,140℃):d=8.61(s,4H)。
13C-NMR(THF-d8,175MHz):d=125.9,133.4,134.8,137.6,176.3。
b)2,7-二溴芘-4,5,9,10-四烷氧基芘
将2,7-二溴芘-4,5,9,10-四酮(0.50g,1.2mmol)、n-Bu4NBr(0.50g,1.5mmol)、Na2S2O4(2.5g,14mmol)、THF(8ml)和H2O(4mL)在25℃下搅拌10分钟。将1-溴-2-己基癸烷(1.7g,7.9mmol)和氢氧化钾水溶液(4ml,36mmol)加入溶液中并且在70℃下搅拌混合物5h。然后,加入THF和盐水并且用盐水洗涤有机相(3次)以及在MgSO4上干燥并且在真空中浓缩。通过柱色谱提纯残留物(SiO2,己烷∶CH2Cl2=10∶1)得到无色油(0.62g),产率为53%。
FD-MS(8KV):m/z 986.3(100%),计算985.1。
1H-NMR(CD2Cl2,250MHz):δ=0.84-0.86(m,24H),0.98-1.00(m,12H),1.47-2.00(m,40H),4.23-4.36(m,8H),8.50(s,4H)。
实施例5
a)根据J.Org.Chem.1986,51,2848中所述合成2,7-二溴芘
将5.3g(25mmol)NaIO4、25ml H2O和0.14g RuCl3xH2O加入1g(2.8mmol)2,7-二溴芘在20ml CH2Cl2和20ml CH3CN的溶液中。将棕褐色悬浮液加热至50℃过夜。将反应混合物倒入100ml H2O中,并且用100ml THF萃取。分离有机相并且浓缩。获得粗产物2,7-二溴芘-4,5,9,10-四酮,为橘红色物质(产率<15%,m/z 420.0)。
实施例6
a)将6,11-二溴-1,2,3,4-四苯基三亚苯(1.1g,1.6mmol)、二频哪醇化二硼(0.9g,3.5mmol)、AcOK(0.5g,4.7mmol)装入Schlenck烧瓶中并且溶于17ml二噁烷中。使全部混合物脱气并且加入催化剂[PdCl2(dppf)]CH2Cl2(0.065g,0.08mmol)以及使全部反应混合物加热至90℃20h。在减压下除去溶剂并且最后通过色谱在己烷∶二氯甲烷(1∶3)下在硅胶上提纯产物,提供期望产物(0.309g,25%)。
b)将2,7-二-4,4,5,5-四甲基(9,10,11,12-四苯基-三亚苯-2-基)-[1,3,2]二氧杂戊硼烷(2,7-di-4,4,5,5-tetramethyl(9,10,11,12-tetraphenyl-triphenylen-2-yl)-[1,3,2]dioxaborolane)(0.309g,0.39mmol)、2,7-二溴-4,5,9,10-四(3,7-二甲基辛氧基)芘(0.388g,0.39mmol)、K2CO3水溶液(3ml/2M)、Aliquat336(0.04g,0.1mmol)和Pd(PPh3)4(0.023g,0.02mmol)在甲苯中的悬浮液装入已经用氩气清洗且密封的装备有磁力搅拌棒的微波管中,在50W和激活的冷却下的CEM Discover微波炉中强烈搅拌混合物;使温度在100℃保持5h。依次将在脱气甲苯(3ml)中的溴苯(0.56g,3.6mmol)和苯硼酸(0.28g,2.3mmol)加入反应混合物中并且在100℃各搅拌1/2h。在室温下萃取有机层并且用氰化钠水溶液(1%,2×50ml)洗涤。再次用甲苯萃取有机层并且真空浓缩溶液直到获得高粘稠溶液。通过缓慢加入300ml甲醇沉淀聚合物。滤出聚合物并且依次用甲醇、水、丙酮和甲醇洗涤。再次将聚合物溶解在甲苯中并且在90℃下在氰化钠水溶液(1%,100ml)中强烈搅拌2h。萃取有机相、浓缩并且最后倒入过量甲醇中。滤出聚合物,并且通过抽提除去低聚馏分(1天/Soxhlet装置/乙酸乙酯)。聚合物的产量:0.28g(52%)。
GPC分析:Mw=12.4×103gmol-1,PDI=1.4(标准PPP)。
Claims (12)
2.根据权利要求1的包含式(I)重复单元的聚合物,其中R1,R2,R3和R4相互独立地为H、F、C1-C18烷基、被E取代和/或被插入D的C1-C18烷基、C1-C18烷氧基、被E取代和/或被插入D的C1-C18烷氧基、C1-C18全氟烷基、C6-C24芳基、被G取代的C6-C24芳基、C2-C20杂芳基、被G取代的C2-C20杂芳基;
在每一情况下,各个基团R5和R6相互独立地为H、卤素,特别是F、C1-C18烷基、被E取代和/或被插入D的C1-C18烷基、C1-C18全氟烷基、C6-C24芳基、被G取代的C6-C24芳基、C2-C20杂芳基、被G取代的C2-C20杂芳基、C2-C18烯基、C2-C18炔基、C1-C18烷氧基、被E取代和/或被插入D的C1-C18烷氧基、C7-C25芳烷基、CN或-CO-R28,
m为0、或1或2的整数,
D为-CO-;-COO-;-S-;-SO-;-SO2-;-O-;-NR25-;-SiR30R31-;-POR32-;-CR23=CR24-;或-C≡C-;且
E为-OR29;-SR29;-NR25R26;-COR28;-COOR27;-CONR25R26;-CN;或卤素,特别是F,
G为E、C1-C18烷基、被插入D的C1-C18烷基、C1-C18全氟烷基、C1-C18烷氧基,或被E取代和/或被插入D的C1-C18烷氧基,
R23、R24、R25和R26相互独立地为H;C6-C18芳基;被C1-C18烷基或C1-C18烷氧基取代的C6-C18芳基;C1-C18烷基;或被插入-O-的C1-C18烷基;
R27为氢;C6-C18芳基;被C1-C18烷基或C1-C18烷氧基取代的C6-C18芳基;特别是C1-C18烷基;或被插入-O-的C1-C18烷基,
R28为氢;C6-C18芳基;被C1-C18烷基或C1-C18烷氧基取代的C6-C18芳基;C1-C18烷基;或被插入-O-的C1-C18烷基,
R29为氢;C6-C18芳基;被C1-C18烷基或C1-C18烷氧基取代的C6-C18芳基;C1-C18烷基;或被插入-O-的C1-C18烷基,
R30和R31相互独立地为C1-C18烷基、C6-C18芳基、或被C1-C18烷基取代的C6-C18芳基,且
R32为C1-C18烷基、C6-C18芳基、或被C1-C18烷基取代的C6-C18芳基。
4.根据权利要求3的聚合物,其中R1、R2、R3和R4相互独立地为,其中n3为0,或1、2、3、4或5的整数,R11在每一情况下可相同或不同且为C1-C25烷基、或C1-C25烷氧基,或R1、R2、R3和R4相互独立地为C1-C18烷基、被插入-O-的C1-C18烷基、C1-C18烷氧基;或被插入-O-的C1-C18烷氧基。
7.一种电子器件或其部件,包含根据权利要求1-6中任一项的聚合物。
8.根据权利要求1-6中任一项的聚合物在聚合物发光二极管(PLED)中,特别是作为电致发光材料的用途。
9.PLED、有机集成电路(O-IC)、有机场效应晶体管(OFET)、有机薄膜晶体管(OTFT)、有机太阳能电池(O-SC)、热电器件、电变色器件、或有机激光二极管,包含根据权利要求1-6中任一项的聚合物。
10.下式的化合物:
其中Ar1、Ar2、n1、n2、R1、R2、R3、R4、R5、R6和m如权利要求1中所定义;
X11在每一情况下独立地为卤素原子,特别是I、CI、或Br;-ZnX12、-SnR207R208R209,其中R207、R208和R209相同或不同且为H或C1-C6烷基,其中两个基团任选形成共同的环并且这些基团任选为支化或未支化的且X12为卤素原子,非常特别是I、或Br;或-OS(O)2CF3、-OS(O)2-芳基,特别是-OS(O)2CH3、-B(OH)2、-B(OY11)2、-BF4Na、或-BF4K,其中Y11在每一情况下独立地为C1-C10烷基且Y12在每一情况下独立地为C2-C10亚烷基,例如-CY13Y14-CY15Y16-、或-CY17Y18-CY19Y20-CY21Y22-,其中Y13、Y14、Y15、Y16、Y17、Y18、Y19、Y20、Y21和Y22相互独立地为氢、或C1-C10烷基,特别是-C(CH3)2C(CH3)2-、或-C(CH3)2CH2C(CH3)2-。
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US (2) | US8841411B2 (zh) |
EP (1) | EP2291469A1 (zh) |
JP (1) | JP5748660B2 (zh) |
KR (1) | KR20110040857A (zh) |
CN (1) | CN102137902B (zh) |
TW (1) | TWI465478B (zh) |
WO (1) | WO2010006852A1 (zh) |
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CN108727566A (zh) * | 2018-04-10 | 2018-11-02 | 苏州和颂生化科技有限公司 | 一类基于咔唑-蒽结构的空穴传输聚合物材料的开发与应用 |
CN111320744A (zh) * | 2018-12-14 | 2020-06-23 | 拜克门寇尔特公司 | 聚合物染料的修饰和应用 |
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EP2513125B1 (de) | 2009-12-14 | 2014-10-29 | Basf Se | Metallkomplexe, enthaltend diazabenzimidazolcarben-liganden und deren verwendung in oleds |
EP2546907B1 (en) * | 2010-03-12 | 2016-11-23 | Panasonic Corporation | Electrode active material for electricity storage device, and electricity storage device using the same |
WO2012086671A1 (ja) * | 2010-12-21 | 2012-06-28 | 住友化学株式会社 | 高分子化合物及びそれを用いた有機el素子 |
JP5716540B2 (ja) * | 2011-05-24 | 2015-05-13 | 住友化学株式会社 | ピレン系高分子化合物及びそれを用いた発光素子 |
WO2013156125A1 (de) * | 2012-04-17 | 2013-10-24 | Merck Patent Gmbh | Vernetzbare sowie vernetzte polymere, verfahren zu deren herstellung sowie deren verwendung |
WO2014000860A1 (de) * | 2012-06-29 | 2014-01-03 | Merck Patent Gmbh | Polymere enthaltend 2,7-pyren-struktureinheiten |
JP6470495B2 (ja) * | 2013-03-07 | 2019-02-13 | キヤノン株式会社 | 電子写真感光体、該電子写真感光体を有する電子写真装置およびプロセスカートリッジ |
JP6005595B2 (ja) * | 2013-06-28 | 2016-10-12 | 株式会社東芝 | ポリマーとそれを用いた太陽電池 |
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US11066351B2 (en) * | 2016-01-28 | 2021-07-20 | Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) | Organic compound, three-dimensional organic framework formed by using organic compound, separation sieve and optical layer, which comprise organic framework, and optical device comprising optical layer as optical amplification layer |
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KR101973261B1 (ko) * | 2016-05-10 | 2019-05-02 | 한양대학교 산학협력단 | 3차원 유기 구조체를 구비하는 분리체 및 이를 구비하는 혼합 유체 분리 모듈 |
US10665545B2 (en) * | 2018-09-19 | 2020-05-26 | Taiwan Semiconductor Manufacturing Co., Ltd. | Semiconductor devices, semiconductor packages and methods of forming the same |
CN111087615B (zh) * | 2018-10-23 | 2022-02-18 | 国家纳米科学中心 | 一种cof膜,其制备方法、转移方法、用途和含有其的芯片 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102617317A (zh) * | 2012-02-21 | 2012-08-01 | 华南理工大学 | 一种合成芘-4,5,9,10-四酮的方法 |
CN102617317B (zh) * | 2012-02-21 | 2013-12-25 | 华南理工大学 | 一种合成芘-4,5,9,10-四酮的方法 |
CN106414399A (zh) * | 2014-05-09 | 2017-02-15 | 巴斯夫欧洲公司 | 氰化苝系化合物 |
CN106414399B (zh) * | 2014-05-09 | 2019-03-29 | 巴斯夫欧洲公司 | 氰化苝系化合物 |
CN108727566A (zh) * | 2018-04-10 | 2018-11-02 | 苏州和颂生化科技有限公司 | 一类基于咔唑-蒽结构的空穴传输聚合物材料的开发与应用 |
CN111320744A (zh) * | 2018-12-14 | 2020-06-23 | 拜克门寇尔特公司 | 聚合物染料的修饰和应用 |
Also Published As
Publication number | Publication date |
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JP5748660B2 (ja) | 2015-07-15 |
JP2011526630A (ja) | 2011-10-13 |
US8841411B2 (en) | 2014-09-23 |
KR20110040857A (ko) | 2011-04-20 |
EP2291469A1 (en) | 2011-03-09 |
TW201008972A (en) | 2010-03-01 |
CN102137902B (zh) | 2014-12-31 |
TWI465478B (zh) | 2014-12-21 |
US20110152491A1 (en) | 2011-06-23 |
WO2010006852A1 (en) | 2010-01-21 |
US20140357898A1 (en) | 2014-12-04 |
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