TWI386478B - 經鹵化之雙二芳胺基多環芳族化合物及其聚合物 - Google Patents
經鹵化之雙二芳胺基多環芳族化合物及其聚合物 Download PDFInfo
- Publication number
- TWI386478B TWI386478B TW093134729A TW93134729A TWI386478B TW I386478 B TWI386478 B TW I386478B TW 093134729 A TW093134729 A TW 093134729A TW 93134729 A TW93134729 A TW 93134729A TW I386478 B TWI386478 B TW I386478B
- Authority
- TW
- Taiwan
- Prior art keywords
- diyl
- group
- substituted
- polymer
- bis
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims description 88
- 150000001491 aromatic compounds Chemical class 0.000 title description 3
- -1 1,4-phenylene, 1,3-phenylene, 1, 2-phenylene Chemical group 0.000 claims description 82
- 239000000203 mixture Substances 0.000 claims description 43
- 125000003118 aryl group Chemical group 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 13
- 125000003367 polycyclic group Chemical group 0.000 claims description 10
- 229920006254 polymer film Polymers 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 4
- 125000001543 furan-2,5-diyl group Chemical group O1C(=CC=C1*)* 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 2
- IULUNTXBHHKFFR-UHFFFAOYSA-N 4-methyl-n,n-diphenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 IULUNTXBHHKFFR-UHFFFAOYSA-N 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 117
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- 239000000243 solution Substances 0.000 description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 22
- 238000001914 filtration Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000178 monomer Substances 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229920000547 conjugated polymer Polymers 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 7
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 239000010455 vermiculite Substances 0.000 description 7
- 229910052902 vermiculite Inorganic materials 0.000 description 7
- 235000019354 vermiculite Nutrition 0.000 description 7
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000005266 diarylamine group Chemical group 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- AGHYMXKKEXDUTA-UHFFFAOYSA-N 4-methyl-n-phenylaniline Chemical compound C1=CC(C)=CC=C1NC1=CC=CC=C1 AGHYMXKKEXDUTA-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 240000008881 Oenanthe javanica Species 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 4
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 4
- 125000005259 triarylamine group Chemical group 0.000 description 4
- WFOZWGDQDLFREE-UHFFFAOYSA-N 1,2-dibromophenazine Chemical compound C1=CC=CC2=NC3=C(Br)C(Br)=CC=C3N=C21 WFOZWGDQDLFREE-UHFFFAOYSA-N 0.000 description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 3
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Natural products C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- JNTHRSHGARDABO-UHFFFAOYSA-N dibenzo[a,l]pyrene Chemical compound C1=CC=CC2=C3C4=CC=CC=C4C=C(C=C4)C3=C3C4=CC=CC3=C21 JNTHRSHGARDABO-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229950000688 phenothiazine Drugs 0.000 description 3
- 229920005594 polymer fiber Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 3
- LCKDOHRDONNZTG-UHFFFAOYSA-N 1,2-dibromo-9h-fluorene Chemical compound C1=CC=C2CC3=C(Br)C(Br)=CC=C3C2=C1 LCKDOHRDONNZTG-UHFFFAOYSA-N 0.000 description 2
- JBJCECYXJKWTRJ-UHFFFAOYSA-N 1,2-dibromodibenzothiophene Chemical compound C1=CC=C2C3=C(Br)C(Br)=CC=C3SC2=C1 JBJCECYXJKWTRJ-UHFFFAOYSA-N 0.000 description 2
- QGZAUMUFTXCDBD-UHFFFAOYSA-N 1,2-dibromonaphthalene Chemical compound C1=CC=CC2=C(Br)C(Br)=CC=C21 QGZAUMUFTXCDBD-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- HKTCLPBBJDIBGF-UHFFFAOYSA-N 1-phenyl-2-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC=C1C1=CC=CC=C1 HKTCLPBBJDIBGF-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- FDHZLQGYOPJXEX-UHFFFAOYSA-N 2,3-dibromo-1h-indole Chemical compound C1=CC=C2C(Br)=C(Br)NC2=C1 FDHZLQGYOPJXEX-UHFFFAOYSA-N 0.000 description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 2
- LKPLXERNWQABDP-UHFFFAOYSA-N 2,4-dibromo-1,3-benzoxazole Chemical compound C1=CC=C2OC(Br)=NC2=C1Br LKPLXERNWQABDP-UHFFFAOYSA-N 0.000 description 2
- WSNLVLNJKOLJKZ-UHFFFAOYSA-N 2,7-dibromo-9,9-bis(4-hexoxyphenyl)fluorene Chemical compound C1=CC(OCCCCCC)=CC=C1C1(C=2C=CC(OCCCCCC)=CC=2)C2=CC(Br)=CC=C2C2=CC=C(Br)C=C21 WSNLVLNJKOLJKZ-UHFFFAOYSA-N 0.000 description 2
- CYKLQIOPIMZZBZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dioctylfluorene Chemical compound C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 CYKLQIOPIMZZBZ-UHFFFAOYSA-N 0.000 description 2
- YOSGCBCAISLPTR-UHFFFAOYSA-N 21,23-dibromoporphyrin Chemical compound BrN1C=2C=CC1=CC=1C=CC(=CC3=CC=C(N3Br)C=C3C=CC(C=2)=N3)N=1 YOSGCBCAISLPTR-UHFFFAOYSA-N 0.000 description 2
- RYKMINHUSADCEZ-UHFFFAOYSA-N 3,4-dibromohexacyclo[10.10.2.02,7.08,24.015,23.017,22]tetracosa-1(23),2(7),3,5,8,10,12(24),13,15,17,19,21-dodecaene Chemical compound BrC=1C=CC2=C(C=3C4=C(C=C5C=CC6=CC=CC2=C6C53)C=CC=C4)C1Br RYKMINHUSADCEZ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- USDIRSJFHPHMAS-UHFFFAOYSA-N ClC1=NC=C(C=2C1=NC=CN=2)F Chemical compound ClC1=NC=C(C=2C1=NC=CN=2)F USDIRSJFHPHMAS-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 125000004799 bromophenyl group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 125000000950 dibromo group Chemical group Br* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000003106 haloaryl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- APZFQORRVULRGX-UHFFFAOYSA-N n,n-diphenyl-9h-fluoren-1-amine Chemical compound C=12CC3=CC=CC=C3C2=CC=CC=1N(C=1C=CC=CC=1)C1=CC=CC=C1 APZFQORRVULRGX-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical compound C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 2
- 229920000412 polyarylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 2
- PSZXPGFNGPBEFR-UHFFFAOYSA-N trisodium butan-1-olate Chemical compound [Na+].[Na+].[Na+].CCCC[O-].CCCC[O-].CCCC[O-] PSZXPGFNGPBEFR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical compound C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 description 1
- ZFQZVHKBKJBOEM-UHFFFAOYSA-N 1,2-dibromo-9,10-dihydrophenanthrene Chemical compound C1=CC=C2C3=CC=C(Br)C(Br)=C3CCC2=C1 ZFQZVHKBKJBOEM-UHFFFAOYSA-N 0.000 description 1
- IEMXKVCEQAQLOJ-UHFFFAOYSA-N 1,2-dibromo-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(Br)C(Br)=C3NC2=C1 IEMXKVCEQAQLOJ-UHFFFAOYSA-N 0.000 description 1
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- MKXZILBIAQNODC-UHFFFAOYSA-N 1,2-dibromodibenzo-p-dioxin Chemical compound C1=CC=C2OC3=C(Br)C(Br)=CC=C3OC2=C1 MKXZILBIAQNODC-UHFFFAOYSA-N 0.000 description 1
- GPOPKCSRDACCHP-UHFFFAOYSA-N 1,2-dibromodibenzofuran Chemical compound C1=CC=C2C3=C(Br)C(Br)=CC=C3OC2=C1 GPOPKCSRDACCHP-UHFFFAOYSA-N 0.000 description 1
- ORRVRBPWVZVRKU-UHFFFAOYSA-N 1,2-dibromophenanthrene Chemical compound C1=CC=C2C3=CC=C(Br)C(Br)=C3C=CC2=C1 ORRVRBPWVZVRKU-UHFFFAOYSA-N 0.000 description 1
- UGYDNPLIENMVEP-UHFFFAOYSA-N 1,2-dibromophenanthridine Chemical compound C1=CC=C2C3=C(Br)C(Br)=CC=C3N=CC2=C1 UGYDNPLIENMVEP-UHFFFAOYSA-N 0.000 description 1
- PZWLRLIAVLSBQU-UHFFFAOYSA-N 1,2-dioctyl-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(CCCCCCCC)C(CCCCCCCC)=C3CC2=C1 PZWLRLIAVLSBQU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- HMDRPWSFMGTTHH-UHFFFAOYSA-N 1,3-dibromo-2h-isoindole Chemical compound C1=CC=CC2=C(Br)NC(Br)=C21 HMDRPWSFMGTTHH-UHFFFAOYSA-N 0.000 description 1
- HPARLNRMYDSBNO-UHFFFAOYSA-N 1,4-benzodioxine Chemical compound C1=CC=C2OC=COC2=C1 HPARLNRMYDSBNO-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- IBGUDZMIAZLJNY-UHFFFAOYSA-N 1,4-dibromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=C(Br)C2=C1 IBGUDZMIAZLJNY-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- PJVKOGKZTRDSAE-UHFFFAOYSA-N 2,2-dibromo-3,4-dihydrochromene Chemical compound BrC1(OC2=CC=CC=C2CC1)Br PJVKOGKZTRDSAE-UHFFFAOYSA-N 0.000 description 1
- FUYYZRSYMOGBMW-UHFFFAOYSA-N 2,3-dibromo-1,10-phenanthroline Chemical compound C1=CC=NC2=C(N=C(C(Br)=C3)Br)C3=CC=C21 FUYYZRSYMOGBMW-UHFFFAOYSA-N 0.000 description 1
- WRMMSWZCRKDBQJ-UHFFFAOYSA-N 2,3-dibromo-1,4-benzodioxine Chemical compound C1=CC=C2OC(Br)=C(Br)OC2=C1 WRMMSWZCRKDBQJ-UHFFFAOYSA-N 0.000 description 1
- TWZSIAFEFBKCNN-UHFFFAOYSA-N 2,3-dibromo-1-benzothiophene Chemical compound C1=CC=C2C(Br)=C(Br)SC2=C1 TWZSIAFEFBKCNN-UHFFFAOYSA-N 0.000 description 1
- VLPBEKHOQWMYTR-UHFFFAOYSA-N 2,3-dibromopyrazine Chemical compound BrC1=NC=CN=C1Br VLPBEKHOQWMYTR-UHFFFAOYSA-N 0.000 description 1
- KWVPZTJLHQKCKD-UHFFFAOYSA-N 2,3-dibromoquinoline Chemical compound C1=CC=C2N=C(Br)C(Br)=CC2=C1 KWVPZTJLHQKCKD-UHFFFAOYSA-N 0.000 description 1
- RXLKWMZHXIYWRB-UHFFFAOYSA-N 2,4-dibromo-1,3-benzodioxole Chemical compound BrC1=CC=CC=2OC(OC=21)Br RXLKWMZHXIYWRB-UHFFFAOYSA-N 0.000 description 1
- AZOZOHCZAFSZIG-UHFFFAOYSA-N 2,4-dibromo-1,3-benzothiazole Chemical compound C1=CC=C2SC(Br)=NC2=C1Br AZOZOHCZAFSZIG-UHFFFAOYSA-N 0.000 description 1
- JQHWHEOFYYOERH-UHFFFAOYSA-N 2,4-dibromo-1h-benzimidazole Chemical compound C1=CC(Br)=C2NC(Br)=NC2=C1 JQHWHEOFYYOERH-UHFFFAOYSA-N 0.000 description 1
- CDBAGRHVFMGOON-UHFFFAOYSA-N 2,4-dibromoquinazoline Chemical compound C1=CC=CC2=NC(Br)=NC(Br)=C21 CDBAGRHVFMGOON-UHFFFAOYSA-N 0.000 description 1
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 1
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- JVPMNAUZMMABSB-UHFFFAOYSA-N 3,3-dibromo-2h-1,4-benzodioxine Chemical compound C1=CC=C2OC(Br)(Br)COC2=C1 JVPMNAUZMMABSB-UHFFFAOYSA-N 0.000 description 1
- AQZJVJXVTVCMCZ-UHFFFAOYSA-N 3,4-dibromopyridazine Chemical compound BrC1=CC=NN=C1Br AQZJVJXVTVCMCZ-UHFFFAOYSA-N 0.000 description 1
- YIUXVMNZXOLRHV-UHFFFAOYSA-N 3,7-dibromo-10-(4-butylphenyl)phenoxazine Chemical compound C1=CC(CCCC)=CC=C1N1C2=CC=C(Br)C=C2OC2=CC(Br)=CC=C21 YIUXVMNZXOLRHV-UHFFFAOYSA-N 0.000 description 1
- ZNFMFLLMYATRMY-UHFFFAOYSA-N 4,5-dibromo-1,2,3-benzothiadiazole Chemical compound BrC1=CC=C2SN=NC2=C1Br ZNFMFLLMYATRMY-UHFFFAOYSA-N 0.000 description 1
- PFIAMJSHYNDDNS-UHFFFAOYSA-N 4-n,7-n-bis(4-bromophenyl)-4-n,7-n-bis(4-methylphenyl)-2,1,3-benzothiadiazole-4,7-diamine Chemical compound C1=CC(C)=CC=C1N(C=1C2=NSN=C2C(N(C=2C=CC(C)=CC=2)C=2C=CC(Br)=CC=2)=CC=1)C1=CC=C(Br)C=C1 PFIAMJSHYNDDNS-UHFFFAOYSA-N 0.000 description 1
- KNDUABXKUVNYAC-UHFFFAOYSA-N 4-n,7-n-bis(4-methylphenyl)-4-n,7-n-diphenyl-2,1,3-benzothiadiazole-4,7-diamine Chemical compound C1=CC(C)=CC=C1N(C=1C2=NSN=C2C(N(C=2C=CC=CC=2)C=2C=CC(C)=CC=2)=CC=1)C1=CC=CC=C1 KNDUABXKUVNYAC-UHFFFAOYSA-N 0.000 description 1
- ZPZBXKVJNVNNET-UHFFFAOYSA-N 5,8-dibromoquinoxaline Chemical compound C1=CN=C2C(Br)=CC=C(Br)C2=N1 ZPZBXKVJNVNNET-UHFFFAOYSA-N 0.000 description 1
- KAOMITMPVNTTIW-UHFFFAOYSA-N 6,7-dibromo-1-benzofuran Chemical compound BrC1=CC=C2C=COC2=C1Br KAOMITMPVNTTIW-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- JBMKAUGHUNFTOL-UHFFFAOYSA-N Aldoclor Chemical class C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NC=NS2(=O)=O JBMKAUGHUNFTOL-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VGMSFJWAVNOQDK-UHFFFAOYSA-N BrC1=C(SCC1)Br Chemical compound BrC1=C(SCC1)Br VGMSFJWAVNOQDK-UHFFFAOYSA-N 0.000 description 1
- SMGMOEFMDVYBTP-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1=C(C=CC(=C1)C(C)(C)C)NC1=C(C=C(C=C1)C(C)(C)C)C1=CC=C(C=C1)Br Chemical compound BrC1=CC=C(C=C1)C1=C(C=CC(=C1)C(C)(C)C)NC1=C(C=C(C=C1)C(C)(C)C)C1=CC=C(C=C1)Br SMGMOEFMDVYBTP-UHFFFAOYSA-N 0.000 description 1
- GMOVHYLKMVDXTB-UHFFFAOYSA-N BrC1=[N+](C=CC=C1)Br Chemical compound BrC1=[N+](C=CC=C1)Br GMOVHYLKMVDXTB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000005224 alkoxybenzenes Chemical class 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical group 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical compound BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XSHCSXZEWYUIDM-UHFFFAOYSA-N chloroform;dioxane Chemical compound ClC(Cl)Cl.C1CCOOC1 XSHCSXZEWYUIDM-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- FGGAOQTXQHKQOW-UHFFFAOYSA-N n,n-diphenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1 FGGAOQTXQHKQOW-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 238000003947 neutron activation analysis Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- NFBOHOGPQUYFRF-UHFFFAOYSA-N oxanthrene Chemical compound C1=CC=C2OC3=CC=CC=C3OC2=C1 NFBOHOGPQUYFRF-UHFFFAOYSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- LYKMMUBOEFYJQG-UHFFFAOYSA-N piperoxan Chemical compound C1OC2=CC=CC=C2OC1CN1CCCCC1 LYKMMUBOEFYJQG-UHFFFAOYSA-N 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001088 polycarbazole Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 239000003451 thiazide diuretic agent Substances 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/58—Naphthylamines; N-substituted derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/59—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/151—Copolymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本發明係有關於經鹵化之雙二芳胺基多環芳族化合物及其聚合物,及使用此等聚合物製得之裝置。
諸如聚芴、聚噻吩、聚對苯撐及聚(對-苯撐乙烯撐)之共軛聚合物係作為發光二極體裝置之半導層。例如,以芴為主之同聚物已知具有高度光致發光能力,其係電致發光(EL)應用之必備品。但是,同聚物非特別適於電致發光元件(亦稱為聚合發光二極體元件或pLEDs),因為電子自同聚合物轉移至陽極不足之故。聚合物主幹內此電子移除(亦稱為電子洞注射)形成基陽離子(電子洞)之緩慢性被推測係由於同聚物之最高佔據分子軌道(HOMO)及陽極功函數間之能力不相配。此不相配已由Woo等人於美國專利第6,309,763號案中藉由使三芳基胺併納於含有9,9-二烷基-芴-2,7-二基之結構單元之聚合物主幹內而於某一程度上解決。三芳基胺重複單元之存在已被發現增加增加電子洞自陽極注射至聚合物之能力,藉此改良元件之效率。相似地,Hsieh於美國專利第5,879,821號案描述將三芳基胺併納於共軛聚合物內製造更有效之共軛運送電荷之聚合物。
因自陽極注射電子洞而於聚合物主幹中形成之基陽離子(電子洞)與經由自陰極注射電子至聚合物最低未被佔據之分子軌道(LUMO)而形成之基陰離子(電子)結合產生激發
態(激子)。然後,此等激子進行輻射鬆弛至基態,且以相對應於聚合物譜帶間隙之波長發射光線。因此,元件之效率及壽命係依經注射之電子及電子洞”發現”彼此且重新組合形成激子之能力而定。因此,雖然將三芳基胺併納於共軛聚合物主幹內已改良自陽極注射電子洞至聚合物之效率,但於此項技藝進一步需要經由聚合物層傳播或運送電子洞及電子之效率以進一步增加元件之壽命及效率。
本發明於第一方面係藉由提供以如下化學式表示之經鹵化之雙二芳胺基多環芳族化合物而處理此項技藝之需求:
其中,Ar及Ar’每一者個別係經取代或未經取代之芳基,且Z係多環芳撐基,其中,至少一Ar’基係鹵芳基。
於第二方面,本發明係一種包含含有如下所示結構單元之主幹之聚合物:
其中,每一Ar個別係經取代或未經取代之芳基;每一Ar”
係經取代或未經取代之芳撐基;且Z係多環芳撐基。
於第三方面,本發明係一種電子元件,其包含置於陽極及陰極間之聚合物薄膜,此聚合物具有如下所示之結構單元:
其中,每一Ar個別係經取代或未經取代之芳基;每一Ar”係經取代或未經取代之芳撐基;且Z係多環芳撐基。
經鹵化之雙二芳胺基多環化合物係以下列結構表示:
其中,Ar及Ar’每一者個別係經取代或未經取代之芳基,且Z係多環芳撐基,其中,至少一Ar’基係鹵芳基。鍵結至相同氮原子之Ar及Ar’可彼此鍵結形成吩噁嗪、吩噻嗪或咔唑基,但較佳地,Ar及Ar’基未彼此鍵結。更佳地鄉雨每一Ar’係鹵芳基,更佳係鹵苯基,且最佳係溴苯基。更佳地,每一Ar係苯基,最佳係經取代之苯基。多環芳撐基係意指具有至少一熔合至另一環(可為芳族或非芳族)之芳族基之基。此等基係至少二價-即,二基之物種。用於本發明
之二基基轉之非限制性例子包含以芴(即,芴二基,特別是芴-2,7-二基)、萘、蒽、菲、并四苯、花、喹啉、異喹啉、喹噁啉、菲啶、菲咯啉、吩嗪、吖啶、二苯并唏喏(silole)、酞嗪、二溴噌啉、喹噁啉、苯并噁唑、苯并咪唑、苯并噻吩、苯并噻唑、咔唑、苯并噁二唑、苯并噻二唑、噻吩[3,4-b]吡嗪、[1,2,5]噻二唑[3,4-g]-嗪噁啉、苯并[1,2-c;3-4c’]雙[1,2,5]-噻二唑、吡嗪[2,3-g]嗪噁啉、苯并呋喃、吲哚、二苯并呋喃、二苯并噻吩、二苯并唏喏、噻蒽、苯并二喔星、苯并二噁烷、二苯并二喔星、吩嗪、吩噁塞因(thiin)、苯并二塞因、苯并間二氧雜環戊烯、苯并環丁烯、二氫苯并二塞因、二氫噻吩二喔星、苯并二氫吡喃、異苯并二氫吡喃、9,10-二氫菲醌、噻嗪、吩噁嗪、吲哚、異吲哚及二苯并噻吩碸為主之經取代或未經取代之基。
經鹵化之雙二芳胺基多環芳族化合物可方便地以二步驟製造。於第一步驟,經二溴化之多環芳族化合物可於鈀催化劑(諸如,乙酸鈀(I))、三芳基膦(諸如,三-對-甲苯基膦)及鹼(諸如,第三丁氧化鉀)存在中與二芳基胺反應,形成未經鹵化之雙二芳胺基多環芳族先質。於第二步驟,雙二芳胺基多環芳族先質可藉由以鹵化劑(諸如,N-溴琥珀醯亞胺)處理而轉化成經鹵化之化合物。
二芳基胺係鍵結至二芳基之胺。芳基可彼此不經鍵結(例如,二苯基胺、苯基萘基胺,及二萘基胺)或彼此鍵結(形成,例如,吩噁嗪、吩噻嗪及咔唑)。較佳地,二芳基胺係經取代或未經取代之二苯基胺,更佳係如下例示之經單取
代之二苯基胺:
其中,R’係較佳與胺基呈間位或對位之取代基。R’較佳係C1
-C20
烷基、碳-C1
-C20
-烷氧基、C1
-C20
-烷氧基,或C6
-C40
芳基,更佳係甲基、乙基、碳甲氧基,或碳乙氧基,最佳係甲基。亦較佳地,R’非溴基。
於此使用時,”多環芳族化合物”係用以描述含有至少一熔合至另一環(可為芳族或非芳族)之芳族基之化合物。為了本發明,聯苯非多環芳族化合物,因為二苯基未熔合。除溴基外,經二溴化之多環芳族化合物可另外含有額外取代基,但較佳係未經取代。適當之經二溴化之多環芳族化合物之例子包含二溴芴、二溴萘、二溴蒽、二溴菲、二溴并四苯、二溴花、二溴喹啉、二溴異喹啉、二溴喹唑啉、二溴菲啶、二溴菲咯啉、二溴吩嗪、二溴吖啶、二溴二苯并唏喏、二溴酞嗪、二溴噌啉、二溴喹噁啉、二溴苯并噁唑、二溴苯并咪唑、二溴苯并噻吩、二溴苯并噻唑、二溴咔唑、二溴苯并噁二唑、二溴苯并噻二唑、二溴噻吩[3,4-b]吡嗪、二溴[1,2,5]噻二唑[3,4-g]-喹噁啉、二溴苯并[1,2-c;3-4c’]雙[1,2,5]-噻二唑、二溴吡嗪[2,3-g]喹噁啉、二溴苯并呋喃、二溴吲哚、二溴二苯并呋喃、二溴二苯并噻吩、二溴二苯并唏喏、二溴噻蒽、二溴苯并二喔星、二溴
苯并二噁烷、二溴二苯并二喔星、二溴吩嗪、二溴吩噁塞因、二溴苯并二塞因、二溴苯并間二氧雜環戊烯、二溴苯并環丁烯、二溴二氫苯并二塞因、二溴二氫噻吩二喔星、二溴苯并二氫吡喃、二溴異苯并二氫吡喃、二溴-9,10-二氫菲、二溴噻嗪、二溴吩噁嗪、二溴吲哚、二溴異吲哚,及二溴二苯并噻吩碸。
較佳之經二溴化之多環芳族化合物包含2,7-二溴-9,9-二辛基芴、2,7-二溴-9,9-二己基苯基芴、2,7-二溴-9,9-雙(4-己氧基苯基)芴、4,7-二溴-2,1,3-苯并噻二唑、5,8-二溴喹噁啉、1,4-二溴萘,及9,10-二溴蒽。
經鹵化之雙二芳胺基多環芳族化合物可為經單鹵化或經多鹵化,且較佳係經二鹵化,更佳係經二溴化。經二溴化之雙二芳胺基多環芳族化合物可藉由經單取代之二芳基胺與如前所述之二溴多環芳族化合物反應,其後以N-溴琥珀醯亞胺處理而製造。若二芳基胺係二苯基胺,則2-步驟之反應流程圖係如下所述:
其中,ZBr2
係如前所述。較佳地,Z係2,1,3-苯并噻二唑-4,7-
二基、9,9-雙(4-己氧基苯基)芴-2,7-二基、9,9-二辛基芴-2,7-二基、9,9-二己基芴-2,7-二基、萘-1,4-二基、蒽-9,10-二基,或喹噁啉-5,8-二基。
單體係作為發光聚合物(較佳係共軛電致發光聚合物,可為同聚物、共聚物、三元聚合物等,含有經鹵化之雙二芳胺基多環單體且較佳地至少一芳族共單體)之先質。於此使用時,”結構單元”一辭係指聚合反應後於聚合物主幹出現之單體的剩餘物。舉例而言,諸如1,4-二溴苯之芳族共單體之結構單元係1,4-苯撐基;9,9-經二取代之芴共單體(諸如,2,7-二溴-9,9-經二取代之芴)之結構單元係9,9-經二取代之芴-2,7-二基;雙二苯基胺基多環芳族單體之結構單元係如下所例示:
其中,Z及Z’係如前所界定。
聚合物可藉由數種手段之任一者製造,例如,藉由美國專利第6,169,163號案(‘162號專利)第41欄第50-67行至第42欄第1-24行所例示之Suzuki偶合反應,其描述內容在此被併入以供參考之用。於本情況中,Suzuki偶合反應可藉由於鈀催化劑、相轉移催化劑(諸如,四級銨鹽)及強鹼存在中
使經二溴化之雙二芳胺基多環芳族單體與經二硼化之芳族共單體(較佳係與經二溴化及經二溴化之芳族共單體)反應而完成。於此使用時,”硼化”及”硼化物”一辭係指以硼烷基、硼酸酯基或硼酸基取代之芳族片斷或化合物。
聚合反應亦可藉由於鎳鹽存在中使一或多種之經二鹵化之雙二芳胺基多環芳族單體與一或多種之經二鹵化之芳族化合物偶合而完成,如’163號專利案第11欄第9-34行所述般,其描述內容在此被併入以供參考之用。
可用以與經鹵化之雙二芳胺基多環芳族單體偶合之芳族共單體係幾近無窮,但代表性之列示包含1,4-二X苯、1,3-二X苯、1,2-二X苯、4,4’-二X聯苯、1,4-二X萘、2,6-二X萘、2,5-二X呋喃、2,5-二X噻吩、5,5-二X-2,2’-二噻吩、9,10-二X蒽、4,7-二X-2,1,3-苯并噻二唑、二X三芳基胺,包含N,N-二(4-X苯基)苯胺、N,N-二(4-X苯基)-對-甲苯基胺;及N-二X苯基-M-苯基苯胺,3,6-二X-N-經代之咔唑、2,7-二X-N-取代之咔唑、3,8-二X-二苯并唏喏、4,7-二X-二苯并唏喏、N-取代-3,7-二X吩噻嗪、N-取代-3,7-二X-吩噁嗪、3,8-二X二苯并唏喏、4,7-二X二苯并唏喏、二X-N,N,N’,N’-四芳基-1,4-二胺基苯、二X-N,N,N’N’-四芳基聯苯胺、二X芳基矽烷,及2,7-二X-9,9-二取代芴,包含其中9,9-取代基結合形成環結構之芴,其等之混合物,其中,每一X係鹵基或硼化物,較佳係溴基或溴基或硼化物,更佳係溴基或硼化物。需瞭解複數(例如,二X苯)之使用表示此等化合物除鹵基或硼化物基外可另包含其它取代基。
特別適合之芳族共單體包含9,9-二取代-2,7-芴基二硼化物及9,9-二取代-2,7-二鹵基芴,如下所示:
其中,Y係鹵素原子或硼化物基,且每一R係取代基。較佳地,每一R個別係C4
-C20
-烷基、C4
-C20
-烷氧基、C7
-C20
-烷基苯基、C7
-C20
-烷氧基苯基,或C6
-C40
-芳基。更佳地,每一R係C6
-C12
-烷基或下列之烷氧基苯基:
其中,R”係C6
-C12
-烷基。
相對應於如上列示之芳族單體之結構單元係1,4-苯撐基、1,3-苯撐基、1,2-苯撐基、4,4’-聯苯撐基、萘1,4-二基、萘-2,6-二基、呋喃-2,5-二基、噻吩-2,5-二基、2,2’-二噻吩-5,5-二基、蒽-9,10-二基、2,1,3-苯并噻二唑-4,7-二基、N-取代咔唑-3,6-二基、N-取代咔唑-2,7-二基、二苯唏喏-3,8-二基、二苯并唏喏-4,7-二基、N-取代-吩噻嗪-3,7-二基、N-取代-吩噁嗪-3,7-二基、三芳基胺-二基,包含三苯基胺-4,4’-二基、二苯基-對-甲苯基胺-4,4’-二基,及N,N-二苯基苯胺-3,5-二基,N,N,N’,N’-四芳基-1,4-二胺基苯-二基、
N,N,N’,N’-四芳基聯苯胺-二基、芳基矽烷-二基,及9,9-二取代之芴-2,7-二基。
聚合物中之雙二芳胺基多環芳族單體之結構單元之濃度係依應用而定,但可少至每一聚合物分子為1結構單元至聚合物主幹之100%。
本發明聚合物較佳係具有至少5000道爾頓之重量平均分子量Mw,更佳係至少10,000道爾頓,更佳係至少50,000道爾頓,且最佳係至少100,000道爾頓;且較佳係少於2,000,000道爾頓,更佳係少於1,000,000道爾頓。Mw係使用凝膠滲透色譜術對比於聚苯乙烯標準物而決定。
本發明聚合物可與一或多種其它聚合物混合製得一摻合物。適當之摻合聚合物之例子包含聚丙烯酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚酯、聚醯亞胺、聚乙烯撐、聚碳酸酯、聚乙烯基醚及酯、氟聚合物、聚咔唑、聚芳撐乙烯撐、聚芳撐、聚噻吩、聚呋喃、聚吡咯、聚吡啶、聚芴之同-或共-聚物(包含三元聚合物或更高),及其等之混合物。
本發明之聚合物或摻合物可與足夠量之一或多種溶劑(其後稱為”溶劑”)混合製得可用作,例如,墨水之溶液。溶劑之量係依溶劑本身及應用而改變,但一般係以至少80重量%,更佳係至少90重量%,且最佳係至少95重量%(其係以發光聚合物、選擇性之添加劑或改質劑及溶劑之重量為基準計)之濃度而使用。
聚合物之適當溶劑之例子包含甲苯、二-及三烷基苯,包含C1-12
烷基苯、二甲苯、、環己基苯及二乙基苯;呋
喃,包含四氫呋喃及2,3-苯并呋喃;1,2,3,4-四氫萘;枯烯;十氫萘;均四甲苯;氯仿;檸檬烯;二噁烷;烷氧基苯,包含苯甲醚,及甲基苯甲醚;苯甲酸烷基酯,包含苯甲酸甲酯;聯苯,包含異丙基聯苯;吡咯烷酮,包含環己基吡咯烷酮;咪唑,包含二甲基咪唑啉酮;及氟化溶劑;及其等之混合物。更佳之溶劑包含C1-8
烷基苯、環己基苯、二甲苯、、1,2,3,4-四氫萘、苯甲酸甲酯、異丙基聯苯,及苯甲醚,及其等之混合物。
於典型之應用,墨水組成物可被沈積於諸如具有置於其上之運送電子洞之材料之銦-錫-氧化物(ITO)玻璃之基材。然後,溶劑被蒸發,而墨水形成發光聚合物薄膜。此膜特別可用作有機發光二極體(OLED)元件(其可用於製造諸如自行發射平板顯示器之顯示器)之注射電荷之層、運送電荷之層、阻絕電荷之層,或發射層。此膜亦可用於其它電子元件,包含光源、光電電池、化學感應器,及場效電晶體元件。
本發明之較佳聚合物造成具改良效率及較長壽命之pLED。雖然不欲受理論所限,但相信此改良性能係由於因共軛聚合物主幹中存在幾何受限之雙二芳胺基多環芳族結構基而造成之電子離域化增加。除改良之性能外,已驚人地發現聚合物之發光性質可藉由改變鍵結至二芳胺基之多環基而調整。例如,含有二苯基胺基芴及二苯基胺基萘結構單元之共軛聚合物發射藍色;含有二苯基胺基蒽結構單元之共軛聚合物發射綠色;且含有二苯基胺基苯并噻二唑
結構單元之共軛聚合物發射紅色。
下列實施例僅係用於例示目的,且非用以限制本發明範圍。聚合物之製造係使用CMOSTM
甲苯完成,且聚合物之沈澱係使用CMOSTM
甲醇完成。(CMOS係J.T.Baker之商標)
A.製造4,7-雙(N-苯基-N-對-甲苯基胺基)-2,1,3-苯并噻二唑
乙酸鈀(0.18克,0.8毫莫耳)及三-鄰-甲苯基膦(0.49克,1.6毫莫耳)被溶於甲苯(25毫升)內。溶液於室溫攪拌15分鐘,於是4,7-二溴-2,1,3-苯并噻二唑(2.94克,10毫莫耳)、4-甲基二苯基胺(5.0克,27.3毫莫耳)及第三丁氧鉀(3.84克,40毫莫耳)被添加。混合物於氮氣下迴流隔夜,然後,冷卻至室溫。水(~20毫升)被緩慢添加至此混合物,且有機部份以數份甲苯萃取。混合之有機萃取物以鹽水清洗,然後,於硫酸鎂乾燥。溶劑於真空中移除,且殘質再次溶於甲苯及己烷之1:1 v/v混合物,並通過矽石凝膠管柱。自乙醇再結晶產生呈紅色固體(1.2克)之標的化合物。
B.製造4,7-雙(N-(4-溴苯基)-N-對-甲苯基胺基)-2,1,3-苯并噻二唑
於DMF(5毫升)中之N-溴琥珀醯亞胺(0.8克,4.5毫莫耳)之溶液添加至於室溫之DMF(10毫升)中之4,7-雙(N-苯基-N-對-甲苯基胺基)-2,1,3-苯并噻二唑(1.1克,2.2毫莫耳)之溶液。反應混合物於室溫攪拌2小時,於是水(~200毫升)被添加而使產物沈澱。沈澱物被收集且以水然後以甲醇清洗。
粗製產物再次溶於甲苯(~10毫升)並於甲醇(~200毫升)中沈澱。紅色產物藉由過濾收集且自DMF再結晶,產生暗紅色產物(1.0克)之標的化合物。
A.製造2,7-雙(4-甲基二苯基胺基)-9,9-二辛基芴
乙酸Pd(II)(0.90克,4毫莫耳)及三-鄰-甲苯基膦(2.435克,8毫莫耳)於室溫時於無水甲苯(125毫升)攪拌15分鐘,於是2,7-二溴-9,9-二辛基芴(27.4克,50毫莫耳)、4-甲基二苯基胺(22.91克,125毫莫耳),及第三丁氧鈉(19.75克)被添加。混合物於氮氣下加熱迴流隔夜,然後,冷卻至室溫,然後,第一份之水(~100毫升)被緩慢添加,其後以水(~200毫升)進一步稀釋。然後,水性相與有機相分離,且溶劑於真空中移除。殘質再次溶於甲苯(~100毫升),且溶液通過氧化鋁管柱。產物於真空中濃縮,且自甲醇沈澱。粗製產物自對-二甲苯再結晶,呈白色結晶,其被再次溶於~100毫升之甲苯。溶液通過具甲苯之中性Al管柱,且收集之溶液被濃縮至~50-100毫升,然後,倒入攪拌之甲醇(~250毫升),使產物沈澱。產物被收集且於室溫真空中乾燥18小時。白色產物(25.0克)被獲得,其藉由HPLC顯示99.9%之純度。
B.製造2,7-雙(4-甲基-4’-溴-二苯基胺基)-9,9-二辛基芴單體
溶於DMF(~20毫升)之N-溴琥珀醯亞胺(5.91克,33.2毫莫耳)之溶液於-10℃攪拌添加至含有溶於二氯甲烷(95毫升)之2,7-雙(4-甲基二苯基胺基)-9,9-二辛基芴(12.5克,16.6毫
莫耳)之溶液。攪拌持續3.5小時,其後,冷的甲醇(~150毫升)被添加至反應混合物。然後,混合物倒至更多之冷的甲醇(~300毫升)並攪拌。粗製產物被過濾並以甲醇清洗,然後,自對-二甲苯再結晶,產生具有藉由HPLC測得為99.45%之純度之產物。於甲苯中再結晶及於甲醇中再次沈澱,其後於30℃真空乾燥20小時,產生12.1克之具99.47%純度之白色固體。
A.製造1,4-雙(4-甲基二苯基胺基)萘
乙酸Pd(II)(78毫克,0.35毫莫耳)及三-對-甲苯基膦(0.21克,0.7毫莫耳)於室溫時於無水甲苯(50毫升)攪拌15分鐘,於是1,4-二溴萘(5.00克,17.48毫莫耳)、4-甲基二苯基胺(6.44克,35.13毫莫耳),及第三丁氧鈉(4.20克,43.7)被添加。混合物於氮氣下加熱迴流隔夜,然後,冷卻至室溫,於是,HCl(~20毫升)被緩慢添加。混合物被過濾,且過濾物通過鹼性氧化鋁管柱。甲苯被移除產生橙色固體。固體自己烷再結晶,產生褐色固體5.3克(62%)。
B.製造1,4-雙(4-甲基-4’-溴-二苯基胺基)萘
溶於DMF(~20毫升)之N-溴琥珀醯亞胺(2.90克,16.3毫莫耳)之溶液於-10℃攪拌添加至含有溶於二氯甲烷(60毫升)之1,4-雙(4-甲基二苯基胺基)萘(4克,8.15毫莫耳)之溶液。攪拌持續1小時,其後,水被添加至此混合物。水性層以二氯甲烷(3 x 100毫升)萃取,且混合之有機部份以水(3 x 200毫升)清洗。溶液被濃縮至~100毫升,且通過矽石凝膠管
柱。起始之淡黃色部份被收集並混合。二氯甲烷於真空中移除,產生淡黃色固體(1克,19%),藉由HPLC-MS測得係97.7%純度。
A.製造9,10-雙(4-甲基二苯基胺基)蒽
乙酸鈀(0.27克,0.4毫莫耳)及三-鄰-甲苯基膦(0.49克,1.6毫莫耳)被溶於甲苯(150毫升)。溶液於室溫攪拌15分鐘,於是9,10-二溴蒽(13.44克,40毫莫耳)、4-甲基二苯基胺(18.3克,100毫莫耳)及第三丁氧鈉(15.4克,160毫莫耳)被添加。混合物於氮氣下迴流隔夜,然後,冷卻至室溫。氫氯酸(1N)被緩慢添加使溶液中和,且500毫升甲醇被添加。沈澱物藉由過濾收集且於室溫真空乾燥。固體被溶於1.5公升之甲苯,且形成之溶液通過酸性氧化鋁管柱,且以甲苯洗提。混合之甲苯溶液被濃縮至~500毫升,且倒至500毫升甲醇內,使粗製產物以黃色粉末沈澱。粗製產物藉由過濾收集,並以甲醇收集。自甲苯及乙醇兩次再結晶提供14.1克之最後產物,呈黃色粉末。
B.製造9,10-雙(4-甲基-4’-溴-二苯基胺基)蒽單體
9,10-雙(4-甲基二苯基胺基)蒽(2.0克,3.7毫莫耳)被分散於氯苯(40毫升)。分散物被加熱迴流使固體溶解,然後,冷卻至室溫,於是,NBS(1.32克,溶於5毫升DMF,7.4毫莫耳)被添加。混合物攪拌1小時,然後,加熱迴流獲得澄清溶液。溶液被緩慢冷卻至室溫,且於室溫維持隔夜,產生黃色結晶。結晶藉由過濾收集,且以小量甲苯清洗,然
後,於40℃真空乾燥隔夜,產生2.1克之最終產物,呈黃色結晶。HPLC顯示99.2%之純度。
2,7-雙(1,3,2-二噁硼烷-2-基)-9,9-二己基芴(99.9%,8.00毫莫耳,3.82克)、4,7-二溴-2,1,3-苯并噻二唑(99.9%,3.60毫莫耳,1.06克)、雙(4-溴苯基-4-第二丁基苯基)胺(99.9%,0.80毫莫耳,0.37克)、2,7-二溴-9,9-二(4-己氧基苯基)芴(99.8%,3.2毫莫耳,2.17克)、4,7-雙(N-(4-溴苯基)-N-對-甲苯基胺基)-2,1,3-苯并噻二唑(99.2%,0.40毫莫耳,0.264克)、水性碳酸氫鈉(2M,17毫升)、Aliquat 336TM
相轉移劑(Henkel之商標,0.8克)、二氯雙(三苯基膦)鈀(5毫克)及甲苯(~50毫升)被添加至容器。反應混合物於氮氣下攪拌加熱迴流6小時,其後,於甲苯中之溴苯溶液(0.14克,於~10毫升)被攪拌添加。混合物被攪拌加熱至95℃持續15小時,然後,冷卻至室溫。水性相與有機相分離,且有機相以水(2 x~100毫升)清洗,然後,添加至DDC水溶液(3克,於~60毫升之水)。此混合物被加熱至85℃並攪拌18小時,然後冷卻。水性相與有機相分離,以2% v/v乙酸(3 x~200毫升)及水(2 x 200毫升)清洗。有機相通過塞里塑料(1”)、矽石(3”)及氧化鋁(1”)之管柱,並以甲苯洗提。收集之聚咳物部份被混合,且溶液於真空濃縮至300毫升。聚合物於甲醇(~3公升)沈澱,且聚合物纖維藉由過濾收集,且於50℃真空乾燥隔夜。產量係4.5克。藉由GPC對比於聚苯乙烯標準物而決定之Mw=272,800;Mn=111,600;聚分散性=2.45。
2,7-雙(1,3,2-二噁硼烷-2-基)-9,9-e一辛基芴(2.85克,5.37毫莫耳)、2,7-二溴-9,9-雙(4-己氧基苯基)芴(3.06克,4.52毫莫耳)、2,7-雙(4-甲基-4’-溴-二苯基胺基)-9,9-二辛基芴(0.73克,0.80毫莫耳)、AliquatTM
336相轉移劑(0.91克)、反-二氯-雙(三苯基膦)鈀(II)(5毫克)於室溫之250毫升三頸燒瓶內攪拌溶於甲苯(50毫升)。然後,反應混合物加熱迴流,於是,碳酸鈉(2M,11.5毫升)被添加。混合物攪拌約4.8小時,然後,苯基硼酸被添加(0.22克),其後添加甲苯(30毫升),且反應混合物被攪拌加熱隔夜,然後,冷卻。水(10毫升)與反應混合物分離,且有機相以額外之水(100毫升)清洗,然後,添加至二乙基二硫氨基甲酸鈉三水合物之水溶液(DDC,3克,溶於30毫升水中),並於85℃氮氣下加熱攪拌4小時。水(16毫升)與聚合物溶液分離,且溶液以2% v/v水性乙酸(2 x~100毫升)清洗,其後以水清洗(3 x~100毫升)。含有聚合物產物之有機相通過塞里塑料(1”)、矽石(3”)及氧化鋁(1”)之管柱,且以甲苯洗提。聚合物部份被混合,且溶液於真空濃縮,產生約3% w/v之於甲苯中之聚合物溶液。產物沈澱於甲醇內。聚合物於60℃真空乾燥隔夜,且收集之纖維(4.3克)以Al箔空氣覆蓋24小時。纖維被溶於甲苯(170毫升),然後,於甲醇中再次沈澱。纖維被收集,且如前述於真空乾燥,產生4.22克(84.4%產率)。聚合物之GPC分析顯示103,867之數平均分子量(Mn)及303,412之重量平均分子量(Mw),及2.92之聚分散性(Mw/Mn)。
二共聚物溶液使用四氫萘作為溶劑製得。A批共聚物(具Mw=311,000之實施例6組成物)與四氫萘混合,製得0.8%溶液(以重量計),其係藉由於玻璃瓶添加共聚物至四氫萘,然後使玻璃瓶封蓋並於60℃加熱至共聚物完全溶解而製得。然後,溶液被冷卻至室溫。此溶液之黏度於25℃使用錐板式流變計測量,且於600-100/s之剪切範圍以平均值報導。黏度係7.99 cP。B批(第二之0.8重量%組成物)使用具較高分子量之實施例6共聚物批次物(具Mw=438,000之實施例6組成物)以相似方式製得。第二溶液之黏度被測得係10.7 cP。使用簡單之混合物規則,此二溶液以黏度為基準摻合,產生具9.0 cP目標黏度之最終溶液。(見方程式1)。計算預測62.82%之A批溶液及37.18%之B批溶液之摻合比例。此二溶液被混合一段短時間,且黏度再次測量,得9.01cP,與預期非常一致。(第1表)。
方程式1:ηT
=ηA *
wA
+ηB *
wB
=ηA *
wA
+ηB *
(1-wA
)其中,ηT
=目標黏度,ηA
=A批聚合物溶液之黏度,wA
=A批聚合物溶液之重量分率,ηB
=B批聚合物溶液之黏度,wB
=B批聚合物溶液之重量分率
相似之實驗使用1.0重量%之相同聚合物批次物溶液為之(第1表)。於此實驗,最終目標黏度於25℃係12 cP。1.0%之A批次組成物之黏度係10.59 cP,且B批次物係15.24 cP。計算預計個別為69.68:30.32之摻合比例。組成物以此混合,且摻合組成物之黏度測量係12.04 cP,再次係與預期非
常一致。
2,7-雙(1,3,2-二噁硼烷-2-基)-9,9-二辛基芴(2.99克,5.65毫莫耳)、2,7-二溴-9,9-雙(4-己氧基苯基)芴(3.52克,5.19毫莫耳)、1,4-(4-甲基-4’-溴-二苯基胺基)萘(0.40克,0.45毫莫耳)、AliquatTM
336相轉移劑(0.85克)、反-二氯-雙(三苯基膦)鈀(II)(4毫克)於室溫之250毫升三頸燒瓶內溶於甲苯(50毫升)內並攪拌。然後,反應混合物被加熱迴流,於是碳酸鈉(2M,11.5毫升)被添加。混合物被攪拌約24小時,然後,苯基硼酸被添加(0.50克),且反應混合物被攪拌加熱隔夜。混合物被轉移至500毫升圓底燒瓶,且DDC之水性溶液(10克,溶於150毫升之水)於80℃氮氣下加熱攪拌24小時。
水與聚合物溶液分離,且溶液以2% v/v水性乙酸清洗(3 x 300毫升),其後以水清洗(1 x 300毫升)。聚合物自甲醇(2公升)沈澱,藉由過濾收集且以甲醇清洗。過量之甲醇於真空中移除,且聚合物被溶於甲苯(500毫升)。溶液通過以矽石凝膠裝填之管柱,且聚合物以甲苯洗提。含聚合物之部份被濃縮至~200毫升,聚合物自甲醇(2公升)沈澱,藉由過濾收集,且以甲醇清洗。纖維被收集且於60℃真空乾燥,產生4.5克(90%)之材料。聚合物之GPC分析顯示32,118之數
平均分子量(Mn)及95,509之重量平均分子量(Mw),及2.97之聚分散性(Mw/Mn)。
2,7-雙(1,3,2-二噁硼烷-2-基)-9,9-二辛基芴(17.09克,32.22毫莫耳)、2,7-二溴-9,9-雙(4-己氧基苯基)芴(18.32克,27.11毫莫耳)、2,7-雙(4-甲基-4’-溴-二苯基胺基)-9,9-二辛基芴(4.37克,4.79毫莫耳)、AliguatTM
336相轉移劑(4.76克)、反-二氯-雙(三苯基膦)鈀(II)(21.2毫克)於室溫之1000毫升三頸燒瓶中溶於甲苯(300毫升)並攪拌。碳酸鈉(2M,67毫升)被添加至溶液,然後,反應混合物被加熱迴流。混合物被攪拌2.2小時,然後,苯基硼酸被添加(1.2克),其後添加甲苯(130毫升),且反應混合物被攪拌加熱隔夜,然後冷卻。水(60毫升)與反應混合物分離,且有機相以額外之水(400毫升)清洗,然後,添加至二乙基二硫氨基甲酸鈉三水合物之水溶液(DDC,15克,溶於150毫升之水),並於85℃之氮氣下加熱攪拌隔夜。水(15毫升)與聚合物溶液分離,且溶液以2% v/v水性乙酸清洗(2 x~500毫升),其後以水清洗(3 x~500毫升)。聚合物溶液被稀釋至3公升,產生1%之粗製聚合物溶液。1公升之聚合物溶液經由標準程序準備。
2公升之聚合物溶液被作為用以比較另類準備之起始材料。
標準聚合物準備
含有聚合物產物之有機相於體積被降至3% w/v溶液,且沈澱於甲醇。纖維被收集(9.4克),且於60℃真空乾燥隔
夜。纖維被溶於甲苯(500毫升),且聚合物溶液通過矽石(6”)及氧化鋁(2”)之管柱,且以甲苯洗提。聚合物部份被混合,且溶液於真空濃縮,產生於甲苯中之約3% w/v聚合物溶液。產物被沈澱於甲醇。纖維被收集,且如前般於真空乾燥,產生8.43克(84.3%產率)。聚合物之GPC分析顯示155,000之數平均分子量(Mn)及387,000之重量平均分子量(Mw),及2.49之聚分散性(Mw/Mn)。自標準準備之最終產物被作為經由恆濾純化之聚合物溶液之對照組。
恆濾準備
恆濾設備:用於此實施例之恆濾設備係由泵、溶液貯存器及恆濾膜所組成。閥被置放於各不同點以操控壓力、流速及流動方向。膜係由20英吋長之陶瓷管柱所組成,其直徑係1.25英吋,且具有37個縱向通過此管柱之”流動通道”。管壁之公稱孔洞尺寸係100nm。~2公升之貯存器(具連續氮氣淨化)被用以容納模品溶液。
恆濾之起始材料:樣品溶液由~1.0 w/w%之實施例7A之共聚物溶液所組成。殘餘水於溶液中視覺上係明顯的。一部份之溶液使用標準準備程序純化(見上述),以與經由恆濾純化方法純化之聚合物比較。
恆濾:一次恆濾係定義為被移除之滲透物體積等於最初起始溶液體積之點。三次恆濾對一起始溶液為之。補充之甲苯係以200毫升之增量加回貯存器,每一次後,200毫升增量之滲透物被移除。每一添加期間,流動方向被反向~2分鐘。一次恆濾費時約1小時。於每一恆濾後,滲透物及
回流液之樣品被取得以供分析。
測試:樣品係使用尺寸排除色譜術、中子活化分析及裝置性能測試技術分析。如下之第1表顯示恆濾方法結果之綜述。如下之第2表顯示自3X恆濾溶液隔離之聚合物及通過以吸收劑裝填之管柱之溶液之結果比較。
分析:此等表明確顯示恆濾係一種降低聚分散性之有用技術。於此情況,25%之降低於三次恆濾後發生。此降低係藉由移除分子量少於或等於302K道爾頓之聚合物而達成。鈉含量大量下降係於一次恆濾後達成。
三次恆濾與經由標準準備方法純化之比較(第2表)顯示此二技術產生約略相同之結果。此外,當比較第1表之經3X恆濾之溶液樣品與第2表之相對應固體聚合物樣品,明顯地
聚合物隔離方法造成聚分散性進一步變窄。
2,7-雙(1,3,2-二噁硼烷-2-基)-9,9-二己基芴(2.91克,6.12毫莫耳)、2,7-二溴-9,9-雙(4-己氧基苯基)芴(3.66克,5.40毫莫耳)、9,10-雙(4-甲基-4’-溴-二苯基胺基)蒽(0.42克,0.60毫莫耳)、AliquatTM
336相轉移劑(1.22毫升)、及反-二氯-雙(三苯基膦)鈀(II)(4.3毫克)於室溫之250毫升三頸燒瓶內分散於甲苯(75毫升)並攪拌。碳酸鈉水溶液(2M,11.5毫升)被添加,且反應混合物於氮氣下攪拌加熱6小時。然後,於甲苯內之溴苯溶液(0.04克,於~10毫升內)被添加,且加熱及攪拌持續16小時,其後,苯基硼酸(0.3克,溶於10毫升THF內)被添加。加熱及攪拌另持續16小時。冷卻至室溫時,水性相與有機相分離,以水清洗(2 x~100毫升),然後添加至DDC之水溶液(5克,於100毫升水中)。混合物加熱至85℃,攪拌18小時,然後冷卻。水性相與有機相分離,以2% v/v乙酸清洗(3 x~200毫升),然後以水清洗(2 x 200毫升)。有機相通過塞里塑料(1”)、矽石(3”)及氧化鋁(1”)之管柱,且以甲苯洗提。收集之聚合物部份被混合,且溶液於真空濃縮至300毫升。聚合物於甲醇(~3公升)中沈澱,且亮檸檬黃之聚合物纖維藉由過濾收集,且於50℃真空乾燥隔夜。產量係4.1克。以GPC對比於聚苯乙烯標準物而決定之Mw=229,880;Mn=92,700;聚分散性=2.48。
80 nm厚之PEDOT膜被自旋塗覆於乾淨之ITO基材上。經塗覆之基材於200℃乾燥15分鐘。實施例5之共聚物膜係以3% w/v之溶液且以~2500 rpm之自旋速率自旋塗覆於以PEDOT塗覆之基材上,產生約80 nm之塗覆物。聚合物膜於130℃乾燥~1小時。鈣膜(35 nm)於真空中藉由熱蒸發而沈積,其後係Al之蒸發層(150 nm)。形成之元件於直流電壓趨動下發射紅光(CIE座標x=0.668;y=0.327),且亮度於6.4V時達200 cd/m2
,光效率係0.43 cd/A,且亮度於10.6V時達1000 cd/m2
,且光效率係0.39 cd/A。
用以產生實施例9之元件之參數被重複,但LiF薄層(3 nm)先被沈積於聚合物膜上,其後沈積Ca(10 nm)及Al(150 nm)。形成之元件於直流電壓趨動下發射紅光(CIE座標x=0.666;y=0.320),且亮度於6.9V時達200 cd/m2
,光效率係0.40 cd/A,且亮度於11.4V時達1000 cd/m2
,且光效率係0.34 cd/A。
實施例6製得之聚合物(52毫克)被溶於二甲苯(4毫升)。溶液被加熱至60℃,且於經由0.22 uL注射器過濾前搖動至少30分鐘。1:16 w/w之聚乙撐二氧噻吩(PEDOT):聚苯乙烯磺酸(PSS)之80 nm膜被沈積於經清理過之以銦-錫-氧化物(ITO)塗覆之玻璃基材上,且於200℃烘烤15分鐘。聚合物/二甲苯溶液(1.3% w/v)之80 nm膜被自旋塗覆於PEDOT:PSS膜上,且經塗覆之基材於130℃之氮氣下烘烤1
小時。然後,陰極金屬LiF(3 nm)、Ca(10 nm)及Al(150 nm)被真空沈積於聚合物膜上。形成之元件於直流電壓趨動下發射藍光(CIE座標x=0.15;y=0.12),且於4.43V時產生200 cd/m2
之亮度,平均光效率係2.254 cd/A。於10V時,平均亮度被測得係43520 cd/m2
。
80 nm厚之PEDOT膜被自旋塗覆於乾淨之ITO基材上。經塗覆之基材於200℃乾燥15分鐘。然後,實施例8之共聚物膜係以1.3% w/v溶液且以~2500 rpm之自旋速率自旋塗覆於以PEDOT塗覆之基材上,產生約80 nm之塗覆物。聚合物膜於130℃乾燥~1小時,然後,鈣膜(35 nm)藉由真空中熱蒸發而沈積,其後沈積Al蒸發膜(150 nm)。形成之元件於直流電壓趨動下發射綠光(CIE座標x=0.340;y=0.610),且亮度於6.5V時達1000 cd/m2
,光效率係3.32 cd/A,且亮度於11.3V時達10000 cd/m2
,且光效率係4.31 cd/A。
2,7-雙(1,3,2-二噁硼烷-2-基)-9,9-二己基芴(12.3926克,23.366毫莫耳)、2,7-二溴-9,9-(雙(4-己氧基苯基)芴(12.4740克,18.438毫莫耳)、9,10-雙(4-甲基-4’-溴-二苯基胺基)蒽(0.0323克,0.046毫莫耳)、3,7-二溴-N-(4-正丁基苯基)吩噁嗪(2.1895克,4.625毫莫耳)、4,7-雙(2’-溴-5’-硫苯基)-2,1,3-苯并噻二唑(0.0106克,0.023毫莫耳)、
AliquatTM
336相轉移劑(3.1克)及反-二氯-雙(三苯基膦)鈀(II)(16.1毫克)於室溫之1公升三頸燒瓶分散於甲苯(180毫升)內並攪拌。然後,碳酸鈉水溶液(2M,45毫升)被添加,且反應混合物於101℃之氮氣下攪拌加熱2.5小時。然後,苯基硼酸溶液(1克,於~10毫升中)被添加,且加熱攪拌持續20小時。冷卻至室溫時,水性相與有機相分離,以水清洗(2 x~500毫升),然後,添加至DDC水溶液(10克,於50毫升水中)。此混合物被加熱至95℃,攪拌18小時,然後冷卻。水性相與有機相分離,以2% v/v乙酸(2 x~500毫升)清洗,然後以水清洗(2 x 500毫升)。有機相通過塞里塑料(1”)、矽石(3”)及氧化鋁(1”)之管柱,且以甲苯洗提。收集之聚合物部份被混合,且溶液於真空濃縮至1000毫升。聚合物被沈澱於甲醇(~7毫升),且淡橙色聚合物纖維藉由過濾收集,且於50℃真空乾燥隔夜。產量係16.8克。藉由GPC對比於聚苯乙烯標準物而決定之Mw=206,138;Mn=95,600;聚分散性=2.40。
實施例13製得之聚合物(75毫克)被溶於二甲苯(5毫升)。溶液於通過0.22 uL注射器前於室溫搖動隔夜。1:16 w/w聚苯撐二氧噻吩(PEDOT):聚苯乙烯磺酸(PSS)之80 nm膜被沈積於經清理過之以銦-錫-氧化物(ITO)塗覆之玻璃基材上,且於200℃烘烤15分鐘。聚合物/二甲苯(1.5% w/v)之80 nm膜被自旋塗覆於PEDOT:PSS膜上,且經塗覆之基材於130℃之氮氣下烘烤1小時。陰極金屬LiF(3 nm)、Ca(10 nm)
及Al(150 nm)被真空沈積於聚合物膜上。形成之元件於直流電壓趨動下發射白光(CIE座標x=0.371;y=0.355),且於5.83V產生1000 cd/m2
之亮度,平均光效率係4.73 cd/A。於10V時,平均亮度係12,890 cd/m2
。
Claims (8)
- 一種聚合物,其係在主鏈上包含:(i)如以下式所示之結構單元:
- 一種聚合物,其係在主鏈上包含:(i)如以下式所示之結構單元:
- 如申請專利範圍第1或2項之聚合物,其中,Ar係選自甲基苯基、乙基苯基、碳甲氧基苯基、碳乙氧基苯基、甲氧基苯基、乙氧基苯基,及己氧基苯基所組成之族群;且Z係選自2,1,3-苯并噻二唑-4,7-二基、9,9-二取代芴-2,7-二基、萘-1,4-二基、蒽-9,10-二基,及喹噁啉-5,8-二基所組成之族群; 其中該9,9-二取代之芴-2,7-二基之取代基為:C4 -C20 -烷基、C4 -C20 -烷氧基、C7 -C20 -烷基苯基、C7 -C20 -烷氧基苯基或C6 -C40 -芳基。
- 如申請專利範圍第3項之聚合物,其中,Ar係對-甲基苯基,且Z係選自2,1,3-苯并噻二唑-4,7-二基、9,9-雙(4-己氧基苯基)芴-2,7-二基、9,9-二辛基芴-2,7-二基、9,9-二己基芴-2,7-二基、萘-1,4-二基、蒽-9,10-二基,及喹噁啉-5,8-二基所組成之族群。
- 一種組成物,包含申請專利範圍第1或2項之聚合物及該聚合物之溶劑之混合物。
- 一種組成物,包含申請專利範圍第1或2項之聚合物及另一聚合物之混合物。
- 一種電子元件,包含配置於陽極及陰極間之聚合物薄膜,該聚合物係在主鏈上包含:(i)如下式所示之結構單元:
- 如申請專利範圍第7項之電子元件,其中,Ar係對-甲基苯基,且Z係選自2,1,3-苯并噻二唑-4,7-二基、9,9-雙(4-己氧基苯基)芴-2,7-二基、9,9-二辛基芴-2,7-二基、9,9-二己基芴-2,7-二基、萘-1,4-二基、蒽-9,10-二基,及喹噁啉-5,8-二基所組成之族群。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US52007003P | 2003-11-14 | 2003-11-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW200525009A TW200525009A (en) | 2005-08-01 |
TWI386478B true TWI386478B (zh) | 2013-02-21 |
Family
ID=34619427
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW093134729A TWI386478B (zh) | 2003-11-14 | 2004-11-12 | 經鹵化之雙二芳胺基多環芳族化合物及其聚合物 |
TW101107696A TW201229206A (en) | 2003-11-14 | 2004-11-12 | Halogenated bisdiarylaminopolycylic aromatic compounds and polymers thereof |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW101107696A TW201229206A (en) | 2003-11-14 | 2004-11-12 | Halogenated bisdiarylaminopolycylic aromatic compounds and polymers thereof |
Country Status (8)
Country | Link |
---|---|
US (1) | US7651746B2 (zh) |
JP (1) | JP4724666B2 (zh) |
KR (3) | KR101283742B1 (zh) |
CN (1) | CN1894199B (zh) |
DE (1) | DE112004002193B4 (zh) |
GB (1) | GB2422838B (zh) |
TW (2) | TWI386478B (zh) |
WO (1) | WO2005049546A1 (zh) |
Families Citing this family (102)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201219350A (en) * | 2003-11-17 | 2012-05-16 | Sumitomo Chemical Co | Crosslinkable arylamine compounds |
DE102004020299A1 (de) | 2004-04-26 | 2005-12-01 | Covion Organic Semiconductors Gmbh | Konjugierte Polymere, deren Darstellung und Verwendung |
JP5217153B2 (ja) * | 2005-11-18 | 2013-06-19 | 住友化学株式会社 | 高分子化合物およびそれを用いた高分子発光素子 |
DE112006002998T5 (de) | 2005-11-18 | 2008-09-18 | Sumitomo Chemical Co., Ltd. | Polymerverbindung und Polymer enthaltende Licht ermittierende Vorrichtung, die diese verwendet |
US20100176377A1 (en) * | 2005-11-18 | 2010-07-15 | Sumitomo Chemical Company, Limited | Polymeric compound and polymeric electroluminescence element using the same |
US8440324B2 (en) | 2005-12-27 | 2013-05-14 | E I Du Pont De Nemours And Company | Compositions comprising novel copolymers and electronic devices made with such compositions |
WO2007142252A1 (ja) * | 2006-05-31 | 2007-12-13 | Sumitomo Chemical Company, Limited | 高分子化合物および高分子発光素子 |
US20090302748A1 (en) * | 2006-08-01 | 2009-12-10 | Sumitomo Chemical Company, Limited | Polymer compound and polymer light emitting device |
EP2069419A2 (en) | 2006-08-24 | 2009-06-17 | E.I. Du Pont De Nemours And Company | Hole transport polymers |
US8465848B2 (en) | 2006-12-29 | 2013-06-18 | E I Du Pont De Nemours And Company | Benzofluorenes for luminescent applications |
JP5281801B2 (ja) * | 2007-02-01 | 2013-09-04 | 住友化学株式会社 | ブロック共重合体および高分子発光素子 |
JP5374908B2 (ja) * | 2007-04-27 | 2013-12-25 | 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てなる発光素子 |
WO2008143272A1 (ja) * | 2007-05-17 | 2008-11-27 | Sumitomo Chemical Company, Limited | アントラセン系高分子化合物及びそれを用いてなる発光素子 |
US20100140601A1 (en) * | 2007-05-23 | 2010-06-10 | Sumitomo Chemical Company, Limited | Polymer compound and method for producing the same, and light-emitting material, liquid composition, thin film, polymer light-emitting device, surface light source, display device, organic transistor and solar cell, each using the polymer compound |
EP2197981B1 (en) | 2007-06-01 | 2013-04-03 | E. I. Du Pont de Nemours and Company | Green luminescent materials |
JP5453249B2 (ja) | 2007-06-01 | 2014-03-26 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 発光用途のための電荷輸送材料 |
WO2008150942A1 (en) * | 2007-06-01 | 2008-12-11 | E.I. Du Pont De Nemours And Company | Blue luminescent materials |
KR101554750B1 (ko) | 2007-06-01 | 2015-09-22 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 진청색 발광 용도를 위한 크라이센 |
JP2009073808A (ja) * | 2007-08-30 | 2009-04-09 | Sumitomo Chemical Co Ltd | 高分子化合物およびそれを用いた有機光電変換素子 |
US8063399B2 (en) | 2007-11-19 | 2011-11-22 | E. I. Du Pont De Nemours And Company | Electroactive materials |
WO2009066666A1 (ja) * | 2007-11-20 | 2009-05-28 | Idemitsu Kosan Co., Ltd. | 高分子化合物及びそれを用いた有機エレクトロルミネッセンス素子 |
EP2233508A4 (en) * | 2007-12-11 | 2012-01-04 | Idemitsu Kosan Co | POLYMER COMPOUND AND ORGANIC ELECTROLUMINESCENT ELEMENT THEREWITH |
WO2009075203A1 (ja) | 2007-12-11 | 2009-06-18 | Idemitsu Kosan Co., Ltd. | 高分子化合物及びそれを用いた有機エレクトロルミネッセンス素子 |
US8580393B2 (en) | 2008-03-05 | 2013-11-12 | Idemitsu Kosan Co., Ltd. | Polymer and organic electroluminescent device including the same |
US8343381B1 (en) | 2008-05-16 | 2013-01-01 | E I Du Pont De Nemours And Company | Hole transport composition |
GB2488258B (en) | 2008-09-02 | 2013-01-16 | Cambridge Display Tech Ltd | Electroluminescent material and device |
DE102008049037A1 (de) * | 2008-09-25 | 2010-04-22 | Merck Patent Gmbh | Neue Polymere mit niedriger Polydispersität |
US7635792B1 (en) * | 2008-10-14 | 2009-12-22 | General Electric Company | 2,5-linked polyfluorenes for optoelectronic devices |
US8052892B2 (en) | 2008-10-14 | 2011-11-08 | General Electric Company | 2,5-linked polyfluorenes for optoelectronic devices |
US7968004B2 (en) | 2008-10-14 | 2011-06-28 | General Electric Company | 2,5-linked polyfluorenes for optoelectronic devices |
EP2352802A4 (en) * | 2008-12-01 | 2012-10-31 | Du Pont | ELECTROACTIVE MATERIALS |
JP2012510474A (ja) | 2008-12-01 | 2012-05-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 電気活性材料 |
US8263973B2 (en) | 2008-12-19 | 2012-09-11 | E I Du Pont De Nemours And Company | Anthracene compounds for luminescent applications |
US8531100B2 (en) | 2008-12-22 | 2013-09-10 | E I Du Pont De Nemours And Company | Deuterated compounds for luminescent applications |
KR20110131194A (ko) * | 2009-01-30 | 2011-12-06 | 휴렛-팩커드 디벨롭먼트 컴퍼니, 엘.피. | 중합체 및 중합체-나노입자 조성물 |
US8759818B2 (en) | 2009-02-27 | 2014-06-24 | E I Du Pont De Nemours And Company | Deuterated compounds for electronic applications |
JP5567656B2 (ja) | 2009-04-03 | 2014-08-06 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 電気活性材料 |
US20100327735A1 (en) * | 2009-06-29 | 2010-12-30 | General Electric Company | Fluorene dimers and trimers |
CN102834483B (zh) | 2009-08-13 | 2015-07-15 | E.I.内穆尔杜邦公司 | *衍生物材料 |
KR101790854B1 (ko) | 2009-09-29 | 2017-10-26 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 발광 응용을 위한 중수소화된 화합물 |
KR101782660B1 (ko) * | 2009-10-19 | 2017-09-27 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 전자적 응용을 위한 트라이아릴아민 화합물 |
KR20120086319A (ko) | 2009-10-19 | 2012-08-02 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 전자적 응용을 위한 트라이아릴아민 화합물 |
EP2493887A4 (en) | 2009-10-29 | 2013-06-19 | Du Pont | DETERERATED COMPOUNDS FOR ELECTRONIC APPLICATIONS |
US8617720B2 (en) | 2009-12-21 | 2013-12-31 | E I Du Pont De Nemours And Company | Electroactive composition and electronic device made with the composition |
WO2011078391A1 (ja) | 2009-12-25 | 2011-06-30 | 住友化学株式会社 | 組成物及び該組成物を用いてなる発光素子 |
CN102695707A (zh) * | 2009-12-28 | 2012-09-26 | 住友化学株式会社 | 化合物以及使用其的有机电致发光元件 |
WO2012087955A1 (en) | 2010-12-20 | 2012-06-28 | E. I. Du Pont De Nemours And Company | Compositions for electronic applications |
GB2487207B (en) * | 2011-01-12 | 2013-07-31 | Cambridge Display Tech Ltd | Electroluminescence |
GB201107905D0 (en) | 2011-05-12 | 2011-06-22 | Cambridge Display Tech Ltd | Light-emitting material, composition and device |
GB2495107A (en) | 2011-09-28 | 2013-04-03 | Cambridge Display Tech Ltd | Organic light emitting diode display device with further small-area sacrificial diodes |
JP5981440B2 (ja) | 2011-10-19 | 2016-08-31 | 出光興産株式会社 | カルバゾール系重合体とそれを用いた有機エレクトロルミネッセンス素子 |
GB201200619D0 (en) * | 2012-01-16 | 2012-02-29 | Cambridge Display Tech Ltd | Polymer |
CN104321362B (zh) | 2012-03-27 | 2017-02-22 | 住友化学株式会社 | 高分子化合物及使用其的发光元件 |
JP6244653B2 (ja) * | 2012-05-16 | 2017-12-13 | 住友化学株式会社 | 高分子化合物およびそれを用いた発光素子 |
EP3023477B1 (en) | 2013-07-17 | 2019-02-06 | Sumitomo Chemical Company Limited | Composition, and light-emitting element using same |
WO2015050067A1 (ja) | 2013-10-01 | 2015-04-09 | 住友化学株式会社 | 発光素子 |
GB201320881D0 (en) | 2013-11-26 | 2014-01-08 | Cambridge Display Tech Ltd | Organic light-emitting device and method |
KR102326217B1 (ko) | 2014-01-08 | 2021-11-15 | 스미또모 가가꾸 가부시키가이샤 | 금속 착체 및 그것을 사용한 발광 소자 |
CN103992335B (zh) | 2014-04-24 | 2015-04-08 | 京东方科技集团股份有限公司 | 芳香胺衍生物及其制备方法、用途、有机电致发光器件 |
EP3373701A4 (en) | 2015-11-04 | 2019-07-31 | Sumitomo Chemical Company, Limited | METHOD FOR CONTROLLING LIGHT EMITTING ELEMENT AND LIGHT EMITTING DEVICE |
WO2017130828A1 (ja) | 2016-01-28 | 2017-08-03 | 住友化学株式会社 | 膜の製造方法 |
JP6427681B2 (ja) | 2016-01-29 | 2018-11-21 | 住友化学株式会社 | 組成物、燐光発光性化合物及び発光素子 |
WO2017170313A1 (ja) | 2016-03-29 | 2017-10-05 | 住友化学株式会社 | 発光素子 |
JP6943241B2 (ja) | 2016-06-24 | 2021-09-29 | 住友化学株式会社 | 発光素子 |
WO2018062278A1 (ja) | 2016-09-29 | 2018-04-05 | 住友化学株式会社 | 発光素子及び該発光素子の製造に有用な組成物 |
WO2018101331A1 (ja) | 2016-11-30 | 2018-06-07 | 保土谷化学工業株式会社 | 置換トリアリールアミン構造単位を含む高分子量化合物 |
WO2018168667A1 (ja) | 2017-03-15 | 2018-09-20 | 保土谷化学工業株式会社 | 置換トリアリールアミン骨格を有する高分子量化合物 |
WO2018198976A1 (ja) | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | 発光素子 |
CN110574496B (zh) | 2017-04-27 | 2022-01-11 | 住友化学株式会社 | 组合物及使用其的发光元件 |
US11021568B2 (en) | 2017-06-30 | 2021-06-01 | Sumitomo Chemical Company, Limited | Polymer compound and light emitting device using the same |
KR102361349B1 (ko) | 2017-09-06 | 2022-02-14 | 스미또모 가가꾸 가부시키가이샤 | 발광 소자 |
EP3689887A4 (en) | 2017-09-29 | 2021-06-09 | Sumitomo Chemical Company Limited | COMPOSITION AND ELECTROLUMINESCENT DEVICE USING THE SAME |
WO2019065389A1 (ja) | 2017-09-29 | 2019-04-04 | 住友化学株式会社 | 発光素子 |
WO2019208647A1 (ja) | 2018-04-26 | 2019-10-31 | 住友化学株式会社 | ブロック共重合体及びそれを用いた発光素子 |
JP7319251B2 (ja) | 2018-04-26 | 2023-08-01 | 住友化学株式会社 | 発光素子 |
US11999818B2 (en) | 2018-07-03 | 2024-06-04 | Hodogaya Chemical Co., Ltd. | High molecular weight triarylamine compound comprising terphenyl structure in molecular main chain and organic electroluminescent element comprising said high molecular weight compound |
JP6545879B1 (ja) | 2018-10-10 | 2019-07-17 | 住友化学株式会社 | 発光素子用膜及びそれを用いた発光素子 |
JP6595069B1 (ja) | 2018-10-25 | 2019-10-23 | 住友化学株式会社 | 発光素子 |
JP6595070B1 (ja) | 2018-10-25 | 2019-10-23 | 住友化学株式会社 | 発光素子 |
GB2581141A (en) | 2019-01-31 | 2020-08-12 | Sumitomo Chemical Co | Light-emitting composition |
JP6827135B2 (ja) | 2019-03-29 | 2021-02-10 | 住友化学株式会社 | 発光素子及び発光素子用組成物 |
JP6934967B2 (ja) | 2019-03-29 | 2021-09-15 | 住友化学株式会社 | 発光素子及び発光素子用組成物 |
WO2020246404A1 (ja) | 2019-06-05 | 2020-12-10 | 保土谷化学工業株式会社 | 置換トリアリールアミン構造単位を含む高分子量化合物および有機エレクトロルミネッセンス素子 |
JP6941711B2 (ja) | 2019-07-26 | 2021-09-29 | 住友化学株式会社 | 金属錯体及びそれを含有する発光素子 |
CN112342016B (zh) * | 2019-08-08 | 2022-04-12 | 天津大学 | 咔唑二苯胺n-n偶联类衍生物在有机发光器件中降低启亮电压和提高发光效率的应用 |
KR20220079517A (ko) | 2019-10-09 | 2022-06-13 | 호도가야 가가쿠 고교 가부시키가이샤 | 고분자량 화합물로 이루어지는 유기층을 갖는 유기 일렉트로 루미네선스 소자 |
CN111116513B (zh) * | 2019-12-30 | 2021-10-15 | 浙江工业大学 | 一种2,1,3-苯并噻二唑衍生物的定点溴代方法 |
EP4108701A4 (en) | 2020-02-20 | 2024-03-06 | Hodogaya Chemical Co., Ltd. | HIGH MOLECULAR WEIGHT COMPOUND AND LIGHT EMITTING DIODE COMPRISING SAID HIGH MOLECULAR WEIGHT COMPOUND |
JP7216754B2 (ja) | 2020-03-31 | 2023-02-01 | 住友化学株式会社 | 組成物及びそれを含有する発光素子 |
JP6956287B2 (ja) | 2020-04-21 | 2021-11-02 | 住友化学株式会社 | 金属錯体、組成物及び発光素子 |
JP2022024744A (ja) | 2020-07-28 | 2022-02-09 | 住友化学株式会社 | 組成物及び発光素子 |
KR20230071117A (ko) | 2020-09-23 | 2023-05-23 | 호도가야 가가쿠 고교 가부시키가이샤 | 열가교성 저분자 화합물을 포함하는 발광 다이오드용 조성물 |
JP7086259B2 (ja) | 2020-09-24 | 2022-06-17 | 住友化学株式会社 | 発光素子及び組成物 |
JP7086258B2 (ja) | 2020-09-24 | 2022-06-17 | 住友化学株式会社 | 発光素子及び組成物 |
JP7079883B2 (ja) | 2020-09-24 | 2022-06-02 | 住友化学株式会社 | 発光素子及び組成物 |
JP7015406B1 (ja) | 2020-09-24 | 2022-02-02 | 住友化学株式会社 | 発光素子及び組成物 |
JP7058792B2 (ja) | 2020-09-24 | 2022-04-22 | 住友化学株式会社 | 発光素子及び組成物 |
KR20230156317A (ko) | 2021-03-12 | 2023-11-14 | 호도가야 가가쿠 고교 가부시키가이샤 | 인데노디벤조헤테롤 구조를 부분 구조로서 갖는 고분자량화합물, 및 이들 고분자량 화합물을 함유하는 유기 일렉트로루미네선스 소자 |
CN117295779A (zh) | 2021-05-21 | 2023-12-26 | 保土谷化学工业株式会社 | 三芳基胺高分子量化合物以及包含其高分子量化合物的有机电致发光元件 |
CN114014742B (zh) * | 2021-11-01 | 2024-05-10 | 上海八亿时空先进材料有限公司 | 一种三芳基苯衍生物、发光材料、发光元件及消费型产品 |
TW202406972A (zh) | 2022-07-07 | 2024-02-16 | 日商保土谷化學工業股份有限公司 | 高分子量化合物及使用其等之有機電致發光元件 |
JP2024127866A (ja) | 2023-03-08 | 2024-09-20 | 保土谷化学工業株式会社 | 高分子量化合物および有機エレクトロルミネッセンス素子 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0525473A (ja) * | 1991-07-22 | 1993-02-02 | Mitsui Toatsu Chem Inc | 有機電界発光素子 |
JP2003316044A (ja) * | 2002-04-26 | 2003-11-06 | Canon Inc | 電子写真感光体、プロセスカートリッジおよび電子写真装置 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4853308A (en) | 1987-11-09 | 1989-08-01 | Xerox Corporation | Photoresponsive imaging members with fluorene hole transporting layers |
US4983482A (en) | 1989-04-03 | 1991-01-08 | Xerox Corporation | Photoconductive imaging members with polyurethane hole transporting layers |
JP3463358B2 (ja) * | 1994-07-08 | 2003-11-05 | 東洋インキ製造株式会社 | 正孔輸送材料およびその用途 |
JP2686418B2 (ja) * | 1994-08-12 | 1997-12-08 | 東洋インキ製造株式会社 | ジアリールアミン誘導体、その製造方法及び用途 |
JP3865406B2 (ja) | 1995-07-28 | 2007-01-10 | 住友化学株式会社 | 2,7−アリール−9−置換フルオレン及び9−置換フルオレンオリゴマー及びポリマー |
EP1146034A1 (en) * | 1995-09-25 | 2001-10-17 | Toyo Ink Manufacturing Co., Ltd. | Light-emitting material for organic electroluminescence device, and organic electroluminescence device for which the light-emitting material is adapted |
US5932383A (en) * | 1996-08-08 | 1999-08-03 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member and process cartridge and electrophotographic apparatus including same |
DE69804529T2 (de) * | 1997-05-19 | 2002-10-02 | Canon Kk | Organisches Material und elektrolumineszente Vorrichtung dasselbe nutzend |
US6309763B1 (en) | 1997-05-21 | 2001-10-30 | The Dow Chemical Company | Fluorene-containing polymers and electroluminescent devices therefrom |
US5879821A (en) | 1997-11-13 | 1999-03-09 | Xerox Corporation | Electroluminescent polymer compositions and processes thereof |
EP0953624B1 (en) * | 1998-04-28 | 2004-02-04 | Canon Kabushiki Kaisha | Triarylamine compound and luminescent device |
JP4220644B2 (ja) * | 2000-02-14 | 2009-02-04 | 三井化学株式会社 | アミン化合物および該化合物を含有する有機電界発光素子 |
JP2002003833A (ja) * | 2000-06-23 | 2002-01-09 | Toyo Ink Mfg Co Ltd | 有機エレクトロルミネッセンス素子用発光材料およびそれを使用した有機エレクトロルミネッセンス素子 |
DE60234029D1 (de) * | 2001-06-22 | 2009-11-26 | Cambridge Display Tech Ltd | Polymer enthaltend substituierte triphenylamin-einheiten |
JP4174391B2 (ja) * | 2002-08-30 | 2008-10-29 | キヤノン株式会社 | 電子写真感光体、プロセスカートリッジおよび電子写真装置 |
DE10249723A1 (de) | 2002-10-25 | 2004-05-06 | Covion Organic Semiconductors Gmbh | Arylamin-Einheiten enthaltende konjugierte Polymere, deren Darstellung und Verwendung |
EP1437395B2 (en) * | 2002-12-24 | 2015-08-26 | LG Display Co., Ltd. | Organic electroluminescent device |
US7651788B2 (en) * | 2003-03-05 | 2010-01-26 | Lg Display Co., Ltd. | Organic electroluminescent device |
-
2004
- 2004-11-03 WO PCT/US2004/036707 patent/WO2005049546A1/en active Application Filing
- 2004-11-03 KR KR1020127021166A patent/KR101283742B1/ko active IP Right Grant
- 2004-11-03 CN CN200480033613XA patent/CN1894199B/zh not_active Expired - Fee Related
- 2004-11-03 DE DE112004002193.6T patent/DE112004002193B4/de not_active Expired - Fee Related
- 2004-11-03 KR KR1020117030381A patent/KR20120003975A/ko active IP Right Grant
- 2004-11-03 GB GB0609500A patent/GB2422838B/en not_active Expired - Fee Related
- 2004-11-03 US US10/579,215 patent/US7651746B2/en not_active Expired - Lifetime
- 2004-11-03 JP JP2006539638A patent/JP4724666B2/ja not_active Expired - Lifetime
- 2004-11-12 TW TW093134729A patent/TWI386478B/zh active
- 2004-11-12 TW TW101107696A patent/TW201229206A/zh unknown
-
2006
- 2006-05-12 KR KR1020067009295A patent/KR101209977B1/ko active IP Right Grant
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0525473A (ja) * | 1991-07-22 | 1993-02-02 | Mitsui Toatsu Chem Inc | 有機電界発光素子 |
JP2003316044A (ja) * | 2002-04-26 | 2003-11-06 | Canon Inc | 電子写真感光体、プロセスカートリッジおよび電子写真装置 |
Also Published As
Publication number | Publication date |
---|---|
KR101209977B1 (ko) | 2012-12-07 |
GB2422838B (en) | 2009-04-08 |
KR20120003975A (ko) | 2012-01-11 |
KR20060107776A (ko) | 2006-10-16 |
KR101283742B1 (ko) | 2013-07-08 |
CN1894199B (zh) | 2011-04-13 |
GB0609500D0 (en) | 2006-06-21 |
JP4724666B2 (ja) | 2011-07-13 |
US20070126345A1 (en) | 2007-06-07 |
US7651746B2 (en) | 2010-01-26 |
DE112004002193B4 (de) | 2017-03-23 |
DE112004002193T5 (de) | 2006-10-12 |
GB2422838A (en) | 2006-08-09 |
JP2007512249A (ja) | 2007-05-17 |
TW201229206A (en) | 2012-07-16 |
KR20120094531A (ko) | 2012-08-24 |
WO2005049546A1 (en) | 2005-06-02 |
CN1894199A (zh) | 2007-01-10 |
TW200525009A (en) | 2005-08-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI386478B (zh) | 經鹵化之雙二芳胺基多環芳族化合物及其聚合物 | |
JP5069401B2 (ja) | ポリマー及びその製造方法 | |
Ego et al. | Triphenylamine‐Substituted Polyfluorene—A Stable Blue‐Emitter with Improved Charge Injection for Light‐Emitting Diodes | |
JP5197911B2 (ja) | 三環アリールアミンモノマー及びポリマー及びそのデバイス | |
KR102013007B1 (ko) | 비대칭 다이아릴아미노플루오렌 단위를 포함하는 중합체 | |
KR102020083B1 (ko) | 중합체 | |
CN102959758A (zh) | 有机发光材料、器件和方法 | |
JP5819581B2 (ja) | ポリマー及びその製造方法 | |
Ma et al. | Recent progress in fluorescent blue light-emitting materials | |
KR20080111968A (ko) | 불소기를 포함하는 전기발광고분자 및 이를 이용한전기발광소자 | |
JP5352968B2 (ja) | 高分子化合物および高分子発光素子 | |
JP6139405B2 (ja) | 有機発光デバイスおよび方法 | |
GB2488258A (en) | Electroluminescent copolymer | |
KR20170048424A (ko) | 유기 발광 조성물, 소자 및 방법 | |
JP2009001777A (ja) | 高分子化合物及びその製造方法、並びに、その高分子化合物を用いた発光材料、液状組成物、薄膜、高分子発光素子、面状光源、表示装置、有機トランジスタ及び太陽電池 | |
JP2007515041A5 (zh) | ||
KR20080103772A (ko) | 트리페닐 아민기를 포함하는 유기 전기발광고분자 및 이를이용한 유기 전기발광소자 | |
US10870726B2 (en) | Polymer |