CN107312164B - Conjugated polymer and its polymerization and application based on ferrocene and phenanthroline derivative - Google Patents
Conjugated polymer and its polymerization and application based on ferrocene and phenanthroline derivative Download PDFInfo
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- CN107312164B CN107312164B CN201710429907.3A CN201710429907A CN107312164B CN 107312164 B CN107312164 B CN 107312164B CN 201710429907 A CN201710429907 A CN 201710429907A CN 107312164 B CN107312164 B CN 107312164B
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 25
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title description 17
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 title description 3
- 238000006116 polymerization reaction Methods 0.000 title description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011368 organic material Substances 0.000 claims abstract 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 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 230000001699 photocatalysis Effects 0.000 claims description 8
- -1 (2- diphenylphosphinoethyl) phosphorus Chemical compound 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical class C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000006539 C12 alkyl 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])C([H])([H])C([H])([H])* 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].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.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 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229930192474 thiophene Chemical class 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- VLQATFWRXJHWJB-UHFFFAOYSA-N azane tetrahydrochloride Chemical compound N.N.Cl.Cl.Cl.Cl VLQATFWRXJHWJB-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- FSRXIRGQJIHEFB-UHFFFAOYSA-N diphenylphosphane;ethane Chemical class CC.C=1C=CC=CC=1PC1=CC=CC=C1 FSRXIRGQJIHEFB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical class S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- AXVOAMVQOCBPQT-UHFFFAOYSA-N triphos Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 AXVOAMVQOCBPQT-UHFFFAOYSA-N 0.000 claims 1
- 239000003504 photosensitizing agent Substances 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QALMOXHIAPMJAB-UHFFFAOYSA-N 4,7-bis(4-bromophenyl)-1,10-phenanthroline Chemical compound C1=CC(Br)=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC(Br)=CC=3)C=CN=C21 QALMOXHIAPMJAB-UHFFFAOYSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- RKEZHXGBECEYGM-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) 5-propylcyclopenta-1,3-diene Chemical compound [Fe++].c1cc[cH-]c1.CCC[c-]1cccc1 RKEZHXGBECEYGM-UHFFFAOYSA-N 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- 150000005045 1,10-phenanthrolines Chemical class 0.000 description 1
- MQYIUZOSUACUCU-UHFFFAOYSA-N C1(=CC=CC=C1)P(CC[P]C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)P(CC[P]C1=CC=CC=C1)C1=CC=CC=C1 MQYIUZOSUACUCU-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229930008407 benzylideneacetone Natural products 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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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
- C08G61/12—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/124—Copolymers alternating
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/145—Side-chains containing sulfur
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/145—Side-chains containing sulfur
- C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
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Abstract
The present invention provides conjugated polymers shown in a kind of formula (I); preparation method are as follows: under inert gas shielding; formula (III) compound represented and formula (IV) compound represented are dissolved in organic solvent; alkaline matter, palladium catalyst, phosphorus ligand is added; 12~120h is reacted at 20~150 DEG C, reaction solution is post-treated later obtains target product；The conjugated polymer can be applied to preparation as luminous organic material, photosensitizer or catalyst；
Description
Technical field
The invention belongs to new material technology fields, and in particular to ferrocene and being total to phenanthroline derivative bifunctional
Conjugated polymer and its polymerization and the application in luminous organic material, photocatalytic system.
Background technique
The energy is various countries' the lifeline of economy, is the power of modern social development.However energy crisis and fossil energy pollution
Always " sword of Damokers " of countries in the world, therefore it is extremely urgent to seek sustainable cleaning new energy.Utilize solar energy
Directly decomposing water makes its luminous energy be converted into hydrogen chemical energy, is the study frontier of current Solar use.Efficient stable, it is inexpensive,
Nontoxic light energy transforming composite (photosensitizer) is the core material in photodissociation aqueous systems, and restricts the efficiency of solar energy utilization at present
Critical issue.
Inorganic, metal oxide, sulfide, the photochemical catalyst based on nitride have been used for photodissociation aqueous systems, the gold at center
Belonging to ion usually has d0And d10Electronic structure.But because its structure and performance are difficult to carry out the tune of system on a molecular scale
It is whole, thus limit the adjusting of inorganic metal photochemical catalyst physical and chemical performance.Also, this kind of photochemical catalysts usually require
Noble metal is added, to enhance the transfer of carrier in hole, to improve photocatalysis performance.
1,10- phenanthroline derivative is made of multiple big plane of a loop conjugation, and complex early has been used for photocatalytic water system, this
Invention is intended to aggregate into 1,10- phenanthroline and ferrocene with delocalization π-system copolymer, and is used for photodissociation water body
System.
Summary of the invention
It is an object of the present invention to provide a kind of novel conjugated polymers, while providing preparation method, and in organic hair
Application in luminescent material, photocatalytic system
The technical solution adopted by the invention is as follows:
A kind of conjugated polymer, molecular structure are as shown in following formula (I):
In formula (I),
R1For phenyl, C1~C12 alkyl-substituted phenyl, naphthalene, thiophene, furans or thieno [3,2-b] thiophene, carbazole；It is excellent
Select R1For 4 substituted-phenyls,
R2For hydrogen, C1~C12 alkyl, phenyl or carbazole；It is preferred that R2For hydrogen；
R3And R4It is respectively hydrogen, C1~C12 alkyl, phenyl；It is preferred that R3、R4For hydrogen.
Preferably, in conjugated polymer of the present invention, R1It is substituted in the 4 of phenanthroline, 7, R2It is substituted in phenanthroline
2,9, i.e. polymer shown in formula (II):
The present invention also provides a kind of preparation method of conjugated polymer shown in formula (I), the preparation methods
Are as follows:
Under inert gas shielding, formula (III) compound represented and formula (IV) compound represented are dissolved in organic solvent
In, alkaline matter, palladium catalyst, phosphorus ligand is added, 12~120h is reacted at 20~150 DEG C, reaction solution is post-treated later
Obtain target product；
In formula (III), X is halogen or sulfonyl.
In preparation method of the present invention,
Formula (IV) compound represented and formula (III) compound represented, alkaline matter the substance that feeds intake amount it
Than being 1: 1~20: 1~100, preferably 1: 1~5: 3-10, particularly preferred 1: 2: 3.
The volumetric usage of the organic solvent is calculated as 1~1000mL/g with the quality of formula (III) compound represented, preferably
10~50mL/g.
The alkaline matter be potassium hydroxide, sodium hydroxide, cesium carbonate, potassium carbonate, sodium carbonate, sodium hydride, sodium methoxide,
The mixture of one of sodium ethoxide, potassium tert-butoxide, potassium phosphate or two or more arbitrary proportions, most preferably potassium carbonate.
The organic solvent be benzene, toluene, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, ether, the alcohol of C1~C6, DMF,
The mixed solvent of one of DMAc, C4~C8 alkane or two or more arbitrary proportions；Most preferably DMF.
The palladium catalyst is tetrakis triphenylphosphine palladium [Pd (PPh3)4], palladium acetate [Pd (OAc)2], three (dibenzylidenes
Acetone) two palladium [Pd2(dba)3], palladium acetylacetonate [Pd (acac)2], palladium charcoal [Pd/C], tetrachloro close palladium acid [H2PdCl4], tetrachloro
Palladium acid sodium [Na2PdCl4], palladium tetrachloride diammonium [(NH4)2PdCl4], four ammonia palladium [Pd (NH of dichloro3)4Cl2], most preferably acetic acid
Palladium.
The phosphorus ligand is triphenylphosphine [PPh3], bis- (the diphenylphosphine ethane) [Ph2PCH of 1,2-2CH2PPh2], it is double
(2- diphenylphosphinoethyl) phenyl phosphorus [(Ph2PCH2CH2)2PPh], three (2- diphenylphosphinoethyl) phosphorus [(Ph2PCH2CH2)3P]、
4,5- bis- diphenylphosphine -9,9- xanthphos；Most preferably triphenyl phosphorus.
The post-processing approach of the reaction solution are as follows: after reaction, at room temperature, reaction solution is slowly dropped into water simultaneously constantly
Stirring is filtered after solid is precipitated, and obtains target product after the solid filtered out is dry.
Compared with prior art, the beneficial effects of the present invention are: polymerize using Heck reaction, prepared this is poly-
Closing object can be applied to luminous organic material, photocatalytic system etc..
Detailed description of the invention
Fig. 1: the uv-visible absorption spectra of formula (I), 1,2,3,4 respectively corresponds conjugation synthesized by embodiment 1,2,3,4
Polymer.
Specific embodiment:
In conjunction with attached drawing, below the technical scheme of the invention is illustrated by a specific example, but protection scope of the present invention is not
It is limited to this:
1 ferrocene of embodiment and 4, the preparation of 7- bis- (4- bromophenyl) -1,10- phenanthroline conjugated copolymer
Under inert gas shielding, by ferrocene (1mmol, 0.186g) and 4,7- bis- (4- bromophenyl) -1,10- phenanthroline
(2mmol, 0.980g) is dissolved in n,N-Dimethylformamide, be added potassium carbonate (3mmol, 0.414g), palladium acetate (0.2mmol,
0.045g), triphenylphosphine (0.6mmol, 0.157g), reacts 72h, the detection of TLC contact plate at 120 DEG C, and raw material point disappears.It is cooling
To room temperature, reaction solution is slowly dropped into distilled water, there are a large amount of black solids to generate.Filtering, obtains conjugated polymer 0.371g,
Yield 55.1%.
2 ferrocene of embodiment and 4, the preparation of 7- bis- (4- chlorphenyl) -1,10- phenanthroline conjugated copolymer
Under inert gas shielding, by ferrocene (1mmol, 0.186g) and 4,7- bis- (4- chlorphenyl) -1,10- phenanthroline
(2mmol, 0.802g) is dissolved in dimethyl sulfoxide, be added potassium carbonate (3mmol, 0.414g), palladium acetate (0.2mmol, 0.045g),
Triphenylphosphine (0.6mmol, 0.157g), reacts 48h, the detection of TLC contact plate at 120 DEG C, and raw material point disappears.It is cooled to room temperature,
Reaction solution is slowly dropped into distilled water, there are a large amount of black solids to generate.Filtering, obtains conjugated polymer 0.270g, yield
46.0%.
3 ferrocene of embodiment and 2,9- diisopropyl -4,7- bis- (4- bromophenyl) -1,10- phenanthroline conjugated copolymer
Preparation
Under inert gas shielding, by ferrocene (1mmol, 0.186g) and 2,9- diisopropyl -4,7- bis- (4- bromophenyl) -
1,10- phenanthroline (2mmol, 1.148g) is dissolved in n,N-Dimethylformamide, and potassium carbonate (3mmol, 0.414g), three (two is added
BENZYLIDENE ACETONE) two palladiums (0.2mmol, 0.183g), triphenylphosphine (0.6mmol, 0.157g), react 72h, TLC at 150 DEG C
Contact plate detection, raw material point disappear.It is cooled to room temperature, reaction solution is slowly dropped into distilled water, there are a large amount of black solids to generate.It crosses
Filter, obtains conjugated polymer 0.593g, yield 78%.
4 ferrocene of embodiment and 4, the preparation of 7- bis- [2- (5- bromine) thienyl] -1,10- phenanthroline conjugated copolymer
Under inert gas shielding, ferrocene (1mmol, 0.186g) and 4,7- bis- [2- (5- bromine) thiophene] -1,10- phenanthrene are coughed up
Quinoline (3mmol, 1.506g) is dissolved in tetrahydrofuran, be added potassium carbonate (3mmol, 0.414g), palladium acetate (0.2mmol, 0.045g),
Triphenylphosphine (0.6mmol, 0.157g), flow back 72h at 78 DEG C, and TLC contact plate detection, raw material point disappears.It is cooled to room temperature, it will
Reaction solution is slowly dropped into distilled water, has a large amount of black solids to generate.Filtering, obtains conjugated polymer 0.265g, yield
38.6%.
5 ferrocene of embodiment and 4, the preparation of 7- bis- (4- methanesulfonylphenYl) -1,10- phenanthroline conjugated copolymer
It is under inert gas shielding, ferrocene (1mmol, 0.186g) and 4,7- bis- (4- methanesulfonylphenYl) -1,10- is luxuriant and rich with fragrance
It coughs up quinoline (2mmol, 0.980g) and is dissolved in n,N-Dimethylformamide, potassium carbonate (3mmol, 0.414g), four (triphenylphosphines) is added
Bis- diphenylphosphine -9, the 9- xanthphos (0.6mmol, 0.347g) of palladium (0.2mmol, 0.231g), 4,5-, at 120 DEG C
72h, the detection of TLC contact plate are reacted, raw material point disappears.It is cooled to room temperature, reaction solution is slowly dropped into distilled water, there is a large amount of black
Solid generates.Filtering, obtains conjugated polymer 0.288g, yield 42.5%.
6 propyl ferrocene of embodiment and 4, the preparation of 7- bis- (4- bromophenyl) -1,10- phenanthroline conjugated copolymer
Under inert gas shielding, by ferrocene (1mmol, 0.228g) and 4,7- bis- (4- bromophenyl) -1,10- phenanthroline
(2mmol, 0.980g) is dissolved in n,N-Dimethylformamide, and potassium carbonate (3mmol, 0.414g), palladium acetylacetonate is added
(0.3mmol, 0.091g), triphenylphosphine (0.6mmol, 0.157g) reacts 60h, the detection of TLC contact plate, raw material point at 120 DEG C
It disappears.It is cooled to room temperature, reaction solution is slowly dropped into distilled water, there are a large amount of black solids to generate.Filtering, obtains conjugated polymers
Object 0.331g, yield 46.2%.
7 propyl ferrocene of embodiment and 2,9- diisopropyl -4,7- bis- (4- bromophenyl) -1,10- phenanthroline conjugation copolymerization
The preparation of object
Under inert gas shielding, by propyl ferrocene (1mmol, 0.228g) and (the 4- bromobenzene of 2,9- diisopropyl -4,7- bis-
Base) -1,10- phenanthroline (2mmol, 1.148g) is dissolved in dimethyl sulfoxide, potassium carbonate (3mmol, 0.414g), palladium acetate is added
(0.2mmol, 0.045g), triphenylphosphine (0.6mmol, 0.157g) reacts 48h, the detection of TLC contact plate, raw material point at 120 DEG C
It disappears.It is cooled to room temperature, reaction solution is slowly dropped into distilled water, there are a large amount of black solids to generate.Filtering, obtains conjugated polymers
Object 0.391g, yield 48.7%.
8 certain herbaceous plants with big flowers base ferrocene of embodiment and 4, the preparation of 7- bis- (4- bromophenyl) -1,10- phenanthroline conjugated copolymer
Under inert gas shielding, by ferrocene (1mmol, 0.326g) and 4,7- bis- (4- bromophenyl) -1,10- phenanthroline
(2mmol, 0.980g) is dissolved in n,N-Dimethylformamide, be added potassium carbonate (3mmol, 0.414g), palladium acetate (0.2mmol,
0.045g), triphenylphosphine (0.6mmol, 0.157g), reacts 120h, the detection of TLC contact plate at 120 DEG C, and raw material point disappears.It is cold
But to room temperature, reaction solution is slowly dropped into distilled water, there are a large amount of black solids to generate.Filtering, obtains conjugated polymer
0.327g, yield 40.1%.
Application of the conjugated polymer in solar energy photocatalytic water shown in 1 formula of Application Example (I)
In anaerobic container, polymer (50mg) and Cu (I) (MeCN) made from embodiment 2 is added4PF6(1.31mg, 3.5
μm ol), THF/Et3N/H2Catalyst Fe is added after stirring several minutes in O (4: 3: 1, volume ratio) mixed solvent 10mL3(CO)12
(2.6mg, 5 μm of ol), 150W xenon lamp irradiate 12 hours, obtain 6.8mL hydrogen.
Application after conjugated polymer shown in 2 formula of Application Example (I) and Phosphine ligands coordination in solar energy photocatalytic water
In anaerobic container, polymer (50mg), Cu (I) (MeCN) made from embodiment 2 is added4PF6(1.31mg, 3.5 μ
Mol) and Phosphine ligands (2.02mg, 3.5 μm of ol), THF/Et3N/H2O (4: 3: 1, volume ratio) mixed solvent 10mL is stirred several minutes
After catalyst Fe is added3(CO)12(2.6mg, 5 μm of ol), 150W xenon lamp irradiate 12 hours, obtain 7.4mL hydrogen.
Claims (10)
1. conjugated polymer shown in a kind of formula (I):
In formula (I),
R1For the following group of divalent: phenyl, C1~C12 alkyl-substituted phenyl, naphthalene, thiophene, furans or thieno [3,2-b] thiophene
Pheno, carbazole；
R2For hydrogen, C1~C12 alkyl, phenyl or carbazole；
R3And R4It is respectively hydrogen, C1~C12 alkyl, phenyl.
2. conjugated polymer as described in claim 1, which is characterized in that in formula (I), R1For 4 substituted-phenyls of divalent, R2For
Hydrogen, R3、R4For hydrogen.
3. conjugated polymer as described in claim 1, which is characterized in that the conjugated polymer is to tie shown in formula (II)
Structure:
4. a kind of preparation method of conjugated polymer as described in claim 1, which is characterized in that it is described the preparation method comprises the following steps:
Under inert gas shielding, formula (III) compound represented and formula (IV) compound represented are dissolved in organic solvent, added
Enter alkaline matter, palladium catalyst, phosphorus ligand, 12~120h is reacted at 20~150 DEG C, reaction solution is post-treated later obtains mesh
Mark product；
In formula (III), X is halogen or sulfonyl.
5. preparation method as claimed in claim 4, which is characterized in that formula (IV) compound represented and formula (III) institute
The ratio between amount for the substance that feeds intake of the compound, alkaline matter that show is 1:1~20:1~100.
6. preparation method as claimed in claim 4, which is characterized in that the organic solvent be benzene, toluene, tetrahydrofuran,
The mixed solvent of one of Isosorbide-5-Nitrae-dioxane, ether, the alcohol of C1~C6, DMF, DMAc or two or more arbitrary proportions,
The volumetric usage of the organic solvent is calculated as 1~1000mL/g with the quality of formula (III) compound represented；The basic species
Matter is potassium hydroxide, sodium hydroxide, cesium carbonate, potassium carbonate, sodium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, phosphoric acid
The mixture of one of potassium or two or more arbitrary proportions.
7. preparation method as claimed in claim 4, which is characterized in that the palladium catalyst and formula (IV) compound represented
The ratio between the amount of substance of feeding intake is 1:1~10；The palladium catalyst is tetrakis triphenylphosphine palladium [Pd (PPh3)4], palladium acetate [Pd
(OAc)2], tris(dibenzylideneacetone) dipalladium [Pd2(dba)3], palladium acetylacetonate [Pd (acac)2], palladium charcoal [Pd/C], tetrachloro
Close palladium acid [H2PdCl4], sodium tetrachloropallate [Na2PdCl4], palladium tetrachloride diammonium [(NH4)2PdCl4] or four ammonia palladium [Pd of dichloro
(NH3)4Cl2]。
8. preparation method as claimed in claim 4, which is characterized in that the throwing of the phosphorus ligand and formula (IV) compound represented
The ratio between amount of material matter is 1:1~8；The phosphorus ligand is triphenylphosphine [PPh3], 1,2- bis- (diphenylphosphine ethanes)
[Ph2PCH2CH2PPh2], bis- (2- diphenylphosphinoethyl) phenyl phosphorus [(Ph2PCH2CH2)2PPh], three (2- diphenylphosphinoethyl) phosphorus
[(Ph2PCH2CH2)3P] or the bis- diphenylphosphine -9,9- xanthphos of 4,5-.
9. preparation method as claimed in claim 4, which is characterized in that the post-processing approach of the reaction solution are as follows: reaction terminates
Afterwards, at room temperature, reaction solution is slowly dropped into water and is stirred continuously, filtered after solid is precipitated, obtained after the solid filtered out is dry
Target product.
10. the application of conjugated polymer as described in claim 1, which is characterized in that be used for luminous organic material and photocatalysis body
System.
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