CN106046044A - Bisfluoro fluorene monomer as well as conjugated polymer and synthesis process thereof - Google Patents
Bisfluoro fluorene monomer as well as conjugated polymer and synthesis process thereof Download PDFInfo
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- CN106046044A CN106046044A CN201610475148.XA CN201610475148A CN106046044A CN 106046044 A CN106046044 A CN 106046044A CN 201610475148 A CN201610475148 A CN 201610475148A CN 106046044 A CN106046044 A CN 106046044A
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- 239000000178 monomer Substances 0.000 title claims abstract description 33
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 18
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title abstract 14
- 230000008569 process Effects 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 41
- IAGDDPYFLFGQCX-UHFFFAOYSA-N 1-fluoro-9h-fluorene Chemical class C12=CC=CC=C2CC2=C1C=CC=C2F IAGDDPYFLFGQCX-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000004044 response Effects 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 5
- OHOVBSAWJQSRDD-UHFFFAOYSA-N thiophen-2-yloxyboronic acid Chemical compound OB(O)OC1=CC=CS1 OHOVBSAWJQSRDD-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- CTFNJPHOILFHEL-UHFFFAOYSA-N CC1=C(C=CC=C1)[P] Chemical compound CC1=C(C=CC=C1)[P] CTFNJPHOILFHEL-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Chemical group 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 235000021050 feed intake Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 claims 1
- 229930008407 benzylideneacetone Natural products 0.000 claims 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 12
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000013086 organic photovoltaic Methods 0.000 abstract 2
- 238000006619 Stille reaction Methods 0.000 abstract 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- -1 tetrabutyl ammonium hexafluorophosphate Acetonitrile Chemical compound 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 229940125898 compound 5 Drugs 0.000 description 5
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 0 *C(*)(c(cc(-c1ccc(*)[s]1)c(F)c1)c1-c1c2)c1cc(-c1ccc(*)[s]1)c2F Chemical compound *C(*)(c(cc(-c1ccc(*)[s]1)c(F)c1)c1-c1c2)c1cc(-c1ccc(*)[s]1)c2F 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 150000002220 fluorenes Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 235000008504 concentrate Nutrition 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 235000014666 liquid concentrate Nutrition 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LYIWMQYRSIWOGU-UHFFFAOYSA-N 3,6-dibromo-9h-fluorene Chemical class C1=C(Br)C=C2C3=CC(Br)=CC=C3CC2=C1 LYIWMQYRSIWOGU-UHFFFAOYSA-N 0.000 description 1
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical class BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910004003 H5IO6 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- TWLXDPFBEPBAQB-UHFFFAOYSA-N orthoperiodic acid Chemical compound OI(O)(O)(O)(O)=O TWLXDPFBEPBAQB-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
-
- 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
- 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
-
- 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
- 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
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the field of synthesis of organic compounds, relates to a novel polymer applied to the field of organic photovoltaic devices and particularly relates to a novel bisfluoro fluorene monomer and preparation of a conjugated polymer material of the novel bisfluoro fluorene monomer. Fluorine atoms capable of powerfully withdrawing electrons are introduced into a fluorene structure and an alkyl chain on the fluorene is adjusted to obtain the bisfluoro fluorene monomer. By adopting a stille coupling polymerization method, the novel bisfluoro fluorene monomer is polymerized with a series of acceptor monomers to obtain the bisfluoro fluorene conjugated polymer which can be used as a very good donor material to be applied to the field of the organic photovoltaic devices.
Description
Technical field
The invention belongs to organic compound synthesis field, invention relates to a kind of being applied to the novel of organic electro-optic device field
Monomer and polymer, relate particularly to a kind of double fluoro fluorenes class monomer, its conjugated polymer material and preparation thereof.
Background technology
Along with being continuously increased and the continuous progress of modern technologies of the demand to the energy, organic electro-optic device relies on its phase
To cheap, devices light, flexibly and to be prone to the advantages such as large area processing of great interest, has obtained greatly
Research puts into, and the most progressively advances towards industrialization.Past 10 years, by the Molecular Design of material and device
Optimizing, organic electro-optic device have also been obtained development at full speed, but compared with the inorganic material with silicon as representative, in spectral response
The aspects such as scope, conversion efficiency and stability, organic photoelectrical material need to improve.The main photoresponse of current limiting factor
Narrow range, bandgap structure are unreasonable, carrier mobility is low.Therefore, the Polymer Optoelectronic body material that design synthesis performance is excellent
Material is still the key of present material research field.
The performance of organic electro-optic device is largely determined by the performance of the receptor in its active layer and donor material.Existing
Some donor materials there are disadvantages that, the narrowest light suction belt, high LUMO and low dissolubility, largely limits
The development of conjugated polymer, therefore to excavate efficient donor material be significantly.On the one hand, fluorenes class conjugated polymer
Owing to stronger π-π interaction, higher mobility, good stability and its structure itself have stronger modifying
The advantages such as property, are widely used in organic electro-optic device field.On the other hand, fluorine atom is minimum electron-withdrawing group
Rolling into a ball, have the strongest electronegativity, this special performance makes fluorine material obtain greatly in organic photoelectrical material is studied
Explore and application.Therefore, it is proposed that fluorenes and fluorine atom group are combined, one has been synthesized by reasonably design, successive optimization
Plant new double fluoro fluorenes class monomers, and this type of monomer is used in synthetic polymer and little molecule, owing to having good dissolving
Property, rational band gap and wider absorption, be combined with excellent donor material in bulk heteroj joint solar cell and formed
Conjugated polymer, is possible not only to promote photoelectric transformation efficiency, thus, before organic solar batteries also has well application
Scape.
Summary of the invention
The technical problem to be solved is to provide a kind of double fluoro fluorenes class monomer and conjugation thereof for above-mentioned condition
Polymeric material and preparation method thereof, the fluorenes the most symmetrical based on flatness structure and the little molecular cell of thiophene-based make it show
Go out good photoelectric property, there is preferable heat stability, adjustable optical band gap and level structure and good solution
Machinability.
The present invention solves that the technical scheme that above-mentioned technical problem is used is: a kind of double fluoro fluorenes class monomers, its structure
Formula as shown in formula I,
Wherein R1Selected from H or C1～C20Alkyl
Above-mentioned pair of fluoro fluorenes class conjugated polymer, its structural formula as shown in formula II,
Wherein R1Selected from H or C1～C20Alkyl, Ar is containing thiophene or benzene unit group, whole in n=1～200
Number.
Preferably, described Ar is selected from any one or a few in following radicals,
Wherein, R2～R7Selected from H, C1～C20Alkyl or alkoxyl；X is selected from oxygen, sulfur, selenium.
The synthesis technique of described double fluoro fluorenes class monomers, it comprises the steps:
1) byFor raw material, NaOH aqueous solution and positive tetrabutylammonium iodide in excess act on jointly
It is synthesized with brominated alkanes down
2) further, with AcOH/H2SO4/H2O mixed solvent dissolves, periodic acid is that catalyst acts on conjunction jointly with elemental iodine
Become
3) further, at Pd (pph3)4、K2CO3Synthesis is jointly acted on 2-thienyl boric acid
4) further, under n-BuLi effect, benzsulfamides double with N-fluoro react, synthesis
5) further, react with trimethyltin chloride under n-BuLi effect, synthesis
R in compound in described each step1Selected from H or C1～C20Alkyl.
By such scheme, step 1) in,Positive tetrabutylammonium iodide and brominated alkanes feed intake mole
The ratio of amount is: 1:(0.29～0.31): (2.4～2.6), and its reaction temperature is at 100～105 DEG C, and the response time is 3～4h, instead
Answering atmosphere is inert atmosphere.
By such scheme, step 2) in,The molar feed ratio of periodic acid and elemental iodine is 1:
(1.45～1.55): (1.05～1.15), described AcOH/H2SO4/H2O mixed solvent volume ratio be followed successively by (24.9～
25.1): (0.4～0.5): 1, reaction temperature is at 80～85 DEG C, and the response time is 5～6h.
By such scheme, step 3) in,2-thienyl boric acid, Pd (pph3)4And K2CO3Rub
Your ingredient proportion is 1:(2.15～2.25): (0.03～0.05): (2.45～2.55), reaction temperature, at 90～95 DEG C, is reacted
Time is 12～13h, and reaction atmosphere is inert atmosphere.
By such scheme, step 4) in,N-BuLi and the double benzsulfamide of N-fluoro
Molar ratio example be 1:(2～2.05): (2.4～2.6), described reaction first reacts 1h, so under the reaction temperature of-78 DEG C
After at room temperature react, the response time is 12～13h, and reaction atmosphere is inert atmosphere.
By such scheme, step 5) in,N-BuLi and the throwing of trimethyltin chloride
Material molar ratio is 1:(2.4～2.5): (3～3.1), described reaction is first reacted 1h under the reaction temperature of-78 DEG C, is then existed
Reacting under room temperature, the response time is 12～13h, and reaction atmosphere is inert atmosphere.
By such scheme, after reaction terminates in described step (1)-(5), also include purification step.
Main chemical reactions process involved by double fluoro fluorenes class monomers is as follows:
Above-mentioned pair of fluoro fluorenes class conjugated polymer
Synthetic method, key step is as follows:
By double fluoro fluorenes class monomersWith containing such as following institute
The compound monomer Ar shown, enters under conditions of with three (dibenzalacetone) two palladium and three (o-methyl-phenyl-) phosphorus as catalyst
Row copolymerization prepares its polymer；
Wherein, R1Selected from H, C1～C20Alkyl；R2～R7Selected from H, C1～C20Alkyl or alkoxyl；X selected from oxygen, sulfur,
Selenium.
By such scheme, double fluoro fluorenes class monomers, monomer, three (dibenzalacetone) two palladium and three (adjacent methyl containing Ar
Phenyl) the molar ratio example of phosphorus is 1:(1～1.05): (0.03～0.04): (0.18～0.19), described reaction is with anhydrous neighbour
Dichloro-benzenes is solvent at 168～170 DEG C of 48h that reflux, and reaction atmosphere is inert atmosphere.
Of the present invention pair of fluoro fluorenes class monomer and conjugated polymer thereof have using value in organic electro-optic device field,
As R in monomer and copolymer thereof can be passed through1Different alkyl chain is selected to adjust the dissolubility of little molecule and polymer.Described
Double fluoro fluorenes class conjugated polymers are mainly used in polymer solar battery aspect, with application preferable 2,7-bis-(thiophene now
Fen-2-base)-9H-fluorenes donor material compares, and show that double fluoro fluorenes class monomer has relatively deep HUMO energy level, wider suction
Receive spectrum and reasonably absorb band gap.
Compared with prior art, the invention has the beneficial effects as follows: double fluoro fluorenes class monomers be a kind of high degree of symmetry containing miscellaneous
Atomic compound, utilizes the electron-withdrawing power that fluorine atom is strong, and fluorenes preferably heat stability itself, adjustable optical band gap and
Energy level and modifiability so that it can be applicable in organic solar batteries as the good donor material of one.
Accompanying drawing explanation
Ultraviolet-ray visible absorbing light under the o-dichlorobenzene solution (room temperature) of polymer P 1 and filminess in Fig. 1 embodiment 2
Spectrum.
The electrochemistry cyclic voltammetry curve of polymer P 1 in Fig. 2 embodiment 2, anhydrous with 0.1M tetrabutyl ammonium hexafluorophosphate
Acetonitrile solution is as electrolyte solution, and sweep speed is 0.08V/s.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with
Example, is further elaborated to the present invention.Should be appreciated that and described herein be embodied as example only in order to explain
The present invention, is not intended to limit the present invention.
Embodiment 1
1. compound 1Preparation, reaction equation is as follows:
With R1For illustrating as a example by 2-ethylhexyl, in the two-neck bottle of 250ml, addition 3,6-dibromo fluorenes (12.96g,
40mmol), after positive tetrabutylammonium iodide (4.54g, 12.3mmol, 30%eqiv) carries out anhydrous and oxygen-free process, it is sequentially added into
60ml DMSO, 50ml 50%NaOH aqueous solution, after being sufficiently stirred for add bromo-iso-octane (20.1g, 100mmol,
2.5eqiv), nitrogen is protected, and at 100 DEG C, stirring reaction, in about 3 hours response time, obtains the thick product solution of compound 1.
Distilled water is added, with petroleum ether extraction three times, collected organic layer in the thick product solution of compound 1；Then use
Anhydrous magnesium sulfate is dried, precipitation；Carry out column chromatography with petroleum ether again, obtain oily liquids, productivity 96%, be compound 1 essence
Product.Nuclear-magnetism1H NMR(500MHz,CDCl3) δ 0.42 (t, J=7.5Hz, 2H), δ 0.50 (t, J=10Hz, 6H), 0.64-0.97
(m, 22H), δ 1.91 (t, J=7.5Hz, 4H), δ 7.24 (d, J=15Hz, 2H), δ 7.41 (d, J=10Hz, 2H), δ 7.78 (s,
2H)。
2. compound 2Preparation, reaction equation is as follows:
With R1For illustrating as a example by 2-ethylhexyl, in the two-neck bottle of 250ml, add compound 1 (3.34g,
6.09mmol), preparation AcOH/H2SO4/H2O mixed solution, volume is followed successively by 90ml, 1.62ml, 3.6ml, adds double after stirring
In neck bottle, stir under room temperature, be sequentially added into H5IO6(2.08g, 9.135mmol) and I2(1.70g, 6.69mmol, 1.1eqiv),
At 80 DEG C, stirring reaction, reacts about 6 hours, obtains the thick product solution of compound 2.
Add in 10%NaOH aqueous solution in the thick product solution of compound 2 and acid, add saturated NaHSO4Aqueous solution
Remove excess iodine, with petroleum ether extraction three times, collected organic layer；Then dried with anhydrous magnesium sulfate, precipitation；Use petroleum ether again
Carry out column chromatography, obtain oily liquids, productivity 88%, be compound 2 fine work.Nuclear-magnetism1H NMR(400MHz,CDCl3)δ0.45
(m, 2H), δ 0.55 (t, J=8Hz, 6H), 0.72-1.04 (m, 22H), δ 1.90 (d, J=4Hz, 4H), δ 7.85 (t, J=8Hz,
2H),δ7.91(s,2H)。
3. compound 3Preparation, reaction equation is as follows:
With R1For illustrating as a example by 2-ethylhexyl, in the two-neck bottle of 250ml, be sequentially added into compound 2 (3.2g,
4mmol), 2-thienyl boric acid (1.12g, 8.8mmol, 2.2eqiv), K2CO3(1.37g, 10mmol, 2.5eqiv) and Pd
(pph3)4(231.1mg, 5%eqiv), after anhydrous and oxygen-free processes, adds dry DMF 80ml, and nitrogen is protected, under 110 DEG C of oil baths
Stirring reaction, reaction overnight, obtain the thick product solution of compound 3.
Distilled water is added, with petroleum ether extraction three times, collected organic layer in the thick product solution of compound 3；Then use
Anhydrous magnesium sulfate is dried, precipitation；Carry out column chromatography with petroleum ether again, obtain oily liquids, productivity 65%, be compound 3 essence
Product.Nuclear-magnetism1H NMR(500MHz,CDCl3) δ 0.59 (s, 2H), δ 0.60 (t, J=7.5Hz, 6H), δ 0.72 (t, J=5Hz,
6H), 0.75-1.02 (m, 16H), δ 1.99 (d, J=4Hz, 4H), δ 7.16 (t, J=5Hz, 2H), δ 7.31 (d, J=5Hz,
2H), δ 7.43 (d, J=5Hz, 2H), δ 7.50 (t, J=5Hz, 2H), δ 8.00 (s, 2H).
4. compound 4Preparation, reaction equation is as follows:
With R1For illustrating as a example by 2-ethylhexyl, after the two-neck bottle of 50ml is carried out Non-aqueous processing, add compound 3
(0.712g, 1mmol), suck-back is inserted in the condenser system of-78 DEG C after entering the anhydrous THF of 15ml, nitrogen is protected, and adds after 10 minutes
The n-BuLi (0.84ml, 2mmol) of 2.4M, after 30 minutes, adds the double benzsulfamide of N-fluoro that anhydrous and oxygen-free processed
(0.82g, 2.6mmol, 2.6eqiv) injects in two-neck bottle with the form of anhydrous THF solution, takes out condensed system after reacting 1 hour
System, at room temperature reaction overnight, obtain the thick product solution of compound 4.
Distilled water is added, with petroleum ether extraction three times, collected organic layer in the thick product solution of compound 4；Then use
Anhydrous magnesium sulfate is dried, precipitation；Carry out column chromatography with petroleum ether again, obtain oily liquids, productivity 40%, be compound 4 essence
Product.Nuclear-magnetism1H NMR(500MHz,CDCl3) δ 0.59 (s, 2H), δ 0.60 (t, J=7.5Hz, 6H), δ 0.68 (t, J=5Hz,
6H), 0.75-1.02 (m, 16H), δ 2.06 (t, J=7.5Hz, 4H), δ 7.18 (t, J=5Hz, 2H), δ 7.42 (d, J=5Hz,
2H), δ 7.43 (d, J=15Hz, 2H), δ 7.55 (s, 2H), δ 7.62 (d, J=5Hz, 2H).
5. compound 5Preparation, reaction equation is as follows:
With R1For illustrating as a example by 2-ethylhexyl, after the two-neck bottle of 50ml is carried out Non-aqueous processing, add compound 4
(0.244g, 0.42mmol), suck-back is inserted in the condenser system of-78 DEG C after entering the anhydrous THF of 10ml, nitrogen is protected, after 10 minutes
Add the n-BuLi (0.43ml, 1.05mmol, 2.5eqiv) of 2.4M, after 1 hour, add Me3SnCl (1.26ml,
1.26mmol, 3eqiv), take out condenser system, at room temperature reaction overnight after reacting 1 hour, obtain the thick product of compound 4
Solution.
In the thick product solution of compound 5, add distilled water, extract three times with ether, collected organic layer；Then nothing is used
Water magnesium sulfate is dried, precipitation, and productivity 98% is compound 5 fine work.Nuclear-magnetism1H NMR(500MHz,CDCl3)δ0.45(s,
18H), δ 0.56 (s, 2H), δ 0.57 (t, J=7.5Hz, 6H), δ 0.68 (t, J=5Hz, 6H), 0.75-1.02 (m, 16H), δ
2.04 (t, J=2.5Hz, 4H), δ 7.26 (d, J=4.35Hz, 2H), δ 7.41 (d, J=15Hz, 2H), δ 7.62 (s, 2H), δ
7.63 (d, J=15Hz, 2H).
Embodiment 2
Polymer P 1Preparation, reaction equation is as follows
Weigh embodiment 1 gained compound 5 (0.275g, 0.30mmol), 4,7-dibromo benzo [c] [1,2,5] thiadiazoles
(i.e. Ar is group a) (88.19mg, 0.30mmol), three (dibenzalacetone) two palladium (8.24mg, 3%equiv), three (adjacent first
Base phenyl) phosphorus (16.42mg, 18%equiv), it is separately added in single neck bottle of 50mL, evacuation, adds the dry toluene of 8mL,
Backflow 48h, obtains the thick product of polymer P 1.
Purify: after thick for polymer P 1 product is cooled to room temperature, be slowly dropped in the absolute methanol of 40mL (while stir
Mix limit dropping), to drain after dropping, obtained solid, through acetone, normal hexane, dichloromethane, chloroform extracting, obtains
The chloroform extraction liquid arrived concentrates；Be subsequently adding 6mL methanol in chloroform extraction liquid concentrate in, through sucking filtration, vacuum drying
Obtain solid, productivity 70%, be polymer P 1.Gel permeation chromatography records: number-average molecular weight Mn=30.99kDa, and weight average divides
Son amount Mw=37.06kDa, breadth coefficient PDI=1.20, n=41～44.
Polymer P 1 has preferably absorption in the range of 350～600nm as shown in Figure 1, and absorption region is wider, additionally,
Can be calculated its optical band gap is 1.97eV, is relatively reasonable wide band gap polymer.
The HOMO that can be calculated polymer P 1 by Fig. 2 is-5.55eV, and LUMO is-3.58eV, HOMO and LUMO phase
To deeper.
Embodiment 3
Polymer P 2Preparation, reaction equation is as follows
With R4For as a example by 2-ethylhexyl illustrate, weigh embodiment 1 gained compound 5 (0.275g, 0.30mmol), 4,7-
Two bromo-2-(2-ethylhexyl) iso-indoles-1,3-diketone (125.1mg, 0.30mmol), three (dibenzalacetone) two palladium
(8.24mg, 3%equiv), three (o-methyl-phenyl-) phosphorus (16.42mg, 18%equiv), be separately added in single neck bottle of 50mL,
Evacuation, adds the dry toluene of 8mL, and reflux 48h, obtains the thick product of polymer P 2.
Purify: after thick for polymer P 2 product is cooled to room temperature, be slowly dropped in the absolute methanol of 40mL (while stir
Mix limit dropping), to drain after dropping, obtained solid, through acetone, normal hexane, dichloromethane, chloroform extracting, obtains
The chloroform extraction liquid arrived concentrates；Be subsequently adding 6mL methanol in chloroform extraction liquid concentrate in, through sucking filtration, vacuum drying
Obtain solid, productivity 60%, be polymer P 2.Gel permeation chromatography records: number-average molecular weight Mn=33.56kDa, and weight average divides
Son amount Mw=44.22kDa, breadth coefficient PDI=1.31, n=38～50.
Embodiment 4
Polymer P 3Preparation, reaction equation is as follows
With R7For as a example by 2-ethylhexyl illustrate, weigh embodiment 1 gained compound 5 (0.275g, 0.30mmol), 3,6-
Double (5-bromothiophene-2-bases)-2, double (2-ethylhexyl) pyrrolo-[3, the 4-c] pyrroles-Isosorbide-5-Nitrae-diketone of 5-(204.8mg,
0.30mmol), three (dibenzalacetone) two palladium (8.24mg, 3%equiv), three (o-methyl-phenyl-) phosphorus (16.42mg, 18%
Equiv), being separately added in single neck bottle of 50mL, evacuation, add the dry toluene of 8mL, reflux 48h, obtains polymer P 3 thick
Product.
Purify: after thick for polymer P 3 product is cooled to room temperature, be slowly dropped in the absolute methanol of 40mL (while stir
Mix limit dropping), to drain after dropping, obtained solid, through acetone, normal hexane, dichloromethane, chloroform extracting, obtains
The chloroform extraction liquid arrived concentrates；Be subsequently adding 6mL methanol in chloroform extraction liquid concentrate in, through sucking filtration, vacuum drying
Obtain solid, productivity 65%, be polymer P 3.Gel permeation chromatography records: number-average molecular weight Mn=28.64kDa, and weight average divides
Son amount Mw=36.89kDa, breadth coefficient PDI=1.29, n=22～29.
Of the present invention pair of fluoro fluorenes class monomer and conjugated polymer thereof are by alkyl chain and the change of Ar group, tool
There are adjustable band gap and energy level so that this micromolecular or polymeric material have extensively in organic electro-optic device field
Application；And, its good dissolubility so that it is huge potentiality can be had in terms of processed and applied at solution.
The above is only the preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
Saying, without departing from the concept of the premise of the invention, it is also possible to make some modifications and variations, these broadly fall into the present invention's
Protection domain.
Claims (10)
1. double fluoro fluorenes class monomers, its structural formula as shown in formula I,
Wherein R1Selected from H or C1～C20Alkyl.
2. a double fluoro fluorenes class conjugated polymer, it is characterised in that its structural formula as shown in formula II,
Wherein R1Selected from H or C1～C20Alkyl, Ar is containing thiophene or benzene unit group, the integer in n=1～200.
The most according to claim 2 pair of fluoro fluorenes class conjugated polymer, it is characterised in that described Ar is in following radicals
Any one or a few,
Wherein, R2～R7Selected from H, C1～C20Alkyl or alkoxyl；X is selected from oxygen, sulfur, selenium.
4. the synthesis technique of the double fluoro fluorenes class monomers described in claim 1, it comprises the steps:
1) byFor raw material, under the NaOH aqueous solution of excess and positive tetrabutylammonium iodide act on jointly with
Brominated alkanes is synthesized
2) further, with AcOH/H2SO4/H2O mixed solvent dissolves, periodic acid is that catalyst acts on synthesis jointly with elemental iodine
3) further, at Pd (pph3)4、K2CO3Synthesis is jointly acted on 2-thienyl boric acid
4) further, under n-BuLi effect, benzsulfamides double with N-fluoro react, synthesis
5) further, react with trimethyltin chloride under n-BuLi effect, synthesis
R in compound in described each step1Selected from H or C1～C20Alkyl.
The synthesis technique of the most according to claim 4 pair of fluoro fluorenes class monomer, it is characterised in that step 1) in,The feed intake ratio of mole of positive tetrabutylammonium iodide and brominated alkanes is: 1:(0.29～0.31): (2.4
～2.6), its reaction temperature is at 100～105 DEG C, and the response time is 3～4h, and reaction atmosphere is inert atmosphere.
The synthesis technique of the most according to claim 4 pair of fluoro fluorenes class monomer, it is characterised in that step 2) in,The molar feed ratio of periodic acid and elemental iodine is 1:(1.45～1.55): (1.05～1.15), described
AcOH/H2SO4/H2O mixed solvent volume ratio is followed successively by (24.9～25.1): (0.4～0.5): 1, and reaction temperature is 80～85
DEG C, the response time is 5～6h.
The synthesis technique of the most according to claim 4 pair of fluoro fluorenes class monomer, it is characterised in that step 3) in,2-thienyl boric acid, Pd (pph3)4And K2CO3Molar feed ratio example be 1:(2.15～2.25):
(0.03～0.05): (2.45～2.55), reaction temperature is at 90～95 DEG C, and the response time is 12～13h, and reaction atmosphere is inertia
Atmosphere.
The synthesis technique of the most according to claim 4 pair of fluoro fluorenes class monomer, it is characterised in that step 4) in,The molar ratio example of n-BuLi and the double benzsulfamide of N-fluoro is 1:(2～2.05):
(2.4～2.6), described reaction first reaction 1h under the reaction temperature of-78 DEG C, the most at room temperature to react, the response time is 12
～13h, reaction atmosphere is inert atmosphere.
The synthesis technique of the most according to claim 4 pair of fluoro fluorenes class monomer, it is characterised in that step 5) in,The molar ratio example of n-BuLi and trimethyltin chloride is 1:(2.4～2.5): (3
～3.1), 1h is first reacted in described reaction under the reaction temperature of-78 DEG C, the most at room temperature reacts, the response time be 12～
13h, reaction atmosphere is inert atmosphere.
10. the synthesis technique of the double fluoro fluorenes class conjugated polymers described in claim 2, it is by double fluoro fluorenes class monomersWith containing compound monomer Ar as shown in following, with three (two
BENZYLIDENE ACETONE) two palladiums and three (o-methyl-phenyl-) phosphorus is to carry out copolymerization under conditions of catalyst to prepare its polymer；
Wherein, R1Selected from H, C1～C20Alkyl；R2～R7Selected from H, C1～C20Alkyl or alkoxyl；X is selected from oxygen, sulfur, selenium.
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