CN106832230A - One kind fluorination di-thiofuran ethylene polymer and preparation method and application - Google Patents
One kind fluorination di-thiofuran ethylene polymer and preparation method and application Download PDFInfo
- Publication number
- CN106832230A CN106832230A CN201710022687.2A CN201710022687A CN106832230A CN 106832230 A CN106832230 A CN 106832230A CN 201710022687 A CN201710022687 A CN 201710022687A CN 106832230 A CN106832230 A CN 106832230A
- Authority
- CN
- China
- Prior art keywords
- formula
- fluorination
- compound
- ethylene polymer
- thiofuran ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JIOVMLYJNWPYPJ-UHFFFAOYSA-N C=C.S1C=CC=C1.S1C=CC=C1 Chemical group C=C.S1C=CC=C1.S1C=CC=C1 JIOVMLYJNWPYPJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 32
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 21
- 230000005669 field effect Effects 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 50
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical class CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims 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 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [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 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 87
- 239000004065 semiconductor Substances 0.000 abstract description 25
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000012805 post-processing Methods 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000037230 mobility Effects 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000003233 pyrroles Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 5- bromo- 2- thienyl Chemical group 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000011982 device technology Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OXDSTEQMQRCOGK-UHFFFAOYSA-N 3-fluorothiophene-2-carbaldehyde Chemical class FC=1C=CSC=1C=O OXDSTEQMQRCOGK-UHFFFAOYSA-N 0.000 description 1
- 241001614291 Anoplistes Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical group C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- C08G61/124—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 nitrogen atom in the ring
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- 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
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
-
- 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
-
- 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
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- 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
-
- 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
-
- 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
- C08G2261/90—Applications
- C08G2261/92—TFT applications
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses one kind fluorination di-thiofuran ethylene polymer, shown in structural formula such as formula (I), the polymer has rigid planar structure, closely intermolecular accumulation is easily formed in film, film stack has stronger long-range order, there is stronger ultravioletvisible absorption and good thermal stability in a semiconductor material, level structure is conducive to carrier to inject, can prepare superior performance bipolarity field-effect transistor.The synthetic route of fluorination di-thiofuran ethylene polymer of the invention is simple, efficient, and reaction yield is high, and post processing is simple, and the degree of polymerization is high, is adapted to extensive synthesis.For organic field effect tube prepared by semiconductor layer has hole mobility and on-off ratio very high in present invention fluorination di-thiofuran ethylene polymer semiconducting material.
Description
Technical field
The invention belongs to organic semiconducting materials technical field, specifically, it is related to a kind of fluorination di-thiofuran ethylene to be polymerized
Thing and preparation method and application.
Background technology
Organic field effect tube is, with organic semiconducting materials as carrier blocking layers, to control material to lead by electric field
The active device of electric energy power, is derivative based on the unique design feature of pi-conjugated molecule and abundant physicochemical properties
Important application.High performance organic field effect tube is had broad application prospects, and it is penetrated in smart card, sensor, electronics
The successful Application in the fields such as frequency marking label, large screen display and integrated circuit can necessarily promote information, the energy, life etc. many
The technological innovation in field, will produce far-reaching influence to economic development and social progress, compared with traditional inorganic material,
Organic semiconducting materials have the advantages that raw material extensively and synthesis technique is simple, while the controllable with physicochemical properties again
Property and good elasticity and pliability, can be processed with solwution method, so as to be extensive manufacture lightweight, flexible electronic
Device is provided may.Therefore, the extensive concern of researcher and industrial circle has just been subject to since being born from it, correlative study is
Through one of the focus for becoming organic electronics research field.
Organic semiconductor layer active material used by organic field effect tube can be to include machine small molecule and polymer
Semi-conducting material etc., polymer semiconducting material has that easily prepared, light weight, good film-forming property, pliability be good, elasticity is good, and soft
Property substrate there is good compatibility so that based on polymer electronics device research turned into organic electronics
Study hotspot.In recent years, polymer field effect transistor device performance research achieves breakthrough progress (Chen, H.J.；
Guo,Y.L.；Yu,G.；Zhao,Y.；Zhang,J.；Gao,D.；Liu,H.T.；Liu,Y.Q.Highlyπ-Extended
Copolymers with Diketopyrrolopyrrole Moieties for High-Performance Field‐
Effect Transistors.Adv.Mater.2012,24,4618-4622；Kang,I.；Yun,H.J.；Chung,D.S.；
Kwon,S.K.；Kim,Y.H.Record High Hole Mobility in Polymer Semiconductors via
Side-Chain Engineering.J.Am.Chem.Soc.2013,135,14896-14899；Luo,C.；Kyaw,A.K.K.；
Perez,L.A.；Patel,S.；Wang,M.；Grimm,B.；Bazan,G.C.；Kramer,E.J.；Heeger,
A.J.General Strategy for Self-Assembly of Highly Oriented Nanocrystalline
Semiconducting Polymers with High Mobility.Nano Lett.2014,14,2764-2771；Kim,
G.；Kang,S.-J.；Dutta,G.K.；Han,Y.-K.；Shin,T.J.；Noh,Y.-Y.；Yang,C.A
Thienoisoindigo-Naphthalene Polymer with Ultrahigh Mobility of 14.4cm2/V·s
That Substantially Exceeds Benchmark Values for Amorphous Silicon
Semiconductors.J.Am.Chem.Soc.2014,136,9477-9483).From the prior art it is contemplated that, with half
The development of conductor material and device technology of preparing, the application prospect of polymer field effect transistor device will be more wide.However,
The performance and stability of existing polymer field effect transistor device still can not meet and be actually needed at present, continually develop new
Material and to explore new device technology of preparing will be the long-standing issues that research workers face, while also giving studies in China machine
There are original, high performance organic semiconducting materials to provide many opportunities for structure exploitation.
Research shows that the polymer with planar structure is prone to form close packing of molecules, strong π-π phase interactions
With, so that carrier mobility higher is more likely obtained, so researchers are devoted to development and have planar structure always
Polymer has simultaneously constructed corresponding FET device (Gao, Y.；Zhang,X.J.；Tian,H.K.；Zhang,J.D.；
Yan,D.H.；Geng,Y.H.；Wang,F.S.High Mobility Ambipolar Diketopyrrolopyrrole-
Based Conjugated Polymer Synthesized Via Direct Arylation
Polycondensation.Adv.Mater.2015,27,6753-6759；Yun,H.-J.；Kang,S.-J.；Xu,Y.；Kim,
S.O.；Kim,Y.-H.；Noh,Y.-Y.；Kwon,S.-K.Dramatic Inversion of Charge Polarity in
Diketopyrrolopyrrole-Based Organic Field-Effect Transistors via a Simple
Nitrile Group Substitution.Adv.Mater.2014,26,7300-7307)。
For these reasons, it is special to propose the present invention.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided one kind fluorination di-thiofuran ethylene
Polymer, the polymer has rigid planar structure, and closely intermolecular accumulation is easily formed in film, and film stack has stronger
Long-range order, in a semiconductor material with stronger ultraviolet-ray visible absorbing and good thermal stability, level structure has
Beneficial to carrier injection, superior performance bipolarity field-effect transistor can be prepared.
The first object of the present invention provides a kind of fluorination di-thiofuran ethylene polymer, and described fluorination di-thiofuran ethylene gathers
Shown in the structural formula of compound such as formula (I)：
Wherein, R1、R2It is C1- C100Straight or branched alkane, R1With R2Identical or different, n is the degree of polymerization, n=10-
1000, preferably n=20-500.
Fluorination di-thiofuran ethylene polymer of the present invention has rigid planar structure, and tight molecule is easily formed in film
Between pile up, film stack has stronger long-range order, in a semiconductor material with stronger ultraviolet-ray visible absorbing and good
Good thermal stability, level structure is conducive to carrier to inject, can prepare superior performance bipolarity field-effect transistor.
The second object of the present invention there are provided a kind of preparation method for being fluorinated di-thiofuran ethylene polymer, described system
Preparation Method comprises the following steps：
(1) under an inert gas, compound and titanium tetrachloride, zinc powder are reacted shown in formula (II), obtain formula (III) institute
Show compound, reactive chemistry equation is as follows：
(2) under an inert gas, compound shown in formula (III) and lithium reagent shown in formula (IV), tin reagent shown in formula (V) enter
Row reaction, obtains compound shown in formula (VI), and reactive chemistry equation is as follows：
Wherein, R3And R4It is C1-C7Straight or branched alkane, R3With R4Identical or difference；
(3) under an inert gas, compound shown in formula (VI), compound shown in formula (VII) are made in palladium catalyst and part
Reacted under, obtained described fluorination di-thiofuran ethylene polymer, reactive chemistry equation is as follows：
Wherein, the R in formula (VI) compound1And R2Respectively with formula (I) compound in R1And R2It is identical.
Further, formula (II) compound, titanium tetrachloride, the mol ratio of zinc powder are 1 in step (1):2.0~4.0:2.0
~4.0, it is preferred that 1:1.58:2.5.
Further, the reaction temperature in step (1) is -20~80 DEG C, and the reaction time is 2~48 hours.
Further, the mol ratio of formula (III) compound, formula (IV) compound and formula (V) compound is 1 in step (2):
2.0~4.0:2.0~4.0, preferred 1:2.4:2.4.
Further, the reaction temperature in step (2) is -80~25 DEG C, and the reaction time is 2~48 hours.
Further, palladium catalyst described in step (3) is three (dibenzalacetone) two palladium or tetrakis triphenylphosphine palladium；
The part is three (o-tolyl) phosphines or triphenylphosphine.
Further, compound shown in formula (V) in step (3), compound, catalyst and part shown in formula (VI) mole
Than being 1:0.95~1.05:0.01~0.10:0.02~0.60, it is preferred that 1.0:1.0:0.05:0.4, reaction temperature be 60~
150 DEG C, the reaction time is 24~48 hours.
Further, the reaction of step (1), step (2) and step (3) is carried out in organic solvent, step (1) and step
Suddenly organic solvent is tetrahydrofuran or ether in (2), and step (3) organic solvent is tetrahydrofuran, DMF, first
Benzene or chlorobenzene.
The synthetic route of fluorination di-thiofuran ethylene polymer of the invention is simple, efficient, and reaction yield is high, post processing letter
Single, the degree of polymerization is high, is adapted to large-scale production.
The third object of the present invention there are provided a kind of fluorination di-thiofuran ethylene polymer recited above to be had in preparation
Application in field effect transistors.
It is the organic effect crystal of semiconductor layer preparation in present invention fluorination di-thiofuran ethylene polymer semiconducting material
Pipe has hole mobility (μ very highh) and on-off ratio, μhUp to 5.42cm2V-1s-1, on-off ratio is 104-105, with compared with
Electron mobility (μ highe)(μeUp to 0.36cm2V-1s-1), have broad application prospects.
Using above-mentioned technical proposal, beneficial effects of the present invention are as follows：
(1) fluorination di-thiofuran ethylene polymer of the present invention has rigid planar structure, easily forms tight in film
Intermolecular accumulation, film stack has stronger long-range order, in a semiconductor material with stronger ultraviolet-ray visible absorbing
With good thermal stability, level structure is conducive to carrier to inject, can prepare superior performance bipolarity field effect transistor
Pipe.
(2) synthetic route of fluorination di-thiofuran ethylene polymer of the invention is simple, efficient, and reaction yield is high, post processing
Simply, the degree of polymerization is high, is adapted to extensive synthesis.
(3) for the organic effect of semiconductor layer preparation is brilliant in present invention fluorination di-thiofuran ethylene polymer semiconducting material
Body pipe has hole mobility (μ very highh) and on-off ratio, μhUp to 5.42cm2V-1s-1, on-off ratio is 104-105, have
Electron mobility (μ highere)(μeUp to 0.36cm2V-1s-1), have broad application prospects.
Brief description of the drawings
Fig. 1：Fluorination di-thiofuran ethylene polymer of the present invention is the synthetic route chart of formula (I) compound；
Fig. 2：Inventive polymers PFDTE1 and polymer P FDTE2 synthetic route charts；
Fig. 3：UV-visible absorption spectrums of the Inventive polymers PFDTE1 and polymer P FDTE2 in chlorobenzene solution；
Fig. 4：The UV-visible absorption spectrum of Inventive polymers PFDTE1 and polymer P FDTE2 films；
Fig. 5：The thermal gravimetric analysis curve figure of Inventive polymers PFDTE1 and polymer P FDTE2；
Fig. 6：Inventive polymers PFDTE1 and polymer P FDTE2 cyclic voltammetry curve maps；
Fig. 7：The AFM shape appearance figure of Inventive polymers PFDTE1；
Fig. 8：The AFM shape appearance figure of Inventive polymers PFDTE2；
Fig. 9：The transistor arrangement schematic diagram of Inventive polymers PFDTE1 and polymer P FDTE2；
Figure 10：The transfer curve figure of Inventive polymers PFDTE1 field-effect transistors；
Figure 11：The output curve diagram of Inventive polymers PFDTE1 field-effect transistors；
Figure 12：The transfer curve figure of Inventive polymers PFDTE2 field-effect transistors；
Figure 13：The output curve diagram of Inventive polymers PFDTE2 field-effect transistors.
Specific embodiment
Embodiment in following embodiments can be further combined or replace, and embodiment is only to of the invention
Preferred embodiment is described, and not the spirit and scope of the present invention are defined, and is not departing from design philosophy of the present invention
Under the premise of, the various changes and modifications that professional and technical personnel in the art make to technical scheme belong to this hair
Bright protection domain.
Fluorination di-thiofuran ethylene polymer of the present invention is that the synthetic route of formula (I) compound is as shown in Figure 1.
Embodiment 1
Poly- { 2,5- bis- (2- decyls myristyl) -2,5- dihydro -1,4- dioxos pyrrolo- [3,4-c] pyrroles -2,5-
(trans- 1,2- double (3- fluorine thiophene -2- bases) ethene) -2,5- diyls } R in hereinafter abbreviated as polymer P FDTE1, i.e. formula (I)1=R2
=2- decyl myristyls, synthetic route is as shown in Fig. 2 preparation method is as follows：
(1) double (the 3- fluorine thiophene -2- bases) ethene of (anti-) -1,2- are the synthesis of formula (III) compound
Under argon gas, reaction temperature is 0 DEG C of condition, to the anhydrous tetrahydrochysene furan containing zinc powder (10.2g, 156.1mmol)
Muttering, (200ml) is middle to be added dropwise titanium tetrachloride (9.02ml, 97.60mmol)；It is added dropwise to complete rear system and is warming up to and be refluxed 2h, then
The fluoro- 2- formylthiophenes (8.00g, 61.5mmol) of 3- are added, continues the 16h that flows back, added water and reaction is quenched, dichloromethane extraction, extraction
Vacuum distillation removes solvent after taking liquid anhydrous sodium sulfate drying, removing drier, and gained solid recrystallizing methanol obtains shallow
Yellow crystals target product 4.7g, yield is 67%.
Structural characterization data are as follows：
Mass spectrum：HRMS:Calcd.for[C10H6F2S2]+:227.9879；Found:227.9876.
Hydrogen is composed:1H NMR(300MHz,CDCl3,δ):7.00 (dd, J=6Hz, J=0.3Hz, 2H), 6.81 (s, 2H),
6.89 (d, J=6Hz, 2H).
Carbon is composed：13C NMR(75MHz,CDCl3)δ(ppm):157.1,153.6,122.6,122.4,120.5,120.3,
118.1,117.7,116.08,116.05,116.02,115.99。
(2) double (the fluoro- 5- trimethyl-tin-radicals of the 3--thiophene -2- bases) ethene of (anti-) -1,2- are the synthesis of formula (VI) compound
Under argon gas, reaction temperature is -78 DEG C of double (3- fluorine thiophene -2- bases) ethene of (anti-) -1,2- obtained to step (1)
The hexane solution of the n-BuLi of 2.5mol/L is added dropwise in the anhydrous tetrahydrofuran solution (20ml) of (1.14g, 5.0mmol)
(4.8mL, 12.0mmol).It is added dropwise to complete and 0 DEG C of stirring 5min is to slowly warm up to after rear system stirs 1h at -78 DEG C；Again by system
Be cooled to -78 DEG C, and disposably injection add the trimethyltin chloride of 1.0mol/L tetrahydrofuran solution (12.0mL,
12.0mmol), cryostat is removed after, system warms naturally to be stirred overnight at room temperature, adds water and reaction is quenched, ether extraction, extract
With anhydrous sodium sulfate drying, vacuum distillation removes solvent after removing drier, and gained solid n-hexane is recrystallized to give pale yellow
Color crystal target product 2.1g, yield is 76%.
Structural characterization data are as follows：
Mass spectrum：HRMS:Calcd.for[C16H22F2S2Sn2]+:551.9170,553.9169,555.9201；Found:
551.9162,553.9167,555.9194。
Hydrogen is composed:1H NMR(300MHz,CDCl3,δ):6.72(s,2H),6.70(s,2H),0.22(s,18H)。
Carbon is composed：13C NMR(75MHz,CDCl3)δ(ppm):158.6,154.9,136.7,125.9,125.7,125.2,
124.9,115.9,115.8,-8.65。
(3) synthesis of polymer P FDTE1
Double (the fluoro- 5- trimethyl-tin-radicals of the 3--thiophene -2- bases) ethene of (anti-) -1,2- that step (2) is obtained (110.8mg,
0.20mmol) double (2- decyls myristyl)-pyrrolo- [3,4-c] pyrroles -1 of (5- bromo- 2- thienyl) -2,5-s double with 3,6-,
4- diketone (226.3mg, 0.2mmol), wherein, 3,6- double double (2- decyls myristyl)-pyrroles of (the bromo- 2- thienyls of 5-) -2,5-
Simultaneously [3,4-c] pyrroles -1,4- diketone is coughed up to prepare referring to document：J.Mater.Chem., 2011,21,8528-8531, three (two Asias
Benzylacetone) two palladiums (9mg), three (o-tolyl) phosphines (24.6mg) and chlorobenzene (5.0mL) be added in reaction bulb, in argon gas
Carry out the deoxygenation of three freezing-pumping-thaw cycles, after reactant mixture is heated to 110 DEG C of argon gas protection reaction 24h.Cooling
Afterwards, 200mL methyl alcohol/6M HCl mixtures (v/v 20 is added:1) 2h, is stirred at room temperature, is filtered.Gained solid surname extraction
Device is extracted.Extraction solvent is methyl alcohol successively, acetone, n-hexane, respectively extract 24h, is finally extracted with chlorobenzene and obtains subject polymer
230 milligrams, yield 96%.
Structural characterization data are as follows：
Molecular weight：GPC:Mn=216.6kDa, Mw=505.2kDa, PDI=2.33.
Elementary analysis：C74H108F2N2O2S4, calculated value：C,72.07；H,9.07；N,2.33；Probe value:C 72.22,H
9.00,N 2.35。
Understand that the compound structure is correct by analysis above, be polymer P FDTE1, the degree of polymerization is 180.
Embodiment 2
Poly- { 2,5- bis- (4- decyls myristyl) -2,5- dihydro -1,4- dioxos pyrrolo- [3,4-c] pyrroles -2,5-
(trans- 1,2- double (3- fluorine thiophene -2- bases) ethene) -2,5- diyls } synthesis, hereinafter referred to as polymer P FDTE2, synthetic route
As shown in Fig. 2 R i.e. in formula (I) compound1=R2=4- decyls myristyl), preparation method is as follows：
(1) double (the 3- fluorine thiophene -2- bases) ethene of (anti-) -1,2- are the synthesis of formula (III) compound with embodiment 1；
(2) double (the fluoro- 5- trimethyl-tin-radicals of the 3--thiophene -2- bases) ethene of (anti-) -1,2- be formula (VI) compound synthesis it is same
Embodiment 1；
(3) synthesis of polymer P FDTE2
Double (the fluoro- 5- trimethyl-tin-radicals of the 3--thiophene -2- bases) ethene of (anti-) -1,2- that step (2) is obtained (110.8mg,
0.20mmol) double (4- decyls myristyl)-pyrrolo- [3,4-c] pyrroles -1 of (5- bromo- 2- thienyl) -2,5-s double with 3,6-,
4- diketone (226.3mg, 0.2mmol), wherein, 3,6- double double (4- decyls myristyl)-pyrroles of (the bromo- 2- thienyls of 5-) -2,5-
Simultaneously [3,4-c] pyrroles -1,4- diketone is coughed up to prepare referring to document：Polym.Chem., 2015,6,6457-6464, three (dibenzylidenes
Acetone) two palladiums (9mg), three (o-tolyl) phosphines (24.6mg) and chlorobenzene (5.0mL) be added in reaction bulb, carried out in argon gas
The deoxygenation of three freezing-pumping-thaw cycles, after reactant mixture is heated to 110 DEG C of argon gas protection reaction 24h.After cooling, plus
Enter 200mL methyl alcohol/6M HCl mixtures (v/v 20:1) 2h, is stirred at room temperature, is filtered.Gained solid is taken out with apparatus,Soxhlet's
Carry.Extraction solvent is methyl alcohol successively, acetone, n-hexane, respectively extract 24h, is finally extracted with chlorobenzene and obtains the milli of subject polymer 228
Gram, yield 95%.
Structural characterization data are as follows：
Molecular weight：GPC:Mn=220.4kDa, Mw=453.9kDa, PDI=2.06.
Elementary analysis：C74H108F2N2O2S4, calculated value：C,72.07；H,9.07；N,2.33；Probe value:C 72.12,H
8.98,N 2.35。
Learn that the compound structure is correct from above, be polymer P FDTE2, the degree of polymerization is 183.
Embodiment 3
Method same as Example 1 prepares polymer P FDTE1, and difference is, formula (II) chemical combination in step (1)
Thing, titanium tetrachloride, the mol ratio of zinc powder are 1:2.0:2.0；Formula (III) compound, formula (IV) compound and formula in step (2)
(V) compound mole ratio is 1:2.0:2.0.
The polymer P FDTE1 structural characterization data for obtaining are substantially the same manner as Example 1.
Embodiment 4
Method same as Example 1 prepares polymer P FDTE1, and difference is, formula (II) chemical combination in step (1)
Thing, titanium tetrachloride, the mol ratio of zinc powder are 1:4.0:4.0；Formula (III) compound, formula (IV) compound and formula in step (2)
(V) compound mole ratio is 1:4.0:4.0.
The polymer P FDTE1 structural characterization data for obtaining are substantially the same manner as Example 1.
Embodiment 5
Method same as Example 2 prepares polymer P FDTE2, and difference is, formula (II) chemical combination in step (1)
Thing, titanium tetrachloride, the mol ratio of zinc powder are 1:2.0:2.0；Formula (III) compound, formula (IV) compound and formula in step (2)
(V) compound mole ratio is 1:2.0:2.0.
The polymer P FDTE1 structural characterization data for obtaining are substantially the same manner as Example 2.
Embodiment 6
Method same as Example 2 prepares polymer P FDTE2, and difference is, formula (II) chemical combination in step (1)
Thing, titanium tetrachloride, the mol ratio of zinc powder are 1:4.0:4.0；Formula (III) compound, formula (IV) compound and formula in step (2)
(V) compound mole ratio is 1:4.0:4.0.
The polymer P FDTE1 structural characterization data for obtaining are substantially the same manner as Example 2.
Embodiment 7
The spectrum property experiment of polymer P FDTE1 and polymer P FDTE2
Fig. 3 and Fig. 4 are respectively embodiment 1 and the polymer P FDTE1 and polymer P FDTE2 chlorobenzenes of the preparation of embodiment 2 are molten
The UV-visible absorption spectrum of liquid and film, from figure 3, it can be seen that there are two absorption bands, secondary suction in such polymer
Take-up is high energy band, and it is absorbed at 300 to 500 nanometers, and prominent absorption bands are low-energy zone, are absorbed as 550 to 950 nanometers.It is stronger
Low-energy zone absorb in explanation polymer molecule and there is stronger D-A to interact.As shown in Figure 4, the absorption curve of film compared with
There is a certain degree of red shift in solution, prominent absorption bands are low-energy zone, are absorbed as 550 to 1000 nanometers.
Embodiment 8
The thermal property experiment of polymer P FDTE1 and polymer P FDTE2
Fig. 5 is the thermal gravimetric analysis curve of polymer P FDTE1 and polymer P FDTE2, as seen from Figure 5, polymer
The heat decomposition temperature of PFDTE1 and polymer P FDTE2 is both greater than 390 DEG C, illustrates polymer P FDTE1 and polymer P FDTE2 tools
There is preferable heat endurance.
Embodiment 9
The chemical property experiment of polymer P FDTE1 and polymer P FDTE2
It is illustrated in figure 6 the cyclic voltammetry curve of polymer P FDTE1 and polymer P FDTE2.
Electrolytic cell uses three-electrode system, wherein platinum, platinum filament, silver/silver chlorate be respectively working electrode, to electrode and reference
Electrode, tetrabutyl ammonium hexafluorophosphate is supporting electrolyte.Sweep limits is -1.5~1.4 volts (vs.Ag/AgCl), scanning speed
Rate is 100 millivolts per second.Curve shows that the initial oxidation current potential of polymer P FDTE1 and polymer P FDTE2 is about 1.05 Hes
1.07 volts, thus estimate that their HOMO energy levels are about -5.45 and -5.47 electron-volts, initial reduction current potential is about -1.09
With -1.06 volts, thus estimate that their lumo energy is about -3.31 and -3.34 electron-volts.
Embodiment 10
It is as shown in Figure 7 and Figure 8 the AFM shape appearance figure of polymer P FDTE1 and polymer P FDTE2, from figure
As can be seen that two polymer can form fibre-like film structure that is fine and close and being cross-linked with each other, show polymer molecule
Between exist stronger intermolecular interaction.
Embodiment 11
The field-effect transistor of polymer P FDTE1 and polymer P FDTE2 is prepared and performance.
Fig. 9 is the organic field effect tube structural representation of polymer P FDTE1 and polymer P FDTE2.
As shown in figure 9, prepared by top-gated-bottom contact (TGBC) device：Jin Yuan-drain electrode, OFET are prepared using photoetching technique
The channel width (W) of device is 1400 μm, and channel length (L) is 40 or 50 μm.Dielectric substrate is the Si/SiO2 of 300nm.Substrate
By acetone, deionized water and a series of cleanings of EtOH Sonicate, one layer of OTS from group is then modified on the SiO2 substrates of drying
Dress individual layer.Semiconductor active layer is prepared by the polymer dichlorobenzene solution of spin coating 3mg/mL.Then film sample is placed in gloves
160 DEG C of annealing 5min in case.Then, one layer of PMMA dielectric layer of about 900nm is molten by the PMMA butyl acetates of spin coating 60mg/mL
Prepared by liquid, the weight average molecular weight of selected PMMA is 1000KDa, and dielectric constant k is about 2.05.Then, whole device is put
30min is toasted in 80 DEG C of vacuum drying chamber to remove butyl acetate solvent.Finally, a thickness is deposited with PMMA dielectric layers
The aluminium of about 100nm is spent as gate electrode.In nitrogen, prepared TGBC devices are in Keithley 4200SCS semiconductor tests
Field effect behavior is tested on instrument.
Figure 10-13 is the transfer curve of field-effect transistor prepared by polymer P FDTE1 and polymer P FDTE2 and defeated
Go out curve, carrier mobility can be calculated by equation：
IDS=(W/2L) Ciμ(VG–VT) 2 (saturation regions, VDS=VG–VT)
Wherein, IDSIt is drain current, μ is carrier mobility, VGIt is grid voltage, VTIt is threshold voltage, W is that raceway groove is wide
Degree, L is channel length, CiIt is insulation body capacitance (Ci=7.5 × 10-9Method is every square centimeter).Utilize (IDS, sat)1/2To VGMake
Figure, and makees linear regression, can the slope of the thus tropic extrapolate carrier mobility (μ), by the tropic and the tie point of X-axis
Try to achieve VT.Mobility can be calculated according to formula from the slope of transfer curve, and on-off ratio can be by Figure 10-13 source-drain currents
The ratio between maxima and minima draws.The device performance of the polymer field effect transistor of preparation is as shown in table 1.
Table 1：The device performance of the field-effect transistor based on polymer P FDTE1 and polymer P FDTE2
Multiple organic field effect tube devices have been constructed by semiconductor layer of polymer P FDTE1 and polymer P FDTE2,
Wherein PFDTE2 hole mobilities (μh) and on-off ratio (μhUp to 5.42cm2V-1s-1, on-off ratio is 104―105), electronics is moved
Shifting rate (μe)(μeUp to 0.36cm2V-1s-1)。
By the interpretation of above performance, described fluorination di-thiofuran ethylene polymer is that a class is excellent
Polymer semiconducting material.The present invention is not limited in the present embodiment the two fluorination di-thiofuran ethylene polymer enumerated, can be with
It is to change different substituent Rs1And R2A series of new polymers is obtained, because length is limited, is not listed one by one herein.
The synthetic route that the present invention is given is simply efficient, and reaction yield is high, and post processing is simple, and the degree of polymerization is high, is suitable for big rule
Mould synthesizes.Relation be- tween structure and properties and design, synthesized high-performance of the result of study for Study Polymer Melts semi-conducting material
Polymer semiconducting material has directive significance.
Claims (10)
1. it is a kind of to be fluorinated di-thiofuran ethylene polymer, it is characterised in that the structural formula of described fluorination di-thiofuran ethylene polymer
As shown in formula (I)：
Wherein, R1、R2It is C1- C100Straight or branched alkane, R1With R2Identical or different, n is the degree of polymerization, n=10-1000,
It is preferred that n=20-500.
2. described in a kind of claim 1 fluorination di-thiofuran ethylene polymer preparation method, it is characterised in that described preparation
Method comprises the following steps：
(1) under an inert gas, compound and titanium tetrachloride, zinc powder are reacted shown in formula (II), obtain formula (III) shownization
Compound, reactive chemistry equation is as follows：
(2) under an inert gas, compound shown in formula (III) and lithium reagent shown in formula (IV), tin reagent shown in formula (V) are carried out instead
Should, compound shown in formula (VI) is obtained, reactive chemistry equation is as follows：
Wherein, R3And R4It is C1-C7Straight or branched alkane, R3With R4Identical or difference；
(3) under an inert gas, compound shown in formula (VI), compound shown in formula (VII) are under palladium catalyst and part effect
Reacted, obtained described fluorination di-thiofuran ethylene polymer, reactive chemistry equation is as follows：
Wherein, the R in formula (VI) compound1And R2Respectively with formula (I) compound in R1And R2It is identical.
3. it is according to claim 2 fluorination di-thiofuran ethylene polymer preparation method, it is characterised in that in step (1)
Formula (II) compound, titanium tetrachloride, the mol ratio of zinc powder are 1:2.0~4.0:2.0~4.0, it is preferred that 1:1.58：2.5.
4. according to Claims 2 or 3 fluorination di-thiofuran ethylene polymer preparation method, it is characterised in that step (1)
In reaction temperature be -20~80 DEG C, the reaction time be 2~48 hours.
5. it is according to claim 2 fluorination di-thiofuran ethylene polymer preparation method, it is characterised in that in step (2)
The mol ratio of formula (III) compound, formula (IV) compound and formula (V) compound is 1:2.0~4.0:2.0~4.0, preferred 1:
2.4:2.4。
6. according to claim 2 or 5 fluorination di-thiofuran ethylene polymer preparation method, it is characterised in that step (2)
In reaction temperature be -80~25 DEG C, the reaction time be 2~48 hours.
7. it is according to claim 2 fluorination di-thiofuran ethylene polymer preparation method, it is characterised in that in step (3)
The palladium catalyst is three (dibenzalacetone) two palladium or tetrakis triphenylphosphine palladium；The part be three (o-tolyl) phosphines or
Triphenylphosphine.
8. according to claim 2 or 7 fluorination di-thiofuran ethylene polymer preparation method, it is characterised in that step (3)
Compound shown in middle formula (V), the mol ratio of compound, catalyst and part shown in formula (VI) are 1:0.95~1.05:0.01~
0.10:0.02~0.60, it is preferred that 1.0:1.0:0.05:0.4, reaction temperature is 60~150 DEG C, and the reaction time is 24~48
Hour.
9. it is according to claim 2 fluorination di-thiofuran ethylene polymer preparation method, it is characterised in that step (1), step
Suddenly the reaction of (2) and step (3) is carried out in organic solvent, in step (1) and step (2) organic solvent be tetrahydrofuran or
Ether, step (3) organic solvent is tetrahydrofuran, DMF, toluene or chlorobenzene.
10. application of the fluorination di-thiofuran ethylene polymer described in a kind of claim 1 in organic field effect tube is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710022687.2A CN106832230A (en) | 2017-01-12 | 2017-01-12 | One kind fluorination di-thiofuran ethylene polymer and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710022687.2A CN106832230A (en) | 2017-01-12 | 2017-01-12 | One kind fluorination di-thiofuran ethylene polymer and preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106832230A true CN106832230A (en) | 2017-06-13 |
Family
ID=59123237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710022687.2A Pending CN106832230A (en) | 2017-01-12 | 2017-01-12 | One kind fluorination di-thiofuran ethylene polymer and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106832230A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503669A (en) * | 2018-05-15 | 2018-09-07 | 北京科技大学 | A kind of efficient diarylethene light-operated switch molecule and preparation method thereof |
| CN108976395A (en) * | 2018-08-10 | 2018-12-11 | 中国科学院化学研究所 | Polymer and its application in organic field effect tube based on fluoro di-thiofuran ethylene derivative |
| CN110872376A (en) * | 2018-08-29 | 2020-03-10 | 中国科学院化学研究所 | Cyclized indigo receptor and polymer as well as preparation method and application thereof |
| CN111285842A (en) * | 2020-02-18 | 2020-06-16 | 中国科学院化学研究所 | Trifluoromethyl thiophene ethylene thiophene donor, polymer and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130240792A1 (en) * | 2012-03-19 | 2013-09-19 | Xerox Corporation | Semiconductor composition for high performance organic devices |
-
2017
- 2017-01-12 CN CN201710022687.2A patent/CN106832230A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130240792A1 (en) * | 2012-03-19 | 2013-09-19 | Xerox Corporation | Semiconductor composition for high performance organic devices |
Non-Patent Citations (2)
| Title |
|---|
| CHAOHUA CUI ET AL.: "Conjugated Oligothiophene Derivatives Based on Bithiophene with Unsaturated Bonds as Building Blocks for Solution-Processed Bulk Heterojunction Organic Solar Cells", 《CHEMISTRY - AN ASIAN JOURNAL》 * |
| WEIFENG ZHANG ET AL.: "Fluorodiphenylethene-Containing Donor−Acceptor Conjugated Copolymers with Noncovalent Conformational Locks for Efficient Polymer Field-Effect Transistors", 《MACROMOLECULES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503669A (en) * | 2018-05-15 | 2018-09-07 | 北京科技大学 | A kind of efficient diarylethene light-operated switch molecule and preparation method thereof |
| CN108976395A (en) * | 2018-08-10 | 2018-12-11 | 中国科学院化学研究所 | Polymer and its application in organic field effect tube based on fluoro di-thiofuran ethylene derivative |
| CN108976395B (en) * | 2018-08-10 | 2020-09-29 | 中国科学院化学研究所 | Polymers based on fluorodithiophene ethylene derivatives and their use in organic field effect transistors |
| CN110872376A (en) * | 2018-08-29 | 2020-03-10 | 中国科学院化学研究所 | Cyclized indigo receptor and polymer as well as preparation method and application thereof |
| CN110872376B (en) * | 2018-08-29 | 2022-07-19 | 中国科学院化学研究所 | Cyclized indigo receptor and polymer as well as preparation method and application thereof |
| CN111285842A (en) * | 2020-02-18 | 2020-06-16 | 中国科学院化学研究所 | Trifluoromethyl thiophene ethylene thiophene donor, polymer and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105198909B (en) | Compound for forming high-molecular compound | |
| Abe et al. | Thermally, operationally, and environmentally stable organic thin-film transistors based on bis [1] benzothieno [2, 3-d: 2′, 3′-d′] naphtho [2, 3-b: 6, 7-b′] dithiophene derivatives: Effective synthesis, electronic structures, and structure–property relationship | |
| CN101056873A (en) | Carbonyl-functionalized thiophene compounds and related device structures | |
| CN106832230A (en) | One kind fluorination di-thiofuran ethylene polymer and preparation method and application | |
| JP5425338B2 (en) | Copolymer containing anthracene and pearselenol, its production method and its application | |
| CN104672434B (en) | A kind of organic semiconducting materials and preparation method and application | |
| CN105348289A (en) | Nanometer grid, nanometer polymer grid material and their preparation method and use method | |
| CN108864137B (en) | Receptor compound, preparation method and application thereof, and photovoltaic cell containing receptor compound | |
| CN106866943B (en) | A kind of naphthalimide-fluorination di-thiofuran ethylene conjugated polymer and the preparation method and application thereof | |
| CN101787020A (en) | Organic conjugated molecule capable of being processed by solution and application thereof in solar cells | |
| CN104761563A (en) | Electron withdrawing group-containing phenylene vinylene compound, and preparation method and application thereof | |
| Kawabata et al. | Synthesis of soluble dinaphtho [2, 3-b: 2′, 3′-f] thieno [3, 2-b] thiophene (DNTT) derivatives: One-step functionalization of 2-bromo-DNTT | |
| CN109096342A (en) | A kind of cyclic conjugated compound of dione pyrrolo-pyrrole and the preparation method and application thereof | |
| CN103403907A (en) | Method for manufacturing organic photoelectric conversion element | |
| CN106749318A (en) | A kind of organic field effect tube material and its synthetic method and application based on oxa- condensed ring class | |
| CN105820316B (en) | Hetero atom replaces naphthalimide polymer semiconductor and the preparation method and application thereof | |
| Hong et al. | A novel small molecule based on dithienophosphole oxide for bulk heterojunction solar cells without pre-or post-treatments | |
| Park et al. | [1] Benzothieno [3, 2-b][1] benzothiophene-based liquid crystalline organic semiconductor for solution-processed organic thin film transistors | |
| Duan et al. | Organic field-effect transistors based on two phenylene–thiophene oligomer derivatives with a biphenyl or fluorene core | |
| Kivrak et al. | Synthesis of thiophenyl-substituted unsymmetrical anthracene derivatives and investigation of their electrochemical and electrooptical properties | |
| Ie et al. | Perfluoroalkyl-annelated conjugated systems toward n-type organic semiconductors | |
| CN108503655B (en) | Heterocyclic compound and organic electronic device using same | |
| CN103113557A (en) | Phenanthro[1,10,9,8-cdefg]carbazolyl copolymer as well as preparation method and application thereof | |
| Park et al. | Semiconducting π-extended porphyrin dimer and its characteristics in OFET and OPVC | |
| CN110964040B (en) | Benzoxadiazole-based acceptor material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170613 |
|
| RJ01 | Rejection of invention patent application after publication |