CN107141456A - A kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application - Google Patents

A kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application Download PDF

Info

Publication number
CN107141456A
CN107141456A CN201710452700.8A CN201710452700A CN107141456A CN 107141456 A CN107141456 A CN 107141456A CN 201710452700 A CN201710452700 A CN 201710452700A CN 107141456 A CN107141456 A CN 107141456A
Authority
CN
China
Prior art keywords
polymer
formulas
ncntvt
formula
thiophene
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
Application number
CN201710452700.8A
Other languages
Chinese (zh)
Inventor
于贵
林祖樟
刘晓彤
张卫锋
王丽萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemistry CAS
University of Science and Technology Beijing USTB
Original Assignee
Institute of Chemistry CAS
University of Science and Technology Beijing USTB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Institute of Chemistry CAS, University of Science and Technology Beijing USTB filed Critical Institute of Chemistry CAS
Priority to CN201710452700.8A priority Critical patent/CN107141456A/en
Publication of CN107141456A publication Critical patent/CN107141456A/en
Pending legal-status Critical Current

Links

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
    • C08G61/126—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
    • 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
    • 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 a potential-jump barrier or a surface barrier
    • 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
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1428—Side-chains containing oxygen containing acyl groups
    • 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
    • C08G2261/143—Side-chains containing nitrogen
    • 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
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-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
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/514—Electron transport
    • 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
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • C08G2261/592—Stability against heat
    • 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

Abstract

The invention discloses a kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application.The structural formula of the polymer is shown in formula I.The polymer has strong interchain interaction, and its structure is rigid planar structure.The material has stronger ultravioletvisible absorption and good thermal stability, relatively low level structure is conducive to carrier to inject, it can be used for preparing the bipolarity organic field effect tube with superior performance, obtained device has very high hole mobility (μh) and on-off ratio, μhUp to 6.41 × 10‑3cm2V‑1s‑1, on-off ratio is 102- 103, with higher electron mobility (μe)(μeUp to 4.82 × 10‑2cm2V‑ 1s‑1), have broad application prospects.

Description

A kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application
Technical field
The invention belongs to organic semiconducting materials technical field, and in particular to a kind of naphthalimide thiophene cyano vinyl polymerization Thing and preparation method and application.
Background technology
Organic field effect tube is exactly the device of having chance with that the electric current between source-drain electrode is controlled by the voltage of grid, with Organic semiconducting materials are used as carrier blocking layers.High performance organic field effect tube has broad application prospects, it Successful application in fields such as smart card, sensor, electronic radio frequency tags, large screen display and integrated circuits can necessarily promote Enter the technological innovation of the numerous areas such as information, the energy, life, far-reaching shadow will be produced to economic development and social progress Ring, compared with traditional inorganic material, the characteristics of organic semiconducting materials have following several respects：1) raw material is readily obtained and closed Into technique it is simple the advantages of, 2) there is the Modulatory character and good elasticity and pliability of physicochemical properties, 3 again) it is available Solwution method is processed, so as to provide possibility for extensive manufacture lightweight, flexible electronic device.Therefore, organic effect The research of crystal is had become by R＆D institution and the extensive concern of researcher for its performance and structure correlative study One of focus of organic electronics research field.
Organic semiconductor layer active material used in 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 the electronics device based on polymer research is as organic electronics Study hotspot.In recent years, polymer field effect transistor device performance research achieves breakthrough progress Persson, N.E.；Chu,P.-H.；McBride,M.；Grover,M.；Reichmanis,E.,Nucleation,Growth,and Alignment of Poly(3-hexylthiophene)Nanofibers for High-Performance OFETs.Accounts of Chemical Research 2017.；James,D.I.；Wang,S.；Ma,W.； S.；Meng,X.；Persson,P.；Fabiano,S.；Crispin,X.；Andersson,M.R.；Berggren,M.；Wang, E.,High-Performance Hole Transport and Quasi-Balanced Ambipolar OFETs Based on D-A-A Thieno-benzo-isoindigo Polymers.Adv.Electron.Mater.2016,2(4), 1500313.；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).According to result of study at this stage, accordingly The development of semi-conducting material and device technology of preparing, the application prospect of polymer field effect transistor device will be more wide.So And, current existing polymer semiconducting material still can not meet reality as the stability of the device of semiconductor layer material Application environment, so, design synthesized high-performance, the good semi-conducting material of stability becomes the top priority of researcher.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of naphthalimide thiophene cyano vinyl polymer And preparation method and application.
The first object of the present invention there is provided a kind of naphthalimide thiophene cyano vinyl polymer, its general structure such as formula Shown in I：
In the Formulas I, R is C1-C100Straight or branched alkyl；
N=10-1000.
Specifically, R is C1-C12Straight or branched alkyl；
N=20-500, more specifically, n can be 25-50, then concretely 29-42, more specifically can be 29-40；
The R can be 2- octyldodecyls or 2- decyl myristyls.
The second object of the present invention is the provision of naphthalimide thiophene cyano vinyl polymer shown in a kind of formula I Method.
As shown in figure 1, this method comprises the following steps：In an inert atmosphere, by shown in compound shown in Formula II and formula III Compound carries out Stille coupling reactions under conditions of palladium catalyst and part are present, and reaction, which is finished, to be obtained shown in the Formulas I Polymer；
In the Formula II, defining for R is identical with the definition of R in the Formulas I.
The palladium catalyst is three (dibenzalacetone) two palladium or tetrakis triphenylphosphine palladium；
The part is three (o-tolyl) phosphines or triphenylphosphine.
Compound described in the Formula II, the mol ratio of compound, palladium catalyst and part shown in formula III are 1.0:0.95~ 1.05:0.01~0.10:0.02~0.60, concretely 1.0:1.0:0.03:0.27.
The inert atmosphere concretely argon gas atmosphere.
In the Stille coupling reactions step, reaction temperature is 60~150 DEG C, concretely 110 DEG C；
Reaction time is 24~48 hours.
The Stille coupling reactions are carried out in organic solvent.The organic solvent concretely toluene or chlorobenzene.
The above method may also include the steps of：After the Stille coupling reactions step, reaction system is cooled down, The mixture for adding methanol and hydrochloric acid is stirred at room temperature, is filtered.Gained solid is extracted with apparatus,Soxhlet's, and extraction solvent is successively Methanol, acetone, n-hexane extracting, are finally extracted and obtained with chloroform.
In the mixture of the methanol and hydrochloric acid, the concentration of hydrochloric acid concretely 6M；The volume ratio of methanol and hydrochloric acid is specific Can be 20：1.It is described the step of stir at room temperature in, time of stirring concretely 2h；In the extraction steps, every kind of extracting The extraction times of solvent concretely 24h.
The third object of the present invention is the provision of a kind of naphthalimide thiophene cyano vinyl polymer recited above and existed Prepare the application in organic field effect tube and constitute the material of semiconductor layer and imitated for the organic field of polymer shown in the Formulas I Answer transistor.
Beneficial effects of the present invention are as follows：
1) naphthalimide thiophene cyano vinyl polymer shown in the Formulas I that the present invention is provided has strong interchain interaction, Its structure is the easily close intermolecular accumulation of formation in rigid planar structure, film, and film stack has stronger long-range order, Solution and film are respectively provided with stronger ultraviolet-ray visible absorbing, and the material has good thermal stability, relatively low level structure Be conducive to carrier to inject, with stronger ultraviolet-ray visible absorbing and good thermal stability, can be used for prepare have compared with High performance bipolarity organic field effect tube, obtained device has very high hole mobility (μh) and on-off ratio, μhMost A height of 6.41 × 10-3cm2V-1s-1, on-off ratio is 102- 103, with higher electron mobility (μe)(μeUp to 4.82 × 10-2cm2V-1s-1), have broad application prospects.
2) synthesis step for preparing naphthalimide thiophene cyano vinyl polymer that the present invention is provided is simple, efficient, reaction High income, post processing is simple, and the degree of polymerization is high, is adapted to extensive synthesis.
Brief description of the drawings
Fig. 1 be naphthalimide thiophene cyano vinyl polymer of the present invention be compound of formula I synthetic route chart；
Fig. 2 is Inventive polymers PNCNTVT-8 and polymer P NCNTVT-10 synthetic route charts；
Fig. 3 is ultraviolet-visibles of the Inventive polymers PNCNTVT-8 and polymer P NCNTVT-10 in chloroform soln Abosrption spectrogram；
Fig. 4 is the uv-visible absorption spectra of Inventive polymers PNCNTVT-8 and polymer P NCNTVT-10 films Figure；
Fig. 5 is Inventive polymers PNCNTVT-8 and polymer P NCNTVT-10 thermal gravimetric analysis curve figure；
Fig. 6 is Inventive polymers PNCNTVT-8 and polymer P NCNTVT-10 cyclic voltammetry curve maps；
Fig. 7 is the atomic force of Inventive polymers PNCNTVT-8 and polymer P NCNTVT-10 under different annealing temperature Microscope shape appearance figure；
Fig. 8 is Inventive polymers PNCNTVT-8 and polymer P NCNTVT-10 transistor arrangement schematic diagram；
Fig. 9 is that Inventive polymers PNCNTVT-8 (schemes a, schemes b, scheme c, figure is d) and polymer P NCNTVT-10 (schemes e, figure F, schemes g, schemes the transfer curve figure and output curve diagram of h) field-effect transistor.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute It is conventional method unless otherwise instructed to state method.The raw material can be obtained from open commercial sources unless otherwise instructed. Embodiment in following embodiments can be further combined or replace, and embodiment is only that the present invention is preferable to carry out Example is described, and not the spirit and scope of the present invention are defined, on the premise of design philosophy of the present invention is not departed from, this The various changes and modifications that professional and technical personnel makes to technical scheme in field, belong to the protection model of the present invention Enclose.
The structural formula such as formula III of double (5- (tin trimethyl) thiophene -2- bases) acrylonitrile of cis- 2,3- used in following embodiments It is shown：
The synthesis of embodiment 1, polymer P NCNTVT-8
By double (2- octyldodecyls) benzo [lmn] [3,8] phenanthroline-1,3,6 of the bromo- 2,7- of 4,9- bis-, Double (5- (tin trimethyl) thiophene -2- bases) third of cis- 2,3- shown in 8 (2H, 7H)-tetrones (0.20mmol, 197.01mg) and formula III Alkene nitrile (0.20mmol, 108.60mg), palladium catalyst is three (dibenzalacetone) two palladium (6mg, 0.0065mmol), part three (o-tolyl) phosphine (16.2mg, 0.053mmol) and organic solvent chlorobenzene (6.0mL) are added in reaction bulb, are entered in argon gas Three freezing-pumping-thaw cycles deoxygenations of row, after reactant mixture is heated to carry out Stille under 110 argon DEG C gas shieldeds it is even Connection reaction 24h.After cooling, 200mL methanol/6M HCl mixtures (v/v 20 is added:1) 2h, is stirred at room temperature, is filtered.Gained Solid is extracted with apparatus,Soxhlet's.Extraction solvent is methanol successively, acetone, n-hexane, respectively extract 24h, finally uses chloroform Extraction obtains 172.53 milligrams of subject polymer, yield 82.74%.
Structural characterization data are as follows：
Molecular weight：GPC:Mn=42.00kDa, Mw=94.37kDa, PDI=2.24, n are 40.
Elementary analysis：C65H91N3O4S2:Calculated value：C 74.88,H 8.80,N 4.03.；Probe value:C 74.26,H 8.56,N 4.05.
Understand that the compound structure is correct by analysis above, be polymer P NCNTVT-8.
Embodiment 2, polymer P NCNTVT-10
By double (2- decyls myristyl) benzo [lmn] [3,8] phenanthroline-1,3,6 of the bromo- 2,7- of 4,9- bis-, Double (5- (tin trimethyl) thiophene -2- bases) third of cis- 2,3- shown in 8 (2H, 7H)-tetrones (0.20mmol, 219.46mg) and formula III Alkene nitrile (0.20mmol, 108.60mg), three (dibenzalacetone) two palladium (6mg, 0.0065mmol), three (o-tolyl) phosphines (16.2mg, 0.053mmol) and chlorobenzene (6.0mL) are added in reaction bulb, and three freezing-pumping-defrostings are carried out in argon gas Circulate deoxygenation, after reactant mixture be heated to 110 argon DEG C gas shieldeds carry out Stille coupling reactions 24h.After cooling, add 200mL methanol/6M HCl mixtures (v/v 20:1) 2h, is stirred at room temperature, is filtered.Gained solid is extracted with apparatus,Soxhlet's. Extraction solvent is methanol successively, acetone, n-hexane, respectively extract 24h, is finally extracted with chloroform and obtains subject polymer 182.26 milligram, yield 78.91%.
Structural characterization data are as follows：
Molecular weight：GPC:Mn=31.40kDa, Mw=66.61kDa, PDI=2.12, n are 29.
Elementary analysis：Elementary analysis：C73H107N3O4S2, calculated value：C 75.93,H 9.34,N 3.64；Probe value:C 75.38,H 9.07,N 3.68。
Learn that the compound structure is correct from above, be polymer P NCNTVT-10.
The spectrum property experiment of embodiment 3, polymer P NCNTVT-8 and polymer P NCNTVT-10
Fig. 3 and Fig. 4 are respectively polymer P NCNTVT-8 and polymer P NCNTVT-10 prepared by embodiment 1 and embodiment 2 Chloroform soln (concentration is 0.005mmol/L) and film UV-visible absorption spectrum, from figure 3, it can be seen that There are two absorption bands in such polymer, prominent absorption bands are high energy band, and it is absorbed at 360 to 470 nanometers, secondary absorption band For low-energy zone, 480 to 750 nanometers are absorbed as.Stronger low-energy zone, which is absorbed in explanation polymer molecule, has stronger D-A mutual Effect.As shown in Figure 4, the absorption curve of film is compared with there is a certain degree of red shift in solution.
The thermal property experiment of embodiment 4, polymer P NCNTVT-8 and polymer P NCNTVT-10
Fig. 5 is polymer P NCNTVT-8 and polymer P NCNTVT-10 thermal gravimetric analysis curve, as seen from Figure 5, is gathered Compound PNCNTVT-8 and polymer P NCNTVT-10 heat decomposition temperature are both greater than 400, DEG C explanation polymer P NCNTVT-8 and Polymer P NCNTVT-10 has preferable heat endurance.
The chemical property experiment of embodiment 5, polymer P NCNTVT-8 and polymer P NCNTVT-10
It is illustrated in figure 6 polymer P NCNTVT-8 and polymer P NCNTVT-10 cyclic voltammetry curve.
Electrolytic cell uses three-electrode system, and wherein platinum, platinum filament, silver/silver chlorate are respectively working electrode, to electrode and reference Electrode, tetrabutyl ammonium hexafluorophosphate is supporting electrolyte.Scanning range is -1.5~1.4 volts (vs.Ag/AgCl), scanning speed Rate is 100 millivolts per second.Curve show polymer P NCNTVT-8 and polymer P NCNTVT-10 initial reduction current potential be about- 0.48 and -0.44 volt, the lumo energy for thus estimating them is about -3.92 and -3.96 electron-volts.According to EHOMO=ELUMO- Eg optIt is -5.53 and -5.57 electron-volts that calculating, which obtains their HOMO energy levels,.
Embodiment 6
It is illustrated in figure 7 the atomic force microscopy of polymer P NCNTVT-8 and polymer P NCNTVT-10 at different temperatures Mirror shape appearance figure, it can be seen that fibre-like film structure that is that two polymer can form densification and being cross-linked with each other, Show there is stronger intermolecular interaction between polymer molecule.
The field-effect transistor of embodiment 7, polymer P NCNTVT-8 and polymer P NCNTVT-10 is prepared and performance.
Fig. 8 is polymer P NCNTVT-8 and polymer P NCNTVT-10 organic field effect tube structural representation.
As shown in figure 8, 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 80 μm, and width is 8800 μm.Dielectric substrate is 300nm glass Glass substrate.Substrate passes through a series of cleanings of acetone, deionized water and EtOH Sonicate, is then modified in the glass substrate of drying One layer of OTS self-assembled monolayer.It is dichloro-benzenes that the solution used in semiconductor layer is prepared by spin coating, and concentration is 10mg/mL, gained half The thickness of conductor layer is 100nm.Then film sample is placed in 120 DEG C of annealing 5min in glove box.Then, one layer of PMMA dielectric layer Prepared by spin coating 60mg/mL PMMA butyl acetates solution, selected PMMA weight average molecular weight is 1000KDa, dielectric Constant k is about 2.05.Then, by whole device be placed in 80 DEG C of vacuum drying chamber toast 30min it is molten to remove butyl acetate Agent.Finally, the aluminium for a layer thickness about 100nm being deposited on PMMA dielectric layers is used as gate electrode.In nitrogen, prepared TGBC Device tests field effect behavior on the SCS semi-conductor test instruments of Keithley 4200.
Fig. 9 is the transfer curve of the field-effect transistor prepared by polymer P NCNTVT-8 and polymer P NCNTVT-10 And curve of output, carrier mobility can calculate by equation：
IDS=(W/2L) Ciμ(VG–VT) 2 (saturation regions, VDS=VG–VT)
Wherein, IDSFor drain current, μ is carrier mobility, VGFor grid voltage, VTFor threshold voltage, W is that raceway groove is wide Degree, L is channel length, CiFor insulation body capacitance (Ci=7.5 × 10-9Method is every square centimeter).Utilize (IDS, sat)1/2To VGMake Figure, and make 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, on-off ratio can by Fig. 9 source-drain currents maximum The ratio between value and minimum value are drawn.The device performance of the polymer field effect transistor of preparation is as shown in table 1.
The device performance of table 1, field-effect transistor based on polymer P NCNTVT-8 and polymer P NCNTVT-10
Multiple organic effect crystal have been constructed by semiconductor layer of polymer P NCNTVT-8 and polymer P NCNTVT-10 Tube device, wherein PNCNTVT-8 hole mobilities (μh) and on-off ratio (μhUp to 6.41 × 10-3cm2V-1s-1, on-off ratio is 102-103), electron mobility (μe)(μeUp to 4.82 × 10-2cm2V-1s-1)。
The naphthalimide thiophene cyano vinyl polymer provided by the analysis of experimental results of above performance, the present invention It is the excellent polymer semiconducting material of a class.The present invention is not limited to the two naphthalimide thiophene cyanogen enumerated in the present embodiment Base ethene polymers, can change different substituent Rs to obtain a series of new polymers, because length is limited, not exist This is listed one by one.
The synthesis step that the present invention is provided 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 is synthesized.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. polymer shown in Formulas I,
In the Formulas I, R is C1-C100Straight or branched alkyl；
N=10-1000.
2. polymer according to claim 1, it is characterised in that：In the Formulas I, R is C1-C12Straight or branched alkane Base；
N=20-500；
The R is 2- octyldodecyls or 2- decyl myristyls.
3. a kind of method for preparing polymer shown in Formulas I described in claim 1, comprises the following steps：
In an inert atmosphere, condition compound shown in compound shown in Formula II and formula III existed in palladium catalyst and part Lower progress Stille coupling reactions, reaction, which is finished, obtains polymer shown in the Formulas I；
In the Formula II, defining for R is identical with the definition of R in the Formulas I.
4. method according to claim 3, it is characterised in that：The palladium catalyst be three (dibenzalacetone) two palladium or Tetrakis triphenylphosphine palladium；
The part is three (o-tolyl) phosphines or triphenylphosphine.
5. the method according to claim 3 or 4, it is characterised in that：Compound described in the Formula II, chemical combination shown in formula III The mol ratio of thing, palladium catalyst and part is 1.0:0.95~1.05:0.01~0.10:0.02~0.60 or 1.0:1.0: 0.03:0.27。
6. according to any described method in claim 3-5, it is characterised in that：In the Stille coupling reactions step, instead It is 60~150 DEG C or 110 DEG C to answer temperature；
Reaction time is 24~48 hours；
The inert atmosphere is argon gas atmosphere.
7. according to any described method in claim 3-6, it is characterised in that：The Stille coupling reactions are in organic solvent It is middle to carry out.
8. method according to claim 7, it is characterised in that：The organic solvent is toluene or chlorobenzene.
9. application of the polymer in organic effect transistor is prepared described in any Formulas I of claim 1 or 2.
10. a kind of organic field effect tube, it is characterised in that：In the organic field effect tube, semiconductor layer is constituted Material is polymer shown in any Formulas I of claim 1 or 2.
CN201710452700.8A 2017-06-15 2017-06-15 A kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application Pending CN107141456A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710452700.8A CN107141456A (en) 2017-06-15 2017-06-15 A kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710452700.8A CN107141456A (en) 2017-06-15 2017-06-15 A kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application

Publications (1)

Publication Number Publication Date
CN107141456A true CN107141456A (en) 2017-09-08

Family

ID=59782487

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710452700.8A Pending CN107141456A (en) 2017-06-15 2017-06-15 A kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application

Country Status (1)

Country Link
CN (1) CN107141456A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014077590A1 (en) * 2012-11-13 2014-05-22 경상대학교산학협력단 Polymer comprising novel naphthalene diimide and organic electronic device using same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014077590A1 (en) * 2012-11-13 2014-05-22 경상대학교산학협력단 Polymer comprising novel naphthalene diimide and organic electronic device using same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHUI-XING DAI ET AL.: "Rylene Diimide and Dithienocyanovinylene Copolymers for Polymer Solar Cells", 《CHINESE JOURNAL OF POLYMER SCIENCE》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
Li et al. A fused-ring based electron acceptor for efficient non-fullerene polymer solar cells with small HOMO offset
Dong et al. Multilevel investigation of charge transport in conjugated polymers
CN105731372B (en) Photovoltaic cell containing optical active polymer
JP5735418B2 (en) Poly (5,5'-bis (thiophen-2-yl) -benzo [2,1-b; 3,4-b '] dithiophene) and method for its use as a high performance solution capable of processing semiconductor polymers
CN106866943B (en) A kind of naphthalimide-fluorination di-thiofuran ethylene conjugated polymer and the preparation method and application thereof
Zhang et al. π-Conjugated oligomers based on aminobenzodifuranone and diketopyrrolopyrrole
Elsawy et al. Isoindigo-based small molecules for high-performance solution-processed organic photovoltaic devices: the electron donating effect of the donor group on photo-physical properties and device performance
CN106589326A (en) Difluoro-bithiophene polymer as well as preparation method and application thereof to FET (field effect transistor)
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
CN106832230A (en) One kind fluorination di-thiofuran ethylene polymer and preparation method and application
CN108503655B (en) Heterocyclic compound and organic electronic device using same
Duan et al. Organic field-effect transistors based on two phenylene–thiophene oligomer derivatives with a biphenyl or fluorene core
Hong et al. New π-extended diketopyrrolopyrrole-based conjugated molecules for solution-processed solar cells: Influence of effective conjugation length on power conversion efficiency
Opoku et al. Facile synthesis and optoelectronic properties of thienopyrroledione based conjugated polymer for organic field effect transistors
CN108409755B (en) Organic photoelectric conversion material, preparation method and application thereof
Park et al. Semiconducting π-extended porphyrin dimer and its characteristics in OFET and OPVC
CN107141456A (en) A kind of naphthalimide thiophene cyano vinyl polymer and preparation method and application
Yan et al. Design, synthesis and photophysical properties of ADADA small molecules for photovoltaic application
CN104927030B (en) Ketone polymer of indoles 2 and preparation method and application
CN107814918B (en) Aza indolone benzofuranone-thiophene diazosulfide conjugated polymer and the preparation method and application thereof
CN105837799B (en) A kind of dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer and preparation method and application
US20130225782A1 (en) Organic semiconductor material, preparation methods and uses thereof
CN107814813A (en) N type quinoid Dithiophene field-effect semiconductor materials and its preparation method and application
CN103746075A (en) Method for improving stability of organic thin-film transistor
Lu et al. Fine-tuning the molecular energy levels by incorporating thiophene units onto the π-backbone of core-expanded naphthalene diimides

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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170908