CN104927030A - Indole-2-ketone polymer as well as preparation method and application thereof - Google Patents
Indole-2-ketone polymer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an indole-2-ketone polymer as well as a preparation method and application thereof. The structural formula of the indole-2-ketone polymer is as shown in the formula I (refer to the Specification), wherein R is selected from any of the followings: a linear chain or branched chain alkyl group of C8-C80 (preferentially C5-C50), X is selected from S and Se and n refers to degree of polymerization and equals to 5-500 (preferentially 10-100). The invention further provides the preparation method of the polymer as shown in the formula I. According to the invention, the synthetic route is simple and practical, fewer in synthesis steps, high in yield and suitable for large-scale synthesis. The mobility ratio and switch ratio of a field effect transistor prepared through adopting the indole-2-ketone polymer as an organic semiconductor layer are higher, the mobility rate is 0.35 cm<2>V<-1>s<-1>, and the switch ratio is greater than 10<6>. The indole-2-ketone polymer has excellent application prospect in organic field effect devices.
Description
Technical field
The invention belongs to organic semiconductor material technical field, be specifically related to indol-2-one base polymer and preparation method thereof and application.
Background technology
Organic field effect tube (organic field-effect transistors, OFETs) be an important branch of organic electronics, just receive the extensive concern of whole world science and technology and academia from its oneself birth, become one of focus of organic electronics research field.Organic field effect tube has potential use very widely, can prepare multiple electronics device, driving element of such as e-book, organic RF tag, smart card, unicircuit, storage and senser element and Flexible Displays etc.In a word, if organic field effect tube can be used widely, great impact will be produced on global science technology and economy, human life style and social progress.Individual for research, take the lead in obtaining core knowledge property right and will obtain larger right of speech in following high-tech industry development, also will obtain huge economic interests simultaneously.So, famous high-tech enterprise on internal and international at present and research institution, as Peking University, Tsing-Hua University, South China Science & Engineering University, Stanford University, Bell Laboratory etc., all drop into the R&D work that huge energy and resource is engaged in high performance semiconductor material and fieldtron thereof.
The organic field effect tube active electronic device that to be based on organic semiconductor material, its performance perameter mainly comprises mobility (μ), on-off ratio (I
on/ I
off) and threshold voltage (V
t).Wherein mobility (μ) and on-off ratio (I
on/ I
off) numerical value larger, indicate that device has good performance.And threshold voltage (V
tH) then more better close to zero volt, such device more can save energy.In addition, the whether simple of preparation condition of fieldtron is also weigh its whether excellent important indicator.This is also one of superior basic reason of the more traditional inorganic field effect transistor device of organic field effect tube device.The purification process that inorganic semiconductor material comprises the high purity elemental such as silicon, gallium can bring a large amount of waste liquids, waste residue and waste water, and the preparation condition of its device is also quite harsh simultaneously, and cost is higher.And organic field effect tube, can by spraying, getting rid of the solution method such as film and printing technique low cost, big area preparation.
Organic semiconductor material comprises the classification such as organic molecule, oligomer and polymer semiconducting material.Compare with oligomer with small molecules, polymer semiconducting material more has synthesis simple, can prepare on a large scale and the feature such as good film-forming property, thus have larger application prospect.So attracted the special concern of related research institutes and workers based on the field-effect transistor (polymer field-effect transistors, PFETs) of polymer semiconducting material, also obtain huge progress in recent years.But, the performance of current existing polymer field effect transistor device still can not meet actual needs, so continue Development of Novel polymer materials still tool be of great significance, also to our development, there is the achievement in research of independent intellectual property right simultaneously and seize scientific and technological commanding elevation and provide opportunity.
Summary of the invention
The object of this invention is to provide a kind of indol-2-one base polymer and preparation method thereof and application.
Indol-2-one base polymer provided by the invention, its general structure is such as formula shown in I:
In described formula I, R is selected from C
5-C
80straight or branched alkyl in any one;
X is selected from S and Se;
N is 5-500.
Concrete, in described formula I, R is selected from C
10-c
50straight or branched alkyl in any one, be specifically selected from C
10c
30straight or branched alkyl in any one, be more specifically 2-decyl dodecyl;
X is S or Se;
N is 10-100, is specially 27 or 17.
More specifically, polymkeric substance shown in described formula I is polymer P VDTOIVT (R=2-decyl dodecyl, X=S) or polymer P VDTOIVS (R=2-decyl dodecyl, X=Se).
Shown in the described formula I of preparation provided by the invention, the method for polymkeric substance, comprises the steps:
Under palladium catalyst existent condition, shown in compound, part and formula Ⅹ shown in formula Ⅸ or formula Ⅺ, compound carries out Stille polyreaction, reacts complete and obtains polymkeric substance shown in described formula I;
In described formula Ⅸ, the definition of R defines identical with the R in described formula I;
In described formula Ⅹ and formula Ⅺ, R
4for C
1-C
4straight or branched alkyl, specifically can be methyl;
In aforesaid method, described palladium catalyst is selected from least one of three (dibenzalacetone) two in palladium and tetrakis triphenylphosphine palladium;
Described part is three (o-tolyl) phosphine or triphenylphosphines;
Compound shown in described formula X is specially the compound 6 of following structural formula:
Compound shown in described formula XI is specially the compound 7 of following structural formula:
Shown in compound shown in described formula Ⅸ and formula Ⅹ or formula Ⅺ, the molar ratio of compound is 1:0.95 ~ 1.05, is specially 1:1;
The consumption of described palladium catalyst to feed intake 1% ~ 10% of mole dosage for compound shown in described formula Ⅸ, is specially 5%;
The consumption of described part to feed intake 10% ~ 50% of mole dosage for compound shown in described formula Ⅸ, is specially 30%;
In described Stille polymerization procedure, temperature is 90 DEG C ~ 150 DEG C, preferably 80 DEG C ~ 120 DEG C, is specially 110 DEG C;
Time is 1 hour ~ 48 hours, preferably 24 hours;
Described Stille polyreaction is carried out in an inert atmosphere; Described inert atmosphere specifically can be argon gas atmosphere;
Described reaction is carried out in a solvent; Described solvent is specifically selected from least one in DMF, toluene and chlorobenzene.
Midbody compound used when present invention also offers preparation formula I, also i.e. compound shown in formula Ⅸ:
In described formula Ⅸ, the definition of R defines identical with the R in described formula I.
Shown in the described formula Ⅸ of preparation provided by the invention, the method for compound, comprises the steps:
In an inert atmosphere, compound shown in compound shown in formula VII, formula VIII and alkali are carried out substitution reaction, react complete and obtain compound shown in described formula Ⅸ;
In described formula VIII, the definition of R defines identical with the R in previously described formula I;
Y is Br or I.
In aforesaid method, described alkali is selected from least one in salt of wormwood, sodium carbonate and Strontium carbonate powder;
Shown in described formula VII, shown in compound, formula VIII, the molar ratio of compound and alkali is 1:2 ~ 4:3 ~ 5, is specially 1:2.4:3;
In described substitution reaction step, temperature is 60 DEG C ~ 130 DEG C, preferably 80 DEG C ~ 100 DEG C; Time is 6 hours ~ 48 hours, preferably 24 hours;
Described addition reaction is carried out in a solvent; Described solvent is specifically selected from DMF, N,N-dimethylacetamide, Isosorbide-5-Nitrae-dioxane, at least one in tetrahydrofuran (THF).
The synthetic route of compound shown in above-mentioned preparation formula I and formula Ⅸ as shown in Figure 1.
In aforesaid method, during preparation formula Ⅸ, shown in starting materials VII used, compound can be prepared in accordance with the following steps and obtain:
(1) in an inert atmosphere, compound shown in compound and formula IV shown in compound shown in formula II, formula III is carried out substitution reaction, obtains compound shown in formula V;
In formula III, R
2for C
4straight or branched alkane, [(CH
3)
2cH]
2n or [(CH
3cH
2)
2cH]
2n;
In formula IV, R
3for N, N-dimethylamino, piperidino, 4-morpholine base;
In formula V, X is selected from S and Se
(2) in an inert atmosphere, compound shown in compound and formula VI shown in alkaline condition following formula V reacts, and obtains compound shown in formula VII;
In aforesaid method step (1), the mole dosage ratio that feeds intake of compound shown in compound and formula IV shown in compound with formula III shown in formula II is followed successively by 1:2.0 ~ 3.0:2.0 ~ 3.0, specifically can be 1:2.1:2.2.
The temperature of described reaction is-80 DEG C ~ 30 DEG C, and preferably-78 DEG C ~ 25 DEG C, the time is 1 hour ~ 12 hours, preferably 2 hours.
Described reaction solvent for use is at least one in tetrahydrofuran (THF) and ether, preferred tetrahydrofuran (THF);
In aforesaid method step (2), described alkali, is selected from piperidines or pyridine.
The temperature of described reaction is 25 DEG C ~ 100 DEG C, preferably 60 DEG C ~ 80 DEG C, and the time is 6 hours ~ 24 hours, preferably 12 hours.
Described reaction solvent for use is at least one in methyl alcohol and ethanol, particular methanol.
In addition, the application of polymkeric substance shown in the described formula I that the invention described above provides in the organic effect transistor of preparation and the organic field effect tube being organic semiconductor layer with polymkeric substance shown in described formula I, also belong to protection scope of the present invention.
The invention has the advantages that:
1, the synthesis material of this new indole-2-ketone polymkeric substance can simply synthesize or a large amount of buying obtains from commercial channels.Synthetic route is simple, and synthesis step is few, and yield is high is suitable for extensive synthesis.
2, this new indole-2-ketone polymkeric substance has wider uv-visible absorption spectroscopy, excellent thermal stability, excellent film-forming properties, is expected to prepare high-performance polymer FET device by solution method.
3. this new indole-2-ketone polymkeric substance is that field-effect transistor prepared by semiconductor layer has higher carrier mobility (μ) and on-off ratio (I
on/ I
off) (μ is up to 0.35cm
2v
-1s
-1, I
on/ I
offbe 10
6-10
7), there is good commercial application prospect.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of the ketone of new indole-2-shown in formula I polymkeric substance.
Fig. 2 is the embodiment of the present invention 1, the synthetic route chart of polymer P VDTOIVT and PVDTOIVS described in 2.
Fig. 3 is the embodiment of the present invention 1, the uv-visible absorption spectra figure of polymer P VDTOIVT and PVDTOIVS chloroform soln described in 2.Absorbance (a.u.): normalization method absorption intensity; Wavelength (nm): wavelength (nanometer)
Fig. 4 is the embodiment of the present invention 1, the uv-visible absorption spectra figure of polymer P VDTOIVT and PVDTOIVS film described in 2.Absorbance (a.u.): normalization method absorption intensity; Wavelength (nm): wavelength (nanometer).
Fig. 5 is the embodiment of the present invention 1, the thermal gravimetric analysis curve figure of polymer P VDTOIVT and PVDTOIVS described in 2.Weight (wt%): mass percent; Temperature (DEG C): temperature (degree Celsius).
Fig. 6 is the embodiment of the present invention 1, the cyclic voltammetry graphic representation of polymer P VDTOIVT and PVDTOIVS described in 2.Current (mA): electric current (milliampere); Potential (V): voltage (volt).
Fig. 7 is the structural representation of polymkeric substance effect transistor provided by the invention.Wherein Au: gold; Si: silicon; SiO
2: silicon-dioxide; PTS: phenyl-trichloro-silicane; Polymer: polymkeric substance (PVDTOIVT or PVDTOIVS).
Fig. 8 is with the Output transfer performance diagram of representative polymer PVDTOIVT field-effect transistor provided by the invention and output characteristic curve figure; Wherein, | I
dS 1/2| [A]
1/2: | electric current |
1/2[ampere]
1/2; V
g[V]: grid voltage [volt]; I
dS[A]: electric current [ampere]; V
dS[V]: source-drain voltage [volt].
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
Reaction substrate 1 reference literature Heterocycles used in following embodiment, 1990,31,1271-1274 or Synthesis, 2002,9,1136-1142 synthesize, and all the other reaction substrate used, solvent and catalyzer all can obtain from commercial channels.
Embodiment 1, polymer P VDTOIVT synthesis (in formula I R=2-decyl dodecyl, X=S) (its synthetic route as shown in Figure 2)
1) synthesis of trans-5,5'-vinyl two (2-formylthiophene) (2)
Anhydrous tetrahydro furan (150 milliliters) solution that trans-1,2-thienyl ethene (1.92 grams, 10 mmoles) will be housed is cooled to the hexane solution (8.4 milliliters, 21 mmoles) slowly dripping 2.5M n-Butyl Lithium after-78 DEG C.After completing, reaction system under nitrogen protection, continues stirring 1 hour at-78 DEG C.Remove cryostat and be slowly warming up to 0 DEG C, continue stirring 5 minutes.Again be cooled to-78 DEG C, reaction system stirs 30 minutes at-78 DEG C by disposable adding after DMF (1.7 milliliters, 22 mmoles) respectively.Slowly be warming up to 0 DEG C of stirring and use ammonium chloride saturated aqueous solution cancellation after 30 minutes, gained solid by filtration be separated, after a small amount of water washing, under room temperature in vacuo condition, drying obtains target product 2.2 grams.Productive rate: 90%.
Structural characterization data are as follows:
Mass spectrum: HRMS (m/z): [M]
+: 247.9970..
Hydrogen is composed:
1h NMR (300MHz, CDCl
3) δ (ppm): 9.89 (s, 2H), 7.69 (d, J=3.9Hz, 2H), 7.24 (s, 2H), 7.23 (d, J=3.9Hz, 2H). carbon is composed:
13c NMR (75MHz, CDCl
3) δ (ppm): 1182.6,150.2,142.8,136.9,128.2,124.5.
2) synthesis of compound 4
Trans-5 will be equipped with; two (the 2-formylthiophene) (2.48 grams of 5'-vinyl; 10 mmoles), 6-bromo indole-2-ketone (4.24 grams; 20 mmoles), the suspension of piperidines (4 milliliters) and methyl alcohol (100 milliliters) is heated to backflow, stirring reaction 12 hours under nitrogen protection.Stop stirring, filter after being cooled to room temperature and obtain solid, with water and methanol wash and under vacuum drying obtains black solid (4.6 grams) respectively.This product is insoluble in common solvent, is not further purified and is directly used in the next step.
Structural characterization data are as follows:
Mass spectrum: HRMS (m/z): [M+Na]
+: 656.8912.
3) synthesis of the compound 5 of formula IX is belonged to
Compound 4 shown in formula VII (1.9 grams will be housed; 3.0 mmoles), ownership formula VIII compound 1-bromo-2-decyl-dodecane (3.0 grams; 7.2 mmoles), (1.2 grams, salt of wormwood; 9.0 mmoles) and N; the suspension of dinethylformamide (50 milliliters) is heated to 100 DEG C, stirs under nitrogen protection and carries out substitution reaction 24 hours.After cooling system to room temperature, system is poured into water (200 milliliters), chloroform extraction, dried over sodium sulfate, solid trichloromethane/methyl alcohol that rear removing organic solvent obtains carries out sedimentation, obtains pure target product 1.7 grams (total recovery of two-step reaction is 32%)
Mass spectrum: MS (m/z): [M]
+: 1306.8...
Hydrogen is composed:
1h NMR (300MHz, CDCl
3) δ (ppm): 7.59 (m, 4H), 7.34 (m, 4H), 7.17 (d, J=8.1Hz, 2H), 7.09 (d, J=3.6Hz, 2H), 6.94 (s, 2H), 3.67 (d, J=7.5Hz, 4H), 1.85-1.97 (m, 4H), 1.32-1.23 (m, 80H), 0.89-0.84 (m, 12H). carbon is composed:
13c NMR (75MHz, CDCl
3) δ (ppm): 166.4,150.3,142.9,138.7,137.4,128.1,127.8,124.3,123.9,122.9,121.8,120.1,119.7,117.8,44.6,36.2,31.9,31.6,30.0,29.7,29.7,29.6,29.38,29.36,26.5,22.7,14.1.
2) synthesis of the polymer P VDTOIVT of formula I is belonged to
By compound (R shown in compound 5 shown in formula IX (R=2-decyl dodecyl) (261.0 milligrams, 0.20 mmole) and formula X
4for methyl) compound 6 (103.6 milligrams; 0.20 mmole), palladium catalyst three (dibenzalacetone) two palladium (9.0 milligrams; 0.01 mmole), part three (o-tolyl) phosphine (18 milligrams; 0.06 mmole) and solvent chlorobenzene (6.0 milliliters) join in reaction flask, in nitrogen, carry out low temperature deoxygenation post-heating carry out Stille polyreaction 24 hours to 110 DEG C of argon shields.After cooling, add 200 ml methanol/6M HCl mixture (volume ratio 20:1), stirred at ambient temperature 2 hours, filter.The solid apparatus,Soxhlet's purifying obtained.Extraction solvent is methyl alcohol, acetone, normal hexane, each extracting 12 hours successively, and rear chlorobenzene extracts and obtains subject polymer 250 milligrams, yield 93%.
Structural characterization data are as follows:
Molecular weight: GPC:M
n=36.8kDa, M
w=66.9kDa, PDI=1.82.n are 27;
Ultimate analysis: C
86h
120n
2o
2s
4, calculated value: C 76.96, H 9.01, N 2.09; Probe value: C 76.31, H 8.40, N 2.06.
Learning that from above this compound structure is correct, is polymer P VDTOIVT.
Embodiment 2, polymer P VDTOIVS synthesis (in formula I R=2-decyl dodecyl, X=Se) (its synthetic route as shown in Figure 2)
1) synthesis of the compound 5 of formula IX is belonged to
The synthesis of compound 5 is carried out with reference to embodiment 1.
2) synthesis of the polymer P VDTOIVS of formula I is belonged to
By (R shown in compound 5 (261.0 milligrams, 0.20 mmole) and formula XI
4for methyl) compound 7 (122.3 milligrams; 0.20 mmole), three (dibenzalacetone) two palladium (6.0 milligrams), three (o-tolyl) phosphine (18 milligrams) and chlorobenzene (6.0 milliliters) join in reaction flask, in nitrogen, carry out low temperature deoxygenation post-heating carry out Stille polyreaction 24 hours to 110 DEG C of argon shields.After cooling, add 200 ml methanol/6M HCl mixture (volume ratio 20:1), stirred at ambient temperature 2 hours, filter.The solid apparatus,Soxhlet's purifying obtained.Extraction solvent is methyl alcohol, acetone, normal hexane, each extracting 12 hours successively, and rear chlorobenzene extracts and obtains subject polymer 260 milligrams, yield 90%.
Structural characterization data are as follows:
Molecular weight: GPC:M
n=24.6kDa, M
w=46.1kDa, PDI=1.90.n are about 17;
Ultimate analysis: C
86h
120n
2o
2s
2se
2, calculated value: C 71.93, H 8.42, N 1.95; Probe value: 70.20, H7.97, N 1.93.
Learning that from above this compound structure is correct, is polymer P VDTOIVS.
The spectrum property of embodiment 3, polymer P VDTOIVT and PVDTOIVS
Fig. 3 and Fig. 4 is embodiment 1, the polymer P VDTOIVT of 2 preparations and the uv-visible absorption spectra figure of PVDTOIVS chloroform soln and film.
As shown in Figure 3, this base polymer presents stronger single tape and absorbs in UV-visible region, illustrate in polymer molecule to have stronger Intramolecular electron transfer.
As shown in Figure 4, these two kinds of polymkeric substance produce stronger molecular interaction in solids.
The thermal property of embodiment 4, polymer P VDTOIVT and PVDTOIVS
Fig. 5 is embodiment 1, the thermogravimetric curve of polymer P VDTOIVT and PVDTOIVS of 2 preparations.
As shown in Figure 5, polymer P VDTOIVT and PVDTOIVS decomposition temperature are all at about 400 DEG C.This result illustrates that this base polymer has good thermal stability.
The electrochemical properties of embodiment 5, polymer P VDTOIVT and PVDTOIVS
Fig. 6 is embodiment 1, the cyclic voltammetry curve of polymer P VDTOIVT and PVDTOIVS of 2 preparations.
The electrochemical properties of polymkeric substance is tested by cyclic voltammetric device.The polymeric film formed in an embrane method to platinum electrode is as tested object.Test adopts traditional three-electrode system, and wherein with platinum rod, platinum filament, silver/silver chloride is respectively work and clicks, to electrode and reference electrode, with the anhydrous acetonitrile of tetrabutyl phosphofluoric acid ammonium salt for supporting electrolyte.Sweep limit is-1.3 ~ 1.6 volts (vs.Ag/AgCl), scanning speed be 100 millivolts per second.
Learn that the initial oxidation current potential of polymer P VDTOIVT and PVDTOIVS is 1.06 and 1.08V from Fig. 6, estimate that their HOMO energy level is respectively-5.46 and-5.48 electron-volts thus, simultaneously their initial reduction current potential be-0.90 with-0.87V.Can estimate that their lumo energy is respectively-3.50 and-3.47 electron-volts.
The field-effect transistor fabrication & properties of embodiment 6, polymer P VDTOIVT and PVDTOIVS.
Fig. 7 is the structural representation of polymer field effect transistor, as shown in the figure, adopts highly doped silicon chip as substrate, gate electrode, and the silicon-dioxide of 300 nanometer thickness is as insulation layer, and gold is source electrode and drain electrode.Silicon-dioxide adopt phenyl-trichloro-silicane modify, prepare by getting rid of embrane method the organic semiconductor layer that thickness is 30 nanometers, and in atmosphere in thermal station 140 degrees Celsius annealing 5 minutes, obtain polymeric long effect transistor.
The transition curve of the field-effect transistor of Fig. 8 prepared by polymer P VDTOIVT and PVDTOIVS and curve of output.Such device has good field-effect performance of control as seen from the figure.Carrier mobility can be drawn by Equation for Calculating:
I
DS＝(W/2L)C
iμ(V
G–V
T)
2(sat.,V
DS＝V
G–V
T)
Wherein, I
dSfor drain current, μ is carrier mobility, V
gfor grid voltage, V
tfor threshold voltage, W is channel width (W=8.8 millimeter), and L is channel length (L=0.08 millimeter), C
ifor isolator electric capacity (C
i=7.5 × 10
-9method every square centimeter).Utilize (I
dS, sat)
1/2to V
gmapping, and does linear regression, the slope of the tropic thus can extrapolate carrier mobility (μ), try to achieve V by the section of the tropic and X-axis
t.The device performance of the polymer field effect transistor prepared in above-mentioned each example is as shown in table 1.
On-off ratio can be drawn by the ratio of the maxima and minima of Fig. 8 source-drain current.
With PVDTOIVT and PVDTOIVS for semiconductor layer has been made more than 10 organic field effect tube devices, these device performances are stablized, and its representational performance perameter is as shown in table 1:
The device performance of table 1, field-effect transistor
All experimental results show that such indol-2-one base polymer is excellent polymer semiconducting material.The present invention is not limited to reported PVDTOIVT and PVDTOIVS two kinds of polymer materialss, change the new indole-2-ketone polymkeric substance that different substituent R and heteroatoms X can obtain series, and the synthetic route that the present invention provides is simple, synthesis step is few, and yield is high is suitable for extensive synthesis.This has important directive significance for researching and developing high performance polymer semiconductor material further.
Claims (9)
1. polymkeric substance shown in formula I:
Formula I
In described formula I, R is selected from C
5-C
80straight or branched alkyl in any one;
X is selected from S and Se;
N is 5 ~ 500.
2. polymkeric substance according to claim 1, is characterized in that: in described formula I, R is selected from C
10-C
50straight or branched alkyl in any one, be specifically selected from C
10~ C
30straight or branched alkyl in any one, be more specifically 2-decyl dodecyl;
N is 10 ~ 100.
3. prepare a method for polymkeric substance shown in the arbitrary described formula I of claim 1 or 2, comprise the steps:
Under palladium catalyst existent condition, shown in compound, part and formula Ⅹ shown in formula Ⅸ or formula Ⅺ, compound carries out Stille polyreaction, reacts complete and obtains polymkeric substance shown in described formula I;
Formula IX
In described formula Ⅸ, the definition of R defines identical with the R in formula I described in claim 1;
Formula X formula XI
In described formula X and formula XI, R
4for C
1~ C
4straight or branched alkyl.
4. method according to claim 3, is characterized in that: described palladium catalyst is selected from least one of three (dibenzalacetone) two in palladium and tetrakis triphenylphosphine palladium;
Described part is three (o-tolyl) phosphine or triphenylphosphines;
Shown in compound shown in described formula Ⅸ and formula Ⅹ or formula Ⅺ, the molar ratio of compound is 1:0.95 ~ 1.05, is specially 1:1;
The consumption of described palladium catalyst to feed intake 1% ~ 10% of mole dosage for compound shown in described formula Ⅸ, is specially 5%;
The consumption of described part to feed intake 10% ~ 50% of mole dosage for compound shown in described formula Ⅸ, is specially 30%;
In described Stille polymerization procedure, temperature is 90 DEG C ~ 150 DEG C, preferably 80 DEG C ~ 120 DEG C, is specially 110 DEG C;
Time is 1 hour ~ 48 hours, preferably 24 hours;
Described Stille polyreaction is carried out in an inert atmosphere;
Described reaction is carried out in a solvent; Described solvent is specifically selected from least one in DMF, toluene and chlorobenzene.
5. compound shown in formula Ⅸ:
Formula IX
In described formula Ⅸ, the definition of R defines identical with the R in formula I described in claim 1.
6. prepare a method for compound shown in formula Ⅸ described in claim 5, comprise the steps:
In an inert atmosphere, compound shown in compound shown in formula VII, formula VIII and alkali are carried out substitution reaction, react complete and obtain compound shown in described formula Ⅸ;
Formula VII formula VIII
In described formula VIII, the definition of R defines identical with the R in formula I described in claim 1;
Y is Br or I.
7. method according to claim 6, is characterized in that: described alkali is selected from least one in salt of wormwood, sodium carbonate and Strontium carbonate powder;
Shown in described formula VII, shown in compound, formula VIII, the molar ratio of compound and alkali is 1:2 ~ 4:3 ~ 5, is specially 1:2.4:3;
In described substitution reaction step, temperature is 60 DEG C ~ 130 DEG C, preferably 80 DEG C ~ 100 DEG C;
Time is 6 hours ~ 48 hours, preferably 24 hours;
Described addition reaction is carried out in a solvent; Described solvent is specifically selected from DMF, N,N-dimethylacetamide, Isosorbide-5-Nitrae-dioxane, at least one in tetrahydrofuran (THF).
8. the application of polymkeric substance shown in any described formula I of claim 1 or 2 in the organic effect transistor of preparation.
9. an organic field effect tube, is characterized in that: in described organic field effect tube, and the material forming organic semiconductor layer is polymkeric substance shown in any described formula I of claim 1 or 2.
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|---|---|---|---|---|
| CN106432694A (en) * | 2016-08-23 | 2017-02-22 | 湖北和昌新材料科技股份有限公司 | Polymer with carbazole as main chain and preparation method and application thereof |
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| CN113881019A (en) * | 2021-10-18 | 2022-01-04 | 福州大学 | 2-indolone-based polymer donor material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106432694A (en) * | 2016-08-23 | 2017-02-22 | 湖北和昌新材料科技股份有限公司 | Polymer with carbazole as main chain and preparation method and application thereof |
| CN106432694B (en) * | 2016-08-23 | 2018-07-24 | 湖北和昌新材料科技股份有限公司 | It is a kind of using carbazole as polymer of main chain and preparation method and application |
| 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 |
| CN113881019A (en) * | 2021-10-18 | 2022-01-04 | 福州大学 | 2-indolone-based polymer donor material and preparation method thereof |
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| CN104927030B (en) | 2017-09-26 |
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