CN105778061B - A kind of sulfone monomer of new benzo [b] thieno [3,2 b] benzo [b] thiophene two and its copolymer and purposes - Google Patents

A kind of sulfone monomer of new benzo [b] thieno [3,2 b] benzo [b] thiophene two and its copolymer and purposes Download PDF

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CN105778061B
CN105778061B CN201610182498.7A CN201610182498A CN105778061B CN 105778061 B CN105778061 B CN 105778061B CN 201610182498 A CN201610182498 A CN 201610182498A CN 105778061 B CN105778061 B CN 105778061B
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benzo
thiophene
thieno
sulfone
compound
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CN105778061A (en
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尤为
高建宏
肖生强
詹春
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Wuhan University of Technology WUT
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Abstract

The invention belongs to organic compound to synthesize field, and invention is related to a kind of new polymers applied to organic semiconductor material field, relates particularly to a kind of the sulfone monomer of new benzo [b] thieno [3,2 b] benzo [b] thiophene two and its copolymer.Benzo [b] thieno [3 of the present invention, 2 b] benzo [b] thiophene two sulfone monomer be that a kind of high degree of symmetry contains heteroatomic compound, because sulfone is strong electron withdraw group, and there is good flatness, it allow as a kind of small molecule receptor material well, can apply with organic solar batteries；And itself has good luminescent effect, therefore can also be applied in the light emitting diode.

Description

A kind of sulfone monomer of new benzo [b] thieno [3,2-b] benzo [b] thiophene two and its Copolymer and purposes
Technical field
The invention belongs to organic compound to synthesize field, and invention is related to a kind of applied to the new of organic semiconductor material field Type polymer, relate particularly to a kind of sulfone monomer of new benzo [b] thieno [3,2-b] benzo [b] thiophene two and its copolymerization Thing.
Background technology
The sub- device of photoconductive organic semiconductor, including organic field effect tube, Organic Light Emitting Diode, organic photovoltaic electricity Pond, organic electrostatic are duplicated, organic laser and organic-biological sensor etc., because having cheap, body is light to take, be easy to big face Accumulate the advantages that processing and obtained extensive development and progressively strided forward to industrialization.Past 10 years, pass through the molecule to material The optimization of structure design and device, organic semiconductor device have also obtained development at full speed, but with inorganic semiconductor material phase Than, in conversion efficiency, spectral response range and stability etc., organic semiconducting materials need to be improved for it.Therefore set Polymer semiconducting material of the meter synthesis with arrowband gap structure, with high carrier mobility and with good dissolubility energy It is the vital task of present material research field.
At present, efficient donor monomer has had a lot of kinds in efficient conjugated polymer, but due to the kind of receptor unit Class is seldom, largely limits the development of conjugated polymer.And some shortcomings be present in existing receptor unit, for example, it is narrow Light suction belt, high LUMO and low dissolubility, therefore it is significantly to excavate efficient receptor unit prospect.Benzo [b] thieno [3,2-b] benzo [b] thiophene-based conjugated polymer is due to strong π-π interactions, flatness and high ionization Can these advantages so that the stability and high mobility that it has had, obtain in scene effect transistor and Light-Emitting Diode It is widely applied.But benzo [b] thieno [3,2-b] benzo [b] thiophene is fresh in polymer or small molecule solar cell Have been reported that, but we have found that sulfuryl is a kind of strong electron withdraw group under study for action, therefore, it is proposed that by benzo [b] thiophene Simultaneously [3,2-b] benzo [b] thiophene is combined with sulfone group for fen, optimum synthesis by reasonably designing, progressively it is a kind of it is new by The sulfone of body molecule benzo [b] thieno [3,2-b] benzo [b] thiophene two, such acceptor molecule is used for synthetic polymer and small point In son, due to good dissolubility, low band gap, high mobility and wide absorption, in body heterojunction solar-electricity The conjugated polymer combined to form in pond with excellent donor material, photoelectric transformation efficiency can be not only lifted, thus, organic Also there is good application prospect in solar cell.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of new benzo [b] thieno for above-mentioned prior art The sulfone monomer of [3,2-b] benzene [b] thiophene two and its copolymer, based on the very symmetrical thiophene sulfone micromolecular of this flatness structure Unit shows good photoelectric property, has preferable heat endurance, adjustable optical band gap and level structure, higher Carrier mobility and good solution machinability.
The present invention is that technical scheme is used by solving above-mentioned technical problem：
A kind of sulfone monomer of new benzo [b] thieno [3,2-b] benzo [b] thiophene two, its general formula of molecular structure such as institute of formula I Show, wherein R1Selected from H or C1~C20Alkyl.
The above-mentioned sulfone copolymer of new benzo [b] thieno [3,2-b] benzo [b] thiophene two, its its general formula of molecular structure is such as Shown in formula II, wherein R1Selected from H or C1~C20Alkyl, Ar be containing thiophene or benzene unit group, it is whole in n=1~200 Number.
Preferably, any one or a few in formula following radicals a-f of the Ar, wherein, R2、R3、R4、R5、R6Choosing From H, C1~C20Alkyl or alkoxy；Y any atoms in H, F, Cl, Br, I.
The synthetic method of the above-mentioned sulfone monomer of new benzo [b] thieno [3,2-b] benzo [b] thiophene two, it is main to include such as Lower three steps：
Step (1)：ByIt is raw material using toluene and water as solvent, in organic base diazabicylo (DBU), urges Agent bi triphenyl phosphorus palladium chloride (Pd (PPh3)2Cl2) and cuprous iodide (CuI) collective effect under synthesize
Step (2)：It is solvent, cuprous iodide (CuI) with 1-METHYLPYRROLIDONE (NMP) Synthesized for catalyst with vulcanized sodium and elemental iodine collective effect
Step (3)：Using dichloroethanes as solvent, by metachloroperbenzoic acid (MCPBA) oxygen Change obtains
Step (4)：Using trifluoroacetic acid as solvent, bromo is carried out by bromine and obtainedThe i.e. new sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two.In each step R in compound1Selected from H or C1~C20Alkyl.
By such scheme, in step (1), organic base diazabicylo, catalyst bi triphenyl phosphorus palladium chloride, iodate are sub- Copper (CuI),The ratio between the mole that feeds intake be：(6~7)：(0.05~0.08)：(0.1~0.11)：1, the water WithThe ratio between amount of material is 1：(0.45~0.55), mixed solvent toluene about press 300 with water:(1~1.2).
By such scheme, in step (1), described reaction temperature is at 25-30 DEG C, reaction time 12-14h.
By such scheme, step (1), which more specifically operates, is：WillWith catalyst bi triphenyl phosphorus dichloride Palladium (Pd (PPh3)2Cl2) and cuprous iodide (CuI) mixing, then add solvent toluene, it is to be dissolved uniformly after, add organic base two Azabicyclic (DBU) and deionized water, it is 25-30 DEG C in temperature, reacts 12-14h, reaction obtains after terminatingCrude product.Crude product obtained by step (1) can through extracting, drying, the means purification such as column chromatography, That is more pure product.Wherein, extraction can use dichloromethane and water, and drying can use anhydrous sodium sulfate, column chromatography Petroleum ether and dichloromethane can be used.
By such scheme, in step (2), catalyst cuprous iodide (CuI), vulcanized sodium, elemental iodine,The ratio between the mole that feeds intake be：(0.48~0.55)：(0.48~0.55)：(6~7)：(3.5~ 4.0)：1.
By such scheme, in step (2), described reaction temperature must be controlled at 108-115 DEG C, reaction time 4- 5h, reaction atmosphere are inert atmosphere.
By such scheme, after reaction terminates in the step (2), the purifications such as extraction, drying, column chromatography step can also be included Suddenly.Wherein, extraction can use ethyl acetate and water or saturated sodium-chloride, and drying can use anhydrous sodium sulfate, column chromatography Petroleum ether and dichloromethane can be used.
By such scheme, in step (3),With feeding intake for metachloroperbenzoic acid (MCPBA) The ratio between mole is 1：(10~12).
By such scheme, in step (3), the control of described reaction temperature is at 75-85 DEG C, reaction time 16-18h.
By such scheme, after reaction terminates in the step (3), can also include recrystallizing, filter, being spin-dried for, column chromatography Etc. purification step.Wherein, recrystallization can use petroleum ether then to have a large amount of solids to separate out (for m-chlorobenzoic acid), filter out i.e. Can；Drying can use anhydrous sodium sulfate, and column chromatography can use petroleum ether and dichloromethane.
By such scheme, in step (4), required bromine and new benzo [b] thieno [3,2-b] benzo [b] thiophene The molar ratio of two sulfones is 1:(6~8)；Reaction temperature is at 25-30 DEG C, reaction time 18-20h.Preferably, reaction terminates Afterwards, the purification steps such as extraction, drying, column chromatography can also be included, to obtain purer benzo [b] thieno [3,2-b] The sulfone monomer of benzo [b] thiophene two.Wherein, extraction can use NaOH solution and chloroform and water, and drying can use anhydrous slufuric acid Sodium, column chromatography can use petroleum ether and dichloromethane.
By such scheme, the above-mentioned new sulfone copolymer of benzo [b] thieno [3,2-b] benzo [b] thiophene two, can pass through The sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two carries out copolymerization preparation with the compound shown in following formula A '-F ' Obtain, wherein, R2、R3、R4、R5、R6Selected from H, C1~C20Alkyl or alkoxy；Y any originals in H, F, Cl, Br, I Son.
Main chemical reactions process involved in the present invention is as follows：
The sulfone monomer of new benzo [b] thieno [3,2-b] benzo [b] thiophene two and its copolymer of the present invention are organic The application of field of photovoltaic materials, R in monomer and its copolymer can be passed through1Different alkyl chains are selected to adjust small molecule and gather The dissolubility of compound, it is such as sensitive in organic photoelectrical material, polymer solar battery, organic electroluminescence device, fluorescence chemical Have in the photoelectric material such as device, organic field effect tube, organic optical memory part, organic non-linear optical properties and organic laser apparatus Have and be widely applied very much.The sulfone copolymer of new benzo [b] thieno [3,2-b] benzo [b] thiophene two is applied to field-effect In terms of transistor and polymer solar battery, mainly with now compared using preferable diazosulfide acceptor material Compared with showing that the sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two has relatively low lumo energy, wide absorption spectrum And narrow absorption band gap.
Compared with prior art, the beneficial effects of the invention are as follows：
First, benzo [b] thieno [3,2-b] benzo [b] thiophene two sulfone monomer is that a kind of high degree of symmetry contains hetero atom Compound, because sulfone is strong electron withdraw group, and there is good flatness, there is preferable heat endurance, adjustable light Learn band gap and level structure, higher carrier mobility allow it as a kind of small molecule receptor material well, can Applied in organic solar batteries；And itself has good luminescent effect, therefore can also be in the light emitting diode It is applied.
Second, synthesizingIn, first from one-pot synthesis, instead of used in forefathers Step synthesis, simplify reaction；Alkali is done from DBU, not only products collection efficiency is high, reaction is gentle, and exchanges different take for Dai Ji, yield are also substantially unaffected.
3rd：SynthesizingIn, add a small amount of CuI and make catalyst, can further be lifted The time of reaction and yield；When using vulcanized sodium cyclization, using the Na after dewater treatment2S.9H2O crystal is i.e. with using Na2S powder End carries out cyclization, not only improves yield, and greatly shortens the reaction time, improves efficiency.
4th：SynthesizingWhen, oxidant is made than hydrogen peroxide, reaction rate from MCPBA It hurry up, and yield is high, will not produce that hydrogen peroxide does oxidant generation has single sulfone accessory substance.
Brief description of the drawings
Ultraviolet-ray visible absorbing light in Fig. 1 embodiments 1 under the o-dichlorobenzene solution (room temperature) and filminess of compound 7 Spectrum.
The electrochemistry cyclic voltammetry curve of compound 7 in Fig. 2 embodiments 1, with the anhydrous of 0.1M tetrabutyl ammonium hexafluorophosphates Acetonitrile solution is as electrolyte solution, sweep speed 0.08V/s.
Embodiment
In order that technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with Example, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining The present invention, it is not intended to limit the present invention.
Initiation material employed in the present inventionCan directly buy, can also bibliography synthesis, this hair It is bright that a kind of synthetic route is provided herein, it is as follows, wherein, R1Selected from H or C1~C20Alkyl.
1st, compound 1Preparation, detailed process is as follows：
250mL two-neck bottle is taken, 3- iodine methoxyl group (52g, 222.2mmol) is dissolved into 160mL acetic acid, it is to be dissolved Afterwards, by Br2(14.82mL, 288.9mmol, 1.3equiv) is added dropwise, and tail gas is absorbed with NaOH solution, stirring at normal temperature 24h； After completion of the reaction, the NaOH solution that 10% is slowly added into resulting solution removes acetic acid, then adds dichloromethane to it, uses water Extracted three times with saturated nacl aqueous solution, collected organic layer, with anhydrous sodium sulfate drying, after precipitation, carried out with petroleum ether Column chromatography, 54.1g oily liquids is obtained, yield 80%, as target product, is denoted as compound 1.Nuclear-magnetism1H NMR (500MHz,CDCl3) δ 3.82 (s, 3H), 6.75 (d, J=5.0Hz, H), 7.13 (d, J=4.0Hz, H), 7.44 (d, J= 10Hz, H), it can thus be appreciated that successfully having obtained target compound 1.
2nd, compound 2Preparation, detailed process is as follows：：
By compound 1 (52g, 166.1mmol) loaded on 500mL two-neck bottle in, take out-inflated with nitrogen three times after, nitrogen protect Under shield, anhydrous 200mL CH is injected thereto2Cl2, after to be dissolved, it is cooled to -78 DEG C, then with dropping funel by BBr3 The 50mL of (49.8g, 1.2equiv, 199.32mmol) CH2Cl2Solution is slowly added dropwise, after dripping off, then slowly rise temperature To room temperature, reaction overnight；After completion of the reaction, slowly it is added portionwise to reacted solution in 200mL water, aqueous phase CH2Cl2 Extracted, collected organic layer, be spin-dried for, that is, obtain target crude product.Purifying is in two steps：Entered first with dichloromethane and petroleum ether The pure crystallization of row, it is principal product to obtain white solid；Still some principal product in mixed liquor, uses petroleum ether：Dichloromethane is carried out Column chromatography, 44.1g target products must be arrived, yield 88.8%, are denoted as compound 2.Nuclear-magnetism1H NMR(500MHz,CDCl3)δ 4.97 (s, H), 6.73 (d, J=2.5Hz, H), 7.39 (d, J=2.5Hz, H), 7.45 (d, J=3.5Hz, H), it can thus be appreciated that into Work(has obtained target compound 2.
3rd, compound 3Preparation, reaction equation is as follows：
By compound 2 (10.0g, 33.44mmol), K2CO3(5.3g, 38.45mmol) is separately added into 100mL two-neck bottle In ,-inflated with nitrogen is taken out, under nitrogen protection, 35mL DMF is injected thereto, is then heated to about 50 DEG C of oil bath, react 10min Afterwards, then thereto brominated alkanes (13.3g, 1.1equiv) are slowly injected into, temperature is then increased to 110 DEG C of oil bath, reacted Night, raw material have reacted, and add distilled water to stop reaction；Appropriate petroleum ether is added into reacted solution, with distilled water and is satisfied Extracted, collected organic layer, be dried with anhydrous sodium sulfate with sodium chloride solution；After precipitation, post layer is carried out with petroleum ether Analysis, obtains 17.2g colourless oil liquid, yield 90%, as target product, is denoted as compound 3.Nuclear-magnetism1H NMR (500MHz,CDCl3) δ 0.90 (t, J=7.5Hz, 6H), 1.30-1.33 (m, 4H), 1.38-1.51 (m, 4H), 1.69-1.74 (m, H), 3.83 (d, J=3.5Hz, 4H), 6.73 (d, J=3.5Hz, H), 7.39 (d, J=3.5Hz, H), 7.45 (d, J= 10Hz, H), it can thus be appreciated that successfully having obtained target compound 3.R1Also include：2- ethylhexyls, 2- butyl octyls, the 2- hexyl last of the ten Heavenly stems Base, 2- octyl group dodecyls etc., but it is not limited only to this.
Embodiment 1
1st, compound 4Preparation, reaction equation is as follows：
With R1To illustrate exemplified by 2- ethylhexyls, in 100mL two-neck bottle, by compound 3 (4.1g, 10.0mmol), Pd(PPh3)2Cl2After (210mg, 6%equiv), CuI (190mg, 10%equiv), anhydrous and oxygen-free processing, under nitrogen protection, Inject 30mL dry toluene, after dissolving, sequentially add DBU (9.0mL, 6equiv), trimethyl silane (0.75mL, 0.5equiv) with distilled water (0.1mL, 40%equiv), react what is carried out under the covering of complete masking foil, stirred under normal temperature, Reaction overnight, produce the crude product solution of compound 4.
Dichloromethane is added into the crude product solution of compound 4, with distilled water extraction three times, collected organic layer；Then After anhydrous sodium sulfate drying, precipitation；Petroleum ether is used again：Dichloromethane=8:1 carries out column chromatography, obtains oily liquids, yield 80%, the as fine work of compound 4.Nuclear-magnetism1H NMR(500MHz,CDCl3) δ 0.93 (t, J=7.5Hz, 12H), 1.29-1.32 (m, 8H), 1.36-1.47 (m, 8H), 1.66-1.72 (m, 2H), 3.77 (d, J=5.5Hz, 4H), 6.78 (d, J=6.0Hz, 2H), 7.13 (d, J=3.0Hz, 2H), 7.46 (d, J=10Hz, 2H), it can thus be appreciated that successfully having obtained target compound 4.
2nd, compound 5Preparation, reaction equation is as follows：
With R1To illustrate exemplified by 2- ethylhexyls, by compound 4 (1.51g, 2.56mmol), CuI (1.28mmol), 2.5gI2(0.25g, 9.8mmol), Na2S (3.7g, 15.4mmol) is sequentially added in 100mL two-neck bottle, anhydrous and oxygen-free processing Afterwards, under nitrogen protection, by 20mL solvent NMP injection bottles, 150 DEG C of oil bath is heated to, reacts 2 days, obtains compound 5 Crude product solution.
Ethyl acetate is added into the crude product solution of compound 5, is extracted respectively with distilled water and saturated sodium-chloride Three times, solvent NMP and other unnecessary inorganic salts, collected organic layer are removed；Then it is dried with anhydrous sodium sulfate, precipitation Afterwards, petroleum ether is used：Dichloromethane=10:1 carries out column chromatography, obtains yellow solid, as yield 60%, the fine work of compound 5.Core Magnetic1H NMR(500MHz,CDCl3) δ 0.97 (t, J=7.5Hz, 12H), 1.36-1.39 (m, 8H), 1.47-1.60 (m, 8H), 1.77-1.82 (m, 2H), 3.95 (d, J=5.5Hz, 4H), 7.04 (d, J=9.0Hz, 2H), 7.30 (d, J=2.0Hz, 2H), 7.46 (d, J=9.0Hz, 2H), it can thus be appreciated that successfully having obtained target compound 5.
3rd, compound 6Preparation, reaction equation is as follows:
With R1To illustrate exemplified by 2- ethylhexyls, compound 5 (1.0g, 2.02mmol) is dissolved in the 35mL chloroethenes of 1,2- bis- Alkane, after solid dissolving, the solution that will be dissolved in the MCPBA (3.5g, 20.2mmol) of 30mL 1,2- dichloroethanes is slow It is added dropwise, after being added dropwise, backflow overnight, obtains the crude product solution of compound 6.
Appropriate petroleum ether is added into the crude product solution of compound 6, then there are a large amount of solids to separate out (for a chlorobenzene first Acid), after filtering, by petroleum ether and 1,2- dichloroethane solutions are spin-dried for；Then petroleum ether is used：Dichloromethane=1:1 carries out post layer Analysis, obtains yellow solid, as yield 75%, the fine work of compound 6.Nuclear-magnetism1H NMR(500MHz,CDCl3) δ 0.94 (t, J= 9.0Hz, 12H), 1.31-1.34 (m, 8H), 1.43-1.53 (m, 8H), 1.73-1.79 (m, 2H), 3.96 (d, J=5.0Hz, 4H), 7.05 (d, J=10.0Hz, 2H), 7.17 (d, J=2.5Hz, 2H), 7.72 (d, J=10.0Hz, 2H), it can thus be appreciated that into Work(has obtained target compound 6.
4th, compound 7Preparation, reaction equation is as follows:
With R1To illustrate exemplified by 2- ethylhexyls, compound 6 (0.28g, 0.5mmol) is dissolved in 15mL trifluoroacetic acids, After to be dissolved, then Br is added to it2(0.48g, 0.15mL, 3mmol), normal-temperature reaction 16h, obtain the crude product of compound 7 Solution.
10% NaOH solution is added into the crude product solution of compound 7, is then extracted with chloroform and water, is collected Organic layer；Then after anhydrous sodium sulfate drying, then petroleum ether is used：Dichloromethane=2:1 carries out column chromatography, obtains yellow solid, Yield is 84%, as the fine work of compound 7.Nuclear-magnetism1H NMR(500MHz,CDCl3) δ 0.96 (t, J=7.5Hz, 12H), 1.34- 1.36 (m, 8H), 1.46-1.60 (m, 8H), 1.81-1.86 (m, 2H), 4.05 (d, J=4.0Hz, 4H), 7.05 (d, J= 10.0Hz, 2H), 7.17 (d, J=2.5Hz, 2H), 7.72 (d, J=10.0Hz, 2H), it can thus be appreciated that successfully having obtained targeted Compound 7.
As shown in Figure 1：In o-dichlorobenzene solution, compound 7 shows the absworption peak of two features：The absorption of short wavelength Peak is 342nm, is attributed to caused by π-pi-electron transition of side chain in compound；The maximum absorption band of long wave strong point is located at 405nm, it is attributed to caused by π-pi-electron transition of agent structure in compound.But under filminess, compound 7 is shown Characteristic peak than red shift under solution state 27nm, positioned at 432nm, while show broader absorption, its absorption spectrum can be with 300nm-490nm is covered, wider absorption spectrum is advantageous to obtain high carrier mobility.Moreover, compound 7 is in film-form Absorption edge under state is located at 475nm, has wide absorption compared with other conventional acceptor materials (such as diazosulfide), especially It can obtain wider spectral absorption in polymer solar cells are applied to, from different donor material copolymerization, so as to obtain Obtain high electric current.
Using the oxidation-reduction process of electrochemical cyclic voltammetry test compound 7, the starting relative to ferrocene is obtained Oxidation-reduction potential, and then it is estimated that the energy level of frontier orbital (HUMO energy levels and lumo energy) of respective material.We adopt With three electric grade systems, the wiring solution-forming of compound 7 of synthesis is dripped to film is prepared on glass-carbon electrode, be then placed on 0.1M Tested in the acetonitrile electrolyte solution of tetrabutyl ammonium hexafluorophosphate, test whole process needs nitrogen to protect.
As can be known from Fig. 2：Compound 7 only has irreversible oxidation-reduction process, corresponding initial reduction electricity in negative electrode Position is -1.15V.According to formula LUMO=- (Ered,onset+ 4.8) eV, we be estimated that the lumo energy of compound 7 for- 3.65eV, HUMO energy level obtain according to the optical band gap and LUMO of material.Compared with diazosulfide (LUMO=-3.5eV), change Compound 7 possesses low lumo energy.
Embodiment 2
Polymer P 1Preparation, reaction equation is as follows:
Weigh the gained compound 7 (0.211g, 0.20mmol) of embodiment 1, (i.e. Ar is 2,5- bis- (trimethyl-tin-radical) thiophene Group a) (82.4mg, 0.2mmol), three (dibenzalacetone) two palladium (5.494g, 3%equiv), three (o-methyl-phenyl) phosphorus (10.944g, 18%equiv), it is separately added into 50mL single neck bottle, vacuumizes, adds 8mL dry toluene, flow back 48h, Obtain the crude product of polymer P 1.
Purification：After the crude product of polymer P 1 is cooled into room temperature, it is slowly dropped in 40mL absolute methanol (while stirring Mix side dropwise addition), drained after being added dropwise, resulting solid passes through acetone, n-hexane, dichloromethane, chloroform and toluene Extracting, obtained toluene extract solution concentration；Then 6mL methanol is added in the concentration of toluene extract solution, through filtering, being dried in vacuo To solid 46mg, as yield 75%, polymer P 1.Gel permeation chromatography measures：Number-average molecular weight Mn=33.46kDa, weight are equal Molecular weight Mw=143.81kDa, breadth coefficient PDI=4.30, n=39~42.
Embodiment 3
Polymer P 2Preparation, reaction equation is as follows:
Weigh the gained compound 7 (0.211g, 0.20mmol) of embodiment 1,9,9- bis- (2- ethylhexyls) -2,7- bis- - ((2- trimethyl-tin-radicals) -5- thienyls) -9H- fluorenes (b) (176mg, 0.2mmol), three (dibenzalacetone) two palladium (5.494g, 3%equiv), three (o-methyl-phenyl) phosphorus (10.944g, 18%equiv), are separately added into 50mL single neck bottle, Vacuumize, add 8mL dry toluene, flow back 48h, obtains the crude product of polymer P 2.
Purification：After the crude product of polymer P 2 is cooled into room temperature, it is slowly dropped in 40mL absolute methanol (while stirring Mix side dropwise addition), drained after being added dropwise, obtained solid is by acetone, n-hexane, dichloromethane extracting, obtained dichloromethane Alkane extract solution concentrates；Then 6mL methanol is added in dichloromethane extract, through filtering, vacuum drying obtains solid 240mg, Yield 85%.Gel permeation chromatography measures：Number-average molecular weight Mn=28.05kDa, weight average molecular weight Mw=81.05kDa, distribution FACTOR P DI=2.89, n=26~28.
Embodiment 4
Polymer P 3Preparation, reaction equation is as follows:
Weigh double (2- ethylhexyls) -2, the 6- bis--(three of the gained compound 7 (0.211g, 0.20mmol) of embodiment 1,4,4- Methyl tinbase) five diene 1,4-Dithiapentalene (c) (145.7mg, 0.2mmol) of -4H- rings, three (dibenzalacetone) two palladium (5.494g, 3%equiv), three (o-methyl-phenyl) phosphorus (10.944g, 18%equiv), are separately added into 50mL single neck bottle, Vacuumize, add 8mL dry toluene, flow back 48h, obtains the crude product of polymer P 3.
Purification：After the crude product of polymer P 3 is cooled into room temperature, it is slowly dropped in 40mL absolute methanol (while stirring Mix side dropwise addition), drained after being added dropwise, obtained solid is by acetone, n-hexane, dichloromethane extracting, obtained dichloromethane Alkane extract solution concentrates；Then add 6mL methanol to extract in concentrate in dichloromethane, through filtering, vacuum drying obtains solid 202mg, yield 77%.Gel permeation chromatography measures：Number-average molecular weight Mn=15.75kDa, weight average molecular weight Mw= 29.42kDa, breadth coefficient PDI=1.87, n=17~18.
Embodiment 5
Polymer P 4Preparation, reaction equation is as follows:
Weigh double (2- ethyl hexyl oxies) -2, the 6- bis- of the gained compound 7 (0.211g, 0.20mmol) of embodiment 1,4,8- - (trimethyl-tin-radical) benzo [1,2-b:4,5-b'] Dithiophene (d) (154mg, 0.2mmol), three (dibenzalacetone) two palladium (5.494g, 3%equiv), three (o-methyl-phenyl) phosphorus (10.944g, 18%equiv), are separately added into 50mL single neck bottle, Vacuumize, add 8mL dry toluene, flow back 48h, obtains the crude product of polymer P 4.
Purification：After the crude product of polymer P 4 is cooled into room temperature, it is slowly dropped in 40mL absolute methanol (while stirring Mix side dropwise addition), drained after being added dropwise, obtained solid is by acetone, n-hexane, dichloromethane extracting, obtained dichloromethane Alkane extract solution concentrates；Then add 6mL methanol to extract in concentrate in dichloromethane, through filtering, vacuum drying is consolidated 230mg, yield 88%.Gel permeation chromatography measures：Number-average molecular weight Mn=30.20kDa, weight average molecular weight Mw= 82.33kDa, breadth coefficient PDI=2.72, n=31~33.
Embodiment 6
Polymer P 5Preparation, reaction equation is as follows:
Weigh the gained compound 7 (0.211g, 0.20mmol) of embodiment 1,2,5- bis--(ethyl hexyl oxy)-Isosorbide-5-Nitrae-two- ((2- trimethylthiophenes base) -5- thienyls) benzene (e) (154mg, 0.2mmol), three (dibenzalacetone) two palladium (5.494g, 3%equiv), three (o-methyl-phenyl) phosphorus (10.944g, 18%equiv), it is separately added into 50mL single neck bottle, vacuumizes, 8mL dry toluene is added, flow back 48h, obtains the crude product of polymer P 5.
Purification：After the crude product of polymer P 5 is cooled into room temperature, it is slowly dropped in 40mL absolute methanol (while stirring Mix side dropwise addition), drained after being added dropwise, obtained solid is by acetone, n-hexane, dichloromethane extracting, obtained dichloromethane Alkane extract solution concentrates；Then add 6mL methanol to extract in concentrate in dichloromethane, through filtering, vacuum drying is consolidated 235mg, yield 86.4%.Gel permeation chromatography measures：Number-average molecular weight Mn=43.23kDa, Weight-average molecular Mw= 112.23kDa, breadth coefficient PDI=2.60, n=43~44.
Embodiment 7
Polymer P 6Preparation, reaction equation is as follows:
Weigh the gained compound 7 (0.211g, 0.20mmol) of embodiment 1,3', 4'- bis--(2- ethylhexyls) -5,5 " - Two-(trimethyl-tin-radical) terthienyls (f) (159.7mg, 0.2mmol), three (dibenzalacetone) two palladium (5.494g, 3% Equiv), three (o-methyl-phenyl) phosphorus (10.944g, 18%equiv), it is separately added into 50mL single neck bottle, vacuumizes, adds 8mL dry toluene, flow back 48h, obtains the crude product of polymer P 6.
Purification：After the crude product of polymer P 6 is cooled into room temperature, it is slowly dropped in 40mL absolute methanol (while stirring Mix side dropwise addition), drained after being added dropwise, obtained solid is by acetone, n-hexane, dichloromethane extracting, obtained dichloromethane Alkane extract solution concentrates；Then add 6mL methanol to extract in concentrate in dichloromethane, through filtering, vacuum drying is consolidated 221mg, yield 87.5%.Gel permeation chromatography measures：Number-average molecular weight Mn=22.75kDa, Weight-average molecular Mw= 53.14kDa, breadth coefficient PDI=2.33, n=23~25.
The sulfone monomer of new benzo [b] thieno [3,2-b] benzo [b] thiophene two and its copolymer of the present invention have height Mobility and wide absorption spectrum so that this micromolecular or polymeric material possess extensively in organic photoelectrical material class Application.Furthermore, it is possible to further by the adjustment to alkyl chain, to change its dissolubility, can be processed in solution for it should Played an important role with aspect.
Described above is only the preferred embodiment of the present invention, it is noted that is come for one of ordinary skill in the art Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's Protection domain.

Claims (9)

  1. A kind of 1. sulfone copolymer of benzo [b] thieno [3,2-b] benzo [b] thiophene two, it is characterised in that its general formula of molecular structure As shown in formula II, wherein R1Selected from H or C1~C20Alkyl, Ar is containing thiophene or benzene unit group, in n=1~200 Integer；
  2. 2. the sulfone copolymer of a kind of benzo [b] thieno [3,2-b] benzo [b] thiophene two according to claim 1, its feature In any one or a few in formula following radicals a-f of the Ar, wherein, R2、R3、R4、R5、R6Selected from H, C1~C20's Alkyl or alkoxy；
  3. A kind of 3. synthetic method of the sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two, it is characterised in that main bag Include following three step：
    Step (1)：ByIt is raw material using toluene and water as solvent, in organic base diazabicylo, the double triphens of catalyst Synthesized under base phosphorus palladium chloride and cuprous iodide collective effect
    Step (2)：It is catalyst and vulcanization by solvent, cuprous iodide of 1-METHYLPYRROLIDONE Sodium and the synthesis of elemental iodine collective effect
    Step (3)：Using dichloroethanes as solvent, aoxidize to obtain by metachloroperbenzoic acid
    Step (4)：Using trifluoroacetic acid as solvent, bromo is carried out by bromine and obtainedThat is the sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two；Compound in each step Middle R1Selected from H or C1~C20Alkyl.
  4. A kind of 4. synthesis side of the sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two according to claim 3 Method, it is characterised in that in step (1), organic base diazabicylo, catalyst bi triphenyl phosphorus palladium chloride, cuprous iodide,The ratio between the mole that feeds intake be：(6~7)：(0.05~0.08)：(0.1~0.11)：1；Described reaction temperature At 25-30 DEG C, reaction time 12-14h.
  5. A kind of 5. synthesis side of the sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two according to claim 3 Method, it is characterised in that in step (2), catalyst cuprous iodide, vulcanized sodium, elemental iodine,Feed intake The ratio between mole is：(0.48~0.55)：(6~7)：(3.5~4.0)：1；Described reaction temperature must be controlled in 108-115 DEG C, reaction time 4-5h, reaction atmosphere is inert atmosphere.
  6. A kind of 6. synthesis side of the sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two according to claim 3 Method, it is characterised in that in step (3),The ratio between the mole that feeds intake with metachloroperbenzoic acid is 1：(10~12)；Described reaction temperature control is at 75-85 DEG C, reaction time 16-18h.
  7. A kind of 7. synthesis side of the sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two according to claim 3 Method, it is characterised in that in step (4),The ratio between the mole that feeds intake with bromine is 1：(6~8)； Described reaction temperature is at 25-30 DEG C, reaction time 16-18h.
  8. A kind of 8. synthesis side of the sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene two according to claim 3 Method, it is characterised in that after reaction terminates in step (1)-(4), in addition to purification step.
  9. 9. a kind of synthetic method of the sulfone copolymer of benzo [b] thieno [3,2-b] benzo [b] thiophene two, it is characterised in that pass through The sulfone monomer of benzo [b] thieno [3,2-b] benzo [b] thiophene twoWith following formula A '-F ' Suo Shi Compound carry out copolymerization the sulfone copolymer of benzo [b] thieno [3,2-b] benzo [b] thiophene two be prepared；Wherein, R1It is selected from H、C1~C20Alkyl；R2、R3、R4、R5、R6Selected from H, C1~C20Alkyl or alkoxy；
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