CN103772661A

CN103772661A - Copolymer containing cyclopentadiene bithiophene-benzo-2 (benzothiadiazole) as well as preparation method and application thereof

Info

Publication number: CN103772661A
Application number: CN201210417492.5A
Authority: CN
Inventors: 周明杰; 管榕; 黎乃元; 黄佳乐; 李满园
Original assignee: Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Engineering Co Ltd
Current assignee: Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date: 2012-10-26
Filing date: 2012-10-26
Publication date: 2014-05-07

Abstract

A benzo [2, 1-b:3, 4-b'] bithiophene-benzo-2 (benzothiadiazole) copolymer has a following structural formula: P: (shown in the Specification), wherein the R1 and R2 are alkyls from C1 to C20; the R3 and R4 are alkyls from C1-C20 or alkoxy groups from C1 to C16, and the n is an integer from 1 to 100. The energy gap of the benzo [2, 1-b:3, 4-b'] bithiophene-benzo-2 (benzothiadiazole) copolymer is relatively narrow. The invention further provides a preparation method of the benzo [2, 1-b:3, 4-b'] bithiophene-benzo-2 (benzothiadiazole) copolymer as well as solar battery devices and organic electroluminescent devices adopting the benzo [2, 1-b:3, 4-b'] bithiophene-benzo-2 (benzothiadiazole) copolymer.

Description

Containing cyclopentadienedithiderivatives-benzo two (diazosulfide) co-polymer and its preparation method and application

Technical field

The present invention relates to a kind of benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer, its preparation method and use this benzo [2,1-b:3,4-b '] solar cell device and the organic electroluminescence device of two thiophene-benzo two (diazosulfide) multipolymer.

Background technology

Energy problem is the significant problem that countries in the world are extremely paid close attention to.Sun power is the optimal substitute energys of the following mankind, and the solar cell that is electric energy by solar energy converting is also the focus of research.The conjugated polymer thin films solar cell of rising in recent years has that cost is low, lightweight, manufacture craft is simple, can be prepared into the outstanding advantages such as flexible device.In addition, organic materials is of a great variety, designability is strong, is hopeful the design by material and optimizes the performance that improves solar cell.

Diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the metallic cathode such as magnesium, aluminium; Belonging to short of electricity subtype aromatic cycle compound, have strong electron-withdrawing power, is that a kind of good body unit that is subject to has good electronic transport property, can also regulate the energy gap of material simultaneously.But, the band gap (energy level difference between HOMO energy level and lumo energy) of the existing polymkeric substance that contains diazosulfide unit is wider, reduce the specific absorption to photon in solar spectral, thereby made to use the effciency of energy transfer of the organic solar batteries that contains the polymkeric substance that joins thiazole unit lower.

Summary of the invention

Based on this, be necessary benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer that provides a kind of energy gap narrower and preparation method thereof.

In addition, be also necessary to provide a kind of solar cell device and organic electroluminescence device that uses this benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer.

A kind of benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer, has following structural formula:

P:

Wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl, R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group; N is 1 ~ 100 integer.

A kind of preparation method of benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer, comprises the steps:

The compd A and the compd B that provide following structural formula to represent,

A is:

b is:

wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl, R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group;

In oxygen-free environment, the compd A and the compd B that are 1: 1.5 ~ 1.5:1 by mol ratio carry out Stille coupling reaction in the organic solvent that contains organic palladium catalyzer, after separating-purifying, obtain the benzo [2 that following structural formula represents, 1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p:

P:

Therein in an embodiment, described organic palladium catalyzer is selected from three (dibenzalacetone) two palladiums, tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, be preferably two (triphenylphosphine) palladium chlorides, the mol ratio of described organic palladium catalyzer and described compd A is 1:2000 ~ 1:5.

In an embodiment, the temperature of reaction of described Stille coupling reaction is 50 ℃ ~ 120 ℃ therein, and the reaction times is 6 hours ~ 100 hours.

Therein in an embodiment, described purification benzo [2, 1-b:3, 4-b '] step of two thiophene-benzo two (diazosulfide) copolymer p is as follows: extracts and retains organic phase to the mixed solution that adds toluene and deionized water in the solution after Stille coupling reaction, to after organic solvent evaporate to dryness, add ethanol precipitating and filter, the pressed powder chloroform obtaining after filtering is dissolved, then use neutral alumina chromatography, remove afterwards organic solvent, again with methyl alcohol precipitating filtration, by the solids acetone extracting obtaining after filtering, after collecting acetone soln, use methyl alcohol precipitating and filter.

In an embodiment, the preparation process of described compd A comprises the steps: therein

The Compound C and the compd E that provide following structural formula to represent,

C is:

e is:

wherein R ₁, R ₂for C ₁~ C ₂₀alkyl;

In oxygen-free environment, the described Compound C that is 1:2 by mol ratio and compd E carry out coupling reaction in the solvent that contains organic bases and catalyzer, obtain described compd A after separating-purifying, and described organic bases is triethylamine, and described catalyzer is palladium.

Therein in an embodiment, the step of described purification compd A is as follows: the reaction solution that described Compound C and compd E are carried out after coupling reaction makes water and dichloromethane extraction successively, retain organic layer, anhydrous sodium sulfate drying, filter, distillation obtains described compd A except using silica gel column chromatography to separate after desolventizing.

In an embodiment, the preparation process of described compd B comprises the steps: therein

Compound D and n-Butyl Lithium are provided,

The structural formula of Compound D is

wherein R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group.

In oxygen-free environment, Compound D is added in tetrahydrofuran (THF), at-78 ℃, add n-Butyl Lithium, the mol ratio of described Compound D and described n-Butyl Lithium is 1:2, stirring reaction 2 hours, at-78 ℃, add tributyltin chloride, the mol ratio of described tributyltin chloride and described Compound D is 2:1, at-78 ℃, react 1 hour, be warming up under room temperature stirring reaction 6 hours, add the aqueous solution termination reaction of saturated sodium-chlor, with anhydrous diethyl ether extractive reaction liquid, by dry the organic phase obtaining rear suction filtration, the solvent of removing in filtrate obtains compd B.

A kind of solar cell device, comprises active coating, and the material of described active coating comprises benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p with following structural formula:

P:

A kind of organic electroluminescence device, comprises luminescent layer, and the material of described luminescent layer comprises benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p with following structural formula:

P:

Above-mentioned benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer and preparation method thereof, synthetic method is simple, improve solvability and the molecular weight of benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer by introducing alkyl, be conducive to film forming processing, benzo two (diazosulfide) is a kind of very excellent donor material, benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, by compound benzo [2, 1-b:3, 4-b '] benzo [2 that forms of two thiophene and benzo two (diazosulfide), 1-b:3, 4-b '] two thiophene-benzo two (diazosulfide) can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material, above-mentioned benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer is applied to solar cell and can increases substantially effciency of energy transfer, above-mentioned benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer is applied to organic electroluminescence device and can increases substantially luminous efficiency.

Accompanying drawing explanation

Fig. 1 is the preparation method's of benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer of an embodiment schema;

Fig. 2 is the structural representation of the solar cell device of an embodiment;

Fig. 3 is the structural representation of the organic electroluminescence device of an embodiment.

Embodiment

Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.

Benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer of one embodiment, has following structural formula:

P:

Above-mentioned benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer, improve benzo [2 by introducing alkyl, 1-b:3,4-b '] solvability and the molecular weight of two thiophene-benzo two (diazosulfide) multipolymer, be conducive to film forming processing, benzo two (diazosulfide) is a kind of very excellent donor material, benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, by compound benzo [2, 1-b:3, 4-b '] benzo [2 that forms of two thiophene and benzo two (diazosulfide), 1-b:3, 4-b '] two thiophene-benzo two (diazosulfide) can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material.

The preparation method of benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer of one embodiment, as shown in Figure 1, comprises the following steps:

Step S100, provide compd A and compd B.

A is:

b is:

wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl, R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group.

Wherein the preparation of compd A comprises the following steps:

Step S111,2-amino-5-N-methyl-p-nitroaniline is added to thionyl chloride (SOCl ₂) in, (structural formula is to drip while stirring pyridine molecular formula is C ₅h ₅n,), wherein the solid-to-liquid ratio of 2-amino-5-N-methyl-p-nitroaniline and pyridine is 3mol:40ml, be heated to afterwards 80 ℃ ~ 90 ℃ back flow reaction 24 hours, remove afterwards excessive thionyl chloride, add deionized water precipitating after cooling, collect dry 5-nitro-2 that obtain of solids wash final vacuum, 1,3 diazosulfide.

The reaction formula of this step is:

Step S112, by 5-nitro-2, after 1,3 diazosulfide and hydrobromic acid solution mix, at 127 ℃, reflux, to 5-nitro-2, in the mixed solution forming after 1,3 diazosulfide and Hydrogen bromide (HBr) solution mixes, drip bromine (Br ₂), back flow reaction 4 hours, heat filtering afterwards, after filtrate is cooling, refilter, the solid obtaining washes with water rear dry, then obtains 4 with Glacial acetic acid and Gossypol recrystallized from chloroform successively, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide, wherein 5-nitro-2,1,3 diazosulfide and hydrobromic mol ratio are 3:5,5-nitro-2, the mol ratio of 1,3 diazosulfide and bromine is 2:7.

The reaction formula of this step is:

Preferably, in hydrobromic acid solution, hydrobromic quality percentage composition is 40%.

Step S113, be 102:95 by mass ratio 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfides and copper powder (Cu) add DMF (DMF), react 3 hours at 120 ℃, after reaction solution is cooling, add toluene agitation and filtration, the aqueous solution and water washing by filtrate with saturated sodium-chlor, merge organic phase, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide.

The reaction formula of this step is:

Preferably, the bromo-5-of 4,7-bis-nitro-2, the solid-to-liquid ratio of 1,3 diazosulfide and DMF is 1mol:3L, the volume ratio of DMF and toluene is 1:1.

Step S114, to be 1: 10 by mol ratio 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfide and SnCl ₂add tetrahydrofuran (THF) (THF), be warming up to 100 ℃, back flow reaction 10 hours, cooling rear use sodium hydroxide solution is adjusted to 8 by the pH value of reaction solution, use afterwards anhydrous diethyl ether extraction, the organic solvent of collecting organic phase and remove wherein obtains solid crude product, after after solid crude product and mixed in hydrochloric acid, drip sodium nitrite solution, carry out below diazotization reaction 30 minutes at 5 ℃, reaction solution is added dropwise in liquor kalii iodide, vigorous stirring reaction 12 hours, then with sodium hydroxide solution, the pH value of reaction solution is adjusted to 7, extract with anhydrous diethyl ether, collect organic phase after washing, filter, the organic solvent of removing afterwards in filtrate obtains Compound C (4, 4 '-bis-bromo-6, 6 '-bis-iodo-2, 1, 3 diazosulfides):

Preferably, 4,4 '-bis-bromo-6, in 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides and hydrochloric acid, the mol ratio of hydrogenchloride is 20:21.7,4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2, the mol ratio of 1,3 diazosulfide and Sodium Nitrite is 20:37.7,4,4 '-bis-bromo-6, the mass ratio of 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides and potassiumiodide is 10.3:62.

Preferably, Compound C is separated with silica gel column chromatography, then purify by recrystallizing methanol.

Step S115, in oxygen-free environment, the Compound C that is 1:2 by mol ratio and compd E carry out coupling reaction in the solvent that contains organic bases and catalyzer, organic bases is triethylamine (Bu ₃n), catalyzer is palladium (Pd (OAc) ₂), after purification, obtain compd A:

E is

a is:

wherein R ₁, R ₂for C ₁~ C ₂₀alkyl.

Preferably, solvent is DMF (DMF).

Preferably, the mol ratio of organic bases and compd E is 1:1.

Preferably, the mol ratio of Compound C and catalyzer is 10:1.

Preferably, the step of purification compd A is as follows: the reaction solution that Compound C and compd E are carried out after coupling reaction makes water and dichloromethane extraction successively, retains organic layer, anhydrous sodium sulfate drying, filter, distillation obtains compd A except using silica gel column chromatography to separate after desolventizing.

Wherein, the preparation process of compd B is as follows:

Step S121, provide Compound D and n-Butyl Lithium.

The structural formula of Compound D is

wherein R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group.

Step S122, in oxygen-free environment, Compound D is added in tetrahydrofuran (THF), at-78 ℃, add n-Butyl Lithium (CH ₃(CH ₂) ₃li), stirring reaction 1 ~ 2 hour adds tributyltin chloride (C at-78 ℃ ₁₂h ₂₇clSn), at-78 ℃, react 1 hour, be warming up under room temperature stirring reaction 6 hours, add the aqueous solution termination reaction of saturated sodium-chlor, with anhydrous diethyl ether extractive reaction liquid, by dry the organic phase obtaining rear suction filtration, the solvent of removing in filtrate obtains compd B.

Preferably, use neutral alumina column chromatography to purify the compd B obtaining.

Preferably, the mol ratio of Compound D and n-Butyl Lithium is 1:2.

Preferably, the mol ratio of Compound D and tributyltin chloride is 1:2.

Preferably, the solid-to-liquid ratio of Compound D and saturated sodium-chloride water solution is 1mol:2L.

Step S200, prepare benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p.

In oxygen-free environment, the compd A and the compd B that are 1: 1.5 ~ 1.5:1 by mol ratio carry out Stille coupling reaction in the organic solvent that contains organic palladium catalyzer, after purification, obtain the benzo [2 that following structural formula represents, 1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p:

P:

In present embodiment, organic palladium catalyzer is selected from three (dibenzalacetone) two palladium (Pd ₂(dba) ₃), tetrakis triphenylphosphine palladium (Pd (pph ₃) ₄) or two (triphenylphosphine) palladium chloride (Pd (pph) ₃cl ₂) at least one, be preferably Pd (pph) ₃cl ₂.Be appreciated that organic palladium catalyzer is not limited to cited kind, as long as energy catalytic cpd A and compd B carry out Stille coupling reaction.

In present embodiment, organic solvent is selected from tetrahydrofuran (THF) (THF), glycol dimethyl ether (DME), ether (C ₄h ₁₀o), benzene (C ₆h ₆) and toluene (C ₇h ₈) at least one.Be appreciated that organic solution also can be used other solvents, as long as can dissolved compound A and compd B.

In present embodiment, the mol ratio of organic palladium catalyzer and compd B is 1:2000 ~ 1:5.The mol ratio that is appreciated that organic palladium catalyzer and compd A is not limited to 1:2000 ~ 1:5, to adding the catalyzer that adds catalytic amount in the organic solvent of compd A and compd B.

In present embodiment, the temperature of reaction of Stille coupling reaction is 50 ℃ ~ 120 ℃, and the reaction times is 6 hours ~ 100 hours.The temperature of reaction that is appreciated that Stille coupling reaction is not limited to 50 ℃ ~ 120 ℃, as long as can make compd A and compd B react; Reaction times is also not limited to 6 hours ~ and 100 hours, as long as can make compd A and compd B react completely as far as possible.

In present embodiment, purification benzo [2, 1-b:3, 4-b '] step of two thiophene-benzo two (diazosulfide) copolymer p is as follows: carries out adding in the solution after Stille coupling reaction the mixed solution of toluene and deionized water to extract to compd A and compd B and retains organic phase, to after organic solvent evaporate to dryness, add ethanol precipitating and filter, after being dissolved, the pressed powder chloroform obtaining after filtering uses neutral alumina chromatography, remove afterwards organic solvent, again with methyl alcohol precipitating filtration, by the solids acetone extracting obtaining after filtering, after collection acetone soln, obtain the benzo [2 of purifying with methyl alcohol precipitating filtration, 1-b:3, 4-b '] two thiophene-benzo two (diazosulfide) copolymer p.

The preparation method of above-mentioned benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer, synthetic method is simple, improve solvability and the molecular weight of benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer by introducing alkyl, be conducive to film forming processing, benzo two (diazosulfide) is a kind of very excellent donor material, benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, by compound benzo [2, 1-b:3, 4-b '] benzo [2 that forms of two thiophene and benzo two (diazosulfide), 1-b:3, 4-b '] two thiophene-benzo two (diazosulfide) can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material.

It should be noted that, each step of above-mentioned reaction is not limited to adopt said sequence to carry out, and such as each step of preparing compd B can be carried out prior to each step of preparing compd A, also can carry out with each step of preparing compd A simultaneously.

Be specific embodiment below.

Embodiment 1

The present embodiment disclose structural formula following poly-{ 4,5-bis-(3,7-dimethyl) octyl group benzo [2,1-b:3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 1):

The preparation process of above-mentioned benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 1 is as follows:

1.1, prepare compound 5-nitro-2,1,3 diazosulfide

In there-necked flask, add 2-amino-5-N-methyl-p-nitroaniline (22.95g, 0.15mol) and 100ml thionyl chloride, stir and slowly drip 2ml pyridine, after heating, in 80 ~ 90 ℃ of back flow reaction 24h, stopped reaction, is heated to 80 ℃ and revolves and steam excessive SOCl ₂after, reaction product is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%;

1.2, prepare compound 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide

In there-necked flask, add 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and 40% Hydrogen bromide 15ml, be warming up to 127 ℃ of backflows, in 30min, slowly drip bromine 11.3ml the 4h that refluxes, heat filtering, after filtrate is cooling, refilter, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 10.2g, productive rate: 50%.

1.3, preparation 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides

In there-necked flask, add the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g, the DMF DMF of 90ml, was heated to 120 ℃ of reactions after 3 hours, stopped reaction, is cooled to room temperature, adds 90ml toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains product 4, and 4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%.

1.4,4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

In there-necked flask, add 4,4 '-bis-bromo-ly 6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides (10.3g, 20mmol), add the tetrahydrofuran THF that 300ml is dry, add 40g SnCl ₂(200mmol), be warming up to 100 ℃, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolves and steams gained organic layer, obtains solid crude product, be put in there-necked flask, add the hydrochloric acid (21.7mmol) of 58ml, agitation and dropping sodium nitrite solution 20ml(37.7mmol in 30 minutes), temperature is controlled at below 5 ℃, it is yellow that solution is, and after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide+100ml water) to vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, with silica gel column chromatography separation, then carry out recrystallizing methanol, obtain 4.1g 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.

1.5, prepare compound 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides)

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), add 2,6,13,17-tetramethyl--9-octadecyne (3.07g, 10mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852), 25ml DMF, pass into nitrogen gas stirring 20min, add Bu ₃n (0.907g, 10mmol) and Pd (OAc) ₂(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography separates, and obtains 2.4g product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 70%.

Product 4,9-bis-is bromo-6, and the structured testing data of 7-bis-(3,7-dimethyl) octyl group benzo [2,1-e:3,4-e] two (diazosulfides) are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.32（d，2H），3.08（dd，4H），1.83（d，2H），1.60-1.64（m，6H），1.22-1.27（m，12H）,1.08-1.10（m，18H）；

¹³CNMR（CDCl ₃）δ（TMS，ppm）：134.0,131.8,130.2,129.9,124.9,123.6,130.0,41.0,39.7,38.0,32.6,28.5,25.6,24.2,23.0,21.0；

1.6, preparation 4,5-bis-(3,7-dimethyl) octyl group-2,7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene

Under the protection of nitrogen; in there-necked flask, add 4; 5-bis-(3; 7-dimethyl) octyl group-2; 7-dibromo benzo [2; 1-b:3,4-b '] two thiophene (9.44g, 0.015mol); add the tetrahydrofuran solvent of 80ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (12.6mL, 2.5M, 0.03mol) with syringe again; continue stirring reaction 2h; under-78 ℃ of conditions, inject tributyltin chloride (8.4mL, 0.03mol) with syringe, react and after 1 hour, be warming up under room temperature stirring reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 72%.

1.7, preparation poly-{ 4,5-bis-(3,7-dimethyl) octyl group benzo [2,1-b:3,4-b '], two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }

Under nitrogen protection, add 4,5-bis-(3; 7-dimethyl) octyl group-2,7-bis-(tributyl tin) benzo [2,1-b:3; 4-b '] two thiophene (209.8mg, 0.2mmol), 4,9-bis-bromo-6; 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3; 4-e] two (diazosulfide) (146.6mg; 0.2mmol), with tetrahydrofuran solvent 40ml, vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh ₃) ₂cl ₂, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance (P1) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 58960, n=55, polymkeric substance monodispersity is 2.2.

Embodiment 2

The present embodiment disclose structural formula following poly-{ 4,5-bis-n-decyloxy benzos [2,1-b:3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 2):

The preparation process of above-mentioned benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 2 is as follows:

2.1,4,9-bis-is bromo-6, and the preparation of 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) is with embodiment 1.

2.2, preparation 4,5-bis-(n-decyloxy)-2,7-bis-(tributyl tinbase) benzo [2,1-b:3,4-b '] two thiophene

Under the protection of nitrogen; in there-necked flask, add 4; 5-bis-(n-decyloxy)-2; 7-dibromo benzo [2; 1-b:3; 4-b '] two thiophene (6.61g; 0.01mol), add the tetrahydrofuran solvent of 80ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.4mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), reaction is warming up to stirring at room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 68%.

2.3, preparation poly-{ 4,5-, bis-n-decyloxy benzos [2,1-b:3,4-b '], two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }

Under nitrogen protection, add 4,5-bis-(n-decyloxy)-2; 7-bis-(tributyl tinbase) benzo [2,1-b:3,4-b '] two thiophene (216.2mg; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl) octyl group-benzo [2; 1-e:3,4-e] two (diazosulfide) (146.6mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh ₃) ₂cl ₂, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance (P2) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 55200, n=50, polymkeric substance monodispersity is 2.3.

Embodiment 3

The present embodiment disclose structural formula following poly-{ 4,5-bis-(3,7-dimethyl) octyl group benzo [2,1-b:3,4-b '] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 3):

3.1, the bromo-6-(2 of preparation 4,9-bis-, 7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfides)

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides (3.4g, 5mmol), 4,4 '-bis-bromo-6, the preparation of 6 '-bis-iodo-2,1,3 diazosulfides is with embodiment 1, (synthetic method is with reference to Chem.Commun. to add 2,6 dimethyl-9-, 30 alkynes (4.47g, 10mmol), 2011,47,8850-8852), 25ml DMF, passes into nitrogen gas stirring 20min, adds Bu ₃n (0.907g, 10mmol) and Pd (OAc) ₂(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography separates, and obtains 2.7g product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 62%

Gained 4, the bromo-6-(3 of 9-bis-, 7-dimethyl) the structured testing data of octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.30（d，2H），3.01（m，4H），1.85(s,1H)，1.60-1.65(m,5H),1.25-1.34（m，40H），1.01-1.07（m，12H）；

¹³CNMR（CDCl ₃）δ（TMS，ppm）：134.0，131.9，130.3，130.1，129.9，124.9，123.8，41.5,39.9,37.8，32.8，32.2，31.9，31.6，29.7，29.3，28.5,28.1，24.2，23.0，22.7，21.0，14.3。

3.2,4,5-bis-(3,7-dimethyl) octyl group-2, the preparation method of 7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene is with embodiment 1.

3.3, preparation poly-{ 4,5-bis-(3,7-dimethyl) octyl group benzo [2,1-b:3,4-b '], two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) }

Under nitrogen protection, add 4,5-bis-(3; 7-dimethyl) octyl group-2,7-bis-(tributyl tin) benzo [2,1-b:3; 4-b '] two thiophene (209.8mg, 0.2mmol), 4, the bromo-6-(3 of 9-bis-; 7-dimethyl) octyl group-7-eicosyl-benzo [2; 1-e:3,4-e] two (diazosulfide) (174.6mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh ₃) ₂cl ₂, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance (P3) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 75144, n=62, polymkeric substance monodispersity is 2.3.

Embodiment 4

The present embodiment disclose structural formula following poly-{ 4,5-bis-(NSC 62789 base)-benzo [2,1-b:3,4-b '] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 4):

4.1,4, the bromo-6-(3 of 9-bis-, 7-dimethyl) preparation of octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfides) is with embodiment 3.

4.2, preparation 4,5-bis-(NSC 62789 base)-2,7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene

Under the protection of nitrogen; in there-necked flask, add 4; 5-bis-(NSC 62789 base)-2; 7-dibromo benzo [2; 1-b:3; 4-b '] two thiophene (9.09g; 0.01mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.4mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1.5h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), reaction is warming up to stirring at room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 58%.

4.3, gather 4,5-bis-(NSC 62789 base)-benzo [2,1-b:3,4-b '], two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides).

Under nitrogen protection, add 4,5-bis-(NSC 62789 base)-2; 7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene (398.7mg; 0.3mmol), 4; the bromo-6-(3 of 9-bis-, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3; 4-e] two (diazosulfide) (174.6mg; 0.2mmol), with tetrahydrofuran solvent 40ml, vacuumize deoxygenation and be filled with nitrogen, then add 28.04mg Pd (PPh ₃) ₂cl ₂, be heated to 120 ℃ of reaction 100h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 149300, n=100, polymkeric substance monodispersity is 3.8.

Embodiment 5

The present embodiment disclose structural formula following poly-{ 4,5-dimethylbiphenyl [2,1-b:3,4-b '] two thiophene-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) } (benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 5):

5.1, preparation 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (diazosulfides).

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (6.8g, 10mmol), add valerylene (1.36g, 20mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852), 50ml DMF, passes into nitrogen gas stirring 20min, adds Bu ₃n (1.814g, 20mmol) and Pd (OAc) ₂(230mg, 1.0mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, obtain 2.6g product 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 52.6%.

Product 4, the structured testing data of the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.31（d，2H），3.03（d，2H），2.67(s,3H)，1.35（d，3H）;

¹³CNMR（CDCl ₃）δ（TMS，ppm）：135.0，131.8，130.5，130.0，129.7，124.9，123.5，24.5，16.8，15.5；

5.2, preparation 4,5-dimethyl-2,7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene.

Under the protection of nitrogen; in there-necked flask, add 4; 5-dimethyl-2; 7-dibromo benzo [2; 1-b:3; 4-b '] two thiophene (7.52g; 0.02mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (16.8mL with syringe again; 2.5M; 0.04mol), continue stirring reaction 2h, under-78 ℃ of conditions, inject tributyltin chloride (11.2mL with syringe; 0.04mol), reaction is warming up to stirring at room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 64%.

5.3, preparation poly-{ 4,5-dimethylbiphenyl [2,1-b:3,4-b '], two thiophene-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }.

Under nitrogen protection, add 4,5-dimethyl-2; 7-bis-(tributyl tin) benzo [2; 1-b:3,4-b '] two thiophene (159.2mg, 0.2mmol), 4; the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2; 1-e:3,4-e] two (diazosulfide) (148.2mg, 0.3mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 0.11mg Pd (PPh ₃) ₂cl ₂, be heated to 50 ℃ of reaction 6h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 100ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 581, n=1.

Embodiment 6

The present embodiment disclose structural formula following poly-{ 4,5-dimethylbiphenyl [2,1-b:3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 6):

6.1,4,5-dimethyl-2, the preparation of 7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene is with embodiment 5.

6.2,4,9-bis-is bromo-6, and the preparation of 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) is with embodiment 1.

6.3, preparation poly-{ 4,5-dimethylbiphenyl [2,1-b:3,4-b '], two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }.

Under nitrogen protection, add 4,5-dimethyl-2; 7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene (159.2mg; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl) octyl group-benzo [2; 1-e:3,4-e] two (diazosulfide) (160mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh ₃) ₂cl ₂, be heated to 90 ℃ of reaction 48h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 28665, n=35, polymkeric substance monodispersity is 2.1.

Embodiment 7

The present embodiment disclose structural formula following poly-{ 4,5-dimethoxy benzo [2,1-b:3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 7):

7.1,4,9-bis-is bromo-6, and the preparation of 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) is with embodiment 1.

7.2, preparation 4,5-dimethoxy-2,7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene

Under the protection of nitrogen; in there-necked flask, add 4; 5-dimethoxy-2; 7-dibromo benzo [2; 1-b:3; 4-b '] two thiophene (4.08g; 0.01mol), add the tetrahydrofuran solvent of 80ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.4mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), reaction is warming up to stirring at room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 68%.

7.3, preparation poly-{ 4,5-dimethoxy benzo [2,1-b:3,4-b '], two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }.

Under nitrogen protection, add 4,5-dimethoxy-2; 7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene (165.6mg; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl) octyl group-benzo [2; 1-e:3,4-e] two (diazosulfide) (146.6mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh ₃) ₂cl ₂, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 25530, n=30, polymkeric substance monodispersity is 2.3.

Embodiment 8

The present embodiment disclose structural formula following poly-{ 4,5-bis-(n-hexadecane oxygen base) benzo [2,1-b:3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 8):

8.1,4,9-bis-is bromo-6, and the preparation of 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) is with embodiment 1.

8.2, preparation 4,5-bis-(n-hexadecane oxygen base)-2,7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene

Under the protection of nitrogen; in there-necked flask, add 4; 5-bis-(n-hexadecane oxygen base)-2; 7-dibromo benzo [2; 1-b:3; 4-b '] two thiophene (8.29g; 0.01mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.4mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), reaction is warming up to stirring at room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 65%.

8.3, preparation poly-{ 7,8-bis-(n-hexadecane oxygen base) benzo [1,2-b:4,3-b '], two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }.

Under nitrogen protection, add 4,5-bis-(n-hexadecane oxygen base)-2; 7-bis-(tributyl tin) benzo [2,1-b:3,4-b '] two thiophene (249.8mg; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl) octyl group-benzo [2; 1-e:3,4-e] two (diazosulfide) (146.6mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh ₃) ₂cl ₂, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 82680, n=65, polymkeric substance monodispersity is 3.2.

Embodiment 9

Refer to Fig. 2, the solar cell device 40 of an embodiment comprises the substrate 41, anode 42, buffer layer 43, active coating 44 and the negative electrode 45 that stack gradually.

In the present embodiment, substrate 41 is glass.

Anode 42 is formed at a side surface of substrate 41.In the present embodiment, anode 72 is ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.In present embodiment, the thickness sum of substrate 41 and anode 42 is 1.1mm.Preferably, substrate 41, before forming anode 42, first cleans, and oxygen plasma treatment.

Buffer layer 43 is formed at the surface of anode 42.The material of buffer layer 43 comprises poly-3,4-Ethylenedioxy Thiophene and polystyrolsulfon acid (PEDOT:PSS, ": " represents the two mixing) (CLEVIOS P VP Al 4083).The thickness of buffer layer 43 is 120nm.Buffer layer 43 is prepared by spin coating.

Active coating 44 is formed at the surface of buffer layer 43.The material of active coating 44 comprises the methyl-butyrate derivative (PCBM) of soccerballene and has benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p of following structural formula:

P:

Wherein benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p ~ with the mass ratio of PCBM be 5:4.The thickness of active coating 44 is 150nm.While preparing active coating 44, by 10mg benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p is dissolved in after 0.4ml dimethylbenzene, and be dissolved in after the solution blending that the chlorobenzene of 0.4ml forms and be dried and obtain in spin coating and buffer layer 43 with 8mgPCBM.

Negative electrode 45 is formed at the surface of active coating 44.The material of negative electrode 45 is aluminium (Al).The thickness of negative electrode 45 is 120nm.Negative electrode 45 is prepared by vacuum evaporation, and vacuum tightness is 2 × 10 ^-3pa.

It should be noted that, substrate 41, anode 42, buffer layer 43 and negative electrode 45 material used are not limited to above cited material, also can be conventional in the industry other materials, also can more need to arrange other functional layers.

Respectively by the benzo [2 of embodiment 1 ~ 3 preparation, 1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p, 1 ~ P3 is applied to solar cell device 40, by Keithley236 current/voltage source-measuring system and a calibrated silicon photo diode test current-voltage characteristic, result is as shown in the table.

From upper table data, the energy conversion efficiency of the organic solar batteries device of preparing as active coating with multipolymer of the present invention is 1.14 ~ 1.68, show of the present invention containing benzo [2, 1-b:3, 4-b '] two thiophene-benzo two (diazosulfide) multipolymer is owing to containing new benzo two (diazosulfide) conjugate unit, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and by improvement or modification to device architecture, can obtain higher effciency of energy transfer.

Embodiment 10

Refer to Fig. 3, a kind of organic electroluminescence device 70 comprises the substrate 71, anode 72, luminescent layer 73, buffer layer 74 and the negative electrode 75 that stack gradually.

In the present embodiment, substrate 71 is glass.

Anode 72 is formed at a side surface of substrate 71.In the present embodiment, anode 72 is ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.The thickness of anode 72 is 150nm.

The material of luminescent layer 73 is benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p with following structural formula:

P:

Specifically in the present embodiment, the material of luminescent layer 73 is benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p 1 prepared by embodiment 1.

The thickness of luminescent layer 73 is 80nm.

Buffer layer 74 is formed at the surface of luminescent layer 73.The material of buffer layer 74 is lithium fluoride (LiF).The thickness of buffer layer 74 is 1.5nm.Buffer layer 74 is formed by evaporation.

Negative electrode 75 is formed at the surface of buffer layer 74.The material of negative electrode is aluminium (Al).The thickness of negative electrode 75 is 150nm.

It should be noted that, substrate 71, anode 72, buffer layer 74 and negative electrode 75 material used are not limited to above cited material, also can be conventional in the industry other materials, also can more need to arrange other functional layers.

By organic electroluminescence device 70 by Keithley source measuring system (Keithley 2400Sourcemeter) test current-brightness-voltage characteristic with correction silicon photoelectric diode, by spectrograph (the French JY SPEX CCD3000 of company) testing electroluminescent spectrum, all tests all complete in atmosphere at room temperature.The maximum lumen efficiency that test obtains organic electroluminescence device 70 is 11.8cd/A, and high-high brightness is 1150cd/m ².

The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims

1. benzo [2,1-b:3, a 4-b '] two thiophene-benzo two (diazosulfide) multipolymer, is characterized in that having following structural formula:

P:

2. the preparation method of benzo [2,1-b:3, a 4-b '] two thiophene-benzo two (diazosulfide) multipolymer, is characterized in that, comprises the steps:

A is:

b is: wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl, R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group;

P:

Wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl, R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group, the integer that n is 1 ~ 100.

3. benzo [2 according to claim 2,1-b:3,4-b '] preparation method of two thiophene-benzo two (diazosulfide) multipolymer, it is characterized in that, described organic palladium catalyzer is selected from three (dibenzalacetone) two palladiums, tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, and the mol ratio of described organic palladium catalyzer and described compd A is 1:2000 ~ 1:5.

4. benzo [2 according to claim 2,1-b:3,4-b '] preparation method of two thiophene-benzo two (diazosulfide) multipolymer, it is characterized in that, the temperature of reaction of described Stille coupling reaction is 50 ℃ ~ 120 ℃, and the reaction times is 6 hours ~ 100 hours.

5. benzo [2 according to claim 2, 1-b:3, 4-b '] preparation method of two thiophene-benzo two (diazosulfide) multipolymer, it is characterized in that, described separating-purifying benzo [2, 1-b:3, 4-b '] step of two thiophene-benzo two (diazosulfide) copolymer p is as follows: extracts and retains organic phase to the mixed solution that adds toluene and deionized water in the solution after Stille coupling reaction, to after organic solvent evaporate to dryness, add ethanol precipitating and filter, after being dissolved, the pressed powder chloroform obtaining after filtering uses neutral alumina chromatography, remove afterwards organic solvent, again with methyl alcohol precipitating filtration, by the solids acetone extracting obtaining after filtering, after collecting acetone soln, use methyl alcohol precipitating and filter.

6. the preparation method of benzo according to claim 2 [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer, is characterized in that, the preparation process of described compd A comprises the steps:

C is:

e is:

wherein R ₁, R ₂for C ₁~ C ₂₀alkyl;

7. benzo [2 according to claim 6,1-b:3,4-b '] preparation method of two thiophene-benzo two (diazosulfide) multipolymer, it is characterized in that, the step of described separating-purifying compd A is as follows: the reaction solution that described Compound C and compd E are carried out after coupling reaction makes water and dichloromethane extraction successively, retains organic layer, anhydrous sodium sulfate drying, filter, distillation obtains described compd A except using silica gel column chromatography to separate after desolventizing.

8. the preparation method of benzo according to claim 6 [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) multipolymer, is characterized in that, the preparation process of described compd B comprises the steps:

Compound D, n-Butyl Lithium and tributyltin chloride are provided,

The structural formula of Compound D is

wherein R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group.

In oxygen-free environment, Compound D is added in tetrahydrofuran (THF), at-78 ℃, add n-Butyl Lithium, the mol ratio of described Compound D and described n-Butyl Lithium is 1:2, stirring reaction 1 ~ 2 hour, at-78 ℃, add tributyltin chloride, the mol ratio of described tributyltin chloride and described Compound D is 2:1, at-78 ℃, react 1 hour, be warming up under room temperature stirring reaction 6 hours, add the aqueous solution termination reaction of saturated sodium-chlor, with anhydrous diethyl ether extractive reaction liquid, by dry the organic phase obtaining rear suction filtration, the solvent of removing in filtrate obtains compd B.

9. a solar cell device, comprises active coating, it is characterized in that, the material of described active coating comprises benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p with following structural formula:

P:

Wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl, R ₃, R ₄for C ₁~ C ₂₀alkyl or C ₁~ C ₁₆alkoxyl group; , the integer that n is 1 ~ 100.

10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, the material of described luminescent layer is benzo [2,1-b:3,4-b '] two thiophene-benzo two (diazosulfide) copolymer p with following structural formula:

P: