CN103665336A - Benzothiazole-containing unit polymer, preparation method and application thereof - Google Patents

Abstract

The invention belongs to the field of solar battery materials, and discloses a benzothiazole-containing unit polymer which has the following structural formula as shown in the specification, wherein in the structural formula, R1 and R2 are C1-C20 alkyl, and n is an integer ranging from 10 to 100. In the benzothiazole-containing unit polymer provided by the invention, dibenzofuran has large planes and conjugated structures to facilitate charge transfer, so that dibenzofuran is an excellent cavity transfer unit. N is modified through alkyls, so that the dissolving property and the film-forming property of the copolymer are improved. The energy level of the copolymer can be adjusted by introducing cyano, so that the light emitting efficiency of an organic electroluminescent device can be improved.

Description

Containing also thiazole unit polymkeric substance, its preparation method and application

Technical field

The present invention relates to solar cell material field, relate in particular to a kind of also thiazole unit polymkeric substance and preparation method thereof that contains.The invention still further relates to containing the also application of thiazole unit polymkeric substance in organic solar batteries.

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.

Containing and thiazole unit polymkeric substance in, because thiazole is typical electron deficiency unit, comprise an electrophilic imine group, therefore contain also thiazole unit polymkeric substance and there is higher carrier mobility, demonstrated good photovoltaic performance, by connecting alkyl, can increase the solubility property of polymkeric substance and regulate photoelectric properties in addition.

Summary of the invention

Problem to be solved by this invention is to provide a kind of to be had higher carrier mobility and shows containing and thiazole unit polymkeric substance of good photovoltaic performance.

Technical scheme of the present invention is as follows:

Contain and a thiazole unit polymkeric substance, there is following structural formula:

In formula, R ₁, R ₂be C ₁～C ₂₀alkyl, the integer that n is 10-100.

In this polymkeric substance, R ₁, R ₂can be identical, can be not identical yet.

The present invention also provides the above-mentioned also preparation method of thiazole unit polymkeric substance that contains, and comprises the steps:

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

Under oxygen-free environment, compd A and B are added into the organic solvent that contains catalyzer according to the ratio of mol ratio 1: 1～1.2, after dissolving, under 70～130 ° of C, carry out Stille coupling reaction 6～60 hours, after cooling, stop polyreaction, obtain described the containing and thiazole unit polymkeric substance that following structural formula represents:

Above-mentioned various in, R ₁, R ₂be C ₁～C ₂₀alkyl, the integer that n is 10-100.

Described containing and the preparation method of thiazole unit polymkeric substance in:

Described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; Or

Described catalyzer is the mixture of organic palladium and organophosphorus ligand, and the mol ratio of described organic palladium and organophosphorus ligand is 1:4～8; Described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Described organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl; The mixture that organic palladium and organophosphorus ligand form can be palladium and tri-o-tolyl phosphine mixture or three or two argon benzyl acetone two palladiums and 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl mixture;

In coupling reaction, the mol ratio of catalyzer and compd A is 1:20 ~ 1: 100;

Organic solvent is at least one in toluene, DMF and tetrahydrofuran (THF).

Containing the also preparation method of thiazole unit polymkeric substance, in oxygen-free environment, gas comprises at least one in nitrogen and rare gas element, preferred nitrogen.

Described containing and the preparation method of thiazole unit polymkeric substance, preferably, described Stille coupling reaction temperature is 90～120 ° ' the C reaction times is 12～48 hours.

Described containing and the preparation method of thiazole unit polymkeric substance in, make containing and thiazole unit polymkeric substance be mixture, also need it to carry out purification processes, as:

After Stille coupling reaction stops, to dripping in the mixed solution that obtains after reaction, in methyl alcohol, carry out sedimentation, after filtering by apparatus,Soxhlet's subsequently, use successively methyl alcohol and normal hexane extracting 24h, then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for the also thiazole unit polymkeric substance that contains that obtains purifying.

It is above-mentioned containing the also application of thiazole unit polymkeric substance in the active coating of organic solar batteries that this law also provides.

Of the present invention containing and thiazole unit polymkeric substance in, benzo two furans have large plane and conjugated structure, are conducive to electric charge transmission, are good hole transport unit; N is upper by alkyl modified, thereby improves solubility property and the film forming properties of multipolymer, can regulate the energy level of multipolymer by introducing cyano group; And thiazole is typical electron deficiency unit, comprise an electrophilic imine group, also on thiazole, introducing the band gap that two thiophene can reduce polymkeric substance; These character can improve the effciency of energy transfer of organic solar batteries.

Separately, the above-mentioned also preparation method of thiazole unit polymkeric substance that contains, has adopted better simply synthetic route, thereby has reduced technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And worth polymeric material novel structure, solubility property is good, and film forming properties is good, applicable to solar cell.

Accompanying drawing explanation

Fig. 1 be embodiment 1 make containing and the ultraviolet-visible absorption spectroscopy figure of thiazole unit polymkeric substance;

Fig. 2 is the structural representation of the organic solar batteries that makes of embodiment 6.

Embodiment

Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.

In order to understand better content of the present invention, below by concrete example and legend, further illustrate technology case of the present invention, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein the monomer of compd A is bought and is obtained from the market, synthetic the obtaining of the disclosed method of monomer reference literature (J.Org.Chem.2010.75.3351) of compd B.

Embodiment 1

The present embodiment containing and thiazole unit polymkeric substance, i.e. poly-{ 2,5-bis-(3-n-octyl-2-thiophene) thiazole also [5,4-d] thiazole-co-2,6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, wherein, R1 is octane base, R2 is octane base, n=65; Its structural formula is as follows:

The preparation process of above-mentioned polymkeric substance is as follows:

Reaction formula is as follows:

Under argon shield, by 2,5-bis-(5-tin trimethyl-3-n-octyl-2-thiophene) thiazole also [5,4-d] thiazole (171mg, 0.2mmol), 2,6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano-4,8-diiodo-benzo [1,2-b:4,5-b'] two furans (188mg, 0.2mmol) add in the flask that fills 10ml toluene solvant fully and dissolve, vacuumize deoxygenation and be filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 ℃ and carries out Stille coupling reaction 36h.Subsequently, after cooling, stop polyreaction, to dripping in flask, in 50ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, under vacuum pump, taking out spends the night is gathered, and { 2,5-bis-(3-n-octyl-2-thiophene) thiazole is [5,4-d] thiazole-co-2 also, 6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } product, productive rate 82%.

Test result is: Molecular weight (GPC, THF, R.I): M _n=67.2kDa, M _w/ M _n=2.2.。

Fig. 1 be embodiment 1 make containing and the ultraviolet-visible absorption spectroscopy figure of thiazole unit polymkeric substance.

As shown in Figure 1, contain also thiazole unit polymkeric substance has large wider absorption between 350nm ~ 700nm, and wherein maximum absorption band is positioned at 556nm left and right.

Embodiment 2:

The present embodiment containing and thiazole unit polymkeric substance, i.e. poly-{ 2,5-bis-(3-methyl-2-thiophene) thiazole also [5,4-d] thiazole-co-2,6-bis-(N, N-bis-NSC 62789 bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, wherein, R1 is methyl, R2 is NSC 62789 base, n=10; Its structural formula is as follows:

The preparation process of above-mentioned polymkeric substance is as follows:

Reaction formula is as follows:

Under nitrogen and the protection of argon gas gas mixture, by 2, 5-bis-(5-tin trimethyl-3-methyl-2-thiophene) thiazole also [5, 4-d] thiazole (198mg, 0.3mmol), 2, 6-bis-(N, N-bis-NSC 62789 bases are amino)-3, 7-dicyano-4, 8-diiodo-benzo [1, 2-b:4, 5-b'] two furans (484mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 ℃ and carry out Stille coupling reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain purified product poly-{ 2,5-bis-(3-methyl-2-thiophene) thiazole is [5,4-d] thiazole-co-2 also, 6-bis-(N, N-bis-NSC 62789 bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }.Productive rate is 78%.

Test result is: Molecular weight (GPC, THF, R.I): M _n=19.5kDa, M _w/ M _n=2.4.

Embodiment 3:

The present embodiment containing and thiazole unit polymkeric substance, i.e. poly-{ 2,5-bis-(3-NSC 62789 base-2-thiophene) thiazole also [5,4-d] thiazole-co-2,6-bis-(N, N-dimethylamino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, wherein, R1 is NSC 62789 base, R2 is methyl, n=100; Its structural formula is as follows:

The preparation process of above-mentioned polymkeric substance is as follows:

Reaction formula is as follows:

Under nitrogen protection, by 2,5-bis-(5-tin trimethyl-3-NSC 62789 base-2-thiophene) thiazole also [5,4-d] thiazole (358mg, 0.3mmol), 2,6-bis-(N, the positive methylamino of N-bis-)-3,7-dicyano-4,8-diiodo-benzo [1,2-b:4,5-b'] two furans (180mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF that fills 12mL and fully dissolve, in flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 130 ℃ and carries out Stille coupling reaction 6h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, be poly-{ 2,5-bis-(3-NSC 62789 base-2-thiophene) thiazole purified product [5,4-d] thiazole-co-2,6-bis-(N, N-dimethylamino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, productive rate is 75%.

Test result is: Molecular weight (GPC, THF, R.I): M _n=117.0kDa, M _w/ M _n=2.0.

Embodiment 4:

The present embodiment containing and thiazole unit polymkeric substance, i.e. poly-{ 2,5-bis-(3-normal butane base-2-thiophene) thiazole also [5,4-d] thiazole-co-2,6-bis-(N, N-bis-n-decane bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, wherein, R1 is normal butane base, R2 is n-decane base, n=42; Its structural formula is as follows:

The preparation process of above-mentioned polymkeric substance is as follows:

Reaction formula is as follows:

Under nitrogen protection, by 2,5-bis-(5-tin trimethyl-3-normal butane base-2-thiophene) thiazole also [5,4-d] thiazole (223mg, 0.3mmol), 2,6-bis-(N, N-bis-n-decane bases are amino)-3,7-dicyano-4,8-diiodo-benzo [1,2-b:4,5-b'] two furans (378mg, 0.36mmol), three or two argon benzyl acetone two palladium (9mg, 0.009mmol), with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins the N that fills 12mL, in the flask of dinethylformamide, fully dissolve, in flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Stille coupling reaction 12h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, obtain purified product poly-{ 2,5-bis-(3-normal butane base-2-thiophene) thiazole also [5,4-d] thiazole-co-2,6-bis-(N, N-bis-n-decane bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, productive rate is 68%.

Test result is: Molecular weight (GPC, THF, R.I): M _n=37.9kDa, M _w/ M _n=2.3.

Embodiment 5:

The present embodiment containing and thiazole unit polymkeric substance, i.e. poly-{ 2,5-bis-(3-dodecyl-2-thiophene) thiazole also [5,4-d] thiazole-co-2,6-bis-(N, N-bis-normal hexane bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, wherein, R1 is dodecyl, R2 is normal hexane base, n=87; Its structural formula is as follows:

The preparation process of above-mentioned polymkeric substance is as follows:

Reaction formula is as follows:

Under nitrogen and the protection of argon gas gas mixture, by 2, 5-bis-(5-tin trimethyl-3-dodecyl-2-thiophene) thiazole also [5, 4-d] thiazole (290mg, 0.3mmol), 2, 6-bis-(N, N-bis-normal hexane bases are amino)-3, 7-dicyano-4, 8-diiodo-benzo [1, 2-b:4, 5-b'] two furans (248mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 90 ℃ and carry out Stille coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain purified product poly-{ 2,5-bis-(3-dodecyl-2-thiophene) thiazole is [5,4-d] thiazole-co-2 also, 6-bis-(N, N-bis-normal hexane bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }.Productive rate is 88%.

Test result is: Molecular weight (GPC, THF, R.I): M _n=96.4kDa, M _w/ M _n=2.1.

Embodiment 6

The present embodiment is organic solar batteries, the electron donor material of its active coating be embodiment 1 make containing and thiazole unit polymkeric substance, gather { 2,5-bis-(3-n-octyl-2-thiophene) thiazole is [5,4-d] thiazole-co-2 also, 6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } (with P1, representing).

Refer to Fig. 2, this organic solar batteries 60 comprises substrate 61, anode layer 62, buffer layer 63, active coating 64 and the negative electrode 65 stacking gradually.

The preparation technology of the organic solar batteries of the present embodiment is as follows:

Use successively sanitising agent, deionized water, ethanol, acetone ultrasonic cleaning substrate 61, substrate 61 is glass;

A side at substrate 61 prepares by magnetron sputtering the anode layer 62 that a layer thickness is 100nm, uses successively subsequently sanitising agent, deionized water, ethanol, acetone ultrasonic cleaning, and processes with oxygen-Plasma; In the present embodiment, anode layer 62 is ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth;

The buffer layer 63 that plays modification that is 80nm in anode layer 62 surface-coated a layer thickness; The material of buffer layer 63, for poly-3,4-Ethylenedioxy Thiophene (PEDOT) and polystyrene-sulfonic acid (PSS) matrix material, is expressed as PEDOT:PSS;

The active coating 64 that is 150nm in buffer layer 63 surface-coated a layer thickness; The material of active coating 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1:2; Wherein, electron acceptor material is (6,6) phenyl-C ₆₁-methyl-butyrate (PCBM), electron donor material is poly-{ 4,4'-di-n-octyl-2,2'-joins thiazole-co-2,6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } (the representing with P1) that the present embodiment 1 makes.

The cathode layer 65 that is 170nm in active coating 64 surface vacuum evaporation a layer thickness; Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc.In the present embodiment, the material of cathode layer 65 is aluminium.

Above-mentioned organic solar energy cell structure is: i.e. glass/ITO/PEDOT:PSS/PCBM:P1/Al.

Be appreciated that buffer layer 63 also can omit, now active coating 64 is directly formed at anode layer 62 surfaces.

In the present embodiment, this organic solar batteries device 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to again room temperature, after solar cell device is annealed, can effectively increase order and the regularity between interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.

At AM1.5; 100mW/cm ²under illumination, the effciency of energy transfer 3.5% of the body heterojunction solar cell that the multipolymer based in embodiment 1 is donor material.

When this solar cell device 60 is used, under illumination, light transmission substrate 61 and anode layer 62, the conduction hole type electroluminescent material in active coating 64 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to cathode layer 65, transmit and be collected by negative electrode, transmit and collected by anode layer 62 along electron donor material anode layer 62 in hole freely, thereby form photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In this process, conduction hole type electroluminescent material, because it has very wide spectral response range, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, be convenient to large batch of preparation.

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 (10)

1. contain and a thiazole unit polymkeric substance, it is characterized in that thering is following structural formula:

In formula, R ₁, R ₂be C ₁～C ₂₀alkyl, the integer that n is 10-100.

2. contain an also preparation method for thiazole unit polymkeric substance, it is characterized in that, comprise the steps:

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

Under oxygen-free environment, compd A and B are added into the organic solvent that contains catalyzer according to the ratio of mol ratio 1: 1～1.2, after dissolving, under 70～130 ° of C, carry out Stille coupling reaction 6～60 hours, after cooling, stop polyreaction, obtain described the containing and thiazole unit polymkeric substance that following structural formula represents:

Above-mentioned various in, R ₁, R ₂be C ₁～C ₂₀alkyl, the integer that n is 10-100.

3. the also preparation method of thiazole unit polymkeric substance that contains according to claim 2, is characterized in that, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium.

4. the also preparation method of thiazole unit polymkeric substance that contains according to claim 2, is characterized in that, described catalyzer is the mixture of organic palladium and organophosphorus ligand; The mol ratio of described organic palladium and organophosphorus ligand is 1:4～8.

5. the also preparation method of thiazole unit polymkeric substance that contains according to claim 4, is characterized in that, described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Described organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.

6. according to the also preparation method of thiazole unit polymkeric substance that contains described in claim 2,3 or 4, it is characterized in that, the mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.

According to claim 2 containing and the preparation method of thiazole unit polymkeric substance, it is characterized in that, described Stille coupling reaction temperature is 90～120 ° ' the C reaction times is 12～48 hours.

8. the also preparation method of thiazole unit polymkeric substance that contains according to claim 2, is characterized in that, described organic solvent is at least one in toluene, DMF and tetrahydrofuran (THF).

9. the also preparation method of thiazole unit polymkeric substance that contains according to claim 2, is characterized in that, after Stille coupling reaction stops, also needing to carry out purification process to containing also thiazole unit polymkeric substance:

After Stille coupling reaction stops, to dripping in the mixed solution that obtains after reaction, in methyl alcohol, carry out sedimentation, after filtering by apparatus,Soxhlet's subsequently, use successively methyl alcohol and normal hexane extracting 24h, then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for the also thiazole unit polymkeric substance that contains that obtains purifying.

One kind claimed in claim 1 containing and the application of thiazole unit polymkeric substance in the active coating of organic solar batteries.

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