阅读说明：本技术 一种含3-己基噻吩的卟啉聚合物及其合成方法 (Porphyrin polymer containing 3-hexylthiophene and synthetic method thereof ) 是由 吴德林 刘廷国 于 2020-12-15 设计创作，主要内容包括：本发明公开了一种含3-己基噻吩的卟啉聚合物及其合成方法,涉及太阳能电池材料领域,本发明设计合成了的一类新型的卟啉化合物,主要由吡咯合成的二吡咯甲烷以及丁香醛与1-溴代正己烷生成的4-己氧基-3,5-二甲氧基苯甲醛相互反应合成卟啉化合物,再通过上溴、配位等操作进一步修饰合成的卟啉化合物,再将该卟啉化合物与2,5-二炔-3-己基噻吩聚合得到目标卟啉聚合物。本发明能够解决现有的卟啉聚合物合成时原料价格高昂、合成过程繁琐、合成条件苛刻。合成成本较高、中间产物收集率较低、副产物较多且占比较大以及在四氢呋喃和氯仿等有机溶剂中的溶解度较低导致测试光电转换效率较为不便的问题。(The invention discloses a porphyrin polymer containing 3-hexylthiophene and a synthesis method thereof, relates to the field of solar cell materials, and discloses a novel porphyrin compound designed and synthesized by the invention, wherein dipyrromethane synthesized by pyrrole and 4-hexyloxy-3, 5-dimethoxybenzaldehyde generated by syringaldehyde and 1-bromo-n-hexane react with each other to synthesize a porphyrin compound, the synthesized porphyrin compound is further modified by operations of bromine adding, coordination and the like, and the porphyrin compound is polymerized with 2, 5-diyne-3-hexylthiophene to obtain a target porphyrin polymer. The invention can solve the problems of high raw material price, complex synthetic process and harsh synthetic conditions in the existing synthesis of the porphyrin polymer. The method has the problems of higher synthesis cost, lower intermediate product collection rate, more byproducts, larger proportion and lower solubility in organic solvents such as tetrahydrofuran, chloroform and the like, which causes inconvenient photoelectric conversion efficiency test.)

1. The porphyrin polymer containing 3-hexylthiophene is characterized in that the structural formula is as follows:

2. a method for synthesizing 3-hexylthiophene-containing porphyrin polymer according to claim 1, comprising the steps of:

(1) mixing syringaldehyde with 1-bromo-n-hexane and anhydrous K₂CO₃Reacting NaI in dimethylformamide, electromagnetically stirring and heating under the protection of nitrogen filling, adding distilled water for washing after the reaction is finished, extracting by using ethyl acetate and petroleum ether, combining organic layers, adding anhydrous magnesium sulfate for drying, and washing by using dichloromethane and petroleum ether as mixed eluent until the mixture is purified to obtain a compound A;

(2) stirring dipyrromethane, a compound A, dichloromethane and trifluoroacetic acid under the protection of nitrogen, adding dichlorodicyanoquinone, continuously stirring, after the reaction is finished, adding triethylamine for alkalization, performing vacuum drying under reduced pressure, and washing the mixture by using dichloromethane and petroleum ether as a mixed eluent until the mixture is purified to obtain a compound B;

(3) dissolving the compound B in dichloromethane, slowly dropwise adding N-bromosuccinimide dissolved in dichloromethane, stirring under the protection of nitrogen, after the reaction is finished, adding acetone for quenching, performing vacuum drying under reduced pressure, and washing with dichloromethane and petroleum ether as mixed eluent until the mixture is purified to obtain a compound C;

(4) the compound C and Zn (OAc) -2H₂Adding O into dichloromethane and methanol solution, reacting under the protection of nitrogen, after the reaction is finished, adding distilled water for washing, extracting by using dichloromethane, combining organic layers, adding anhydrous magnesium sulfate for drying, performing vacuum drying under reduced pressure, and washing by using dichloromethane and petroleum ether as mixed eluent until the mixture is purified to obtain a compound D;

(5) dissolving 2, 5-dibromo-3-hexylthiophene in tetrahydrofuran, adding anhydrous triethylamine, filling nitrogen into a reaction container for deoxidation, and then adding cuprous iodide and bistriphenyleneReacting phosphine palladium dichloride and trimethylsilyl acetylene, filling nitrogen into the mixture for sealing and storing, magnetically stirring the mixture at room temperature for reaction, removing the solvent by rotary evaporation, washing the product with saturated NaCl solution, and washing the product with CHCl₂Extracting, finally combining organic phases, drying by using anhydrous sodium sulfate, carrying out rotary evaporation to obtain a mixture E, eluting the mixture E by using petroleum ether and ethyl acetate until the mixture is purified to obtain 2, 5-trimethylsilyl diyne-3-hexylthiophene, adding tetrahydrofuran and tetrabutylammonium fluoride into the 2, 5-trimethylsilyl diyne-3-hexylthiophene, stirring at room temperature, adding distilled water, extracting by using dichloromethane, washing by using a saturated NaCl solution, combining the organic phases, adding the anhydrous sodium sulfate, fully oscillating, standing, carrying out suction filtration and spin drying to obtain a mixture F, eluting the mixture F by using dichloromethane and petroleum ether until the mixture is purified to obtain the 2, 5-diyne-3-hexylthiophene;

(6) adding the compound 4 and 2, 5-diyne-3-hexylthiophene into a reaction vessel, adding anhydrous tetrahydrofuran and anhydrous triethylamine, and adding Pd (PPh)₃)₂Cl₂And CuI, introducing nitrogen to exhaust air in the flask, carrying out reflux reaction, after the reaction is finished, adding water, extracting by using dichloromethane, adding anhydrous sodium sulfate for drying, carrying out reduced pressure rotary evaporation to remove the solvent, and carrying out column chromatography by using dichloromethane and petroleum ether to obtain the porphyrin polymer.

3. The method for synthesizing 3-hexylthiophene-containing porphyrin polymer according to claim 2, wherein in step (1), syringaldehyde, 1-bromo-n-hexane and anhydrous K₂CO₃The reaction temperature of NaI in dimethylformamide is 85-90 ℃, the reaction time is 12h, the volume ratio of ethyl acetate and petroleum ether used in extraction after washing with distilled water is 1:1, the drying time is 30min after adding anhydrous magnesium sulfate, and the volume ratio of dichloromethane and petroleum ether used after drying with anhydrous magnesium sulfate is 3: 2.

4. The method for synthesizing 3-hexylthiophene-containing porphyrin polymer according to claim 2, wherein in step (2), the stirring temperature of dipyrromethane, compound A, dichloromethane and trifluoroacetic acid under the protection of nitrogen is 23 ℃, the stirring time is 4h, dichlorodicyanobenzoquinone is added, the stirring time is continued for 1h, and the volume ratio of dichloromethane to petroleum ether used in elution is 2: 1.

5. The method for synthesizing 3-hexylthiophene-containing porphyrin polymer according to claim 2, wherein in step (3), the compound B is dissolved in dichloromethane, N-bromosuccinimide dissolved in dichloromethane is slowly added dropwise thereto, and then the mixture is stirred at 0 ℃ under the protection of nitrogen for 6 hours, wherein the volume ratio of dichloromethane to petroleum ether used for elution is 3: 2.

6. The method for synthesizing 3-hexylthiophene-containing porphyrin polymer according to claim 2, wherein in the step (4), the compound C is added into a dichloromethane and methanol solution, the reaction is carried out for 3h at 23 ℃ under the protection of nitrogen, anhydrous magnesium sulfate is added, the drying time is 30min, and the volume ratio of dichloromethane to petroleum ether used in elution is 5: 2.

7. The method for synthesizing 3-hexylthiophene-containing porphyrin polymer according to claim 2, wherein in step (5), the reaction vessel is filled with nitrogen gas for deoxygenation for 15min, the reaction vessel is filled with nitrogen gas for 15min and then sealed for storage, the reaction vessel is magnetically stirred for 72h, anhydrous sodium sulfate is added for drying for 30min, mixture E is eluted with petroleum ether and ethyl acetate in a volume ratio of 30:1 in a VZ-purifier preparative liquid chromatograph, tetrahydrofuran and tetrabutylammonium fluoride are added to 2, 5-trimethylsilyldiyne-3-hexylthiophene, the reaction vessel is stirred at room temperature for 30min, the reaction vessel is sufficiently shaken and then allowed to stand for 30min, and mixture F is eluted with dichloromethane and petroleum ether in a volume ratio of 20:1 in a VZ-purifier preparative liquid chromatograph.

8. The method for synthesizing 3-hexylthiophene-containing porphyrin polymer according to claim 2, wherein in the step (6), the reaction temperature of the reflux reaction is 70 ℃, the reaction time is 24h, anhydrous sodium sulfate is added, the drying time is 30min, and the volume ratio of dichloromethane to petroleum ether used in the column chromatography is 3: 2.

9. Use of a porphyrin polymer comprising 3-hexylthiophene according to claim 1 in a solar cell for collecting, capturing and transmitting solar light energy.

Technical Field

The invention relates to the field of solar cell materials, in particular to a porphyrin polymer containing 3-hexylthiophene and a synthetic method thereof.

Background

Solar cells are one of the most rapidly and energetically studied hotspots in recent years. The polymer solar cell has the potential of low cost and is easy to process, and can realize the preparation of a flexible device on a flexible substrate, so that the polymer solar cell is widely concerned by scientific research and the industry. Porphyrins as one of organic photosensitive elements play an important role in the construction of organic solar cells, are responsible for collecting, capturing and transmitting solar energy in nature, and have chemical stability and structural adjustability.

The existing porphyrin polymer as the material responsible for collecting, capturing and transmitting the solar energy in the organic solar cell mainly has the following defects:

1. the raw materials for synthesizing the prior porphyrin polymer are high in price, complex in synthesis process, harsh in synthesis conditions and high in synthesis cost.

2. In the process of synthesizing the existing porphyrin polymer, the collection rate of intermediate products is low, and the number of byproducts is large and the ratio is large.

3. The existing porphyrin polymer has low solubility in organic solvents such as tetrahydrofuran, chloroform and the like, and the photoelectric conversion efficiency is inconvenient to test.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a porphyrin polymer containing 3-hexylthiophene and a synthetic method thereof, and solve the problems of high raw material price, complex synthetic process and harsh synthetic conditions in the conventional synthesis of the porphyrin polymer. The method has the problems of higher synthesis cost, lower intermediate product collection rate, more byproducts, larger proportion and lower solubility in organic solvents such as tetrahydrofuran, chloroform and the like, which causes inconvenient photoelectric conversion efficiency test.

The technical scheme adopted by the invention for solving the technical problems is as follows: a porphyrin polymer containing 3-hexylthiophene has the following structure:

the invention also provides a method for synthesizing the porphyrin polymer containing 3-hexylthiophene, which comprises the following steps:

(1) mixing syringaldehyde with 1-bromo-n-hexane and anhydrous K₂CO₃Reacting NaI in dimethylformamide, electromagnetically stirring and heating under the protection of nitrogen, washing with distilled water after the reaction is finished, extracting with ethyl acetate and petroleum ether, combining organic layers, adding anhydrous magnesium sulfate for drying, and eluting with dichloromethane and petroleum etherIt is washed to purification to obtain a compound A;

(2) stirring dipyrromethane, a compound A, dichloromethane and trifluoroacetic acid under the protection of nitrogen, adding dichlorodicyanoquinone, continuously stirring, after the reaction is finished, adding triethylamine for alkalization, performing vacuum drying under reduced pressure, and washing the mixture by using dichloromethane and petroleum ether as a mixed eluent until the mixture is purified to obtain a compound B;

(3) dissolving the compound B in dichloromethane, slowly dropwise adding N-bromosuccinimide dissolved in dichloromethane, stirring under the protection of nitrogen, after the reaction is finished, adding acetone for quenching, performing vacuum drying under reduced pressure, and washing with dichloromethane and petroleum ether as mixed eluent until the mixture is purified to obtain a compound C;

(4) the compound C and Zn (OAc) -2H₂Adding O into dichloromethane and methanol solution, reacting under the protection of nitrogen, after the reaction is finished, adding distilled water for washing, extracting by using dichloromethane, combining organic layers, adding anhydrous magnesium sulfate for drying, performing vacuum drying under reduced pressure, and washing by using dichloromethane and petroleum ether as mixed eluent until the mixture is purified to obtain a compound D;

(5) dissolving 2, 5-dibromo-3-hexylthiophene in tetrahydrofuran, adding anhydrous triethylamine, filling nitrogen into a reaction container for deoxidation, adding cuprous iodide, bis (triphenylphosphine) palladium dichloride and trimethylsilyl acetylene, filling nitrogen into the reaction container for sealing and storing after reaction, performing magnetic stirring reaction at room temperature, removing the solvent by rotary evaporation, washing with saturated NaCl solution, washing with CHCl₂Extracting, finally combining organic phases, drying by using anhydrous sodium sulfate, carrying out rotary evaporation to obtain a mixture E, eluting the mixture E by using petroleum ether and ethyl acetate until the mixture is purified to obtain 2, 5-trimethylsilyl diyne-3-hexylthiophene, adding tetrahydrofuran and tetrabutylammonium fluoride into the 2, 5-trimethylsilyl diyne-3-hexylthiophene, stirring at room temperature, adding distilled water, extracting by using dichloromethane, washing by using a saturated NaCl solution, combining the organic phases, adding the anhydrous sodium sulfate, fully oscillating, standing, carrying out suction filtration and spin drying to obtain a mixture F, eluting the mixture F by using dichloromethane and petroleum ether until the mixture is purified to obtain the 2, 5-diyne-3-hexylthiophene;

(6) the compoundAdding 4 and 2, 5-diyne-3-hexylthiophene into a reaction vessel, adding anhydrous tetrahydrofuran and anhydrous triethylamine, and adding Pd (PPh)₃)₂Cl₂And CuI, introducing nitrogen to exhaust air in the flask, carrying out reflux reaction, after the reaction is finished, adding water, extracting by using dichloromethane, adding anhydrous sodium sulfate for drying, carrying out reduced pressure rotary evaporation to remove the solvent, and carrying out column chromatography by using dichloromethane and petroleum ether to obtain the porphyrin polymer.

Further, in the step (1), syringaldehyde, 1-bromo-n-hexane and anhydrous K₂CO₃The reaction temperature of NaI in dimethylformamide is 85-90 ℃, the reaction time is 12h, the volume ratio of ethyl acetate and petroleum ether used in extraction after washing with distilled water is 1:1, the drying time is 30min after adding anhydrous magnesium sulfate, and the volume ratio of dichloromethane and petroleum ether used after drying with anhydrous magnesium sulfate is 3: 2.

Further, in the step (2), the stirring temperature of dipyrromethane, the compound A, dichloromethane and trifluoroacetic acid under the protection of nitrogen is 23 ℃, the stirring time is 4 hours, dichlorodicyanobenzoquinone is added, the stirring time is continued for 1 hour, and the volume ratio of dichloromethane to petroleum ether used in elution is 2: 1.

Further, in the step (3), the compound B is dissolved in dichloromethane, N-bromosuccinimide dissolved in dichloromethane is slowly dripped, and then the mixture is stirred for 6 hours at 0 ℃ under the protection of nitrogen, wherein the volume ratio of dichloromethane and petroleum ether used in elution is 3: 2.

Further, in the step (4), the compound C is added into dichloromethane and methanol solution, the reaction is carried out for 3h at 23 ℃ under the protection of nitrogen, anhydrous magnesium sulfate is added, the drying time is 30min, and the volume ratio of dichloromethane and petroleum ether used in elution is 5: 2.

Further, in the step (5), the reaction vessel is filled with nitrogen for deoxygenation for 15min, the reaction vessel is filled with nitrogen for 15min and then sealed for storage, the magnetic stirring time is 72h, anhydrous sodium sulfate is added for drying for 30min, the mixture E is eluted by petroleum ether and ethyl acetate in a volume ratio of 30:1 in a VZ-purifier preparation liquid chromatograph, tetrahydrofuran and tetrabutylammonium fluoride are added in 2, 5-trimethylsilyl diyne-3-hexylthiophene, the stirring time at room temperature is 30min, the mixture F is fully shaken and then stands for 30min, and the mixture F is eluted by dichloromethane and petroleum ether in a volume ratio of 20:1 in a VZ-purifier preparation liquid chromatograph.

Further, in the step (6), the reaction temperature of the reflux reaction is 70 ℃, the reaction time is 24 hours, anhydrous sodium sulfate is added, the drying time is 30min, and the volume ratio of dichloromethane to petroleum ether used in column chromatography is 3: 2.

The invention also provides an application of the porphyrin polymer, and the porphyrin polymer is applied to a solar cell for collecting, capturing and transmitting solar energy.

The invention has the following beneficial effects:

the raw materials for synthesizing the porphyrin polymer have low price, the synthesis process is simple, the synthesis conditions are simple and easy to implement, and the synthesis cost is lower.

In the process of synthesizing the existing porphyrin polymer, the collection rate of intermediate products is high, and the by-products are fewer and occupy a small amount.

The existing porphyrin polymer has high solubility in organic solvents such as tetrahydrofuran, chloroform and the like, and the photoelectric conversion efficiency is tested conveniently.

Detailed Description

Example 1:

porphyrin polymer was synthesized according to the following procedure:

(1) syringaldehyde (2.12g,0.0116mol), 1-bromo-n-hexane (5.76g,0.035mol), anhydrous K₂CO₃(2.04g,0.015mol), NaI (0.05g,0.006mol) in 20ml DMF, charging nitrogen gas, stirring electromagnetically, heating to 85 ℃ -90 ℃, reacting for 12 hours. After the reaction was complete, the mixture was washed with 3X 20ml of distilled water and 3X 30ml of ethyl acetate/petroleum ether (V)₁:V₂1:1), the organic layers were combined, and dried for 30min with anhydrous magnesium sulfate. Then with dichloromethane/petroleum ether (V)₁：V₂3: 2) it was washed to purification for mixed eluents to give compound a2.32g, 89% yield.

Compound a has the following structural formula:

(2) a solution of dipyrromethane (1.05g,7.19mmol) and Compound A (1.91g,7.19mmol) in 0.5L of dichloromethane was added trifluoroacetic acid (0.48L,7.44mol), stirred at 23 ℃ under nitrogen for 4h, DDQ (2.88g, 12.24mmol) was added and the mixture stirred for a further 1 h. After the reaction was complete, triethylamine (1.4ml) was added to basify, and spin-dried under reduced pressure. Then with dichloromethane/petroleum ether (V)₁：V₂2: 1) it was washed to purify for mixed eluents to obtain compound b0.75g, yield 28%.

Compound B is of the formula:

(3) compound B (0.5g,0.640mmol) was dissolved in 300ml dichloromethane and NBS (0.22,12.8mmol) dissolved in 120ml dichloromethane was slowly added dropwise and stirred at 0 ℃ under nitrogen for 6 h. After the reaction was complete, 10ml of acetone was added for quenching and vacuum spin-dried under reduced pressure. Then with dichloromethane/petroleum ether (V)₁：V₂3: 2) it was washed to purification for mixed eluents to give compound c0.38g, 56% yield.

Compound C has the following structural formula:

(4) compound C (0.30g, 0.319mmol) and Zn (OAc). 2H₂O (0.700g, 3.19mmol) was added to a solution of 65ml of dichloromethane and 32ml of methanol, reacted at 23 ℃ for 3 hours under nitrogen protection, after completion of the reaction, washed with 2X 30ml of distilled water, extracted with 2X 30ml of dichloromethane, the organic layers were combined and dried for 30min with anhydrous magnesium sulfate. And (5) decompressing, vacuum and spin-drying. With methylene chloride/petroleum ether (V)₁：V₂5: 2) washing with mixed eluent until purification to obtainCompound D0.19g, yield 37%.

Compound D is of the formula:

(5) 0.3260g (1mmol) of 2, 5-dibromo-3-hexylthiophene was weighed and dissolved in 20mL of THF in a 150mL two-way round-bottomed flask, and 10mL of anhydrous triethylamine was added. The reaction vessel was purged with nitrogen for 15min to effect deoxygenation. Further, 10mg (0.05mmol) of cuprous iodide, 35mg (0.05mmol) of bistriphenylphosphine palladium dichloride and 0.4g (5mmol) of trimethylsilylacetylene were added. Charging nitrogen gas into the reaction for 15min, sealing, magnetically stirring at room temperature for 72 hr, removing solvent by rotary evaporation, washing with saturated NaCl solution for three times (8.0 mL each time), and adding CHCl₂Extraction was carried out three times, 5.0mL each time, the organic phases were finally combined, dried over an appropriate amount of anhydrous sodium sulfate for 30 minutes and then rotary evaporated to give 0.2987g of crude product E as a dark yellow oil, which was purified by elution in a VZ-purifier preparative liquid chromatograph using petroleum ether and ethyl acetate (V: V ═ 30:1) eluent to give 0.2282g of 2, 5-trimethylsilyldiyne-3-hexylthiophene as a pale yellow viscous liquid with a yield of 70.0%. Then 0.200g (0.6097mmol) of the above product was weighed into a 50ml round bottom flask, 50ml of THF was added, and tetrabutylammonium fluoride (0.5g, 75% in water) was added. After stirring at room temperature for 30min, 50mL of distilled water was added to the reaction flask, followed by extraction with dichloromethane three times in an amount of 10.0mL each time, washing with saturated NaCl solution three times in an amount of 10.0mL each time, combining the organic phases, adding an appropriate amount of anhydrous sodium sulfate, after sufficient shaking, standing for 30min, suction filtration, spin-drying to obtain 0.1647g of a viscous crude product mixture F. Purification by elution with developing solvent methylene chloride and petroleum ether (V: V ═ 1:20) in VZ-purifier preparative liquid chromatograph gave 0.1224g of 2, 5-diyne-3-hexylthiophene as a yellow viscous liquid with a yield of 61.2%.

(6) Adding compound D (100mg0.0996mmol) and 2, 5-diyne-3-hexylthiophene (37.5mg0.0996mmol) into a round-bottom flask, adding 10ml of anhydrous tetrahydrofuran and 5ml of anhydrous triethylamine, adding Pd (PPh)₃)₂Cl₂(13.75mg0.02mmol) and CuI (5.87mg0.03mmol), introducing nitrogen to exhaust the air in the flask, refluxing the reaction system at 70 ℃ for 24h, adding 30ml of water after the reaction is finished, extracting with dichloromethane for several times, adding anhydrous sodium sulfate, drying for 30min, decompressing, evaporating to remove the solvent, adding dichloromethane: petroleum ether is 3:2 (volume ratio) manual column chromatography to obtain 50mg of porphyrin polymer product.

The raw materials for synthesizing the porphyrin polymer have low price, the synthesis process is simple, the synthesis conditions are simple and easy to implement, and the synthesis cost is lower.

In the process of synthesizing the existing porphyrin polymer, the collection rate of intermediate products is high, and the by-products are fewer and occupy a small amount.

The existing porphyrin polymer has high solubility in organic solvents such as tetrahydrofuran, chloroform and the like, and the photoelectric conversion efficiency is tested conveniently.

The porphyrin polymer has high crystallinity and forms good pi-pi action under a thin film, so that a device based on the porphyrin polymer has better field effect mobility. When the material is applied to a battery device, the device performance is preliminarily researched, and the photoelectric conversion efficiency of about 2.08% is obtained. Although the photoelectric efficiency of the porphyrin-containing oligomer is low, the porphyrin-containing oligomer has stronger and wider spectral absorption in the long wavelength direction, and a new design idea is provided for designing high-efficiency solar cell materials.

The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in any way, and those skilled in the art can make various changes and modifications to the equivalent embodiments without departing from the scope of the present invention, and all such changes, modifications, equivalents and improvements that can be made to the above embodiments without departing from the technical spirit of the present invention are within the spirit and principle of the present invention.