阅读说明：本技术 一种利用微波技术高效制备聚噻吩衍生物的方法 (Method for efficiently preparing polythiophene derivative by using microwave technology ) 是由 陆燕 韩洪停 于 2021-01-07 设计创作，主要内容包括：本发明提供了一种利用微波技术高效制备聚噻吩衍生物的方法,涉及共轭聚合物合成技术领域,所述制备方法包括以下步骤,在微波条件下,单体M、钯催化剂、氧化剂、碱和溶剂在60～150℃下反应5min～24h,提纯,得到聚噻吩衍生物,本制备方法以噻吩衍生物为单体,在微波条件下,利用过渡金属催化的直接C-H/C-H偶联缩聚制备噻吩衍生物。本发明与Suzuki、Stille偶联聚合法相比,具有反应时间短、合成步骤少、所得聚合物无需封端、成本低、效率高的优势。(The invention provides a method for efficiently preparing a polythiophene derivative by using a microwave technology, which relates to the technical field of conjugated polymer synthesis and comprises the following steps of reacting a monomer M, a palladium catalyst, an oxidant, alkali and a solvent for 5 min-24H at 60-150 ℃ under the microwave condition, and purifying to obtain the polythiophene derivative. Compared with Suzuki and Stille coupled polymerization methods, the method has the advantages of short reaction time, few synthesis steps, no end capping of the obtained polymer, low cost and high efficiency.)

1. A method for efficiently preparing polythiophene derivatives by using a microwave technology is characterized in that a monomer M, a catalyst, an oxidant, alkali and a solvent react for 5 min-24 h at 60-150 ℃ under the microwave condition, and the polythiophene derivatives are obtained through purification;

the structural formula of the monomer M is as follows:

wherein R is₁And R₃Is C₁-C₃₀Alkyl-substituted carboxylate groups, alkyl-substituted sulfone groups, alkyl-substituted sulfoxide groups; r₂Is hydrogen, an aromatic hydrocarbon or a heteroaromatic hydrocarbon; r₄And R₅Is C₁-C₃₀An alkyl substituent.

2. The method for producing a polythiophene derivative according to claim 1, wherein C is₁-C₃₀The substituents in the alkyl substituents are selected from the following groups: cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, halo, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, thiocyanato, nitro, trihalomethanesulfonyl or silyl;

the R is₂Is an arene or heteroarene selected from the group consisting of:

wherein R is₆-R₁₄Is hydrogen, alkyl or alkyl substituent; alkyl or alkyl substituents selected to be C₁-C₃₀Alkyl or C₁-C₃₀An alkyl substituent; c₁-C₃₀The substituents in the alkyl substituents are selected from the following groups: cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, halo, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, thiocyanato, nitro, trihalomethanesulfonyl or silyl; x is C, Si or N.

3. The process for producing a polythiophene derivative according to claim 1, wherein said catalyst is pd (oac)₂、Pd(dppf)Cl₂、PdCl₂、Pd₂(dba)₃、Pd(TFA)₂Herrmann's catalyst, PdCl₂(PPh₃)₂、Pd(OH)₂、Pd(PPh₃)₄Or palladium on carbon;

the oxidant is Ag₂CO₃、AgF、AgOAc、Ag₂O、Cu(OAc)₂、Cu(OTf)₂、CuCl₂Or AgNO₃One of (1);

the alkali is Na₂CO₃、K₂CO₃、Cs₂CO₃、NaHCO₃One of NaOAc, KOAc, CsOAc or KF;

the solvent is one or a mixture of more of toluene, 1, 4-dioxane, o-xylene, tetrahydrofuran, N-dimethylacetamide, N-diethylformamide, N-diethylacetamide, N-dimethylformamide, toluene or dimethyl sulfoxide.

4. The method for preparing a polythiophene derivative according to claim 1, wherein the reaction is carried out by stirring at 60 to 150 ℃;

microwave conditions are as follows: the mode is one of Standard, Dynamic, Power Cycling, Fixed Power or SPS; the power is 30-150W.

5. The method for producing a polythiophene derivative according to claim 1, wherein the ratio of the monomer M, the catalyst, the oxidizing agent and the base is 1: (0.05-0.2): (1-4): (1-4).

6. The method for producing a polythiophene derivative according to claim 1, wherein a concentration of said monomer M in said solvent is 0.01 to 1 mol/L.

7. The process for producing a polythiophene derivative according to claim 1, wherein said purification is performed by soxhlet purification, and further, by the steps of: after the reaction is stopped, dropwise adding the reaction solution into methanol for precipitation, and performing suction filtration to obtain a crude product; sequentially performing Soxhlet extraction on the crude product by using methanol and n-hexane, performing Soxhlet extraction on the residue by using chloroform, collecting chloroform extract, concentrating, dropwise adding the chloroform extract into the methanol for settling, performing suction filtration, and drying to obtain the polythiophene derivative.

8. Polythiophene derivative obtained by the production method according to any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of conjugated polymer synthesis, in particular to a method for efficiently preparing polythiophene derivatives by utilizing a microwave technology.

Background

The polythiophene derivative has good solubility, high conductivity and excellent environmental stability, and thus is widely applied to photoelectric devices such as organic solar cells, organic light emitting diodes, organic field effect transistors and the like. Currently polythiophene derivatives are mainly prepared by Suzuki and Stille coupling reactions. Although these polymerization methods can synthesize polythiophenes having reliable chemical structures, the following problems still remain: these polymerization processes require the pre-functionalization of the monomers, i.e. the preparation of the corresponding halide and metallic tin compound or borate derivative monomers in advance, followed by polycondensation to give the polymer. Therefore, these methods have problems of many reaction steps, high cost, severe synthesis conditions, poor stability of the prepared metal tin compound, difficult preservation, and the possibility of generating toxic by-products. In addition, when the polymer prepared by the method is used for photoelectric devices, the polymer is subjected to an additional end capping treatment to obtain good device performance.

The direct C-H/C-H coupled polymerization catalyzed by transition metal is a new method for preparing conjugated polymer developed in recent years, and the method does not need any functional pre-modification on the monomer, so the atom economy is high, the raw materials are easy to obtain, and the cost is low. However, the molecular weight of the conjugated polymer prepared by the method is usually low, which severely restricts the practical application of the polymer materials in photoelectric devices. In addition, the direct C-H/C-H coupling polymerization reaction time is long, and the stirring reaction at high temperature is usually required for 24 to 72 hours, so that the energy loss is large.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a novel method for preparing thiophene derivatives by utilizing a microwave technology with high efficiency, low cost and simplicity.

It is another object of the present invention to provide a polythiophene derivative obtained by the above preparation method.

The technical scheme adopted for realizing the purpose of the invention is as follows:

a novel method for efficiently preparing thiophene derivatives by utilizing a microwave technology comprises the following steps: under the microwave condition, reacting the monomer M, a catalyst, an oxidant, alkali and a solvent at 60-150 ℃ for 5 min-24 h, and purifying to obtain the polythiophene derivative:

the structural general formula of the monomer M is as follows:

wherein R is₁And R₃Is C₁-C₃₀Alkyl-substituted carboxylic acid ester groups, C₁-C₃₀Alkyl-substituted sulfone group, C₁-C₃₀An alkyl-substituted sulfoxide group; r₂Is hydrogen, an aromatic hydrocarbon or a heteroaromatic hydrocarbon; r₄And R₅Is C₁-C₃₀An alkyl substituent.

In the above technical solution, said C₁-C₃₀The substituents in the alkyl substituents may be selected from the following groups: cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, halo, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, thiocyanato, nitro, trihalomethanesulfonyl or silyl.

The R is₂Is an arene or heteroarene selected from the group consisting of:

wherein R is₆-R₁₄Is hydrogen, alkyl or alkyl substituent; preferably C₁-C₃₀Alkyl or C₁-C₃₀An alkyl substituent; c₁-C₃₀The substituents in the alkyl substituents may be selected from the following groups: cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, halo, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, thiocyanato, nitro, trihalomethanesulfonyl or silyl. Wherein X is C, Si or N.

In the technical scheme, the catalyst is Pd (OAc)₂、Pd(dppf)Cl₂、PdCl₂、Pd₂(dba)₃、Pd(TFA)₂Herrmann's catalyst, PdCl₂(PPh₃)₂、Pd(OH)₂、Pd(PPh₃)₄Or palladium on carbon;

in the above technical scheme, the oxidant is Ag₂CO₃、AgF、AgOAc、Ag₂O、Cu(OAc)₂、Cu(OTf)₂、CuCl₂Or AgNO₃One of (1);

in the technical scheme, the alkali is Na₂CO₃、K₂CO₃、Cs₂CO₃、NaHCO₃One of NaOAc, KOAc, CsOAc or KF;

in the technical scheme, the solvent is one or a mixture of more of toluene, 1, 4-dioxane, o-xylene, tetrahydrofuran, N-dimethylacetamide, N-diethylformamide, N-diethylacetamide, N-dimethylformamide, toluene or dimethyl sulfoxide;

in the above technical scheme, the preferred catalyst is Pd (OAc)₂Or Pd (PPh)₃)₄Or Herrmann's catalyst; preferably, the oxidant is Ag₂CO₃Or Cu (OAc)₂(ii) a Preferably the base is K₂CO₃、Cs₂CO₃Or KOAc; preferably, the solvent is N, N-dimethylacetamide or tetrahydrofuran.

In the technical scheme, the reaction temperature is 60-150 ℃.

In the technical scheme, the microwave mode is one of Standard, Dynamic, Power Cycling, Fixed Power and SPS; the power is 30-150W.

In the above technical scheme, the ratio of the monomer M, the catalyst, the oxidant, and the base is 1: (0.05-0.2): (1-4): (1-4).

In the technical scheme, the concentration of the monomer M in the solvent is 0.01-1 mol/L, preferably 0.1-0.5 mol/L.

In the above technical scheme, the purification is performed by soxhlet purification, and further, the purification is performed by the following steps: after the reaction is stopped, dropwise adding the reaction solution into methanol for precipitation, and performing suction filtration to obtain a crude product; sequentially performing Soxhlet extraction on the crude product by using methanol and n-hexane, performing Soxhlet extraction on the residue by using chloroform, collecting chloroform extract, concentrating, dropwise adding the chloroform extract into the methanol for settling, performing suction filtration, and drying to obtain the polythiophene derivative.

Compared with the prior art, the invention has the beneficial effects that:

the preparation method takes the thiophene derivative as a monomer, and prepares the thiophene derivative by direct C-H/C-H coupling polycondensation catalyzed by transition metal under the microwave condition. Compared with Suzuki and Stille coupled polymerization methods, the method has the advantages of short reaction time, few synthesis steps, no end capping of the obtained polymer, low cost and high efficiency.

1) The raw materials required by the invention are simple and easy to obtain, and can be directly polymerized without pretreatment, thereby avoiding the use of reagents sensitive to air (such as n-butyllithium and the like) and other toxic metal reagents and generating toxic byproducts;

2) the polymerization method has high efficiency, short reaction time and high product molecular weight;

3) the polymerization method of the invention can be compatible with various functional groups, such as ester groups, sulfone groups, sulfoxide groups and the like, and is suitable for preparing various polythiophene derivatives.

Detailed Description

The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The general course of the reaction is as follows:

adding a monomer M, a transition metal catalyst, an oxidant, alkali and a solvent into a reaction vessel, and reacting for 5 min-24 h under the microwave condition at the temperature of 60-150 ℃ in a reaction system. Stopping the reaction, cooling to room temperature, dropwise adding the reaction solution into methanol for settling, and performing suction filtration to obtain a crude polymer product.

General procedure for polymer purification: the crude polymer product is purified by soxhlet extraction. Respectively performing Soxhlet extraction on the crude product for 24 hours by using methanol and normal hexane in sequence, performing Soxhlet extraction by using chloroform until the chloroform is colorless in a Soxhlet extraction tube, collecting a chloroform extracting solution, removing the solvent by rotary evaporation, and drying in vacuum to obtain the pure polymer product.

The purchase sources of the drugs involved in the following examples are as follows:

the following examples relate to the following types of instruments:

laboratory apparatus	Model number
		400M Nuclear magnetic resonance spectrometer (NMR)	BrukerAV400MHz
Gel Permeation Chromatography (GPC)	Waters1525
		Ring focusing single-mode microwave synthesizer	CEMDiscoverSP
Vacuum drying oven	Medical instruments Limited in the Normal market

Example 1:

the first step is as follows: synthesis of Compound 1

2-butyl-1-octanol (40mmol) and 5-bromothiophene-3-carboxylic acid (20mmol) were dissolved in 100mL of CHCl₃Then, 4-dimethylaminopyridine (7mmol) and dicyclohexylcarbodiimide (24mmol) were added and reacted at room temperature for 40 hours. The reaction was stopped, the reaction solution was extracted with chloroform, the chloroform phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to give a crude product. Column chromatography was performed with petroleum ether as eluent to give colorless transparent liquid (6.98g, yield 93.1%).¹H NMR(400MHz,CDCl₃)δ7.97(d,J＝0.8Hz,1H),7.45(d,J＝0.8Hz,1H),4.16(d,J＝5.7Hz,2H),1.72(dd,J＝11.4,5.7Hz,1H),1.36–1.25(m,16H),0.88(t,J＝7.3Hz,6H).

The second step is that: synthesis of Compound 2

Compound 1(5.33mmol) and pinacol diboron (2.67mmol) were dissolved in 30mL of dimethyl sulfoxide, followed by addition of potassium acetate (15.9mmol) and [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride dichloromethane complex (0.16mmol) was reacted at 80 ℃ for 8 h. Stopping the reaction, extracting the reaction liquid by ethyl acetate, drying the ethyl acetate phase by anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain a crude product. Column chromatography was performed with petroleum ether/ethyl acetate 4:1(v/v) as eluent to give a clear white solid (0.9g, 58%).¹H NMR(400MHz,CDCl₃)δ7.99(d,J＝1.3Hz,2H),7.57(d,J＝1.3Hz,1H),4.19(d,J＝5.7Hz,4H),2.03-1.62(m,2H),1.33(ddd,J＝16.5,13.8,7.6Hz,34H),0.89(dt,J＝12.3,6.9Hz,13H).

The third step: synthesis of Polymer P1

Mixing compound 2(0.1mmol) and Ag₂CO₃(0.2mmol), KOAc (0.2mmol) and Pd (OAc)₂(0.005mmol) was dissolved in 1mL of N, N-dimethylacetamide (DMAc), and the resulting solution was placed in a microwave synthesizer for reaction. The microwave synthesizer parameters were set as follows: SPS mode, power 100W, temperature 110 deg.C, time 13 min. After the reaction of the reaction mixture liquid in the set mode is finishedThe reaction mixture was cooled to room temperature and poured into 60mL of methanol to precipitate to obtain a crude product. The crude product was sequentially extracted with methanol, n-hexane, and chloroform, the chloroform extract was collected, rotary evaporated, and dried in a vacuum oven at 40 ℃ for 12 hours to give polymer P1(23.3mg, yield 39.4%).¹H NMR(400MHz,CDCl₃)δ8.02(s,1H),7.63(s,2H),4.05(s,4H),1.67(d,J＝68.0Hz,2H),1.20(s,32H),0.85(s,13H)；M_n＝56100，PDI＝1.63(GPC，THF)。

Example 2

The synthesis of compound 1 was the same as that described in example 1 above.

The second step is that: synthesis of Compound 3

Compound 1(7.99mmol) and 5, 5-bistrimethylsilyl-2, 2' -bithiophene (3.81mmol) were dissolved in 54mL of N, N-dimethylacetamide, followed by the addition of tetrakis (triphenylphosphine) palladium (0.3806mmol) and reacted at 80 ℃ for 8 h. Stopping the reaction, extracting the reaction liquid by ethyl acetate, drying the ethyl acetate phase by anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain a crude product. Column chromatography purification was performed with petroleum ether/ethyl acetate 50:1(v/v) eluent to afford a bright yellow solid powder (2.42g, 84.2%) after spin drying of the solvent.¹H NMR(400MHz,CDCl₃)δ7.96(s,2H),7.55(s,2H),7.11(q,J＝3.8Hz,4H),4.20(d,J＝5.7Hz,4H),1.76(dd,J＝11.3,5.6Hz,2H),1.41-1.24(m,33H),0.95–0.85(m,12H).

The third step: synthesis of Polymer P2

Mixing compound 3(0.1mmol) and Ag₂CO₃(0.2mmol), KOAc (0.21mmol) and Herrmann's catalyst (0.005mmol) were dissolved in 1mL of N, N-dimethylacetamide (DMAc) and placed in a microwave synthesizer for reaction. The microwave synthesizer parameters were set as follows: SPS mode, power 120W, temperature 100 deg.C, 20 min. After the reaction of the mixed solution in the set mode is finished, the mixed solution is cooled to room temperature, and the reaction mixture is poured into 60mL of methanol for sedimentation to obtain a crude product. Extracting the crude product with methanol, n-hexane and chloroform in sequence, and collectingThe chloroform extract was rotary evaporated and dried in a vacuum oven at 40 ℃ for 12 hours to give polymer P2(59.6mg, 78.9% yield).¹H NMR(400MHz,CDCl₃)δ7.97(d,J＝1.2Hz,1H),7.64–7.57(m,2H),7.13(d,J＝4.1Hz,4H),4.20(d,J＝5.7Hz,1H),4.02(dd,J＝27.0,5.3Hz,4H),1.84–1.64(m,1H),1.17(d,J＝13.1Hz,32H),0.87(dt,J＝11.6,4.7Hz,12H).M_n＝23260，PDI＝3.44(GPC，THF)。

Example 3

Mixing compound 4(0.1mmol) and Ag₂CO₃(0.3mmol), KOAc (0.2mmol) and Pd (dppf) Cl₂(0.005mmol) was dissolved in 1mL of N, N-Dimethylformamide (DMF) and placed in a microwave synthesizer for reaction. The microwave synthesizer parameters were set as follows: SPS mode, power 50W, temperature 90 deg.C, time 1 h. And after the reaction of the reaction mixed solution in the set mode is finished, cooling to room temperature, and pouring the reaction mixture into 60mL of methanol for sedimentation to obtain a crude product. The crude product was sequentially extracted with methanol, n-hexane, and chloroform, the chloroform extract was collected, rotary evaporated, and dried in a vacuum oven at 40 ℃ for 12 hours to give polymer P3(50.8mg, 55.3% yield).¹H NMR(400MHz,CDCl₃)δ7.78(s,2H),7.04(s,2H),3.15(m,4H),0.85-1.91(m,64H)；M_n＝15629，PDI＝1.39(GPC，THF)。

Example 4

Compound 5(0.1mmol), Cu (OAc)₂(0.21mmol)、K₂CO₃(0.3mmol) and palladium acetate (0.01mmol) were dissolved in 1mL of N-dimethylacetamide (DMAc) and then placed in a microwave synthesizer for reaction. The microwave synthesizer parameters were set as follows: standard mode, power 150W, temperature 150 ℃ and time 15 min. After the reaction mixture liquid is cooled to room temperature after the reaction in the set mode is finished, the reaction mixture is cooledPouring the mixture into 60mL of methanol for sedimentation to obtain a crude product. The crude product was sequentially extracted with methanol, n-hexane, and chloroform, the chloroform extract was collected, rotary evaporated, and dried in a vacuum oven at 40 ℃ for 12 hours to give polymer P4(19.2mg, yield 44.4%).¹H NMR(400MHz,CDCl₃)δ7.93-7.82(m,1H),3.51(s,2H),1.17(s,33H),0.79(s,6H)；M_n＝33195，PDI＝1.43(GPC，THF)。

Example 5

Compound 6(0.1mmol), Cu (OAc)₂(0.21mmol)、K₂CO₃(0.3mmol) and PdCl₂(PPh₃)₂(0.01mmol) was dissolved in 1.2mL of N, N-dimethylacetamide (DMAc) and placed in a microwave synthesizer for reaction. The microwave synthesizer parameters were set as follows: standard mode, power 60W, temperature 110 ℃ and time 5 min. And after the reaction of the reaction mixed solution in the set mode is finished, cooling to room temperature, and pouring the reaction mixture into 60mL of methanol for sedimentation to obtain a crude product. The crude product was extracted with methanol and n-hexane in sequence to give a black solid, which was dried in a vacuum oven at 40 ℃ for 12 hours to give polymer P4(19.0mg, 99% yield). P4 is insoluble in common organic solvents.

Example 6

Mixing compound 7(0.1mmol) with AgNO₃(0.4mmol), KOAc (0.2mmol) and palladium acetate (0.005mmol) were dissolved in 1mL of N, N-dimethylacetamide (DMAc), and the resulting solution was placed in a microwave synthesizer for reaction. The microwave synthesizer parameters were set as follows: standard mode, power 100W, temperature 110 ℃ and time 5 h. And after the reaction of the reaction mixed solution in the set mode is finished, cooling to room temperature, and pouring the reaction mixture into 60mL of methanol for sedimentation to obtain a crude product. Extracting the crude product with methanol, n-hexane, and chloroform in sequence, collecting chloroform extract, rotary evaporating, and treating at 40 deg.CAfter drying in a vacuum oven for 12h, polymer P6(13.5mg, 56.1% yield) was obtained.¹H NMR(400MHz,CDCl₃)δ7.86(s,1H),7.79(d,J＝5.0Hz,1H),7.54(s,1H),4.23(t,J＝5.4Hz,2H),4.04(t,J＝16.3Hz,1H),1.68(s,2H),1.17(d,J＝18.5Hz,10H),0.79(s,3H)；M_n＝21470，PDI＝2.83(GPC，THF)。

Example 7

Mixing compound 8(0.1mmol) with Ag₂CO₃(0.2mmol), KOAc (0.2mmol) and Pd₂(dba)₃(0.01mmol), dissolved in 1.5mL Tetrahydrofuran (THF), and placed in a microwave synthesizer for reaction. The microwave synthesizer parameters were set as follows: standard mode, power 100W, temperature 60 ℃ and time 10 h. And after the reaction of the reaction mixed solution in the set mode is finished, cooling to room temperature, and pouring the reaction mixture into 60mL of methanol for sedimentation to obtain a crude product. The crude product was sequentially extracted with methanol, n-hexane, and chloroform, the chloroform extract was collected, rotary evaporated, and dried in a vacuum oven at 40 ℃ for 12 hours to give polymer P7(16.8mg, yield 64.7%).¹H NMR(400MHz,CDCl₃)δ8.02(s,1H),7.63(s,2H),4.05(s,4H),1.67(d,J＝68.0Hz,2H),1.20(s,32H),0.85(s,13H)；M_n＝15030，PDI＝1.37(GPC，THF)。

Example 8

Compound 9(0.1mmol), AgOAc (0.2mmol), CsCO₃(0.2mmol) and palladium acetate (0.02mmol) were dissolved in 1mL of a mixed solution of dimethyl sulfoxide (DMSO)/xylene (v/v ═ 3:1), and then placed in a microwave synthesizer to react. The microwave synthesizer parameters were set as follows: standard mode, power 100W, temperature 90 ℃ and time 20 min. And after the reaction of the reaction mixed solution in the set mode is finished, cooling to room temperature, and pouring the reaction mixture into 60mL of methanol for sedimentation to obtain a crude product. Crude product isExtracting with methanol, n-hexane and chloroform, collecting chloroform extract, rotary evaporating, and drying in vacuum drying oven at 40 deg.C for 12 hr to obtain polymer P8(8.3mg, yield 34.2%).¹H NMR(400MHz,CDCl₃)δ7.90-7.47(m,1H),2.96(d,J＝59.5Hz,2H),1.73(s,2H),1.40(s,2H),1.20(s,8H),0.79(s,3H)；M_n＝14321，PDI＝3.76(GPC，THF)。