阅读说明：本技术 一种基于芳基二卤代物和芳基二锡烷的Stille交叉偶联室温聚合方法 (Stille cross-coupling room temperature polymerization method based on aryl dihalide and aryl distannane ) 是由 黄辉 史钦钦 马博维 于 2021-08-05 设计创作，主要内容包括：本发明提供了一种在室温条件下的基于芳基体系的普适性Stille交叉偶联共聚反应制备有机半导体材料的方法学。采用惰性气体保护,在甲磺酸(三-叔丁基膦基)(2’-氨基-1,1’-联苯-2-基)钯(II)(即P(t-Bu)-(3)Pd G3)的催化剂作用下,加入磷酸钾作为添加剂,将芳基二卤代物与芳基二锡烷置于四氢呋喃或甲苯中,并在室温条件下进行反应,得到混合物。将混合物滴入甲醇中沉淀过滤,并将沉淀物采用索氏提取器通过丙酮、正己烷及三氯甲烷分别进行提取,将三氯甲烷提取得到的聚合物溶液浓缩后滴入甲醇中制得高分子量D-A共轭聚合物。采用本方法制得的共轭聚合物可以应用于有机场效应晶体管、有机太阳能电池、细胞成像和光热、光动力治疗等领域。(The invention provides a method for preparing an organic semiconductor material based on a universal Stille cross-coupling copolymerization reaction of an aryl system at room temperature. Under the protection of inert gas, in methanesulfonic acid (tri-tert-butyl phosphino) (2 '-amino-1, 1' -biphenyl-2-yl) palladium (II) (namely P (t-Bu) 3 Pd G3), adding potassium phosphate as additive, putting aryl dihalide and aryl distannane in tetrahydrofuran or toluene, and reacting at room temperature to obtain mixture. Dripping the mixture into methanol for precipitation and filtration, respectively extracting precipitates with acetone, n-hexane and chloroform by a Soxhlet extractor, concentrating a polymer solution obtained by extracting the chloroform, and dripping the polymer solution into the methanol to obtain the high-molecular-weight D-A conjugated polymer. The conjugated polymer prepared by the method can be applied to the fields of organic field effect transistors, organic solar cells, cell imaging, photo-thermal treatment, photodynamic treatment and the like.)

1. Method for preparing diaryl coupled polymer by taking aryl dihalide as electrophilic reagent and aryl distannane as nucleophilic reagent under catalyst/alkali/solvent condition, and diaryl coupled polymerThe catalyst described in (1) is (tri-tert-butylphosphino) (2 '-amino-1, 1' -biphenyl-2-yl) palladium (II) (i.e., P (t-Bu)₃Pd G3), characterized in that its general structural formula is as shown in formula I:

wherein Ar is₁And Ar₂Represent the same or different aryl systems;

wherein n represents the degree of polymerization;

wherein, X represents halogen, preferably chlorine, bromine and iodine;

wherein R is^aAnd R^bEach independently represents hydrogen or C₁-C₃₀Alkyl, preferably C₁-C₂₀Alkyl, more preferably C₁-C₁₀An alkyl group;

wherein the alkaline condition is Cs₂CO₃,K₃PO₃,Na₂CO₃,NaHCO₃Any one or a combination of NaOH;

wherein the solvent is selected from any one or combination of THF, DMSO, DMF, dioxane, carbon dichloride, chloroform, methanol, ethanol, toluene, acetone and n-hexane;

wherein, P (t-Bu)₃The structural formula of Pd G3 is:

2. the method of claim 1 wherein said aryl dihalide is any of the following compounds:

wherein X is a chlorine atom, a bromine atom or an iodine atom;

wherein R, R₁,R₂,R₃Is independently hydrogen or C₁-C₃₀Wherein the straight chain alkyl groups containing a total number of carbon atoms of 6 to 16 include: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl; and branched alkyl groups having a total number of carbon atoms of 8 to 30 include: 2-ethylhexyl group, 2-ethyloctyl group, 2-butylhexyl group, 2-hexyloctyl group, 4-hexyldecyl group, 3-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 3-octyltridecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 3-decylpentadecyl group, 2-dodecylhexadecyl group, 4-octyltetradecyl group, 4-decylcetyl group, 4-hexyldecyl group, 4-octyldodecyl group, 4-decyltetradecyl group, 4-dodecylhexadecyl group.

3. The method of claim 1, wherein said aryldistannane is any one of the following compounds:

wherein R, R₁,R₂Is independently hydrogen or C₁-C₃₀Wherein the straight chain alkyl groups containing a total number of carbon atoms of 6 to 16 include: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl; and the total number of carbon atoms isBranched alkyl groups of 8 to 30 include: 2-ethylhexyl group, 2-ethyloctyl group, 2-butylhexyl group, 2-hexyloctyl group, 4-hexyldecyl group, 3-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 3-octyltridecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 3-decylpentadecyl group, 2-dodecylhexadecyl group, 4-octyltetradecyl group, 4-decylcetyl group, 4-hexyldecyl group, 4-octyldodecyl group, 4-decyltetradecyl group, 4-dodecylhexadecyl group.

4. A method according to any of claims 1-3, characterized in that the method steps comprise:

(1) under the protection of inert gas, in P (t-Bu)₃Adding potassium phosphate as an additive under the catalytic action of Pd G3, and placing aryl dihalide and aryl distannane in tetrahydrofuran or toluene for reaction to obtain a mixture;

(2) dripping the mixture into methanol for precipitation and filtration, respectively extracting precipitates with acetone, n-hexane and chloroform by a Soxhlet extractor, concentrating a polymer solution obtained by extracting the chloroform, and dripping the polymer solution into the methanol to prepare the high-molecular-weight D-A conjugated polymer with more than 10 repeating units.

5. The process of any one of claims 1-4 wherein the aryl dihalide and aryl distannane are polymerized at room temperature.

The technical field is as follows:

the invention relates to the technical field of synthesis of donor-acceptor (D-A) conjugated polymers of an organic semiconductor active layer, in particular to a Stille cross-coupling room temperature polymerization method based on aryl dihalide and aryl distannane.

Background art:

organic conjugated polymers are attracting attention due to their great potential in plastic electronics, such as chemical structure tunability, band gap and light absorption tunability, excellent charge transport mobility, flexible fabricability, and solution processability. The pi-conjugated D-A copolymer without defects and with perfectly alternating structure has better charge transmission performance than the D-A copolymer with structural defects.

The traditional preparation method of the D-A conjugated polymer is to use a system (namely Pd) of tris (dibenzylideneacetone) dipalladium and bis (tri-o-tolylphosphine) palladium (0)₂(dba)₃/P(o-tol)₃Systems) or tetrakis (triphenylphosphine) palladium systems (i.e. Pd (PPh)₃)₄System) is a catalyst, aryl dihalide and aryl distannane are subjected to Stille cross-coupling polymerization reaction under the conditions of heating and nitrogen protection. Under such conditions, not only is the energy consumption required for the reaction increased, but it is more likely that the copolymer will develop structural defects. The generation of structural defects can reduce the charge mobility of the D-A copolymer. Therefore, how to realize a copolymer without defects or with low defects at room temperature becomes a problem to be solved in the field of organic semiconductors.

The invention content is as follows:

in view of the above problems, the present invention provides a Stille cross-coupling polymerization method using aryl dihalide as electrophile and aryl distannane as nucleophile, which uses methanesulfonic acid (tri-tert-butylphosphino) (2 '-amino-1, 1' -biphenyl-2-yl) palladium (II) (i.e., P (t-Bu)₃Pd G3) as a catalyst and potassium phosphate as an additive, and the Stille cross-coupling copolymerization reaction is realized under the condition of normal temperature.

The invention is based on a Stille cross-coupling copolymerization reaction with aryl dihalide as electrophilic reagent and aryl distannane as nucleophilic reagent. The reaction formula is as follows:

wherein Ar is₁And Ar₂Represent the same or different aryl systems;

wherein n represents the degree of polymerization;

wherein, X represents halogen, preferably chlorine, bromine and iodine;

wherein R is^aAnd R^bEach independently represents hydrogen or C₁-C₃₀Alkyl, preferably C₁-C₂₀Alkyl radicalMore preferably C₁-C₁₀An alkyl group;

wherein the alkaline condition is Cs₂CO₃,K₃PO₃,Na₂CO₃,NaHCO₃Any one or a combination of NaOH;

wherein the solvent is selected from any one or combination of THF, DMSO, DMF, dioxane, carbon dichloride, chloroform, methanol, ethanol, toluene, acetone and n-hexane;

wherein, P (t-Bu)₃The structural formula of Pd G3 is:

in the method of the present invention, wherein the aryl dihalide is any of the following compounds:

wherein X is a chlorine atom, a bromine atom or an iodine atom. R, R₁,R₂,R₃Is independently hydrogen or C₁-C₃₀Wherein the straight chain alkyl groups containing a total number of carbon atoms of 6 to 16 include: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl; and branched alkyl groups having a total number of carbon atoms of 8 to 30 include: 2-ethylhexyl group, 2-ethyloctyl group, 2-butylhexyl group, 2-hexyloctyl group, 4-hexyldecyl group, 3-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 3-octyltridecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 3-decylpentadecyl group, 2-dodecylhexadecyl group, 4-octyltetradecyl group, 4-decyltetradecyl group, 4-hexyldecyl group, 4-octyldecadecyl groupDialkyl, 4-decyltetradecyl, 4-dodecylhexadecyl.

In the method of the present invention, the aryldistannane is any one of the following compounds:

R,R₁,R₂is independently hydrogen or C₁-C₃₀Wherein the straight chain alkyl groups containing a total number of carbon atoms of 6 to 16 include: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl; and branched alkyl groups having a total number of carbon atoms of 8 to 30 include: 2-ethylhexyl group, 2-ethyloctyl group, 2-butylhexyl group, 2-hexyloctyl group, 4-hexyldecyl group, 3-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 3-octyltridecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 3-decylpentadecyl group, 2-dodecylhexadecyl group, 4-octyltetradecyl group, 4-decylcetyl group, 4-hexyldecyl group, 4-octyldodecyl group, 4-decyltetradecyl group, 4-dodecylhexadecyl group.

The invention is based on the use of aryl dihalides with aryl distannanes in P (t-Bu)₃The method is realized under the catalytic action of Pd G3, and the specific synthesis method comprises the following steps:

1 equivalent of an aryldihalogen, 1 equivalent of an aryldistannane, P (t-Bu)₃Pd G3(10 mol%) and 1 equivalent of potassium phosphate were placed in a reaction flask. After nitrogen gas was replaced three times, dried tetrahydrofuran or toluene was added (to maintain the concentration of the solution at 0.05M). After stirring at room temperature for 24 hours (part of the system may be prolonged to 72 hours), methanol was added to precipitate. After filtration, the filter cake was subjected to soxhlet extraction with acetone, n-hexane and chloroform, respectively. The chloroform extract is concentrated and then precipitated by methanol. And (5) filtering and drying the precipitate to obtain the target polymer.

The invention has the advantages that:

(1) the reaction is carried out at room temperature, the energy consumption required by the reaction is low, and the synthesis cost can be greatly reduced;

(2) the reaction is carried out at room temperature, so that the safety of a laboratory and the safety in industrial production are effectively guaranteed;

(3) the reaction speed is high, and the molecular weight reaches ten thousand within thirty minutes;

(4) the reaction has strong universality and can be effectively applied to the construction of a polymer conjugated structure of a plurality of electron-deficient or electron-rich aromatic systems;

(5) compared with the heated Stille polymerization reaction, the structural defects of the conjugated high molecular polymer prepared by the synthesis method are greatly reduced;

(6) the reaction can be applied to a reaction system with more than one gram, and the molecular weight equivalent to the micro reaction is obtained.

The specific implementation mode is as follows:

example 1

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) selenophene (23.0mg, 0.05mmol), 3, 6-bis (5-bromothienyl) -2, 5-bis (2-decyltetradecyl) pyrrolo [3,4-c ] is added]Pyrrole-1, 4-dione (56.4mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After adding 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 24 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark green polymer solid (52.2mg, 95%).¹H NMR(500MHz,CDCl₃)：δ9.27-8.86(br,2H),7.49-6.73(br,4H),4.62-3.47(br,4H),2.07-1.96(br,2H),1.85-0.98(br,80H),0.99-0.68(br,12H)。GPC:M_n 39.4kDa,M_w88.9kDa,Elemental analysis calculated value { (C)₆₆H₁₀₄N₂O₂S₂Se)_n}: c, 72.02; h, 9.52; and N, 2.55. Measured value: c, 70.21; h, 9.21; and N, 2.46. Thermal decomposition temperature of the polymer: 435 ℃. Maximum absorption wavelength: 848nm (chloroform solution), 871nm (film).

Example 2

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) selenophene (23.0mg, 0.05mmol), 3, 6-bis (5-bromothien-2-yl) -2, 5-bis (2-octyldodecyl) -2, 5-dihydropyrrolo [3,4-c ] is added]Pyrrole-1, 4-dione (50.8mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After adding 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 24 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark green polymer solid (46.5mg, 94%).¹H NMR(500MHz,CDCl₃):δ9.26-8.82(br,2H),7.58-6.72(br,4H),4.34-3.65(br,4H),2.09-1.80(br,2H),1.53-0.98(br,64H),0.93-0.74(br,12H)。GPC:M_n32.2kDa,M_w 69.8kDa,Elemental analysis calculated value { (C)₅₈H₈₈N₂O₂S₂Se)_n}: c, 70.48; h, 8.97; n, 2.83. Measured value: c, 68.88; h, 8.75; and N, 2.66. Thermal decomposition temperature of the polymer: 431 ℃. Maximum absorption wavelength: 850nm (chloroform solution), 875nm (thin film).

Example 3

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) selenophene (23.0mg, 0.05mmol) and 3, 6-bis (5-bromothiophene [3,2-b ]]Thien-2-yl) -2, 5-bis (2-octyldodecyl) -2, 5-dihydropyrrolo [3,4-c]Pyrrole-1, 4-dione (56.4mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After adding 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 24 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark green polymer solid (51.5mg, 89%).¹H NMR(500MHz,CDCl₃):δ9.51-8.63(br,2H),7.51-5.82(br,4H),4.55-3.50(br,4H),2.49-2.11(br,2H),2.09-1.00(br,64H),1.00-0.65(br,12H)。GPC:M_n 11.3kDa,M_w 32.2kDa,Elemental analysis calculated value { (C)₆₂H₈₈N₂O₂S₄Se)_n}: c, 67.66; h, 8.06; and N, 2.55. Measured value: c, 66.66; h, 7.96; and N, 2.40. Thermal decomposition temperature of the polymer: 316 ℃. Maximum absorption wavelength: 772nm (chloroform solution), 834nm (film).

Example 4

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) selenophene (23.0mg, 0.05mmol), 6 '-dibromo-N, N' - (2-octyldodecyl) -isoindigo (48.9mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After the addition of 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 72 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered.Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark green polymer solid (40.1mg, 84%).¹H NMR(500MHz,CDCl₃):δ9.93-8.87(br,2H),7.60-7.32(br,2H),7.19-6.92(br,2H),6.89-6.55(br,2H),4.26-3.14(br,4H),2.13-1.81(br,2H),1.76-1.08(br,64H),1.02-0.76(br,12H)。GPC:M_n 77.8kDa,M_w171.1kDa,Elemental analysis calculated value { (C)₆₀H₉₀N₂O₂Se)_n}: c, 75.83; h, 9.55; and N, 2.95. Measured value: c, 74.95; h, 9.43; n, 2.84. Thermal decomposition temperature of the polymer: 416 deg.C. Maximum absorption wavelength: 703nm (chloroform solution), 715nm (thin film).

Example 5

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) selenophene (23.0mg, 0.05mmol) and 4, 9-dibromo-2, 7-bis (2-octyldodecyl) benzo [ lmn%][3,8]Phenanthroline-1, 3,6,8(2H,7H) -tetraone (49.1mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After the addition of 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 72 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark purple polymer solid (37.7mg, 79%).¹H NMR(500MHz,CDCl₃):δ9.04-8.96(br,2H),7.70-7.56(br,2H),4.21-4.16(br,4H),2.05-2.01(br,2H),1.57-1.01(br,64H),0.89-0.81(br,12H)。GPC:M_n29.3kDa,M_w 52.6kDa,Elemental analysis calculated value { (C)₅₈H₈₆N₂O₄Se)_n}: c, 73.00; h, 9.08; and N, 2.94. Measured value: c, 73.43; h, 9.18; and N, 2.75. Thermal decomposition temperature of the polymer: 436 deg.C. Maximum absorption wavelength: 563nm (chloroform solution), 628nm (thin film).

Example 6

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) selenophene (23.0mg, 0.05mmol) and 2, 6-dibromo-4, 8-bis [ (2-octyldodecyl) oxy]Benzo [1,2-b:4,5-b']Dithiophene (46.9mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After adding 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 24 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark purple polymer solid (24.2mg, 53%).¹H NMR(500MHz,CDCl₃):δ7.53-7.29(br,2H),4.91-3.71(br,2H),4.30-3.90(br,4H),2.03-1.78(br,2H),1.75-1.09(br,64H),1.04-0.72(br,12H)。GPC:M_n 50.1kDa,M_w 136.7kDa,Elemental analysis calculated value { (C)₅₄H₈₆O₂S₂Se)_n}: c, 71.25; h, 9.52. Measured value: c, 70.34; h, 9.07. Thermal decomposition temperature of the polymer: 445 ℃. Maximum absorption wavelength: 511nm (chloroform solution), 547nm (thin film).

Example 7

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) selenophene (23.0mg, 0.05mmol), 2, 7-dibromo-4, 4,9, 9-forty-hexaalkyl-4, 9-dihydro-s-indeno [1,2-b:5,6-b']Dithiophene (65.9mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After the addition of 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 72 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a red polymer solid (61.3mg, 95%).¹H NMR(500MHz,CDCl₃):δ7.31-7.27(br,2H),6.05-5.41(br,2H),4.73-3.92(br,2H),2.26-1.04(br,120H),0.96-0.80(br,12H)。GPC:M_n 27.1kDa,M_w 77.3kDa,Elemental analysis calculated value { (C)₈₄H₁₃₈S₂Se)_n}: c, 78.14; h, 10.77. Measured value: c, 76.55; h, 9.67. Thermal decomposition temperature of the polymer: 414 deg.C. Maximum absorption wavelength: 568nm (chloroform solution), 573nm (thin film).

Example 8

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) thiophene (20.6mg, 0.05mmol), 2, 7-dibromo-4, 4,9, 9-forty-hexaalkyl-4, 9-dihydro-s-indeno [1,2-b:5,6-b']Dithiophene (65.9mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After the addition of 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 72 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then the polymer precipitated is sequentially and respectively treated with acetone, normal hexane and trichloromethaneAnd (5) performing Soxhlet extraction. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a red polymer solid (59.1mg, 95%).¹H NMR(500MHz,CDCl₃):δ7.26-7.17(br,2H),7.16-7.11(br,2H),7.10-7.04(br,2H),1.08-1.03(br,120H),0.94-0.81(br,12H)。GPC:M_n 26.3kDa,M_w 65.0kDa,Elemental analysis calculated value { (C)₈₄H₁₃₈S₃)_n}: c, 81.09; h, 11.18. Measured value: c, 80.89; h, 10.97. Thermal decomposition temperature of the polymer: 435 ℃. Maximum absorption wavelength: 549nm (chloroform solution), 552nm (thin film).

Example 9

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) thiophene (20.6mg, 0.05mmol), 3, 6-bis (5-bromothienyl) -2, 5-bis (2-decyltetradecyl) pyrrolo [3,4-c ] is added]Pyrrole-1, 4-dione (56.4mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After the addition of 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 72 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark green polymer solid (43.7mg, 83%).¹H NMR(500MHz,CDCl₃):δ9.11-8.64(br,2H),7.17-6.81(br,4H),4.27-3.69(br,4H),1.99-1.87(br,2H),1.68-1.05(br,80H),0.93-0.79(br,12H)。GPC:M_n 37.8kDa,M_w71.2kDa,Elemental analysis calculated value { (C)₆₆H₁₀₄N₂O₂S₃)_n}: c, 75.23; h, 9.95; and N, 2.66. Measured value: c, 75.59; h, 9.88; and N, 2.61. Thermal decomposition temperature of the polymer: 433 deg.c. Maximum absorption wavelength: 814nm (chloroform solution), 848nm (film).

Example 10

Under the protection of nitrogen, 2, 5-bis (trimethylstannyl) furan (19.8mg, 0.05mmol), 3, 6-bis (5-bromothienyl) -2, 5-bis (2-decyltetradecyl) pyrrolo [3,4-c ] is added]Pyrrole-1, 4-dione (56.4mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After the addition of 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 72 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark green polymer solid (46.7mg, 90%).¹H NMR(500MHz,CDCl₃):δ9.58-8.63(br,2H),7.71-6.35(br,4H),5.18-2.82(br,4H),2.02-1.74(br,2H),7.13-0.98(br,80H),0.98-0.27(br,12H)。GPC:M_n 43.6kDa,M_w80.5kDa,Elemental analysis calculated value { (C)₆₆H₁₀₄N₂O₃S₂)_n}: c, 76.39; h, 10.10; and N, 2.70. Measured value: c, 75.71; h, 9.84; and N, 2.63. Thermal decomposition temperature of the polymer: 446 deg.C. Maximum absorption wavelength: 797nm (chloroform solution), 815nm (film).

Example 11

Under the protection of nitrogenThen, (4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b:4,5-b']Dithiophene-2, 6-diyl) bis (trimethylstannane) (45.3mg, 0.05mmol), 3, 6-bis (5-bromothienyl) -2, 5-bis (2-decyltetradecyl) pyrrolo [3,4-c]Pyrrole-1, 4-dione (56.4mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After the addition of 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 72 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then, soxhlet extraction is carried out on the precipitated polymer by using acetone, normal hexane and chloroform respectively in sequence. The solution obtained after chloroform extraction was concentrated, then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark green polymer solid (68.1mg, 88%).¹H NMR(500MHz,CDCl₃):δ9.49-8.92(br,2H),8.13-6.77(br,8H),4.43-3.64(br,4H),3.29-2.85(br,4H),2.11-1.80(br,4H),1.80-0.98(br,96H),0.98-0.78(br,24H)。GPC:M_n 31.4kDa,M_w83.0kDa,Elemental analysis calculated value { (C)₉₆H₁₄₂N₂O₂S₆)_n}: c, 74.46; h, 9.24; n, 1.81. Measured value: c, 74.12; h, 9.07; n, 1.81. Thermal decomposition temperature of the polymer: 434 ℃. Maximum absorption wavelength: 756nm (chloroform solution), 770nm (thin film).

Example 12

Under the protection of nitrogen, 5 '-bis (trimethylstannyl) -2, 2' -dithiophene (24.7mg, 0.05mmol), 4, 9-dibromo-2, 7-bis (2-octyldodecyl) benzo [ lmn][3,8]Phenanthroline-1, 3,6,8(2H,7H) -tetraone (49.1mg, 0.05mmol), P (t-Bu)₃Pd G3(2.9mg, 0.005mmol) and potassium phosphate (10.6mg, 0.05mmol) were placed in a reaction flask. After the addition of 1.0mL of tetrahydrofuran, the mixture was stirred at room temperature for 72 hours. After addition of 20.0mL of methanol, the resulting precipitate was filtered. Then precipitating outThe polymer of (a) is subjected to Soxhlet extraction sequentially with acetone, n-hexane and chloroform respectively. The solution obtained after chloroform extraction was concentrated, and then the polymer was precipitated with 20.0mL of methanol, filtered and dried to obtain a dark blue polymer solid (43.3mg, 87%).¹H NMR(500MHz,CDCl₃):δ8.86-8.42(br,2H),7.74-7.27(br,4H),4.55-3.76(br,4H),2.17-1.83(br,2H),1.79-1.03(br,64H),1.02-0.70(br,12H)。GPC:M_n 29.1kDa,M_w 53.0kDa,Elemental analysis calculated value { (C)₆₂H₈₈N₂O₄S₂)_n}: c, 75.26; h, 8.96; n, 2.83. Measured value: c, 75.12; h, 8.81; and N, 2.82. Thermal decomposition temperature of the polymer: 486 deg.C. Maximum absorption wavelength: 651nm (chloroform solution), 709nm (thin film).

The above-mentioned embodiments are merely exemplary embodiments for fully illustrating the present invention, and the scope of the present invention is not limited to the above-mentioned embodiments, but defined by the contents of the claims. All matters disclosed in the specification including the abstract and all methods and steps disclosed herein may be combined in any combination, except combinations where the features and/or steps are mutually exclusive. Each feature disclosed in this specification, including the abstract, can be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features. Those skilled in the art should also realize that such equivalent substitutions and alterations can be made without departing from the spirit and scope of the present invention. Such modifications are also intended to be within the scope of the present invention. Each reference cited in this application is incorporated herein in its entirety.