A method for preparing a polythiophene-based conjugated polymer

Abstract

The present application relates to a kind of preparation method of polythiophene conjugated polymer, in the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deproton ligand and solvent, to be activated aromatic hydrocarbon is directly arylated polymerization reaction one step synthesis polythiophene conductive polymer by oxidation;To be activated aromatic hydrocarbon is one or more of thiophene and its derivatives;The coordination number of nitrogen-containing heterocyclic ligand and palladium is 1, and the coordination number of deproton ligand and palladium is 2;Or, the coordination number of nitrogen-containing heterocyclic ligand and palladium is 2, and the coordination number of deproton ligand and palladium is 1;The reaction transition state of metal synergistic deprotonation step participated by ligand and deproton ligand calculated by density functional theory, the W Pd‑C and W C‑H Sum calculated is not less than 0.75;The method of the present application is simple, fast, and does not need to be pre-activated for monomer, solves the problem of low yield and polymerization degree in the prior art by oxidation direct arylated polymerization to prepare polythiophene polymer.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and relates to a preparation method of a polythiophene conjugated polymer. BACKGROUND

[0002] Conjugated polymers have been widely used in organic electronic devices. Due to the positive nature of the sulfur atoms in polythiophene polymers, the polymers are easily doped with negative ions, which promotes the transmission of holes on the polymer chain, so that the polymer material has the characteristics of high capacitance, high conductivity and the like.

[0003] At present, the polymerization methods for synthesizing polythiophene conjugated polymers are usually electrochemical polymerization, oxidative polymerization and transition metal catalytic polymerization.

[0004] The polymers prepared by electrochemical polymerization and oxidative polymerization have low yield, poor monomer utilization, low molecular weight, large dispersion coefficient, and the obtained polymers are easy to crosslink, which leads to poor solubility and limits the mechanical processability.

[0005] Literature 1 (Chemical Review, 2016, 116, 14225) and Literature 2 (Acta Polymerica Sinica, 2019, 50, (6), 109.) describe that the transition metal catalytic polymerization method has high monomer utilization, and the controllability and high catalytic efficiency of the polymerization reaction can be realized by controlling the reaction conditions and additives. However, the polymer monomers are usually pre-activated, such as Literature 3 (ACS Catalysis, 2015, 5, 3040-3053) describes introducing organic selenium groups and halogen groups (Still polymerization method) at the reaction site of the polymer unit, Literature 4 (ACS Sensors, 2020, 5, 191-198) describes introducing boronic acid groups and halogen groups (Suzuki) at the reaction site of the polymer unit, and Literature 5 (Progress in Polymer Science, 2018, 83, 135-201) describes introducing halogen groups at the reaction site of the polymer unit. Such methods complicate the polymerization process, are high in cost, and the by-products are not environmentally friendly, which greatly limits the industrial development of functional conductive polymer materials.

[0006] With the further derivation of direct arylation reaction to oxidative direct arylation polymerization system, the process is more concise and environmentally friendly, which is expected to upgrade the technology. However, according to the existing technical conditions of oxidative direct arylation system, the catalytic efficiency of polymerization monomer is poor, and high-performance polythiophene polymers cannot be prepared, which makes the application of this technology fall into a bottleneck. Literature 6 (Polymer Journal, 2013, 45, 281-286) synthesized poly-3-hexylthiophene by oxidative direct arylation polymerization under the catalysis of palladium catalyst for the first time, but the yield was only 20% and the polymerization degree was 23. In this literature, oxygen atmosphere was used as an oxidant to regenerate the palladium catalyst. The catalytic efficiency of this condition is low, the reaction time is long, and it is difficult to be applied to large-scale industrial production. Literature 7 (Polymer Chemistry, 2016, 7, 1623-1631) used silver carbonate and copper acetate as oxidants for oxidative polymerization when synthesizing ester-functionalized polythiophene. The experimental conditions of different oxidants were explored, and it was found that the oxidation efficiency of silver carbonate (yield 68%, polymerization degree 49) was higher than that of copper acetate (yield 33%, polymerization degree 31), but both were much lower than that of Stille method (yield 78%, polymerization degree 202), which could not realize industrial upgrading. At the same time, we tried to prepare poly-3,4-ethylenedioxythiophene derivatives from 3,4-ethylenedioxythiophene derivatives under the same reaction conditions, but no product was obtained. Literature 8 (ACS Marcro Letters, 2019, 8, 931-936) synthesized alkyl-functionalized poly-3,4-propylenedioxythiophene under the oxidation of silver carbonate oxidant, and selected different phosphine ligands for oxidative arylation polymerization. Among them, under the action of palladium catalyst, ligand and silver acetate, the reaction was carried out for 48 hours to obtain a yield of 92%, but the polymerization degree was only 26; Literature 9 (European Polymer Journal, 2022, 178, 111436) used oxygen atmosphere as an oxidant (yield 72%, polymerization degree only 17), and the reaction condition without ligand was environmentally friendly, but the process was too complex due to the slow increase of temperature, and the polymerization degree was not high, which had a great gap compared with the traditional direct arylation polymerization method in terms of catalytic efficiency.

[0007] Generally speaking, the greater the degree of polymerization of the conjugated polymer, the higher its electrical conductivity, and at the same time, it has stronger deformation resistance. The conjugated polymer with high degree of polymerization has excellent electrochemical performance and mechanical performance, and has broad prospects in different demand electrochemical application scenarios. In order to solve the problem of low degree of polymerization of polythiophene derivatives prepared by direct arylation polymerization method, improving the catalytic efficiency of the reaction site of the polymerization unit in the reaction system is the key to solving the problem. Literature 10 (Journal of the American Chemical Society, 2022, 144, 6123-6135) records that according to the Carothers equation, a slight decline in the conversion rate of monomers will exponentially weaken the growth of polymer chains. Therefore, it is particularly important to improve the catalytic efficiency of the polymerization unit under palladium catalysis. Compared with the existing direct arylation polymerization method, the oxidation direct arylation polymerization method continues to use monodentate phosphine ligand modification to improve reaction efficiency, which obviously cannot meet the preparation of high-performance polythiophene conjugated polymer materials.

[0008] Therefore, there are still certain challenges in efficiently synthesizing high-performance polythiophene conjugated polymers by oxidation direct arylation polymerization method. SUMMARY

[0009] In order to solve the problem of low yield and degree of polymerization of polythiophene polymers prepared by oxidation direct arylation polymerization in the prior art, the present application provides a preparation method of polythiophene conjugated polymer;

[0010] To achieve the above purpose, the present application adopts the following scheme:

[0011] A preparation method of polythiophene conjugated polymer, in the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidizing agent, a deprotonating ligand and a solvent, an activated aromatic hydrocarbon is subjected to an oxidation direct arylation polymerization reaction to synthesize a conductive polymer of polythiophene in one step;

[0012] The activated aromatic hydrocarbon is one or more of thiophene and its derivatives;

[0013] The coordination number of the nitrogen-containing heterocyclic ligand with palladium is 1, and the coordination number of the deprotonating ligand with palladium is 2; or, the coordination number of the nitrogen-containing heterocyclic ligand with palladium is 2, and the coordination number of the deprotonating ligand with palladium is 1;

[0014] The reaction transition state of the metal-assisted deprotonation step involving the ligand and the deprotonating ligand is calculated by density functional theory, and the calculated W Pd-C and W C-H The sum of W Pd-C is not less than 0.75, wherein W C-HWeber bond order of a transition state chemical bond formed by a carbon atom of an activation site of an aromatic hydrocarbon to be activated and a hydrogen atom connected to the carbon atom.

[0015] As a preferred technical solution:

[0016] The preparation method of the polythiophene conjugated polymer as described above, the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidizing agent and the deproton ligand is 1:0.01-0.2:0.02-0.5:2-10:2-10, and the ratio of the volume of the solvent to the number of moles of the aromatic hydrocarbon to be activated is 0.001-1 L / mol.

[0017] The preparation method of the polythiophene conjugated polymer as described above, the reaction is carried out under an inert atmosphere, the reaction temperature is 100-160°C, and the reaction time is 0.2-36 h.

[0018] The preparation method of the polythiophene conjugated polymer as described above, the inert atmosphere is helium, nitrogen or argon atmosphere.

[0019] The preparation method of the polythiophene conjugated polymer as described above, the nitrogen-containing heterocyclic ligand is The deproton ligand is acetylglycine;

[0020] Wherein, R1-R5 are each independently selected from one of alkyl, alkoxy, fluorine atom group, chlorine atom, cyano, nitro, dimethylamino and trifluoromethyl.

[0021] The preparation method of the polythiophene conjugated polymer as described above, the nitrogen-containing heterocyclic ligand is The deproton ligand is carboxylate or carbonate;

[0022] Wherein, R6-R 13 are each independently selected from one of fluorine atom group, chlorine atom, cyano, nitro and trifluoromethyl.

[0023] The preparation method of the polythiophene conjugated polymer as described above, the carboxylate is potassium pivalate or cesium pivalate; and the carbonate is potassium carbonate or cesium carbonate.

[0024] The preparation method of the polythiophene conjugated polymer as described above, the palladium catalyst is palladium acetate, palladium neopentanoate or palladium chloride, the oxidizing agent is copper acetate, copper valerate, copper sulfate or copper chloride, and the solvent is N,N-dimethylformamide or N,N-dimethylacetamide.

[0025] The preparation method of the polythiophene conjugated polymer as described above, the thiophene derivative is specifically 3,4-vinyldioxothiophene or 3,4-propylenedioxothiophene, and the structural formula of the thiophene and its derivative is

[0026] Where R is a hydrogen atom,

[0027] For hydrogen atoms, methyl, hydroxyl, hexafluoroisopropanol group, carboxyl group, x and y are integers, and 0 ≤ x ≤ 20, 0 ≤ y ≤ 20.

[0028] Invention principle:

[0029] The maximum coordination number of palladium is 4. If the four coordination numbers surrounding the palladium atom are filled, the reaction intermediate exhibits higher stability and thus higher reactivity. Based on this, we attribute the low efficiency of existing oxidative direct arylation polymerization methods to the following: the presence of a tetraligand cannot be guaranteed in the presence of a intermediate under the action of monodentate ligands and carboxylates; that is, the reaction intermediate is unstable and therefore difficult to activate the α-site of thiophene derivatives. Furthermore, the compatibility between the ligand / deprotonated ligand and the polythiophene monomer needs to be qualitatively assessed. Therefore, bidentate ligands can provide better stability to stably activate the α-site of thiophene derivatives. Simultaneously, density functional theory can be used to qualitatively assess the compatibility between the ligand / deprotonated ligand and the polythiophene monomer.

[0030] The method provided by this invention can be applied to the preparation of polythiophene conjugated polymers, and is not limited to polythiophene and poly3,4-propenyldioxothiophene. Based on the exploration of the oxidative direct arylation polymerization method of the polythiophene system, this invention proposes two ligand selection modes: one is a combination of a nitrogen-nitrogen bidentate ligand / pentovatate; the other is a combination of a monodentate nitrogen ligand / acetylglycine. These two combinations, in a palladium catalytic system, are more beneficial for catalyzing the α-position of the thiophene polymerization unit, and can prepare polythiophene polymers with higher degrees of polymerization. Both combinations share a common feature: the nitrogen-containing heterocyclic ligand and the deprotonated ligand jointly occupy a coordination site of 3, which is conducive to the activation of the thiophene derivative polymerization unit. Simultaneously, each polymerization unit has two α-position active sites. After activating the first polymerization site, a Pd-C bond is formed, requiring the breaking of an empty coordination bond formed by the existing ligand to make room for the activation of the second α-position.

[0031] The combination of a nitrogen-nitrogen bidentate ligand / tervapotranose salt, i.e., the coordination number of the nitrogen-containing heterocyclic ligand is 2, and the coordination number of the deprotonated ligand is 1; taking pyridine as the ligand / acetylglycine as the deprotonated ligand as an example, the reaction mechanism diagram is as follows. Figure 2 As shown;

[0032] The combination of monodentate nitrogen ligand / acetylglycine, i.e., the coordination number of the nitrogen-containing heterocyclic ligand is 1, and the coordination number of the deprotonated ligand is 2; taking 2,2-bipyridine as the ligand / acetate as the deprotonated ligand as an example, the reaction mechanism diagram is as follows. Figure 1 As shown;

[0033] Furthermore, based on quantitative calculations extending to the direct arylation reaction mechanism (ACS catalysis, 2019, 9, 6921-6836), and density functional theory calculations of the reaction transition state involving ligands and deprotonated ligands in the metal-cooperative deprotonation step, the calculated W... Pd-C With W C-H When the sum is not less than 0.75, polythiophene monomers exhibit higher catalytic efficiency than existing technologies in oxidative direct arylation polymerization systems. That is, within a specified reaction time, the prepared polythiophene derivatives have higher yields and degrees of polymerization.

[0034] Beneficial effects

[0035] (1) The preparation method of the present invention is simple, fast and does not require pre-activation of monomers, and is suitable for industrial production;

[0036] (2) The preparation method of the present invention solves the problem of low yield and degree of polymerization of polythiophene polymers prepared by direct oxidative arylation polymerization in the prior art. Attached Figure Description

[0037] Figure 1 This is a reaction mechanism diagram of Example 8 of the present invention, using 2,2-bipyridine as a ligand and acetate as a deprotonated ligand;

[0038] Figure 2 This is a reaction mechanism diagram of Example 1 of the present invention, using pyridine as a ligand and acetylglycine as a deprotonated ligand.

[0039] Figure 3 This is the UV-Vis spectrum of a conductive polymer prepared in Example 1.

[0040] Figure 4 The above is a hydrogen nuclear magnetic resonance spectrum of a conductive polymer prepared in Example 1. Detailed Implementation

[0041] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0042] The testing or calculation methods involved in the embodiments are as follows:

[0043] W Pd-C With W C-HThe sum was calculated using Gaussian 09 software and structural optimization was performed using M06L functional theory. The Pd atom was calculated using the SDD basis set, while the other atoms were calculated using the 6-31G(d) basis set. The atomic charges and Weber bond order of the over-gain state were calculated using Gaussian 09 (the input keywords were POP=NBORead,BNDIDX).

[0044] Degree of polymerization: The degree of polymerization of a polymer is determined by measuring the hydrogen spectrum signal of the polymer using proton NMR. The ratio of the integral area of ​​the cycloalkyl group of the dioxane moiety on the PEDOT backbone to the integral area of ​​the hydrogen spectrum signal of the terminal CH bond is then divided by the average number of hydrogen atoms in the cycloalkyl group of a single polymer unit.

[0045] Taking Example 1 as an example, the terminal peak (CH) position of the polymer is 6.45 ppm, and the chemical shift of the cycloalkyl group in the dioxane moiety connected to thiophene in the polymer is 3.92-4.80. The integral area ratio of the two is 298.6:1. The number of C-H bonds in the cycloalkyl group of each two polymer units is 7. Therefore, the degree of polymerization n = integral area of ​​cycloalkyl group * 2 / (7 * integral area of ​​terminal hydrogen group), and n is calculated to be 85.

[0046] Yield: Amount of polymer product obtained / Amount of aromatic hydrocarbon to be activated * 100.

[0047] Example 1

[0048] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0049] (1) Preparation of raw materials;

[0050] Palladium catalyst: Palladium acetate;

[0051] Nitrogen-containing heterocyclic ligands:

[0052] Oxidizing agent: copper acetate;

[0053] Deprotonated ligand: acetylglycine;

[0054] Solvent: N,N-dimethylformamide;

[0055] Aromatic hydrocarbons to be activated:

[0056] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.059, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium.C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0057] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand, and a solvent, under a helium atmosphere, the aromatic hydrocarbon to be activated was subjected to a one-step direct arylation polymerization reaction at 100°C for 6 hours to synthesize a conductive polymer of polythiophene. The reaction mechanism is as follows: Figure 2 As shown; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.1:0.2:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.01 L / mol.

[0058] like Figure 3 , 4 As shown, the structural formula of the obtained polythiophene conjugated polymer is: The yield was 58%, and the degree of polymerization was 85.

[0059] like Figure 3 The ultraviolet spectrum shows that the polymer has a maximum absorption wavelength of 588 nm.

[0060] like Figure 4 As shown in the 1H NMR spectrum, 2.7–3.4 ppm represents the 1H NMR signal of the O-CH2-CH2-N bond, 3.95–4.65 ppm represents the 1H NMR signal of the cycloalkyl group of the dioxane moiety on the dioxane PEDOT backbone, and 6.45 ppm represents the 1H NMR signal of the CH bond at the polymer terminal group.

[0061] Example 2

[0062] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0063] (1) Preparation of raw materials;

[0064] Palladium catalyst: Palladium acetate;

[0065] Nitrogen-containing heterocyclic ligands:

[0066] Oxidizing agent: copper acetate;

[0067] Deprotonated ligand: acetylglycine;

[0068] Solvent: N,N-dimethylformamide;

[0069] Aromatic hydrocarbons to be activated:

[0070] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W...Pd-C With W C-H The sum is 1.065, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0071] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 120°C for 1 h under a helium atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.01 L / mol.

[0072] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 78%, and the degree of polymerization was 45.

[0073] Example 3

[0074] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0075] (1) Preparation of raw materials;

[0076] Palladium catalyst: Palladium acetate;

[0077] Nitrogen-containing heterocyclic ligands:

[0078] Oxidizing agent: Copper valerate;

[0079] Deprotonated ligand: acetylglycine;

[0080] Solvent: N,N-dimethylacetamide;

[0081] Aromatic hydrocarbons to be activated:

[0082] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.062, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0083] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 140°C for 3 hours under nitrogen atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.1 L / mol.

[0084] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 88%, and the degree of polymerization was 35.

[0085] Example 4

[0086] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0087] (1) Preparation of raw materials;

[0088] Palladium catalyst: Palladium neopentanoate;

[0089] Nitrogen-containing heterocyclic ligands:

[0090] Oxidizing agent: Copper valerate;

[0091] Deprotonated ligand: acetylglycine;

[0092] Solvent: N,N-dimethylformamide;

[0093] Aromatic hydrocarbons to be activated:

[0094] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.098, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0095] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated was subjected to direct arylation polymerization at 160°C for 6 hours under nitrogen atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.05:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.05 L / mol.

[0096] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 93% and the degree of polymerization was 41.

[0097] Example 5

[0098] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0099] (1) Preparation of raw materials;

[0100] Palladium catalyst: Palladium neopentanoate

[0101] Nitrogen-containing heterocyclic ligands:

[0102] Oxidizing agent: Copper sulfate;

[0103] Deprotonated ligand: acetylglycine;

[0104] Solvent: N,N-dimethylformamide;

[0105] Aromatic hydrocarbons to be activated:

[0106] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.064, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0107] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 100°C for 12 h under argon atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:10:10, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.1 L / mol.

[0108] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 98%, and the degree of polymerization was 55.

[0109] Example 6

[0110] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0111] (1) Preparation of raw materials;

[0112] Palladium catalyst: Palladium chloride;

[0113] Nitrogen-containing heterocyclic ligands:

[0114] Oxidizing agent: copper chloride;

[0115] Deprotonated ligand: acetylglycine;

[0116] Solvent: N,N-dimethylacetamide;

[0117] Aromatic hydrocarbons to be activated:

[0118] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.991, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0119] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 120°C for 24 h under argon atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.1:0.2:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 1 L / mol.

[0120] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 100%.

[0121] Example 7

[0122] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0123] (1) Preparation of raw materials;

[0124] Palladium catalyst: Palladium chloride;

[0125] Nitrogen-containing heterocyclic ligands:

[0126] Oxidizing agent: copper chloride;

[0127] Deprotonated ligand: acetylglycine;

[0128] Solvent: N,N-dimethylacetamide;

[0129] Aromatic hydrocarbons to be activated:

[0130] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.879, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0131] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated was subjected to direct arylation polymerization at 140 °C for 36 h under argon atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0132] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 91%, and the degree of polymerization was 210.

[0133] Example 8

[0134] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0135] (1) Preparation of raw materials;

[0136] Palladium catalyst: Palladium acetate;

[0137] Nitrogen-containing heterocyclic ligands:

[0138] Oxidizing agent: copper acetate;

[0139] Deprotonated ligand: potassium pivalate;

[0140] Solvent: N,N-dimethylformamide;

[0141] Aromatic hydrocarbons to be activated:

[0142] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.751, where WPd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0143] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand, and a solvent, under a helium atmosphere, the aromatic hydrocarbon to be activated is subjected to a one-step direct arylation polymerization reaction at 100°C for 0.2 h to synthesize a conductive polymer of polythiophene in one step. The reaction mechanism is as follows: Figure 1 As shown; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0144] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 58%, and the degree of polymerization was 45.

[0145] Example 9

[0146] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0147] (1) Preparation of raw materials;

[0148] Palladium catalyst: Palladium acetate;

[0149] Nitrogen-containing heterocyclic ligands:

[0150] Oxidizing agent: copper acetate;

[0151] Deprotonated ligand: cesium pivalate;

[0152] Solvent: N,N-dimethylformamide;

[0153] Aromatic hydrocarbons to be activated:

[0154] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.78, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0155] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 120°C for 1 h under a helium atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0156] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 71%, and the degree of polymerization was 88.

[0157] Example 10

[0158] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0159] (1) Preparation of raw materials;

[0160] Palladium catalyst: Palladium acetate;

[0161] Nitrogen-containing heterocyclic ligands:

[0162] Oxidizing agent: copper acetate;

[0163] Deprotonated ligand: acetylglycine;

[0164] Solvent: N,N-dimethylformamide;

[0165] Aromatic hydrocarbons to be activated:

[0166] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.059, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0167] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated was subjected to direct arylation polymerization at 100°C for 0.2 h to synthesize a conductive polymer of polythiophene in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0168] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 45%, and the degree of polymerization was 21.

[0169] Example 11

[0170] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0171] (1) Preparation of raw materials;

[0172] Palladium catalyst: Palladium acetate;

[0173] Nitrogen-containing heterocyclic ligands:

[0174] Oxidizing agent: copper acetate;

[0175] Deprotonated ligand: acetylglycine;

[0176] Solvent: N,N-dimethylformamide;

[0177] Aromatic hydrocarbons to be activated:

[0178] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.065, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0179] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 120°C for 1 h under a helium atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0180] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 68%, and the degree of polymerization was 38.

[0181] Example 12

[0182] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0183] (1) Preparation of raw materials;

[0184] Palladium catalyst: Palladium acetate;

[0185] Nitrogen-containing heterocyclic ligands:

[0186] Oxidizing agent: Copper valerate;

[0187] Deprotonated ligand: acetylglycine;

[0188] Solvent: N,N-dimethylacetamide;

[0189] Aromatic hydrocarbons to be activated:

[0190] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.062, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0191] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated was subjected to direct arylation polymerization at 140°C for 3 hours under nitrogen atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0192] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 74%, and the degree of polymerization was 49.

[0193] Example 13

[0194] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0195] (1) Preparation of raw materials;

[0196] Palladium catalyst: Palladium chloride;

[0197] Nitrogen-containing heterocyclic ligands:

[0198] Oxidizing agent: copper chloride;

[0199] Deprotonated ligand: acetylglycine;

[0200] Solvent: N,N-dimethylacetamide;

[0201] Aromatic hydrocarbons to be activated:

[0202] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.991, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0203] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 120°C for 24 h under argon atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0204] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 90%, and the degree of polymerization was 98.

[0205] Example 14

[0206] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0207] (1) Preparation of raw materials;

[0208] Palladium catalyst: Palladium chloride;

[0209] Nitrogen-containing heterocyclic ligands:

[0210] Oxidizing agent: copper chloride;

[0211] Deprotonated ligand: acetylglycine;

[0212] Solvent: N,N-dimethylacetamide;

[0213] Aromatic hydrocarbons to be activated:

[0214] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-HThe sum is 0.997, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0215] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated was subjected to direct arylation polymerization at 140 °C for 36 h under argon atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0216] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 91%, and the degree of polymerization was 78.

[0217] Example 15

[0218] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0219] (1) Preparation of raw materials;

[0220] Palladium catalyst: Palladium acetate;

[0221] Nitrogen-containing heterocyclic ligands:

[0222] Oxidizing agent: copper acetate;

[0223] Deprotonated ligand: acetylglycine;

[0224] Solvent: N,N-dimethylformamide;

[0225] Aromatic hydrocarbons to be activated:

[0226] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.979, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0227] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 100°C for 12 h under a helium atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0228] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 91%, and the degree of polymerization was 49.

[0229] Example 16

[0230] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0231] (1) Preparation of raw materials;

[0232] Palladium catalyst: Palladium acetate;

[0233] Nitrogen-containing heterocyclic ligands:

[0234] Oxidizing agent: copper acetate;

[0235] Deprotonated ligand: acetylglycine;

[0236] Solvent: N,N-dimethylformamide;

[0237] Aromatic hydrocarbons to be activated:

[0238] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.919, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0239] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated was subjected to direct arylation polymerization at 120°C for 12 h under a helium atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0240] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 87%, and the degree of polymerization was 44.

[0241] Example 17

[0242] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0243] (1) Preparation of raw materials;

[0244] Palladium catalyst: Palladium acetate;

[0245] Nitrogen-containing heterocyclic ligands:

[0246] Oxidizing agent: Copper valerate;

[0247] Deprotonated ligand: acetylglycine;

[0248] Solvent: N,N-dimethylacetamide;

[0249] Aromatic hydrocarbons to be activated: mass ratio of 1:99 A mixture;

[0250] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.874, where W Pd -C is The Weber bond sequence of the transition state chemical bond formed by the carbon atom at the activation site and palladium, W C-H for The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site and the hydrogen atom attached to it;

[0251] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.059, where W Pd-C for The Weber bond sequence of the transition state chemical bond formed by the carbon atom at the activation site and palladium, W C-H for The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site and the hydrogen atom attached to it.

[0252] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 120°C for 12 h under nitrogen atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0253] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 96%, and the degree of polymerization was 121.

[0254] Example 18

[0255] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0256] (1) Preparation of raw materials;

[0257] Palladium catalyst: Palladium acetate;

[0258] Nitrogen-containing heterocyclic ligands:

[0259] Oxidizing agent: copper acetate;

[0260] Deprotonated ligand: acetylglycine;

[0261] Solvent: N,N-dimethylformamide;

[0262] Aromatics to be activated: mass ratio 50:50 A mixture;

[0263] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.059, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0264] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated was subjected to direct arylation polymerization at 120°C for 12 h under a helium atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0265] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 87%, and the degree of polymerization was 55.

[0266] Example 19

[0267] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0268] (1) Preparation of raw materials;

[0269] Palladium catalyst: Palladium acetate;

[0270] Nitrogen-containing heterocyclic ligands:

[0271] Oxidizing agent: copper acetate;

[0272] Deprotonated ligand: acetylglycine;

[0273] Solvent: N,N-dimethylformamide;

[0274] Aromatics to be activated: mass ratio of 25:75 A mixture;

[0275] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.979, where W Pd-C for The Weber bond sequence of the transition state chemical bond formed by the carbon atom at the activation site and palladium, W C-H for The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site and the hydrogen atom attached to it;

[0276] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 1.059, where W Pd-C for The Weber bond sequence of the transition state chemical bond formed by the carbon atom at the activation site and palladium, WC-H for The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site and the hydrogen atom attached to it.

[0277] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated was subjected to direct arylation polymerization at 120°C for 12 h under a helium atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0278] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 89%, and the degree of polymerization was 61.

[0279] Example 20

[0280] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0281] (1) Preparation of raw materials;

[0282] Palladium catalyst: Palladium acetate;

[0283] Nitrogen-containing heterocyclic ligands:

[0284] Oxidizing agent: Copper valerate;

[0285] Deprotonated ligand: acetylglycine;

[0286] Solvent: N,N-dimethylacetamide;

[0287] Aromatic hydrocarbons to be activated: mass ratio of 99:1 A mixture;

[0288] The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.979, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

[0289] (2) In the presence of palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, deprotonated ligand and solvent, the aromatic hydrocarbon to be activated is subjected to direct arylation polymerization at 120°C for 12 h under nitrogen atmosphere to synthesize a conductive polymer of polythiophene in one step; wherein, the molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant and deprotonated ligand is 1:0.01:0.02:2:2, and the volume ratio of solvent to the number of moles of aromatic hydrocarbon to be activated is 0.125 L / mol.

[0290] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 96%, and the degree of polymerization was 89.

Claims

1. A method for preparing a polythiophene-based conjugated polymer, characterized in that: In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand, and a solvent, a conductive polymer of polythiophene is synthesized in one step by direct arylation polymerization of the aromatic hydrocarbon to be activated. The aromatic hydrocarbon to be activated is one or more of thiophene and its derivatives; The structural formulas of thiophene and its derivatives are as follows: , or ; Where R is a hydrogen atom, , , , , or Y represents a hydrogen atom, methyl group, hydroxyl group, hexafluoroisopropanol group, carboxyl group, etc. , or x and y are integers, and 0 ≤ x ≤ 20, 0 ≤ y ≤ 20; Nitrogen-containing heterocyclic ligands are The deprotonated ligand is acetylglycine; Or nitrogen-containing heterocyclic ligands are or The deprotonated ligands are carboxylates or carbonates; the carboxylates are potassium pivalate or cesium pivalate; the carbonates are potassium carbonate or cesium carbonate. R1 to R5 are each independently selected from one of alkyl, alkoxy, fluorine, chlorine, cyano, nitro, dimethylamino, and trifluoromethyl groups; R6 to R 13 Each is independently selected from one of the following groups: fluorine atom, chlorine atom, cyano group, nitro group, and trifluoromethyl group; The coordination number of the nitrogen-containing heterocyclic ligand with palladium is 1, and the coordination number of the deprotonated ligand with palladium is 2; or, the coordination number of the nitrogen-containing heterocyclic ligand with palladium is 2, and the coordination number of the deprotonated ligand with palladium is 1. The palladium catalyst is palladium acetate, palladium neopentanoate, or palladium chloride; the oxidant is copper acetate, copper pentanoate, copper sulfate, or copper chloride; and the solvent is N,N-dimethylformamide or N,N-dimethylacetamide. The molar ratio of the aromatic hydrocarbon to be activated, palladium catalyst, nitrogen-containing heterocyclic ligand, oxidant, and deprotonated ligand is 1:0.01~0.2:0.02~0.5:2~10:2~10; The reaction transition state of the metal-cooperative deprotonation step involving ligands and deprotonated ligands was calculated using density functional theory, and the calculated W... Pd-C With W C - H The sum is not less than 0.75, where W Pd-C The W represents the Weber bond sequence of the transition state bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C - H The Weber sequence of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom attached to it.

2. The method for preparing a polythiophene conjugated polymer according to claim 1, characterized in that, The reaction was carried out under an inert atmosphere at a temperature of 100–160 °C for a time of 0.2–36 h.

3. The method for preparing a polythiophene conjugated polymer according to claim 2, characterized in that, The inert atmosphere is helium, nitrogen, or argon.

Images