A low-impedance zwitterionic conductive polymer and a preparation method thereof

Abstract

The application relates to a low-impedance zwitterion conductive polymer and a preparation method thereof. In the presence of a palladium catalyst, an oxidant, a solvent and an electron-deficient group-containing nitrogen-containing heterocyclic ligand, an anti-non-specific adhesion polymer is synthesized through one-step direct arylization polymerization of an activated aromatic hydrocarbon and a halogenated aromatic hydrocarbon; the activated aromatic hydrocarbon is a functional monomer containing a zwitterion functional group; the ligand containing an electron-deficient group is a nitrogen-containing heterocyclic ligand; the structural general formula of the prepared anti-non-specific adhesion polymer is wherein R1 and R2 are independent of each other, and n is a natural number greater than 20. The preparation method provided by the application is simple, fast, and the functional groups are stable in the reaction, and is suitable for industrial production; the anti-non-specific adhesion polymer has high molecular weight, a regular structure and high yield, and has a wide application prospect in the field of bioelectronic materials.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and relates to a low-resistivity zwitterionic conductive polymer and its preparation method. Background Technology

[0002] Polyethylene dioxythiophene (PED-THP) and polypropylene dioxythiophene (PPD-THP) polymers are widely studied as next-generation implantable and wearable electronic materials due to their mechanical flexibility, high electrical conductivity, and biocompatibility. As implantable bioelectrode materials, PED-THP and PPPD-THP exhibit mixed ion-electron conductivity and high capacitance. The mechanical flexibility and high electrical conductivity of biomaterial conductive polymers correspond to their high molecular weight. However, unmodified polymers cannot solve the problem of non-specific protein adsorption, which leads to increased interfacial impedance and even chronic immune responses, causing glial scar tissue to form around electronic devices. Inactive scar tissue reduces or even eliminates stimulation signals.

[0003] Furthermore, the impedance of the surface coating material is also crucial. A study in Reference 1 (Proceedings of SPIE, 2016, 9944, 994404) on the frequency dependence of electrode / electrolyte impedance showed that signal transmission at the bioelectrode-tissue interface is related not only to the difference in interface capacitance but also significantly to the difference in interface resistance. Low resistance can minimize signal noise and can be used to reduce the inherent noise floor of the system. Therefore, reducing the impedance of conductive polymers is essential.

[0004] Currently, the synthesis of poly(3,4-propylene-dioxothiophene) is typically achieved through electrochemical polymerization, oxidative polymerization, and transition metal-catalyzed polymerization. Reference 2 (J. Mater. Chem. B, 2021, 9, 2717) points out that the development of poly(3,4-propylene-dioxothiophene) derivatives prepared by electrochemical polymerization is limited by low yield, low molecular weight, poor polymer regularity, and the inability to produce on a large scale. Meanwhile, the complex reaction conditions of oxidative polymerization may cause the bridging groups connecting the side groups to break, resulting in the loss of the conductive polymer's resistance to non-specific adhesion and leading to chronic immune reactions. Reference 3 (Chemistry of Materials, 2022, 34, 2752-2763) shows that chemical bond breaking occurred in oxidative polymerization using ferric chloride as an oxidant. Transition metal-catalyzed polymerization typically involves mild reaction conditions, and the chemical bonds formed are highly resistant to reaction. Direct arylation polymerization, an extension of this method, offers advantages such as simple reaction, environmental friendliness, and atom economy, and can serve as a potential means of preparing conductive polymers containing zwitterionic groups.

[0005] Therefore, this invention aims to prepare conductive polymer materials with high antifouling properties and extremely low electrochemical impedance, while also developing efficient and high-quality synthesis methods. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a low-resistance zwitterionic conductive polymer and its preparation method;

[0007] To achieve the above objectives, the present invention adopts the following solution:

[0008] A low-resistance zwitterionic conductive polymer, wherein the repeating unit contains two independent zwitterionic groups.

[0009] The low-resistance zwitterionic conductive polymer described above has a significantly lower electrochemical impedance than conductive polymers that do not contain zwitterionic groups and conductive polymers whose repeating units contain only one zwitterionic group.

[0010] The low-resistance zwitterionic conductive polymer described above exhibits significantly better resistance to the adhesion of biomolecules, viruses, cells, bacteria, and fungi than conductive polymers with repeating units containing only one zwitterionic group.

[0011] As described above, a low-resistance zwitterionic conductive polymer has the following general structural formula. Its polymer has a significantly lower electrochemical impedance than that of polymers without zwitterions. A repeating unit containing only one zwitterionic group Wherein, R1 and R2 are independent zwitterionic groups, and n is a natural number greater than 20.

[0012] The above describes a low-resistance zwitterionic conductive polymer, which contains zwitterionic functionalized monomers. Where R1 and R2 are respectively Any two mutually independent ones, where Y is In any of the following, x and y are integers, and 0 ≤ x ≤ 20, 0 ≤ y ≤ 20.

[0013] As a preferred technical solution:

[0014] The method for preparing a low-impedance zwitterionic conductive polymer as described above involves a one-step synthesis of an anti-nonspecific adhesion polymer by direct arylation polymerization of an aromatic hydrocarbon to be activated, in the presence of a palladium catalyst, an oxidant, a solvent, and a nitrogen-containing heterocyclic ligand; the aromatic hydrocarbon to be activated is a functionalized monomer containing a double-chain zwitterionic functional group.

[0015] In the preparation method of the low-resistance zwitterionic conductive polymer described above, the molar ratio of the aromatic hydrocarbon to be activated, the haloaromatic hydrocarbon, the palladium catalyst, the nitrogen-containing heterocyclic ligand and the oxidant is 1:1:0.01~0.2:0.02~0.5:1~10, and the volume ratio of the solvent to the molar number of haloaromatic hydrocarbons is 0.001~1L / mol.

[0016] The method for preparing a low-resistance zwitterionic conductive polymer as described above involves a reaction carried out under an inert atmosphere, at a temperature of 60–140°C, for a reaction time of 1–120 h, more preferably 100–160°C, for a reaction time of 1–36 h.

[0017] The method for preparing a low-resistance zwitterionic conductive polymer as described above uses a nitrogen-containing heterocyclic ligand as... R3 to R7 are each independently selected from one of hydrogen atom, alkyl, alkoxy, fluorine atom group, chlorine atom, cyano, nitro, dimethylamino and trifluoromethyl.

[0018] The method for preparing a low-resistance zwitterionic conductive polymer as described above uses palladium acetate, palladium neopentanoate, or palladium chloride as the palladium catalyst, copper acetate, copper pentanoate, copper sulfate, or copper chloride as the oxidant, and N,N-dimethylformamide or N,N-dimethylacetamide as the solvent.

[0019] Invention principle:

[0020] Generally, for zwitterionic functionalized conductive polymers, the introduction of large-volume zwitterionic groups can lead to several problems: the introduction of insulating zwitterionic side chains reduces the overall conductivity of the polymer; larger side chains increase the distance between molecular chains, which is detrimental to charge conduction; and the introduction of large side chains also causes distortion of the π-π plane of the conjugated polymer, reducing its charge conduction capacity. However, experimental results show that poly(dioxythiophene) functionalized without zwitterionic side chains has an impedance of 14.69 Ω / cm. 2 The impedance of poly(dioxythiophene) functionalized with a zwitterionic side chain is 6.39 Ω / cm. 2 The impedance of poly(dioxythiophene) functionalized with two zwitterionic side chains can be as low as 2.08 Ω / cm. 2In other words, the introduction of zwitterionic groups significantly reduces the electrochemical impedance of polymer materials. Particularly interesting is that when one zwitterionic side chain is introduced into a repeating unit, the impedance of the conductive polymer material decreases to 43% of that of poly(dioxythiophene) without zwitterionic groups; while when two zwitterionic side chains are introduced into a repeating unit, the impedance decreases to 33% of that of poly(dioxythiophene) with one zwitterionic side chain. The possible reasons for these phenomena are as follows: the introduction of zwitterionic groups into conductive polymer materials can significantly improve the ionic conductivity of the polymer. This enhancement mechanism is mainly attributed to the large dipole moment of zwitterions, which is typically 7-8 times larger than that of polar solvents. The large dipole moment gives the material a large dielectric constant, thus shielding the electrostatic attraction between anions and cations, facilitating the dissociation of ions with opposite charges. Furthermore, zwitterions also provide migration channels for ions under an applied electric field, allowing one ion to jump to the next binding site. Simultaneously, the degree of hydration is also crucial for ion transport in polymer materials. When hydration weakens, ion mobility typically decreases. Because zwitterionic polymers possess a dense, stable hydration layer and strong water retention, enriching zwitterions in zwitterionic conductive polymers also facilitates ion transport. Although the electronic conductivity of zwitterionic functionalized conductive polymers decreases, the significantly enhanced ionic conductivity can still significantly improve the material's impedance.

[0021] The palladium-catalyzed direct arylation mechanism described in this invention is as follows: Under the action of a divalent palladium catalyst, pyridine ligands / acetylglycine ligands complex with palladium to form a reaction intermediate. First, oxidative addition occurs, followed by halogen removal to form a Pd-C bond, creating a stable intermediate. Polypropylene dioxothiophene derivative polymerization units approach this intermediate, and their CH bonds undergo a metal-coordinated deprotonation process, causing the CH bonds to break. The proton is transferred to acetylglycine, forming a Pd-C bond. Next, a second polypropylene dioxothiophene derivative polymerization unit continues to participate in the reaction, undergoing a similar metal-coordinated deprotonation process to form a second Pd-C bond. Subsequently, reductive elimination forms a C-C bond and zero-valent palladium (Pd). Finally, the divalent copper catalyst has an oxidizing effect, oxidizing the zero-valent palladium to divalent palladium to complete the cycle, thereby increasing the polymer chain length.

[0022] Beneficial effects

[0023] (1) The present invention provides a low-impedance zwitterionic conductive polymer with simple and rapid steps, and the functional groups have good stability in the reaction, making it suitable for industrial production;

[0024] (2) The anti-nonspecific adhesion polymer obtained by the present invention has low impedance and can resist cell adhesion, and has broad application prospects in the field of bioelectronic materials. Attached Figure Description

[0025] Figure 1 The image shows the UV-Vis spectrum of a low-impedance zwitterionic conductive polymer prepared in Example 1.

[0026] Figure 2 The image shows the proton NMR spectrum of a low-impedance zwitterionic conductive polymer prepared in Example 1.

[0027] Figure 3 The electrochemical impedance spectroscopy diagram is shown for a low-impedance zwitterionic conductive polymer prepared in Example 1.

[0028] Figure 4 This is an anti-cell adhesion diagram of a low-resistance zwitterionic conductive polymer prepared in Example 1. Detailed Implementation

[0029] 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.

[0030] Example 1

[0031] A method for preparing a low-resistance zwitterionic conductive polymer, the specific steps of which are as follows:

[0032] (1) Preparation of raw materials:

[0033] Palladium catalyst: Palladium acetate;

[0034] Oxidizing agent: copper acetate;

[0035] Solvent: N,N-dimethylformamide;

[0036] Nitrogen-containing heterocyclic ligands: pyridine;

[0037] Aromatic hydrocarbons to be activated:

[0038] (2) In an argon atmosphere, in the presence of palladium catalyst, oxidant, solvent and pyridine ligand, the aromatic hydrocarbons to be activated and the halogenated aromatic hydrocarbons were directly arylated and polymerized at 120°C for 12 h to synthesize an anti-nonspecific adhesion polymer in one step.

[0039] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the pyridine ligand, and the oxidant is 1:1:0.1:0.2:2.5, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.125 L / mol.

[0040] The structural formula of the obtained anti-nonspecific adhesion polymer is as follows: The degree of polymerization is 37; the yield is 86%; the impedance is 4.69Ω; and it has antifouling properties.

[0041] like Figure 1 The ultraviolet spectrum shows that the polymer has a maximum absorption wavelength of 478 nm.

[0042] like Figure 2 The hydrogen NMR spectrum shows the H atoms at different chemical shifts in the molecule.

[0043] Example 2

[0044] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0045] (1) Preparation of raw materials;

[0046] Palladium catalyst: Palladium neopentanoate;

[0047] Nitrogen-containing heterocyclic ligands:

[0048] Oxidizing agent: Copper valerate;

[0049] Deprotonated ligand: acetylglycine;

[0050] Solvent: N,N-dimethylformamide;

[0051] Aromatic hydrocarbons to be activated:

[0052] (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.

[0053] The structural formula of the obtained polythiophene conjugated polymer is as follows: The degree of polymerization is 45; the yield is 89%; the impedance is 3.5Ω; and it has anti-fouling properties.

[0054] Example 3

[0055] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0056] (1) Preparation of raw materials;

[0057] Palladium catalyst: Palladium neopentanoate

[0058] Nitrogen-containing heterocyclic ligands:

[0059] Oxidizing agent: Copper sulfate;

[0060] Deprotonated ligand: acetylglycine;

[0061] Solvent: N,N-dimethylformamide;

[0062] Aromatic hydrocarbons to be activated:

[0063] (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.

[0064] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 98%, the degree of polymerization is 55, and the impedance is 2.2Ω; it has anti-fouling properties.

[0065] Example 4

[0066] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0067] (1) Preparation of raw materials;

[0068] Palladium catalyst: Palladium chloride;

[0069] Nitrogen-containing heterocyclic ligands:

[0070] Oxidizing agent: copper chloride;

[0071] Deprotonated ligand: acetylglycine;

[0072] Solvent: N,N-dimethylacetamide;

[0073] Aromatic hydrocarbons to be activated:

[0074] (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.

[0075] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 100%, the degree of polymerization is 77, and the impedance is 3.33Ω; it has anti-fouling properties.

[0076] Example 5

[0077] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0078] (1) Preparation of raw materials;

[0079] Palladium catalyst: Palladium chloride;

[0080] Nitrogen-containing heterocyclic ligands:

[0081] Oxidizing agent: copper chloride;

[0082] Deprotonated ligand: acetylglycine;

[0083] Solvent: N,N-dimethylacetamide;

[0084] Aromatic hydrocarbons to be activated:

[0085] (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.

[0086] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield was 91%, and the degree of polymerization was 55.

[0087] Example 6

[0088] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0089] (1) Preparation of raw materials;

[0090] Palladium catalyst: Palladium acetate;

[0091] Nitrogen-containing heterocyclic ligands:

[0092] Oxidizing agent: copper acetate;

[0093] Deprotonated ligand: potassium pivalate;

[0094] Solvent: N,N-dimethylformamide;

[0095] Aromatic hydrocarbons to be activated:

[0096] (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.

[0097] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 58%, the degree of polymerization is 45, and the impedance is 1.69Ω; it has anti-fouling properties.

[0098] Example 7

[0099] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0100] (1) Preparation of raw materials;

[0101] Palladium catalyst: Palladium acetate;

[0102] Nitrogen-containing heterocyclic ligands:

[0103] Oxidizing agent: copper acetate;

[0104] Deprotonated ligand: cesium pivalate;

[0105] Solvent: N,N-dimethylformamide;

[0106] Aromatic hydrocarbons to be activated:

[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 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.

[0108] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 71%, the degree of polymerization is 88, and the impedance is 3.9Ω; it has anti-fouling properties.

[0109] Example 8

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

[0111] (1) Preparation of raw materials;

[0112] Palladium catalyst: Palladium acetate;

[0113] Nitrogen-containing heterocyclic ligands:

[0114] Oxidizing agent: copper acetate;

[0115] Deprotonated ligand: acetylglycine;

[0116] Solvent: N,N-dimethylformamide;

[0117] Aromatic hydrocarbons to be activated:

[0118] (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.

[0119] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 45%, the degree of polymerization is 21, and the impedance is 1.6Ω; it has anti-fouling properties.

[0120] Example 9

[0121] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0122] (1) Preparation of raw materials;

[0123] Palladium catalyst: Palladium acetate;

[0124] Nitrogen-containing heterocyclic ligands:

[0125] Oxidizing agent: copper acetate;

[0126] Deprotonated ligand: acetylglycine;

[0127] Solvent: N,N-dimethylformamide;

[0128] Aromatic hydrocarbons to be activated:

[0129] (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.

[0130] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 68%, the degree of polymerization is 38, and the impedance is 3.4Ω; it has anti-fouling properties.

[0131] Example 10

[0132] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0133] (1) Preparation of raw materials;

[0134] Palladium catalyst: Palladium acetate;

[0135] Nitrogen-containing heterocyclic ligands:

[0136] Oxidizing agent: Copper valerate;

[0137] Deprotonated ligand: acetylglycine;

[0138] Solvent: N,N-dimethylacetamide;

[0139] Aromatic hydrocarbons to be activated:

[0140] (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.

[0141] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 74%, the degree of polymerization is 49, and the impedance is 2.5Ω; it has anti-fouling properties.

[0142] Example 11

[0143] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0144] (1) Preparation of raw materials;

[0145] Palladium catalyst: Palladium chloride;

[0146] Nitrogen-containing heterocyclic ligands:

[0147] Oxidizing agent: copper chloride;

[0148] Deprotonated ligand: acetylglycine;

[0149] Solvent: N,N-dimethylacetamide;

[0150] Aromatic hydrocarbons to be activated:

[0151] (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.

[0152] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 90%, the degree of polymerization is 98, and the impedance is 1.9Ω; it has anti-fouling properties.

[0153] Example 12

[0154] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0155] (1) Preparation of raw materials;

[0156] Palladium catalyst: Palladium chloride;

[0157] Nitrogen-containing heterocyclic ligands:

[0158] Oxidizing agent: copper chloride;

[0159] Deprotonated ligand: acetylglycine;

[0160] Solvent: N,N-dimethylacetamide;

[0161] Aromatic hydrocarbons to be activated:

[0162] (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.

[0163] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 91%, the degree of polymerization is 78, and the impedance is 2.2Ω; it has anti-fouling properties.

[0164] Example 13

[0165] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0166] (1) Preparation of raw materials;

[0167] Palladium catalyst: Palladium acetate;

[0168] Nitrogen-containing heterocyclic ligands:

[0169] Oxidizing agent: copper acetate;

[0170] Deprotonated ligand: acetylglycine;

[0171] Solvent: N,N-dimethylformamide;

[0172] Aromatic hydrocarbons to be activated:

[0173] (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 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.

[0174] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 91%, the degree of polymerization is 49, and the impedance is 2.8Ω; it has anti-fouling properties.

[0175] Example 14

[0176] A method for preparing a polythiophene conjugated polymer, comprising the following specific steps:

[0177] (1) Preparation of raw materials;

[0178] Palladium catalyst: Palladium acetate;

[0179] Nitrogen-containing heterocyclic ligands:

[0180] Oxidizing agent: copper acetate;

[0181] Deprotonated ligand: acetylglycine;

[0182] Solvent: N,N-dimethylformamide;

[0183] Aromatic hydrocarbons to be activated:

[0184] (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.

[0185] The structural formula of the obtained polythiophene conjugated polymer is as follows: The yield is 87%, the degree of polymerization is 44, and the impedance is 3.1Ω; it has anti-fouling properties.

Claims

1. A low-resistance zwitterionic conductive polymer, characterized in that: Its repeating unit contains two independent zwitterionic groups; Its electrochemical impedance is significantly lower than that of conductive polymers that do not contain zwitterionic groups and conductive polymers that contain only one zwitterionic group in their repeating unit; Its ability to resist the adhesion of biomolecules, viruses, cells, bacteria, and fungi is significantly better than that of conductive polymers with only one zwitterionic group in repeating units; zwitterionic conductive polymers have a general structural formula The electrochemical impedance of its polymer is significantly lower than that of polymers without zwitterions. A repeating unit containing only one zwitterionic group and Where n is a natural number greater than 20; zwitterionic conductive polymers contain zwitterionic functionalized monomers. Where R1 and R2 are respectively , , , , and Any two mutually independent ones, where Y is , and In any of the following, x and y are integers, and 0 ≤ x ≤ 20, 0 ≤ y ≤ 20.

2. The method for preparing a low-resistance zwitterionic conductive polymer as described in claim 1, characterized in that: An anti-nonspecific adhesion polymer is synthesized in one step by direct arylation polymerization of aromatic hydrocarbons to be activated under the conditions of palladium catalyst, oxidant, solvent and nitrogen-containing heterocyclic ligand; the aromatic hydrocarbons to be activated are functionalized monomers containing double-chain zwitterionic functional groups.

3. The method for preparing a low-resistance zwitterionic conductive polymer according to claim 2, characterized in that, The reaction was carried out under an inert atmosphere at a temperature of 60–140 °C for 1–120 h.

4. The method for preparing a low-resistance zwitterionic conductive polymer according to claim 2, characterized in that, Nitrogen-containing heterocyclic ligands are R3 to R7 are each independently selected from one of hydrogen atom, alkyl, alkoxy, fluorine atom group, chlorine atom, cyano, nitro, dimethylamino and trifluoromethyl.

5. A method for preparing a low-resistance zwitterionic conductive polymer according to claim 2, characterized in that, 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.

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