A non-specific adhesion resistant conductive polymer and a method for preparing the same

Abstract

This invention relates to an anti-nonspecific adhesion conductive polymer and its preparation method. Under the conditions of a palladium catalyst, an alkaline salt, a solvent, and an arylphosphine ligand containing an electron-deficient group, the anti-nonspecific adhesion conductive polymer is synthesized in one step by direct arylification polymerization of an aromatic hydrocarbon to be activated and a haloaromatic hydrocarbon. The aromatic hydrocarbon to be activated is a functionalized monomer containing a zwitterionic functional group; the arylphosphine ligand containing an electron-deficient group is wherein R1-R3 are each independently selected from hydrogen atoms, fluorine atoms, and trifluoromethyl groups, and R1-R3 are not simultaneously hydrogen atoms; the structural formula of the obtained anti-nonspecific adhesion conductive polymer is a natural number n not less than 36. The preparation method provided by this invention is simple, rapid, and the functional groups have good stability during the reaction, making it suitable for industrial production. The anti-nonspecific adhesion conductive polymer of this invention has a high molecular weight, regular structure, and high yield, and has broad application prospects in the field of bioelectronic materials.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology and relates to an anti-nonspecific adhesion conductive polymer and its preparation method. Background Technology

[0002] Currently, most commercially available bioelectronic devices primarily use metals or inorganic semiconductors as electrode materials. Conductive polymers, due to their mechanical flexibility, high conductivity, and biocompatibility, are widely studied as next-generation implantable and wearable electronic materials. Conductive polymers, as implantable bioelectrode materials, possess characteristics such as low impedance, mixed ion-electron conductivity, and high capacitance. However, unmodified conductive 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. To eliminate this negative impact and enhance the biocompatibility of conductive polymers, introducing zwitterionic groups into the conductive polymer chain can effectively prevent fouling, improve water stability, and reduce the probability of inflammation, thereby solving the problem of non-specific protein adsorption. The mechanical flexibility and high conductivity of biomaterial conductive polymers correspond to the high molecular weight of the polymers.

[0003] Currently, the synthesis of poly(3,4-vinyldioxothiophene) (PEDOT) is typically achieved through electrochemical polymerization, oxidative polymerization, and transition metal-catalyzed polymerization. The development of PEDOT derivatives prepared by electrochemical and oxidative polymerization is limited by low yields, low molecular weights, poor solubility, poor machinability, and the inability to produce them on a large scale. Furthermore, complex reaction conditions can cause the bridging groups connecting the side groups to break, leading to a loss of the conductive polymer's resistance to non-specific adhesion and resulting in chronic immune reactions. For example, chemical bond breaking occurred in oxidative polymerization using ferric chloride as an oxidant, as described in reference 1 (Chemistry of Materials, 2022, 34, 2752-2763). 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. However, according to references 2 (Marcomolecules, 2012, 45, 7783-7790; Chemistry of materials, 2022, 34, 2752-2763), the degree of polymerization of PEDOT materials prepared using existing ligand selection methods is not high. The highest degree of polymerization measured by gel permeation chromatography is 27 (the degree of polymerization would be even lower if calculated using NMR). Furthermore, there are currently no reports on the synthesis of conductive polymers containing zwitterionic functional groups as side groups via direct arylation polymerization.

[0004] Therefore, the synthesis of high molecular weight conductive polymers containing zwitterionic functional groups via direct arylation polymerization is of great significance. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides an anti-nonspecific adhesion conductive polymer and its preparation method;

[0006] To achieve the above objectives, the present invention adopts the following solution:

[0007] A method for preparing an anti-nonspecific adhesion conductive polymer involves directly arylizing and polymerizing an aromatic hydrocarbon to be activated and a halogenated aromatic hydrocarbon in the presence of a palladium catalyst, an alkaline salt, a solvent, and an arylphosphine ligand containing an electron-deficient group to synthesize the anti-nonspecific adhesion conductive polymer in one step.

[0008] The aromatic hydrocarbon to be activated is a functionalized monomer containing zwitterionic functional groups;

[0009] Arylphosphine ligands containing electron-deficient groups are Among them, R1 to R3 are each independently selected from hydrogen atoms, fluorine atoms, and trifluoromethyl groups, and R1 to R3 are not all hydrogen atoms at the same time.

[0010] As a preferred technical solution:

[0011] In the preparation method of the conductive polymer against non-specific adhesion as described above, the molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt 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 the halogenated aromatic hydrocarbon is 0.001~1L / mol.

[0012] The preparation method of the conductive polymer against non-specific adhesion 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.

[0013] The method for preparing an anti-nonspecific adhesion conductive polymer as described above uses a functionalized monomer containing zwitterionic functional groups.

[0014] In the formula, R is Where Y is x and y are integers, and 0 ≤ x ≤ 20, 0 ≤ y ≤ 20.

[0015] As described above, in the preparation method of the conductive polymer with anti-non-specific adhesion, the halogenated aromatic hydrocarbon is a... The structure of Ar is a monomer with the following structure:

[0016] In the formula, R4 is methyl, methoxy, hydroxymethyl, hexafluoroisopropanol methyl, carboxymethyl, Any one of them.

[0017] In the preparation method of the conductive polymer against nonspecific adhesion as described above, the palladium catalyst is palladium acetate, palladium neopentanoate, or palladium chloride; the basic salt is potassium carbonate, cesium carbonate, potassium pivalate, potassium acetate, or cesium pivalate; and the solvent is N,N-dimethylformamide or N,N-dimethylacetamide.

[0018] This invention also provides an anti-nonspecific adhesion conductive polymer prepared by the method described in any of the preceding claims, characterized in that: the general structural formula of the anti-nonspecific adhesion conductive polymer is as follows:

[0019] Where n is a natural number not less than 36.

[0020] Invention principle:

[0021] The reaction mechanism of palladium-catalyzed direct arylation is as follows: Under the action of a palladium catalyst, the brominated aromatic hydrocarbon first undergoes oxidative addition, halogen removal to form a Pd-C bond, creating a stable intermediate. Subsequently, the activated aromatic hydrocarbon approaches this intermediate, the coordination bond between the carboxylate or carbonate ion and palladium is opened, the polymerization site moves closer to palladium, and the CH bond breaks, transferring a proton to the carboxylate or carbonate ion. Finally, the carbon-carbon coupling reaction is completed through reductive elimination. For divalent palladium catalysts, they typically exist in a four-coordinate form in the reaction system. The four ligands in the transition state are the oxidized aromatic hydrocarbon, the auxiliary ligand, the aromatic hydrocarbon to be activated, and the carboxylate / carbonate ligand.

[0022] Based on the experimental results of this invention, zwitterionic functional groups are stable in the reaction system of direct arylification polymerization. However, the most fundamental problem that urgently needs to be solved in preparing high-performance zwitterionic functionalized PEDOT polymers is the low efficiency of activating the α-site of EDOT polymerization units with commonly used ligands in existing technologies. Due to the electron-rich interaction of sulfur atoms and oxygen atoms at the β-site, the α-site of EDOT exhibits extremely strong nucleophilicity. Simultaneously, due to the limited number of empty orbitals surrounding palladium and the strong nucleophilicity of phosphorus atoms in phosphine ligands, the α-site of EDOT and the phosphine ligand cannot simultaneously complex with palladium, thus failing to efficiently activate the α-site of EDOT. Based on existing technologies, commonly used arylphosphine ligands and alkylphosphine ligands cannot meet the requirements for preparing zwitterionic functionalized PEDOT polymers. This invention, through density functional theory calculations, concludes that when the carboxylic acid / carbonic acid ligands and bromoaryles remain constant, phosphine ligands compete with the aromatic hydrocarbon to be activated for the remaining empty d orbitals of palladium; that is, the chelation effect of the two with palladium is inversely proportional to the relative strength of the ligands. Therefore, by introducing electron-deficient groups to weaken the nucleophilicity of phosphine ligands, the α-site reactivity of EDOT is effectively improved, which is beneficial for preparing high-molecular-weight zwitterionic functionalized PEDOT polymers. Based on the experimental results of this invention, arylphosphine ligands containing electron-deficient groups play a crucial role in activating EDOT derivatives.

[0023] Based on the existing direct arylation polymerization method, as described in reference 3 (Progress in Polymer Science, 2018, 83, 135–201), the auxiliary ligands are usually selected from two types: one is arylphosphine ligands (such as tri(2-methoxyphenyl)phosphine), and the other is alkylphosphine ligands (such as tri-tert-butylphosphine, tricyclohexylphosphine).

[0024] However, the use of arylphosphine ligands modified with electron-deficient groups (taking tris(pentafluorophenyl)phosphine as an example) has been rarely studied. As described in reference 4 (Journal of Organometallic Chemistry, 2015, 780, 63-69), when tris(pentafluorophenyl)phosphine is combined with palladium acetate, the phosphine spectrum shows that the chemical shift of phosphine does not change. Moreover, in the synthesis of the target product, tris(pentafluorophenyl)phosphine and the reaction conditions without the addition of additional ligands yield similar reaction results. The two reaction results prove that the ligand may not complex with palladium and thus promote the reaction. Therefore, phosphine ligands modified with electron-deficient groups have not been widely used in direct arylation polymerization.

[0025] Currently used arylphosphine ligands and alkylphosphine ligands suffer from reduced catalytic efficiency because the strong chelating ability of phosphine atoms prevents the α-position of EDOT from directly arylifying with palladium. Introducing electron-deficient groups into arylphosphine ligands weakens their chelating ability, promoting the bonding of the carbon atom at the α-position of the polymerization unit with palladium, thereby improving catalytic efficiency.

[0026] Furthermore, reference 5 (ACS catalysis, 2019, 9, 6921-6836) describes how, through quantitative calculations extending from the direct arylation reaction mechanism, the W in the metal-cooperative deprotonation step involving auxiliary ligands in the reaction transition state was calculated. Pd-C With W C-H Among them, W Pd-C The W represents the Weber bond sequence of the transition state chemical bond formed between the carbon atom at the activation site of the aromatic hydrocarbon and palladium. C-H This refers to 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. Based on experimental results and quantitative calculations, the inventors determined that in the synthesis of most PEDOT polymers, when W... Pd-C With W C-H When the sum of the two is not less than 0.75, the EDOT derivative monomer exhibits higher catalytic efficiency than existing technologies in the direct arylation polymerization system. That is, within a specified reaction time, the prepared zwitterionic conductive polymer has a higher yield and degree of polymerization.

[0027] The zwitterionic functional groups on the EDOT polymerization unit involved in this invention are These groups contain phosphine-oxygen double bonds, carbon-oxygen double bonds, and sulfur-oxygen double bonds, respectively. The lone pair of electrons on the oxygen atom readily complexes with palladium to form relatively stable complexes, and these complexes exhibit significant steric hindrance. For this reason, the electron-deficient arylphosphine ligands selected in this invention cannot have substituents at the ortho position of the phosphorus atom; that is, the ortho substituent can only be a hydrogen atom. Simultaneously, the calculation results of the transition state using this ligand simultaneously satisfy W...Pd-C +W C-H ≥0.75.

[0028] Reference 6 (Science, 2018, 362, 670–674) states that when the ortho-substituent of the phosphorus atom in an electron-deficient arylphosphine ligand is substituted, the pyramid angle of the ligand increases, thus increasing the steric hindrance of the phosphine ligand. This prevents the ligand from complexing with the polymer unit containing zwitterionic functional groups and palladium, and simultaneously releases the coordination bond between the zwitterionic functional group and palladium, leading to a decrease in catalytic efficiency. In other words, it is impossible to obtain a high-polymerization-degree, non-specific adhesion-resistant PEDOT conductive polymer. For example, in example 1, the electron-deficient arylphosphine ligand is P(C6F5)3, and the ortho-substituent of this ligand is a fluorine atom. Quantitative calculations yield W... Pd-C +W C-H =0.834, but this ligand cannot synthesize high-polymerization-degree, non-specific adhesion-resistant PEDOT conductive polymers; Example 2, electron-deficient arylphosphine ligands are W obtained through quantitative calculation Pd-C +W C-H =0.762, this ligand can be used to synthesize highly polymerized PEDOT conductive polymers with resistance to non-specific adhesion.

[0029] Therefore, based on quantitative calculations and experimental results, the arylphosphine ligand containing an electron-deficient group suitable for this invention was determined to be... R1 to R3 are each independently selected from hydrogen atoms, fluorine atoms, and trifluoromethyl groups, and R1 to R3 are not all hydrogen atoms at the same time (when R1 to R3 are all hydrogen atoms, the arylphosphine ligand is triphenylphosphine, and the calculated result WP of this ligand is...). d-C +W C-H =0.712, the conclusion does not meet the requirement of ≥0.750, therefore, R1~R3 are not all hydrogen atoms at the same time.

[0030] Beneficial effects

[0031] (1) The preparation method of the non-specific adhesion conductive polymer of the present invention is simple and fast, and the functional groups have good stability in the reaction, which is suitable for industrial production;

[0032] (2) The non-specific adhesion conductive polymer obtained by the present invention has a high molecular weight, regular structure and high yield, and has a wide application prospect in the field of bioelectronic materials. Attached Figure Description

[0033] Figure 1 The UV-Vis spectrum of an anti-nonspecific adhesion conductive polymer prepared in Example 1 is shown.

[0034] Figure 2 The image shows the proton NMR spectrum of a conductive polymer that resists non-specific adhesion, prepared in Example 1. Detailed Implementation

[0035] 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.

[0036] The testing or calculation methods involved in the embodiments are as follows:

[0037] W Pd-C With W C-H The 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 6-311G(d,p) basis set. The atomic charges and Weber bond order of the reaction transition state were calculated using Gaussian 09 (the input keywords were POP=NBORead,BNDIDX).

[0038] Degree of polymerization: The degree of polymerization of a polymer is determined by measuring the 1H NMR spectrum of the polymer. The ratio of the integral area of ​​the cycloalkyl group of the dioxane moiety on the PEDOT backbone to the integral area of ​​the 1H NMR spectrum of the terminal CH bond is then divided by the average number of hydrogen atoms in the cycloalkyl group of a single polymer unit.

[0039] Taking Example 1 as an example, the terminal peak (CH) position of the polymer is 6.55 ppm, and the chemical shift of the cycloalkyl group in the dioxane moiety connected to thiophene in the polymer is 3.87-4.60. The integral area ratio of the two is 1350:1. The number of C-H bonds in the cycloalkyl group of each polymerization unit is 3. Therefore, the degree of polymerization n = integral area of ​​cycloalkyl group / (3 * integral area of ​​terminal hydrogen group), and n is calculated to be 450.

[0040] Yield: Amount of polymer product obtained / Amount of aromatic hydrocarbon to be activated * 100.

[0041] Example 1

[0042] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0043] (1) Preparation of raw materials:

[0044] Palladium catalyst: Palladium acetate;

[0045] Alkaline salt: potassium carbonate;

[0046] Solvent: N,N-dimethylformamide;

[0047] Arylphosphine ligands containing electron-deficient groups:

[0048] Aromatic hydrocarbons to be activated:

[0049] Halogenated aromatics:

[0050] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.779, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0051] (2) In the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 120°C for 12 h to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0052] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt 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.

[0053] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 450; the yield was 86%.

[0054] like Figure 1 The ultraviolet spectrum shows that the polymer has a maximum absorption wavelength of 596 nm.

[0055] like Figure 2 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.

[0056] Example 2

[0057] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0058] (1) Preparation of raw materials:

[0059] Palladium catalyst: Palladium neopentanoate;

[0060] Basic salt: cesium carbonate;

[0061] Solvent: N,N-dimethylacetamide;

[0062] Arylphosphine ligands containing electron-deficient groups:

[0063] Aromatic hydrocarbons to be activated:

[0064] Halogenated aromatics:

[0065] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.786, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0066] (2) In the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 60°C for 1 h to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0067] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.05:0.1:6, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 1 L / mol.

[0068] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 36; the yield was 89%.

[0069] Example 3

[0070] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0071] (1) Preparation of raw materials:

[0072] Palladium catalyst: Palladium chloride;

[0073] Alkaline salt: Potassium pivalate;

[0074] Solvent: N,N-dimethylformamide;

[0075] Arylphosphine ligands containing electron-deficient groups:

[0076] Aromatic hydrocarbons to be activated:

[0077] Halogenated aromatics:

[0078] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.762, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0079] (2) In the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 140°C for 6 hours to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0080] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.2:0.5:10, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.01 L / mol.

[0081] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 56; the yield was 77%.

[0082] Example 4

[0083] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0084] (1) Preparation of raw materials:

[0085] Palladium catalyst: Palladium acetate;

[0086] Alkaline salt: potassium acetate;

[0087] Solvent: N,N-dimethylacetamide;

[0088] Arylphosphine ligands containing electron-deficient groups:

[0089] Aromatic hydrocarbons to be activated:

[0090] Halogenated aromatics:

[0091] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.779, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0092] (2) In the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 120°C for 24 h to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0093] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.1:0.5:1, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.5 L / mol.

[0094] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 91; the yield was 91%.

[0095] Example 5

[0096] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0097] (1) Preparation of raw materials:

[0098] Palladium catalyst: Palladium neopentanoate;

[0099] Basic salt: Cesium pivalate;

[0100] Solvent: N,N-dimethylformamide;

[0101] Arylphosphine ligands containing electron-deficient groups:

[0102] Aromatic hydrocarbons to be activated:

[0103] Halogenated aromatics:

[0104] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.786, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0105] (2) In the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 60°C for 48 h to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0106] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.1:0.2:5, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.8 L / mol.

[0107] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 38; the yield was 95%.

[0108] Example 6

[0109] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0110] (1) Preparation of raw materials:

[0111] Palladium catalyst: Palladium chloride;

[0112] Alkaline salt: potassium carbonate;

[0113] Solvent: N,N-dimethylacetamide;

[0114] Arylphosphine ligands containing electron-deficient groups:

[0115] Aromatic hydrocarbons to be activated:

[0116] Halogenated aromatics:

[0117] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.762, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0118] (2) In the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 140°C for 120 h to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0119] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.1:0.2:5, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.75 L / mol.

[0120] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 210; the yield was 89%.

[0121] Example 7

[0122] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0123] (1) Preparation of raw materials:

[0124] Palladium catalyst: Palladium acetate;

[0125] Alkaline salt: potassium acetate;

[0126] Solvent: N,N-dimethylformamide;

[0127] Arylphosphine ligands containing electron-deficient groups:

[0128] Aromatic hydrocarbons to be activated:

[0129] Halogenated aromatics:

[0130] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.779, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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 an Ar atmosphere, in the presence of a palladium catalyst, an alkaline salt, a solvent and an arylphosphine ligand containing an electron-deficient group, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 120°C for 6 hours to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0132] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.1:0.2:5, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.075 L / mol.

[0133] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 140; the yield was 84%.

[0134] Example 8

[0135] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0136] (1) Preparation of raw materials:

[0137] Palladium catalyst: Palladium neopentanoate;

[0138] Basic salt: Cesium pivalate;

[0139] Solvent: N,N-dimethylacetamide;

[0140] Arylphosphine ligands containing electron-deficient groups:

[0141] Aromatic hydrocarbons to be activated:

[0142] Halogenated aromatics:

[0143] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.786, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0144] (2) In the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 60°C for 12 h to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0145] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.1:0.2:5, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.5 L / mol.

[0146] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 158; the yield was 92%.

[0147] Example 9

[0148] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0149] (1) Preparation of raw materials:

[0150] Palladium catalyst: Palladium chloride;

[0151] Alkaline salt: potassium carbonate;

[0152] Solvent: N,N-dimethylformamide;

[0153] Arylphosphine ligands containing electron-deficient groups:

[0154] Aromatic hydrocarbons to be activated:

[0155] Halogenated aromatics:

[0156] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.762, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0157] (2) In the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 140°C for 72 h to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0158] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.1:0.2:5, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.5 L / mol.

[0159] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 99; the yield was 91%.

[0160] Example 10

[0161] A method for preparing a conductive polymer that resists non-specific adhesion, comprising the following steps:

[0162] (1) Preparation of raw materials:

[0163] Palladium catalyst: Palladium chloride;

[0164] Alkaline salt: potassium carbonate;

[0165] Solvent: N,N-dimethylformamide;

[0166] Arylphosphine ligands containing electron-deficient groups:

[0167] Aromatic hydrocarbons to be activated:

[0168] Halogenated aromatics:

[0169] The reaction transition state of the metal-cooperative deprotonation step involving phosphine ligands was calculated using density functional theory, and the calculated W... Pd-C With W C-H The sum is 0.779, where W Pd-C The W represents the Weber bond sequence of the transition state chemical 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.

[0170] (2) In a He atmosphere, in the presence of palladium catalyst, basic salt, solvent and arylphosphine ligand containing electron-deficient groups, the aromatic hydrocarbon to be activated and the halogenated aromatic hydrocarbon were directly arylated and polymerized at 140°C for 24 h to synthesize an anti-nonspecific adhesion conductive polymer in one step.

[0171] The molar ratio of the aromatic hydrocarbon to be activated, the halogenated aromatic hydrocarbon, the palladium catalyst, the arylphosphine ligand containing an electron-deficient group, and the basic salt is 1:1:0.1:0.2:5, and the volume ratio of the solvent to the molar number of halogenated aromatic hydrocarbons is 0.5 L / mol.

[0172] The structural formula of the obtained conductive polymer against non-specific adhesion is as follows: The degree of polymerization was 138; the yield was 88%.

Claims

1. A method of preparing an antinon-specific adhesion conductive polymer, characterized by: The non-specific adhesion resistant conductive polymer is synthesized by direct arylization polymerization of an activated aromatic hydrocarbon and a halogenated aromatic hydrocarbon in the presence of a palladium catalyst, a basic salt, a solvent and an electron-deficient group-containing aryl phosphine ligand; The activated aromatic hydrocarbon is a functional monomer containing a zwitterionic functional group; Functionalized monomers containing zwitterionic functionality are wherein R is wherein Y is x, y are integers and 0 < x < 20, 0 < y < 20; The aryl phosphine ligand containing an electron-deficient group is wherein R1 to R3 are each independently selected from a hydrogen atom, a fluorine atom, a trifluoromethyl group, and R1 to R3 are not simultaneously a hydrogen atom.

2. The method for preparing an anti-nonspecific adhesion conductive polymer according to claim 1, characterized in that, The molar ratio of the activated aromatic hydrocarbon, the halogenated aromatic hydrocarbon, the palladium catalyst, the electron-deficient group-containing aryl phosphine ligand and the basic salt is 1:1:0.01-0.2:0.02-0.5:1-10, and the volume ratio of the solvent to the moles of the halogenated aromatic hydrocarbon is 0.001-1 L / mol.

3. The method for preparing an anti-nonspecific adhesion conductive polymer according to claim 1, characterized in that, The reaction is carried out under an inert atmosphere, the reaction temperature is 60-140 ℃, and the reaction time is 1-120 h.

4. The method for preparing an anti-nonspecific adhesion conductive polymer according to claim 1, characterized in that, Haloarenes are monomers having the structure Ar has the structure wherein R4is methyl, methoxy, hydroxymethyl, hexafluoroisopropyl alcohol methyl, carboxymethyl, any one of the following:

5. The method for preparing an anti-nonspecific adhesion conductive polymer according to claim 4, characterized in that, The palladium catalyst is palladium acetate, palladium pivalate or palladium chloride, the basic salt is potassium carbonate, cesium carbonate, potassium pivalate, potassium acetate or cesium pivalate, and the solvent is N,N-dimethylformamide or N,N-dimethylacetamide.

6. A method of preparing an antinon-specific adhesion conductive polymer according to claim 4 or 5, characterized in that: The general structure of the anti-non-specific adhesion conductive polymer is In the formula, n is a natural number not less than 36.

Images