CN115124650A

CN115124650A - Intrinsic conductive high polymer material, preparation method and application

Info

Publication number: CN115124650A
Application number: CN202211068788.0A
Authority: CN
Inventors: 王震宇; 李江波
Original assignee: Institute of Corrosion Science and Technology
Current assignee: Institute of Corrosion Science and Technology
Priority date: 2022-09-02
Filing date: 2022-09-02
Publication date: 2022-09-30

Abstract

The application discloses an intrinsic conductive high polymer material, a preparation method and application thereof, and belongs to the field of conductive high polymer materials. An intrinsic conductive polymer material comprises a conductive polymer-modified dopamine-organic sulfonate copolymer; the conductive polymer-modified dopamine-organic sulfonate copolymer contains an aliphatic chain structure, a hydroxyl group and a benzene ring group; the conductive polymer is at least one selected from polyethylene dioxythiophene, polyaniline and polypyrrole; the modified dopamine contains a dihydroxy group and a benzene ring group; the organic sulfonate is sulfonate polyanion containing an aliphatic chain structure. The material has excellent dispersibility and chemical stability in aqueous solution, the adhesive force on the surface of low-surface-energy materials such as PET (polyester resin) and the like can reach more than 1.5 MPa, the electric conductivity can reach 2.5S/cm, and the material can still keep good electric conductivity in the deformation process.

Description

Intrinsic conductive high polymer material, preparation method and application

Technical Field

The application relates to an intrinsic conductive polymer material, a preparation method and application thereof, belonging to the field of conductive polymer materials.

Background

At present, conductive polymer materials have been widely used in the fields of electronics, electric power, communication, energy, chemical industry, aerospace, and the like, and are considered to be one of the most promising polymer materials. For example, the conductive polymer packaging material in the electronic industry has the advantages of low interconnection temperature, high bonding strength, good flexibility, high packaging resolution, low cost, printing, environmental friendliness and the like, and has great application potential in the field of flexible electronics such as printed RFID, flexible printed circuits and stretchable sensors. The conductive polymer grounding material in the power industry can fundamentally solve the problem of easy corrosion of the traditional metal grounding material and realize the full-life cycle service of a grounding system. The conductive polymer electromagnetic shielding material in the communication industry has the advantages of good electromagnetic shielding performance, light weight, easy forming, high production efficiency and the like. In recent years, with the continuous development of new industries such as intelligent manufacturing and new energy, higher and more recent requirements are also put on the performance of conductive materials.

However, the conventional conductive polymer material is usually a composite composed of an organic matrix and a conductive filler, the organic matrix provides mechanical properties, adhesion properties, and the like, and the conductive filler provides conductivity for the organic matrix, which play their respective roles. In the practical application process, the conductive polymer material is subjected to various environmental tests, and the proportion of the polymer matrix in the conductive composite material cannot be greatly reduced only for the requirement of the conductive performance. When the conductive material is applied to fields with higher reliability requirements, the consumption of high polymer materials is increased and the conductive performance is sacrificed. In addition, for some electronic materials with drastically changed volume (charge and discharge, mechanical action, etc.), the conductive particles are easily squeezed apart and lose effective electronic contact, resulting in collapse of the whole conductive network structure and reduced conductivity. In addition, the conductive particles are easy to agglomerate in the organic matrix and difficult to disperse, and the conductivity of the conductive polymer material is also seriously influenced. Therefore, a novel material capable of replacing the conventional composite conductive polymer material is sought, which has important significance for solving the problems of conductive particle dispersibility, conductive performance, good mechanical performance, conductive stability improvement and the like, and is also a difficult problem to be broken through urgently in the current conductive polymer material.

Intrinsic conductive polymer materials (polyacetylene, polythiophene, polyaniline, polypyrrole, poly (3, 4-ethylenedioxythiophene), etc.) have been widely used in recent years as they have a special pi-pi conjugated structure, regular chain orientation and excellent physicochemical properties. For example, patent CN114032688A discloses a method for preparing an intrinsically stretchable conductive polymer material by depositing polypyrrole on the surface of an elastic material, which solves the problem of conductivity reduction of a conductive polymer composite material under stretching. Patent CN103396500A also discloses a natural polymer derivative-conductive polymer aqueous composite binder, which is prepared by physically mixing a water-soluble natural polymer derivative (chitosan derivative, etc.) and a water-soluble conductive polymer (poly (3, 4-ethylenedioxythiophene), polyaniline, polypyrrole), so as to overcome the disadvantages of poor wettability and easy agglomeration and dispersion of conductive particles, and significantly improve the coulombic efficiency and the cycling stability of the electrode material.

Disclosure of Invention

According to one aspect of the application, an intrinsic conductive polymer material is provided, and the intrinsic conductive polymer material is obtained by two-step polymerization reaction of a double-bond graft modified dopamine monomer, a double-bond containing organic sulfonate monomer and a conductive polymer monomer. The polymer material is endowed with good bonding performance by the dihydroxyl group in the dopamine structure, excellent flexibility and doping effect are simultaneously endowed by the polyanion structure, and good conductivity is endowed by the conductive polymer group. In addition, the benzene ring group in the dopamine structure further strengthens the electron transfer rate of the pi-pi conjugated structure, and further improves the conductivity of the material. The conductive material has excellent dispersibility and chemical stability in aqueous solution, the adhesive force on the surface of low-surface-energy materials such as PET (polyester resin) and the like can reach more than 1.5 MPa, the conductivity can reach 2.5S/cm, and the conductive performance can still be kept well in the deformation process.

An intrinsic conductive polymer material comprises a conductive polymer-modified dopamine-organic sulfonate copolymer;

the conductive polymer-modified dopamine-organic sulfonate copolymer contains an aliphatic chain structure, a hydroxyl group and a benzene ring group;

the conductive high molecular monomer is selected from at least one of polyethylene dioxythiophene, polyaniline and polypyrrole;

the modified dopamine contains a dihydroxy group and a benzene ring group;

the organic sulfonate is sulfonate polyanion containing an aliphatic chain structure.

Alternatively, the hydroxyl group is a phenolic hydroxyl group.

According to a second aspect of the present application, there is provided a method of preparing an intrinsically conductive polymeric material.

A method for preparing an intrinsic conductive polymer material comprises the following steps:

s1, reacting a mixture containing modified dopamine, an organic sulfonate comonomer, an initiator I and a solvent I to obtain a modified dopamine-organic sulfonate copolymer;

s2, reacting the mixture containing the modified dopamine-organic sulfonate copolymer, the conductive polymer monomer, the initiator II, the catalyst and the solvent II to obtain the conductive polymer-modified dopamine-organic sulfonate copolymer.

Optionally, in step S1, the modified dopamine is phenolic hydroxyl silanized protected acrylic modified dopamine.

Optionally, in step S1, the initiator i is an oil-soluble initiator.

Optionally, in step S1, the initiator i is at least one selected from azobisisobutyronitrile, azobisisoheptonitrile, and benzoyl peroxide.

Optionally, in step S1, the solvent i is a mixed solvent.

Optionally, in step S1, the solvent i is prepared from water and dioxane in a volume ratio of 1:1, preparation.

Optionally, in step S1, the organic sulfonate comonomer is selected from at least one of 3-sulfopropyl methacrylate potassium salt, 2-acrylamido-2-methyl-1-propanesulfonic acid.

Optionally, in step S1, the mass ratio of the modified dopamine to the organic sulfonate comonomer is 0.16 to 0.66.

Optionally, the mass ratio of the modified dopamine to the organosulfonate comonomer is independently selected from any of 0.16, 0.26, 0.36, 0.46, 0.56, 0.66, or a range between any two.

Optionally, in step S1, the mass ratio of the modified dopamine to the initiator i is 10 to 40.

Optionally, the mass ratio of the modified dopamine to the initiator i is independently selected from any of 10, 15, 20, 25, 30, 35, 40 or a range between any two.

Optionally, in step S1, the ratio of the mass of the modified dopamine to the volume of the solvent i is 0.05 g/mL to 0.2 g/mL.

Optionally, the ratio of the mass of the modified dopamine to the volume of the solvent I is independently selected from any of 0.05 g/mL, 0.07 g/mL, 0.09 g/mL, 0.11 g/mL, 0.13 g/mL, 0.15 g/mL, 0.17 g/mL, 0.19 g/mL, 0.2 g/mL, or a range between any two.

Alternatively, in step S1, the conditions for reaction i are as follows:

the temperature is 50-75 ℃;

the time is 12-20 h.

Optionally, the temperature is independently selected from any value of 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, or a range value between any two.

Optionally, the time is independently selected from any of 12 h, 14 h, 16 h, 18h, 20 h, or a range of values between any two.

Alternatively, in step S1, reaction i is carried out under a protective atmosphere.

Optionally, in step S1, the protective atmosphere is selected from at least one of nitrogen, argon, and neon.

Optionally, in step S1, before the reaction i, oxygen in the mixed solution is removed;

and (4) after the reaction I, dialyzing and drying to obtain a product.

Optionally, in step S2, the conductive polymer monomer is 3, 4-ethylenedioxythiophene.

Optionally, in step S2, the initiator ii is a peroxide initiator.

Optionally, in step S2, the initiator ii is at least one selected from potassium persulfate and ammonium persulfate.

Optionally, in step S2, the catalyst is hydrated iron sulfate.

Optionally, in step S2, the solvent ii is water.

Optionally, in step S2, the mass ratio of the modified dopamine-organic sulfonate copolymer to the conductive polymer monomer is 2 to 32.

Optionally, the mass ratio of the modified dopamine-organic sulfonate copolymer to the conductive polymeric monomer is independently selected from any of 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32 or a range between any two thereof.

Optionally, in step S2, the mass ratio of the modified dopamine-organic sulfonate copolymer to the initiator ii is 1 to 10.

Optionally, the mass ratio of the modified dopamine-organic sulfonate copolymer to the initiator ii is independently selected from any of 1, 2, 3,4, 5, 6, 7, 8, 9, 10 or a range between any two.

Optionally, in step S2, the mass ratio of the modified dopamine-organic sulfonate copolymer to the catalyst is 20 to 800.

Optionally, the mass ratio of the modified dopamine-organic sulfonate copolymer to the catalyst is independently selected from any of 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 250, 350, 450, 550, 650, 750, 800 or a range of values between any two.

Optionally, in step S2, the ratio of the mass of the modified dopamine-organic sulfonate copolymer to the volume of the solvent ii is 0.05 g/mL-0.15 g/mL.

Optionally, the ratio of the mass of the modified dopamine-organic sulfonate copolymer to the volume of the solvent II is independently selected from any of 0.05 g/mL, 0.07 g/mL, 0.09 g/mL, 0.11 g/mL, 0.13 g/mL, 0.15 g/mL or a range between any two.

Alternatively, in step S2, the conditions for reaction ii are as follows:

the temperature is 2-10 ℃;

the time is 16-48 h.

Optionally, the temperature is independently selected from any value of 2 ℃, 3 ℃,4 ℃, 5 ℃, 6 ℃, 7 ℃,8 ℃, 9 ℃, 10 ℃ or a range value between any two.

Optionally, the time is independently selected from any of 16 h, 18h, 20 h, 22 h, 24h, 26 h, 28h, 30 h, 32 h, 34 h, 36 h, 38h, 40 h, 42 h, 44 h, 46 h, 48h, or a range of values between any two.

Alternatively, reaction II is carried out with stirring.

Optionally, the stirring speed is 800 r/min-1000 r/min.

Optionally, the stirring speed is independently selected from any of 800 r/min, 850 r/min, 900 r/min, 950 r/min, 1000 r/min, or a range between any two.

Alternatively, reaction II is carried out under a protective atmosphere.

Optionally, the protective atmosphere is selected from at least one of nitrogen, argon, neon.

Optionally, before the initiator II and the catalyst are added, removing oxygen in the mixture and cooling to 2-10 ℃.

Optionally, after the reaction II, dialyzing and drying to obtain the product.

Optionally, the preparation method of the modified dopamine comprises acrylic acid modification and phenolic hydroxyl silanization protection.

Optionally, the preparation method of the modified dopamine comprises the following steps:

a1, adjusting the pH of a mixture containing dopamine, borate and water, and mixing to obtain a first mixed solution;

a2, adding a mixture containing methacryloyl chloride into the first solution, adjusting the pH, and mixing to obtain acrylic acid modified dopamine;

a3, mixing a mixture containing acrylic acid modified dopamine, tert-butylchlorosilane, an organic solvent and 1, 8-diazabicyclo [5.4.0] undec-7-ene to obtain the modified dopamine.

Optionally, in step a1, the dopamine is levodopa.

Optionally, in step a1, the borate is sodium tetraborate decahydrate.

Optionally, in the step A1, the mass ratio of the dopamine to the borate is 0.16-1.5.

Optionally, the mass ratio of dopamine to borate is independently selected from any of 0.16, 0.17, 0.18, 0.19, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.10, 1.20, 1.30, 1.40, 1.50, or a range between any two.

Optionally, in the step A1, the ratio of the mass of the dopamine to the volume of the water is 0.01-0.03 g/mL.

Optionally, in the step A1, sodium carbonate is added to adjust the pH value to 9-10.

Optionally, in step a1, the mixing is performed under a protective atmosphere.

Optionally, in step a1, the protective atmosphere is selected from at least one of nitrogen, argon, neon.

Optionally, in the step A1, the mixing time is 40-60 min.

Optionally, in step a2, the ratio of the mass of methacryloyl chloride to the volume of the first solution is 0.005 g/mL to 0.02 g/mL.

Alternatively, the mass of methacryloyl chloride to volume ratio of the first solution is independently selected from any of 0.005 g/mL, 0.006 g/mL, 0.007 g/mL, 0.008 g/mL, 0.009 g/mL, 0.010 g/mL, 0.011 g/mL, 0.012 g/mL, 0.013 g/mL, 0.014 g/mL, 0.015 g/mL, 0.016 g/mL, 0.017 g/mL, 0.018 g/mL, 0.019 g/mL, 0.020 g/mL, or a range of values therebetween.

Optionally, in the step A2, cooling to 0 ℃, and adding sodium carbonate to adjust the pH value to 9-10.

Alternatively, in step a2, the mixing is performed at room temperature under a protective atmosphere.

Optionally, in step a2, the protective atmosphere is selected from at least one of nitrogen, argon, neon.

Optionally, in the step A2, the mixing time is 3-4 h.

Optionally, in step a2, after mixing, the pH is adjusted to 2 or less, and the acrylic acid modified dopamine is obtained after extraction, washing and drying.

Optionally, in the step A3, the mass ratio of the acrylic modified dopamine to the tert-butyl chlorosilane is 0.1-2.

Alternatively, the mass ratio of the acrylic modified dopamine, the t-butylchlorosilane is independently selected from any value of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 or a range between any two.

Optionally, in the step A3, the mass ratio of the acrylic modified dopamine to the 1, 8-diazabicyclo [5.4.0] undec-7-ene is 0.15-2.

Alternatively, the mass ratio of the acrylic modified dopamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene is independently selected from any of 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.10, 1.20, 1.30, 1.40, 1.50, 1.60, 1.70, 1.80, 1.90, 2.00 or a range of values therebetween.

Optionally, in the step A3, the ratio of the mass of the acrylic modified dopamine to the volume of the organic solvent is 0.05 g/mL-2 g/mL.

Alternatively, the mass to volume ratio of the acrylic-modified dopamine to the organic solvent is independently selected from the group consisting of 0.05 g/mL, 0.07 g/mL, 0.09 g/mL, 0.11 g/mL, 0.13 g/mL, 0.15 g/mL, 0.17 g/mL, 0.19 g/mL, 0.2 g/mL, 0.30 g/mL, 0.40 g/mL, 0.50 g/mL, 0.60 g/mL, 0.70 g/mL, 0.80 g/mL, 0.90 g/mL, 1.00 g/mL, 1.10 g/mL, 1.20 g/mL, 1.30 g/mL, 1.40 g/mL, 1.50 g/mL, 1.60 g/mL, 1.70 g/mL, 1.80 g/mL, 1.90 g/mL, 2.00 g/mL, or a range between any two.

Alternatively, in step a3, the organic solvent is acetonitrile.

Alternatively, in step a3, the mixing is performed at room temperature under a protective atmosphere.

Optionally, in step a3, the protective atmosphere is selected from at least one of nitrogen, argon, neon.

Optionally, in the step A3, the mixing time is 15-20 h.

According to a third aspect of the present application, there is provided a use of an intrinsically conductive polymer material.

The intrinsic conductive polymer material or the intrinsic conductive polymer material prepared by the preparation method is applied to the fields of electric grounding materials, microelectronic assembly and electromagnetic shielding.

Optionally, the method comprises the following steps:

mixing the intrinsic conductive high polymer material and water according to the mass ratio of 1: 18-40 to obtain a bonding solution;

and coating the bonding liquid on the interface.

In order to achieve the purpose, the invention adopts the technical scheme that:

an intrinsic conductive polymer material is characterized in that the intrinsic conductive polymer material is prepared by polymerizing acrylic acid modified dopamine protected by phenolic hydroxyl silanization, an organic sulfonate comonomer and a conductive polymer monomer in two steps, and the preparation method of the intrinsic conductive polymer material comprises the following steps:

the first step is as follows: 2-4 parts of acrylic acid modified dopamine protected by phenolic hydroxyl silanization, 6-12 parts of organic sulfonate comonomer and 0.1-0.2 part of oil-soluble initiator are dissolved in 20-40 parts of deionized water/dioxane (volume ratio is 1: 1) solution. Stirring for 15-30 min under the protection of nitrogen (with the purity of 99.99%) to expel oxygen in the solution to obtain a first-step solution;

the second step is that: heating the first-step solution to 65 DEG ^o C, after stirring for 16 hours under the nitrogen protection atmosphere, pouring the obtained solution into a dialysis bag (section)Molecular weight cut off 10 kD). The dialysis bag was placed in ethanol for dialysis, and the ethanol solution was changed every 3h and repeated 4 times. And finally, placing the dialysis bag in deionized water for dialysis for 4 times, and freeze-drying to obtain a white polymer sample, namely the modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization.

The third step: adding 2-8 parts of the obtained phenolic hydroxyl silanization protected acrylic acid modified dopamine-organic sulfonate copolymer and 0.25-1 part of conductive high molecular monomer into 60-80 parts of deionized water, stirring for 20min under the protection of nitrogen (with the purity of 99.99%) to remove oxygen in the solution, and reducing the temperature of the mixed solution to 4 DEG C ^o And C, obtaining a third step mixed solution.

The fourth step: and adding 0.75-2 parts of peroxide initiator and 0.01-0.1 part of catalyst into the mixed solution in the third step, and then, continuously and violently stirring for 24 hours under the nitrogen protection atmosphere at the stirring speed of 800-1000 r/min. The resulting solution was poured into dialysis bags (cut-off molecular weight 1 kD) and stirred under nitrogen for 24 h. The resulting solution was poured into dialysis bags and dialyzed against deionized water for 24 h. After concentrated brine (concentration: 1mol/L, volume ratio to the polymer solution after dialysis is 1: 1) was added to the polymer solution obtained by dialysis, the mixture was poured into a dialysis bag (cut-off molecular weight: 10 kD) again, and dialyzed in ethanol and deionized water successively for 4 times, each for 3 hours. And finally, freeze drying to obtain the intrinsic conductive polymer material.

Further, the acrylic acid modified dopamine protected by phenolic hydroxyl silanization is prepared from levodopa, sodium tetraborate decahydrate, sodium carbonate, methacryloyl chloride and tert-butyldimethylchlorosilane, and comprises the following specific steps:

the first step is as follows: dissolving 1-3 g of levodopa (L-DOPA) and 2-6 g of sodium tetraborate decahydrate in 100 g of deionized water, and stirring for 20-30 min under the protection of nitrogen (with the purity of 99.99%) to expel oxygen to obtain a uniform and well-dispersed first-step solution;

the second step is that: adding 1.5-3 g of sodium carbonate into the solution in the first step, adjusting the pH value to 9-10, and continuing to add nitrogen gas (f)Purity 99.99%) for 20-30 min under the protective atmosphere, and cooling to 0 deg.C ^o C, obtaining a second-step mixed solution;

the third step: dropwise adding 1-2 g of methacryloyl chloride into the mixed solution obtained in the second step, adding 0.5-3 g of sodium carbonate after completely dropwise adding to adjust the pH value of the solution to 9-10, transferring to room temperature, and continuously stirring for 2 hours under the atmosphere of nitrogen (with the purity of 99.99%) to obtain a mixed solution obtained in the third step;

the fourth step: concentrated hydrochloric acid (concentration: 1 mol/L) was added to the mixture in the third step to adjust the pH of the solution to 2 or less, and extraction was performed with an ethyl acetate solution to obtain an organic layer. Washing the organic layer by hydrochloric acid (0.1 mol/L) and saline water in sequence, adding anhydrous magnesium sulfate for drying, and finally distilling to remove the solvent to obtain the acrylic acid modified dopamine;

the fifth step: adding 0.5-2 g and 1-4 g of the prepared acrylic acid modified dopamine solution into 10 ml of acetonitrile solution, and stirring to obtain a uniform and well-dispersed solution in the fifth step;

and a sixth step: cooling the solution of the fifth step to 0 ^o C, maintaining for 30 min, and then dropwise adding 1-3 g of 1, 8-diazabicyclo [5.4.0]Stirring undec-7-ene (DBU) for 4h, transferring to room temperature, and continuously stirring for 18h to obtain a mixed solution in the sixth step;

the seventh step: and (3) sequentially passing the mixed solution obtained in the sixth step through dichloromethane and a 2% v/v ethanol-dichloromethane chromatographic column for purification, and finally evaporating to obtain light yellow viscous powder, namely the acrylic acid modified dopamine protected by phenolic hydroxyl silanization.

Further, the organic sulfonate comonomer is one or a mixture of two of 3-propyl methacrylate potassium sulfonate and 2-acrylamido-2-methyl-1-propane sulfonic acid.

Further, the oil-soluble initiator is one or a mixture of azodiisobutyronitrile, azodiisoheptonitrile and benzoyl peroxide.

Further, the conductive polymer monomer is one or more of thiophene, aniline and pyrrole monomers. Preferably, the conductive polymer monomer is 3, 4-Ethylenedioxythiophene (EDOT).

Further, the peroxide initiator is one or a mixture of two of potassium persulfate and ammonium persulfate, and the catalyst is ferric sulfate hydrate.

The invention also provides the application of the intrinsic conductive polymer material, and the intrinsic conductive polymer material can be applied to electric power grounding materials (such as novel grounding materials, interface packaging products of grounding materials and surface anti-corrosion protection layers), microelectronic assembly (such as thin wires and printed circuits, electroplating chassis and metal chassis), electromagnetic shielding fields (such as replacement of conductive cloth or conductive cotton) and the like.

The invention also provides an application method of the intrinsic conductive polymer material in the field of ground material interface packaging, wherein 1 part of the intrinsic conductive polymer material is added into 18-40 parts of deionized water, and the intrinsic conductive polymer solution is prepared by fully dissolving the intrinsic conductive polymer material for 24-48 hours at room temperature. When in use, the intrinsic conductive polymer solution can be coated on a part needing an interface, and the excellent sealing effect and the excellent conductive function can be achieved after curing for 24h at room temperature, or the intrinsic conductive polymer solution can be injected into a special interface mould and cured for 24h at room temperature, an intrinsic conductive polymer sealing layer with good conductive performance can be formed at the interface part, and the intrinsic conductive polymer sealing layer has good bonding effect with a polymer on the surface of an original grounding material

The beneficial effect that this application can produce includes:

1) according to the intrinsic conductive polymer material provided by the application, the dihydroxyl group in the dopamine structure of the material endows the polymer material with good adhesive property, and even on the surface of a low-surface-energy material such as PET (polyethylene terephthalate), the intrinsic conductive polymer material has excellent adhesive property. Meanwhile, the benzene ring structure in the dopamine structure strengthens the electron transfer rate of a pi-pi conjugated structure, and further improves the conductivity of the material; the material uses the existing water-soluble high-conductivity PEDOT: structure design in the PSS material technology. On the basis, the modified dopamine-organic sulfonate copolymer is used for replacing a sodium polystyrene sulfonate (PSS) structure, so that the conductive polymer material is endowed with excellent adhesive property. Furthermore, sulfonate polyanion containing an aliphatic chain structure is selected to replace sodium polystyrene sulfonate containing benzene rings, so that the conductive polymer material has better flexibility. The sulfonate also plays a role in doping, so that a doping agent is not required to be additionally introduced in the preparation process of the conductive polymer; the intrinsic conductive polymer material overcomes the problem that conductive particles are difficult to agglomerate and uniformly disperse in the traditional conductive composite material, realizes uniform distribution of conductive phases, can ensure efficient transmission of electrons in the material, and has excellent conductive stability.

2) The intrinsic conductive polymer material provided by the application has excellent dispersibility and chemical stability in aqueous solution, the adhesion force on the surface of low-surface-energy materials such as PET (polyester resin) and the like can reach more than 1.5 MPa, the conductivity can reach 2.5S/cm, and good conductivity can be still maintained in the deformation process.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials and catalysts in the examples of the present application were purchased commercially.

The analysis method in the examples of the present application is as follows:

conductivity analysis was performed using an RTS-9 four-probe tester.

And (5) analyzing the bonding strength by using a small universal test tensile machine.

Example 1

(1) Preparation of acrylic modified dopamine protected by phenolic hydroxyl silanization

Dissolving 1.2 g of levodopa (L-DOPA) and 2.6 g of sodium tetraborate decahydrate in 100 g of deionized water, and stirring for 20min under the protection of nitrogen (with the purity of 99.99%) to expel oxygen; adding 1.75 g of sodium carbonate into the solution, adjusting the pH value to 9-10, continuously stirring for 20min under the nitrogen protection atmosphere, and cooling to the solution temperature of 0 ^o C; dropwise adding 1.4 g of methacryloyl chloride into the solution, adding 1.3 g of sodium carbonate after complete dropwise addition to adjust the pH of the solution to 9-10, and transferringCooling to room temperature, and continuously stirring for 2 hours in a nitrogen atmosphere; to the above solution was added concentrated hydrochloric acid (concentration: 1 mol/L) to adjust the pH of the solution to 2 or less, and extraction was performed with an ethyl acetate solution to obtain an organic layer. Washing the organic layer with hydrochloric acid (0.1 mol/L) and brine in sequence, adding anhydrous magnesium sulfate, drying, and distilling to remove the solvent to obtain the acrylic acid modified dopamine; adding 0.75 g and 2g of the prepared acrylic acid modified dopamine solution into 10 ml of acetonitrile solution, fully dissolving, and cooling to 0 ^o C, keeping for 30 min, and then dropwise adding 1.8 g of 1, 8-diazabicyclo [ 5.4.0%]Undec-7-ene (DBU), stirring for 4h, transferring to room temperature, and continuing stirring for 18 h; and finally, purifying the obtained mixed solution by sequentially passing through dichloromethane and a 2% v/v ethanol-dichloromethane chromatographic column, and finally evaporating to obtain light yellow viscous powder, namely the acrylic acid modified dopamine protected by phenolic hydroxyl silanization.

(2) Preparation of intrinsic conductive polymer material

2.1 g of phenolic hydroxyl silanized protected acrylic modified dopamine, 7 g of 3-sulfopropyl methacrylate potassium salt and 0.12 g of azobisisobutyronitrile were dissolved in 25 g of deionized water/dioxane (volume ratio 1: 1) solution. Stirring for 20min under the protection of nitrogen (purity 99.99%) to remove oxygen in the solution; heating the solution to 65 DEG ^o And C, continuously stirring for 16 hours under the nitrogen protection atmosphere, pouring into a dialysis bag (with the molecular weight cut off being 10 kD), placing into ethanol for dialysis, and replacing the ethanol solution every 3 hours and repeating for 4 times. Finally, placing the dialysis bag in deionized water for dialysis for 4 times, and freeze-drying the product to obtain a white polymer sample, namely the modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization. 4.2 g of the obtained acrylic acid modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization and 0.75 g of 3, 4-ethylenedioxythiophene are added into 65 g of deionized water, the mixture is stirred for 20min under the protection of nitrogen (with the purity of 99.99 percent) to drive off oxygen in the solution, and the temperature of the mixture is reduced to 4 percent ^o After the temperature is lower than C, 0.75 g of potassium persulfate and 0.02 g of hydrated ferric sulfate are added, the mixture is stirred vigorously for 24 hours under the protection of nitrogen,the stirring speed is 800 r/min-1000 r/min. The resulting solution was poured into dialysis bags (cut-off molecular weight 1 kD) and stirred under nitrogen for 24 h. The resulting solution was poured into dialysis bags and placed in deionized water for dialysis for 24 h. After concentrated brine (concentration: 1mol/L, volume ratio to the polymer solution after dialysis is 1: 1) was added to the polymer solution obtained by dialysis, the mixture was poured into a dialysis bag (cut-off molecular weight: 10 kD) again, and dialyzed in ethanol and deionized water successively for 4 times, each for 3 hours. Finally, freeze drying to obtain the intrinsic conductive polymer material.

1 g of the intrinsic conductive polymer material prepared in example 1 was added to 30 g of deionized water and swelled at room temperature for 28 hours to obtain an intrinsic conductive polymer solution. Coating the intrinsic conductive polymer solution on a glass slide, curing for 24h at room temperature, and measuring the electronic conductivity of the intrinsic conductive polymer solution by using an RTS-9 four-probe tester, wherein the conductivity is 2.5S/cm; two PET films are bonded by using the intrinsic conductive polymer solution (the size of the PET film is 1.4 cm x 9 cm, the bonding area is 1.4 cm x 0.7 cm), after curing is carried out for 24 at room temperature, a small universal test tensile machine is used for testing (the tensile rate is 1 mm/min), and the bonding strength is 2.2 MPa.

Example 2

(1) Preparation of acrylic acid modified dopamine protected by phenolic hydroxyl silanization

Dissolving 2g of levodopa (L-DOPA) and 4 g of sodium tetraborate decahydrate in 100 g of deionized water, and stirring for 20-30 min under the protection of nitrogen (with the purity of 99.99%) to drive off oxygen; adding 1.75 g of sodium carbonate into the solution, adjusting the pH value to 9-10, continuously stirring for 25 min under the nitrogen protection atmosphere, and cooling to the solution temperature of 0 ^o C; dropwise adding 1.75 g of methacryloyl chloride into the solution, adding 0.5-3 g of sodium carbonate after completely dropwise adding to adjust the pH of the solution to 9-10, transferring to room temperature, and continuously stirring for 2 hours under a nitrogen atmosphere; to the above solution was added concentrated hydrochloric acid (concentration: 1 mol/L) to adjust the pH of the solution to 2 or less, and extraction was performed with an ethyl acetate solution to obtain an organic layer. The organic layer was washed successively with hydrochloric acid (0.1 mol/L) and brineAdding anhydrous magnesium sulfate for drying, and finally distilling to remove the solvent to obtain the acrylic acid modified dopamine; adding 0.6 g and 2.4 g of the prepared acrylic acid modified dopamine solution into 10 ml of acetonitrile solution, fully dissolving, and cooling to 0 ^o C, keeping for 30 min, and then dropwise adding 1.5 g of 1, 8-diazabicyclo [ 5.4.0%]Undec-7-ene (DBU), stirring for 4h, transferring to room temperature, and continuously stirring for 18 h; and finally, purifying the obtained mixed solution by sequentially passing through dichloromethane and a 2% v/v ethanol-dichloromethane chromatographic column, and finally evaporating to obtain light yellow viscous powder, namely the acrylic acid modified dopamine protected by phenolic hydroxyl silanization.

(2) Preparation of intrinsic conductive high polymer material

3 g of phenolic hydroxyl silanized protected acrylic modified dopamine, 9 g of 3-sulfopropyl methacrylate potassium salt and 0.16 g of azobisisobutyronitrile were dissolved in 30 g of deionized water/dioxane (volume ratio 1: 1) solution. Stirring for 20min under the protection of nitrogen (purity 99.99%) to remove oxygen in the solution; heating the solution to 65 DEG ^o And C, continuously stirring for 16 hours under the nitrogen protection atmosphere, pouring into a dialysis bag (with the molecular weight cut off being 10 kD), placing into ethanol for dialysis, and replacing the ethanol solution every 3 hours and repeating for 4 times. Finally, the dialysis bag is placed in deionized water for dialysis for 4 times, and a white polymer sample, namely the modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization, is obtained by freeze drying the product. Adding 4 g of the obtained acrylic acid modified dopamine-organic sulfonate copolymer with phenolic hydroxyl silanization protection and 0.8 g of 3, 4-ethylenedioxythiophene into 75 g of deionized water, stirring for 20min under the protection of nitrogen (with the purity of 99.99 percent) to drive off oxygen in the solution, and reducing the temperature of the mixed solution to 4 percent ^o And (3) adding 1.3 g of potassium persulfate and 0.02 g of hydrated ferric sulfate after the temperature is lower than the temperature C, and violently stirring for 24 hours under the nitrogen protection atmosphere at the stirring speed of 800-1000 r/min. The resulting solution was poured into a dialysis bag (cut-off molecular weight 1 kD) under nitrogen atmosphere and stirred for 24 h. The resulting solution was poured into dialysis bags and dialyzed against deionized water for 24 h. To the dialyzed polymerAfter concentrated brine (concentration: 1mol/L, volume ratio to polymer solution after dialysis is 1: 1) was added to the solution, the solution was poured into a dialysis bag (cut-off molecular weight: 10 kD) again, and dialyzed in ethanol and deionized water sequentially for 4 times, each for 3 hours. And finally, freeze drying to obtain the intrinsic conductive polymer material.

1 g of the intrinsic conductive polymer material prepared in example 2 was added to 30 g of deionized water and swelled at room temperature for 28h to obtain an intrinsic conductive polymer solution. Coating the intrinsic conductive polymer solution on a glass slide, curing at room temperature for 24h, and measuring the electronic conductivity of the glass slide by using an RTS-9 four-probe tester, wherein the conductivity is 2.2S/cm; two PET films are bonded by using the intrinsic conductive polymer solution (the size of the PET film is 1.4 cm x 9 cm, the bonding area is 1.4 cm x 0.7 cm), after curing for 24 hours at room temperature, a small universal test tensile machine is used for testing (the tensile rate is 1 mm/min), and the bonding strength is 1.7 MPa.

Example 3

Dissolving 2.6 g of levodopa (L-DOPA) and 5.3 g of sodium tetraborate decahydrate in 100 g of deionized water, and stirring for 20-30 min under the protection of nitrogen (with the purity of 99.99%) to expel oxygen; adding 2.2 g of sodium carbonate into the solution, adjusting the pH value to 9-10, continuously stirring for 20min under the nitrogen protection atmosphere, and cooling to the solution temperature of 0 ^o C; dropwise adding 1.5 g of methacryloyl chloride into the solution, adding 2.4 g of sodium carbonate after complete dropwise addition to adjust the pH of the solution to 9-10, transferring to room temperature, and continuously stirring for 2 hours under a nitrogen atmosphere; to the above solution was added concentrated hydrochloric acid (concentration: 1 mol/L) to adjust the pH of the solution to 2 or less, and extraction was performed with an ethyl acetate solution to obtain an organic layer. Washing the organic layer by hydrochloric acid (0.1 mol/L) and saline water in sequence, adding anhydrous magnesium sulfate for drying, and finally distilling to remove the solvent to obtain acrylic acid modified dopamine; adding 1.65 g and 3.3 g of the prepared acrylic acid modified dopamine solution into 10 ml of acetonitrile solution, fully dissolving, and cooling to 0 ^o C, andafter 30 min of maintenance, 2.1 g of 1, 8-diazabicyclo [5.4.0] are added dropwise]Undec-7-ene (DBU), stirring for 4h, transferring to room temperature, and continuously stirring for 18 h; and finally, purifying the obtained mixed solution by sequentially passing through dichloromethane and a 2% v/v ethanol-dichloromethane chromatographic column, and finally evaporating to obtain light yellow viscous powder, namely the acrylic acid modified dopamine protected by phenolic hydroxyl silanization.

(2) Preparation of intrinsic conductive high polymer material

3.2 g of phenolic hydroxyl silanized protected acrylic modified dopamine, 9.6 g of 3-sulfopropyl methacrylate potassium salt and 0.18 g of azobisisobutyronitrile were dissolved in 35 g of deionized water/dioxane (volume ratio 1: 1) solution. Stirring for 15-30 min under the protection of nitrogen (with the purity of 99.99%) to expel oxygen in the solution; heating the solution to 65 DEG ^o And C, continuously stirring for 16 hours under the nitrogen protection atmosphere, pouring into a dialysis bag (with the molecular weight cut off being 10 kD), placing into ethanol for dialysis, and replacing the ethanol solution every 3 hours and repeating for 4 times. Finally, placing the dialysis bag in deionized water for dialysis for 4 times, and freeze-drying the product to obtain a white polymer sample, namely the modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization. 3.3 g of the obtained acrylic acid modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization and 0.7 g of 3, 4-ethylenedioxythiophene are added into 75 g of deionized water, the mixture is stirred for 20min under the protection of nitrogen (with the purity of 99.99 percent) to drive off oxygen in the solution, and the temperature of the mixture is reduced to 4 percent ^o And (3) adding 1.5 g of potassium persulfate and 0.01-0.1 g of hydrated ferric sulfate after the temperature is lower than the temperature C, and violently stirring for 24 hours at the stirring speed of 800-1000 r/min in the nitrogen protection atmosphere. The resulting solution was poured into dialysis bags (cut-off molecular weight 1 kD) and stirred under nitrogen for 24 h. The resulting solution was poured into dialysis bags and placed in deionized water for dialysis for 24 h. After concentrated brine (concentration: 1mol/L, volume ratio to the polymer solution after dialysis is 1: 1) was added to the polymer solution obtained by dialysis, the mixture was poured into a dialysis bag (cut-off molecular weight: 10 kD) again, and dialyzed in ethanol and deionized water successively for 4 times, each for 3 hours. Final freezingDrying to obtain the intrinsic conductive polymer material.

1 g of the intrinsic conductive polymer material prepared in example 3 was added to 30 g of deionized water, and swelled at room temperature for 28 hours to obtain an intrinsic conductive polymer solution. Coating the intrinsic conductive polymer solution on a glass slide, curing at room temperature for 24h, and measuring the electronic conductivity of the glass slide by using an RTS-9 four-probe tester, wherein the conductivity is 2.2S/cm; two PET films are bonded by using the intrinsic conductive polymer solution (the size of the PET film is 1.4 cm x 9 cm, the bonding area is 1.4 cm x 0.7 cm), after curing for 24 hours at room temperature, a small universal test tensile machine is used for testing (the tensile rate is 1 mm/min), and the bonding strength is 1.6 MPa.

Example 4

(1) Preparation of intrinsic conductive polymer material

3.6 g of the phenolic hydroxyl silanized protected acrylic modified dopamine prepared in example 1, 9 g of 2-acrylamido-2-methyl-1-propanesulfonic acid and 0.75 g of azobisisoheptonitrile were dissolved in 36 g of a deionized water/dioxane (volume ratio 1: 1) solution. Stirring for 25 min under the protection of nitrogen (with the purity of 99.99%) to drive off oxygen in the solution; heating the solution to 65 DEG ^o And C, continuously stirring for 16 hours under the nitrogen protection atmosphere, pouring into a dialysis bag (with the molecular weight cut off being 10 kD), placing into ethanol for dialysis, and replacing the ethanol solution every 3 hours and repeating for 4 times. Finally, placing the dialysis bag in deionized water for dialysis for 4 times, and freeze-drying the product to obtain a white polymer sample, namely the modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization. 6.6 g of the acrylic acid modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization and 0.9 g of aniline are taken to be added into 78 g of deionized water, the mixture is stirred for 20min under the protection of nitrogen (with the purity of 99.99 percent) to drive off oxygen in the solution, and the temperature of the mixture is reduced to 4 DEG ^o And (3) adding 0.9 g of ammonium persulfate and 0.07 g of hydrated ferric sulfate after the temperature is lower than the temperature C, and violently stirring for 24 hours at the stirring speed of 800-1000 r/min in the nitrogen protection atmosphere. The resulting solution was poured into dialysis bags (cut-off molecular weight 1 kD) under nitrogenStirring is continued for 24h under the protection of atmosphere. The resulting solution was poured into dialysis bags and placed in deionized water for dialysis for 24 h. After concentrated brine (concentration: 1mol/L, volume ratio to the polymer solution after dialysis is 1: 1) was added to the polymer solution obtained by dialysis, the mixture was poured into a dialysis bag (cut-off molecular weight: 10 kD) again, and dialyzed in ethanol and deionized water successively for 4 times, each for 3 hours. And finally, freeze drying to obtain the intrinsic conductive polymer material.

1 g of the intrinsic conductive polymer material prepared in example 4 was added to 30 g of deionized water, and swelled at room temperature for 28 hours to obtain an intrinsic conductive polymer solution. Coating the intrinsic conductive polymer solution on a glass slide, curing for 24h at room temperature, and measuring the electronic conductivity of the intrinsic conductive polymer solution by using an RTS-9 four-probe tester, wherein the conductivity is 1.6S/cm; two PET films are bonded by using the intrinsic conductive polymer solution (the size of the PET film is 1.4 cm x 9 cm, the bonding area is 1.4 cm x 0.7 cm), after curing for 24 hours at room temperature, a small universal test tensile machine is used for testing (the tensile rate is 1 mm/min), and the bonding strength is 2.1 MPa.

Example 5

(1) Preparation of intrinsic conductive polymer material

3.1 g of the phenolic hydroxysilanized protected acrylic modified dopamine prepared in example 1, 4 g of potassium 3-sulfopropyl methacrylate and 3 g of 2-acrylamido-2-methyl-1-propanesulfonic acid and 0.14 g of benzoyl peroxide were dissolved in 30 g of a deionized water/dioxane (volume ratio 1: 1) solution. Stirring for 22 min under the protection of nitrogen (with the purity of 99.99%) to drive off oxygen in the solution; heating the solution to 65 DEG ^o And C, after stirring for 16 hours under the nitrogen protection atmosphere, pouring into a dialysis bag (with the molecular weight cut off being 10 kD), placing into ethanol for dialysis, and replacing the ethanol solution every 3 hours and repeating for 4 times. Finally, the dialysis bag is placed in deionized water for dialysis for 4 times, and a white polymer sample, namely the modified dopamine-organic sulfonate copolymer protected by phenolic hydroxyl silanization, is obtained by freeze drying the product. Taking the obtained acrylic acid modified dopamine-organic sulfonate protected by phenolic hydroxyl silanization5 g of copolymer and 0.6 g of pyrrole are added to 62 g of deionized water, the mixture is stirred under a nitrogen (purity 99.99%) protective atmosphere for 20min to drive off oxygen in the solution, and the temperature of the mixture is lowered to 4% ^o And (3) adding 1.3 g of ammonium persulfate and 0.07 g of hydrated ferric sulfate after the temperature is lower than the temperature C, and violently stirring for 24 hours at the stirring speed of 800-1000 r/min in the nitrogen protection atmosphere. The resulting solution was poured into dialysis bags (cut-off molecular weight 1 kD) and stirred under nitrogen for 24 h. The resulting solution was poured into dialysis bags and dialyzed against deionized water for 24 h. After adding concentrated saline (concentration: 1mol/L, volume ratio to the polymer solution after dialysis is 1: 1) to the polymer solution obtained by dialysis, pouring into a dialysis bag (molecular weight cut-off of 10 kD) again, and dialyzing in ethanol and deionized water sequentially for 4 times each for 3 hours. And finally, freeze drying to obtain the intrinsic conductive polymer material.

1 g of the intrinsic conductive polymer material prepared in example 5 was added to 30 g of deionized water, and swelled at room temperature for 28 hours to obtain an intrinsic conductive polymer solution. Coating the intrinsic conductive polymer solution on a glass slide, curing for 24h at room temperature, and measuring the electronic conductivity of the intrinsic conductive polymer solution by using an RTS-9 four-probe tester, wherein the conductivity is 1.6S/cm; two PET films are bonded by using the intrinsic conductive polymer solution (the size of the PET film is 1.4 cm x 9 cm, the bonding area is 1.4 cm x 0.7 cm), after curing for 24 hours at room temperature, a small universal test tensile machine is used for testing (the tensile rate is 1 mm/min), and the bonding strength is 2.0 MPa.

Comparative example 1

(1) Preparation of organic sulfonate polymers

7 g of 3-sulfopropyl methacrylate potassium salt and 0.12 g of azobisisobutyronitrile were dissolved in 25 g of a deionized water/dioxane (volume ratio 1: 1) solution. Stirring for 20min under the protection of nitrogen (with the purity of 99.99%) to drive off oxygen in the solution; heating the solution to 65 DEG ^o And C, continuously stirring for 16 hours under the nitrogen protection atmosphere, pouring into a dialysis bag (with the molecular weight cut off being 10 kD), placing into ethanol for dialysis, and replacing the ethanol solution every 3 hours and repeating for 4 times.Finally, the dialysis bag is placed in deionized water for dialysis for 4 times, and the product is frozen and dried to obtain a white polymer sample, namely the organic sulfonate polymer.

Comparative example 2

(1) Preparation of modified dopamine-organic sulfonate copolymer

1 g of the phenolic hydroxyl silanization-protected modified dopamine-organic sulfonate copolymer prepared in example 1 was added to a mixed solution of 100 g of deionized water and 20 g of concentrated brine (concentration: 1 mol/L) to 60 g ^o Stirring for 12 h at C, pouring into dialysis bag (cut-off molecular weight of 10 kD), and dialyzing in ethanol and deionized water for 4 times for 3 hours. Finally, freeze drying to obtain the modified dopamine-organic sulfonate copolymer.

Comparative example 3

(1) Preparation of organic sulfonate-conductive high-molecular copolymer

4.2 g of the organic sulfonate copolymer prepared in comparative example 1 and 0.75 g of 3, 4-ethylenedioxythiophene were added to 65 g of deionized water, the mixture was stirred under a nitrogen (99.99% purity) protective atmosphere for 20min to drive off oxygen in the solution, and the temperature of the mixture was lowered to 4 deg.C ^o And after the temperature is below C, adding 0.75 g of potassium persulfate and 0.02 g of hydrated ferric sulfate, and violently stirring for 24 hours at the stirring speed of 800-1000 r/min in the nitrogen protection atmosphere. The resulting solution was poured into dialysis bags (cut-off molecular weight 1 kD) and stirred under nitrogen for 24 h. The resulting solution was poured into dialysis bags and dialyzed against deionized water for 24 h. Finally, freeze drying to obtain the organic sulfonate-conductive high molecular copolymer.

Adding 1 g of the polymer in the comparative examples 1-3 into 30 g of deionized water, swelling at room temperature for 28h to obtain corresponding polymer solutions, and performing conductivity test by using the same test method as in example 1. Among them, the organic sulfonate polymer in comparative example 1 is non-conductive because of no conjugated structure in the structure, and has a conductivity of less than 10 ^-5 S/cm. In comparative example 2, the modified dopamine-organic sulfonate copolymer has a certain conductivity due to the same existence of a pi-pi conjugated structure in the dopamine structure, and the conductivity reaches8.9*10 ^-5 S/cm. The conductivity of the organic sulfonate-conductive polymer copolymer was 2.3 x 10 ^-2 S/cm, while the conductivity of the intrinsic conductive polymer material in the embodiment 1 reaches 2.5S/cm, it can be seen that the introduced dopamine group has a promoting effect on the conductivity of the material, so that the migration capability of electrons in the material is further enhanced, and the conductivity of the material is improved. The adhesion property test was performed by the same test method as in example 2. Wherein, the bonding strength of the organic sulfonate polymer in the comparative example 1 is only 0.1 MPa, the bonding strength of the organic sulfonate-conductive high molecular copolymer in the comparative example 3 is 0.65 MPa, and the bonding strength of the modified dopamine-organic sulfonate copolymer in the comparative example 3 reaches 2.1 MPa, and the introduction of dopamine group can be seen to remarkably improve the bonding performance of the material by combining the bonding strength in the example 1.

The conductive polymer material in example 1 of the present invention was compared with the conductive adhesive in patent CN107663428A, patent CN112863889A, and patent CN114133900A in terms of conductivity or adhesion. The patent CN1070663428A also discloses a conductive composite aqueous adhesive prepared by using intrinsic conductive polymer, but its conductivity is only 5.26 x 10 at maximum ^-3 S/cm, which is 3 orders of magnitude less than the conductivity of the conductive polymer material prepared in example 1. Patent CN112863889A adopts a conductive filler to prepare a heteropoly acid compounded conductive polymer material, and although the conductivity can reach 15-16S/cm, the bonding strength of the heteropoly acid compounded conductive polymer material on the surface of a polymer (polypropylene, polyether ether ketone, stainless steel, polycarbonate and the like) is only 37.1 +/-5.7 kPa at most. The conductive polymer material prepared in patent CN114133900A has a volume resistivity as high as 7.2 omega.m (conductivity of 0.14 x 10) although the bonding strength on the ceramic or glass plate can reach 8.4 MPa ^-3 S/cm) which is 3 orders of magnitude lower than the resistivity of the conductive polymer of the present invention, it can be seen that the conductive polymer of the present invention has advancement in conductivity and adhesion property.

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims

1. An intrinsic conductive polymer material is characterized by comprising a conductive polymer-modified dopamine-organic sulfonate copolymer;

the conductive polymer is at least one selected from polyethylene dioxythiophene, polyaniline and polypyrrole;

the modified dopamine contains a dihydroxy group and a benzene ring group;

2. The intrinsically conductive polymer material of claim 1, wherein the hydroxyl group is a phenolic hydroxyl group.

3. A method for preparing an intrinsically conductive polymer material as claimed in any one of claims 1 to 2, which comprises the steps of:

4. The method according to claim 3, wherein in step S1, the modified dopamine is an acrylic modified dopamine protected by phenolic hydroxyl group silanization;

the initiator I is an oil-soluble initiator;

the initiator I is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide;

the solvent I is a mixed solvent;

the solvent I is prepared from water and dioxane according to a volume ratio of 1:1, preparation;

the organic sulfonate comonomer is selected from at least one of 3-sulfopropyl methacrylate potassium salt and 2-acrylamido-2-methyl-1-propanesulfonic acid;

the mass ratio of the modified dopamine to the organic sulfonate comonomer is 0.16-0.66;

the mass ratio of the modified dopamine to the initiator I is 10-40;

the volume ratio of the mass of the modified dopamine to the solvent I is 0.05 g/mL-0.2 g/mL;

the conditions for reaction I were as follows:

the temperature is 50-75 ℃;

the time is 12-20 h;

the reaction I is carried out in a protective atmosphere;

the protective atmosphere is selected from at least one of nitrogen, argon and neon;

before the reaction I, removing oxygen in the mixed solution;

and after the reaction I, dialyzing and drying to obtain a product.

5. The method of claim 3, wherein in step S2, the initiator II is a peroxide initiator;

the initiator II is at least one selected from potassium persulfate and ammonium persulfate;

the catalyst is hydrated ferric sulfate;

the solvent II is water;

the mass ratio of the modified dopamine-organic sulfonate copolymer to the conductive high molecular monomer is 2-32;

the mass ratio of the modified dopamine-organic sulfonate copolymer to the initiator II is 1-10;

the mass ratio of the modified dopamine-organic sulfonate copolymer to the catalyst is 20-800;

the volume ratio of the mass of the modified dopamine-organic sulfonate copolymer to the volume of the solvent II is 0.05 g/mL-0.15 g/mL;

the conditions for reaction II were as follows:

the temperature is 2-10 ℃;

the time is 16-48 h;

reaction II is carried out under stirring;

the stirring speed is 800 r/min-1000 r/min;

reaction II is carried out in protective atmosphere;

before the initiator II and the catalyst are added, removing oxygen in the mixture and cooling to 2-10 ℃;

and after the reaction II, dialyzing and drying to obtain a product.

6. The method of claim 3, wherein the modified dopamine is prepared by acrylic modification and phenolic hydroxyl silanization protection.

7. The method of claim 3, wherein the modified dopamine is prepared by the following steps:

8. The method of claim 7, wherein in step A1, the dopamine is levodopa;

the borate is sodium tetraborate decahydrate;

the mass ratio of the dopamine to the borate is 0.16-1.5;

the volume ratio of the mass of the dopamine to the volume of the water is 0.01-0.03 g/mL;

adding sodium carbonate to adjust the pH value to 9-10;

mixing under a protective atmosphere;

the mixing time is 40-60 min;

in the step A2, the ratio of the mass of the methacryloyl chloride to the volume of the first solution is 0.005 g/mL-0.02 g/mL;

cooling to 0 ℃, and adding sodium carbonate to adjust the pH value to 9-10;

mixing at room temperature under protective atmosphere;

the mixing time is 3-4 h;

after mixing, adjusting the pH value to be below 2, extracting, washing and drying to obtain acrylic acid modified dopamine;

in the step A3, the mass ratio of the acrylic acid modified dopamine to the tert-butylchlorosilane is 0.1-2;

the mass ratio of the acrylic acid modified dopamine to the 1, 8-diazabicyclo [5.4.0] undec-7-ene is 0.15-2;

the volume ratio of the mass of the acrylic acid modified dopamine to the volume of the organic solvent is 0.05 g/mL-2 g/mL;

the organic solvent is acetonitrile;

mixing at room temperature under protective atmosphere;

the mixing time is 15-20 h.

9. The intrinsic conductive polymer material according to any one of claims 1 to 2 or the intrinsic conductive polymer material obtained by the preparation method according to any one of claims 3 to 8, and the application thereof in the fields of electric grounding materials, microelectronic assembly and electromagnetic shielding.

10. Use according to claim 9, characterized in that it comprises the following steps:

mixing the intrinsic conductive high polymer material and water according to a mass ratio of 1: 18-40 to obtain a bonding solution;

and coating the bonding liquid on the interface.