Novel PEDOT (poly (3, 4-ethylenedioxythiophene)) aqueous dispersion as well as preparation method and application thereof

Abstract

The invention relates to a novel PEDOT aqueous dispersion and a preparation method and application thereof.The aqueous dispersion comprises a PIB-b-PSS: PEDOT polymer, the structural formula of the PIB-b-PSS: PEDOT polymer is # imgabs0 #, m ranges from 2 to 200, n ranges from 2 to 500, and x ranges from 2 to 500, on one hand, amphiphilic block copolymers PIB-b-PSS with different molecular weights are synthesized, and the PEDOT aqueous dispersion is prepared with PIB-b-PSS as a template; and on the other hand, the PEDOT aqueous dispersion not only has better conductivity and film-forming property, can reduce the resistance of the prepared capacitor, but also can improve the capacity extraction rate of the capacitor.

Description

Technical Field

[0001] The invention belongs to the technical field of conductive polymers, relates to solid capacitors, and specifically relates to a novel PEDOT aqueous dispersion, a preparation method and application thereof in solid capacitors. Background Art

[0002] Conductive polymer poly (3,4-ethylenedioxythiophene), PEDOT, is a polymer of 3,4-ethylenedioxythiophene (EDOT) monomer, which is widely used due to its simple molecular structure, small energy gap, high conductivity, good environmental stability and film transparency. However, PEDOT is insoluble and infusible, which makes it difficult to process and cannot be well used in industrial production. In order to improve the water solubility of PEDOT and make it better for capacitors, researchers used PSSNa (sodium polyvinylbenzenesulfonate) as a template and prepared PEDOT:PSS through oxidative polymerization, which can improve the water solubility of PEDOT. The film formed by PEDOT:PSS has good light transmittance and environmental stability.

[0003] This system also has many disadvantages in capacitor applications. For example, since polyvinylbenzenesulfonic acid PSS is insulating, the conductivity of the PEDOT:PSS film will decrease, the resistance of the capacitor will increase, and the performance of the capacitor will be reduced.

[0004] PEDOT:PSS particles have poor dispersibility and are easy to settle. The resulting coating has large roughness and haze, which limits its application in the field of optical films. CN104151565A discloses that APEG is introduced into the template PSS by copolymerization to make the PEDOT dispersion more stable and have better film-forming properties. However, the resulting copolymer is not amphiphilic and cannot be well compatible with the monomer EDOT, which affects the performance of the PEDOT aqueous dispersion. Summary of the invention

[0005] The present invention proposes a novel PEDOT aqueous dispersion, and clarifies a novel PEDOT aqueous dispersion synthesized using an amphiphilic block copolymer PIB-b-PSS (PIB: polyisobutylene) as a template. The novel PEDOT aqueous dispersion has better conductivity and film-forming properties, and can be applied to capacitors to significantly reduce resistance and improve capacity extraction rate.

[0006] In one aspect, the present invention provides a novel PEDOT aqueous dispersion, wherein the aqueous dispersion comprises a PIB-b-PSS:PEDOT polymer, wherein the structural formula of the PIB-b-PSS:PEDOT polymer is:

[0007]

[0008] Among them, m is 2 to 200, n is 2 to 500, and x is 2 to 500.

[0009] On the other hand, the present invention provides a method for preparing a novel PEDOT aqueous dispersion, the preparation method comprising the following steps:

[0010] 1) Preparation of PIB-Br

[0011] 1.1) Preparation of polymer PIB-Cl

[0012] Isobutylene (IB) and 1,3-butadiene (BD) are polymerized in the presence of initiator A and catalyst A to obtain polymer PIB-Cl;

[0013] 1.2) Preparation of PIB-Br

[0014] The polymer PIB-Cl is refluxed in the presence of an inorganic base to obtain a terminal hydroxylation product PIB-OH; PIB-OH reacts with 2-bromoacetyl bromide at room temperature to obtain PIB-Br;

[0015] 2) Preparation of PIB-b-PSS

[0016] PIB-Br is used as a macromolecular ATRP initiator to initiate the free radical polymerization of the monomer SSNa: the monomer SSNa (sodium vinylbenzenesulfonate) and PIB-Br are polymerized in the presence of a copper catalyst and a ligand to obtain PIB-b-PSS;

[0017] 3) Preparation of PEDOT aqueous dispersion

[0018] PIB-b-PSS was used as a template to prepare a PEDOT aqueous dispersion: PIB-b-PSS and monomer EDOT reacted at room temperature in the presence of an acetic acid solution, an oxidant and a catalyst B to obtain a PEDOT aqueous dispersion, which was a dark blue mixed liquid.

[0019] According to an embodiment of the present invention, step 1.1) of the above method may further include at least one of the following additional technical features:

[0020] In some embodiments, in step 1.1), the polymerization reaction temperature is -100 to -70°C.

[0021] Specifically, the polymerization reaction in step 1.1) is carried out at -100°C, -90°C, -80°C, -78°C, -75°C, -70°C or any value within the range of -100 to -70°C.

[0022] In some embodiments, the polymerization reaction in step 1.1) is carried out in a solvent, and the solvent is one of n-hexane and methyl chloride or a combination thereof; preferably a combination of n-hexane and methyl chloride.

[0023] Methyl chloride is a gas at room temperature and pressure, but it is a liquid in the temperature range of -100 to -70°C.

[0024] In some embodiments, in step 1.1), when the solvent used is a combination of n-hexane and methyl chloride, the volume ratio of n-hexane to methyl chloride (in liquid state) is 3:2.

[0025] In the present invention, the mixture of n-hexane and methyl chloride will not solidify at -100 to -70°C, while other solvents have a higher solidification temperature and are easy to solidify.

[0026] In some embodiments, in step 1.1), the initiator A is α,α-dimethylbenzyl chloride; α,α-dimethylbenzyl chloride is relatively active, and under the action of catalyst A, due to the combined action of benzyl and methyl groups, a stable benzyl anion can be formed to initiate monomer polymerization.

[0027] In some embodiments, in step 1.1), the molar ratio of the monomer isobutylene (IB) to the initiator A (α,α-dimethylbenzyl chloride) is 300:1-100.

[0028] Specifically, in step 1.1), the molar ratio of the monomer isobutylene (IB) to the initiator A (α,α-dimethylbenzyl chloride) is any value within the range of 50:1, 52.4:1, 100:1, 108.4:1, 150:1 or 300:1 (1-100).

[0029] In some embodiments, in step 1.1), the catalyst A is one of titanium tetrachloride, zirconium tetrachloride, and chromium trichloride, preferably titanium tetrachloride.

[0030] In some embodiments, in step 1.1), the molar ratio of the monomer isobutylene (IB) to the catalyst A is 50 to 100:1.

[0031] Specifically, in step 1.1), the molar ratio of the monomer isobutylene (IB) to the catalyst A is 50:1, 55:1, 60:1, 65.5:1, 67.75:1, 70:1, 75:1, 80:1, 90:1, 100:1 or any value within the range of 50 to 100:1.

[0032] In some embodiments, in step 1.1), the molar ratio of 1,3-butadiene (BD) to initiator A is 2 to 6:1.

[0033] Specifically, in step 1.1), the molar ratio of 1,3-butadiene (BD) to initiator A is 2:1, 2.5:1, 2.7:1, 3:1, 5.4:1, 6:1 or any value within the range of 2 to 6:1.

[0034] In some embodiments, in step 1.1), isobutylene (IB) is reacted in the presence of initiator A and catalyst A for 0.5 to 2 hours, and then 1,3-butadiene (BD) is added.

[0035] Specifically, in step 1.1), the reaction time of isobutylene (IB) in the presence of initiator A and catalyst A is 0.5 h, 0.7 h, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h or any value within the range of 0.5 to 2 h.

[0036] In some embodiments, in step 1.1), 1,3-butadiene (BD) is added, reacted for 0.5 to 2 hours, and then methanol is added to terminate the BD end-capping.

[0037] Specifically, in step 1.1), after adding 1,3-butadiene (BD), the reaction time is 0.5 h, 0.7 h, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h or any value within the range of 0.5 to 2 h.

[0038] In some embodiments, in step 1.1), the volume of the added methanol is equal to the volume of the added isobutylene (IB).

[0039] In some embodiments, in step 1.1), the methanol needs to be cooled to -60°C to -40°C before being added to prevent a large temperature difference between the methanol and the reaction solution, which may cause side reactions.

[0040] In some embodiments, the step 1.1) is as follows: isobutylene (IB) is dissolved in a mixed solvent of n-hexane-monochloromethane, in the presence of an initiator α,α-dimethylbenzyl chloride and a catalyst titanium tetrachloride, at -100 to -70°C for a reaction for 0.5 to 2 hours, 1,3-butadiene (BD) is added, the temperature is maintained at -100 to -70°C, after a reaction for 0.5 to 2 hours, methanol at -60°C to -40°C is added to terminate the BD end-capping to obtain a polymer PIB-Cl.

[0041] According to an embodiment of the present invention, step 1.2) of the above method may further include at least one of the following additional technical features:

[0042] In some embodiments, in step 1.2), the polymer PIB-Cl is refluxed in tetrahydrofuran.

[0043] In the present invention, the polymer PIB-Cl is easily soluble in tetrahydrofuran, and tetrahydrofuran has a high boiling point and can meet the requirements of the reflux reaction.

[0044] In some embodiments, in step 1.2), the inorganic base is one or a combination of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate.

[0045] Furthermore, in step 1.2), the inorganic base is preferably potassium hydroxide or sodium hydroxide.

[0046] In some embodiments, in step 1.2), the molar ratio of the polymer PIB-Cl to the inorganic base is 1:5-20.

[0047] Specifically, in step 1.2), the molar ratio of the polymer PIB-Cl to the inorganic base is 1:5, 1:10, 1:15, 1:20 or any value within the range of 1:5 to 20.

[0048] In some embodiments, in step 1.2), the reflux time is 5 to 20 hours.

[0049] Specifically, in step 1.2), the reflux time is 5 h, 6 h, 7 h, 10 h, 15 h, 20 h or any value within the range of 5 to 20 h.

[0050] In some embodiments, in step 1.2), the solvent used in the reaction of PIB-OH with 2-bromoacetyl bromide is one or a combination of dichloromethane, chloroform or tetrahydrofuran.

[0051] In some embodiments, in step 1.2), the molar ratio of PIB-OH to 2-bromoacetyl bromide is 1:5-20.

[0052] Specifically, in step 1.2), the molar ratio of PIB-OH to 2-bromoacetyl bromide is 1:5, 1:6, 1:8, 1:10, 1:12, 1:15, 1:20 or any value in the range of 1:5 to 20.

[0053] In some embodiments, in step 1.2), the reaction system of PIB-OH and 2-bromoacetyl bromide further comprises an acid binding agent.

[0054] In some embodiments, in step 1.2), the acid binding agent is one or a combination of triethylamine or pyridine.

[0055] In some embodiments, in step 1.2), the molar ratio of 2-bromoacetyl bromide to the acid binding agent is 1:1-2.

[0056] Specifically, in step 1.2), the molar ratio of the 2-bromoacetyl bromide to the acid binding agent is 1:1, 1:1.2, 1:1.5, 1:1.67, 1:2 or any value within the range of 1:1 to 2.

[0057] In some embodiments, in step 1.2), the reaction time of PIB-OH and 2-bromoacetyl bromide at room temperature is 10 to 15 hours.

[0058] Specifically, in step 1.2), the reaction time of the PIB-OH and 2-bromoacetyl bromide at room temperature is 10 h, 12 h, 13 h, 14 h, 15 h or any value within the range of 10 to 15 h.

[0059] In some embodiments, step 1.2) is: dissolving the polymer PIB-Cl in tetrahydrofuran, adding an inorganic base, and refluxing for 5 to 20 hours to obtain a terminal hydroxylation product PIB-OH, and then reacting PIB-OH with 2-bromoacetyl bromide in the presence of an acid binding agent at room temperature for 10 to 15 hours to obtain a macromolecular ATRP initiator PIB-Br.

[0060] According to an embodiment of the present invention, step 2) of the above method may further include at least one of the following additional technical features:

[0061] In some embodiments, the solvent used in the polymerization reaction in step 2) is hot THF.

[0062] In some embodiments, in step 2), the temperature of the hot THF is 50-60°C.

[0063] Specifically, in step 2), the temperature of the hot THF is 50°C, 52°C, 55°C, 56°C, 60°C or any value within the range of 50-60°C.

[0064] In some embodiments, in step 2), the monomer SSNa is dissolved in a hot THF solution, cooled to room temperature, and then PIB-Br is added.

[0065] In some embodiments, in step 2), the molar ratio of the monomer SSNa to PIB-Br is 1000:1-300.

[0066] Specifically, in step 2), the molar ratio of the monomer SSNa to PIB-Br is 50:1, 100:1, 120:1, 200:1, 240:1, 300:1, 480:1, 500:1 or any value in the range of 1000:1 to 300.

[0067] In some embodiments, in step 2), the copper catalyst is selected from cuprous bromide, cuprous chloride, cuprous sulfate, or a combination thereof.

[0068] In some embodiments, in step 2), the molar ratio of the copper catalyst to PIB-Br is 1:1-10.

[0069] Specifically, in step 2), the molar ratio of the copper catalyst to PIB-Br is 1:1, 1:2, 1:5, 1:8, 1:10 or any value in the range of 1:1 to 10.

[0070] In some embodiments, in step 2), after adding the copper catalyst, the reaction system needs to be sealed and purged with N2 three times for 10 minutes to eliminate oxygen.

[0071] In some embodiments, in step 2), the ligand is one of N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA), 2,2'-bipyridine, tris(2-methylaminoethyl)amine, or a combination thereof.

[0072] In some embodiments, in step 2), the molar ratio of the ligand to PIB-Br is 1 to 2:1.

[0073] Specifically, in step 2), the molar ratio of the ligand to PIB-Br is 1:1, 1.2:1, 1.5:1, 1.7:1, 2:1 or any value within the range of 1 to 2:1.

[0074] In some embodiments, in step 2), the polymerization reaction temperature is 70°C to 80°C.

[0075] Specifically, in step 2), the polymerization reaction temperature is 70°C, 72°C, 75°C, 78°C, 80°C or any value within the range of 70°C to 80°C.

[0076] In some embodiments, in step 2), the polymerization reaction is carried out at 70° C. to 80° C. for 20 to 30 hours.

[0077] Specifically, in step 2), the polymerization reaction is carried out at 70° C. to 80° C. for 20 h, 22 h, 25 h, 27 h, 30 h or any value within the range of 20 to 30 h.

[0078] In some embodiments, in step 2), the ligand is added by adding a THF solution of the ligand via a gas-tight syringe.

[0079] In some embodiments, in step 2), after the ligand is added, the reaction system needs to be further deoxygenated through three freeze-pump-thaw cycles.

[0080] In some embodiments, in step 2), the polymerization reaction is terminated by immersing the reaction system in liquid nitrogen to terminate the polymerization.

[0081] In some embodiments, step 2) is: dissolving the monomer SSNa (sodium vinylbenzenesulfonate) in hot THF, cooling to room temperature, adding PIB-Br and copper catalyst, sealing, purging with N2 three times for 10 minutes to eliminate oxygen, adding ligand, deoxygenating through three freeze-pump-thaw cycles, reacting at 70°C to 80°C for 20 to 30 hours, and terminating the polymerization by immersing the reaction system in liquid nitrogen to obtain PIB-b-PSS.

[0082] According to an embodiment of the present invention, step 3) of the above method may further include at least one of the following additional technical features:

[0083] In some embodiments, the reaction in step 3) is carried out in a mixed solvent consisting of dimethyl sulfoxide (DMSO) and deionized water.

[0084] Furthermore, in step 3), the volume ratio of dimethyl sulfoxide (DMSO) to deionized water is 1:2-5.

[0085] Preferably, in step 3), the volume ratio of dimethyl sulfoxide (DMSO) to deionized water is 1:2, 1:3, 1:4, 1:5 or any value in the range of 1:2 to 5.

[0086] In the present invention, the solubility of PIB-b-PSS in dimethyl sulfoxide (DMSO) is relatively high, and dimethyl sulfoxide (DMSO) can increase the conductivity of the final PEDOT aqueous dispersion after film formation.

[0087] In some embodiments, in step 3), the mass ratio of the monomer EDOT to PIB-b-PSS is 10:1-20.

[0088] Specifically, in step 3), the mass ratio of the monomer EDOT to PIB-b-PSS is 10:1, 5:1, 5:2, 2:1, 5:3, 5:4, 1:1, 2:3, 1:2 or any value in the range of 10:1 to 20.

[0089] In some embodiments, in step 3), the mass ratio of the acetic acid solution to deionized water is 1:60-200.

[0090] Specifically, in step 3), the mass ratio of the acetic acid solution to deionized water is 1:60, 1:70, 1:74, 1:80, 1:90, 1:100, 1:150, 1:160, 1:180 or any value in the range of 1:60 to 200.

[0091] In some embodiments, in step 3), the mass fraction of the acetic acid solution is 0.5% to 1.6%.

[0092] Specifically, in step 3), the mass fraction of the acetic acid solution is 0.5%, 0.7%, 1%, 1.2%, 1.5%, 1.6% or any value in the range of 0.5%-1.6%.

[0093] In the present invention, the acetic acid solution is used to adjust the pH so that the pH of the PEDOT aqueous dispersion is between 2 and 5. If the pH is too high, the PEDOT aqueous dispersion will lose its conductivity after film formation.

[0094] In some embodiments, in step 3), the oxidant is selected from one or a combination of ammonium persulfate, potassium persulfate, sodium persulfate.

[0095] In some embodiments, in step 3), the molar ratio of the oxidant to EDOT is 0.3 to 3:1.

[0096] Specifically, in step 3), the molar ratio of the oxidant to EDOT is 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1 or any value within the range of 0.3 to 3:1.

[0097] In some embodiments, in step 3), the catalyst B is ferric sulfate. In the present invention, the catalyst cannot be a halogen-containing catalyst such as ferric chloride or ferric bromide, because the PEDOT aqueous dispersion is to be used in capacitors, and the halogen contained will corrode the electrode foil.

[0098] In some embodiments, in step 3), the molar ratio of the catalyst B to EDOT is 0.001 to 0.006:1.

[0099] Specifically, in step 3), the molar ratio of the catalyst B to EDOT is 0.001:1, 0.002:1, 0.003:1, 0.004:1, 0.005:1, 0.006:1 or any value within the range of 0.001 to 0.006:1.

[0100] In some embodiments, in step 3), the mass ratio of dimethyl sulfoxide to EDOT is 0.2 to 10:1.

[0101] Specifically, in step 3), the mass ratio of dimethyl sulfoxide to EDOT is 0.2:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7.15:1, 10:1 or any value within the range of 0.2 to 10:1.

[0102] In some embodiments, in step 3), the PIB-b-PSS and monomer EDOT are reacted in the presence of acetic acid solution, oxidant and catalyst B at room temperature for 15 to 30 hours.

[0103] Specifically, in step 3), the PIB-b-PSS and monomer EDOT are reacted in the presence of acetic acid solution, oxidant and catalyst B at room temperature for 15 h, 18 h, 20 h, 23 h, 25 h, 27 h, 30 h or any value within the range of 15 to 30 h.

[0104] In some embodiments, in step 3), the solid content of the PEDOT aqueous dispersion is 1-15%.

[0105] Specifically, in step 3), the solid content of the PEDOT aqueous dispersion is 1%, 5%, 8%, 10%, 12%, 15% or any value within the range of 1 to 15%.

[0106] In some embodiments, step 3) is: adding PIB-b-PSS to a mixed solvent consisting of dimethyl sulfoxide (DMSO) and deionized water, adding acetic acid solution, monomer EDOT, oxidant, and catalyst B, and reacting at room temperature for 15 to 30 hours to obtain a PEDOT aqueous dispersion, wherein the PEDOT aqueous dispersion is a dark blue mixed liquid.

[0107] In some embodiments, the PEDOT aqueous dispersion comprises a PIB-b-PSS:PEDOT polymer, wherein the molecular weight M of the PIB in the PIB-b-PSS:PEDOT polymer is n 3000~6000g mol -1 , the molecular weight M of the PSS n 20000~40000g mol -1 .

[0108] Specifically, the PIB-b-PSS:PEDOT polymer is: PIB(3000)-b-PSS(20000):PEDOT, PIB(3000)-b-PSS(40000):PEDOT, PIB(6000)-b-PSS(20000):PEDOT, PIB(6000)-b-PSS(40000):PEDOT or other polymers having a molecular weight M of PIB. n 3000~6000g mol -1 , the molecular weight of PSS is M n 20000~40000g mol -1 Any polymer.

[0109] The present invention provides a novel PEDOT aqueous dispersion, wherein the PEDOT aqueous dispersion comprises a PIB-b-PSS:PEDOT polymer, an EDOT monomer, dimethyl sulfoxide and water, and the PEDOT aqueous dispersion is prepared by the method of the present invention.

[0110] In some embodiments, the mass ratio of the PIB-b-PSS:PEDOT polymer, EDOT monomer, dimethyl sulfoxide and water is 20-50:1:50-200:200-500.

[0111] In some embodiments, the sheet resistance of the PEDOT aqueous dispersion is 100-500Ω.

[0112] Furthermore, the sheet resistance of the PEDOT aqueous dispersion is 150-350Ω.

[0113] Specifically, the sheet resistance of the PEDOT aqueous dispersion is 150Ω, 172Ω, 253Ω, 296Ω, 300Ω, 337Ω, 350Ω, or any value within the range of 150 to 350Ω.

[0114] In a third aspect, the present invention provides a solid capacitor, wherein the capacitor is obtained by immersing a wound capacitor core into a PEDOT aqueous dispersion.

[0115] In some embodiments, the capacitor core comprises: immersed in a PEDOT aqueous dispersion, vacuumed to 0.1 MPa for ten minutes, pressurized to 0.1 MPa for ten minutes, dried at 130° C. for 1 hour, repeated three times, and assembled using an assembling machine.

[0116] Wherein, the size of the assembled solid capacitor is The specifications are 35V270μF.

[0117] The beneficial effects of the present invention are:

[0118] The invention synthesizes amphiphilic block copolymers PIB-b-PSS with different molecular weights, and prepares a novel PEDOT aqueous dispersion using PIB-b-PSS as a template; the PEDOT aqueous dispersion in the invention not only has better conductivity and film-forming property, can reduce the resistance of the prepared capacitor, but also can improve its capacity extraction rate.

[0119] Specific implementation scheme

[0120] The following description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

[0121] The preparation of the novel PEDOT aqueous dispersion of the present invention comprises the following steps:

[0122] 1) Preparation of macroinitiator PIB-Br

[0123] 1.1) Preparation of polymer PIB-Cl

[0124] Dissolve isobutylene (IB) in n-hexane-methylene chloride (V 正己烷 / V CH3Cl =3 / 2), in the presence of an initiator α,α-dimethylbenzyl chloride and a catalyst titanium tetrachloride, at -100 to -70°C, react for 0.5 to 2h, then add 1,3-butadiene (BD), keep the temperature in the range of -100 to -70°C, react for 0.5 to 2h, then add methanol at -60°C to -40°C to terminate the BD end-capping, and obtain a polymer PIB-Cl.

[0125] The molar ratio of the monomer isobutylene (IB) to α,α-dimethylbenzyl chloride is 300:1-100.

[0126] The molar ratio of the monomer isobutylene (IB) to titanium tetrachloride is 50 to 100:1.

[0127] The molar ratio of the 1,3-butadiene (BD) to α,α-dimethylbenzyl chloride is 2 to 6:1.

[0128] The volume of the added methanol was equal to the volume of the added isobutylene (IB).

[0129] 1.2) Preparation of macroinitiator PIB-Br

[0130] The polymer PIB-Cl was dissolved in tetrahydrofuran (THF), potassium hydroxide was added, refluxed for 5 to 20 hours, diluted with water, extracted with ethyl acetate, the organic solvent was removed, and vacuum dried at room temperature for 12 to 24 hours to obtain the terminal hydroxylation product PIB-OH. PIB-OH was reacted with 2-bromoacetyl bromide at room temperature for 10 to 15 hours in the presence of an acid binding agent, washed with water, the organic solvent was removed, and vacuum dried at room temperature for 12 to 24 hours to obtain the macromolecular ATRP initiator PIB-Br.

[0131] The molar ratio of the polymer PIB-Cl to potassium hydroxide is 1:5-20.

[0132] The PIB-OH is reacted with 2-bromoacetyl bromide in one or a combination of dichloromethane, chloroform or tetrahydrofuran.

[0133] The molar ratio of the PIB-OH to 2-bromoacetyl bromide is 1:5-20.

[0134] The acid binding agent is one of triethylamine and pyridine or a combination thereof.

[0135] The molar ratio of the 2-bromoacetyl bromide to the acid binding agent is 1:1-2.

[0136] 2) Using PIB-Br as the macromolecular ATRP initiator to initiate the free radical polymerization of the monomer SSNa

[0137] The monomer SSNa was dissolved in THF at 50-60°C, cooled to room temperature, and PIB-Br and cuprous bromide were added. The mixture was sealed and purged with N2 three times for 10 minutes to eliminate oxygen. A THF solution of N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA) was added through a gas-tight syringe. The reaction system was deoxygenated by three freeze-pump-thaw cycles, and then the reaction was carried out at 70-80°C for 20-30 hours, and the polymerization was terminated by immersing the reaction system in liquid nitrogen. The reaction mixture was diluted with THF, and the residual cuprous bromide was removed by an alumina column. After concentration, the mixture was precipitated in methanol and dried at 60°C to obtain PIB-b-PSS.

[0138] The molar ratio of the monomer SSNa to PIB-Br is 1000:1-300.

[0139] The molar ratio of the cuprous bromide to the initiator PIB-Br is 1:1-10.

[0140] The molar ratio of the N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA) to the initiator PIB-Br is 1 to 2:1.

[0141] The reaction formula of steps 1.1), 1.2) and 2) is as follows:

[0142]

[0143] 3) Preparation of PEDOT aqueous dispersion using PIB-b-PSS as template.

[0144] PIB-b-PSS was added to a mixed solvent consisting of dimethyl sulfoxide (DMSO) and deionized water, and then acetic acid solution, monomer EDOT, ammonium persulfate and ferric sulfate were added. After reacting at room temperature for 15 to 30 hours, a dark blue mixed liquid PEDOT aqueous dispersion was obtained.

[0145] The volume ratio of the dimethyl sulfoxide to deionized water is 1:2-5.

[0146] The mass ratio of the monomer EDOT to PIB-b-PSS is 10:1-20.

[0147] The mass ratio of the acetic acid solution to deionized water is 1:60-200.

[0148] The mass fraction of the acetic acid solution is 0.5% to 1.6%.

[0149] The molar ratio of the ammonium persulfate to EDOT is 0.3 to 3:1.

[0150] The molar ratio of the ferric sulfate to EDOT is 0.001-0.006:1.

[0151] The mass ratio of dimethyl sulfoxide to EDOT is 0.2 to 10:1.

[0152] The solid content of the aqueous dispersion is 1-15%.

[0153] The embodiments of the present invention will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. In the examples, if specific conditions are not specified, the conditions described in the specification, normal conditions or conditions recommended by the manufacturer are followed. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0154] Embodiment 1:

[0155] Preparation of PEDOT aqueous dispersion using PIB(3000)-b-PSS(20000) as template

[0156] 1) Preparation of macroinitiator PIB-Br

[0157] 1.1) Preparation of polymer PIB-Cl

[0158] In a 500 mL flask, add isobutylene (21.8 mL, 262 mmol), α,α-dimethylbenzyl chloride (0.770 g, 5.0 mmol), n-hexane-CH3Cl mixed solvent (100 mL, V 正己烷 / V CH3Cl =3 / 2), add TiCl4 (2.0 molL -1 , 2.0 mL) of n-hexane-CH3Cl (V 正己烷 / V CH3Cl =3 / 2) solution, and after reacting for 1 hour, 1,3-butadiene (BD) (1.0 mol L -1 , 13.5 mL) of n-hexane-CH3Cl (V 正己烷 / V CH3Cl =3 / 2) solution, maintained at -78°C, reacted for 1 hour, and then -50°C methanol was added to terminate the BD end-capping. The polymerization system was heated to room temperature under stirring, and after CH3Cl was completely evaporated, it was washed three times with deionized water, dried with MgSO4, and n-hexane was evaporated. The polymer PIB-Cl was vacuum dried at room temperature for 24 hours. The molecular weight and dispersity measured by GPC were: M n =3000 g mol -1 ,M w / Mn =1.13.

[0159] 1.2) Preparation of macromolecular ATRP initiator PIB-Br

[0160] PIB-Cl (M n =3000 g mol -1 , 5mmol) was dissolved in THF (100mL), KOH (2.80g, 50mmol) was added, and after reflux for 10 hours, it was diluted with water, extracted with ethyl acetate, the organic solvent was removed, and the terminal hydroxylation product PIB-OH (M was obtained after vacuum drying at room temperature for 24 hours. n =3000 g mol -1 , 5mmol). Then dichloromethane (100mL) was added to dissolve, and 2-bromoacetyl bromide (10.0g, 50mmol) and triethylamine (6.06g, 60mmol) were added, and the mixture was reacted at room temperature for 12h, washed with water, the organic solvent was removed, and vacuum dried at room temperature for 24h to obtain the macromolecular ATRP initiator PIB-Br.

[0161] 2) Using PIB-Br as a macromolecular ATRP initiator, free radical polymerization of monomer SSNa was initiated to prepare PIB-b-PSS

[0162] The monomer SSNa (24.70 g, 120 mmol) was dissolved in THF (500 mL) at 60 °C, cooled to room temperature, and PIB-Br (3.0 g, 1.0 mmol) and cuprous bromide (0.14 g, 1.0 mmol) were added. The mixture was sealed and purged with N2 three times for 10 minutes to eliminate oxygen. Then, a THF solution (10 mL) of N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA) (0.17 g, 1.0 mmol) was added through a gas-tight syringe. The flask was deoxygenated by three freeze-pump-thaw cycles, reacted at 70 °C for 24 h, and the polymerization was terminated by immersing the flask in liquid nitrogen. The reaction mixture was diluted with THF and the residual cuprous bromide was removed by passing through an alumina column. After concentration, it was precipitated in methanol and dried at 60 °C for 12 h to obtain PIB(3000)-b-PSS(20000).

[0163] 3) Preparation of PEDOT aqueous dispersion using PIB(3000)-b-PSS(20000) as template

[0164] PIB(3000)-b-PSS(20000) (20.0 g, 0.87 mmol) was added to a mixed solvent consisting of dimethyl sulfoxide and deionized water (500 mL, V DMSO / V 去离子水=13 / 37), added acetic acid solution (5.0 mL, mass fraction 1%), monomer EDOT (20.0 g, 141 mmol), ammonium persulfate (16.0 g, 70 mmol), ferric sulfate (0.10 g, 0.26 mmol), reacted at room temperature for 20 h, and obtained a dark blue mixed liquid PEDOT aqueous dispersion.

[0165] 4) Using the obtained aqueous dispersion to prepare a capacitor

[0166] The wound capacitor core was immersed in the above PEDOT aqueous dispersion, vacuumed to 0.1 MPa for 10 minutes, pressurized to 0.1 MPa for 10 minutes, and dried at 130°C for 1 hour, and repeated three times. The specification is 35V270μF solid capacitor.

[0167] Example 2

[0168] Preparation of PEDOT aqueous dispersion using PIB(3000)-b-PSS(40000) as template

[0169] 1) Preparation of macroinitiator PIB-Br

[0170] 1.1) Preparation of polymer PIB-Cl

[0171] In a 500 mL flask, add isobutylene (21.8 mL, 262 mmol), α,α-dimethylbenzyl chloride (0.770 g, 5.0 mmol), n-hexane-CH3Cl mixed solvent (100 mL, V 正己烷 / V CH3Cl =3 / 2), add TiCl4 (2.0 molL -1 ,2.0mL) of n-hexane-CH3Cl(V 正己烷 / V CH3Cl =3 / 2) solution, after 1 h of reaction, 1,3-butadiene (BD) (1.0 mol L -1 ,13.5mL) of n-hexane-CH3Cl(V 正己烷 / V CH3Cl =3 / 2) solution, maintained at -78°C, reacted for 1 hour, and then -50°C methanol was added to terminate the BD end-capping. Then, the polymerization system was heated to room temperature under stirring, and after CH3Cl was completely evaporated, it was washed three times with deionized water, then dried with MgSO4, n-hexane was evaporated, and vacuum dried at room temperature for 24 hours to obtain the polymer PIB-Cl. Its molecular weight and dispersity were measured by GPC: M n =3000 g mol -1 ,M w / M n =1.13.

[0172] 1.2) Preparation of macromolecular ATRP initiator PIB-Br

[0173] PIB-Cl (M n =3000 g mol -1 , 5mmol) was dissolved in THF (100mL), KOH (2.80g, 50mmol) was added, refluxed for 10 hours, diluted with water, extracted with ethyl acetate, the organic solvent was removed, and vacuum dried at room temperature for 24h to obtain the terminal hydroxylation product PIB-OH (M n =3000 g mol -1 , 5mmol). Then dichloromethane (100mL) was added to dissolve, and then 2-bromoacetyl bromide (10.0g, 50mmol) and triethylamine (6.06g, 60mmol) were added, reacted at room temperature for 12h, washed with water, the organic solvent was removed, and vacuum dried at room temperature for 24h to obtain the macromolecular ATRP initiator PIB-Br.

[0174] 2) Using PIB-Br as a macromolecular ATRP initiator, free radical polymerization of monomer SSNa was initiated to prepare PIB-b-PSS

[0175] The monomer SSNa (49.44 g, 240 mmol) was dissolved in THF (800 mL) at 60 °C, cooled to room temperature, and PIB-Br (3.0 g, 1.0 mmol) and cuprous bromide (0.14 g, 1.0 mmol) were added. The mixture was sealed and purged with N2 three times for 10 minutes to eliminate oxygen. Then, a THF solution (10 mL) of N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA) (0.17 g, 1.0 mmol) was added through a gas-tight syringe. The flask was deoxygenated by three freeze-pump-thaw cycles, reacted at 70 °C for 24 h, and the flask was immersed in liquid nitrogen to terminate the polymerization. The reaction mixture was diluted with THF, passed through an alumina column to remove residual cuprous bromide, concentrated and precipitated in methanol, and dried at 60 °C for 12 h to obtain PIB(3000)-b-PSS(40000).

[0176] 3) Preparation of PEDOT aqueous dispersion using PIB(3000)-b-PSS(40000) as template

[0177] PIB (3000) -b-PSS (40000) (20.0 g, 0.47 mmol) was added to a mixed solvent consisting of dimethyl sulfoxide and deionized water (500 mL, V DMSO / V 去离子水=13 / 37), added acetic acid solution (5.0 mL, mass fraction 1%), monomer EDOT (20.0 g, 141 mmol), ammonium persulfate (16.0 g, 70 mmol), ferric sulfate (0.10 g, 0.26 mmol), reacted at room temperature for 20 h to obtain a dark blue mixed liquid PEDOT aqueous dispersion.

[0178] 4) Using the obtained aqueous dispersion to prepare a capacitor

[0179] The wound capacitor core was immersed in the above PEDOT aqueous dispersion, vacuumed to 0.1 MPa for 10 minutes, pressurized to 0.1 MPa for 10 minutes, and dried at 130°C for 1 hour, and repeated three times. The specification is 35V270μF solid capacitor.

[0180] Example 3

[0181] Preparation of PEDOT aqueous dispersion using PIB(6000)-b-PSS(20000) as template

[0182] 1) Preparation of macroinitiator PIB-Br

[0183] 1.1) Preparation of polymer PIB-Cl

[0184] In a 500 mL flask, add isobutylene (22.6 mL, 271 mmol), α,α-dimethylbenzyl chloride (0.385 g, 2.5 mmol), n-hexane-CH3Cl mixed solvent (100 mL, V 正己烷 / V CH3Cl =3 / 2), add TiCl4 (2.0 molL -1 ,2.0mL) of n-hexane-CH3Cl(V 正己烷 / V CH3Cl =3 / 2) solution, after 1 h of reaction, 1,3-butadiene (BD) (1.0 mol L -1 ,13.5mL) of n-hexane-CH3Cl(V 正己烷 / V CH3Cl =3 / 2) solution, maintained at -78°C, reacted for 1 hour, and then -50°C methanol was added to terminate the BD end-capping. The polymerization system was heated to room temperature under stirring, and after CH3Cl was completely evaporated, it was washed three times with deionized water, dried with MgSO4, and n-hexane was evaporated. The polymer PIB-Cl was vacuum dried at room temperature for 24 hours. The molecular weight and dispersity measured by GPC were: M n =6000 g mol -1 ,M w / M n =1.26.

[0185] 1.2) Preparation of macromolecular ATRP initiator PIB-Br

[0186] PIB-Cl (M n =6000 g mol -1 , 5mmol) was dissolved in THF (100mL), KOH (2.80g, 50mmol) was added, refluxed for 10 hours, diluted with water, extracted with ethyl acetate, the organic solvent was removed, and vacuum dried at room temperature for 24h to obtain the terminal hydroxylation product PIB-OH (M n =6000 g mol -1 , 5mmol). Dichloromethane (100mL) was added to dissolve, 2-bromoacetyl bromide (6.0g, 30mmol) and triethylamine (5.05g, 50mmol) were added, and the mixture was reacted at room temperature for 12h, washed with water, the organic solvent was removed, and the mixture was dried under vacuum at room temperature for 24h to obtain the macromolecular ATRP initiator PIB-Br.

[0187] 2) Using PIB-Br as a macromolecular ATRP initiator, free radical polymerization of monomer SSNa was initiated to prepare PIB-b-PSS

[0188] The monomer SSNa (24.70 g, 120 mmol) was dissolved in THF (500 mL) at 60°C, cooled to room temperature, and PIB-Br (6.0 g, 1.0 mmol) and cuprous bromide (0.14 g, 1.0 mmol) were added. The mixture was sealed and purged with N2 three times for 10 minutes to eliminate oxygen. A THF solution (10 mL) of N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA) (0.17 g, 1.0 mmol) was added through a gas-tight syringe. The flask was deoxygenated by three freeze-pump-thaw cycles, reacted at 70°C for 24 hours, and the flask was immersed in liquid nitrogen to terminate the polymerization. The reaction mixture was diluted with THF, and the residual cuprous bromide was removed by an alumina column. After concentration, it was precipitated in methanol and dried at 60°C for 12 hours to obtain PIB(6000)-b-PSS(20000).

[0189] 3) Preparation of PEDOT aqueous dispersion using PIB(6000)-b-PSS(20000) as template

[0190] PIB(6000)-b-PSS(20000) (20.0 g, 0.77 mmol) was added to a mixed solvent consisting of dimethyl sulfoxide and deionized water (500 mL, V DMSO / V 去离子水=13 / 37), added acetic acid solution (5.0 mL, mass fraction 1%), monomer EDOT (20.0 g, 141 mmol), ammonium persulfate (16.0 g, 70 mmol), ferric sulfate (0.10 g, 0.26 mmol), reacted at room temperature for 20 h, and obtained a dark blue mixed liquid PEDOT aqueous dispersion.

[0191] 4) Using the obtained aqueous dispersion to prepare a capacitor

[0192] The wound capacitor core is immersed in the above PEDOT aqueous dispersion, vacuumed to 0.1 MPa for ten minutes, pressurized to 0.1 MPa for ten minutes, and dried at 130°C for 1 hour, and repeated three times. The specification is 35V270μF solid capacitor.

[0193] Example 4

[0194] Preparation of PEDOT aqueous dispersion using PIB(6000)-b-PSS(40000) as template

[0195] 1) Preparation of macroinitiator PIB-Br

[0196] 1.1) Preparation of polymer PIB-Cl

[0197] In a 500 mL flask, add isobutylene (22.6 mL, 271 mmol), α,α-dimethylbenzyl chloride (0.385 g, 2.5 mmol), n-hexane-CH3Cl mixed solvent (100 mL, V 正己烷 / V CH3Cl =3 / 2), add TiCl4 (2.0 molL -1 ,2.0mL) of n-hexane-CH3Cl(V 正己烷 / V CH3Cl =3 / 2) solution, react for 1 h, add 1,3-butadiene (BD) (1.0 mol L -1 ,13.5mL) of n-hexane-CH3Cl(V 正己烷 / V CH3Cl =3 / 2) solution, keep the temperature at -78°C, react for 1 hour, add -50°C methanol to terminate BD end-capping. Then, heat the polymerization system to room temperature under stirring, and after CH3Cl is completely evaporated, wash with deionized water three times, and then dry with MgSO4. Evaporate n-hexane, and vacuum dry at room temperature for 24 hours to obtain polymer PIB-Cl. Its molecular weight and dispersity measured by GPC are: M n =6000 g mol -1 ,M w / M n =1.26.

[0198] 1.2) Preparation of macromolecular ATRP initiator PIB-Br

[0199] PIB-Cl (M n =6000 g mol -1 , 5mmol) was dissolved in THF (100mL), KOH (2.80g, 50mmol) was added, refluxed for 10 hours, diluted with water, extracted with ethyl acetate, the organic solvent was removed, and vacuum dried at room temperature for 24h to obtain the terminal hydroxylation product PIB-OH (M n =6000 g mol -1 , 5mmol). Then dichloromethane (100mL) was added to dissolve, 2-bromoacetyl bromide (6.0g, 30mmol) and triethylamine (5.05g, 50mmol) were added, reacted at room temperature for 12h, washed with water, the organic solvent was removed, and the macromolecular ATRP initiator PIB-Br was obtained after vacuum drying at room temperature for 24h.

[0200] 2) Using PIB-Br as a macromolecular ATRP initiator, free radical polymerization of monomer SSNa was initiated to prepare PIB-b-PSS

[0201] The monomer SSNa (49.44 g, 240 mmol) was dissolved in THF (800 mL) at 60 °C, cooled to room temperature, and PIB-Br (3.0 g, 0.50 mmol) and cuprous bromide (0.070 g, 0.05 mmol) were added. The mixture was sealed and purged with N2 three times for 10 minutes to eliminate oxygen. Then, a THF solution (10 mL) of N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA) (0.17 g, 1.0 mmol) was added through a gas-tight syringe. The flask was deoxygenated by three freeze-pump-thaw cycles, reacted at 70 °C for 24 h, and the flask was immersed in liquid nitrogen to terminate the polymerization. The reaction mixture was diluted with THF, and the residual cuprous bromide was removed by an alumina column. After concentration, it was precipitated in methanol and dried at 60 °C for 12 h to obtain PIB(6000)-b-PSS(40000).

[0202] 3) Preparation of PEDOT aqueous dispersion using PIB(6000)-b-PSS(40000) as template

[0203] PIB (6000) -b-PSS (40000) (20.0 g, 0.43 mmol) was added to a mixed solvent consisting of dimethyl sulfoxide and deionized water (500 mL, V DMSO / V 去离子水=13 / 37), added acetic acid solution (5.0 mL, mass fraction 1%), monomer EDOT (20.0 g, 141 mmol), ammonium persulfate (16.0 g, 70 mmol), ferric sulfate (0.10 g, 0.26 mmol), reacted at room temperature for 20 h, and obtained a dark blue mixed liquid PEDOT aqueous dispersion.

[0204] 4) Using the obtained dispersion to prepare capacitors

[0205] The wound capacitor core was immersed in the above PEDOT aqueous dispersion, vacuumed to 0.1 MPa for 10 minutes, pressurized to 0.1 MPa for 10 minutes, and dried at 130°C for 1 hour, and repeated three times. The specification is 35V270μF solid capacitor.

[0206] Comparative Example 1

[0207] Preparation of PEDOT aqueous dispersion using PSS (20000) synthesized by conventional free radical polymerization as template

[0208] 1) Using ethyl 2-bromoacetate as ATRP initiator, free radical polymerization of monomer SSNa was initiated

[0209] The monomer SSNa (24.70 g, 120 mmol) was dissolved in THF (500 mL) at 60 ° C, cooled to room temperature, and ethyl 2-bromoacetate (0.167 g, 1.0 mmol) and cuprous bromide (0.14 g, 1.0 mmol) were added. Seal and purge with N2 three times for 10 minutes to eliminate oxygen, then add N, N, N', N', N "-pentamethyldiethylenetriamine (PMDETA) (0.17 g, 1.0 mmol) THF solution (10 mL) through a gas-tight syringe, deoxygenate the flask through three freeze-pump-thaw cycles, react at 70 ° C for 24 hours, and immerse the flask in liquid nitrogen to terminate the polymerization. The reaction mixture was diluted with THF, and the residual cuprous bromide was removed by an alumina column. After concentration, it was precipitated in methanol and dried at 60 ° C for 12 hours to obtain PSS (20000).

[0210] 2) Using PSS (20000) as a template, prepare PEDOT aqueous dispersion

[0211] PSS (20000) (20.0 g, 1.00 mmol) was added to a mixed solvent consisting of dimethyl sulfoxide and deionized water (500 mL, V DMSO / V 去离子水=13 / 37), added acetic acid solution (5.0 mL, mass fraction 1%), monomer EDOT (20.0 g, 141 mmol), ammonium persulfate (16.0 g, 70 mmol), ferric sulfate (0.10 g, 0.26 mmol), reacted at room temperature for 20 h, and obtained a dark blue mixed liquid PEDOT aqueous dispersion.

[0212] 3) Preparation of capacitors using the obtained aqueous dispersion

[0213] The wound capacitor core was immersed in the above PEDOT aqueous dispersion, vacuumed to 0.1 MPa for 10 minutes, pressurized to 0.1 MPa for 10 minutes, and dried at 130°C for 1 hour, and repeated three times. The specification is 35V270μF solid capacitor.

[0214] Comparative Example 2

[0215] Preparation of PEDOT aqueous dispersion using PSS (40000) synthesized by conventional free radical polymerization as template

[0216] 1) Using ethyl 2-bromoacetate as ATRP initiator, free radical polymerization of monomer SSNa was initiated

[0217] The monomer SSNa (49.44 g, 240 mmol) was dissolved in THF (800 mL) at 60 °C, cooled to room temperature, ethyl 2-bromoacetate (0.167 g, 1.0 mmol) and cuprous bromide (0.14 g, 1.0 mmol) were added, sealed, purged with N2 three times for 10 minutes to eliminate oxygen, and then a THF solution (10 mL) of N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA) (0.17 g, 1.0 mmol) was added through a gas-tight syringe. The flask was deoxygenated by three freeze-pump-thaw cycles, reacted at 70 °C for 24 h, and the polymerization was terminated by immersing the flask in liquid nitrogen. The reaction mixture was diluted with THF and the residual cuprous bromide was removed by an alumina column. After concentration, it was precipitated in methanol and dried at 60 °C for 12 h to obtain PSS (40000).

[0218] 2) Preparation of PEDOT aqueous dispersion using PSS (40000) as template

[0219] PSS (40000) (20.0 g, 0.50 mmol) was added to a mixed solvent consisting of dimethyl sulfoxide and deionized water (500 mL, V DMSO / V 去离子水=13 / 37), added acetic acid solution (5.0 mL, mass fraction 1%), monomer EDOT (20.0 g, 141 mmol), ammonium persulfate (16.0 g, 70 mmol), ferric sulfate (0.10 g, 0.26 mmol), reacted at room temperature for 20 h, and obtained a dark blue mixed liquid PEDOT aqueous dispersion.

[0220] 3) Preparation of capacitors using the obtained dispersion

[0221] The wound capacitor core was immersed in the above PEDOT aqueous dispersion, vacuumed to 0.1 MPa for 10 minutes, pressurized to 0.1 MPa for 10 minutes, and dried at 130°C for 1 hour, and repeated three times. The specification is 35V270μF solid capacitor.

[0222] Test Data

[0223] The prepared PEDOT aqueous dispersion was made into a film by spin coating, cut into 10 cm×10 cm films, and its sheet resistance was measured using a four-probe tester. The sheet resistance of the PEDOT aqueous dispersions of Examples 1 to 4 and Comparative Examples 1 to 2 was measured as shown in the following table:

[0224] Table 1: Test data of sheet resistance of PEDOT aqueous dispersions prepared in various embodiments and comparative examples

[0225] Example Polymers in PEDOT aqueous dispersions Sheet resistance(Ω) Example 1 PIB(3000)-b-PSS(20000):PEDOT 253 Example 2 PIB(3000)-b-PSS(40000):PEDOT 337 Example 3 PIB(6000)-b-PSS(20000):PEDOT 172 Example 4 PIB(6000)-b-PSS(40000):PEDOT 296 Comparative Example 1 PEDOT:PSS(20000) 1183 Comparative Example 2 PEDOT:PSS(40000) 1451

[0226] The parameters of the prepared capacitor were measured using an LCR bridge tester, and the results are shown below

[0227] Table 2: Test data of capacitor parameters prepared in various embodiments and comparative examples

[0228] Example Capacitance C / μF tgδ / % ESR / mΩ Z / mΩ Extraction rate Example 1 278 1.07 6.9 7.8 92.6％ Example 2 276 1.09 7.4 8.2 92.0％ Example 3 280 1.06 6.8 7.7 93.3％ Example 4 278 1.07 7.0 8.0 92.6％ Comparative Example 1 269 1.16 13.5 14.3 89.7％ Comparative Example 2 267 1.18 15.4 16.7 89.0％

[0229] As shown in Table 1, the conductivity of the PEDOT aqueous dispersion prepared using the amphiphilic block copolymer PIB-b-PSS as a template has been significantly improved. As shown in Table 2, the resistance of the solid capacitor prepared using the PEDOT aqueous dispersion prepared using the amphiphilic block copolymer PIB-b-PSS as a template has been reduced and the extraction rate has been improved.

[0230] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0231] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A novel PEDOT aqueous dispersion, characterized in that: The PEDOT aqueous dispersion comprises a PIB-b-PSS:PEDOT polymer, and the structural formula of the PIB-b-PSS:PEDOT polymer is: Among them, m is 2 to 200, n is 2 to 500, and x is 2 to 500.

2. A method for preparing the novel PEDOT aqueous dispersion according to claim 1, characterized in that: The following steps are involved: 1) Preparation of PIB-Br 1.1) Preparation of polymer PIB-Cl Isobutylene and 1,3-butadiene are polymerized in the presence of initiator A and catalyst A to obtain polymer PIB-Cl; 1.2) Preparation of PIB-Br The polymer PIB-Cl is refluxed in the presence of an inorganic base to obtain a terminal hydroxylation product PIB-OH; PIB-OH reacts with 2-bromoacetyl bromide at room temperature to obtain PIB-Br; 2) Preparation of PIB-b-PSS The monomers SSNa and PIB-Br are polymerized in the presence of a copper catalyst and a ligand to obtain PIB-b-PSS; 3) Preparation of PEDOT aqueous dispersion PIB-b-PSS and EDOT monomer react at room temperature in the presence of acetic acid solution, oxidant and catalyst B to obtain PEDOT aqueous dispersion.

3. The preparation method according to claim 2, characterized in that: In step 1.1), The solvent of the polymerization reaction is one of n-hexane and methyl chloride or a combination thereof; The initiator A is α,α-dimethylbenzyl chloride; The catalyst A is one of titanium tetrachloride, zirconium tetrachloride, chromium trichloride or a combination thereof.

4. The preparation method according to claim 2, characterized in that: In step 1.1), The molar ratio of isobutylene to initiator A is 300:1-100; The molar ratio of isobutylene to catalyst A is 50 to 100:1; The molar ratio of the 1,3-butadiene to the initiator A is 2 to 6:

1.

5. The preparation method according to claim 2, characterized in that: In step 1.2), The inorganic base is one or a combination of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; The molar ratio of the polymer PIB-Cl to the inorganic base is 1:5 to 20; The molar ratio of PIB-OH to 2-bromoacetyl bromide is 1:5-20; The reaction system of PIB-OH and 2-bromoacetyl bromide also includes an acid binding agent; The acid binding agent is one of triethylamine or pyridine or a combination thereof; The molar ratio of the 2-bromoacetyl bromide to the acid binding agent is 1:1-2.

6. The preparation method according to claim 2, characterized in that: In step 2), The molar ratio of the monomer SSNa to PIB-Br is 1000:1-300; The copper catalyst is selected from cuprous bromide, cuprous chloride, cuprous sulfate or a combination thereof; The molar ratio of the copper catalyst to PIB-Br is 1:1 to 10; The ligand is one of N,N,N',N',N"-pentamethyldiethylenetriamine, 2,2'-bipyridine, tris(2-methylaminoethyl)amine or a combination thereof; The molar ratio of the ligand to PIB-Br is 1 to 2:

1.

7. The preparation method according to claim 2, characterized in that: In step 3), The solvent of the reaction consists of dimethyl sulfoxide and deionized water; The volume ratio of dimethyl sulfoxide to deionized water is 1:2-5; The mass ratio of the monomer EDOT to PIB-b-PSS is 10:1-20; The mass ratio of the acetic acid solution to deionized water is 1:60-200; The mass fraction of the acetic acid solution is 0.5% to 1.6%.

8. The preparation method according to claim 7, characterized in that: In step 3), The oxidant is selected from one of ammonium persulfate, potassium persulfate, sodium persulfate or a combination thereof; The molar ratio of the oxidant to the monomer EDOT is 0.3 to 3:1; The catalyst B is ferric sulfate; The molar ratio of the catalyst B to the monomer EDOT is 0.001 to 0.006:1; The mass ratio of dimethyl sulfoxide to monomer EDOT is 0.2 to 10:1; The solid content of the PEDOT aqueous dispersion is 1-15%.

9. The preparation method according to claim 2, characterized in that: In step 1.1), the polymerization reaction temperature is -100 to -70°C, isobutylene is reacted in the presence of initiator A and catalyst A for 0.5 to 2 hours, 1,3-butadiene is added, and the reaction is continued for another 0.5 to 2 hours; In step 1.2), the reaction time of PIB-OH and 2-bromoacetyl bromide at room temperature is 10 to 15 hours; In step 2), the polymerization reaction temperature is 70-80°C and the reaction time is 20-30h; In step 3), the reaction time is 15 to 30 hours.

10. A solid capacitor, characterized in that: The solid capacitor is obtained by immersing a wound capacitor core into the PEDOT aqueous dispersion according to claim 1 or the PEDOT aqueous dispersion prepared by the method according to any one of claims 2 to 8.

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