CN102321341B - Conductive polymer material and capacitor comprising the same - Google Patents
Conductive polymer material and capacitor comprising the same Download PDFInfo
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- CN102321341B CN102321341B CN 201110253245 CN201110253245A CN102321341B CN 102321341 B CN102321341 B CN 102321341B CN 201110253245 CN201110253245 CN 201110253245 CN 201110253245 A CN201110253245 A CN 201110253245A CN 102321341 B CN102321341 B CN 102321341B
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Abstract
The present invention provides a conductive polymer material, and a capacitor comprising the conductive polymer material. According to the present invention, the conductive polymer material comprises a conductive polymer and 1-napsylate ion doped in the conductive polymer; the conductive polymer is prepared through oxidative polymerization of a polymer monomer. The conductive polymer material provided by the present invention has characteristics of high conductivity and strong voltage resistance. With adopting the conductive polymer material as the electrolyte, the solid aluminum conductive polymer capacitor has advantages of high temperature resistance, low equivalent series resistance (ESR), strong treatment capacity for low leakage current, and high breakdown voltage.
Description
Technical field
The present invention relates to the electrical condenser manufacture field, especially relate to a kind of conducting polymer composite and comprise its electrical condenser.
Background technology
Electrical condenser is a kind of device that can store electric charge, and they can be by two pole plates that are oppositely arranged, and negative plate and positive plate consist of; Also can consist of by insulating trip being inserted between two pole plates.It is the most basic in the electronics also be one of most important assembly.The output of electric capacity accounts for more than 40% of global electronic components and parts product, and all electronicss basically are little of USB flash disk, digital camera, can see greatly its figure in space shuttle, the rocket.As the most basic a kind of electronic devices and components, electric capacity for the electronics just as food for indispensable the people.
But be the fully embodiment of a national industrial technology ability though electric capacity is little, especially high-grade electric capacity representative be that the requirement that manufactures and designs of the high-grade electric capacity product of level (U.S., Japan are in the world two the highest countries of capacitor design Research Ability) of national precision sizing, chemical industry, material, fundamental research even is not second to CPU.Electric capacity is almost ubiquitous, and is upper to god five, lower to USB flash disk, has the place of power supply that it is just arranged.The effect of electric capacity is very many, as: stopping direct current, bypass (decoupling), filtering, the tuning rectification energy storage of temperature compensation timing etc.
Electrical condenser can be divided into alminium electrolytic condenser, tantalum chemical capacitor, niobium chemical capacitor according to the anode of chemical capacitor.Traditional view was that the tantalum capacitive property is better than aluminum capacitor in the past, because the medium of tantalum electric capacity is the tantalum pentoxide that generates after the anodic oxidation, its dielectric properties (usually representing with ε) is higher than the aluminium sesquioxide medium of aluminum capacitor.Therefore in the situation of same capacity, the volume energy of tantalum electric capacity is done littlely than aluminum capacitor.The character of adding tantalum is more stable, so it has been generally acknowledged that the tantalum capacitive property is better than aluminum capacitor.
But this method with anode judgement capacitive property is out-of-date, determines at present the crucial of chemical capacitor performance and does not lie in anode, and be ionogen, namely negative electrode.Because different negative electrodes can be combined into different types of chemical capacitor with different anodes, its performance also differs widely.Adopt the electric capacity of same anode owing to electrolytical difference, performance can have a long way to go, and anode is far smaller than negative electrode for the impact of capacitive property in a word.
The negative electrode of electric capacity has electrolytic solution, Manganse Dioxide, TCNQ, solid polymer conductor (PPY/PEDT) and CVEX mixed type (solid polymer conductor+electrolytic solution) at present substantially.Use different anodes and cathode material can be combined into the chemical capacitor of plurality of specifications.For example the tantalum chemical capacitor also can use the solid polymer conductor as negative electrode, and alminium electrolytic condenser both can use electrolytic solution, also can use TCNQ, PPY and PEDT etc.
At present, it is very fast that novel chemical capacitor develops, and chemical capacitor is being replaced some inorganic and organic dielectric capacitor.Because nowadays the progress of technology also begins to be widely used chemical capacitor in the military countermeasures set that miniaturization is had relatively high expectations.
With respect to traditional aluminum electrolytic capacitor and organic semiconductor electrical condenser, aluminium matter solid state conductive polymer electrical condenser, use electroconductive polymer to conduct, have under high conductivity and the condition of high temperature and stablize, equivalent series resistance is low and can bear larger filtered circuit.Its conductivity is 10000 times of conventional aluminum electrolytic capacitor.It has following advantage: 1. have high-transmission rate and high electrical conductivity in visible spectrum; 2. least surface resistance can reach 150 Ω/cm2 (depend on and create conditions); 3. better resistance to hydrolysis, light stability and thermostability; 4. when high pH value, electroconductibility can not descend.It is low impedance at high frequency that the selling point of aluminium solid conduction polymer capacitor shows as; Good temperature profile; Volume is little; Life-span is long, without the phenomenon of leakage.And then this macromolecule conducting material (PEDT) has replaced the solid electrolytic capacitor of traditional electrolytic solution gradually.
The use properties of aluminium matter solid state conductive polymer electrical condenser is subjected to the performance impact of its conducting polymer composite that adopts, anticipation strengthens high-temperature stability, the low electric leakage processing power of aluminium matter solid state conductive polymer electrical condenser and strengthens voltage breakdown, and the conducting polymer composite of seeking a kind of better effects if is imperative.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of conducting polymer composite is provided, this conducting polymer composite has specific conductivity height, characteristics that proof voltage is strong, while is had high temperature resistant by the prepared electrical condenser of this conducting polymer composite, equivalent series resistance (ESR) is lower, leakage current (LC) is less, resist the higher characteristics of voltage of wearing.
For this reason, the invention provides a kind of conducting polymer composite, comprise conductive polymers and the 1-naphthalene sulfonic aicd radical ion that mixes with described conductive polymers, conductive polymers is to be made through oxypolymerization by polymerization single polymerization monomer.
Further, the doping level of 1-naphthalene sulfonic aicd radical ion is 40%～65% in the above-mentioned conducting polymer composite.
Further, the 1-naphthalene sulfonic aicd radical ion is that form with 1-naphthalene sulfonic aicd iron is incorporated in the reaction system in the above-mentioned conducting polymer composite.
Further, the mol ratio of the add-on of the introducing amount of above-mentioned 1-naphthalene sulfonic aicd iron and polymerization single polymerization monomer is 1.5: 1～2.4: 1.
Further, the 1-naphthalene sulfonic aicd radical ion is that form with the mixing solutions of 1-naphthalene sulfonic aicd iron and 1-naphthalene sulfonic aicd is incorporated in the reaction system in the above-mentioned conducting polymer composite.
Further, the add-on of above-mentioned 1-naphthalene sulfonic aicd be polymerization single polymerization monomer and 1-naphthalene sulfonic aicd iron join total mass 1%～5%.
Further, the add-on of above-mentioned 1-naphthalene sulfonic aicd is 2%～3% of polymerization single polymerization monomer and 1-naphthalene sulfonic aicd iron total mass.
Further, above-mentioned 1-naphthalene sulfonic aicd iron is with 3 water crystallizations, and the 1-naphthalene sulfonic aicd iron form of 6 water crystallizations or 9 water crystallizations adds.
Further, above-mentioned polymerization single polymerization monomer is EDOT, perhaps for having the mixture of the monomer of structure in following structural formula (1), (2) and (3):
Structural formula (1) structural formula (2) structural formula (3)
Wherein, R is alkyl.
Simultaneously, also provide in the present invention a kind of electrical condenser, comprised above-mentioned conductive polymer material in this electrical condenser.
Beneficial effect of the present invention is as follows: have specific conductivity height, strong, the resistant to elevated temperatures characteristics of proof voltage by conductive polymer material provided by the present invention.It is strong to adopt it to have lower, the low electric leakage processing power of equivalent series resistance (ESR) as electrolytical aluminium matter solid state conductive polymer electrical condenser, the advantage that voltage breakdown is high.
Except purpose described above, feature and advantage, the present invention also has other purpose, feature and advantage.The below is with reference to embodiment, and the present invention is further detailed explanation.
Embodiment
Be noted that following detailed description all is exemplary, is intended to the invention provides further instruction.Unless otherwise, all technology used herein and scientific terminology have the identical meanings of usually understanding with the general technical staff of the technical field of the invention.
Term " doping " refers to the redox reaction that occurs at the conjugated structure macromolecular chain its essence is charge transfer in the present invention.The δ electronics can't move along main chain on the conjugated polymer chain, though and π-electron is more mobile, but also suitable localization, therefore must remove portions of electronics on the main chain (oxidation) or introduce portions of electronics (reduction), these holes or extra electron can be mobile at molecular chain, make this polymer become electrical conductor.Conducting polymer not only can mix, but also can " dedoping ", and this process completely reversibility of doping-dedoping.
In the present invention " doping " refer to that the ferric ion in the oxygenant carries out peroxidation with the high molecular polymer main chain, make the macromolecular chain positively charged, for keeping electric neutrality, 1-naphthalene sulfonic aicd radical ion with negative electricity also enters main polymer chain, make whole main polymer chain be electric neutrality, make it become conduction state through this doping process." dedoping " refers to that macromolecular chain is subject to external voltage, electric field in conducting polymer composite, can cause the negatively charged ion destabilization during high temperature, and then causes negatively charged ion to break away from the process of macromolecular chain.
Term " doping level " refers to the delocalization positive and negative charge weight (mark) that each link units is occupied on the macromolecular chain in the present invention.Doping level refers to the ratio of molar weight and the monomer molar amount of negatively charged ion in the whole system in the present invention, and wherein, the negatively charged ion of whole system has comprised anionicsite in the 1-naphthalene sulfonic aicd iron and the anionicsite in the 1-naphthalene sulfonic aicd.
In a kind of typical embodiment of the present invention, provided a kind of conducting polymer composite, this conducting polymer composite comprises conductive polymers and the 1-naphthalene sulfonic aicd radical ion that mixes with conductive polymers, and conductive polymers is made through oxypolymerization by polymerization single polymerization monomer.Wherein, the 1-naphthalene sulfonic aicd radical ion has structure in the following structural formula (4):
Structural formula (4)
In this embodiment, adopted that volume is large, space structure is complicated, sterically hindered large 1-naphthalene sulfonic aicd radical ion and conductive polymers mix, and then formation the present invention conducting polymer composite required for protection.The 1-naphthalene sulfonic aicd radical ion has larger steric hindrance in this conducting polymer composite, form larger steric hindrance, even under high-temperature and high-pressure conditions, also be not easy dedoping from conducting polymer composite, this also can keep the advantage of high conductivity, high withstand voltage just so that conducting polymer composite provided by the present invention uses under High Temperature High Pressure.
The electric conductivity of conducting polymer composite and withstand voltage electrically and the performance of conductive polymers and direct relation is arranged with the performance of its negatively charged ion that mixes, in this embodiment of the present invention, emphasis has provided a kind of anion structure that is entrained in conductive polymers, in actual applications, no matter adopt which kind of conductive polymers, as long as wherein being doped with 1-naphthalene sulfonic aicd radical ion provided by the present invention just can make conducting polymer composite keep use under high temperature, high pressure, keep high conductance, low leakage property and withstand voltage properties.
In the present invention, the doping level of 1-naphthalene sulfonic aicd radical ion can be 10%～90% in the above-mentioned conducting polymer composite, just can be so that prepared conducting polymer composite have preferably specific conductivity in this scope, and withstand voltage properties, but still not enough.Preferably, in the present invention best doping level is 40%～65%, and doping level is the most suitable in this scope, the electroconductibility of macromolecular material, and the stability of thermotolerance and film all reaches best effect.
In a kind of concrete embodiment of the present invention, the 1-naphthalene sulfonic aicd radical ion is that form with 1-naphthalene sulfonic aicd iron is incorporated in the reaction system in the above-mentioned conducting polymer composite.In the process of conducting polymer composite preparation provided by the present invention, polymerization single polymerization monomer is mixed with 1-naphthalene sulfonic aicd iron, the polymkeric substance that generates after the polymerization single polymerization monomer polymerization itself is without electric charge, that ferric ion in the reaction system continues the part of atoms in the polymkeric substance is carried out peroxidation, make it with positive charge, and then 1-naphthalene sulfonic aicd root negatively charged ion is doped in the high molecular polymer, form the high conductivity conductive polymers, the anion doped process of 1-naphthalene sulfonic aicd root has formed conducting polymer composite of the present invention.
Preferably, when above-mentioned conducting polymer composite prepared, the mol ratio of the introducing amount of 1-naphthalene sulfonic aicd iron and the add-on of polymerization single polymerization monomer was 1.5: 1～2.4: 1.Both ratio control are conducive to introduce suitable ferric ion with oxypolymer in this scope, form conductive polymers, and then formation conducting polymer composite, simultaneously, both ratio control is conducive to control the doping level of 1-naphthalene sulfonic aicd radical ion in the conducting polymer composite in this scope, is located in the above-mentioned preferable range.
In a kind of concrete embodiment of the present invention, the 1-naphthalene sulfonic aicd radical ion is that form with the mixing solutions of 1-naphthalene sulfonic aicd iron and 1-naphthalene sulfonic aicd is incorporated in the reaction system in the above-mentioned conducting polymer composite.In the process of conducting polymer composite preparation provided by the present invention, 1-naphthalene sulfonic aicd is joined in the mixing solutions of 1-naphthalene sulfonic aicd iron and polymerization single polymerization monomer, more be conducive to control the molar weight of ferric ion in the reaction system and the molar weight of 1-naphthalene sulfonic aicd radical ion.
In the preparation engineering of conducting polymer composite, the part of atoms of ferric ion in can oxypolymer, make it with electric charge, and then mix with the 1-naphthalene sulfonic aicd radical ion, in case but the input amount of ferric ion is too much, on the contrary can be so that the peroxidation heighten degree of part of atoms in the polymkeric substance, so that the conducting polymer composite backbone breaking that generates, reduced the conductance of macromolecular material and withstand voltage.For fear of this phenomenon that generates the conducting polymer composite splitting of chain, can only control the input amount of ferric ion.If only with the introducing source of 1-naphthalene sulfonic aicd iron as the 1-naphthalene sulfonic aicd radical ion, just limit the input amount of 1-naphthalene sulfonic aicd radical ion in the time of the input amount of control ferric ion.So just be unfavorable for controlling the doping level of 1-naphthalene sulfonic aicd radical ion in the conducting polymer composite.
In this embodiment, by in reaction system, introducing 1-naphthalene sulfonic aicd, on the basis of the input amount of controlling ferric ion, increase the input amount of 1-naphthalene sulfonic aicd radical ion, and then so that in the prepared conducting polymer composite doping level of 1-naphthalene sulfonic aicd radical ion be positioned at above-mentioned preferable range.
In this embodiment, the add-on of above-mentioned 1-naphthalene sulfonic aicd is 1%～5% of monomer and 1-naphthalene sulfonic aicd iron total mass.Preferably, the add-on of 1-naphthalene sulfonic aicd is 2%～3%.The consumption of 1-naphthalene sulfonic aicd is controlled at the doping level that is conducive to control 1-naphthalene sulfonic aicd radical ion in the conducting polymer composite in this scope, is located in the above-mentioned preferred scope.
Preferably, above-mentioned 1-naphthalene sulfonic aicd iron is with 3 water crystallizations, and the form of 6 water crystallizations or 9 water crystallization 1-naphthalene sulfonic aicd iron adds.
The selection of preparation conductive polymers employed polymerization single polymerization monomer has multiplely in conducting polymer composite provided by the present invention, has two conjugatedπbonds, and material that can the open loop chaining can use as polymerization single polymerization monomer.
In a kind of concrete embodiment of the present invention, above-mentioned polymerization single polymerization monomer is EDOT, the structure of EDOT such as structural formula (5)
Structural formula (5)
EDOT is a kind of common monomer, it also is the raw material commonly used that the preparation electrical condenser is used conducting polymer composite in the prior art, this raw material obtains easily, in this embodiment, the conductive polymers that is generated by the EDOT monomer polymerization in the conducting polymer composite and 1-naphthalene sulfonic aicd radical ion mix, because 1-naphthalene sulfonic aicd radical ion volume is large, space structure is complicated, sterically hindered large characteristics are so that prepared conducting polymer composite has good specific conductivity and resistance to pressure.
In this embodiment, monomer is EDOT, and the negatively charged ion that mixes is the 1-naphthalene sulfonic aicd radical ion.The difference of the process of mixing according to reality, it may have various structures, below provides 4 kinds of possible structures, comprises structural formula (6), (7), (8), (9).Because it is larger that the structure of 1-naphthalene sulfonic aicd radical ion takes up space, in structural formula (6), (7), (8), (9), the 1-naphthalene sulfonic aicd radical ion replaces with Y.
Structural formula (6)
Structural formula (7)
Structural formula (8)
Structural formula (9)
In the concrete embodiment of another kind of the present invention, above-mentioned polymerization single polymerization monomer is for having the mixture of the monomer of structure in following structural formula (1), (2) and (3).
Polymerization single polymerization monomer is for having the mixture of the monomer of structure in following structural formula (1), (2) and (3):
Structural formula (1) structural formula (2) structural formula (3)
Wherein, R is alkyl.
Contain 5%～40% the monomer with structural formula (1) in the above-mentioned polymerization single polymerization monomer according to quality percentage composition meter, 5%～40% the monomer with structural formula (2), 55%～65% the monomer with structural formula (3).When polymer monomer is that its preparation method can be referring to the Chinese patent of number of patent application 201110179797.2 when having the mixture of the monomer of structure in said structure formula (1), (2) and (3).
In this embodiment, the polymkeric substance and the 1-naphthalene sulfonic aicd radical ion that have the monomer of structure in said structure formula (1), (2) and (3) in the conducting polymer composite mix, because 1-naphthalene sulfonic aicd radical ion volume is large, space structure is complicated, sterically hindered large characteristics are so that prepared conducting polymer composite has good specific conductivity and resistance to pressure.
Provide in the present invention a kind of preparation method of above-mentioned conducting polymer composite, wherein polymerization single polymerization monomer is EDOT, concrete steps are as follows: will comprise that the solution of EDOT monomer and oxygenant 1-naphthalene sulfonic aicd ferrous solution mix, under 20 ℃～80 ℃ temperature, reaction 1～3h makes conducting polymer composite.
Among the preparation method of above-mentioned conducting polymer composite, preferably the EDOT monomer solution is to be formed by EDOT monomer and volatile solvent configuration, and its concentration is 30%～60%.Above-mentioned oxidizing agent solution is to be 40%～60% 1-naphthalene sulfonic aicd ferrous solution by the concentration that the configuration of 1-naphthalene sulfonic aicd iron and volatile solvent forms.Adopt respectively volatile solvent to be configured to solution polymerization single polymerization monomer and oxygenant, more be conducive to the catalyst reaction between polymerization single polymerization monomer and the oxygenant, more be conducive to the formation of conducting polymer composite.Simultaneously, volatile solvent can volatilize under hot environment after the above-mentioned reaction finishing, and can not stay in the prepared macromolecular material, more is conducive to the close structure of prepared conducting polymer composite.
The preparation method of the another kind of above-mentioned conducting polymer composite that provides in the present invention, wherein polymerization single polymerization monomer is EDOT, concrete steps are as follows: will comprise that the solution of EDOT monomer and oxygenant 1-naphthalene sulfonic aicd ferrous solution mix rear adding 1-naphthalene sulfonic aicd solution, under 20 ℃～80 ℃ temperature, reaction 1～5h makes conducting polymer composite.
Among the preparation method of above-mentioned conducting polymer composite, preferably the EDOT monomer solution is to be formed by EDOT monomer and volatile solvent configuration, and its concentration is 30%～60%.Above-mentioned oxidizing agent solution is to be 40%～60% 1-naphthalene sulfonic aicd ferrous solution by the concentration that the configuration of 1-naphthalene sulfonic aicd iron and volatile solvent forms.Adopt respectively volatile solvent to be configured to solution polymer and oxygenant, more be conducive to the catalyst reaction between polymerization single polymerization monomer and the oxygenant, more be conducive to the formation of conducting polymer composite.Simultaneously, volatile solvent can volatilize under hot environment after the above-mentioned reaction finishing, and can not stay in the prepared macromolecular material, more is conducive to the close structure of prepared conducting polymer composite.
Among the preparation method of above-mentioned conducting polymer composite, optional volatile solvent comprises the nitride such as the alcohols such as the ketones such as ester class, acetone, methyl alcohol, acetonitrile such as the ethers, ethyl formate of the hydrocarbon class of pentane, tetrahydrofuran (THF), wherein preferably uses methyl alcohol, ethanol, acetone mixing solutions or or the mixing solutions of methyl alcohol, ethanol.More preferably use methyl alcohol, alcohol mixed solution, the content of methyl alcohol is 40%～60% in methyl alcohol, the alcohol mixed solution.
Simultaneously, also provide in the present invention a kind of electrical condenser, this electrical condenser comprises above-mentioned conducting polymer composite.The following concrete preparation method who provides a kind of electrical condenser:
Nail volume: will and change into the anode foils (Al foil) of processing and draw guide pin by nail joint respectively above the Cathode Foil (Al foil or Carbon foil) through excessive erosion, as plate lead and cathode leg, folder is reeled with electrolytic paper and is formed capacitor body (sub-prime) between anode foils and Cathode Foil again, and is fixed with high temperature resistant adhesive tape;
Welding: the sub-prime that nail is spooled is welded to above the T plate, and puts into the dish of quenching;
Change into: the sub-prime that will be welded to the T plate be immersed in the deployed forming liquid (1%～5% ammonium adipate solution) anode foils is all immersed and in addition corresponding formation voltage change into processing, the edge that cuts that is used for repairing aluminium foil prevents electric leakage and short circuit;
Carbonization: electrolytic paper is carried out carbonizing treatment;
The impregnation polymerization: capacitor body (sub-prime) the impregnation oxidizing agent solution concentration after carbonization finished is 40%～55% oxygenant 1-naphthalene sulfonic aicd iron, then impregnation EDOT monomer, then add in the volatile solvent, so that the concentration of monomer solution is 30%～60%; Chemical polymerization occurs in capacitor body (sub-prime), forms conducting polymer composite solid electrolyte layer provided by the present invention.
Can be the nitride such as the alcohols such as the ketones such as ester class, acetone, methyl alcohol, acetonitrile such as ethers, ethyl formate of the hydrocarbon class of pentane, tetrahydrofuran (THF) as above-mentioned volatile solvent, wherein preferably select the mixing solutions of methyl alcohol, ethanol, acetone or methanol/ethanol.The mixing solutions of methanol/ethanol 40%～60% is particularly outstanding.
Group is vertical: the sub-prime that polymerization is good is contained in glue and covers and put it in the aluminum hull, carries out subsequently the rolling sealing.Obtain the naked product of electrical condenser.
Clean: guide pin is because through changing into and carbonization and polymerization high temperature, surface stain is so will clean up guide pin with corresponding solution.
Aging: as the naked product of electrical condenser to be carried out high-temperature charging process, repaired its dielectric medium---the damage of aluminium sesquioxide, reduce leakage current.And sort by ageing machine.
Following examples 1-10 is the performance that example further specifies macromolecular material of the present invention and comprises its electrical condenser, and the specification of prepared electrical condenser is 68 μ F/32v among the embodiment 1-5, and Φ 8 * 8.
Embodiment 1
Raw material: 1 mole of polymeric monomer intermixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the said mixture according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3), 1.5 moles of 1-naphthalene sulfonic aicd ferroxidants.1-naphthalene sulfonic aicd iron adds with three water crystallization 1-naphthalene sulfonic aicd iron forms.
Making method: it is 30% monomer mixture solution that the monomer that will have structure in the structural formula (1), (2), (3) is made as concentration with volatile solvent in proportion, it is 60% oxidizing agent solution that 1-naphthalene sulfonic aicd ferroxidant and volatile solvent are formulated as concentration, polymerization single polymerization monomer mixing solutions and oxidizing agent solution are mixed under 20 ℃ temperature, reaction 5h makes conducting polymer composite; And use this conducting polymer composite and make aluminium matter solid state conductive polymer electrical condenser.
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 35% in the prepared conducting polymer composite.
Embodiment 2
Starting material: 1 mole of monomer mixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the above-mentioned monomer according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3); 1.6 mole 1-naphthalene sulfonic aicd ferroxidant.
Making method: with embodiment 1
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 41% in the prepared conducting polymer composite.
Embodiment 3
Starting material: 1 mole of monomer mixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the above-mentioned monomer according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3); 2.2 mole 1-naphthalene sulfonic aicd ferroxidant; Massfraction is 2% 1-naphthalene sulfonic aicd of polymerization single polymerization monomer and oxygenant total mass.
Making method: it is 30% monomer mixture solution that the monomer that will have structure in the structural formula (1), (2), (3) with volatile solvent is made as concentration in proportion at 1: 1: 3, it is 60% oxidizing agent solution that 1-naphthalene sulfonic aicd ferroxidant and volatile solvent are formulated as concentration, polymerization single polymerization monomer mixing solutions and oxidizing agent solution are mixed, 1-naphthalene sulfonic aicd adds in proportion, under 20 ℃ temperature, reaction 5h makes conducting polymer composite; And use this conducting polymer composite and make aluminium matter solid state conductive polymer electrical condenser.
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 49% in the prepared conducting polymer composite.
Embodiment 4
Starting material: 1 mole of monomer mixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the above-mentioned monomer according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3); 2.2 mole 1-naphthalene sulfonic aicd ferroxidant; Massfraction is 3% 1-naphthalene sulfonic aicd of polymerization single polymerization monomer and oxygenant total mass.
Making method: with embodiment 3.
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 55% in the prepared conducting polymer composite.
Embodiment 5
1 mole of monomer mixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the above-mentioned monomer according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3); 2.4 mole 1-naphthalene sulfonic aicd ferroxidant; Massfraction is 5% 1-naphthalene sulfonic aicd of polymerization single polymerization monomer and oxygenant total mass.
Making method: with embodiment 3.
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 68% in the prepared conducting polymer composite.
Embodiment 6
1 mole of monomer mixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the above-mentioned monomer according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3); 1.6 mole 1-naphthalene sulfonic aicd ferroxidant; Massfraction is 1% 1-naphthalene sulfonic aicd of polymerization single polymerization monomer and oxygenant total mass.
Making method: with embodiment 3.
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 43% in the prepared conducting polymer composite.
Embodiment 7
1 mole of monomer mixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the above-mentioned monomer according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3); 1.2 mole 1-naphthalene sulfonic aicd ferroxidant.
Making method: with embodiment 1.
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 28% in the prepared conducting polymer composite.
Embodiment 8
1 mole of monomer mixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the above-mentioned monomer according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3); 2.8 mole 1-naphthalene sulfonic aicd ferroxidant; Massfraction is the 1-naphthalene sulfonic aicd of polymerization single polymerization monomer and oxygenant total mass 1%.
Making method: with embodiment 3.
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 78% in the prepared conducting polymer composite.
Embodiment 9
Starting material: 1 mole of EDOT monomer, 1.4 moles of 1-naphthalene sulfonic aicd ferroxidants, massfractions be polymerization single polymerization monomer and oxygenant total mass be 2% 1-naphthalene sulfonic aicd.
Making method: it is 30% monomer mixture solution that monomer EDOT and volatile solvent are made as concentration, it is 60% oxidizing agent solution that 1-naphthalene sulfonic aicd ferroxidant and volatile solvent are formulated as concentration, 1-naphthalene sulfonic aicd adds in proportion, monomer mixture solution and oxidizing agent solution are mixed, under 20 ℃ temperature, reaction 5h makes conducting polymer composite; And use this conducting polymer composite and make aluminium matter solid state conductive polymer electrical condenser.
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 43% in the prepared conducting polymer composite.
Embodiment 10
Starting material: 1 mole of EDOT monomer, 1.8 moles of 1-naphthalene sulfonic aicd ferroxidants, massfractions are the 1-naphthalene sulfonic aicd of polymerization single polymerization monomer and oxygenant total mass 3%.
Making method: with embodiment 9
Infrared, nuclear-magnetism detects: the doping level of 1-naphthalene sulfonic aicd radical ion is 52% in the prepared conducting polymer composite.
Comparative Examples 1
1 mole of monomer mixture with structure in structure (1), (2), (3), contain 20% the monomer with structural formula (1) in the above-mentioned monomer according to quality percentage composition meter, 20% the monomer with structural formula (2), 60% the monomer with structural formula (3); 1.4 mole p-methyl benzenesulfonic acid iron.
Making method: it is 30% monomer mixture solution that the monomer that will have structure in the structural formula (1), (2), (3) with volatile solvent is made as concentration in proportion at 1: 1: 3, it is 60% oxidizing agent solution that p-methyl benzenesulfonic acid ferroxidant and volatile solvent are formulated as concentration, monomer mixture solution and oxidizing agent solution are mixed, under 20 ℃ temperature, reaction 5h makes conducting polymer composite; And use this conducting polymer composite and make aluminium matter solid state conductive polymer electrical condenser.
Infrared, nuclear-magnetism detects: the doping level of p-methyl benzenesulfonic acid radical ion is 39% in the prepared conducting polymer composite.
Comparative Examples 2
Starting material: 1 mole of EDOT monomer, 1.8 moles of p-methyl benzenesulfonic acid iron.
Making method: it is 30% monomer mixture solution that 1 mole of EDOT monomer and volatile solvent are made as concentration, it is 60% oxidizing agent solution that p-methyl benzenesulfonic acid ferroxidant and volatile solvent are formulated as concentration, monomer mixture solution and oxidizing agent solution are mixed, under 20 ℃ temperature, reaction 5h makes conducting polymer composite; And use this conducting polymer composite and make aluminium matter solid state conductive polymer electrical condenser.
Infrared, nuclear-magnetism detects: the doping level of p-methyl benzenesulfonic acid radical ion is 43% in the prepared conducting polymer composite.
Will by the prepared conducting polymer composite of embodiment 1-10 and the electrical condenser that comprises it with by the prepared conducting polymer composite of Comparative Examples and comprise that its electrical condenser carries out performance test.Testing method is those skilled in the art's common method, and test result sees Table 1.
Table 1
By data in the table 1 as can be known, by the prepared conducting polymer composite of the prepared conducting polymer composite of embodiment of the invention 1-10 and Comparative Examples Comparatively speaking, be better than the specific conductivity of the prepared conducting polymer composite of Comparative Examples by the specific conductivity of the prepared conducting polymer composite of embodiment of the invention 1-10, and the resistance to pressure of the prepared conducting polymer composite of embodiment of the invention 1-10 also is better than the prepared conducting polymer composite of Comparative Examples.
By the prepared electrical condenser of embodiment of the invention 1-10 and the prepared electrical condenser of Comparative Examples compare as can be known by the first characteristic of the made electrical condenser of embodiment 1-10 all will be good than the performance of Comparative Examples many, particularly the prepared electrical condenser of leakage current LC and Comparative Examples is little a lot, and breakdown voltage resistant much higher.
Wherein embodiment 1-8 utilizes the monomer polymerization with structure in structure (1), (2), (3) to make conductive polymers, in embodiment 1-8, the performance of the conducting polymer composite that embodiment 3-6 is prepared is better than embodiment 7-8, this is because the mol ratio of oxide compound 1-naphthalene sulfonic aicd iron and polymerization single polymerization monomer is in 1.5: 1～2.4: 1 scopes, so that the doping level of prepared conducting polymer composite is between 40%-65% among the embodiment 1-6.And then so that prepared conducting polymer composite has good characteristic.
The performance of the conducting polymer composite that embodiment 3-6 is prepared is better than the prepared conducting polymer composite of embodiment 1-2, this is because increased the raw material 1-naphthalene sulfonic aicd among the embodiment 3-6, and then accent has increased the concentration of 1-naphthalene sulfonic aicd radical ion in the reaction system effectively, and then the doping level of having regulated better conducting polymer composite.
The performance of the conducting polymer composite that embodiment 3-4 is prepared is better than the prepared conducting polymer composite of embodiment 5-6, and this is because the consumption of the raw material 1-naphthalene sulfonic aicd that increases accounts for 2%～3% of mixing solutions total mass that polymerization single polymerization monomer and 1-naphthalene sulfonic aicd iron prepares among the embodiment 3-4.In this scope, have preferably doping level, polymeric membrane is even, under the prerequisite that does not affect conductivity, has good pressure-resistant performance, the electric leakage clear superiority such as low.
Electrical condenser provided by the present invention not only is applicable to low temperature control and has the field of electric frequency response characteristic, the i.e. loop of time constant and tuner; Simultaneously little because of its electric leakage, also be applicable on the amplifiers such as stereophony, sound-track engraving apparatus.
Be the preferred embodiments of the present invention only below, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. conducting polymer composite, it is characterized in that, it comprises conductive polymers and the 1-naphthalene sulfonic aicd radical ion that mixes with described conductive polymers, described conductive polymers is made through oxypolymerization by polymerization single polymerization monomer, and described polymerization single polymerization monomer is for having the mixture of the monomer of structure in following structural formula (1), (2) and (3):
Wherein, R is alkyl.
2. conducting polymer composite according to claim 1, it is characterized in that, the doping level of 1-naphthalene sulfonic aicd radical ion described in the described conducting polymer composite is 40%～65%, and described doping level refers to the ratio of molar weight and the monomer molar amount of negatively charged ion in the whole system.
3. conducting polymer composite according to claim 2 is characterized in that, 1-naphthalene sulfonic aicd radical ion described in the described conducting polymer composite is that the form with 1-naphthalene sulfonic aicd iron is incorporated in the reaction system.
4. conducting polymer composite according to claim 3 is characterized in that, the mol ratio of the introducing amount of described 1-naphthalene sulfonic aicd iron and the add-on of described polymerization single polymerization monomer is 1.5:1～2.4:1.
5. conducting polymer composite according to claim 2 is characterized in that, 1-naphthalene sulfonic aicd radical ion described in the described conducting polymer composite is that the form with the mixing solutions of 1-naphthalene sulfonic aicd iron and 1-naphthalene sulfonic aicd is incorporated in the reaction system.
6. conducting polymer composite according to claim 5 is characterized in that, the add-on of described 1-naphthalene sulfonic aicd is 1%～5% of polymerization single polymerization monomer and 1-naphthalene sulfonic aicd iron total mass.
7. conducting polymer composite according to claim 6 is characterized in that, the add-on of described 1-naphthalene sulfonic aicd is 2%～3% of polymerization single polymerization monomer and 1-naphthalene sulfonic aicd iron total mass.
8. according to claim 3 or 5 described conducting polymer composites, it is characterized in that described 1-naphthalene sulfonic aicd iron is with 3 water crystallizations, the 1-naphthalene sulfonic aicd iron form of 6 water crystallizations or 9 water crystallizations adds.
9. an electrical condenser is characterized in that, comprises each described conducting polymer composite among the claims 1-8 in the described electrical condenser.
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