CN102993643A - Stabilized thiophene derivative - Google Patents
Stabilized thiophene derivative Download PDFInfo
- Publication number
- CN102993643A CN102993643A CN 200910253042 CN200910253042A CN102993643A CN 102993643 A CN102993643 A CN 102993643A CN 200910253042 CN200910253042 CN 200910253042 CN 200910253042 A CN200910253042 A CN 200910253042A CN 102993643 A CN102993643 A CN 102993643A
- Authority
- CN
- China
- Prior art keywords
- residue
- stabilization
- monomer composition
- monomer
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WJHXNARILADKCG-QMMMGPOBSA-N C[C@]1(Oc2c[nH]cc2OCC1)P Chemical compound C[C@]1(Oc2c[nH]cc2OCC1)P WJHXNARILADKCG-QMMMGPOBSA-N 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to a stabilized thiophene derivative, and specifically relates to a stabilized monomer composition. According to the total weight of the stabilized monomer composition, the composition comprises at least 50wt% of a thiophene derivative monomer with a general formula (I), wherein R1 and R2 independently represents hydrogen, optionally substituted C1-C20-alkyl or C1-C20-alkoxy group, which is optionally interrupted by 1-5 oxygen atoms and/or sulfur atoms. Or R1 and R2 together represent optionally substituted C1-C20-dioxoalkylene or C6-C20-dioxoarylene. Based on the total weight of the stabilized monomer composition, the composition also comprises 0.001-10wt% of a stabilizer. The invention also relates to a method for manufacturing a capacitor, a capacitor manufactured with the method, the application of the stabilized monomer composition, and the application of the stabilizer.
Description
Technical field
The present invention relates to a kind of monomer composition of stabilization, a kind of method of making electronic capacitor and electronic capacitor, a kind of application of monomer composition of stabilization and a kind of application of stablizer of making by the method.
Background technology
Adopt conductive polymers as the solid electrolytic capacitor of cathode material, because be widely used in electronic industry in the advantage aspect the failure mode of low ESR (ESR) and " not firing/not on fire ".Comprise polypyrrole, polyaniline and poly-(3,4-ethylidene dioxy thiophene) multiple conductive polymers (PEDOT) is applied to the cathode material of electrolytic condenser, and is used as anode such as the valve metal (or claiming valve metal (valvemetal)) of Ta, Al, Nb and such as the conductive oxide of NbO pottery.In a kind of manufacture method of production based on the conductive polymers electrical condenser of valve metal, for example the Ta powder has been formed the Ta tinsel by mechanical compaction, and this Ta tinsel is high temperature sintering under vacuum subsequently.Tinsel behind the sintering has formed dielectric layer (Ta in the polarization of electrolytic solution middle-jiao yang, function of the spleen and stomach at anode surface
2O
5).Then, applied for example conductive polymer coating of poly-3,4-ethylidene dioxy thiophene (PEDOT) of multilayer by repeatedly flooding polymerization technique.In polymerization process, a kind of oxidizing agent solution, for example the iron in solvent (III) p-tosylate at first is coated on the anode in some cases.Then, according to D Wheeler etc. at disclosed application liquid monomer or the monomer solution in U.S. Patent No. 6334966 such as U.S. Patent No. 6136176 and R.Hahn.
In order in connection, to obtain high electroconductibility, play a crucial role for the preparation of the purity of the thiophene derivant monomer of conductive polymers.Usually, distillation method is the habitual purification process of thiophene derivant.
Such as the thiophene of disclosed by this method purifying in EP1860111A1, the coloured variation of tool and/or generate the trend of the secondary component do not expect in storage process, for example generate below having shown in dimerization or three Polythiophenes of structure.This has caused the sizable infringement of performance of prepared Polythiophene.
For fear of these negative impacts of unconjugated dimerization or three polythiofuran derivatives, the EP1860111A1 suggestion is before making electrical condenser with monomer, with basic material (alkaline materiall) pre-treatment thiophene derivant.Basic material separates from monomer, for example by filtering.Selectively, two files all advise transmitting monomer solution by basic anion-exchange column.
Although according to the disclosed method of EP1860111A1, the storage time of thiophene can be significantly improvement, but in fact also can see the shortcoming of the method, namely no matter when use monomer, all must carry out extra pre-treatment step to monomer with basic material.
Summary of the invention
A target of the present invention is exactly to reduce even overcome the defective of prior art.
The special target of the present invention provides a kind of monomer composition of stabilization of thiophene derivant, and it does not need to carry out pre-treatment with the basic material that must remove subsequently from the composition before making electronic capacitor.
The further target of the present invention provides a kind of manufacturing and has the repeatably method of the electronic capacitor of low ESR value, is compared to the disclosed method of prior art, and it has processing step still less.
All kinds of themes and relevant claim that form by independent principle, to solving working one of at least of above-mentioned target, the dependent claims that relies on thus shows preferred implementation of the present invention.Similar theme of the present invention works to solving at least one target.
The present invention relates to a kind of monomer composition of stabilization, be preferably a kind of transparent solution, it comprises
-under every kind of situation based on the gross weight of stablizing monomer, contain at least 90wt%, preferred 95wt%, more preferably at least 97.5wt% and most preferably the thiophene derivant monomer with general formula (I) of 98.5wt%
R wherein
1And R
2Represent independently of each other hydrogen, optional substituted C
1-C
20-alkyl or C
1-C
20-alkoxyl group, it is optional by 1-5 Sauerstoffatom and/or sulphur atom interruption, perhaps the optional substituted C of jointly representative
1-C
20-two oxyalkylenes or C
6-C
20-dioxy arylidene, and
-under every kind of situation based on the gross weight of stablizing monomer, contain 0.001-10wt%, preferred 0.01-5wt%, more preferably 0.05-2.5wt% and the most preferably stablizer of 0.1-1.5wt%, it is preferably free-radical scavengers, amine or UV/VIS-absorption agent.
Beat allly be that finding now may stabling thiophene derivatives by for example adding free-radical scavengers, amine or these stablizers of UV/VIS-absorption agent, does not need to remove these stablizers before making electronic capacitor with thiophene derivant.Those skilled in the art can not expect, the ESR by the formed electrical condenser of polymerization thiophene derivant in the situation that has these stablizers can keep low value in mode repeatably.Especially beat all in the present invention is to add such as free-radical scavengers and these stablizers of UV/VIS-absorption agent, can stop the formation of dimerization and three Polythiophenes, known to the formation of these stabilizer compounds are acid catalyzed ionic reactions.
Thiophene derivant in the scope of the invention preferably has general formula (II),
Wherein substituted C is chosen in the A representative wantonly
1-C
5-alkylidene residue or C
6-C
14-arylidene residue, the optional substituted C of preferred representative
2-C
3-alkylidene residue;
That R represents line style or branch, optional substituted C
1-C
18-alkyl residue, preferred line style or branch, optional substituted C
1-C
14-alkyl residue, optional substituted C
5-C
12-cycloalkyl residues, optional substituted C
6-C
14-aromatic yl residue, optional substituted C
7-C
18-aralkyl residue, optional substituted C
1-C
4-hydroxyalkyl residue, preferably optional substituted C
1-C
2-hydroxyalkyl residue, or hydroxyl residue;
X represents the integer of 0-8, preferred 0-6, and especially preferred 0 or 1, and when several residue R were bonded to A, they can be identical or different.
This general formula (II) should be understood by this way, and x identical or different substituent R can be bonded to alkylidene residue or arylidene residue A.
Thiophene derivant in the scope of the invention particularly preferably has general formula (IIa)
Wherein R has identical meaning with x with general formula (II).
Embodiment
Thiophene derivant is 3,4-ethylidene dioxy thiophene in one of the present invention preferred embodiment.
C in the scope of the invention
1-C
5-alkylidene residue A is methylene radical, ethylidene, n-propylidene, n-butylidene or n-pentylidene.C in the scope of the invention
6-C
14-arylidene residue A can be for example phenylene, naphthylidene or anthrylene.C in the scope of the invention
1-C
18C-alkyl represent line style or branch
1-C
18-alkyl residue, for example methyl, ethyl, n-propyl group, sec.-propyl, n-butyl, isobutyl-, sec-butyl, tertiary butyl, n-amyl group, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl propyl, 1,1-dimethyl propyl, 1,2-dimethyl propyl, 2,2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.C
1-C
20-alkyl further comprises for example n-nonadecyl and n-eicosyl.C in the scope of the invention
5-C
12The cycloalkyl base represent C
5-C
12-cycloalkyl residues, for example cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl; C
5-C
14Aryl represent C
5-C
14-aromatic yl residue, for example phenyl, naphthyl; C
7-C
18Aralkyl represent C
7-C
18-aralkyl residue, for example benzyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl or sym-trimethylbenzene base.C in the scope of the invention
1-C
20Alkoxyl group represent C
1-C
20-alkoxy residue, methoxyl group for example, oxyethyl group, the n-propoxy-, isopropoxy, the n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, the n-pentyloxy, 1-methyl butoxy, 2-methyl butoxy, 3-methyl butoxy, 1-ethyl propoxy-, 1,1-dimethyl propoxy-, 1,2-dimethyl propoxy-, 2,2-dimethyl propoxy-, the n-hexyloxy, n-oxygen in heptan base, the n-octyloxy, the 2-ethyl hexyl oxy, n-oxygen in ninth of the ten Heavenly Stems base, n-oxygen in last of the ten Heavenly stems base, n-11 oxygen bases, n-ten dioxy bases, n-13 oxygen bases, n-14 oxygen bases, n-16 oxygen bases, n-19 oxygen bases or n-20 oxygen bases.Above-mentioned listed material should not be considered as limitation of the present invention as exemplary illustration of the present invention.
But the numerous organic group arbitrarinesses ground that can consider is substituted alkylene residue or arylidene residue A further; For example alkyl, cycloalkyl, aryl, halogen, ether, thioether, disulphide, sulfoxide, sulfone, sulfonate, amino, aldehyde, ketone, carboxylicesters, carboxylic acid, carbonate, carboxylate salt, cyano group, alkyl silane, organoalkoxysilane and carboxylic acid amide group.
When thiophene derivant showed the degree of one or more stereocenters (stereocentres), thiophene derivant may be racemite, enantiomer-pure or diastereomer pure compound or enantiomorph enrichment or diastereomer enrichment compound.Term " enantiomorph enrichment compound " should be understood to enantiomeric excess (ee) and surpasses 50% compound.Term " diastereomer enrichment compound " should be understood to diastereomeric excess (de) and surpasses 30% compound.Yet, according to the present invention, also have the problem of any mixture of diastereomer.
Thiophene derivant with general formula (I), (II), (IIa) can prepare with method well known in the art.For example, EP-A-1142888 has described so a kind of preparation method.
Monomer composition according to stabilization of the present invention comprises, except previously described thiophene derivant, also comprises stablizer.Stablizer on the meaning of the present invention is interpreted as at the memory period of monomer and particularly is exposed to UV/VIS light lower time, the compound that stops dimerization and three polythiofuran derivatives to form when this monomer.
According to first preferred implementation of the monomer composition of stabilization of the present invention, stablizer can be free-radical scavengers.
" free-radical scavengers " on the meaning of the present invention is interpreted as a kind of compound, itself and free radical reaction, formed reactive ratio with the free radical of compound reaction a little less than reaction product.
The monomer composition of stabilization preferred implementation according to the present invention, wherein this stablizer is free-radical scavengers, this stablizer is called as " HALS " (" hindered amine as light stabilizer ").
In the present invention, this free-radical scavengers can have and comprises that at least one has the chemical structure of the structural unit of general formula (III)
Wherein, R
1Represent the C of hydrogen atom, hydroxyl, line style or branch
1-C
18The C of-alkyl residue or line style or branch
1-C
18-alkoxy residue, wherein residue R
1Particularly preferably hydrogen atom, methyl or H
17C
8-O-base, and R
2, R
3And R
4Represent independently of each other hydrogen atom or organic residue.
According to this preferred implementation of the monomer composition of stabilization of the present invention, this free-radical scavengers has the chemical structure that comprises general formula (IV)
R wherein
1Be and aforementioned residue with same meaning, n is the integer among the 2-20, wherein residue R
1Particularly preferably hydrogen atom, methyl or H
17C
8-O-base, the integer of the preferred 6-10 of value of n, most preferably the value of n is 8.Can be used for suitable free-radical scavengers of the present invention for example can be from Ciba AG, the product that Basel, Switzerland obtain
123,
292,
765,
770DF.
This preferred implementation of the monomer composition of stabilization according to the present invention, this free-radical scavengers also can have the chemical structure that comprises logical formula V
Wherein, R
1Be and aforementioned residue with same meaning, n is the integer among the 2-20, wherein residue R
1Particularly preferably hydrogen atom, methyl or H
17C
8-O-base, the integer of the preferred 4-8 of value of n, most preferably the value of n is 6.Can be used for suitable free-radical scavengers of the present invention for example from BASF AG, Ludwigshafen, the product that Germany obtains
4050H.
Another preferred implementation of the monomer composition of stabilization according to the present invention, wherein stablizer is free-radical scavengers, this stablizer can be phenol derivatives, for example steric hindrance type amphyl, pyrocatechin derivatives, hydroquinone derivative.
This preferred implementation of the monomer composition of stabilization according to the present invention, this free-radical scavengers also can have and comprise that at least one has the chemical structure of the structural unit of general formula (VI)
R wherein
5, R
6, R
7, R
8And R
9Represent independently of each other hydrogen atom, hydroxyl or organic residue, and R
5, R
6, R
7, R
8And R
9At least residue of one of them preferred contiguous at least OH-base be-C (CH
3) residue.2 at the example that can be used for suitable free-radical scavengers of the present invention, 2 '-methylene radical-two-(the 6-tertiary butyl-4-ethyl)-phenol, tertiary butyl hydroxyanisol, tert.-butyl pyrocatechol and 4-tert-butyl catechol.The further preferred residue R of the present invention
5And R
7At least one of them is hydroxyl.
This preferred implementation of the monomer composition of stabilization according to the present invention, this free-radical scavengers also can have and comprise that at least one has the chemical structure of the structural unit of general formula (VII)
R wherein
10Represent hydrogen atom, hydroxyl or organic residue, wherein residue R particularly preferably
10Also comprise the structural unit with general formula (VII).What can be used for suitable free-radical scavengers of the present invention for example can be from CibaAG, Basel, the product that Switzerland obtains
1076,
MD 1024 Hes
1010,076, and can be from BASF AG, Ludwigshafen, the product that Germany obtains
1130.
This preferred implementation of the monomer composition of stabilization according to the present invention, this free-radical scavengers also can further have and comprise that at least one has the chemical structure of the structural unit of general formula (VIII)
Wherein, R
11, R
12And R
13Represent independently of each other hydrogen atom or organic residue, wherein be particularly preferably hydrogen atom and C
1-C
10-alkyl residue.Can be used for suitable free-radical scavengers of the present invention for example Tenox PG and pyrogallol.
According to the second preferred implementation of the monomer composition of stabilization of the present invention, this stablizer can be amine.
According to a preferred implementation of the monomer composition of stabilization of the present invention, wherein this stablizer is amine, and this stablizer can have the chemical structure that comprises general formula (IX)
R wherein
14, R
15And R
16Represent independently of each other hydrogen atom, C
1-C
20-alkyl residue or C
1-C
5-hydroxyalkyl residue, wherein preferred, residue R
14, R
15And R
16Be C one of at least
1-C
5-hydroxyalkyl residue.Can be used for suitable free-radical scavengers of the present invention for example N methyldiethanol amine, DMAE and trolamine.
According to the 3rd preferred implementation of the monomer composition of stabilization of the present invention, this stablizer can be the UV/VIS-absorption agent, preferred UV-absorption agent.Can be used for suitable UV/VIS-absorption agent of the present invention for example can be from Ciba AG, Basel, the product that Switzerland obtains
1130, and can be from BASF AG, Ludwigshafen, the product that Germany obtains
DS49.
Further preferably this stablizer is at least part of according to the present invention may be dissolved in the thiophene derivant monomer.Stablizer is interpreted as at least part of may be dissolved in the thiophene derivant monomer, if when this stablizer with above specified relative amount when monomer is combined, then stablizer can be dissolved in completely in the monomer and not generate the liquid phase of separation or keep solid matter.
According to stabilized thiophene derivant of the present invention, the variation that forms the secondary component of dimerization for example or three Polythiophenes is tending towards reducing significantly, therefore has obviously high stability when storage.At aspect of performance, significantly be different from the thiophene derivant that stabilization is not crossed according to the present invention.
The present invention relates to a kind of method of making electrical condenser equally, and preferred a kind of electronic capacitor comprises
The anode of-formation valve metal (or claiming valve metal (valve metal));
-formation comprises described anode and dielectric precursor;
-adding intrinsic conducting polymer at described precursor, wherein said intrinsic conducting polymer is based on the monomer composition according to stabilization of the present invention.
Except dielectric medium and anode, this precursor can comprise one or more layers other layer.According to an embodiment of the invention, being used for the dielectric of anode can act directly on the dielectric medium or the use adhesive accelerant according to monomer of the present invention, silane for example, such as organic SiClx alkane or its hydrolysate, 3-glycidyl ether-propyl trialkoxy silane (3-glycidoxy-propyltrialkoxysilane) for example, APTES (3-aminopropyltriethoxysilane), 3-thiohydroxy propyl trimethoxy silicane (3-mercaptopropyltrimethoxysilane), 3-methacryloxypropyl trimethoxy silane (3-methacryloyloxypropyltrimethoxysilane), ethene Trimethoxy silane or octyl triethoxyl silane, and/or one or more layers other functional layer.If described polymkeric substance forms by monomer polymerization of the present invention, this intrinsic conducting polymer is then based on monomer according to the present invention so.
In the first step that forms anode with valve metal, the valve metal powder that wherein has high surface area is pressed and sinters into the electrode body of porous, after this finishes, and electric connection line preferred valve metal wire, for example tantalum also typically is pressed into electrode body inside.Perhaps, but also the etching tinsel to obtain the film of porous.When being convoluted electrical condenser, forming the anonite membrane of porous of this electrode body and cathodic coating by the spacer interval and be wound on together.
Understand within the scope of the invention valve metal, it represents that its oxide skin does not allow the electric current metal that uniform-flow is crossed on both direction.When anode applies voltage, the zone of oxidation of valve metal stops current flowing, otherwise when applying voltage on the negative electrode, large electric current may damage oxide skin.Valve metal comprises alloy or the compound of at least a and other element of Be, Mg, Al, Ge, Si, Sn, Sb, Bi, Ti, Zr, Hf, V, Nb, Ta and W and these metals.Be well known that most Al, Ta and Nb in the valve metal.Compound with comparable performance be those can be oxidized and its oxide skin have aforementioned properties, show the compound of metallic conductivity.For example NbO shows metallic conductivity, but it is not considered to valve metal usually.Yet oxidized NbO layer has but shown the performance of typical valve metal oxides layer, and therefore, the alloy of NbO or NbO and other element or compound are the representative instances with compound of comparable performance.
Therefore term " metal that can be oxidized " not only comprises metal, but also comprises alloy or the compound of metal and other element, as long as they show metallic conductivity and energy is oxidized.
The present invention correspondingly particularly preferably provides a kind of method of making electrical condenser, and the valve metal or the compound that it is characterized in that having comparable performance are the alloy of at least a and other element in tantalum, niobium, aluminium, titanium, zirconium, hafnium, vanadium, these metals or alloy or the compound of compound, NbO or NbO and other element.
In second step, formed and comprised described anode and dielectric precursor.
This dielectric medium is preferably formed on the described anode.This dielectric medium preferably is made of the oxide compound of electrode materials, and perhaps when oxide compound having been arranged on the electrode materials, the oxide form higher by electrode materials consists of.This dielectric medium selectively comprises other element and/or compound.As an example, this can oxidized metal be with the electrode body that forms porous or be compressed on vesicular structure on the metallic object with the form sintering of powder.As an example, the latter's operation may be implemented by etched film.As an example, the electrode body of porous is for example oxidized by applying voltage in the phosphoric acid at suitable electrolytic solution, and this just is called " electrode body of oxidation ".The amplitude of the voltage that applies depends on the thickness of the zone of oxidation that will obtain or the applied voltage of follow-up electrical condenser.Voltage preferred 1 to 300V particularly preferably 1 arrives 80V.
In the 3rd step of an embodiment of the invention, intrinsic conducting polymer (intrinsicallyconductive polymer) is added on the described precursor, and wherein said intrinsic conducting polymer is based on the monomer composition of stabilization of the present invention.The preferred described precursor of the present invention is applied by the solution according to the monomer composition of stabilization of the present invention, the dielectric medium of preferred described precursor is applied by the solution according to the monomer composition of stabilization of the present invention, follow the described monomer of polymerization, the preferably mode polymerization by oxypolymerization or electrochemical polymerization, particularly preferably use suitable oxygenant by the mode polymerization of oxypolymerization, thereby obtained intrinsic conducting polymer.
Randomly use other layer, for example polymeric outer layer.The coating that comprises the high conductivity layer, for example graphite and silver, or metallic cathode body are as discharge electrode.Last electrical condenser is touched and seals.
Oxygenant can be with all suitable metal-salts for the oxypolymerization thiophene known in those skilled in the art.
Be suitable for metal-salt as oxygenant and be main group metal on the periodic table of elements or the metal-salt of subgroup metal, the latter is also referred to as transition metal salt hereinafter.Suitable transition metal salt is in particular inorganic or organic acid salt, or comprising the inorganic acid salt of organic group, transition metal for example is the transition metal salt of iron (III), copper (II), chromium (VI), cerium (IV), manganese (IV), manganese (VII) and ruthenium (III).
The preferred iron of transition metal salt (III) transition metal salt.Advantageously, habitual iron (III) salt is cheap, obtain easily and easy handling, the iron of mineral acid (III) salt for example, for example halogenide of iron (III) (FeCl for example
3) or iron (III) salt of other mineral acid, for example Fe (ClO
4)
3Or Fe
2(SO
4)
3, and organic acid and iron (III) salt with mineral acid of organic group.
Have iron (III) salt of the mineral acid of organic group, as an example, can be the C that mentions
1-C
20The iron of-alkanol Monosulfate (III) salt, for example iron of dodecyl sulfuric acid (III) salt.
Particularly preferably transition metal salt is the organic acid transition metal salt, especially is organic acid iron (III) salt.
As organic acid iron (III) salt, for example next mention: C
1-C
20The iron of-alkane sulfonic acid (III) salt, described C
1-C
20-alkane sulfonic acid is methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid or higher sulfonic acid ten disulfonic acid for example for example; Iron (III) salt of aliphatic series Perfluorooctane sulfonates (aliphatic perfluorooctane sulfonic acid), described aliphatic Perfluorooctane sulfonates is trifluoromethanesulfonic acid, perfluor fourth sulfonic acid or perfluorooctane sulfonate for example; Aliphatic series C
1-C
20The iron of-carboxylic acid (III) salt, described aliphatic C
1-C
20-carboxylic acid is 2-ethylhexyl carboxylic acid for example; Iron (III) salt of aliphatic series perfluorocarboxylic acid, described aliphatic perfluorocarboxylic acid is trifluoroacetic acid or Perfluorocaprylic Acid for example; By C
1-C
20Iron (III) salt of the aromatic sulfonic acid that-alkyl replaces arbitrarily, described by C
1-C
20The aromatic sulfonic acid that-alkyl replaces arbitrarily is Phenylsulfonic acid, o-toluenesulphonic acids, p-toluenesulphonic acids or dodecyl Phenylsulfonic acid for example; And the iron of cycloalkyl sulfonic acid (III) salt, described cycloalkyl sulfonic acid is camphorsulfonic acid for example.
Any mixture of these organic acid iron (III) salt noted earlier also can be used as oxygenant.
Use organic acid and iron (III) salt with mineral acid of organic group to have huge advantage, because they do not have the impact of corrosion.
Most preferred metal-salt is the mixture of p-toluenesulphonic acids iron (III), o-toluenesulphonic acids iron (III) or p-toluenesulphonic acids iron (III) and o-toluenesulphonic acids iron (III).
The oxygenant that is fit in addition is superoxide, peracetic dithionite (persulphate) for example, the an alkali metal salt of peroxo disulfate acid ammonium or peroxo disulfate acid particularly, for example sodium peroxydisulfate and potassium peroxydisulfate, the perhaps an alkali metal salt of peroxyboric acid-can have arbitrarily the catalytic amount of metallics, for example iron, cobalt, nickel, molybdenum or vanadium particle also can be transition metal oxides, for example the oxide compound of Manganse Dioxide (oxide compound of manganese (IV)) or cerium (IV).
For the oxypolymerization of thiophene, need the oxygenant (referring to for example J.Polym.Sc.Part A Polymer Chemistry Vol.26, p.1287 (1988)) of 2.25 equivalents on every mole of thiophene molecular theory.Yet oxygenant less or larger equivalent also may be used to.
Be included in that this conductive polymers as solid electrolyte is positively charged ion in the electrical condenser of the method according to this invention manufacturing.In order to compensate positive charge, this cationic electroconductive polymkeric substance needs negatively charged ion as counter ion.
Counter ion can be monomer negatively charged ion or polymerization negatively charged ion, and the latter is called as polyanion hereinafter.As an example, the polymerization negatively charged ion can be the negatively charged ion of poly carboxylic acid, and poly carboxylic acid is polyacrylic acid, polymethyl acrylic acid or polymaleic acid for example; Or the negatively charged ion of poly-sulfonic acid, poly-sulfonic acid is polystyrolsulfon acid and polyvinyl sulfonic acid for example.These poly carboxylic acid and poly-sulfonic acid also can be the multipolymer of vinylcarboxylic acid and vinyl sulfonic acid and other polymerisable monomer, for example acrylate and vinylbenzene.
The preferred monomers negatively charged ion is used for solid electrolyte, because it penetrates oxidized electrode body easilier.
The below lists the example that can be used as the monomer negatively charged ion: C
1-C
20The monomer negatively charged ion of-alkane sulfonic acid, described C
1-C
20-alkane sulfonic acid is methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid or higher sulfonic acid for example, for example ten disulfonic acid; The monomer negatively charged ion of aliphatic series perfluorinated sulfonic acid, described aliphatic perfluorinated sulfonic acid is trifluoromethanesulfonic acid, perfluor fourth sulfonic acid or perfluorooctane sulfonate for example; Aliphatic series C
1-C
20The monomer negatively charged ion of-carboxylic acid, described aliphatic C
1-C
20-carboxylic acid is 2-ethylhexyl carboxylic acid for example; The monomer negatively charged ion of aliphatic series perfluorocarboxylic acid, described aliphatic perfluorocarboxylic acid is trifluoroacetic acid or Perfluorocaprylic Acid for example; By C
1-C
20The monomer negatively charged ion of the aromatic sulfonic acid that-alkyl replaces arbitrarily, described by C
1-C
20The aromatic sulfonic acid that-alkyl replaces arbitrarily is Phenylsulfonic acid, o-toluenesulphonic acids, p-toluenesulphonic acids or dodecyl Phenylsulfonic acid for example; The monomer negatively charged ion of cycloalkyl sulfonic acid, described cycloalkyl sulfonic acid is camphorsulfonic acid for example; Or a tetrafluoro borate, hexafluorophosphate, perchlorate, hexafluoro antimonate, hexafluoro arsenate or hexa chloro-antimonate.The monomer negatively charged ion of sulfonic acid is not limited to the monomer negatively charged ion of these monomer sulfonic acid, also can be the monomer negatively charged ion of disulfonic acid, trisulfonic acid or poly-sulfonic acid, for example the monomer negatively charged ion of benzene disulfonic acid or naphthalene disulfonic acid.
The negatively charged ion of preferred p-toluenesulphonic acids, methylsulfonic acid or camphorsulfonic acid.
These counter anions preferably add oxygenant or stable monomer to their alkali metal salt or with the form of free acid according to the present invention.
The negatively charged ion that may exist in the oxygenant also can be used as counter ion, this means not to be to need utterly to add extra counter ion.
As mentioned above, precursor has applied the solution according to the monomer composition of stabilization of the present invention, and monomer composition is solution in some cases, and is other in other cases.Next the referred especially organic solvent that does not react is produced the solvent of the stable monomer of conductive polymers and/or oxygenant and/or counter ion as the present invention: Fatty Alcohol(C12-C14 and C12-C18) is methyl alcohol, ethanol, Virahol and butanols for example; Aliphatic ketone is acetone and methyl ethyl ketone for example; Alphatic carboxylic acid ester is ethyl acetate and butylacetate for example; Aromatic hydrocarbons is toluene and dimethylbenzene for example; Aliphatic hydrocarbon is normal hexane, heptane and hexanaphthene for example; Chlorinated hydrocarbon is methylene dichloride and ethylene dichloride for example; Fatty nitrile is acetonitrile for example; Aliphatic sulphoxide and sulfone be dimethyl sulfoxide (DMSO) and sulfone for example; Aliphatic carboxylic acid amine is methylacetamide, N,N-DIMETHYLACETAMIDE and dimethyl formamide for example; Aliphatic ether and aromatic oxide be diethyl ether and methyl-phenoxide for example.In addition, the mixture of water or water and above-mentioned organic solvent also can be used as solvent.
The method according to this invention further preferred described interpolation comprises:
-use the solution according to the monomer composition of stabilization of the present invention to apply described precursor;
Thereby the described monomer of-polymerization forms described intrinsic conducting polymer.
The intrinsic conducting polymer that is used for solid electrolyte can add precursor to by the monomer composition with oxygenant polymerization stabilization of the present invention, perhaps is formed on the precursor by the electrochemical polymerization monomer.During with the oxygenant polymerization single polymerization monomer, the form that monomer and oxygenant can mixtures is applied in or is applied to continuously and covered on dielectric precursor.
According to the monomer composition of stabilization of the present invention and oxygenant can solid and/or the form of liquid be mixed together, and then be applied on the anode of electrode body of oxidation to form solid electrolyte layer.But, preferably in mixture, add one or more solvents.The solvent of particularly above having listed can be here as suitable solvent.
Also can be in some cases be applied to continuously on the electrode body of oxidation to form solid electrolyte layer with the form of solution according to the monomer composition of stabilization of the present invention and oxygenant.When applying monomer in the ban, preferred monomers solvent cut mistake.The solvent of particularly above having listed can be here as suitable solvent.
Monomer composition according to stabilization of the present invention also can carry out electrochemical polymerization to form solid electrolyte layer in the electrode body of oxidation.
Oxypolymerization is being carried out under-10 ℃ to 300 ℃ temperature, and preferred 10 ℃ to 200 ℃, particularly preferably 30 ℃ to 150 ℃.The heat treated time length depends on for the polymkeric substance itself that applies, from 5 seconds by several hours.Temperature profile with differing temps and residence time also can be used for thermal treatment.
Wash residual salt and excessive oxygenant is favourable with suitable solvent preferably water and ethanol from coat.Here the residual salt of mentioning is interpreted as the salt of the reduced form oxygenant that may exist and possible other.
Metal-oxide dielectric, the oxide compound of valve metal for example, preferably this oxide film of electrochemical treatment is to repair the defective that may exist on the described oxide film and therefore to reduce residual current on the electrical condenser that makes.Reparation capacitor body described here is capacitor body to be impregnated in the electrolytic solution and in electrode body apply positive voltage.Flow to the electric current of conductive polymers from the whole fault location of the oxide film of electrode body, repaired oxide film or destroyed the electroconductibility of conductive polymers at these fault locations at these fault locations.
Character according to the electrode body of oxidation, be preferably in before the matting and/or after it, once, twice or more times use according to the mixture of the monomer composition of stabilization of the present invention and oxygenant or flood continuously the electrode body of this oxidation with monomer and oxygenant, forms thicker polymer layer with the inside in electrode body.The composition of mixture herein also can be different.This solid electrolyte can be made of the multilayer system that has comprised a plurality of functional layers arbitrarily.
According to a preferred implementation of the method for making electrical condenser, preferably in the situation that has at least a portion stablizer, carry out the polymerization of thiophene derivant monomer.Further preferably before this monomer is applied on the dielectric medium with the form of solution, do not use basic material pretreated, wherein said basic material is removed from monomer after carrying out pre-treatment at least in part.
The present invention relates to a kind of electrical condenser made according to the method for the present invention, preferred electron electrical condenser equally.
The electrical condenser that the present invention makes is because low ESR is suitable for as element application in electronic circuit, significantly for example as filter condenser or decoupling capacitor.These purposes have also formed the part of theme of the present invention.At present, partially be used for electronic circuit, for example computer (desk-top, portable, server), computer fittings (for example PC card), portable electron device, for example mobile telephone, digital camera or recreation electronic, recreation electronic for example is CD/DVD player and computer games controller, is used for navigationsystem, telecommunication path equipment, household electrical appliance, power supply or automotive electronics.
The present invention relates to the monomer composition manufacturing electrical condenser with stabilization of the present invention, preferred electron electrical condenser equally.The monomer composition of preferred stabilization refers to monomer composition described above and stabilization of the present invention relevant and relevant with electrical condenser of the present invention monomer composition and electrical condenser with electrical condenser in this specification sheets.
The present invention relates to equally with the free-radical scavengers that limits before a kind of and stablize the thiophene derivant monomer that limits before.
The following examples are used for exemplary elaboration the present invention and are not considered as limitation of the present invention.
Embodiment
Embodiment 1-15
In an opening beaker, mixing the pure 3 of 5g, 4-ethylidene dioxy thiophene (" EDOT " under 23 ℃ with agitator; Clevios M V2, H.C.Starck Clevios GmbH) and the different stabilizers (50mg) of 1.0 quality %.Utilize high voltage mercury lamp (DESAGA HP-UVIS; Desaga GmbH, Wiesloch, Germany) be placed on the mixture 6 hours of every kind of 1ml in the glass beaker with the UV rayed of wavelength X=366nm.The sample that should open wide does not cover with glass cover, and keeps Hg lamp and sample surfaces to have the distance of 10cm.
After 6 hours, by
1H-NMR-spectroscope CDCl
3EDOT dipolymer and the EDOT trimer content of sample have been analyzed.The intensity that simple substance absorbs is 5.42ppm (δ), utilize corresponding 2,2 ', 3,3 ', 5,7-, six hydrogen-5, the content of EDOT dipolymer is calculated in the position 5 of 5 '-two thieno-s [3,4-b] [Isosorbide-5-Nitrae] dioxin (" EDOT-dipolymer ").2,2 ', 2 ", 3,3 ', 3 ", 5,5 ", 7,7 "-and decahydro-5,5 ': 7,5 " C atom site 5 and the position 5 of-three thieno-[3,4-b] [Isosorbide-5-Nitrae] dioxins (" EDOT-trimer ") ", the resonance of proton is consistent with the absorption of proton.Because in EDOT dimerization and trimerization reaction, the EDOT dipolymer is major product (referring to EP1375560B1, H.C.Starck GmbH), uses
1Can not distinguish dipolymer and trimer when H-NMR-is absorbed as 5.42ppm, calculate the reactor product of EDOT with dipolymer, 100ppm is limit of detection.
Following table 1 has provided the result who has used different stablizers (embodiment 1-15), and has proved inhibition or reduced formation photochemistry dipolymer.
1)Comparative example
2)N.d.=can not detect
Embodiment 16-28
Except (using with the EDOT dipolymer that comprises 1490ppm
1H-NMR-calculates, referring to above) pre-EDOT (continuing storage after several years) the instead of pure EDOT that has degenerated outside, repeat the step of embodiment 1-15.Following table has proved that by different stablizers the generation of extra photochemistry dipolymer has reduced:
1)Comparative example
Embodiment 29 and comparative example C
Utilize in the present embodiment according to the monomer composition of stabilization of the present invention and made a kind of electrical condenser.Comparative example C has then used the not monomer of stabilization according to the present invention.
1.
Make the oxidizing electrode sheet
Tantalum powder (VFI-50KD with ratio electric capacity of 48500 μ FV/g, H.C.Starck GmbH) mixes with camphor as tackiness agent, then with have diameter be 0.49mm the tantalum anode line with lateral pressure compressed together, formed the porous electrode body (anode ball) that is of a size of 4.4mm * 3.1mm * 1.0mm, green density is 5.5g/cm
3This camphor tackiness agent by being removed 190 ℃ of lower thermal treatments in 90 minutes.Then, electrode slice was 1315 ℃ of lower sintering 20 minutes.This electrode slice under 30V voltage in 85 ℃ at the phosphoric acid electrolyte middle-jiao yang, function of the spleen and stomach 4300 μ S that polarize.The current density of used tantalum powder is set to the 150mA/ gram.Electrode slice cleans 60 minutes then dryings under 85 ℃ after anodizing.
2.
Form copolymer solid electrolyte
2.1 the solution that preparation is made of the ethanolic soln of the p-toluenesulphonic acids iron (III) (Clevios C-E, H.C.Starck Clevios GmbH) of the 40wt% of the monomer composition of the stabilization of the embodiment 4 of 1 weight part and 20 weight parts.Comparative example C uses as a comparison sample A of pure EDOT.
2.2 this solution is used for 9 anode balls of dipping.The anode ball impregnated in this solution by the speed of automatic dipping machine with 0.3mm/s, and after dipping 60s, takes out from solution with the speed of 1mm/s.Be under 95% the environment 15 minutes with this anode ball being exposed to relative atmospheric moisture under 25 ℃ afterwards.
2.3 afterwards repeating step 2.1 and 2.2 operation on the anode ball.
2.4 next, in loft drier in 50 ℃ of lower antianode balls thermal treatment 30 minutes.Then anode purge ball 60 minutes in 2% the p-toluenesulphonic acids aqueous solution.With the voltage of 30V, in the p-toluenesulphonic acids aqueous solution, forming again this anode ball 4300 μ S under 25 ℃, then clean and drying with distilled water.
2.5 twice of the technique of repeating step 2.1-2.4.
3.
Form external coating (EC) and electrical testing
In a 2-1 three-necked bottle with agitator and internal thermometer, put into the deionized water of 868g, 330g have 70000 molecular-weight average and by weight solid content be 3.8% polystyrene aqueous sulfuric acid.Temperature of reaction remains between 20 to 25 ℃.When stirring, add 3 of 5.1g, 4-ethylidene dioxy thiophene.Stirred this solution 30 minutes.Stirring in addition this solution after 24 hours, add the ferric sulfate (III) of 0.03g and the Sodium Persulfate of 9.5g.In case reaction is finished, add the strong-acid cation exchanger of 100ml and the weak base anion exchanger of 250ml, in order to removing inorganic salt, and further stirred this solution 2 hours.Ion-exchanger is filtered off, and has obtained poly-(3,4-ethylidene dioxy thiophene)/polystyrene sulfate dispersion.
In having the 5-1 glass reactor of agitator and thermometer, put into the softening water of 2.5l.When stirring, add the water p-toluenesulphonic acids of 214.2g and the green vitriol (III) of 2.25g.In case whole mixture has all dissolved, add 3 of 85.8g, 4-ethylidene dioxy thieno-continues to stir 30 minutes.When stirring, add the 192.9g Sodium Persulfate, further stirred at ambient temperature this mixture 24 hours.After reaction finishes, with porcelain suction strainer filtering processed PEDT/ toluene sulfuric acid powder, clean with the softening water of 3l, at last 100 ℃ of lower dryings 6 hours, obtained bluish black PEDT toluene vitriol powder of 89g.
In a beaker with agitator, the nonionic alkynes based on wetting agent of the dimethyl sulfoxide (DMSO) of poly-(3,4-ethylidene dioxy thiophene)/polystyrene sulfate dispersion of 170g, the water base polyester dispersions of 15g, 8g, the 3-glycidyl oxypropyl trimethyl silica alkane of 1g and 0.4g is concentrated to stir 1 hour.With pearl mill formula splitter unit decomposition the PEDT/ toluene vitriol powder of 6g.For this purpose, when using water cooling, added the zirconium oxide bead (φ 1mm) of 300g and stirred this mixture 1 hour with 7000rpm.At last, the sieve by 0.8 μ m has separated the pearl that grinds.
Then, in prepared dispersion, dip the anode ball according to part 1 and 2 manufacturings, lower dry 10 minutes at 120 ℃ subsequently.In dispersion to dip with a speed be that the automatic dipping machine of 0.15mm/s carries out.Through after the dipping of 10s, from dispersion, take out the anode ball with the speed of 1mm/s.
Then, with graphite (the Electrodag PR406 (Acheson) of 1 weight part and the diethyl glycol butyl (Aldrich) of 3 weight parts) dipping anode ball, and 25 ℃ of lower dryings 30 minutes, in 50 ℃ of lower dryings 30 minutes and lower dry 15 minutes at 150 ℃.Then with silver (Electrodag 503, Acheson) this anode ball of dipping, and 25 ℃ lower dry 15 minutes, lower dry 45 minutes at 150 ℃.
Use LCR analyser (Agilent 4284A) to use four probe method, under 120Hz, measure electrical capacity and under 100KHz, measure equivalent series resistance (ESR).
Table 1 has provided the average electric parameter result of these 9 electrical condensers.The standard deviation of average result, electrical capacity are that 0.5%, ESR is 1m Ω.
Claims (25)
1. the monomer composition of a stabilization, it comprises
-based on the gross weight of the monomer composition of described stabilization, at least the thiophene derivant monomer with general formula (I) of 50wt%
R wherein
1And R
2Represent independently of each other hydrogen, optional substituted C
1-C
20-alkyl or C
1-C
20-alkoxyl group, it is optional by 1-5 Sauerstoffatom and/or sulphur atom interruption, perhaps the optional substituted C of jointly representative
1-C
20-two oxyalkylenes or C
6-C
20-dioxy arylidene, and
-based on the gross weight of the monomer composition of stabilization, the stablizer of 0.001-10wt%.
2. according to claim 1 the monomer composition of stabilization, wherein this thiophene derivant monomer has general formula (II),
Wherein
The optional substituted C of A representative
1-C
5-alkylidene residue or C
6-C
14-arylidene residue, the optional substituted C of preferred representative
2-C
3-alkylidene residue;
That R represents line style or branch, optional substituted C
1-C
18-alkyl residue, preferred line style or branch, optional substituted C
1-C
14-alkyl residue, optional substituted C
5-C
12-cycloalkyl residues, optional substituted C
6-C
14-aromatic yl residue, optional substituted C
7-C
18-aralkyl residue, optional substituted C
1-C
4-hydroxyalkyl residue, preferably optional substituted C
1-C
2-hydroxyalkyl residue, or hydroxyl residue;
X represents the integer of 0-8, preferred 0-6, and especially preferred 0 or 1, and
When several residue R were bonded to A, they can be identical or different.
3. according to claim 1 and 2 the monomer composition of stabilization, wherein this thiophene derivant monomer has general formula (IIa)
Wherein R and x have with claim 1 in identical meaning.
4. the monomer composition of each stabilization according to claim 1-3, wherein this thiophene derivant monomer is 3,4-ethylidene dioxy thiophene.
5. the monomer composition of each stabilization according to claim 1-4, wherein this stablizer is free-radical scavengers.
6. according to claim 5 the monomer composition of stabilization, wherein this free-radical scavengers has and comprises that at least one has the chemical structure of the structural unit of general formula (III)
Wherein, R
1Represent the C of hydrogen atom, hydroxyl, line style or branch
1-C
18The C of-alkyl residue or line style or branch
1-C
18-alkoxy residue, and R
2, R
3And R
4Represent independently of each other hydrogen atom or organic residue.
7. according to claim 6 the monomer composition of stabilization, wherein this free-radical scavengers has the chemical structure that comprises general formula (IV)
R wherein
1Be with claim 5 in have the residue of same meaning, and n is the integer of 2-20.
8. according to claim 6 the monomer composition of stabilization, wherein this free-radical scavengers has the chemical structure that comprises logical formula V
Wherein, R
1Be with claim 5 in have the residue of same meaning, and n is the integer of 2-20.
9. according to claim 5 the monomer composition of stabilization, wherein this free-radical scavengers is phenol derivatives.
10. according to claim 9 the monomer composition of stabilization, wherein this free-radical scavengers has and comprises that at least one has the chemical structure of the structural unit of general formula (VI)
R wherein
5, R
6, R
7, R
8And R
9Represent independently of each other hydrogen atom, hydroxyl or organic residue, prerequisite is residue R
5, R
6, R
7, R
8And R
9One of at least be-C (CH
3) residue.
11. the monomer composition of stabilization according to claim 10, wherein residue R
5And R
7One of them be hydroxyl.
12. the monomer composition of stabilization according to claim 10, wherein this free-radical scavengers has and comprises that at least one has the chemical structure of the structural unit of general formula (VII)
R wherein
10Represent hydrogen atom, hydroxyl or organic residue.
13. the monomer composition of stabilization according to claim 9, wherein this free-radical scavengers has and comprises that at least one has the chemical structure of the structural unit of general formula (VIII)
Wherein, R
11, R
12And R
13Represent independently of each other hydrogen atom or organic residue.
14. the monomer composition of each stabilization according to claim 1-4, wherein this stablizer is amine.
15. the monomer composition of stabilization according to claim 14, wherein this amine has the chemical structure that contains general formula (IX)
R wherein
14, R
15And R
16Represent independently of each other hydrogen atom, C
1-C
20-alkyl residue or C
1-C
5-hydroxyalkyl residue.
16. the monomer composition of each stabilization according to claim 1-4, wherein this stablizer is the UV/VIS-absorption agent.
17. a method of making electrical condenser comprises
The anode of-formation valve metal;
-formation comprises described anode and dielectric precursor;
-adding intrinsic conducting polymer at described precursor, wherein said intrinsic conducting polymer is based on the monomer composition of each stabilization that limits of claim 1-16.
18. method according to claim 17, wherein said interpolation comprises:
-apply described precursor with the solution of described monomer;
The described monomer of-polymerization is to obtain intrinsic conducting polymer.
19. wherein there is the polymerization of carrying out described monomer under the condition of stablizer in the method for claim 17 and 18.
20. each method in the claim 17 to 19, it is pretreated that wherein the monomer composition of this stabilization is not used basic material, and wherein said basic material can be removed from the monomer composition of this stabilization after carrying out pre-treatment at least in part.
21. the electrical condenser that each method makes in 20 according to claim 17.
22. the application of the monomer composition of the stabilization that each limits in the claim 1 to 16 is for the manufacture of electrical condenser.
23. application according to claim 22, wherein said thiophene derivant monomer are 3,4-ethylidene dioxy thiophene.
24. the application of the stablizer that each limits in the claim 5 to 16 is used for stablizing each thiophene derivant that limits of claim 1 to 4.
25. application according to claim 24, wherein said thiophene derivant monomer are 3,4-ethylidene dioxy thiophene.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910253042 CN102993643A (en) | 2009-09-30 | 2009-09-30 | Stabilized thiophene derivative |
| JP2010221757A JP5524795B2 (en) | 2009-09-30 | 2010-09-30 | Stabilized thiophene derivatives |
| US12/894,952 US8420671B2 (en) | 2009-09-30 | 2010-09-30 | Stabilised thiophene derivatives |
| KR1020100095697A KR101516838B1 (en) | 2009-09-30 | 2010-09-30 | Stabilised thiophene derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910253042 CN102993643A (en) | 2009-09-30 | 2009-09-30 | Stabilized thiophene derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102993643A true CN102993643A (en) | 2013-03-27 |
Family
ID=47922786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910253042 Pending CN102993643A (en) | 2009-09-30 | 2009-09-30 | Stabilized thiophene derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102993643A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822433A (en) * | 2018-06-08 | 2018-11-16 | 江苏嘉仁禾科技有限公司 | A kind of dedicated low smell of toy film is without phenol barium zinc stabilizer and preparation method thereof |
-
2009
- 2009-09-30 CN CN 200910253042 patent/CN102993643A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822433A (en) * | 2018-06-08 | 2018-11-16 | 江苏嘉仁禾科技有限公司 | A kind of dedicated low smell of toy film is without phenol barium zinc stabilizer and preparation method thereof |
| CN108822433B (en) * | 2018-06-08 | 2021-02-19 | 江苏嘉仁禾科技有限公司 | Special low-odor barium-zinc phenol-free stabilizer for toy film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11600449B2 (en) | Layer compositions with improved electrical parameters comprising PEDOT/PSS and a stabilizer | |
| EP2622616B1 (en) | A method for improving electrical parameters in capacitors comprising pedot/pss as a solid electrolyte through a polyalkylene glycol | |
| CN101884078B (en) | Method for the production of electrolyte capacitors with polymer intermediate layer | |
| EP2161293B1 (en) | Conductive polymer suspension and method for producing the same, conductive polymer material, electrolytic capacitor, and solid electrolytic capacitor and method for producing the same | |
| CN103534318B (en) | Electric conductive polymer suspension and preparation method thereof, conductive polymer material and electrolysis condenser and preparation method thereof | |
| JP5524795B2 (en) | Stabilized thiophene derivatives | |
| KR101644770B1 (en) | Dispersion of electrically conductive polymer, and electrically conductive polymer and use thereof | |
| JP5465025B2 (en) | Conductive polymer suspension and manufacturing method thereof, conductive polymer material, solid electrolytic capacitor and manufacturing method thereof | |
| CN101110297B (en) | Electrolytic capacitors having polymeric outer layer and process of their production | |
| JP2010275378A (en) | Conductive polymer suspension, method of production thereof, conductive polymer material, solid electrolytic capacitor and manufacturing method thereof | |
| TW200523961A (en) | Electrolytic capacitors with a polymeric outer layer | |
| TWI464173B (en) | Monomers of selected colour numbers and capacitors prepared therefrom | |
| JP5745881B2 (en) | Solid electrolytic capacitor | |
| US20130100585A1 (en) | Electroconductive polymer suspension and method for producing the same, electroconductive polymer material, and solid electrolytic capacitor and method for producing the same | |
| CN102731970A (en) | Electroconductive polymer suspension, its preparation method, conductive organic material, electrolytic capacitor and its preparation method | |
| CN102993643A (en) | Stabilized thiophene derivative | |
| JP6223703B2 (en) | Conductive polymer solution and method for producing the same, conductive polymer material, and solid electrolytic capacitor | |
| JP2012222146A (en) | Conductive polymer suspension aqueous solution and manufacturing method thereof, conductive organic material, solid electrolytic capacitor and manufacturing method thereof | |
| JP6266236B2 (en) | Conductive polymer solution and manufacturing method thereof, conductive polymer material, solid electrolytic capacitor and manufacturing method thereof | |
| CN102030760B (en) | Monomer with selected chromatic number and capacitor prepared by same | |
| TWI486365B (en) | Stabilised thiophene derivatives | |
| CN103951674A (en) | Monomer with selected chromatic number and capacitor prepared by the same | |
| JP2010098258A (en) | Oxidizer for manufacturing conductive polymer, solid electrolytic capacitor using the same, and method of manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: HERAEUS PRECIOUS METALS GMBH + CO.KG Free format text: FORMER OWNER: H. C. STARCK CLEVIOS GMBH Effective date: 20150331 |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20150331 Address after: Hanau Applicant after: Heraeus Gmbh W C Address before: Goslar, Germany Applicant before: H.C. Starck Clevios GmbH |
|
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20160323 |
|
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |